text:
Your search for
Volvo returned 134 results
Volvo V40 1.9D SE (2003)A small Volvo for the more conservative motorist. Volvo V70 Cross Country (2000)Was it a large estate car or an SUV? Well, it was sort of both. Volvo V70 T5 (2001)Large estate practicality - and 250bhp. Volvo XC90 D5 SE (2003)First UK drive of the immensely popular XC90. Volvo S80 D5 S (2004)S80 suggested that Volvo was at its happiest building large cars. Volvo S40 1.8 SSometimes the cheapest model in a range can also be the most appealing. Volvo V50 2.0D SE (short test)Fine engine, odd packaging. Volvo V50 2.0D SE (long test)A good car for two people and their luggage, but no more. Volvo XC90 2.5T SE (2005)Great on tarmac, fairly good off-road, but exceptionally thirsty. Volvo XC90 D5 Euro IV SE Geartronic (2006)A very good SUV, spoiled in this case by too many expensive extras. Volvo XC90 Ocean Race Edition (2006)Special XC90 seemed to be nothing more than a way for Volvo to make money. Volvo XC90 SE Sport D5 (2006)UK-specific version of the XC90 was the best in the range. Volvo C30 2.0d SEVolvo challenges Audi and BMW's premium compact cars. Volvo C30 1.6D SEVolvo compares its smallest model to Marmite. Volvo XC70 D5 SE Geartronic (2007)Want to carry a fridge without folding down the back seats? The V70 is the car for you. Volvo V70 D5 SE (2007)Already superb V70 became even better in 2007. Volvo S80 D5 SE (2007)It's a nice enough car, as long as you don't try to rush it. Volvo XC70 D5 SE Geartronic (2008)Testing Volvo's emergency service (without meaning to). Volvo C30 1.6 R-Design SportIf any Volvo is likely to appeal to younger customers, it's this one. Volvo C70 D5 SE Lux Geartronic (2008)Clever and good-looking, but not easy to love. Volvo S80 D5 SE Lux Premium Geartronic (2009)Formerly described as dull and lifeless, the S80 suddenly becomes a driver's car. Volvo V70 2.0D R-Design (2008)This, we're sure, is the car that Volvo itself feels most comfortable with. Volvo XC60 2.4D DRIVe SEWe can't help admiring this XC60's safety features and splendid fuel economy. Volvo V50 1.6D DRIVe SE With Start-Stop (2009)Things became even better later, but in 2009 this V50's 104g/km CO2 emissions were considered remarkable. Volvo S60 D3 SEIf you're interested in buying a Volvo S60, the D3 diesel version is the one to go for. Volvo V60 T3 R-Design PremiumIt isn't really very sporty, but it looks it. Which may be enough. Volvo XC90 D5 SE AWD (2011)A new D5 turbo diesel engine is one of the few changes to the very successful XC90. Volvo V50 DRIVe SE StartStop (2011)Volvo brings the CO2 rating of its V50 below 100g/km. Volvo V60 1.6 D2 R-Design DRIVe53mpg in a Volvo estate? Yes, that's what we got. Volvo S60 D5 SE Start Stop2012 S60 has the best power/CO2 combination on the market. Volvo S80 DRIVe SE (2011)A comfortable executive saloon that costs just £30 a year to tax. Volvo V60 T6Volvo makes an interesting fast estate - but there's a Skoda we prefer. Volvo XC90 D5 SE (2012)Still a very fine SUV a decade after its launch. Volvo V40 Cross Country T5 Lux GeartronicThe most expensive, and least appealing, car in the V40 range. Volvo V60 D4 SE NavThe first time we've suggested a 99g/km car might be too powerful for its own good. Volvo V70 D4 SE Lux GeartronicGreat engine and gearbox, but the rest of the V70 is showing its age. Volvo S60 D4 SE Nav GeartronicVolvo gets it very wrong. Volvo V60 PolestarExcellent work by Sweden's leading motor racing team. BMW 330 Ci Convertible (2003)A "babe magnet", apparently, almost regardless of who's sitting in it. Mitsubishi Shogun 3.2 TD DI-D Field Automatic (2003)A diesel automatic SUV was still a rarity in 2003. Subaru B9 Tribeca SE5A thirsty SUV, but one that handled beautifully. Ford Mondeo 2.5i Titanium X EstateA great long-distance load-carrier, though not economical with this engine. BMW 330 Ci Convertible (2003)BMW's powerful soft-top proves to be quite a hit with the ladies. Ford Focus Estate 1.6 EcoBoost TitaniumNice engine, but the economy is disappointing. Peugeot 508 RXHA semi-off-road estate with a clever diesel/electric hybrid system. SEAT Leon ST 2.0 TDI 184 FRST is reasonably, though not class-leadingly, roomy. 182bhp is too much for it. BMW 220d SEOne step away from being a superb little coupe. 2010 Volvo V60 estate review
A compact estate that boasts style and comfort
2012 Volvo V40 hatchback review
This premium family hatchback takes on the German premium brands
2006 Volvo S80 saloon review
Volvo's largest saloon is an alternative to premium brand offerings
2013 Volvo V40 Cross Country hatchback review
Family hatchback with some 4x4 characteristics
2008 Volvo XC60 crossover review
Attractive crossover which challenges other premium entries


text:
I had to leave you with something fun this week. With Valentine's right around the corner, here are a few more Lunchbox Laughs for your kids (or spouse's) lunch.
May their lunches be filled with smiles and giggles!
You can find the free Lunchbox Laughs HERE.
You can find other Lunchbox Laughs HERE.

subset: commoncrawl


text:
I can only hope the runway is durable and well-enforced.
Ugh, it's like seeing a sack of groceries in swim wear.
And by work I mean strip club. And by strip club I mean the unmarked dumpster behind the Jiffy Lube.
What did this outfit need more of? Honey mustard, apparently.
The "Mouth in front of a powerful fan" look is symbolic. Symbolic of how much this blows.


text:
Academic Enrichment
Academic Enrichment Camp
Adaptive Services
Advice & News
Advocacy & Social Services
Alternative Medicine
Apple, Berry & Pumpkin Picking
Art Camp
Art Class
Baby Products
Baseball & Softball
Behavior & Discipline
Behavior Management
Birthday Ideas & Inspiration
Birthday Party Places
Camp Advice & Tips
Camp Advisors & Consultants
Child Care
Classes, Fun & Socialization: Special Needs
Cooking Camp
Cooking Class
Creative Arts Therapies
Dance Camp
Dance Class
Day Camp
Day Care & Child Care
Dentists & Dental Providers
Developmental Disorders
Divorce & Custody Rights
Doctors & Medical Providers
Doctors & Treatment Providers
Doula & Baby Nurse
Early Intervention
Education Stores & Resources
Emotional & Socialization Disorders
Family Law & Legal Services
Finance & Insurance
Food & Nutrition
Food Services & Catering
Foreign Language
Foreign Language Camp
Foreign Language Class
GENERAL - Table of Contents
Gymnastics & Cheerleading
Home Services
Horseback Riding
Hospitals & Medical Centers
Indoor Play Spaces
Kid's Products
Kids' Health
Learning Disabilities & Dyslexia
Legal & Future Planning
Martial Arts
Math & Science Class
Mental Health & Depression
Mental Health: Special Needs
Mommy & Me Class
Museums & Planetariums
Music Camp
Music Class
Nanny, Babysitter & Au Pair Services
Occupational & Physical Therapy
Parent Groups & Playgroups
Parent Support
Party Entertainment
Party Stores & Resources
Physical Disabilities
Play Therapy
Pregnancy & Baby
Private School
Public School
Religious School
Sensory Integration
Skating & Ice Hockey
Special Education
Special Education
Special Needs Camp
Special Needs Schools
Speech Therapy
Sporting Events
Sports & Fitness Classes
Sports Camp
Sports Programs
STEM, Science & Tech Camp
Swimming & Water Sports
Theater & Acting Camp
Theater & Acting Class
Therapy & Counselors
Tutors & Test Prep
Video & Photo
Video of the Week
Vision Therapy
Vocational Training
Women's Health
Zoos & Aquariums
While conducting research for my new book, Dr. Susan's Fit and Fun Family Action Plan, I discovered that parents struggle with how to pack a healthy school lunch that their kids will actually eat! I found that often moms and dads avoid - or give in to - whining, temper tantrums, or begging, so that school lunch becomes a sugar-stuffed, fat-filled, no-protein meal.
Your child may be smiling for the moment, but a school lunch with no quality protein or too much fat and sugar will not give your child the sustained energy he needs to fuel his brain and body throughout the school day for learning and playing. In fact, he may experience a steep drop in energy about an hour after eating a high-sugar meal - making it difficult to focus during afternoon classes or even playtime. In addition, an unhealthy lunch is a sure contributor to weight gain and poor eating habits, both of which can last a lifetime.
Indeed, every child - no matter what her weight - needs to learn how to eat healthy, and just as importantly, how to stand up to peer pressure ("But, Mommmmyyyy, everyone brings cookies and chips..."), even when it comes to school lunch. In fact, if you give your child the tools early on to resist peer pressure about lunchbox choices, she will be better equipped to do so when she is older and faced with more serious decisions - like alcohol and drugs.
Begin by explaining that lunch must always have a serving of healthy protein such as peanut butter (if your school allows nuts), lean cold cuts, tuna, or cheese. Add a serving of a carbohydrate (preferably whole grain, such whole wheat bread or crackers), and always add a fruit and even a vegetable (baby carrots, celery, sliced cucumbers, grape tomatoes, raw cauliflower or broccoli). Last, offer your child a single serving of a 'junk food' snack for either lunch or snack. Read the label to determine the serving size of each snack. If your child chooses the 'junk food' snack for his lunchbox, then pack fruit, veggies, cheese, yogurt, pretzels, or another low-fat, high protein food for snack time. One more important tweak is to replace juice boxes with small bottles of water. For some children, this is a difficult change, so if necessary do so gradually, making the substitution for either lunch or snack until she gets used to it.
You may experience some resistance to these changes, but don't give in! Remember, your child's health is important, as is teaching him that just because other people make less healthy choices, it doesn't make them correct!
You will find that involving your child in preparing school lunch will make her much more invested in eating it. Preschool and young elementary children can help by putting in the prepared items (water, snacks). Older kids can make their own sandwiches and eventually make the entire lunch without supervision. This level of independence should be encouraged, and each healthy choice applauded. And don't be surprised if you find that your child's new knowledge starts to spill over to other areas of eating and food preparation.
DR. SUSAN BARTELL is a nationally recognized child, teen, and parenting psychologist and award-winning author. Her latest book is Dr. Susan's Fit and Fun Family Action Plan: 301 Things You Can Do Today. Learn more at www.drsusanbartell.com.
Tips to Choosing the Right Nanny for Your Family
How to Raise Your Son to Be a Gentleman
14 Fun Ways to Celebrate Valentine's Day with Your Kids
How to Keep Kids Active and Healthy in the Winter
6 Ways to Make History More Fun for Kids
local zones
Nassau cont.
Suffolk cont.
Westchester cont.
Rockland cont.
Queens cont.
Brooklyn cont.


text:
Franciscan Sisters Christmas Hymn
Version 8 and above required to view videos
Uploaded by Kolter Creative Counsel on Dec 10, 2007
Two Franciscan Sisters of Christian Charity, Conservatory teacher and one of their new Postulants, perform "I Wonder As I Wander"
Franciscan Sisters Catholic Vocation Calling Discerning Religious women Saint Francis Holy Li
0 Comments
Leave a Comment
Suggested Videos
Events at Catholic Familyland 15,034 views View Video
St. Mary's Cistercian Abbey, Ireland 15,941 views View Video
Little Brothers of Saint Francis-Boston, ... 19,609 views View Video
Franciscan Peace 27,534 views View Video
Franciscan Sisters Education Ministry- ... 14,461 views View Video
Want to share your informative and entertaining video with an international audience? Sign In
Most Popular
Rare video shows 'successful' exorcism on woman 'possessed by devil' Read More
CO-PILOT LOCKED CAPTAIN OUT OF COCKPIT: Chilling last minutes of Germanwings Airbus crash revealed Read More
Where's the most hate in the United States? A look into the top states with the highest amount of hate groups may shock you Read More
For the first time in over 150 years -- Blood of St. Januarius liquefies during Francis' visit to Naples Read More
STANDING FIRM: Nearly 500 British priests urge synod to stand firm on Communion for the remarried Read More


text:
Recetas-faciles.com is at the age of #8. Alexa ranks on #9,313,823 in the world ranking. This site service in Spain. It has 16 category. Its IP address is 184.108.40.206. Last updated on Monday, 18 August 2014.
Essential word weight demonstrates the significance of catchphrase that expressed in page. Numerous components influence catchphrase weight. The things that web crawler considers - title and take a rate of the magic word in labels, ascertain the rate of the catchphrase in the content of page, assess striking and italic names, and so on. Currently, we found 16 categories on Recetas-faciles.com.
Google Trends give you to take after word question power with graph. As indicated by inquiry structure that you require, it displays you to classify them as news and pictures. Investigate the five essential catchphrase on Recetas-faciles.com since 2004 in the around the world. Watch looking subjects inclinations with Google Hot Searches.
HTTP header is messages header of requests and responses in the Hypertext Transfer Protocol (HTTP). The HTTP Headers of Recetas-faciles.com.
Recetas-faciles.com HTML information: charset, page size and text size.
There are 1 records on this site title.
There are 19 website metas on Recetas-faciles.com.
There are 5 website important html tags Recetas-faciles.com.
There are 10 internal links on Recetas-faciles.com. Your website address or its sub-links called deep link. Those links are very important, because search engines and the users are reaching those links.
You can create links by adding rel="nofollow" tag, which is not searched by search engines. These kinds of links called nofollow links. You also should add nofollow tag to the links, you think it doesn't need it. The links on the other websites are called external link. You should not have too much external links on your website. Other wise this will affects your website negatively. It's very important to use pictures on your website to bring up the main concepts of your website. This will increase your potential visitor number. Search engines understand the pictures by their alt tags. If there is no alt tag, search engine doesn't understand anything from the image. That's why you should use alt tag on your all pictures, which you use in your website. It's crucial to use alt tag and to make sure search engines know what you are talking about.
The Sitemaps contains URLs to these pages so that web crawlers can easily find them. We found sitemap on this Recetas-faciles.com.
Domain name is page's name and address on web. Without this address, an Internet client can achieve the page just with IP addresses. Case in point, page that you are going by now domain name is recetas-faciles.com. Domain name is the simple sort that the via the path of least resistance of number framework that we say IP addresses. Surely domain name is not the administration that we purchase however the administration that we lease, so you can revive your name's opportunity in greatest 10 years, ordinarily domain names that spared least one year could be enlisted up to 10 years. Recetas-faciles.com has 8 years old, It will be expired on 2006-10-17. Domain registrar is DOMAIN.COM, LLC
Domain is either you or your company's ID in the Internet, when you apply to connect to Internet, they will give you protocol number. This called IP address (Internet Protocol Number). Every device connected to Internet has an IP number. Each computer has to have an IP number to connect with other computers. For example your computer's IP address is 126.96.36.199. The other computers find you with this number. Domain is just appearance of this numbers.
IP (Internet Protocol Address) is an address that gadgets' utilization for information Exchange on system joined with other bundle locking for utilizing web or TCP/IP convention. IP addresses are in the size for Ipv4 32 bit that is basic and indicated with 4 bit of 8 bit number that distinguish with focuses. For example: 18.104.22.168 The server IP location of Recetas-faciles.com is 220.127.116.11, we have discovered 4+ site facilitated on this server.
Alexa rank is a scoring framework that measuring an activity and making characterization as per this movement those Alexa Toolbar clients are going to sites. Webmasters, publicists and ad networks assess your website that base on alexa rank estimation of your site or online journal. On the off chance that you have site that have high fame, both you are gone to by more guest and you pick up high benefit on promotions that you show. We discovered aggregate 20+ domain names. The sites that positioned in the middle of #9,313,833 and #9,313,813 on the web just before or after Recetas-faciles.com.
We found total 1+ domain names like recetas-faciles.com. Their owners may be the same company or not.
Traffic Rank Graph
Pageviews Graph
Reach Graph
Bounce(Percent) Graph
Pageviews/User Graph
Time on Site Graph
Search(Percent) Graph
Recetas-faciles.com Alexa information
Recetas-faciles.com page load time is the time required for website visitors open, the less load time and means to open the site faster.
Ranchhuntandfish.comCalifornia Hunting Clubs,Public Lands,hunt pigs,hogs, boar, turkey, pheasant, Oregon, BLM, national forests
Tags: - Click for more tags (0) at Ranchhuntandfish.com page.
Tvslivestream.comWatch Live Stream Online TV
Tags: tvslivestreamcom, tvslivestream, tv live stream. Click for more tags (3) at Tvslivestream.com page.
Mindfiremedia.co.ukResponsive Website Design and Social Seo Media Company Mind Fire Media
Tags: mind fire media seo & social seo, Social SEO, responsive website designers. Click for more tags (3) at Mindfiremedia.co.uk page.
Mannypacquiaovsfloydmayweatherlive.netFloyd Mayweather vs Manny Pacquiao Live | Pacquiao vs Mayweather Live on May 02, 2015
Tags: - Click for more tags (0) at Mannypacquiaovsfloydmayweatherlive.net page.
Tags: - Click for more tags (0) at Grafikdiyeti.com page.
Constructive, overall criticism will be received and we can inform the website owner, if the owner registers and confirms site ownership according to Webpagesinfo.com policies.
All trademarks and trade names are the property of their respective owners and used here for identification purposes only.
"Flash cardz tools"
© Copyright 2015 Webpagesinfo. All Rights Reserved.


text:
East Lake Camping
Hopkins, Michigan
Phone: (269) 793-7177
Sites: 110
Recent Rate: $50 6/2011
These reviews are the opinion of an RVParkReviews' member and not the views of RVParkReviews.com
Date of Stay: June, 2011 - $50.00
Spacious park with spotless bathrooms, showers, pools and laundry room. Roomy level sites with excellent utilities and good Wi-Fi. Many seasonal campers, but all units and sites well maintained. We stayed in rear of the park on top of the hill and near pool, showers and bathrooms. Huge and beautiful log home on premises is used as the community center containing library, kitchen, TV room, and video and game room. Small lake/large pond and paddle boats available, but very weedy. Pool was great but crowded. Nice quiet place with space to spread out. We camped at East Lake Camping in a Motorhome.Undo
Date of Stay: September, 2009 - $34.00
This is a very nice family campground off the beaten path. The owners keep the campground very clean. Hot clean showers. Very nice playground area, including shuffleboard and volleyball. They had a few boats for rent. They had a nice campstore and a barn with some arcade games, ping pong, and a pool table. We stayed in the campsites right across from the playground and they were nice size lots, grassy, and plenty of shade. We would definitely camp here again. We camped at East Lake Camping in a Travel Trailer.Undo
35 Ratings
Scottsdale, Arizona
29 Ratings
Shipshewana, Indiana
Pre-Register below to access free and enhanced features coming in the near future.
Access to marketing tools, ability respond to reviews and monitor performance as well as expanded listings.
Essential Marketing resources, page insights, daily reports, setup and manage notifications of newly posted reviews.
Expand your listing, Add photos and videos, update business details and more.
More Information about our Campground Owner Management and its enhancements are coming very soon. Features subject to change.


text: Q: My cycle is 32 days, when do I ovulate? A: If your cycle lasts 32 days, then you likely ovulate around cycle day 18 plus/minus 2 days (18 days from the first day of your menses -- 32 minus 14). Keyword Tags: ovulationOvulationcyclemenses Previous: 28-Day Cycle and OvulationNext: 26-Day Cycle and Ovulation


text:
Ho Ho Ho…Hum
Sometimes Christmas just seems so far away. Sure we've put up the tree but then we have to wait for the big guy in the red suit to stop by with the goods. What happens in between now and then. I will tell you what happens your Roommate gets all bored and does things you wish she wouldn't and then she posts them on her blog.
It's shaping up to be THAT kind of week.
Posted on December 4, 2012, in Autumn, Bob Almighty!, Christmas, In The Neighborhood, Pennsylvania, Teddy B. Malestrom, The Roomie, What happened today and tagged Bah Humbug, OMG Files. Bookmark the permalink. Leave a comment.


text:
Book your room at Days Inn & Conference Centre - Montreal Airport
Standard Room, 1 King BedMax Occupancy: 3 guests (up to 2 children)
Standard Room, 2 Queen BedsMax Occupancy: 5 guests (up to 4 children, 4 infants)
Hotel with a restaurant, in Montreal (Saint-Laurent)
This hotel is located in Montreal (Saint-Laurent), near the airport, Place Vertu Shopping Center, Bombardier Aerospace, and CAE. Local attractions also include Bois-de-Liesse Nature Park and Hippodrome de Montreal.
Hotel Features
In addition to a restaurant, Days Inn & Conference Centre - Montreal Airport features a fitness center. Other amenities include complimentary high-speed (wired) Internet access and dry cleaning/laundry services.
Room Amenities
Televisions come with cable channels. Guestrooms also feature complimentary wireless Internet access, refrigerators, and microwaves.Information missing or incorrect? Tell us!
Hotel Amenities
Hotel Amenities
The hotel offers a restaurant. Public areas are equipped with complimentary wired high-speed Internet access. A business center is on site at this 3-star property. This Montreal hotel also offers a fitness center, multilingual staff, and coffee/tea in the lobby. Complimentary self parking is available on site.
- Total number of rooms - 92
- Number of floors - 3
- Restaurant
- Business center
- Dry cleaning/laundry service
- Free wired high-speed Internet
- Breakfast available (surcharge)
- Coffee/tea in lobby
- Conference space
- Elevator/lift
- Fitness facilities
- Airport transportation
- Multilingual staff
- Free self parking
Available in all rooms: Free WiFi
Available in some public areas: Free wired high-speed Internet
Free self parking
Room Amenities
- Free WiFi
- Cribs/infant beds (surcharge)
- Refrigerator
- Microwave
- Rollaway/extra beds available
- Free newspaper
- Coffee/tea maker
- Hair dryer
- Iron/ironing board
- Cable TV service
- Room service (limited hours)
Where to Eat
Magik Bar - This restaurant serves breakfast, lunch, and dinner. Guests can enjoy drinks at the bar.
Room service (during limited hours) is available.
Nearby Activities
The recreational activities listed below are available either on site or nearby; fees may apply.
- Golfing nearby
Hotel Policies
Minimum check-in age is 18
Check-in time starts at 3 PM
Check-out time is noon
Payment types
You need to know
Extra-person charges may apply and vary depending on hotel policy.
Government-issued photo identification and a credit card or cash deposit are required at check-in for incidental charges.
Special requests are subject to availability upon check-in and may incur additional charges. Special requests cannot be guaranteed.
- Breakfast fee: between CAD 5.00 and CAD 15.00 per person (approximately)
- Crib (infant bed) fee: CAD 15.00 per night
- Rollaway bed fee: CAD 15.00 per night
We should mention
This property offers transfers from the airport. Guests must contact the property with arrival details before travel, using the contact information on the booking confirmation. Children 17 years old and younger stay free when occupying the parent or guardian's room, using existing bedding.


text:
Very simple android game type dev
Closed - This job posting has been filled.
Job Description
App will have a text box to input a start number and finish number
user enters start number and finish number then presses submit
numbers cycle through randomly on screen
user presses a button and a number is picked at random between the start and finish number.
This number is shown on screen.
user can press another button to start the numbers cycling again so that they can pick another random number,
previous drawn numbers are displayed at bottom of screen.
I will provide a flash app that does exactly what is needed. you can just duplicate the functionality exactly of this flash app.
This is very simple,,, i dont need any crap like helping me upload it to the app store, I dont need it to look good... its just for internal use by my company.
its a simple app and I will provide the exact instructions along with a flash app that does exactly what is needed. So I will pick whoever is cheapest. A proper android dev should be able to do this within a few hours
Skills: android-development


text:
The World's No.1 Matchmaking Service
1 of
View Album
Profile created by Self
36 yrs,
5' 6",
Never Married
, Punjabi
Bachelors degree in Computers/ IT
Sr. Manager / Manager
Lives in Hounslow, United Kingdom
Detailed profile
Partner Preference
About her
I find it difficult to describe myself but will give it a go...
I am a highly ambitious, motivated, hard-working individual. I have good traditional values followed with a strong family background. I am spontaneous and am blessed with a creative flair.
Enjoy all types of music, have traveled afar sampling local cultures. Enjoy many sports.
If you reside in UK contact me to find out more...IF YOU LIVE IN INDIA PLEASE DO NOT SEND ME ANY REQUESTS
lifestyle & appearance
Doesn't Drink
Doesn't Smoke
Fair skinned, Athletic Build
, Punjabi
Lives in Hounslow, Greater London / Middlesex, United Kingdom (Citizen)
Grew up in United Kingdom
View Family Details
her family
I personally have a traditional approach to life. My father runs a business and my mother is a homemaker. I have 1 brother (unmarried) and 1 sister (unmarried).
Education & career
Bachelors degree in Computers/ IT
Sr. Manager / Manager in government/public sector
Earns GBP 30K to 40K annually
WHAT she IS LOOKING FOR
30 to 40
5' 10"(177cm) to 6' 2"(187cm)
Religion / Community
Hindu, Sikh, No Religion, Spiritual - not religious, Other
Mother Tongue
Country Living in
United Kingdom
Residency Status
Citizen / Permanent Resident
Premium Service
Premium Members are entitled to view horoscope details.
Upgrade Now
Premium Members Benefits
To access
profile at Shaadi.com type the link below in your browser window:


text:
9 New Applications for Soybean Biodiesel Glycerol Vera L. P. Soares, Elizabeth R. Lachter, Jorge de A. Rodrigues Jr, Luciano N. Batista and Regina S. V. Nascimento Universidade Federal do Rio de Janeiro Brazil 1. Introduction Glycerol (Fig. 1.1) is a viscous and polar substance that has long been known for its useful properties. As long ago as 1779, the Swedish scientist Karl Wilhelm Scheelle obtained glycerol from olive oil. In 1813, Michael E. Chevreul showed that glycerol was involved in the triglyceride structure, and called it glycerin, from the greek word that means sweet. The elucidation of its structure as a trihydroxylated alcohol was due to Wurtz in 1855. The name glycerin was changed to glycerol to indicate its alcohol nature. It is now common to refer to the pure chemical product as glycerol and refer to the commercial grades with varying glycerol content as glycerin (or glycerine). The first example of a chemical industrial application of glycerol is nitroglycerin which was synthesized by Ascanio Sobrero. In 1860 it was transformed into a safer and more convenient form of use by Alfred Nobel [Jerôme et al, 2008; Shreve & Brink, 1977; Kirk & Otmer, 1951]. OH HO OH Fig. 1.1. Glycerol structure – 1,2,3-propanetriol A large range of applications has been made possible due to its non-toxicity and biodegradability, mainly in cosmetic and food industries. As an additive in industry and in consumer goods it can be applied as a humectant, plasticizer, solvent or viscosifier, providing hydrodynamic lubrication [Kirk & Otmer, 1951]. In the polymer industry it is added as a stabilizer, plasticizer, and co-solvent in emulsion polymerization. Glycerol is also an important raw material for the synthesis of several valuable compounds. It was used as the basis for the first production of alkyd resins [Guner et al, 2006] while its partial fatty acid esters, the mono- and diesters of palmitic and stearic acids, have been widely employed as emulsifiers in processed foods. The cosmetics, pharmaceuticals and food industries account for at least 45% of glycerol production. Besides being the basis for nitroglycerin, which also finds application as a medicinal drug, glycerol is transformed in glycerol carbonate which is an intermediate in chemical synthesis and used as a gelation agent, in polyglycerols which are used in cosmetics, www.intechopen.com 152 Soybean - Applications and Technology in medical applications and in controlled drug release, to quote some well known glycerol derivatives and their useful applications [Berh et al, 2008; Guner et al, 2006]. The initial route to glycerol production was the hydrolysis or the saponification of triglycerides from vegetable oils or animal fats (Fig 1.2 and 1.3). This process results in crude glycerin containing approximately 88% glycerol in mass. The introduction of petroleum derived detergents brought a decline in soap production from vegetable oils which decreased the availability of glycerol. As a consequence, a synthetic route for glycerol was developed from the petroleum derivative propene, also known as propylene (Fig. 1.4), with large scale production starting in 1948, in the USA. The glycerol from both processes is purified by bi-distillation to guarantee a minimum of 99.5% purity and enable it to meet US phamacopoedia (USP) specifications that regulate products for the cosmetics, pharmaceutical and food industries. O O C H2 O C R1 C H2 OH O HO C R1 cat. O CH O C R2 + H 2O CH OH + HO C R2 O O C H2 O C R3 C H2 OH HO C R3 Fig. 1.2. Hydrolysis of a triglyceride showing the formation of glycerol and fatty acids O O C H2 O C R1 C H2 OH +- O Na O C R1 O CH O C R2 + N aOH CH OH + Na +- O C R2 O O +- C H2 O C R3 C H2 OH Na O C R3 Fig. 1.3. Saponification of triglycerides showing the formation of glycerol and salts of fatty acids OH Cl2 O Cl NaOH HO OH H2 O H2 O Fig. 1.4. Chemical reaction to obtain glycerol from propene, through several intermediates (Bell et. al, 2008). The transesterification of triglycerides with methanol is the current route to biodiesel production, generating fatty acid methyl esters (biofuel) and glycerol (Fig. 1.5). It can be estimated that for each 100kg of biodiesel, around 10kg of crude glycerol are produced. Glycerol supply and demand have been kept in a reasonable equilibrium, with glycerol prices oscillating very little up to the start of the biodiesel production boom. In the last 10 years biodiesel production has had such an increase that glycerin supply has more than doubled whereas its demand has remained largely unchanged. This means that a surplus of glycerol is being added, consistently, to an otherwise stable market. As the increase of www.intechopen.com New Applications for Soybean Biodiesel Glycerol 153 biodiesel production is a worldwide trend, the quantity of crude glycerol being generated is considerable. Fig. 1.6 shows the enormous increase in glycerol supply after biodiesel production started all over the world. O O CH2 O C R1 CH2 OH CH3O C R1 O cat. O CH O C R2 + CH3OH CH OH + CH3O C R2 O O CH2 O C R3 CH2 OH CH3O C R3 Fig. 1.5. Transesterification of triglycerides with methanol to form methyl fatty acid esters Before considering crude glycerol for possible value-added products, it is necessary to purify it to a grade acceptable for most traditional applications. This is costly and generally not economically feasible for small to medium-sized plants. Several steps are necessary to free it of sodium salts and methanol and also of water, which needs to be treated before being discarded. This calls for large plants and investments to produce high quality and low price glycerol. The accumulation of glycerin and the difficulty to introduce its surplus in the market became a problem for some small biodiesel producers, and this led to solutions such as its discharge in rivers. It is clear that glycerin may become an environmental issue if adequate demand is not stimulated in the near future. 2500 2000 Glycerol production 1000ton 1500 1000 500 0 1920 1930 1940 1950 1962 1968 1975 1989 1998 1999 2003 2004 2008 2010 Year Fig. 1.6. Growth of glycerol production in the USA between 1920 and 1970 and the world production from 1975 compiled by the present authors from Shreve and Brinks, 1977 ; Kirk & Othmer, 1951; Sofiproteol, 2007. www.intechopen.com 154 Soybean - Applications and Technology 1.1 Applications of glycerol and its derivatives: Literature review. Alternative uses for the crude or partially purified glycerol are being pursued to make biodiesel more competitive in the growing global market. Research activities worldwide have started to focus on new applications for glycerol and its derivatives and also on processes to use glycerol as a raw material for the production of already known useful compounds. Immediate use of glycerol as a low price substitute for polyhydroxylated alcohol (commonly abbreviated to polyols) was possible for some industrial segments, such as the paint industry, which benefits from its lubricating properties, or in cosmetic, food and pharmaceuticals industries to whose products it could be added to improve humectancy or sweetness. The increasing price of crude oil motivated the chemical industry to search for alternatives routes for the synthesis of essential chemicals. The surplus glycerol was the main candidate for several products with a large market, in particular the monomers propylene glycol and epychlorohydrin, synthesis gas (H2 + CO) and a number of other useful intermediates for the chemical process industries commonly prepared from petroleum derivatives. 1.1.1 New routes to well known products having glycerol as raw material The investigation of processes which have glycerol as a raw material necessarily require knowledge of fundamental industrial processes such as hydrogenation, oxidation, hydrolysis, chlorination, etherification and esterification, among others. This knowledge has been the basis for the discovery and proposal of new processes for glycerol transformation into valuable products. Several literature reviews can be found that focus their presentation on these processes rather than on the product applications [Zhou et al, 2008; Jerôme et al, 2008; Berh et al, 2008]. In the last decade an important process, the aqueous phase reforming process (APR), was developed to produce the synthesis gas H2 + CO from glycerol which is an important source of hydrogen [Soares et al, 2006]. This is an alternative to the steam reforming processes of methane to prepare synthesis gas which, in its turn, is the raw material for the Fisher– Tropsch synthesis of liquid fuels; alkanes and low molecular alcohols [Suppes et al, 2005]. The development of a thermally efficient combination of the two processes resulted in the commercial production of methanol by Biomethanol Chemie Nederland [Simonetti et al, 2007]. This biomethanol can then be used in the biodiesel production. These developments made possible the economical utilization of glycerol in the production of hydrogen to be used as a fuel or as a reagent in chemical reactions. Propylene glycol (propanediol) which has a high global demand is a monomer for the production of polyesters. It is also used as an anti-freeze fluid, and additive in cosmetics, food and pharmaceutical formulations to cite some of its uses. Its synthetic pathway has been through propylene (propene), a petroleum derivative, resulting in the formation of the isomers 1,2- and 1,3-propanediol and some ethylene glycol. It is now produced with a lower cost by the hydrogenolysis of glycerol over a copper chromite catalyst with 90% yield [Dasari et al, 2005; Shelley, 2007]. Further investigations led to a synthetic pathway for the selective preparation of 1,2-propanediol from glycerol by the Davy Process Technology [Pagliaro & Rossi, 2008].. The selective preparation of 1,3-propanediol is traditionally achieved by processes involving petroleum derivatives (dehydration of acrolein or ethylene oxide conversion), however biological process, where glycerol is the feedstock for the www.intechopen.com New Applications for Soybean Biodiesel Glycerol 155 fermentation process, has been proposed that can become a cheap alternative to corn syrup fermentation to produce one of the isomers preferentially [Shelley, 2007]. Another major resin ingredient compound that is already being prepared from glycerol, by its chlorination and epoxidation, is epychlorohydrin. This compound is a reagent in the synthesis of epoxy resins which are useful coating materials for marine appliances, in automotive industry and has many other applications [Guner et al, 2006]. Epychlorohydrin is traditionally prepared by propene chlorination, a process that involves one more step than the glycerol process. As glycerol used to be prepared from epychclorohydrin, the process is now reversed [Siano et al, 2006]. Yet another possibility for transforming glycerol into a value-added product is its conversion to acrolein, which is relied upon for many fine chemical products, and it is also the raw material for acrylic acid. Although its conversion from glycerol has long been known, for economic reasons the reaction has not been applied industrially; it is traditionally manufactured from propene. However, with the possibility of lower glycerol prices ahead, acrolein production from glycerol might be an elegant green alternative to the petrochemical route [Centi &Santen, 2007]. Polyglycerol is a useful derivative of glycerol which is extensively employed in controlled drug release and in cosmetics. It is comprised of several units of glycerol forming a branched ether structure with terminal hydroxyl groups. [Sunder et al, 1999; Marquez- Alvarez et al, 2004] 1.1.2 New applications for the glyceryl esters of fatty acids A well known group of glycerol derivatives is that of mono- and diglycerides of fatty acids, usually abbreviated to MAG and DAG respectively, after the expressions monoacylglycerides and diacylglycerides. They are added to cosmetic and food formulations to prepare emulsions having components of different polarities that would otherwise separate in immiscible layers. The main glycerides are the palmitates, stearates and oleates (oleins). Their industrial production is accomplished trough the direct esterification of glycerol with fatty acids or through the glycerolysis or hydrolysis of triglycerides, from vegetable oils or animal fat, which are processes that result in a mixture of mono- and diglyceryl esters [Corma et al, 2006]. An alternative route being studied is the enzymatic esterification of fatty acids with glycerol which is considered an environmentally friendly approach. Conditions for the enzymatic process are being searched to increase monoglyceride selectivity, with results of approximately 60% monoglycerides [Nandi et al, 2008; Freitas et al, 2010; Bogalhos et al, 2010]. These are good results considering that the directives of the World Health Organization for food emulsifiers require that these mixtures comprises at least 70% of both mono- and diglycerides with a minimum of 30% monoglyceride [Da Silva et al, 2000 and 2003]. To obtain MAG with a high purity for food additive usage, a purification step by distillation is required. The DAG derivatives are also a target, specifically the 1,3-isomers. These are being produced from vegetable oils and lipase by the Japanese company Kao, as a substitute for triglycerides oils for cooking due to their higher thermal stability [Watanabe et al, 2003]. A biosurfactant derived from glyceryl ester was produced by a fermentation process with a strain of Pseudomonas aeruginosa PA1 isolated from the water of oil production in Northeast of Brazil. They used different carbons sources (n-hexadecane, paraffinic oil, glycerol and babassu oil) and different nitrogen sources. The best results were achieved with glycerol as substrate [Santa Anna et al, 2001; Ciapila et al, 2006]. www.intechopen.com 156 Soybean - Applications and Technology Monoglycerides are widely used as emulsifiers in food and cosmetic industries due to their active surfaces. As a consequence, their selective synthesis, by method other than the enzymatic approach, has been the object of several scientific papers in the search for a proper selective catalytic system [Abro et al, 1997; Pouilloux et al, 1999; Diaz et al, 2001, 2003, 2005; Marquez-Alvarez et al, 2004; Sakthivel et al, 2007; Jerôme et al, 2008]. Among the several heterogeneous catalysts studied, so far the best result has been 80% in selectivity at 93% conversion, using a specially tailored mesoporous material prepared by an environmentally friendly process [Karam et al, 2007]. Preparation of monoglycerides with high selectivity is a challenging issue still being investigated by researchers. Importantly cosmetics and food markets are not increasing at the same rate as the glycerol production from biodiesel. Other markets that require compounds with lubricating and emulsifying properties could benefit from such esters derivatives. This could be the case for the fluids used for drilling wells which is a promising sector since glycerol technical grade could be used without further purification. Actually, glycerol is already a component of some formulations for water based drilling fluids in order to avoid gas hydrate formation in the well and to stabilize the water-sensitive formations, reactive shales, during drilling. [Fink, 2003; Youssif & Young, 1993; Hale & Dewan, 1989; Chenevert & Pernot, 1988; Pomerleau, 2009]. Since glycerol is a polar and highly water-soluble molecule, it cannot be used directly as an additive for boundary lubrication or as an emulsifier, while the monoglycerides, being amphiphilic molecules, can act as both. Only a few citations are found in the literature describing the use of glycerides in drilling fluids. Mueller et al. (2004) and Maker & Mueller (2009) developed water based drilling fluid formulations that use partial glycerides and olygoglycerides from fatty acids as lubricants. Al-Sabagh et al (2009) synthesized and evaluated glycerol oleates (mono-, di- and trioleate) as primary emulsifiers in oil based drilling fluids formulations. They have found that the fluid formulated with glycerol monooleate presented higher emulsion stability due to the surface activity properties of this molecule, related to its adequate hydrophilic-lipophilic balance (HLB). In the case of oil based drilling fluids where fatty acid methyl esters are the continuous phase, another problem is met related to its operation at low temperatures and high pressures, as found while drilling in deep waters. Under these conditions the drilling fluid may gellify, due to ester crystallization, which makes pumping difficult. Nascimento et al (2005) have shown the effect of several low mass esters on methyl palmitate and biodiesel crystallization behaviour and Albinante (2007) has found good results adding both partial oleins (MAG and DAG) to fatty acid methyl esters [Soares et al, 2009]. Thus, it is evident that drilling fluids represents an interesting niche to be explored for the application and development of glycerol derivatives. One natural line of reasoning among researchers and those involved in fuel development in the search for other options for glycerol use was its conversion in oxygenated fuel additives. This would valorize the co-product of biodiesel and increase the fuel yield. Glycerol by itself can not be used as a diesel additive due to its high viscosity, its tendency to polymerize under combustion chambers conditions and, chiefly, because of its insolubility in diesel. Given that ethers (eg methyl tertiary butyl ether) are already known to act as gasoline octane boosters, glycerol ethers (mainly tert-butyl glyceryl ether) were proposed and investigated as a fuel additive [Gupta, 1995; Klepacova et al, 2006]. In the case of gasoline it has been demonstrated that ethers from glycerol are capable of reducing particulate matter, hydrocarbons and carbon monoxide (CO) in emissions and acting as an anti-knock additive and an octane enhancer while, in biodiesel, they are capable of improving cold flow and reducing viscosity [Nouredini, 2001]. In spite of these properties a decrease in diesel and www.intechopen.com New Applications for Soybean Biodiesel Glycerol 157 biodiesel cetane number occurred as a consequence of the glycerol ethers branched chains [Spooner-Wyman & Appleby, 2003]. They are commercialized as gasoline additives in United States by CPS Biofuels [2010]. Other oxygenated additives are being considered as potential additives for diesel and biodiesel such as the higher glyceryl ethers, the glyceryl esters of acetic acid known as acetins, and acetals and ketals of glycerol with some patents being issued on their preparation processes [Rahmat et al, 2010; Melero et al, 2010]. This is the subject of another proposal to be presented in the following section. 1.2 Our proposals: Glycerol derivatives as fluid and fuels additives The emulsifying and lubricating properties of glyceryl esters of fatty acids turn them into potential candidates to be applied as developed water additive to drilling fluids. This segment represents a large slice of a potential market for glycerol derivatives, solving, in part, the problem of providing a market for the glycerol excess. Another potentially significant market to be explored for glycerol derivatives is the sector of fuels for transport. As described above, a product from glycerol is already commercialized as an octane booster for gasoline. Glycerol oxygenated compounds with properties adequated to improve diesel and/or biodiesel is another possibility to be discussed. Additives for Drilling Fluids Oil well drilling is performed by a complex apparatus that includes a drill pipe stem and a drill bit that perforates the formations with the aid of a drilling fluid. Drilling fluids are, in general, multi-phasic liquid systems, consisting of mixtures of solids in suspension, dissolved salts, and organic compounds dissolved or emulsified in water. These fluids play several important functions in the drilling process, including removal of the cuttings from the well, keeping the sides of the well stable, and transporting them up to the surface where they are eliminated. They are also responsible for the control of formation pressures, for sealing permeable formations, maintaining wellbore stability, minimizing formation damages and for transmitting hydraulic energy to the drilling tools to the bit. Another significant function of the drilling fluids is to lubricate the bit and the stem. It is a critical function, particularly while drilling directional wells, since the frictional forces between the drillstring and wellbore or casing are so significant that they can lead to several problems such as high torque and drag, which can lead to premature damage to the drilling tools, as a consequence of excessive wear and heat. Drilling fluids may be air, water or oil based, depending on the nature of the continuous phase. In general, oil based fluids present lower coefficient of friction (COF) than water based fluids. However, most of the oil based fluids are not environmentally friendly and/or are considerably expensive, especially when compared with water. Thus, there is an imminent demand for new biodegradable and atoxic additives that perform as lubricants of high efficiency in water based drilling fluids. In spite of the previously mentioned problems, oil based fluids have recently received great attention because of their high performance in drilling water-sensitive formations such as reactive shales and salt domes. Drilling these kinds of formations with water based fluids, in most cases, leads to wellbore instability problems. Reactive shales hydrate and swell in the presence of water and dome salt may dissolve significantly, both cases resulting in undesired enlargement of the well. An alternative is to work with oil based fluids. Since oil based fluids are inverted emulsions, there is no significant contact between water and the www.intechopen.com 158 Soybean - Applications and Technology formations, which prevents or at least minimizes wellbore instability. However, one of the main challenges in oil based fluids formulation is to obtain emulsions that persist over long periods of time. By definition, emulsions are thermodynamically unstable, because of the interfacial tension between oil and water, which increases the energy of an emulsified system, leading to emulsion breakage. Emulsions may be kinetically stabilized, for example through the use of emulsifiers, which reduce oil/water interfacial tension. There is a demand in the oil industry for high efficiency emulsifiers that are ecologically sound and have a low cost. Molecules that have a polar segment (which has water affinity) and a nonpolar segment (which has oil affinity) show surfactant characteristics, due to their ability to adsorb at surfaces and interfaces. For this reason, these kinds of molecules are widely used as lubricant and emulsifiers. Since glycerol esters present such structural features they have a potential application in drilling fluids as lubricants and emulsifiers. Glycerol obtained from soybean biodiesel production seems to be an available and cheap resource for the production of these esters and their evaluation in drilling fluid formulation is one of our proposals. Additives for Fuels Compounds are added to fuel with different purposes that include the cleaning of several engine parts, the increase in combustion conversion and reduction in the emissions of undesirable or toxic substances. In diesel combustion a high level of particulates and nitrogen oxides (NOx) are emitted. There are many techniques capable of improving combustion processes in diesel engines, such as the retarding of fuel injection, the recirculation of exaust gas, a high pressure injection and an air intake supercharging. However due to the trade–off between the particulated matter (PM) and NOx emissions, it is very difficult to have both reductions simultaneously [Wang et al, 2009]. One possible solution is to use oxygenated additives which are compounds capable of decreasing carbon monoxide (CO), NOx and PM while improving the autoignition properties in diesel engines. The cetane number (CN) is the conventional term which characterizes the ignition quality and the flammability of diesel fuels. A high CN usually results in lower exhaust gas and smoke emissions, fuel consumption and engine noise, thus providing an overall better engine yield and drivability [Abu-Rachid et al, 2003]. A high cetane number depends on a high oxygen to carbon ratio and on the predominance of linear alkyl chains (high CH2/CH3.). The capacity of some ether oxygenated additives to improve cetane number can be explained by the presence of an oxygen bridge that increase the reactivity of the hydrogen atoms in the hydrocarbon chain of the neighboring carbons contributing to the onset of combustion [Abu-Rachid et al, 2003; Marrouni et al, 2008]. For example, the comparison between CN values of dimethyl ether (DME) (55–60) and propane (−20) suggests that the 6 hydrogen atoms of the methyl groups of CH3–O–CH3 are much more reactive toward oxygen than the ones in CH3–CH2–CH3. Table 1 compares CN of some compounds [Taylor et al, 2004]. This property led to the production of ether additives that are already commercialized as gasoline additives and stimulated further investigation on oxygenated compounds from glycerol. Three main classes of oxygenated glycerol derivatives have been developed and investigated in relation to their capacity to improve fuels properties. One such glycerol derivative is the commercialized glyceryl tert-butyl ether. Another group of ethers that has driven much attention are that of mono-, di- and triacetate of glycerol called acetins and, finally, the acetal or ketals of glycerol [Dubois et al, 2009; Melero et al, 2010]. www.intechopen.com New Applications for Soybean Biodiesel Glycerol 159 Hydrocarbon Cetane number Oxigenated Compound Cetane Number Propane -20 Dimethyl ether 55-78 Pentane 30 Diethyl ether 140-160 Octane 63,8- 65 Hexyl methyl ether 97 Nonane 72-74 Dibuthyl ether 91 – 100 Table 1. Cetane number of hydrocarbons and oxygenated compounds These last proposals are based in the fact that the ketalization of glycerol hydroxyl groups retains the oxygen atoms in the molecular structure, while the esterification reduces its viscosity. The ketalization of glycerol with acetone yields the cyclic ether [3,3-dimethyl-2,4- dioxolan-4-yl] methanol (DDM), commercially known as solketal [Fig 2.1]. There are studies about the effect of a dioxolane ring on diesel emissions indicating reduction of particulate matter [Song et al, 2005; Boot et al, 2009]. In biodiesel, it has improved oxidative stability and low temperature properties [Melero et al, 2010]. This compound was the object of some patents. Delfort et al (2005) produced DDM and other analogous ketals derivatives to be used as diesel additives. Puche (2003) described a procedure to obtain a biodiesel with improved properties at low temperature, using DDM as component. Hillion et al (2005) described a method to produce biodiesel, ethers and soluble glycerol acetals. Miller et al (2008) presented an innovative procedure using reactive distillation to prepare biodiesel and DDM on the same process using acid catalyst, without a pre-separation of glycerol. None of the above proposals contemplate a structure of a ketal-glyceryl ester. A compound containing both ester and ether groups could benefit from each group property. The ether group would be responsible for a better ignition whereas the ester group would provide a better lubricity. In this manner a single compound would provide both properties. In applying this concept to glycerol ketal, it is proposed that the glycerol hydroxyl be esterified with long chain fatty acids as the long hydrocarbon chains would then behave as a fuel just as in biodiesel. One could think of a fuel in a similar way to biodiesel in which the methanol had been changed by an alcohol prepared from the ketal-glycerol (DDM in this case). One such derivative has been proposed that uses the short chain acetic acid [Garcia et al, 2008]. Similarly to glycerol ethers, this ketal-glyceryl acetate compound is a volatile product and, consequently, it can only be added to diesel and biodiesel in low concentrations in order to not affect diesel and biodiesel volatilization behaviour. A glycerol derivative that could contribute to diesel and biodiesel performance would create a large market for this co-product. This paper presents the preliminary studies on the evaluation of thermal properties of ketal- glyceryl esters of long chain fatty acids developed to perform as a biofuel additive and the study of their influence on the soybean biodiesel thermal properties. The paper also presents some results on the performance of glycerol esters in drilling fluids as lubricants for water based drilling fluids and as emulsifiers and anti-crystallization additives for oil based drilling fluids. 2. Methods The synthetic routes for the preparation of several glyceryl esters and ketal-glyceryl esters both derived from fatty acids and their respective characterization methods are described. The techniques employed to essay their applications as lubrifiers, emulsifiers and anti- crystallization additives in drilling fluids and as a cetane enhancer additive in biodiesel are presented. www.intechopen.com 160 Soybean - Applications and Technology 2.1 Preparation and characterization of glyceryl esters The esterification reactions of glycerol with saturated and unsaturated carboxylic acids (octanoic, decanoic, dodecanoic and 9-(cis)-octadecenoic or oleic), catalyzed by p- toluenosulfonic acid, were conducted under a nitrogen atmosphere, at 1250C for 3 to 5h. The glycerol:acid molar proportion was 3:1 and 6:1 [Yaakoub, 2007]. A scheme for the esterification reaction is presented in Fig. 2.1. O O R O OH OH cat. HO O R HO O R R OH + HO OH + a O OH b O + R O O R O O b Fig. 2.1. Esterification of glycerol with carboxylic acids showing the products structures (a) monoglyceride (b) diglyceride. R represents a hydrocarbon chain having 9 to 17 carbon atoms. The reaction mixture was washed with water to extract glycerol and ethyl ether was added to the organic phase containing the esters. After being dried with anhydrous magnesium sulfate, the solvent was evaporated and the product submitted to Fourier-transformed infrared (FTIR) and to 1H e 13C nuclear magnetic resonance (NMR) analyses. By this reaction process both mono- and diglycerides were obtained as shown by FTIR that revealed ester carbonyl absorption bands (1745cm-1), hydroxyl groups and the disappearance of acid carbonyls. Due to its nondestructive and noninvasive character, NMR spectroscopy provides the most convenient method for the determination of acyl positional distribution in glyceryl esters [Simova et al, 2003]. NMR allowed the quantitative determination of monoglycerides, diglycerides and acid conversion. Acid conversions for all reactions were found above 70%. The reaction performed at 6:1 resulted in higher monoglycerides proportions and the product of these reactions were used in application essays. These analytical results are presented in table 2.1. Glyceryl Esters Partial Ester distribution determined by 13C- NMR Mono Di Tri Glyceryl octanoate 80.6 19.4 - Glyceryl decanoate 77.5 18.7 3.8 Glyceryl laurate 78.5 21.5 - Glyceryl Oleate 75.5 25.5 - Glyceryl Oleate 60 40 - Table 2.1. Glyceryl esters distribution as determined by 13 C- NMR. 2.2 Evaluation of glyceryl esters in drilling fluids The glyceryl esters, containing mainly monoglycerides, were evaluated as lubricants in water based fluids formulations and as emulsifiers in oil based fluids formulations. First, the www.intechopen.com New Applications for Soybean Biodiesel Glycerol 161 general procedure for the drilling fluids formulations is described, followed by the specific techniques used to evaluate the additives for each of the desired properties. Finally, glyceryl oleate was evaluated as an anti-cristallyzing additive for fatty acid methyl esters, used in ester oil based fluids. 2.2.1 Drilling fluids formulations Several drilling fluids were formulated using the synthesized glyceryl esters as lubricants, in water based formulations, or emulsifiers in oil based formulations. The synthesized glycerides contained a minimum of 60% of monoglyceride, as presented in the section 2.1. Both water and oil based fluids were formulated in Hamilton Beach® shakers. The general compositions of the water and oil based fluids are respectively presented at Tables 2.2 and 2.3. At table 2.2, the lubricant component was either polyethyleneglycol 400 dioleate (a commercial lubricant for water based fluids) or the synthesized glyceryl esters. At table 2.3, the emulsifier component was either sorbitan monooleate (a commercial emulsifier for water-in-oil emulsions) or the synthesized glyceride. Component Amount Function Water Up to 350 ml Base Xanthan Gum 2.5 g Rheology modifier Hydroxypropyl amide (HPA) 2.0 g Filtrate control PDADMAC1 3.0 wt% Shale inhibition Potassium Chloride (KCl) 3.0 wt% Shale inhibition Sodium Hydroxide (NaOH) pH 9,0 pH control Barite 28.0 g Weight control Lubricant 7.0g Lubricant 1 Polydiallyl dimethyl ammonium chloride, cationic polymer Table 2.2. General water based fluids composition and the components functions Component Amount Function n-paraffin 157.5 g Base Brine (10wt% NaCl in water) 140.0 g Dipersed phase Emulsifier 11.78 g Emulsifier Tween® 80 1 2.22 g Co-emulsifier ECOTROL® 2 2.25 g Filtrate control Barite 28.0 g Weight control 1 polyoxyethylene sorbitan monooleate; polymeric additive produced by MI-SWACO 2 Table 2.3. General oil based fluids composition and the components functions 2.2.2 Lubricity measurements Efficiency of the synthesized additives as lubricants in water based fluids formulations was evaluated through coefficient of friction (COF) measurements, in a Baroid Lubricity Tester www.intechopen.com 162 Soybean - Applications and Technology Model 212. In the experiments, a steel test block that simulates the well casing is pressed against a test ring by a torque arm. The torque is measured by intensity of current that is required to turn the ring at a constant rpm when immersed in the evaluated formulation. The applied rotational velocity and torque were, respectively, 60 rpm and 150 lb/inch, following the API procedure (RP 13B). Under these conditions, torque readings are related to COF by COF = torque reading/135.5, where COF is a dimensionless value. All the measurements in this work were performed at room temperature. 2.2.3 Determination of the relative stability of the emulsion The efficiency of the synthesized additives as emulsifiers in oil based fluids formulations was evaluated through Electrical Stability (ES) tests. In these experiments, a pair of permanently spaced electrode plates is immersed in a fluid emulsion sample, and an increasing AC voltage is applied to the electrodes in a constant rate. The voltage at which the emulsion allows the current to flow is reported as relative emulsion stability (ES). High values of ES mean more kinetically stable emulsions, since a higher voltage is required to promote emulsion breakage. A commercial glyceryl oleate containing 50% of each partial ester was also essayed as emulsifier. 2.2.4 Evaluation of glyceryl ester as an anti-crystallizing agent The anticrystallizing effect of a glyceryl oleate containing mono-, di- and triester in the proportion 60:37:3, respectively, was tested in an ester base drilling fluid consisting of a mixture of methyl fatty acid esters. These methyl esters were a commercial preparation obtained from Miracema, SA, Brazil, that will be named FAME to differentiate from other fatty acid methyl esters prepared to be used for other purposes. The FAME base fluid containing 5% of the additive in moles per weight and without the additive were both submitted to analysis in a Perkin Elmer, model 7, differential scanning calorimeter (DSC), for the determination of their temperatures of crystallization. These measurements were conducted in dynamic mode at a cooling rate of 10ºC/min, from room temperature down to -35°C, in a nitrogen atmosphere. Isothermal measurements for the determination of the induction time for crystallization were conducted by visual inspection, at the bench, of the same solutions kept in a water-salt bath at -4°C. 2.3 Preparation and characterization of ketal–esters of glycerol Preparation of the product of interest - (2,2-dimethyl-1,3-dioxolan-4-yl) methyl ester, product II shown in Fig 2.2-II, involved the ketalization of glycerol to (2,2-dimethyl-1,3- dioxolan-4-yl) methanol ( product I shown in Fig 2.2-I) in a first step and the esterification of this intermediate in a second step. In the first step, a mixture of glycerol, propanone in excess, p-toluenesulfonic acid (catalyst) and chloroform were refluxed for 10h, while the water that was being formed was simultaneouly removed by azeotropic distillation at 49°C. A Dean-Stark apparatus helped to separate the distilled solvent from the water so as to return it to the reaction flask. The ketal-glycerol (I) was isolated by: adding sodium carbonate to neutralize the catalyst, filtration of the catalyst and vacuum fractional distillation. The second step was the transesterification of product I with a mixture of methyl esters derived from palmitic (hexadecanoic), oleic (9-(cis)-octadecenoic) and stearic (octadecanoic) acids, for 6h at 125-140ºC, in the presence of anhydrous sodium carbonate, to generate product II. This product was purified by filtration of the catalyst and distillation of www.intechopen.com New Applications for Soybean Biodiesel Glycerol 163 the excess of product I. The transesterification of methyl palmitate with product I was also conducted which produced (2, 2-dimethyl-1,3-dioxolan-4-yl) methyl palmitate (PDM). R2 R2 R1 O O R1 O HO O O O R I II Fig. 2.2. Structure of intermediate I and product II (R =15-17 carbons; R1, R2 = CH3) These products were analysed by Fourier–transformed infrared spectrometry (FTIR) in a Nicolet, model Magma 750, by nuclear resonance spectrometry (1H and 13C NMR) in a Bruker apparatus, Avance 200, at 200 and 50MHz, respectively, and by gas chromatography with mass detector (CG-MS) in a GC Agilent 5500. These analyses confirmed the formation of the ketals (I) and the ketal-esters (II). The FTIR spectra of the ketals (I) after distillation presented: the typical C-O band at 1090cm-1, which differs from that of glycerol (1042cm-1), an OH band at 3404cm-1 relative to the non-reacted-hydroxyl, as expected, and the typical CH3 bend vibration from the acetonyl radical at 1375cm-1. The presence of a ketal C-O bond was signalled by the 13C-NMR spectra at 109.4 ppm. The FTIR spectra of ketal-glyceryl esters (II) showed typical ester bands at 1734cm-1 and 1200cm-1 and the absence of acid OH bands, while 13C- NMR spectra showed chemical shifts at 173.6 and 174.3ppm for ester carbonyls, besides that for ketal carbon at 109ppm. The carbonyl displacement at 174.3ppm was due to residual methyl ester from the transesterification step. The chromatographic analysis (with mass detector) also confirmed the presence of ketal-ester and residual methyl esters (Batista, 2008). Two product batches were prepared so as to contain the glyceryl-ketal esters and biodiesel in the proportions 65:35 (BDM65) and 25:75 (BDM25), respectively. A commercial biodiesel from soybean oil was used. These two mixtures were evaluated in relation to some fuel critical thermal properties. 2.5 Evaluation of ketal-glyceryl esters properties as fuel additives The two products batches BDM65 and BDM25 containing ketal–glyceryl esters and biodiesel were evaluated in relation to the following thermal properties: temperature of crystallization at a cooling rate of 10ºC/min in N2 atmosphere and oxidation stability from 30 to 300ºC in air atmosphere in a differential scanning calorimeter (Perkin-Elmer model 7); and distillation behaviour according to ASTM D1160. A sample of biodiesel and a sample of (2, 2-dimethyl-1,3-dioxolan-4-yl) methyl palmitate (PDM) were analysed under the same conditions. 3. Results The glyceryl esters synthesized were essayed in relation to their performance: as a lubricant in water based drilling fluid, as an emulsifier in oil based drilling fluids and as an anti- crystallizing agent in ester (FAME) based drilling fluids. The ketal-glyceryl oleate was essayed in relation to its thermal properties that could affect those of biodiesel. www.intechopen.com 164 Soybean - Applications and Technology 3.1 Glyceryl esters as lubricant for water based drilling fluid Adsorption lubricants in an oil medium are widely known as surfactant molecules that adsorbs onto surfaces, minimizing the direct contact between those surfaces. In this lubricity model, the lubricant molecule must have a polar segment that strongly adsorbs onto the surface, and a long apolar chain, which interact their neighbours chains through weak Van der Waals forces, differently from the unlubricated surface, where strong interactions cause friction. However, in an aqueous medium this mechanism is difficult because even if the polar segment has good interaction with the surface, the apolar segment does not have a favorable interaction with water, leading to phase separation, instead of adsorption. The control of this equilibrium is a key challenge in the development of lubricants for aqueous systems. In this work, the potential of synthesized glycerides are evaluated as lubricants in water based drilling fluids formulations. Table 3.1 presents the results obtained for the coefficient of friction (COF) measurements in formulations containing different lubricants at 2 wt%. The content of monoglycerides in these products is presented in table 2.1. All the systems containing the glyceryl esters presented considerably low COF values, when compared with the fluid without lubricant. In addition, their performance was even better than that obtained with the commercial lubricant used in aqueous formulations, polyethyleneglycol 400 dioleate. Lubricant (2,0 wt%) COF of fluids Glyceryl octanoate (C8) 0.07 Glyceryl decanoate (C10) 0.06 Glyceryl laurate (C12) 0.08 Glyceryl monooleate (C18.1)* 0.04 Polyethyleneglycol 400 dioleate 0.18 Without Lubricant 0.23 * The glyceryl oleate evaluated as lubricants was the one with 74% of monoglyceride. Table 3.1. Coefficient of Friction (COF) of the formulated water based fluids with different lubricants Since the hydrophilic segment of the four evaluated glyceryl esters is the same, it would be expected that the efficiency of the products would increase together with the length of the hydrophobic segment, but this effect was not observed. As observed in Table 3.1, the additive that presented the best performance as lubricant in aqueous media was glyceryl oleate (C18.1), but no significant difference between the other glyceryl esters was observed. This behavior can be mainly attributed to the hydrophobic chain's length and to the additive's physical state. As glyceryl laurates (C12) and glyceryl decanoates (C10) are solid at room temperature, their dispersion is difficult, even with vigorous agitation of the Hamilton Beach shaker, resulting in a less effective performance. On the other hand, C8 and C18:1 are liquid at room temperature, which enables them to disperse easily within the media, and consequently cover the metal surface. The better results obtained by the oleates (C18:1) can be attributed to its longer hydrophobic segment, which leads to easier sliding between the covered surfaces. It is interesting to observe the role of the cis –insaturation www.intechopen.com New Applications for Soybean Biodiesel Glycerol 165 present in the structure of the C18.1 molecule on its potential as a lubricant. This configuration is responsible for the ester's physical state in opposition to the trans isomer, glyceryl elaidate, which is a solid. In the case of the commercial lubricant, polyethyleneglycol 400 dioleate, even considering that it is liquid and presents the same hydrophobic chain as glyceryl monooleate, it does not have hydroxyls on the polar segment of its structure, which is a key structural parameter to promote the adsorption on the surface and consequently potential activity as lubricant. 3.1.2 Glyceryl esters as emuilsifiers for oil based drilling fluids Table 3.2 shows the electrical stability (ES) values obtained with the different formulations of paraffin based drilling fluids. In this study, the content of the glyceryl monooleate in relation to the dioleate was evaluated, as well as the nature of the emulsifier. It is observed that the commercial emulsifier sorbitan monooleate led to a lower ES value, while the synthesized glyceryl esters showed better results. In addition, the higher the amount of glyceyl monooleate in the composition of the oleic glyceride, the higher was the electrical stability presented by the fluid. Emulsifier % of monoderivative in ES (Volts) emulsifiers Sorbitan monooleate - 489 Glyceryl laurate - 593 Commercial Glyceryl 50 484 oleate Glyceryl oleate 60 638 Glyceryl oleate 74 746 Table 3.2. Electrical stability (ES) values of oil based drilling fluids formulated with different emulsifiers. For a molecule to perform as an emulsifier it requires a specific structure where it presents a hydrophilic and a hydrophobic segment. Depending on the nature and the length of these segments, the molecule can promote a direct emulsion (oil-in-water) or an inverted emulsion (water-in-oil). Surfactants in which a hydrophilic nature predominates tends to form direct emulsions, while the predominantly lipophilic surfactants usually form inverted emulsions. The Hydrophilic-Lipophilic-Balance (HLB) is a key parameter that guides the choice of the appropriate surfactant to the target application. A high HLB surfactant is predominantly hydrophilic, whereas a low HLB surfactant is lipophilic in nature. As sorbitan monooleate is used as an emulsifier in inverted emulsions, due to its low HLB, its performance was compared to that of synthesized glyceryl esters. When comparing the structures of glyceryl monooleate with sorbitan monooleate it is observed that they have the same hydrophobic segments, but different hydrophilic segments. The ES results show that the glyceryl segment led to better emulsion stability. That is probably due to the fact that the glyceryl segment is less polar than the sorbitan segment, leading to a lower HLB, what would favour the emulsification in this case. Glycerin monolaurate showed a good performance even presenting a shorter lipophilic segment, suggesting that the nature of the www.intechopen.com 166 Soybean - Applications and Technology hydrophilic segment is in fact the key parameter. As discussed in previous sections, the selectivity of monoglycerides syntheses has to be optimized. When comparing the performance of products obtained in the esterification of glycerin with oleic acid where different monoderivatives yields were formed, we observe that better results were reached with systems that contained a higher amount of glyceryl monooleate and less glyceryl dioleate. This may suggest that the disubstituted product is excessively lipophilic, presenting a high affinity with the oil phase, which makes it migrate to this phase, instead of retaining it in the interface, and so minimizing its performance as an emulsifier of oil based fluid. 3.1.3 Glyceryl ester as an anti-crystallizing agent for ester based drilling fluids The methyl esters of fatty acids (FAME) used as fluid base presented crystallization temperatures (Tc), at the present experimental conditions, at – 6.4ºC while by the addition of glyceryl oleate this temperature went down to -8.4ºC. The effect of esters-additives prepared with monoalcohols and acids with up to 12 carbon atoms on the Tc of methyl fatty acid esters from soybean oil has already been registered to be able to decrease its Tc down to - 7.6ºC [Nascimento et al, 2005; Soares et al, 2009]. These same authors observed similar results for the ester-additives from di- and trihydroxylated alcohols other than glycerol. However the glyceryl oleate was able to decrease further the Tc of these methyl esters. Even more relevant was the data obtained for the induction time for crystallization as observed by the naked eye. A two fold increase in the induction time was observed for the FAME base fluid. The FAME crystallized after 30 minutes at -4ºC without additive and upon its addition it delayed 50 minutes to start crystallization. 3.2 The ketal-glyceryl ester as fuel additive The mixtures of biodiesel (B100) and the proposed additives (mixtures BDM65 and BDM25) were evaluated in relation to critical fuels thermal properties. The properties discussed are: the temperature of crystallization, the oxidation behaviour and the distillation range. 3.2.1 Temperature of crystallization Temperature of crystallization (Tc) is one of the most critical properties of a biodiesel for, as crystallization starts, the viscosity increases leading to a higher pour point. In biodiesel this behaviour depends on the composition of methyl esters, specifically, on the percentages of methyl esters of stearic and palmitic acids [Knothe, 2005]. These are both solids at ambient temperature, and precipitate or form a gel, when their solutions are cooled, as it happens in biodesel [Nascimento et al, 2005]. The calorimetric analysis (DSC) of biodiesel (B100) showed a crystallization onset at -6.9ºC with two peak maxima at about -7.7ºC and -15ºC, which is typical of soybean-methyl-biodiesel at the present DSC experimental conditions. The products BDM65 and BDM25 presented a similar qualitative behaviour, but with less intense peaks, that means a smaller variation of enthalpy per gram, and a small increase in Tc. These data are shown in Table 3.3 for BDM65, which is the product containing the highest amount of ketal-glyceryl-ester. A higher crystallization temperature would be expected for the products containing ketal-glyceryl-esters, because of their greater average molecular mass. Corroborating with this expectation, the (2,2-dimethyl-1,3-dioxolan-4-yl) methyl palmitate (PDM), prepared in this work, presented a higher melting point (66°C) than methyl palmitate (30°C) and crystallized at 51°C. However, the palmitate derivative is www.intechopen.com New Applications for Soybean Biodiesel Glycerol 167 not the main component in these mixtures but the ketal-glyceryl esters prepared have a high contribution of unsaturated chain fatty acids as is common in biodiesel esters. This could explain the small effect of these additives on the Tc of the final mixture containing as much as 65% of ketal-glyceryl esters. 3.2.2 Oxidative stability of BDM Products Another important characteristic to be considered in a soybean oil derived biofuel is its oxidative stability during storage. The process of oxidation of soybean oil or of its methyl esters, by the action of atmospheric oxygen, starts at the allyl carbon present in the chains of oleate, linoleate and linoleniate, which constitute about 80% of soybean oil biodiesel. Hydroperoxides formed at the initiation step can either react with other radicals, resulting in high molecular weight insoluble sediments and gums, or break apart to form carboxylic acids [McCormick et al, 2007]. In the present study this process would be of a concern because unsaturated chains are present. By differential scanning calorimetry (DSC), the product BDM65 presented oxidation onset at 143ºC, BDM25 presented it at 127ºC while B100 presented it at 128ºC. This is a significant result indicating that the glycerol part of the structure did not enhance the oxidation process. Its presence in a higher amount, as in BDM65, seemed to work in the opposite direction helping to delay oxidation, while a smaller amount, as in BDM25 did not change the oxidative behaviour of B100. Temperature of distillation (°C) Distilled Volume 10% 50% 90% B100 188.6 192.9 357.9 BDM25 199 214.8 356.8 Table 3.3. Thermal properties of BDM mixtures containing biodiesel and ketal-glyceryl esters in different proportions measured by DSC. 3.3.3 Distillation range of BDM products The distillation curve gives a pattern of the volatility of the components providing important information. The boiling range is directly related to viscosity, vapor pressure, heating value, average molecular weight, and many other chemical, physical, and mechanical properties. Any of these properties can be the determining factor in the suitability of the product in its intended application. Petroleum product specifications often include distillation limits based on data by the ASTM D1160. This test method covers the determination, at reduced pressures, of the range of boiling points for petroleum products that can be partially or completely vaporized at a maximum liquid temperature of 400°C. In the case of diesel, the distillation curve following ASTM 1160 is used to determine the cetane index by applying the distillation data to ASTM D4737. According to the Brazilian agency for fuel regulation (ANP), 90% of biodiesel B100 must distillate below 360ºC. Table 1 gives the temperature of distillation determined by ASTM 1160 for a biodiesel (B100) and BDM25 at 10, 50 and 90% volume cuts as established by the referred method. The product BDM25 and B100 were inside the 90% limit, while a smaller percentage of BDM65 (87%) distilled below 360°C. www.intechopen.com 168 Soybean - Applications and Technology Temperature of distillation (°C) Distilled Volume 10% 50% 90% B100 188,6 192,9 357,9 BDM25 199 214,8 356,8 Table 3.4. Distillation behaviour of biodiesel and BDM25, following ASTM 1160 These results showed that (2,2-dimethyl-1,3-dioxolan-4-yl)-methyl esters contributed to an increase in the final temperature of distillation, but that a maximum amount of 25% can be added to biodiesel in order to maintain its volatilization performance. If the BDM mixtures are diluted in diesel, for example mixed with B20, which is a diesel containing 20% biodiesel, these properties will also be diluted and will not affect the studied biodiesel thermal behaviour. It will be necessary, though, to test its performance under a higher amount of oxygen for longer times as they occur in the combustion chambers of compression ignition engines to investigate gum formation. This is a known problem detected in biodiesels that contain a certain amount of glycerol and partial glycerides. 4. Conclusions Glyceryl oleates containing a minimum of 74% of monoglyceryl oleates have shown great potential for application as lubricants for water based fluids and as emulsifiers in oil based fluids, leading to excellent results, when compared to the commercially available additives. In addition, they are environmentally friendly and low cost, since they may be obtained from an abundant raw material which is the glycerin by product of biodiesel production. The evaluation of the thermal properties of mixtures of biodiesel and the ketal-glyceryl esters allows one to say that the substitution of methyl alcohol by a glycerol derivative in the structure of fatty esters has resulted in a product that is not detrimental to some critical biodiesel properties. The conversion of such a glycerol derivative into a product to be added to biodiesel could be a solution to the problem of utilising the excess of co-product glycerol. However it is not a "ready to use" product as some modifications must be made to compression ignition engines to avoid gum formation from the glycerol moiety. 5. Future research Improvement in the synthesis of monoesters of glycerol must be focused on reaching higher selectivity in this product. It would be useful to have pure compounds to precisely establish the role of monoesters structures of polyhydroxylated alcohols as emulsifiers, lubricants and anti-crystallizing agents. 6. References Aboud-Rachid, H., Bonneviot, L., Xu, G. & Kaliaguine, S. (2003). On the correlation between kinetic rate constants in the autoignition process of some oxygenates and their cetane number: a quantum chemical study. J Mol Struct, Vol. 3, (February 2003) 293- 304, ISSN: 0166-1280 Abro, S.; Pouilloux, Y.; Barroult, J. Selective synthesis of monoglycerides from glycerol and oleic acid in the presence of solid catalysts. Stud. Surf. Sci. Catal,Vol. 108, (1997) 539- 546, ISSN 0167-2991 www.intechopen.com New Applications for Soybean Biodiesel Glycerol 169 Albinante, S. R.(2007) Aditivos Inibidores de Cristalização para Fluidos de Perfuração de Base Orgânica Sintética para Poços de Petróleo em Águas Profundas. MSc Thesis, Instituto de Quimica, Universidade Federal do Rio de Janeiro. Al-Sabagh, A.M.; Noor El-Din, M.R.& Mohamed, H.M. (2009). Oil Base Mud. Part I: Synthesis of some local surfactants used as primary emulsifiers for oil base mud and evaluation of their rheology properties. Journal of Dispersion Science and Technology, Vol 30, 1079-1090, 2009. ASTM Standard D-1160 (2006). Standard Test Method for Distillation of Petroleum Products at Reduced Pressure", ASTM International, West Conshohocken, PA, 2006, DOI:10.1520/D1160-06, www.astm.org ASTM Standard D-4737 (2009). Standard Test Method for Calculated Cetane Index by Four Variable Equation" ASTM International, West Conshohocken, PA, 2009, DOI:10.1520/D4737-09A, www.astm.org Batista, L.N. (2008) Desenvolvimento de um biocombustivel a partir de glycerol. MSC Thesis. Instituto de Química, Universidade Federal do Rio de Janeiro (May 2008). Behr, A; Eilting, J.; Irawadi, K.; Leschinski, J. &Lindner, F.(2008) Improved utilisation of renewable resources: New important derivatives of glycerol. Green Chem, Vol 10, No. 1 (January 2008) 1–140 Bell, B.M.; Briggs, J.R.; Campbell, R.M.; Chambers, S.M.; Gaarestroom, P.D.; Hippler, J.G.; Hook, B.D.; Kearns, K.; Kenney, J.M.; Kruper, W.J.; Schreck, D.J.; Therialt, C.N.; Wolfe, C.P. (2008). Glycerin as a renewable feedstock for epichorohydrin production. The GTE process. Clean, Vol 36, No.8, 657. Bogalhos, P.; Fregolente, L.; Pinto, G.M.F.; Wolf-Maciel, M.R.; Maciel, R. (2010) Monoglyceride and Diglyceride Production Through Lipase-Catalyzed Glycerolysis and Molecular Distillation. Appl. Biochem. Biotech Vol 160, No.7, (April 2010) 1879-1887 Boot, M.; Frijters, P.; Luijten, C.; Somers, B; Baert, R.; Donkerbroek, A; Klein-Douwel, R.J.H & Dam, N.( 2009) . Cyclic Oxygenates: A New Class of Second-Generation Biofuels for Diesel Engines. Energy & Fuels, Vol.23, 1808–1817 (2009) Centi, G. & van Santen, R.A. (2007). Catalysis for renewable: from feedstock to energy production, Wiley-VCH, Weinheim, 2007. ISBN: 978-3-527-31788-2 Chevernet, M.E.; Pernot, V. (1998) Control of Shale Swelling Pressures Using Inhibitive Water-base Muds. SPE Paper 49263, presented at 1998 SPE Annual Technical Conference and Exhibition, New Orleans, LA (1998). Ciapina, E.M.P.; Melo, W.C.; Santa Anna, L.M.M.; Santos, A.S.; Freire, D.M.G.; Pereira, N. (2006). Biosurfactant production by Rhodococcus erythropolis grown on glycerol as sole carbon source. Appl. Biochem & Biotechn., Vol. 131, No. 1-3 (March, 2006) 880- 886. Corma, A., Iborra, S., Chornet, A.I.L Velty, S. Bee Abd Hamid,. Preparación de monoésteres de acidos grasos. Universidad Politecnica de Valencia, ES 2 229 948, 14 October 2003, 1 June 2006 CPS Biofuels (2010). Site of the company www.cpspowershot.com Acess in September 2010. da Silva-Machado, M.; Pérez-Pariente, J. ; Sastre, E.; Cardoso, D.; Martinez-Guerenu, A. Selective synthesis of glycerol monolaurate with zeolitic molecular sieves . Appl. Catal. A, Vol 203, No. 2, (October, 2000) 321-28. ISSN: 0926-860X. Da Silva, M.A.M.; Medeiros, V.C.; Langone, M.A.P.; Freire, D.M.G. (2003) Synthesis of monocaprin catalyzed by lipase. App Biochem & Biotechnol, Vol 105, (April 2003) 757-768. www.intechopen.com 170 Soybean - Applications and Technology Dasari, M.; Kiatsimkul, P.; Suterlin, W.; Suppes, G.J. (2005). Low-pressure hydrogenolysis of glycerol to propylene glycol, Appl.Catal.A, Vol.281, No.1-2, (March, 2005), 225 -231, ISSN: 0926-860X. Delfort, B.; Durand, I.; Jaecker, A.; Lacome, T.; Montagne, X. & Paille, F. (2005) Fuel compounds containing glycerol acetals patent: US6890364 (May 2005) Diaz, I.; Mohino, F.; Pérez-Pariente, J. ; Sastre, E. (2001) Synthesis, characterization and catalytic activity of MCM-41-type mesoporous silicas functionalized with sulfonic acid. Appl. Catal. A: Gen., 205, 1-2, (January, 2001) 19-30, ISSN: 0926-860X. Diaz, I.; Mohino, F.; Pérez-Pariente, J.; Sastre, E. (2003) Synthesis of MCM-41 materials functionalised with dialkylsilane groups and their catalytic activity in the esterification of glycerol with fatty acids. Appl. Catal. A:Gen.,Vol 242, No.1, (March, 2003) 161-169. ISSN: 0926-860X. Diaz, I.; Mohino, F.; Blasco, T.; Sastre, E.; Pérez-Pariente, J. (2005) Influence of the alkyl chain length of HSO3-R-MCM-41 on the esterification of glycerol with fatty acids. Microporous and Mesoporous Materials, Vol. 80, No.1-3, (May, 2005) 33-42, ISSN: 1387- 1811. Dubois, J. L., Iborra-Chornet, S., Canos, A. C. & Velty, A, I. (2009). Diesel Fuel containing long chain glycerol acetals. EP application May 2008; patent: WO08050030/EP209482, sep. 2009. Fink, J. K. (2003). Oil Field Chemicals. Gulf Publishing Company, First Edition, New York, 2003, ISBN: 0-7506-7703-1. Freitas, L.; Paula, A.V.; dos Santos, J.C.; Zanin, G.M.; de Castro, H.F. (2010). Enzymatic synthesis of monoglycerides by esterification reaction using Penicillium camembertii lipase immobilized on epoxy SiO2-PVA composite, J. Molec Catal B- enzimatic, Vol.65, No 1-4 (August 2010) 87-90. Garcia, E.; Laca,M.;Perez,E.; Garrido, A.; & Peinado, J. (2008). New class of acetal derived from Glycerin as a biodiesel fuel component. Energy& Fuel, Vol. 22, No.6, 4274-4280. Gupta, V.P. (1995). Glycerine Ditertiary Butyl Ether Preparation. Publication date: December 1995. Patent No.US5476971. Guner, F.S.; Yager, Y. & Erciyes, A.T. (2006) Polymers from triglyceride oils. Prog Polym Sci, Vol.31, (July 2006) 633-670. Hale, A.H., Dewan, A.K.R. (1989). Inhibition of Gas Hydrates in Deepwater Drilling. SPE/IADC Paper 18638, presented at the SPE/IADC 1989 Drilling Conference, New Orleans, LA (1989) Hillion, G.; Delford. B. & Durand. I. (2005). Method for producing biofuels, transforming triglycerides into at least two biofuel families: fatty acid monoesters and ethers and/ or soluble glycerol acetals. WO 2005/093015 A1 Jerome, F; Pouilloux, Y.; Barrault, J. (2008). Rational Design of Solid Catalysts for the Selective Use of Glycerol as a Natural Organic Building Block. ChemSusChem, Vol.1, No. 7, (July, 2008) 586 – 613, ISSN:1864-564X. Karam, A.; Gu, Y.; Jerome, .F.; Douillez, J.P.; Barrault, J. (2007) Significant enhancement on selectivity in silica supported sulfonic acids catalyzed reactions. Chem Commun., 22, (2007), 2222-2224, ISSN: 1359-7345. Kirk, R.E. & Othmer, D.F. (1951) Encyclopedia of Chemical Technology. Vol7, Interscience Pub. New York, 216-228 Knothe G.(2005). Dependence of biofuel fuel properties on the structure of fatty acid alkyl esters. Fuel Process Technol ; Vol.86, No.10, 1059–70, ISSN: 0378-3820 Klepacova, K., Mravec, D. & Bajus, M. (2006). Etherification of glycerol with tert-Butyl Alcohol Catalysed by ion-Exchange Resins. Chem Papers, Vol 60, (2006) 224 www.intechopen.com New Applications for Soybean Biodiesel Glycerol 171 Marrouni, K. E., Abou-Rachid, H. and Kaliaguine, S. (2008), Theoretical study of ignition reactions of linear symmetrical monoethers as potential diesel fuel additives: DFT calculations. International Journal of Quantum Chemistry, Vol.108, No 1,.40–50 (2008). Maker, D & Muller, H (2009) Lubricants for drilling fluids. European Patent application, jun 2001, EP 2201082 Márquez-Alvarez, C.; Sastre, E.;& Pérez-Pariente, J. (2004) Solid Catalysts for the Synthesis of Fatty Esters of Glycerol, Polyglycerols and Sorbitol from Renewable Resources. Top. Catal,Vol.27, No.1-4, (February, 2004) 105-117, ISSN: 1022-5528. McCormick, R.;L.; Ratcliff, M.; Moens, L. & Lawrence, R. (2007). Several factors affecting the stability of biodiesel in standard accelerated tests. Fuel Process Technol, Vol.88, No.7, (July 2007) 651-7, ISSN: 0378-3820. Melero, J. A.; Vicente, G; Morales, G.; Paniagua, M. & Bustamante, J. (2010) Oxynated Compounds derived from glycerol for biodiesel formulation:influence on EM 14214 quality parameters. Fuel, Vol. 89, No.8, (August 2010) 2011-2018. Miller, D. J.; Peereboom, L.; Kolah, A. K.; Asthana, N. S. & Lira, C. T. (2008). Process for production of composition useful as a fuel. Patente US7321052B (January 2008). Mueller, H., Claus-Peter, H / Bongardt, F.; Herzog, N. & von Tapavicza, S. (2004). Lubricants for drilling fluids. US Patent 6806235, (October 2004). Nandi, S.; Gangopadhyay, S.; Ghosh, S. (2008).Lipase Catalyzed Synthesis of Neutral Glycerides Rich in Micronutrients from Rice Bran Oil Fatty Acid Distillate . Journal of Oleo Science, 57, 11, 599-603. ISSN 1345-8957. Nascimento, R.S.V., Soares, V.L.P., Albinante, S.R.& Barreto, L.R. (2005). Effect of ester- additives on the crystallization temperature of methyl hexadecanoate. J Therm Anal Calorim.,Vol . 79, No.2, (January 2005) 249–54, ISSN: 1388-6150. Nouredini, H. (2001). System and Process for producing biodiesel fuel with reduced viscosity and a cloud point below thirty two degrees Fahrenheit. US Patent 6174,501 (2001). Pagliaro, M & Rossi, M. (2008). The Future of Glycerol. RSC Publishing, London, ISBN: 978- 0-85404-124-4. Pomerleau, D.G.; "Glycerol Based Drilling Fluids", US Patent Application 20090143254, 2009. Pouilloux, Y.; Abro, S.; Vanhove, C.; Barraoult, J. (1999). Reaction of glycerol with fatty acids in the presence of ion-exchange resins: Preparation of monoglycerides. J. Mol. Catal., 149, 1-3 (December, 1999) 243- 54, ISSN: 1381-1169. Puche, J. D. (2003). Procedure to obtain biodiesel fuel with improved properties at low temperature. Publication date: November 2003. Patent No. 20030167681. Rahmat, N., Abdullah, A.Z. & Mohamed, A.R. (2010). Recent progress on innovative and potential technologies for glycerol transformation into fuel additives: A critical review. Reenwable and Sustainable Eenergy Reviews, Vol 14, No 3 (April 2010) 987- 1000. Sakthivel, A.; Nakumara, R.; Komura, K. & Sugi, Y. (2007). Esterification of glycerol by lauric acid over aluminium and zirconium containing mesoporous molecular sieves in supercritical carbon dioxide medium J. of Supercritical Fluids 42, 2, (2007) 219-25, ISSN: 0896-8446. Santa Anna, L.M.S.; Sebastian, G.V.; Pereira, N. ; Alves, T.L.M.; Menezes, E.P.& Freire, D.M.G. Production of biosurfactant from a new and promising strain of Pseudomonas aeruginosa PA1. Appl. BioChem & Biothechnol, Vol. 91, No.3, (April, 2001) 459-467 Shelley, S. (2007). A Renewable Route to Propylene Glycol. Chem. Eng. Prog,, 2007, Vol.103, No. 8 (August 2010) 6. htpp: www.senergychem.com, acessed in August 2010. www.intechopen.com 172 Soybean - Applications and Technology Shreve, R.N. & Brink, J.A. (1977) Chemical Process Industries, 4th ed., Mc Graw-Hill, New York. Siano, D.; Santacesaria, E.; Fiandra, V.; Tesser, R.; Nuzzi, G.Di; DiSerio, M.; Natasi, M. (2006). Process for the production of alpha, gamma-dichlorohydrin from glycerin and hydrochloric acid. Publication date: October 2006. Pub No.WO2006111810. Simonetti, D.A., Rass-Hansen, J., Kunkes, E.L., Soares, R.R. & Dumesic, J.A. (2007). Coupling of Glycerol Processing with Fisher-Tropsch synthesis for production of liquid fuels. Green Chem.,Vol 9, No.10, 1073-1083, ISSN:1463-9262 Simova, S.; Ivanova, G.; Spassov, S.L. (2003). Alternative method for quantitative determination of acyl positional distributions in triacylglycerols and related compounds. Chem. Phys. Lipids, 126, 2, (2003),167-176, ISSN: 0009-3084 Soares, R.R.; Simonetti, D.A.; Dumesic, J.A. (2006) Glycerol as a source for fuels and chemicals by low-temperature catalytic processing. Angew. Chem. Int. Ed., 45, 24, (2006), 3982-3985, ISSN: 1433-7851. Soares, V.L.P, Albinante, S.R. & Nascimento, R.S.V. (2009) Ester-additives as inhibitors of the solidification of soybean oil methyl esters. J Therm Anal Calorim, Vol 97, No.2 (November 2009) ISSN 1382-6150. Sofiproteol (2007). www.fas.usda.gov/gainfiles/200702/146280213.pdf Song, J.; Zello, V. & Boehman, J. (2005). Comparison of the Impact of Intake Oxygen Enrichment and Fuel Oxygenation on Diesel Combustion and Emissions. Energy & Fuels, Vol 19, 403-410 (2005) Spooner- Wyman, J.K. & Appleby, D.B.( 2005). Fuel composition for producing heat and power,. Patent US2005000150-A1; WO2005003264-A1; EP1641901-A1 Sunder, A.; Hanselmann, R.; Frey, H.; Mulhaupt, R. (1999) Controlled synthesis of hyperbranched polyglycerols by ring-opening multi-branching polymerization. Macromolecules, Vol.199, No.32, 4240. Sunder, A.; Kramer, M.; Hanselmann, R.; Mulhaupt, R.; Frey, H. (1999). Molecular nanocapsules based on amphiphilic hyperbranched polyglycerols. Angew. Chem.Int. Ed. 1999, 38, 3552. Suppes, G.J.; Sutterlin, W.R. & Dasar, M.A. (2005). Method for producing lower alcohols from glycerol. WO2005095536. Taylor, J.D.; McCormick, R.L. & Murphy, M.J. (2004). Compendium of Experimental Cetane Number Data. National Renewable Energy Laboratory NREL http:// www.nrel.gov/vehiclesandfuels/pdfs/sr368051.pdf http://www.nrel.gov/vehiclesandfuels/pdfs/sr368051.pdf Wang, J.X.; Wu, F.J.; Xiao, J.H.& Shuai, S.J. (2009) Oxygenated blend design and its effects on reducing diesel particulate emissions, Fuel, Vol 88 (2009) 2037–2045. Watanabe, T; Shimizu, M.; Sugiura, M.; Sato, M.; Kohori, J.; Yamada, N.; Nakashi, K. (2003) Optimization of reaction conditions for the production of DAG using immobilized 1,3-regiospecific lipase lipozyme RM IM. J. Am. Oil Chem. Soc., 2003, 80, 1201. Yaakoub, M. C. (2008). Obtenção de aditivos para fluidos de perfuração a partir da glicerina" MSc Thesis, Instituto de Química, Universidade Federal do Rio de Janeiro, March, 2008. Yousif, M.H. & Young, D.B. (1993) A Simple Correlation to Predict the Hydrate Point Suppression in Drilling Fluids. SPE/IADC Paper 25705, presented at the SPE/IADC 1993 Drilling Conference, Amsterdan (1993). Zhou, C-H; Beltramini, J. N.; Fan, Y-X & Lu, G.Q. (2008). Chemoselective catalytic conversion as a biorenewable source to valuable commodity chemicals. Chem.Soc. Rev., Vol 37 (2008) 527-49, ISSN 0306-0012. www.intechopen.com Soybean - Applications and Technology Edited by Prof. Tzi-Bun Ng ISBN 978-953-307-207-4 Hard cover, 402 pages Publisher InTech Published online 26, April, 2011 Published in print edition April, 2011 Soybean is an agricultural crop of tremendous economic importance. Soybean and food items derived from it form dietary components of numerous people, especially those living in the Orient. The health benefits of soybean have attracted the attention of nutritionists as well as common people. How to reference In order to correctly reference this scholarly work, feel free to copy and paste the following: Vera L. P. Soares, Elizabeth R. Lachter, Jorge de A. Rodrigues Jr, Luciano N. Batista and Regina S. V. Nascimento (2011). New Applications for Soybean Biodiesel Glycerol, Soybean - Applications and Technology, Prof. Tzi-Bun Ng (Ed.), ISBN: 978-953-307-207-4, InTech, Available from: http://www.intechopen.com/books/soybean-applications-and-technology/new-applications-for-soybean- biodiesel-glycerol InTech Europe InTech China University Campus STeP Ri Unit 405, Office Block, Hotel Equatorial Shanghai Slavka Krautzeka 83/A No.65, Yan An Road (West), Shanghai, 200040, China 51000 Rijeka, Croatia Phone: +385 (51) 770 447 Phone: +86-21-62489820 Fax: +385 (51) 686 166 Fax: +86-21-62489821 www.intechopen.com
Pages to are hidden for
"New applications for soybean biodiesel glycerol"Please download to view full document