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Me: WHOOO! We did it! 200 reviews! You guys are INCREDIBLE! And this is also the 10th chapter of Road Trip so I guess you can call it the 10th chapter anniversary. XD This chapter will be FAR longer then all the other ones as the author notes of this chapter is going to be pretty long and every tenth chapter will be just as long as this one.
Percy: *Yawns* Get on with it will you?
Me: Right, right. So, last chapter I said I was going to give out the mega shout-outs to the 180th, 185th, 190th, 195th, and 200th reviewers and review all of their stories and all the chapters IN the story and after many incredible evenings, I have read and reviewed ALL of the winners stories (Still working on one though, I WILL FINISH IT! XD). If you didn't win last time, don't worry, I will keep going on with these contests and in this very chapter is one too. Details at the bottom. :)
Percy: So, looks like I am beginning. This is for the 180th reviewer who is Velocity Drew Warren who is an incredible author and is hands down one of the kindest people on FF. Though she only has only one story, a collection of one-shots, they are guaranteed to you laugh or even cry. It is a beautiful collection and definitely take your time to read it as you will most definitely not be disappointed. This is for Velocity Drew Warren, the 180th reviewer!
Zeus:*Sigh, grumbles* Again? Gods. Okay, okay. This is for the 185th reviewer, ThePrinceofOlympus, who's two stories are exciting, adventurous, and very interesting. These are a great collection of stories and are worth reading. This is to ThePrinceofOlympus, the 185th reviewer!
Nico: 'Sup? So, this is for the 190th reviewer,storyteller155, who's three stories are all awesome cool. (As the son of Hades, I know what I'm talking about) These stories will make you think and are definitely worth reading. Her story about us going to school is quite interesting an a good read. This is for storyteller155, the 190th reviewer!
Me: The shout-outs will continue the bottom of the page and if you could take the time to answer the question to win a shout-out and *Coughreviewcough*, you do not know how happy that would make me. :) So have fun reading, and thanks for helping me get so far!
Zeus's POV
Breakfast, sadly, was rather uneventful as the children were still shocked at Poseidon's 'transformation' and the sea-god was childishly giving us the silent treatment, as if that would change anything. We, of course, did not eat breakfast in the hotel room as the room did not have a kitchen so instead, we went down to the hotel buffet room, which was actually a small, rather unattractive looking room with a peat green carpet and paisley walls. It was strangely vacant but then again, it was pretty late and most of the other people must've ate already.
As we walked into the small, rectangular room the three demigods rushed in their faces expectant and with an expression like they hadn't eaten for days written on their face.
"I. Am. Starving." Percy exclaimed, seeming to come out of the shock of seeing his father look younger than he was. "Oh man, I could really use a-" He took a deep breath, to breath in the normally present scent of breakfast pastries but then seemed to choke. "EEGHH what is that smell?!"
Thalia gagged and clasped one hand on her nose. "It smells like Ares' gym socks in here-"
"Been there, definitely not pleasant" Percy muttered.
"-That wouldn't be breakfast would it?"
"If it is, I'm not touching it." The son of Hades now also had one hand over his nose and his normally pale complexion was now tinged green, almost the same shade as the rather slimy looking carpet. "I think my nose just died."
"Ditto. You know what, I don't think I'm hungry or ever going to be hungry again."
Sure, the room didn't smell pleasant, perhaps slightly worst then Hera's perfume but there was no reason we would have to go to another restaurant when we had food here right?
Hades, obviously, did not agree. "Zeus," he growled, "We are not eating in this...place. The carpet is as old as the fates themselves, the wall paper looks about the same shade as Chimera poison and the food, if you can still call it that, looks like a one-eyed harpy threw Kronos' remains into a blender and topped it off with gasoline. If you wish to ingest this mess, go ahead. I'm going to a place where they actually serve food."
For a god who stared at the dead all day, his descriptions unnaturally colorful and now even I was starting to feel slightly queasy. So for the first time in what must've been a millennium, I gave in to my annoying, ignorant older brother. "Fine." I reluctantly grumbled. "I spotted a Starbucks on the way here. Out the door, 'round the corner."
"Starbucks sounds good. I could do with some coffee." Hades turned to leave and the demigods and god scrambled after him, sighing in relief and taking deep breaths of air. "Oh, and Zeus?"
"What?" I snapped, trying to take my own share of Hera free air while trying not to appear doing so.
"You, little bro, are paying because you were the one that got us here in the first place."
I sighed. For a god nicknamed 'The Rich One', Hades was awfully picky about spending his money. "Of course. Lead the way."
It didn't take us long as in their eagerness the demigods practically ran to the small, green, (expensive) café with the traditional mermaid on it. Pretty soon, we had two tables pushed together and warm pastries steaming in front of us.
Poseidon, who had still not spoken scowled at his doughnut. Hard.
"Eat the doughnut Poseidon. Don't just stare at it."
The sea-god scowled even harder.
"Hello? Is this... yes. Thank you. I would like a reservation." The sound Hades's voice caught my attention and I turned to see him using the pay phone out side. From the way the door was still shut and the fact that he was wearing a baseball cap that kept flicking through the mist, I had a feeling that instead of taking normal methods, he had just passed straight through the walls.
Though the thick glass windows muffled his voice, it could still be faintly heard from the inside. Curious about what what Hades could be calling for, I listened closely.
"For 6, one adult five children..." A dinner reservation? Nice. But wait. Five children? Poseidon's scowl lifted slightly and he turned to smirk at me. "I'm taking my niece and nephews out for dinner..." Hades's nephew. Huh. What an honor. "7:30.. that will be fine. Put it under the name of..." Hades looked like he was thinking hard. As gods don't have a last name, I was interested to see what he was going to call himself. Better think fast, bro. "Mr. Olympia. Thank you."
"Mr. Olympia, huh?" Hades's pale skin colored slightly as he walked in. "Very creative, Hades"
He snorted. "Like you can do better."
Admittedly, I was too familiar with mortal last names either but I wasn't going to tell Hades that. "You're paying for dinner, Mr. Olympia? I presume the children, Poseidon and I are going to be your 'niece and nephews'?"
Poseidon continued to glare at his doughnut.
"Lord Hades?" Percy suddenly broke in, a hint of worry in his voice. "We aren't eating... sea food are we?" At seafood, Poseidon's glare wavered slightly and he turned green.
Nico finished the rest of his doughnut and snorted. "No, Percy, of course we're eating sea food. My dad has noooo idea that his brother, who he's known since the beginning of time-"
"We aren't that old. Try beginning of your known world."
"-is the sea-god and he and his son don't eat fish."
Hades and I suppressed chuckles but Percy seemed unperturbed."Just checking. Besides, everyone knows that fish are friends, not food."
"Are you seriously quoting 'Find Nemo'?" Thalia joined in, snickering.
Percy nodded and thumped his chest. "That's what real men do."
"Seaweed Brain."
"Thanks, Pinecone face."
Hades's son, who had wisely not joined in the nickname contest, turned to me instead. "Lord Zeus," He asked, "Where are we going today? Universal Studio again?"
Pulling back my chair, I stood and stretched. "Actually, Nephew, no." With all eyes suddenly on, me, I grinned.
"We're going to Disney."
Thalia's POV
Disney. Of all places, Disney. The happiest place on earth, the place where dreams came true, and the year of a million dreams.
Or so the brightly colored banners proclaimed.
The park was big, perhaps even bigger then Universal was and through the mobs of vendors, gift shops, food stands, and ridiculously tall figures of "Micky and Minnie Mouse" that looked suspiciously like Laistrygonians in jump suits and mouse hats, I could still clearly see the large, world famous rearing marble and white castle with royal blue turrets.
Well that was perfect. The giant castle had to be the one and only Cinderella Castle and that would mean the Disney park that we were in was...
"Magic Kingdom." Hades read. He and Zeus were, of course, in teenaged form and I had to admit that I was having a pretty amusing time watching the Lord of the Underworld realize that he was going to have to spend all day around fairy tales, princesses, and hundreds upon hundreds of little girls in yet more princess dresses calling for their 'Prince Charming's to arrive.
I shared his pain.
Nobody could decide what they wanted- or rather, didn't want- to do and we ending up standing in the middle of 'Princess Drive' for about ten minutes trying to find a ride that wasn't pink, princessey, or only able to move at 2 kilometers per hour.
That left about, oh, 3 rides.
As we contemplated whether or not 'The Great Nemo Adventure' would be more interesting then "Cars; The Race of Speed' which despite it's fancy title was actually a couple of brightly painting automobiles in a track going at about the speed of Kronos reforming, a brightly clothed Photographer came skipping over, waving a camera.
"Good day, Lady and Germs!" He spoke unnecessarily loudly and with a thick Australian accent which made Percy flinch and mutter about something about cruises and bowling practice. "Would you care to take part in our fun photo contest?"
"Photo contest?"
He nodded brightly, his hat bobbing. "Oh yes! You see, you take these cameras," he quickly produced tow cheap disposable cameras and handed one to Nico and one to Hades, who looked at them curiously. "And you look for these special signs implanted around the park, in, you know, our most famous locations! They will tell you what to do, how to pose, and if you complete three out of four of the photos, you get a seventy-five percent discount at the gift shop!" The photographer smiled, though it was too unnaturally wide for any normal smile. "Isn't that great?"
What sounded great to me was to slam him in the face with Aegis- this man sounded far too happy and definitely deserved a good knock on the head- but I persisted. "So, we look for signs, read the signs, do what they want us to, and hand in the photos?"
"Exactly! And to make it more interesting it can be a race! Three on three!" He then glanced rapidly down at his large, rather old looking watch and jumped. "Alas, I most leave now for my other part time job on a cruise! Good bye and have a good day!" With that, he dashed off, leaving us with two cameras, an overwhelming sensation to hit something, a distinct impression that the man was mad and what was beginning to look like a good competition.
"Demigods against gods." For the first time all morning, Poseidon spoke. I wasn't sure what surprised me more, the fact that he sounded just like Percy or the fact that he, a god, was the one who was suggesting that we start a competition. As he continued, a small, mischievous smile beginning to form on the young sea-gods face. "And since there's a discount at the end for both teams... losing team has to wear whatever crown or hat the winning team chooses. For the whole day, where ever they go."
Wow. Tough punishment, though I could just see my dad in a pink feather tiara. "I'm cool with that idea. Better then standing in 'Princess Drive' all day."
"I second that" Hades agreed, looking immensely relieved to be able to escape from standing around pink laced curtains and excited little 'princesses'. "We'll start in three, first team to finish wins."
The rest of the group nodded and I noticed that Nico and Percy's eyes were bright with excitement.
We were totally going to rule this contest.
Hades started to count down. "Three," everybody got in running positions "Two," Percy cocked his head to one side, as it listening to something, "One," Percy whispered something to Nico and he nodded, his eyes shining. "GO!"
"Thalia! This way!" Nico immediately called as he and Percy began running full-out towards Cinderella castle. I dashed after them, noticing that the gods were running in the other direction. "Come on, Thalia! There's a sign over there!"
"How do you know?"
Percy turned back to face me with a crooked smile on his face, his eyes gleaming. "We've got air force"
Thank the gods for Annabeth and Blackjack! As we neared the castle, I spotted the sign and raced towards it.
"What does it say?" Percy asked, hopping up and down in agitation.
"It says..." wot eolpep upt on hte utoftis dna seop keli uory ropsgnipo. "Er..." I blinked, trying to stop the words from doing ballet. Finally- "I got it! Two people put on the outfits and pose like your proposing." I read triumphantly. Then- wait. PROPOSING?!
"I called taking the pictures!" Percy called, grinning. That's weird. Percy never had shown any liking to photography before and-
That's when it hit me. AGH that was so stupid! Why didn't I- AAAAGGGGHHH.
"Me and him?!"
"Me and her?!"
Percy just smirked. "Come on, guys, hurry it up."
"But-but-" Nice stuttered, looking frantic. "Percy, can't I take the pictures?"
"Nope, I called dibs. Oh, and you guys have to put these on, I think." He held out two articles of clothing, one of a jacket that looked like chain mail and a large, flowy dress. His grin could've made the even the Cheshire cat jealous.
I was torn. One part of me wanted to take the clothes and chuck it to Tartarus while the other part of me desperately wanted to see three of the most powerful beings in the world wearing Micky Mouse ears. UGH.
I sighed. "Come on, Death boy. Let's get this over with."
Minutes later, Nico and I were posed in front of the castle and I was feeling considerably better about this photos out come.
Why, you ask?
"How in Hades did I end up being the one in the dress?"
I looked him over, struggling not to burst out laughing. Nico di Angelo, the 'Ghost King', the oh so scary son of Hades was now in a big, fluffy wedding dress. The wedding veil had somehow been flipped over his face but underneath it, I could tell that he was blushing profusely. "Well..." I mused, "It fits you Nicole. And plus, I'm a hunter, I can't be the one being proposed to now can I? You're just a guy so why not?"
"Well, maybe 'cause as you said, I'm a GUY?"
I couldn't help it. Neither could Nico.
We both cracked up.
"Done, guys." Percy's mouth twitched and his green eyes were sparkling. "I now pronounce you the strangest couple in the world. You," He turned towards me, already starting laugh. "May now kiss the... thing facing you. I don't even know what to call this."
All three of us burst into spontaneous fits of laughter.
That was only the first of three photos.
Oh boy.
Me: As I said, this was the longest chapter I've ever written, the story it's self (Not including the A/N) being a mighty 2,326 words. Definite high score for me :) Plus the A/N... let's just say it's somewhere are the 3000's. XD For now on, all the tenth chapters will be supppppeerr long, so- Right, shout-outs. 2 left!
Thalia: 'Kay, that shout out is for the 195th reviewer, Apollo's Child! Her stories are a incredibly amusing and if you want a good laugh, that's the place too look. The stories range from Warriors, Harry Potter, and Percy Jackson and despite the wide variety of different stories, they all retain the same humor that just gives that special ring to her stories. This is to Apollo's Child, the 195th reviewer!
Poseidon: Last shout-out, what and honor. :) Okay, this shout-out is for the 200th reviewer, Anna C. Poseidon who also covers a wide variety of different stories. They also gave that laugh out loud humor that we just need on certain days and they are a great read so definetely take the time to look at them. This is to Anna C. Poseidon, the 200th reviewer!
Me: And we're done! Thanks so much you guys, all those reviews really made my day! Now, for the contest, it's not Percy Jackson trivia this time but I would like your advice. Any one who answers the two questions receive a shout-out and of course, cookies. :) The questions are:
1. Which team, demigods or gods, should win the photo contest?
2. For the losing team, what type of crown or hat should they have to wear? the more ridiculous the better. :)
You will have two chapters time to submit your answers (If you can, vote on the poll about it too!) and if you happen to the 225th reviewer, you will receive the lucky privileged by having ALL you stories read and reviewed by Moi. :)
This is the for the 225th reviewer, so good luck and hope you had fun reading the story!


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subset: commoncrawl


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Saturday, October 28 - Saturday, October 28
Painting with a Twist Family Class (Age 7+)
1:00pm, Painting with a Twist, 17723 Coastal Highway, Lewes. Bring family and friends to paint "Skeleton!" Bring the kids and grandkids too! All Ages Family Class (Age 7+), just $25. For a complete schedule of classes or to purchase tickets, call 302-313-5769 or visit https://paintingwithatwist.com/lewes/.


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oh no , your an x factor GEEK eurgh lol i only watched it when it was audition season , i dont watch it nowadays. i cant believe ur puttin gay x factor before the contender, what a TRAITOR !


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Separate names with a comma.
Discussion in 'Industry Surveys & Polls' started by LawnMastersTx, Jan 19, 2008.
Simple question - Do you think the 2008 season will be better or worse than 2007?
here were i'm @ it will be better. we are already getting a few calls for new service for the spring.. more calls then last year..
From last year to this year.We are also getting more calls and work sold for this upcoming season.
With a deep recession seeming inevitable, I think the big time lawn care guys will be thinned out, and I think if a lot of people end up losing jobs, that every guy with a mower, trailer, and a truck will be out undercutting all the big guys. I hate to be pessimistic, but If that recession hits look out... but let's hope I'm wrong.
Isn't that already going on? haha.
Yea I'm waiting for it to get worse. Figured make as much money as I can while I can and wait for the bad times to roll.
This winter seemed to have thinned out a lot of companies that popped up due to the heavy rainfall here last year. I plan on getting my name out there more and went ahead and got my irrigation license. If everyone starts mowing, i can fall back on doing sprinkler repairs, at least with that, you have to have a state license to work on them.


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Lancia news
Feb 05, 2008
Geneva 2008: The Lancia Delta has its world premiere
The Lancia Delta will debut at the 78th Geneva International Motor Show. Delta is a historical name associated with a peak in Lancia's motoring past but it is also a mathematical symbol that stands for change, difference and evolution.
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um well you can love someone, but being in love you feel more connected like they are your soul mate you don't normally want to part from them, and you usually feel it if you do seperate than if you were just loving someone.
I can tell the difference from when I was married I loved him, but we were not intimate, shared things as deeply, or true to eachother with our feelings, emotions, and honest with who we were.
On the other hand the person I am with now, nothing is really held back and we put it out on the table communicate everything without judgement and criticizing. We don't get in mean arguments, we have disagreements, but we don't hurt each other. It is more of a peaceful thing when you are in love with someone, and can be totally naked emotionally, intimately, spiritually. It is not so much the romantic/physical/sexual love, but those things can add to it.
It is something totally different.
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I think we aim to be in love...we crave that feeling of being a little hopeless and a little helpless. Important distinction, I think.
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If a person doesn't know the difference between "loving someone" and "being in love", that person either hasn't ever truly loved someone without being in love with him/her or else hasn't ever even truly in love - or both.
The real trick is sorting out the difference between temporary infatuation (that occurs in some new relationships) and being truly and permanently in love. Maybe one indicator would be whether it's "all about you" or "all about the other person". Infatuation can tend to be "all about you" (what being with this person offers you, how much it makes you happy to be with him/her, etc.) Maybe another indicator is whether both people feel "in love" - or just one of them. If it's only one, there's a good chance one of the most important elements of "true love" is missing.
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Thank you both for your answers.
I suppose that only few people will answer my question because being in love is very seldom found,like most precious jewel.
Including me.
Ive been with many girls,but Ive never experienced anything you both described.
Maybe one day...................
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I have a friend that I have known for ten years. Everyone thought we would marry. Yes, I loved her we were extremely close. We had even talked about marriage, but we both knew that it was just reason. Sure we could think of 1000`s of good reasons to marry and every councilor and his Mother would have agreed with us.
Yes, I loved her very much and would have even died for her as any good friend would, because we give our all for those we love, after all true love is unconditional.
Yes, I loved her and still do but I am not In Love with her.
Then I met my true soul mate by the time I met Cynthia I was a healthy man with a healed heart...long story for another time....But my heart and soul was "in love with her" and she with me. I did not see her picture for a while before we physically met, because when you are true soul mates and In Love It does not matter and you do not ask anyone's opinion you just know.
It has been quite a few years now and I`m still in love with her and it keeps getting stronger. I still love my friend....but most Importantly I daily keep my relationship with the true source of Love, true unconditional love, My heavenly father, after all he healed my unhealthy heart that did not know true love in its unblemished form so that my heart and soul could tell the difference between being in Love with someone and loving someone...
Ok that is my ten cents worth...hope I did not confuse you!
Great question!
Thanks for asking
Mike :0)
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|13 Jun 2010
Need to fix "Open With" menu for Image files
Windows 7 32bit OS
Intel Quad CPU
4GB DDR2 Ram
I did a clean install of Windows 7 a couple weeks ago.
I have 1,000's of jpg file I want to edit using Microsoft Digital Image Suite. When I right-click the file and choose "Open With" the only option listed is "Open With" again, which does nothing.
Before the clean install the "Open With" menu for image files had all my graphics programs listed. How do I get them back?
I have already tried using the Restore Default Windows 7 File Extension Type Associations reg file for jpg's I found in the forums here, but it did not solve it.
|My System Specs
|13 Jun 2010
Windows 10 Pro X64
Try uninstalling then reinstalling Microsoft Digital Image Suite, see if that gives you the correct Open With option.
|My System Specs
|13 Jun 2010
Hello johnnieq, welcome to Seven Forums.
Start> Type in the search box> Associations > Click on Make a file type always open in a specific program
Click on the file type you want to associate> Click on Change Program in upper right> Click on a choice amongst the programs listed, or click on browse, and browse to the program you want to use> OK your way out.
Repeat for any other file types.
A Guy
Actually, reread your post, you want to restore choices to open with, not have 1 program always open a file type. Do you not get the choice on open with to Choose default program?
|My System Specs
|14 Jun 2010
A Guy
Actually, reread your post, you want to restore choices to open with, not have 1 program always open a file type. Do you not get the choice on open with to Choose default program?
|My System Specs
|14 Jun 2010
That fix lasted all of 5 minutes. I checked a few image context menus before my last post and all was well. I just now clicked on an bmp file and it opened in PS4. I closed PS4 and right-clicked the image to open it in a different app. All gone. Again. Back to no "Open With" Options.
This is frustrating.
I think I see another Windows 7 clean install in my near future...
First I'll try uninstalling PhotoShop 4 as I might be upgrading to 5 soon anyway. Perhaps PhotoShop is trying to restore it's file associations?
|My System Specs
|14 Jun 2010
I'd try a repair install before you resort to a clean install.
Repair Install
Good luck. A Guy
|My System Specs
|15 Jun 2010
I didn't get back just the association with Microsoft Digital Image Suite, the entire "open with" menu option was back with all the appropriate image apps listed. Minutes later it was gone. It isn't a virus causing it, as I check regularly for infections.
As soon as I get some spare time I'll try the repair install and post my results. Thanks agasin!
|My System Specs
|15 Jun 2010
Windows 7 x64 Ultimate
It could be an ANTIvirus causing it.
Are you using any AV software? Some of them like to try to clean up your OS for you when it thinks something was changed
There have been some mighty odd things caused by AV software in these forums. Mostly software that was not specifically W7 compatible...
|My System Specs
|15 Jun 2010
For AV I use Windows Securtity Essentials and Malwarebytes Anti-Malware, both of which seem to be doing an excellent job in preventing vuruses.
I just finished a Repair Install, and nothing has changed in the right-click menu for image files.
I work on ncomputers. A LOT. I build them, repair, troubleshoot, etc. I do it almost every day, all day, and most evenings. I don't understand this one. I've searched the registry manually, tried ShellExView and ShellMenuView, everything looks ok. I've Googled, searched many of the tech forums, including Microsoft's Support site with no answers that worked. Very unusual, this one's got me beat...
|My System Specs
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remove the "open" and "merge" entries from context menu?
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|Vol 11, No 3 (2015)
|Kind word treatment
|Gerasimov G.
|Vol 12, No 4 (2016)
|Terrible force
|Gerasimov G.A.
|Vol 10, No 4 (2014)
|On WHO Guidelines "Fortification of food grade salt"
|Gerasimov G.A.
|"... Issues of implementation of WHO Guidelines on fortification of food grade salt with iodine ..."
|Vol 7, No 2 (2011)
|Use of iodized salt in the households improves the iodine status of pregnant women and school-age children in Donetsk, Ukraine: A double-blind randomized controlled trial
|, , , , ,
|"... This study analyzed the effect of iodized salt consumption on the iodine status of pregnant women ..."
|Vol 12, No 2 (2016)
|Medium to severe iodine deficiency still exists in Abkhazia
|Gerasimov G.A., Tulisov A.V., Belyaeva A.I., Tuzhba A.V., Petrenko S.V.
|"... –39 years). The content of iodine has been studied in the urine, and the use of iodized salt has been ..."
|Vol 12, No 1 (2016)
|Assessment of the provision of iodine supply to pregnant and lactating women in Kyrgyzstan
|Sultanalieva R.B., Beishekeyeva G.I., Gerasimov G.A.
|"... of inadequate iodine provision. Conclusion. Current measures to improve the quality of iodized salt ..."
|Vol 11, No 3 (2015)
|Prevention of iodine deficiency in the Tyumen region: success or failure?
|Suplotova L.A., Makarova O.B., Kovalzhina L.S., Sharuho G.V.
|"... 75% of parents and 46.6% of students. Regular use of iodized salt in the home diet ("always used ..."
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Fall Out Boy, "Young and Menace"
M.A.N.I.A. (Universal)
Recommended If You Like: Post-emo emo
We're not even halfway through May and we're already hearing about albums that won't be out until September. Case in point: the seventh album from Fall Out Boy. Make sure you hang in until about the 1:12 mark when Pete Wentz has his testicles electronically squeezed. Your next chance to see them in these parts will be October 25 when their Mania Tour hits the ACC.
grandson, "Bury Me Face Down"
Single (Latium/RCA)
RIYL: people who capitalize like ee cummings
Born in New Jersey but now working in Toronto, grandson says he occupies musical headspace somewhere between Rage Against the Machine, Twenty One Pilots and The Weeknd. Curious about what that sounds like, aren't you?
The Headstones, "Devil's on Fire"
Little Army (Cadence Music)
RIYL: Properly dirty Canadian rock'n'roll
With a new album (due June 2) and plenty of shows scheduled for the summer, this will feel a lot like 1997. That's a good thing, by the way. The album's release will be celebrated with two shows on one night at the Velvet Underground (8pm and 11pm). Proceeds will benefit CAMH (Centre for Addiction and Mental Health).
Middle Kids, "Edge of Town"
In the Battle Years (Virgin)
RIYL: Parachutes-era Coldplay if the singer was Florence Welch
Emerging trio from Sydney, Australia, with sunny Florence + the Machine-ish harmonies and more than a touch of early Coldplay strumming in their strumming habits. Point of trivia: singer Hannay Joy is married to bandmate Tim Fitz.
Catfish and the Bottlemen, "Twice"
The Ride (Capitol Records)
RIYL: Kasbian, Nothing But Thieves, a less wordy Arctic Monkeys
This Welsh four-piece indie rock outfit is earning something of a reputation as a fearsome live act who aren't afraid to bust it open with the occasional instrumental. Green Day has picked them to open their Revolution Radio tour.


text:
MOVIE SYNOPSIS [ General Audiences ] With production of USA, this 2011 film was directed by Teal Greyhavens. You can watch Cinema is Everywhere online on TV cable or theaters with original audio in English at different dates. This film premiered in theaters in 2011.
Rating: 5 by 11 users./
Runtime: 86 minutes
Tilda Swinton, Javed Akhtar, Fruit Chan, Sudhir Mishra, Mark Cousins, Shyam Benegal, Stanley Kwan, Ryan Chan and Karim Souaki.
86-minute film (full movie) directed by Teal Greyhavens.
The original audio of Cinema is Everywhere has dialogues in Dolby Digital, it was produced in USA.
It premiered in cinemas or television in 2011.
Marcy Levitas Hamilton, Priscilla Ross, Jason E. Gordon, Breven Angaelica Warren and Strathford Hamilton.
This film was produced and / or financed by Spiral Pictures.
Composed by Brandon K. Verrett.
Captive Entertainment and Spiral Pictures.
Without commercial breaks, the full movie Cinema is Everywhere has a duration of 86 minutes; the official trailer can be watched in streaming on the Internet. You can watch this full movie free in EnglishDolby Digital in movie TV channels, renting the DVD or with VoD services (Video On Demand player, Hulu) and PPV (Pay Per View, Netflix).
See the page of this full movie, Cinema is Everywhere in FULLTV Movies.


text:
Find Smyrna commercial real estate for sale and for lease on 42Floors, the commercial real estate search engine. Listings cover all types of properties including Retail, Office Space, Industrial, Medical and much more. Find a Smyrna commercial real estate broker in Smyrna's Top Broker Directory. Learn about Smyrna commercial real estate trends in 42Floors Research. Learn tips, tricks, and jargon about leasing or buying commercial real estate in 42Floors EDU.
Most commerial real estate listings for lease are in the $10's per square foot per year. The Smyrna submarket is seeing a decline in rates. In the last 3 months, the median rate for lease decreased $6 per sqft per year.
In the last 90 days, 44 commercial real estate listings have been posted online, so you'll want to check back regularly for new listings. There aren't many listings below 2,000 square feet posted, so finding a space for a small business might be tough.
The standard size for office space in this area is around 1,280 sqft. Most buildings in this region are close to 3 floors. Most buildings in this market were built close to 2007 and are Class A.
Real time and historical data on commercial real estate listings in Smyrna.
Get email notifications when new listings are posted that match your requirements.


text:
MOVIE SYNOPSIS [ General Audiences ] With the film direction of Alexandra Eaton, Giulia Achilli leads the cast of this feature film originally of India and USA, with original script in English (see subtitles), whose premiere was scheduled for 2014. You can watch Bombay Movie online on TV cable or theaters with original audio in English at different dates. This film premiered in theaters in 2014.
Rating: 5 by 10 users./
Runtime: 58 minutes
Giulia Achilli, Arjun Mathur, Raja Menon, Vijay Raaz, Naseeruddin Shah and Raj Yerasi.
Documental, Adventure, Biographic.
58-minute film (full movie) directed by Alexandra Eaton.
The original audio of Bombay Movie has dialogues in Dolby Digital, it was produced in India, USA.
It premiered in cinemas or television in 2014.
Alexandra Eaton.
Gill Holland, Vinay Singh and Aditya Bhattacharya.
Composed by Ian Turner.
Without commercial breaks, the full movie Bombay Movie has a duration of 58 minutes; the official trailer can be watched in streaming on the Internet. You can watch this full movie free in EnglishDolby Digital in movie TV channels, renting the DVD or with VoD services (Video On Demand player, Hulu) and PPV (Pay Per View, Netflix).
See the page of this full movie, Bombay Movie in FULLTV Movies.


text:
|Número da publicaçăo
|Tipo de publicaçăo
|Número do pedido
|Data de publicaçăo
|12 abr. 2011
|Data de depósito
|6 out. 2009
|Data da prioridade
|8 jun. 2007
|Status da taxa
|Também publicado como
|Número da publicaçăo
|Robert Hickey, Rahul Basu, Rathin Datta, Shih-Perng Tsai
|Cessionário original
|Coskata, Inc.
|Exportar citaçăo
|BiBTeX, EndNote, RefMan
|Citaçőes de patente (6), Citaçőes de năo patente (1), Citada por (9), Classificaçőes (18), Eventos legais (4)
|Links externos: USPTO, Cessăo do USPTO, Espacenet
This application is a continuation in part of U.S. application Ser. No. 11/972,454 filed Jan. 10, 2008 which is a continuation in part of U.S. application Ser. No. 11/781,717 filed Jul. 23, 2007 which is an application claiming benefit under 35 USC 119(c) of U.S. Provisional Patent Application Ser. No. 60/942,938 filed Jun. 8, 2007 and a continuation in part of U.S. application Ser. No. 12/036,007 filed Feb. 22, 2008.
This invention relates to the biological conversion of CO and mixtures of CO2 and H2 to liquid products.
Biofuels production for use as liquid motor fuels or for blending with conventional gasoline or diesel motor fuels is increasing worldwide. Such biofuels include, for example, ethanol and n-butanol. One of the major drivers for biofuels is their derivation from renewable resources by fermentation and bioprocess technology. Conventionally, biofuels are made from readily fermentable carbohydrates such as sugars and starches. For example, the two primary agricultural crops that are used for conventional bioethanol production are sugarcane (Brazil and other tropical countries) and corn or maize (U.S. and other temperate countries). The availability of agricultural feedstocks that provide readily fermentable carbohydrates is limited because of competition with food and feed production, arable land usage, water availability, and other factors. Consequently, lignocellulosic feedstocks such as forest residues, trees from plantations, straws, grasses and other agricultural residues may become viable feedstocks for biofuel production. However, the very heterogeneous nature of lignocellulosic materials that enables them to provide the mechanical support structure of the plants and trees makes them inherently recalcitrant to bioconversion. Also, these materials predominantly contain three separate classes of components as building blocks: cellulose (C6 sugar polymers), hemicellulose (various C5 and C6 sugar polymers), and lignin (aromatic and ether linked hetero polymers).
For example, breaking down these recalcitrant structures to provide fermentable sugars for bioconversion to ethanol typically requires pretreatment steps together with chemical/enzymatic hydrolysis. Furthermore, conventional yeasts are unable to ferment the C5 sugars to ethanol and lignin components are completely unfermentable by such organisms. Often lignin accounts for 25 to 30% of the mass content and 35 to 45% of the chemical energy content of lignocellulosic biomass. For all of these reasons, processes based on a pretreatment/hydrolysis/fermentation path for conversion of lignocellulose biomass to ethanol, for example, are inherently difficult and often uneconomical multi-step and multi conversion processes.
An alternative technology path is to convert lignocellulosic biomass to syngas (also known as synthesis gas, primarily a mix of CO, H2 and CO2 with other components such as CH4, N2, NH3, H2S and other trace gases) and then ferment this gas with anaerobic microorganisms to produce biofuels such as ethanol, n-butanol or chemicals such as acetic acid, butyric acid and the like. This path can be inherently more efficient than the pretreatment/hydrolysis/fermentation path because the gasification step can convert all of the components to syngas with good efficiency (e.g., greater than 75%), and some strains of anaerobic microorganisms can convert syngas to ethanol, n-butanol or other chemicals with high (e.g., greater than 90% of theoretical) efficiency. Moreover, syngas can be made from many other carbonaceous feedstocks such as natural gas, reformed gas, peat, petroleum coke, coal, solid waste and land fill gas, making this a more universal technology path.
However, this technology path requires that the syngas components CO and H2 be efficiently and economically dissolved in the aqueous medium and transferred to anaerobic microorganisms that convert them to the desired products. And very large quantities of these gases are required. For example, the theoretical equations for CO or H2 to ethanol are:
Thus 6 moles of relatively insoluble gases such as CO or H2 have to transfer to an aqueous medium for each mole of ethanol. Other products such as acetic acid and n-butanol have similar large stoichiometric requirements for the gases.
Furthermore, the anaerobic microorganisms that bring about these bioconversions generate very little metabolic energy from these bioconversions. Consequently they grow very slowly and often continue the conversions during the non-growth phase of their life cycle to gain metabolic energy for their maintenance. To get high yields and production rates the cell concentrations in the bioreactor need to be high and this requires some form of cell recycle or retention.
Cell retention by formation of biofilms is a very good and often inexpensive way to increase the density of microorganisms in bioreactors. This requires a solid matrix with large surface area for the microorganisms to colonize and form a biofilm that contains the metabolizing microorganisms in a matrix of biopolymers that the microorganisms generate. Trickle bed and some fluidized bed bioreactors make use of biofilms to retain microorganisms on solid surfaces while providing dissolved gases in the liquid by flow past the solid matrix. They suffer from either being very large or unable to provide sufficient gas dissolution rates.
Particular forms of membranes have found use in supporting specific types of microorganisms for waste water treatment processes. U.S. Pat. No. 4,181,604 discloses the use of hollow fiber membranes for waste treatment where the outer surface of the fibers supports a layer of microorganisms for aerobic digestion of sludge.
U.S. Ser. No. 11/781,717 filed Jul. 23, 2007, U.S. Ser. No. 11/833,864 filed Aug. 3, 2007 and U.S. Ser. No. 11/972,454 filed Jan. 10, 2008 disclose a membrane based bioreactor wherein anaerobic bacteria that have the ability to convert syngas to ethanol or other liquids have formed biofilms on the outer surface of hydrophobic membranes with the syngas fed to the bacterial biofilm through the inner surface of the membrane. Such a bioreactor system has been able to directly convert the primary components of synthesis gas, CO and H2/CO2, to ethanol and other liquid products such as n-butanol, acetic acid and butyric acid. In these systems the gas flows through a porous region of a hydrophobic membrane and then reaches a biofilm which is hydrophilic. One drawback of this arrangement is that if water reaches and deposits/condenses on the hydrophobic porous region it will severely decrease the gas transfer rate.
U.S. Ser. No. 12/036,007 filed Feb. 22, 2008 discloses an asymmetric membrane based bioreactor wherein anaerobic bacteria that have the ability to convert syngas to ethanol or other liquids have formed biopores to the retain biofilms therein on the outer, spongy, surface of the membrane to feed the syngas directly to the bacterial biofilm and not through membrane. The lumen of the membrane transports fermentation liquid or broth past the membrane for feeding of nutrients to the biofilm and reflux of liquid products from the biofilm back through the membrane and into the fermentation liquid. Asymmetric membranes are known for use in a variety of membrane separations processes such as ultra and nano filtration. Asymmetric membranes are typically hydrophilic and have a relatively tight semi permeable "skin" layer on one side supported on a porous "spongy" polymer layer. U.S. Pat. Nos. 4,442,206 and 4,440,853 show the use of the "spongy" polymer layer in an asymmetric membrane to immobilize microorganisms for certain biological processes that use soluble carbon sources. However, the spongy layer of the asymmetric membrane may cause the biofilm to adhere too tightly to the membrane and prevent suitable cleaning of the membrane pores when needed. In certain cases this can result in excessive downtime and loss of production capacity. The build-up of biological products and cell debris within the pores can limit the run time between necessary cleanings in the Biopore approach.
This invention is a process for using anaerobic microorganisms in the form of a biofilm to convert syngas (herein defined to include any gas containing CO and/or a mixture of CO2 and H2 as its principal components) in an improved retaining arrangement to provide a stable system for enhancing the production of liquid products such as ethanol, butanol, hexanol, and other chemicals from a syngas stream while facilitating maintenance of the biofilm and periodic scouring of the biofilm. A hydrophilic membrane provides pores that permit the permeation of fermentation liquid and nutrients from the liquid side of a membrane to the gas side while promoting the growth of microorganism colonies on the surface of the gas side of the membrane. Simultaneously, the other side (gas side) of the hydrophilic membrane remains exposed to fermentation liquid that permeates to the biofilm. The invention retains the biofilm on a surface of the membrane that excludes any substantial penetration of the biofilm beyond the support surface and into the membrane.
During syngas fermentation with the bioreactor process of this invention, carbon monoxide or hydrogen/carbon dioxide from the syngas diffuses into the biofilm on the surface of the gas side of the microporous porous membrane wall and is converted by the immobilized microorganisms into ethanol or other water-soluble products, which is then diffused into the aqueous stream flowing over the liquid side of the membrane that gets carried out of the bioreactor. The immobilized microorganisms remain hydrated through contact with the aqueous stream that passes through the hydrophilic membrane.
Therefore, the hydrophilic membrane establishes an interface to provide moisture and trace nutrients that permeate from the liquid side toward the contained microorganisms while simultaneously extracting liquid products formed by the microorganisms. The extracted permeate flows across the membrane into the liquid medium. Thus the desired products and the syngas from which they are produced flow through the membrane in the same direction, from the gas side to the liquid side.
Placement of the membrane layer between the microorganisms and the liquid simplifies the operation of downstream separation facilities. The membrane provides a substantial barrier between the microorganisms and the product containing liquid that keeps the liquid flowing to separation facilities free of microorganisms and other biological contaminants. Preventing virtually all biological contaminants from entering the liquid effluent removes the need for filtering and/or recycling of such materials.
The hydrophilic membrane may be formed from any material or assemblage of materials that provide the necessary occluding of microorganisms from the membrane pores in contact therewith and the desired hydration of the biofilm with fermentation liquid from the opposite side of the membrane. The use of hydrophilic materials enhances performance of the membrane by allowing easy movement of the water through the membrane. In most cases the membrane will comprise a single material but multiple materials and layers may be used.
The membrane may take on a variety of configurations. For example the membrane may comprise hollow fibers or flat sheets whether in flat or spiral wound configurations. Suitable housings may retain the membrane for co-current, counter-current, or cross-flow with respect to the circulation of the liquid on one side of the membrane and the bulk gas flow on the opposite side. In the case of hollow fibers, circulation of the syngas on the outside of the fibers facilitates a horizontal orientation of the fibers so that the bioreactor may work well whether extending in a principally horizontal or vertical direction.
This invention also improves operations for the circulation of liquid on the lumen side of hollow fiber membranes by providing a well defined liquid flow path and providing a contiguous space for gas flow on the outside of the membrane. This permits very high density packing of the membrane elements into membrane assemblies without fear of disrupting liquid flow patterns and creating stagnant areas for the circulating fluid. As a result the bioreactor system of this invention requires an overall smaller working volume than other proposed systems for conversion of syngas by fermentation.
In a variety of different arrangements depicted herein the CO and H2/CO2 from the syngas are utilized and a gradient for their transport from the gas feed side is created due to biochemical reaction in the biofilm retained on the gas side of the membrane. This reaction creates liquid fuel or chemicals such as ethanol, acetic acid and other products which diffuse into the liquid and are removed via circulation of the liquid that refluxes back across the membrane carrying the liquid products.
Accordingly this invention merges the advantages of both the liquid submerged biofilm and the hydrophilic membrane in the above described membrane bioreactor approaches. In this Membrane Supported Biofilm Reactor [MSBR] configuration the fermentation liquid is fed to one side of a hydrophilic microporous membrane to a biofilm on the surface of the membrane. The syngas is on the opposite side of the membrane so that microorganisms have direct gas phase contact of the syngas with the biofilm. The instant invention typically pumps the fermentation liquid containing nutrients to the side of the membrane opposite the biofilm. The liquid readily diffuses through the membrane to the biofilm that grows on the biofilm side of the membrane surface. Ethanol and other liquid products produced from the syngas by the biofilm readily diffuse back through the membrane into the fermentation liquid for recovery and ultimate separation and purification. Thus the advantages of both the biofilm and biopore type MSBR are obtained and the disadvantages of each mitigated using this hybrid of these two other approaches.
The principal advantage of this approach is that the biofilm is on the surface and not in the membrane pores. As a result control of the biofilm depth and cleaning of the membrane surface is much easier and requires much less time. Filling the gas contact space up with water and sparging this space with gas, such as tail gas from the process or fresh syngas, can be used to control/waste excess biomass. The liquid can be quickly drained and the biomass sent to processing.
By controlling the pressure on the liquid side the depth of the biofilm can be regulated by limiting the water penetration. This can be important in ensuring sufficient dissolved CO penetrates into the entire biofilm to achieve high selectivity for the production of desired products, for example ethanol versus acetate.
One unique feature of the instant invention is seeding or biofilm formation, which is easier in this approach than the other designs. For example when this hybrid system uses hollow fiber membranes (HF), inoculum can be fed into the shell side and the pump that normal feeds flow through the lumen used in the suction mode. This will allow the biomass to be drawn onto the shell side surface as a film immediately. Reversal of the flow from vacuum to slight pressure and hydration of the biofilm is maintained.
In one form this invention is a process for converting a feed gas containing at least one of CO or a mixture of CO2 and H2 to a liquid product under anaerobic conditions and delivering the liquid product to a fermentation liquid. The process passes a feed gas to a biofilm comprising microorganisms that produce liquid products from the feed gas. A biofilm exclusion surface of the gas contacting side of a hydrophilic membrane retains the biofilm inhibits penetration of the biofilm therein. The biofilm exclusion surface may do so in any manner for example by limiting only having pores with effective diameters of no greater than 0.5 μm on its surface or providing sufficient tortuosity that the biofilm cannot grow significantly past the surface. A fermentation liquid comprising water and nutrients passes across a porous surface of a liquid contacting side of the membrane. Fermentation liquid permeates from the liquid contacting side through the membrane and into contact with the biofilm. Fermentation liquid containing liquid products from the biofilm refluxes from the biofilm through the membrane and to the liquid contacting side of the membrane. The process collects fermentation liquid containing liquid products from the liquid contacting side of the membrane to recover liquid products from the process.
In a more specific form of this invention for converting the feed gas the process passes the feed gas to a feed gas chamber having fluid communication with a biofilm retained on a biofilm exclusion surface on the outside of a hydrophilic membrane having a hollow fiber form with a central lumen wherein the biofilm exclusion surface is the outer surface of the hollow fiber membrane and the biofilm exclusion surface inhibit penetration of the biofilm into the membrane by no more than 10 μm into the biofilm exclusion surface. Typically the hollow fiber membrane will have an outer diameter of between 0.4 to 2.8 mm, a lumen with a diameter of 0.3 to 1.2 mm, and a pore size of 0.5 μm or less for inhibiting penetration of the biofilm into the pores. The fermentation liquid comprising water and nutrients flows from a liquid supply chamber through the lumen and across a porous surface of the membrane to permeate fermentation liquid from the lumen through the membrane wall and into contact with the biofilm. The liquid products from the biofilm reflux through the membrane wall and into the lumen for collection in a liquid recovery chamber. The fermentation liquid passes from the liquid recovery chamber to a product recovery section to recover liquid products from the process.
In another specific form the process converts the feed gas to ethanol by passing the feed gas to a feed gas chamber that houses a plurality of hollow fiber membranes. The feed gas chamber communicates the feed gas with a biofilm formed on the membrane comprising microorganisms that produce ethanol from the feed gas. The outer surface of the membrane has a pore size of 0.5 μm or less for inhibiting penetration of the biofilm into the pores of the membrane. The fermentation liquid flows from a liquid supply chamber through the lumens of the membranes and across a porous surface of the membrane to permeate fermentation liquid from the lumen through the membrane wall and into contact with the biofilm. Fermentation liquid containing ethanol passes from the biofilm, through the membrane wall and into the lumen for collection of fermentation liquid containing ethanol in a liquid recovery chamber and recovery of ethanol from the fermentation liquid in a product recovery section. The process maintains the pressure of the liquid in the lumen higher than the pressure in the feed gas chamber and the thickness of the biofilm on the membranes is adjusted by changing the relative pressure between the feed gas chamber and the liquid in the lumen.
In yet another form of this invention the syngas may pass through multiple banks of asymmetric membranes in parallel or serial flow. A particularly useful form of the invention includes the preferential removal of the carbon dioxide (CO2) gas that is formed in the bioconversion process from the syngas as it passes serially through multiple banks of hydrophilic membranes.
Bioconversions of CO and H2/CO2 to acetic acid, ethanol and other products are well known. For example, in a recent book concise description of biochemical pathways and energetics of such bioconversions have been summarized by Das, A. and L. G. Ljungdahl, Electron Transport System in Acetogens and by Drake, H. L. and K. Kusel, Diverse Physiologic Potential of Acetogens, appearing respectively as Chapters 14 and 13 of Biochemistry and Physiology of Anaerobic Bacteria, L. G. Ljungdahl eds., Springer (2003). Any suitable microorganisms that have the ability to convert the syngas components: CO, H2, CO2 individually or in combination with each other or with other components that are typically present in syngas may be utilized. Suitable microorganisms and/or growth conditions may include those disclosed in U.S. patent application Ser. No. 11/441,392, filed May 25, 2006, entitled "Indirect Or Direct Fermentation of Biomass to Fuel Alcohol," which discloses a biologically pure culture of the microorganism Clostridium carboxidivorans having all of the identifying characteristics of ATCC no. BAA-624; and U.S. patent application Ser. No. 11/514,385 filed Aug. 31, 2006 entitled "Isolation and Characterization of Novel Clostridial Species," which discloses a biologically pure culture of the microorganism Clostridium ragsdalei having all of the identifying characteristics of ATCC No. BAA-622; both of which are incorporated herein by reference in their entirety. Clostridium carboxidivorans may be used, for example, to ferment syngas to ethanol and/or n-butanol. Clostridium ragsdalei may be used, for example, to ferment syngas to ethanol.
Suitable microorganisms and growth conditions include the anaerobic bacteria Butyribacterium methylotrophicum, having the identifying characteristics of ATCC 33266 which can be adapted to CO and used and this will enable the production of n-butanol as well as butyric acid as taught in the references: "Evidence for Production of n-Butanol from Carbon Monoxide by Butyribacterium methylotrophicum," Journal of Fermentation and Bioengineering, vol. 72, 1991, p. 58-60; "Production of butanol and ethanol from synthesis gas via fermentation," FUEL, vol. 70, May 1991, p. 615-619. Other suitable microorganisms include Clostridium Ljungdahli, with strains having the identifying characteristics of ATCC 49587 (U.S. Pat. No. 5,173,429) and ATCC 55988 and 55989 (U.S. Pat. No. 6,136,577) and this will enable the production of ethanol as well as acetic acid and Clostridium autoethanogemum sp. nov., an anaerobic bacterium that produces ethanol from syngas. Jamal Abrini, Henry Naveau, Edomond-Jacques Nyns, Arch Microbiol., 1994, 345-351; Archives of Microbiology 1994, 161: 345-351. All of these references are incorporated herein in their entirety.
The microorganisms found suitable thus far for this invention require anaerobic growth conditions. Therefore the system will employ suitable control and sealing methods to limit the introduction of oxygen into the system. Since the microorganisms contact the liquid that circulates through the bioreactor system, a suitable redox potential will be maintained and monitored to insure anaerobic conditions. Anaerobic conditions in the liquid volume are usually defined as having a redox potential of less than −200 mV and preferably a redox potential in the range of from −300 to −500 mV. To further minimize exposure of the microorganisms to oxygen, the feed gas will preferably have an oxygen concentration of less than 1000 ppm, more preferably less than 100 ppm, and even more preferably less than 10 ppm.
The invention uses hydrophilic microporous membranes. At minimum the hydrophilic membrane must be operated at conditions such that there is restricted liquid permeability with respect to the biofilm. The restricted permeability prevents excessive fermentation liquid from migrating into the biofilm during normal operation of the system and interfering with contact between the gas and microorganisms.
The hydrophilic membrane must also have a surface for retaining the biofilm that restricts the penetration of the biofilm into the adjacent surface of the membrane. The surface of the membrane adjacent to the membrane thereby acts as a biofilm exclusion surface. Some minor penetration of the biofilm past the surface and into pores or surface irregularities of the membrane will occur but preferably such penetration of the biofilm is less than 10 μm, more preferably less than 5 μm and most preferably less than 2 μm. Some pores are necessary in the pore exclusion surface for the exchange of fermentation liquid between the membrane and the biofilm. Ways in which the pore exclusion surface may prevent the penetration of the biofilm are by pore size exclusion or by providing a high tortuosity factor for any pores in the biofilm exclusion surface.
Where the membrane use pore exclusion as the mean to inhibit migration to the biofilm past the surface upon which it form, the maximum pore size of the biofilm exclusion surface is typically no more than 0.5 μm. The biofilm exclusion surface may comprise a separate layer of the membrane that provides pores of the required diameter to inhibit the biofilm entry therein.
The biofilm exclusion surface may present pores greater than 0.5 μm and still inhibit the penetration of the biofilm past the adjacent surface if the pores at the surface of the biofilm have a high tortuosity factor. The tortuosity factor is described in many ways but for the purposes of this invention it is defined as the specific surface area S/V multiplied by the thickness of the exclusion layer L, where S is the total interior pore surface in the exclusion layer and V the volume of the layer. With this definition, the tortuosity is dimensionless. A membrane surface with a tortuosity of 10 or greater and an average interior pore size of no more than 10 μm will effectively inhibit the penetration of the biofilm . . . .
Hydrophilic, microporous membranes are widely available commercially, thus this invention requires little to no technology development with respect to the membrane itself. Most commonly the membranes take the form of hollow fibers or flat sheets. These membranes find extensive use for wastewater treatment. Membrane, membrane modules and cassettes are commercial products that could be adapted for use in this invention. Both ambient pressure or submerged membrane modules are commercially available as are pressure modules or cartridges.
The membranes are typically made of poly(vinylidene fluoride) (PVDF), polysulfone (PS), polyethersulfone (PES), polyethylene (PE), polypropylene (PP), poly(vinyl chloride) (PVC), or other polymeric materials. The pore size of the hydrophilic membrane is usually less than 0.5 μm, preferably less than 0.4 μm, more preferably less than 0.25 μm and most preferably in the ultrafiltration range of nominal MWCO of 10 to 500 kDa and more preferably in the range of 50 to 300 kDa. A typical pore size range is from 0.01 to 0.5 μm. The typical hollow fiber outer diameter is 0.4 to 2.8 mm and inner diameter 0.3 to 1.2 mm. For this invention, a pore size of 0.2 micron or less is desirable.
A hollow fiber membrane SteraporeSUN™, available from Mitsubishi Rayon (Tokyo, Japan), is made of PE with modified hydrophilic membrane surface. The hollow fiber has a nominal pore size of 0.4 μm and a fiber outer diameter of 0.54 mm. A SteraporeSUN™ membrane unit Model SUN21034LAN has a total membrane surface area of 210 m2, containing 70 membrane elements Model SUR334LA, each with 3 m2 membrane area.
The Microza® membranes from Asahi Kasei Chemicals (Tokyo, Japan) are hydrophilic hollow fiber membranes available in the ultrafiltration (MWCO 3,000 to 80,000) and microfiltration (0.1 to 0.25 μm) ranges. The Microza® ultrafiltration membranes have a "double skin" construction with a selective skin layer on both the inner and outer surface of the hollow fibers. Thus, the Microza® membranes, both the ultrafiltration and microfiltration types, can be used for both outside-in and inside-out filtration modes.
Another commercial hydrophilic hollow fiber membrane is the PVDF microfiltration membrane used for water filtration in the MEMCOR® CS submerged membrane systems from Siemens Water Technologies (Shrewsbury, Mass.). Another commercial hydrophilic hollow fiber membranes is the Zenon ZeeWeed® 500 membranes from GE Water & Process Technologies (Oakville, Ontario, Canada), which is a reinforced, composite membrane, comprising a porous woven inner support and a selective ultrafiltration layer made of PVDF coated on the outer surface of the support. Both the MEMCOR® CS membranes and the Zenon ZeeWeed® membranes are typically used in the outside-in filtration mode, rejecting microorganisms and other contaminants at the outer surface of the hollow fibers.
Hydrophilic hollow fiber membranes normally used in the inside-out mode for water filtration can be used for this invention, provided there is a biofilm exclusion zone near the outer surface to inhibit to penetration of the biofilm into the membrane by no more than 10 μm. Examples of such membranes include but are not limited to the ultrafiltration membranes from GE Healthcare and the HYDRAcap polyethersulfone ultrafiltration membranes from Hydranautics (Oceanside, Calif.). These membranes have the selective skin layer on the lumen surface but have finely porous structure in the membrane wall near the outer surface. Although pores greater than 0.5 μm exist on the outer surface, cells can be prevented from penetration deep into the membrane wall due to the tortuous path in the finely porous structure. It is also well know in the art that normally hydrophobic microporous membranes can be converted into hydrophilic membranes with surfactant treatment. U.S. Pat. No. 4,525,374 discloses a method to treat hydrophobic polypropylene or polytetrafluoroethylene membrane with a solution of triethanolamine dodecylbenzene sulfonate to render the membrane hydrophilic and is incorporated herein.
Membranes of the various geometries and compositions described above may be used in arrangements of unitary arrays or assemblies of varied composition in the process of this invention. Any suitable potting technique can be used to collect and provide the necessary assembly of individual membrane elements. In such membranes the gas and liquid can be brought into direct and intimate contact at the gas contact surface of the biofilm. Liquid is passed in the liquid side of the membranes via pumping, stirring or similar means to remove the liquid products such as ethanol and other soluble products formed; the products are recovered via a variety of suitable methods.
The syngas flows through the gas chamber or channels of the bioreactor system continuously or intermittently. The feed gas pressure is in the range of 1 to 1000 psig, preferably 5 to 400 psig, and most preferably 10 to 200 psig. Operating at higher gas pressures has the advantage of increasing the solubilities of gases in the liquid and the biofilm potentially increasing the rates of gas transfer and bioconversion. The differential pressure between the liquid and gas phases is managed in a manner that the membrane integrity is not compromised (e.g., the burst strength of the membrane is not exceeded) and the desired gas-liquid interface phase is maintained.
The reaction rate, gas concentration gradient and the thickness of the microorganisms can be maintained in equilibrium by control of the pressure differential across the membrane. Controlling the relative pressure on the liquid side of the membrane allows regulation of the and limiting of the fermentation broth across the membrane and into the biofilm. Such a limitation can affect the selectivity of the process for example the ensuring that sufficient dissolved CO penetrates into the entire biofilm will help achieve high selectivity for the production of ethanol versus acetate.
When the feed syngas contains moisture, condensation of water can occur at the microorganism/gas interface as consumption of syngas results in supersaturation of water. This condensed water leaves the biofilm/gas interface by dripping to the bottom of the bioreactor due to gravity.
In this invention, a hydrophilic membrane arrangement, suitable for permeation of the fermentation liquid provides the separation between the liquid phase and feed gas comprising at least one of CO or a mixture of H2 and CO2 and a liquid phase.
side 10 that retains the microorganisms in biofilm 16 in contact with the gas stream provides equilibrium partitioning across the membrane 12 to keep the liquid and gas phases separated from each other. The pores that open to gas contact side 10 are much smaller than the width of the microorganisms retained in biofilm 16 so that contact side 10 occludes prevents the microorganisms from passing through membrane 12 and to liquid contacting surface 22. As a result the microorganisms 14 stay within biofilm 16 to gain metabolic energy by converting CO and H2/CO2 thereby growing and sustaining themselves within the biofilm 16.
The fermentation liquid flows back and forth across membrane 12. The hydrophilic membrane causes a portion of the liquid to flow toward the gas contact side 10 of the membrane and into biofilm 16 in the direction indicated by arrows C. Some circulation of liquid to the liquid phase side of the membrane occurs as indicated by the direction of arrow B and the fermentation liquid is withdrawn and separated to recover the desired products.
In one method of inoculating or seeding the membrane to form the biofilm, an aqueous solution containing microorganisms is introduced to the gas contacting side of the hydrophilic membrane, and then a slight trans-membrane pressure is applied to pass the solution through the membrane, creating a microorganism-free filtrate out of the liquid contact surface 22 and entrapping cells at the gas contact side surface. The microorganism-containing membrane is incubated for further microorganism growth and formation of the biofilm by supplying a syngas to the gas contact side and a liquid solution containing nutrients to the liquid contact side. During seeding, the seed solution containing microorganisms can either be static (dead end filtration) or circulated over the membranes (cross-flow filtration). Circulation of the seed solution can help achieve more uniform deposition of cells over the membrane surface.
In most operations the membrane arrangements will benefit from occasional purging, scouring or flushing of the biofilm on the gas contacting surfaces. For this purpose, periodically during syngas fermentation, the liquid pressure can be increased for a short time to create a water flow through the membrane to purge some accumulated dead microorganisms or biopolymers out of the biofilm and from the gas contacting surface. This water is collected from the gas stream side of the bioreactor. Optionally this water stream may be treated for removal of suspended solids and recirculated to the bioreactor system.
Occasionally it is also desirable to clean the surface of the gas contacting side of the membrane by removal of the biofilm or other materials. One approach to this procedure begins with substantially removing the immobilized cells and the cleaning the membrane. To do this the gas supply is stopped, and the membrane is cleaned with cleaning solutions in manners similar to typical cleaning of microfiltration and ultrafiltration membranes. For example, the membrane is first soaked in a cleaning solution from both the sides, e.g. the biofilm side and the fermentation liquid side. The cleaning solution is formulated or selected to facilitate solubilization of microorganism and biopolymers. One of such solutions is an aqueous solution containing 2% NaCl and 0.4% NaOH, but many other formulations have been used for membrane cleaning, including some containing surfactants and hydrolytic enzymes. After soaking, the cleaning solution is circulated and a positive trans-membrane pressure is applied from the liquid contacting side to create a convective flow through the membrane and flush microorganism and biopolymers out of the gas contacting surface of the membrane. The soaking-filtration procedures can be repeated as needed, and different cleaning solutions can be used. After membrane cleaning, the membrane can be used for loading and growing new cells for syngas fermentation again.
Use of the hydrophilic membrane in the process of this invention allows simplification of the procedures for cleaning the surface of the membrane, removing debris and other material, and/or controlling the thickness of the biofilm. The gas distributing space outside the gas contacting side of the membrane may be flooded with a cleaning solution or any desired treating liquid. In most cases this amounts to filling a shell space that surrounds a plurality of hollow fiber membranes with liquid. Because the biofilm does not penetrate into the hydrophilic membrane the biofilm adheres much less to the gas contact side of the membrane and does not get trapped in the pores of the membrane leaving the biofilm more exposed and is easier to remove. This allows the use of milder chemical and physical conditions for membrane cleaning and helps maintain a long use life of the membrane. Thus the added solution may have enough solvent strength to remove the biofilm on its own. Agitating the liquid around the biofilm by sparging or dispersing a controlled amount of a gas stream into the liquid can serve to scour the biofilm to a desired degree further enhancing the ability to clean the gas contact face. It may also be possible to do a partial removal of the material in the biofilm by use of a gas stream to cause a reduction of the thickness of the biofilm without effecting its complete removal.
Any suitable gas stream can be used to sparge the liquid and create turbulence during the cleaning or biofilm removal step. The gas stream recovered from the bioreactor, i.e. tail gas, is highly suited for this purpose.
A feed gas distribution chamber that surrounds the membrane elements 32 receives the feed gas stream and distributes it into direct contact with the outer surface of the membrane elements 32. The feed gas exits the vessel 35 via a line 34 such that a continuous addition of feed gas is established around the outer surface of membrane elements 32. The relative locations of the feed gas lines provide a downward direction of the bulk gas flow in the bioreactor 33.
Vessel 35 also contains a line 29 for draining liquid. Liquid may accumulate at the bottom of the vessel 35 for a variety of reasons as previously described such as condensation from moisture in the gas, flushing or purging of the membrane elements or periodic cleaning operations. Alternately line 34 may provide an outlet for liquid drainage. Liquid from condensation or flushing may be withdrawn from either location and treated for return to the fermentation liquid.
Fermentation liquid enters bioreactor 33 via a conduit 38 under pressure supplied by a pump 39 and at rate recorded by a flow meter 28. A chamber 37 distributes fermentation liquid to the tubular membranes 32 via the bottom ends of the lumens. At the top end of bioreactor 33 a chamber 43 collects the fermentation liquid from the top of the lumens for withdrawal of the liquid via a conduit 44. The relative locations of chambers 37 and 43 establish upward flow of the liquid through bioreactor 33 so that there is countercurrent flow with respect to the bulk gas flow and the liquid flow.
A line 40 withdraws a net portion of the liquid from line 44 while the remainder of the liquid returns to the bioreactor 33 via a recirculation line 36 and mixing chamber 48, a line 41 and line 38. Line 40 carries the liquid to product recovery facilities that recover liquid products. Depending on the nature of the desired product, there are a number of technologies that can be used for product recovery. For example, distillation, dephlegmation, pervaporation and liquid-liquid extraction can be used for the recovery of ethanol and n-butanol, whereas electrodialysis and ion-exchange can be used for the recovery of acetate, butyrate, and other ionic products. In all cases the product recovery step removes the desirable product from stream 40, while leaving substantial amounts of water and residual nutrients in the treated stream, part of which is returned to the bioreactor system via line 42 and mixing chamber 48.
Means for temperature and pH control for the liquid can be added anywhere along the re-circulating liquid loop, which consists of lines 38, 44, 36, and 41 as well as chambers 37, 43, and 48. A line 45 provides the nutrients needed to sustain the activity of the microorganisms to the re-circulating liquid loop chamber 48. Chamber 48 provides mixing of the nutrients and the other streams.
The flow rates of Streams 38 and 44, recirculated through the membrane unit, are selected so that there is no significant liquid boundary layer that impedes mass transfer near the liquid-facing side of the membrane. The linear velocity (define as total liquid flow rate divided by the total lumen cross sectional area of membrane elements 32) of the liquid tangential to the membrane should be in the range of 0.01 to 20 cm/s, preferably 0.05 to 5 cm/s, and most preferably 0.2 to 1.0 cm/s.
The membranes can be configured into typical modules as shown as an example in
During the bioconversion excess CO2 is generated and this gas can diffuse back and dilute out the concentrations of CO and H2 in the feed gas and thus reduce their mass transfer rates. Other types of membranes that preferentially permeate CO2 over CO and H2 can be used in the multi stage configuration as shown as an example in
An Xampler™ ultrafiltration membrane cartridge Model UFP-100-C-4X2MA from GE Healthcare is used as a membrane bioreactor for the conversion of carbon monoxide and hydrogen/CO2 into ethanol. This membrane cartridge contains hydrophilic hollow fibers with 1 mm inner diameter and rated at 100 kDa nominal MWCO. The active membrane surface area of the module is 0.085 m2 (based on lumen area). The temperature of the membrane cartridge is maintained at 37° C. with flexible heater attached around the cartridge and regulated with a temperature controller.
The membrane module is connected to a 7.5-liter BioFlo® 310 Fermentor from New Brunswick Scientific (Edison, N.J.). The fermentor contains 3 liters of the fermentation medium, which is agitated at 100 rpm and maintained at 37° C. and pH 5.9 with 1 N NaOH and 1 N HCl. The fermentation medium has the compositions shown in Tables 1&2. The medium is pumped from the fermentor, flows through the lumen side of the membrane module, and returns to the fermentor at a recirculation flow rate of 500 ml/min, unless otherwise stated. The fermentor is sparged with N2 at 100 std ml/min initially to maintain anaerobic conditions and switched to syngas overlay as described below.
Initially, the membrane cartridge is inoculated with 150 ml of an active culture of Clostridium ragsdalei ATCC No. BAA-622 by injecting the inoculum into the shell space. The inoculum solution is slightly pressurized to allow liquid to pass through the membrane into the lumen and retain the microbial cells on the outer surface of the membrane. Subsequently, a gas containing 40% CO, 30% H2, and 30% CO2 is fed to the shell side of the membrane cartridge at about 5 psig to displace the remaining inoculum liquid. The gas continues to be fed at 300 std ml/min throughout the remainder of the fermentation run and the residual gas from the module is directed to the fermentor headspace and exits the fermentor through a condenser and a vent filter. The gas pressure in the shell side of the membrane cartridge is maintained at about 1-5 psi greater than the liquid pressure in the lumen by adjusting a back-pressure valve downstream the gas outlet of the membrane cartridge.
The system is first operated in the batch mode for 2 days then switched to continuous operation, with continuous withdrawal of the fermentation liquid for product recovery and replenishing of fresh medium at 15 ml/hr. After 20 days of continuous operation, the withdrawn fermentation liquid contains 10 g/L ethanol and 2 g/L acetate.
Fermentation Medium Compositions
Amount per liter
Mineral solution, See Table 2(a)
Trace metal solution, See Table 2(b)
Vitamins solution, See Table 2(c)
Yeast Extract
Adjust pH with NaOH
Reducing agent, See Table 2(d)
TABLE 2(a)
Mineral Solution
Concentration (g/L)
TABLE 2(b)
Trace Metals Solution
Concentration (g/L)
Nitrilotriacetic acid
Adjust the pH to 6.0 with KOH
TABLE 2(c)
Vitamin Solution
Concentration (mg/L)
Calcium Pantothenate
Thioctic acid
p-Aminobenzoic acid
Nicotinic acid
Vitamin B12
Mercaptoethanesulfonic acid
Folic acid
TABLE 2(d)
Reducing Agent
Concentration (g/L)
Cysteine (free base)
A membrane module containing the hydrophilic PES HYDRAcap® ultrafiltration hollow fiber membranes from Hydranautics (Oceanside, Calif.) was used as a membrane bioreactor for the conversion of carbon monoxide and hydrogen into ethanol and acetate. The hollow fibers had 0.83 mm inner diameter and a permeability rated at 100 kDa nominal MWCO. The active membrane surface area of the module is 0.09 m2 based on the fiber outer diameter. The temperature of the membrane cartridge is maintained at 37° C. with flexible heater attached around the cartridge and regulated with a temperature controller.
The membrane module was connected to a 3.0-liter BioFlo® 110 Fermentor from New Brunswick Scientific (Edison, N.J.). The fermentor contained 1.5 liters of the fermentation medium, which was agitated at 50-100 rpm and maintained at 37° C. and pH 5.8 with 1 N NaOH and 1 N HCl. The fermentation medium had the compositions shown in Tables 3&4. The medium was pumped from the fermentor, flows through the lumen side of the membrane module, and returned to the fermentor at a recirculation flow rate of 100-200 ml/min, unless otherwise stated. The fermentor was sparged with N2 at 100 std ml/min initially to maintain anaerobic conditions and switched to syngas overlay as described below.
Initially, the membrane module was inoculated with 300 ml of an active culture of Clostridium ragsdalei ATCC No. BAA-622 by injecting the inoculum into the shell space. The inoculum was slightly pressurized to allow liquid volume to pass through the membrane into the lumen and the microbial cells to deposit on the exterior membrane surface. Subsequently, a gas containing 38% CO, 34% H2, 23.5% CO2 and 4.5% N2 was fed to the shell side of the membrane module at about 5 psig to displace the remaining inoculum liquid. The gas continued to be fed at 50 std ml/min initially and increased to 150 std ml/min later during the fermentation run and the residual gas from the module was directed to the fermentor headspace and exited the fermentor through a condenser and a vent filter. The gas pressure in the shell side of the membrane module is maintained at about 1-15 psi greater than the liquid pressure in the lumen by adjusting a back-pressure valve downstream the gas outlet of the membrane module.
The system was first operated in the batch mode for 3 days and then switched to continuous operation, with continuous withdrawal of the fermentation liquid for product recovery and replenish of fresh medium at 30 ml/hr. The fermentation liquid effluent contained 0.4 g/L ethanol and 4.2 g/L acetate at elapsed time of 193 hours and 0.0 g/L ethanol and 3.6 g/L acetate at 406 hours. The fermentation was terminated after 406 hours. The used hollow fibers were examined by using scanning electron microscopy, and a biofilm layer of 30-40 μm was found to be on the exterior surface of the fibers as shown in
Fermentation Medium Compositions
Amount per liter
Mineral solution, See Table 4(a)
Trace metal solution, See Table 4(b)
Vitamins solution, See Table 4(c)
Yeast Extract
Adjust pH with NaOH
Reducing agent, See Table 4(d)
TABLE 4(a)
Mineral Solution
Concentration (g/L)
TABLE 4(b)
Trace Metals Solution
Concentration (g/L)
Nitrilotriacetic acid
Adjust the pH to 6.0 with KOH
TABLE 4(c)
Vitamin Solution
Concentration (mg/L)
Calcium Pantothenate
Thioctic acid
p-Aminobenzoic acid
Nicotinic acid
Vitamin B12
Mercaptoethanesulfonic acid
Folic acid
TABLE 4(d)
Reducing Agent
Concentration (g/L)
Cysteine (free base)
|Data de depósito
|Data de publicaçăo
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|10 abr. 1984
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|12 jun. 2012
|Coskata, Inc.
|Process for converting syngas to liquid products with microorganisms on two-layer membrane
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|Classificaçăo nos Estados Unidos
|435/161, 435/41, 435/297.3, 435/297.1, 435/297.4, 435/297.2, 435/136, 435/157
|Classificaçăo internacional
|Classificaçăo cooperativa
|Classificaçăo europeia
|13 out. 2014
|Fee payment
Year of fee payment: 4
|23 out. 2015
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text:
Cliff Anderson, whose real name is actually Rocky, is the main antagonist of A Perfect Getaway. He along with Cydney are drug addicted sociopath couple who had been killing other couples in Hawaii and stealing their identities and names.
- To kill as many couples as he and Cydney can.
- Betrayed by his girlfriend for ruining her life and is shot in the head by a police sniper.