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
Now more than ever, the message behind the holidays provides a wonderful learning opportunity for children. With the economy in turmoil this season, families may be forced to cut their holiday spending. Rather than focusing on what you cannot afford, make a lesson out of what you already have and what the holidays are really about.
Studies have revealed various negative effects that come from too many presents being thrown at children during the holiday season. These include decreased concentration, overstimulation, desensitization to things and people, the loss of any concept of "enough," and causing children to value themselves based on what they receive.
Nevertheless, some parents feel obligated to spoil their children. Some believe that gift giving is a display of love. Others feel guilty about working too long or hard outside the home and attempt to compensate by buying gifts. Parents might be trying to "keep up with the Jones'" by purchasing for their children everything they see their friends purchasing for their children.
There are many alternatives to giving material presents. Studies show that, more than gifts, children love to spend time with their parents. Make coupons for "a day at the park with dad" or a "day at the museum with mom." Homemade presents instill the notion of making something from nothing, and represent not only the item but also the time that mom and dad took to, say, build a picture frame or knit a sweater. Encourage children to pick a charity to support instead of receiving a gift. Sponsoring a needy child, for instance, teaches the joy of giving. You can still give gifts, but giving less makes each present more special.
Try making the present an educational process. If a child requests a guitar, one gift can be a book about guitars, another can be a research trip to a guitar store, a third can be a movie or play about guitars, a fourth can be a journal where the child can write about learning the instrument — and the final gift is the guitar. By giving one larger gift and other supporting gifts, you are teaching your child while highlighting the special quality of the larger gift.
Ask your children: "What are some ways we can give to others during this time?" Together, you can bring toys to sick children or donate them to a local shelter. Besides spending time as a family, you are encouraging your children to think about others.
Explain to your children the difference between "gifts" and "things," and between "needing" and "wanting." Help them understand that going to the park or reading a book together is a kind of gift. Most important, remind your children that the true gifts in life are being with family and friends.
TAMMY GOLD is the founder of Gold Parent Coaching (recently featured in Redbook, Pregnancy and Forbes) and one of the first to pioneer the trend of parent coaching. Certified in both life and parent coaching, she is also a licensed psychotherapist. Tammy graduated from the University of Pennsylvania and Columbia University.
Alternatives to Overindulging Your Child
Moments of Meaning During the Holiday Rush
Holiday Concerns for Special Needs
Money Lessons: Teach Your Children Well
Birthday Parties at Home: Are they Budget-Friendly?
local zones
Nassau cont.
Suffolk cont.
Westchester cont.
Rockland cont.
Queens cont.
Brooklyn cont.


text: We were here in September with sailing friends. -- Location: excellent, with a view of the marina. Beware mosquitoes if sitting outside. -- Food: We were told by the friends that they'd previously had some excellent Sardinian pasta, but the fritto misto I ordered was almost inedible because, as... read more

subset: commoncrawl


text:
Speed Indiana Golf Courses
|Speed Employees Country Club
Additional Golf Course Reviews:
|Hidden Valley Golf Club -- Very unique and challenging
|Review by: Jason Chasele
|This was one of the most challenging courses I have ever played on and I can't wait to go back. The 9 holes added in 2004 are beautifully designed and very unique.
|From Coldwater, MI


text:
Plaza Mexico
3100 E. Imperial Highway
Lynwood, CA 90262-3202
Lynwood, CA 90262-3202
Best Of
- Patio/Sidewalk Dining
Located in Lynwood, just off the 105 East midway between LAX and the 605, Plaza Mexico rises up from beyond the endless neighborhoods lining the highway, a pastel-colored beacon with its Spanish conquistador–influenced colonial architecture. There are peaceful, gurgling fountains, tiled courtyards and, of course, mariachi bands. And while there are a few chain stores, mostly the plaza boasts small independent businesses, including a bustling — but not overwhelmingly crowded — mercado; authentic restaurants with handmade tortillas and spicy fresh salsa; the divinely decadent and famous ice cream shop Paletería la Michoacana; an assortment of clothing and Mexican crafts stores; and a carousel for the kids.


text:
|Tennessee Great Dane Rescue
|Great Dane Rescue Groups
|New Location ▼
|Change Breed ▼
|Find a Home for an Animal ▼
|Rescue Alerts ▼
|Donate to Great Dane Rescue as a gift or memorial, and we will mail a free acknowledgement card within 24 hours.
3,123 Great Dane Dogs have been adopted on Rescue Me!
|Tennessee Great Dane Dogs for Adoption
|Page 1
|Options: Reset
|Urgent: This animal could be euthanized if not adopted soon.
|Rescue Me ID: 15-03-28-00014Momma (female)
This lady needs a new home where she will be loved and cared for. She can come with her male counterpart who is a 5 year old male Great Dane pure bred as well. Our owners bred us and don't need us any more so please help save us.
Clay County Memphis, TN MAP IT!
|Animal ID: 15-03-19-00623LUCY (female)
This sweet pup is 16 weeks old and will be ready soon for adoption. Loves to run and play . She is full of personality. If you are interested in Lucy go to www.lifehouse.petfinder.com and fill out an application. Or email is at email@example.com. Her adoption fee is $200 includes deworming, spaying. Distemper. Parvo, hipto .. Microchip.
Lifehouse Animal Refuge and Rehabilitation
Wilson County Mt Juliet, TN 37122 MAP IT!
|Rescue Me ID: 15-02-18-00524Marley (male)
Very, very, very, sweet! Always looking for attention and to please! Playful and smart. Very close with his brother (litter mate), MiLo, and I would prefer for them to be placed together, for their own comfort, but am not requiring that. (See MiLo's description). Great temperament, gets along wonderfully with everyone! A real lover! (Watch out men, he may push you out of the bed)! Spoke his first words at 9weeks. He says, 'I love you', 'run around', and 'hamburger', (but only when he's really hungry) amongst other phrases yet to be determined. Kisses are a must! Even when your not wanting or expecting them. Hope slobber is not a problem, he ... (Read More)often has shoelaces hanging from both sides of his mouth, but mostly just dribbles out of the mysterious hole in his lower jaw. (Less)
Hamblen County Morristown, TN MAP IT!
|Urgent: This animal could be euthanized if not adopted soon.
|Rescue Me ID: 15-02-18-00505MiLo (mee-LO) (male)
Very sweet but a little intimidating to strangers, mainly men, due to being protective over myself and my kids (daughter 19, son 9). Loves to run! Large yard or lots of room to run highly recommended! Very attached to his brother (litter mate) and would prefer to place them together, but that is not required. A frozen tree limb fell through our fence and I can no longer keep MiLo contained and he is wreaking havoc on my entire neighborhood. The Animal Shelter has already been out twice in less than 8 hours, as much as I hate to, I may have to surrender him tomorrow morning if I have no other home lined up. He is a WONDERFUL companion, very ... (Read More)smart, a little stuborn sometimes, (like a rebelious teenager) and extremely strong! And I believe he may be made of jello b/c he seems to be able to squeeze through anything! JK :) But he is Houdini reincarnated. He truly deserves a good and loving home, he just needs a little training. (Less)
Hamblen County Morristown, TN MAP IT!
|Check All That Apply Duplicate Post Spam/Possible Scam Inappropriate Photo Wrong Phone Number My Calls Not Returned
No Response to My Email "+JSVpcv+" Breeder Selling Animals (Posing as Rescue) Cancel
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This is my posting. I adopted this animal. Someone told me by phone or email. My calls or emails were never responded to. Other.
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|PIease Read Before Adopting a Great Dane in Tennessee
Great Dane Dogs can make good pets in Tennessee if they match your IifestyIe. The Great Dane is an enormous, but extremely gentle breed often referred to as the Gentle Giant. Great Danes are kind, loyal, and sociable. They need to be around people. Great Danes are gentle, devoted, and wonderful with children, but should be supervised with little ones because of their large size. Great Danes should be well trained as puppies. Great Danes can live in an apartment with enough daily exercise but do best with a large yard.
Rescue Me! - HeIpingAnimaIs in Need.
|♥ This page is in fond memory of these Great Dane Dogs who are no longer with us... ♥
If you have experienced the loss of a beloved pet, or if you know someone who has... [POST A MEMORIAL HERE]
|Help Spread the Word! Please link to Tennessee Great Dane Rescue from your website.
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Infinity-Alaska August 8th
We are on the Infinity going out of Vancouver on August 8th. We are a middle age gay male couple based in the Boston area, attractive, bearish, down to earth, easy going and we are looking to meet other gay travelers on this cruise. We have friends (another gay couple from Indy) who are joining us on the cruise as well as a mixed group of friends. We have a Celebrity suite and we plan to hold gatherings in our suite several times during the cruise. Come and join us...we are a blast!
Paul and Paul
(no, you aren't seeing double, we both have the same first name!)
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text:
K brah :^)
Find me on steam? Deathparade is the name
K brah :^)
Whatcho doin' mon?
Yes very much and "help" is welcome
Just noticed you're back i've been inactive alot myself not so much in the community how have you been man?
Just one thing... Where are the eyes? O_o
Why do you want to know if its on the Nexus if you can download it here?
Holy **** that looks amazing!
Was actually some troll attack by 4chan... again
nah dafuq on you
Whats with all the whining about it being called HL3 or HL2 EP3?
It depends EP1 and EP2 where called that because they connected with each other and if they weren't 2 seperate things it would be you getting on the train and than crashing on that train.
If Ep3 follows with you taking off in the heli or landing somewhere with it it means it will be called Ep3 if it's later in the story it will probably be called Half-Life 3
Yea and that would be saying every mod is like a copy of this... because it was first... in anyway Gmod has much more to offer...
Welcome to the club Kizzy i hate tasting new things too!
You can in Half-Life 1 Which is what he is refering to!
I do hope they make a actual Assassin kill him instead that he gets shot from nothing!
Yea with his evil Creeper plush
Last blue item? idk
11 inch (dafuq is a inch)
85% oow good!
No **** you!
Oh some **** looked quite retarded and being inactive alot and stuff
Nice but the next button KINDA sucks...
Profile clean up: COMPLETED!
well the little battery's where always there there is no reloading to this gun you just pick up ammo untill you hit the max of 100
Kilo* sorry coulden't resist! :D
well that is your own problem and not theirs
nah yahoo sucks
i have a WON i get "key in use" i still have a other account with HL on steam though
all it needs is a giant room made of fans...
apple is all wrong this is apple:
why did speedy get downvoted and orange up voted while Speedy is clearly right... sometimes...
ok... i don't get the hate xbox hate PS thing but i have a decent PC and PS3 whining about money? go work... or something similair... you know
yea what did you expect? i mean it's a suprise they don't randomly ban people in the first place to hope people buy a second copy
LOL @ speed
yea... but the developers want COD to be realistic but it ain't... i dont know why i preordered black ops... but i will never again! the gun looks awesome dont care if its a real one or not!
and this is what makes game lame too much time into god damn reality and too little time into making the game fun this is half-life not Call of Duty! i dont know but weren't games supposed to be the opposite of reality? just to go wild and shoot something...
and how does he know that that is gay porn?...
now it looks more like NOD is a alien race not humans put in a SUPER AWESOME suit (i wish they sold them HIGH QUALITY)
dont think you are able to create a new dimension...
in shops i see them alot mostly they are clean just the lower part is rusty cause of the uses also i agree with MR.sugers whole comment
he posted that on 19th...
wtf are those bad textures...
are. you. on. crack?
kinda useless but i liked the scene there was this all rebel EVA and then she became the slave EVA still kinda useless to make
driving it would be more cool infantry are no match for the harvesters front grinders :D
1. karmad up (karma ****)
2. what is that mod?
3. LOL need more units
4. aircrafts somewhere to be found?
looks abit like water with a grass texture :D nice anyways
nothing 3D that is not it's style just the other stuff would be totally cool and i agree i never come in the nether there is just nothing to do there
nice model really just take your time i dont care if we get a little peak with a half model :)
it's cause he is fake...
pills save all!
and this is why you got thumpe... WAIT WE HAVE NO THUMBS HERE it's karma here!
so that is freeman's daughter (incest is sex with family)
i already turned monsters off on my server because of those things... ._.
just multiple modes like:
no blood/only gore
no gore/only blood
no gore and blood
normal amounts
lots amounts
lol geinig
*stares at boobs*
DAMNIT you found it :(
now we will be waiting for volition to follow this with RF:G ._.
well he is showing them pubicly right now...
nothing HD and HL2 weapon models in HL1 is illegal
i have it worse dude... 100%
more: FUUUUUUUUUUUUUUUUUUUU
i know they are just art work i have WON too
you have a leak...
i like the name XD 666 666 666 666 666 666 666 666 666
it looks good i hope they dont add another year to that release date O_o
blood there can just never be enough of it... XD and i played it too
you have my download going to try it out :D look if it works and i get what you wanna do with it and proof with it
al 4 online people playing gmod D: OMG
the textures aren't that high anyway cause the engine they build on is pretty old
it's almost no difference since it just has other textures and it's a different angle
nukepb is his name he is the new bear in town...
netherlands and hookers? yeah right
you need to be in the gaySA for that
LOL i once had that as bug in normal HL
look my army ^^
not **** sherlock
yea... eeeh WoW, quake aren't valve's dumb **** and some other in that list aren't either it's just retarded cause they dont use the same commands
i know you mean
a really dedicated fanbase i mean look at the escape map they made bosses and other kinda fights even with the limits of only having turret's and player and entity's but no NPC's and they still did stuff like that (area49 map serie's)
i always loved TFC just because there where over 500 playable maps made by others just for all of us to have fun kill and escape
i wanna steal that and hump it at night....
EEEH I MEAN eeh i wanna stare at those shelves for 9000 years
yeah maybe some enterable houses etc WITH tables and stuff like that i think that would be good for posing and stuff
nice i like dark blue
i hope the new go-mod will come out totally great
i wish you guys luck
totally forgot how it looked O_o
nice nice nice indead!
i exterminate noobs :) and i exterminate runescape..
nvidia pwns <3
looking good i but why add those 3 bullets there? :P
it's not a G but a @ >.>
it's not totally stand alone... you still need a source game LOL
none... drive as fast as you can
who knows
LOL @ about 4 barreta models
torr3 that is because this is a model/sound/sprite pack and does not include textures
LOL i just see it says what is you bidding master
should be your
if it is a real tank you see from close than the begin of the barrel looks too thin it would be blown off by the tank itself
looking good keep it up
naah :P
Nukey approves of nuking this pic... NOT
yeah... i mean a livebox is serious it's not like you want your kid to play with it...
WOW i dont remember his arm to be that big O_O
1. google chrome apears to hold virusses (says my friend who knows alot about pcs)
2. firefox always loads up slow... (for me atleast)
3. who now wants to browse the internet with something that keeps you thinking about dirty animals and black people (iam no racist)
pin a strider I DARE YOU :D
wtf tfc doesn't have those retarded **** that is the ****** gay game called tf2
the female barney is still stolen!
fatty cyborg with retard face
no more like:
EA Games! rapes everything
EA Games! kills all games
i laughed i want driving bombs XD
i soo much hated that damn voice i whas like: ooh god just DIE!
warcraft :D
i laughted but my face whas like: D: WTF!
it is... you go further where gordon gets knocked down
/\ those things
they recreate the WHOLE thing by there selfs... and these look to much like the normal gravity gun so i think he ported them...
you just killed me with the face this this is my last message...
eeem LOL? i play go-mod has nothing illigal in it nothing from other games than 1 OP4 enemy and some 1.5 CS models (which is legal) nothing from source
no it's boring
really good keep on going ;)
you made this one on my server? :P from 2 days ago or 1 idk
back it whas just a chicken...
dude that's damn nice
yeah sometimes it's just getting boring i mean soon there will be a big valve this big valve that later we get a ***** model and he will be too big for his own damn ***** it's getting boring get something better...
can you make a anti-spam system for it? it gets kinda anoying with those key bindings...
yup that's my server
hmm utorrent are we downloading illigal? XD
monster's dont talk
so they are like my lil brother? autism + ADHD and what not O_O
wait wait wait who now puts the end of the mod as a image? the ending must always stay a secret this whas once said by the god name nukepb XD
but we were already in... script fail ERROR
more reminds me of a TFC map but than the parts where far away
you sucks? wtf
i dont see alot of change no
14. dont love BOOM or you will be destroyed
saw it HAHHAAHAHA
this barrel needs to get laid O_O
change keyboard to: kill keyboard :D
you can only have 2 barney's with you dumb ****
than they come with banshee's and blow it up because i hate GDI NOD FTW!
ok... and those truck's do? :D
pedobear is first :D and for the people who dont get it: she is a little girl and has pedobear ears and adore's pedobear than something is going to happen soon enough :D
i always assume something with stalking... :P
iam old enough to remember the whole game you just saw the games 1 second and you thought: let's make a retard mod for it!
i should have stucked the playerspawn in the floor -_-'
first time i did it whas hard too and second than i got on the idea to throw grenade's at the wood and just sneak past them i still love the whole scene when they die :D... men i can still hear those beasts scream like hell...
nothing style it looks gay how does that door open anyways? i dont see anything to support it at all? it would drop off >.>
this is the only pic with some NOD structures? O_O
played it XD and i still have it
the first link doesn't ******* work in holland :'( retarded youtube i once uploaded a video and it said that my video whas banned in germany O_O the country next to holland WTF! it contained some stuff about my own map >.>
that's why i have that "feeling"
you must not steal it you must destroy this mod since that gun looks too good that one of you can even make that
TF2? O_O real men play old school games
damn i forgot i lived in a militairy nuke launch base >.>
it should be that all of sudden taht thing O__O eats that whole hand :P
thos things are just stolen from the half-life level but they seem to have ruined the texture HAHA
you get raped by the makers in this level O_o
texture rotation failure...
what has this to do with battlefield?
and maybe just maybe is that grenade the same as in OP4 redux
why is there red text all over?
*cough* *cough* from HLWE and it doesn't even have sounds and sprite's so it's just the normal rocket launcher sound...
i think it's stolen or has been training mapping for 5 years but than in 2 seconds...
the maker of this post fails YOU CAN'T JUST SAY THAT YOUR MOD IS THE BEST SINCE IT IS SO BAD MAPPED! AND SOME TEXTURES ARE JUST BLACK/PURPLE BLOCKS!!!! DESTROY THIS MOD PLEASE!!! AND WHAT (C)? it's not copyrighted that isnt possible for a mod...
reminds me of a massive ion cannon satalite in the form of swoop da whoop...
the captain is called hitler i supose?
this got to be gay....
just tanks iam gaurded by: alot of space ships even a EDS hydra and alot of ground forces
damn O_o
*cough* *cough* gay.. *cough* *cough*
all over his pics he is dieing O_o
really failing
even my mapping is better
wtf has that to do with this picture? -_-'
i whas here..... :P
if you where me she wouldent be gone for just 2/3 minutes *yoink*
maybe gman has the power to grow and remove hair XD
first a game is good than it becomes better and at the end the lastes games will suck
i love that script :O it's nice and i wish i could stay longer there :(
when do you people STFU about tf2 taunts
eeem i think this guy will blow tf2 to hell XD
that has nothing to do with tfc roster312
gman: gordon freeman i come to take you to my van outside and you will get icecream
gordon: hmm yummy icecream
if all metrocops really looked like that i wouldent even kill them O_O
maker of STUFF :D
CAT-LIFE YAY! damn its just a demo lol
that's why i play older games like half-life 1 and call of duty 1
noooh text explosion lol
your avater that thing i got on my pc :P
naah i keep it 2 nukes and a pedobear avatar :D
sorry XD
1. wtf are you talking about firefox starts up like it works on the source engine -.- it take a minute to load up before i can use it and 2. this is about the text in the picture not what ******* browser you ******* use
ik ben soms dom nou en :P
snap em niet :(
can i live there?? >:D
sweetness :D love this game even its for kids and i play bloody games this is awesome >:D
boom! headshot
i loved them to use one the sharks somewere in the labs jsut when your teleported or before i dont know
gman: gordon freeman in 2D
origanal from ending for noobs who didnt play half-life (Über awesome game)
lets go..... to hell
left 4 dead 2 is from valve -.-'
aka valve?
the half-life engine has a limit
garg's are awesome specialy with the airstrike part of half-life :P
sign: otis is banned from the cantina for eating all food :P
they are included in my hammer when i downloaded it
the generator room (dont know where that came from again) freeman: SHUT UP :P
i always loved generators :D
kicking in metal door FAIL :P
the portal reopened lol
it only cost 200000000000 eem yeah nevermind :D
not the best drawning of a gun lol
yeah that i see a half picture when i press "view original"
looks like the antlion from hal-life 2 but not totaly just a bit the form of it
damn how can you load in multiplayer??? -.-'
yeah this thing and nil where more looking like massive big headed baby's lol
developed by the makers of red faction :O
2007? spring? yo dude its 2009 welcome to this year
lifeless people make account for nothing -.-'
zombie's do cry?
whats hf2?
looks good even for a beta :)
xen lamps :D now is the next question were is the light switch? :D
this mod is half-life 1 not source
the head kinda looks like a combine head CHOP IT OFF :D
I LOVE THAT GUN ITS AWESOME (the one on the pic and the one on wikipedia) (wikipedia always wrong) :D
:| some mapper won a engine :| omfg i didnt even know what to do with that engine
i just found this on the torque engines comments:
Have you heard about this illegal HL copy called Black Mesa Source?
it is :D
iam not really mapping that much anymore i still had this unreleased on my pc so
and ppl play this in multiplayer if you want the health and batterys to respawn or else you may could die by monster fire :P
damn i didnt made any of the idea's i put into my hl mapping thingy
omg i wanna map like this :'( but iam noob :'(
lol nice map i wish i whas so good in mapping :(
yeah the vest is a bit big (not that big) and the hands are a bit in a wierd position but the textures of the vest and the grenade looks awesome
awesome :O i can't make a joke with this one damnit --
yo guy reading the playboy i need some more ammo XD
bomb has been planted all noobs runs into the bomb and die by camping terrorist :P than the pro's come kill the campers and disable bomb :D
black barney???
the role is not die and kill the zombie
are we ever going to see some strogg things???
hmmmm in CnC generals zero hours:
china headqaurters: GDI is getting to strong what should we do?
some guy: we have to use the..... nuke
*nuke launches and destroys GDI base*
would be freaky funny :P
LOL your life just began mine already ended :P
1.1??? dont see but cool now i canp lay an source game and lucky they added an amsterdam mirror
XD really funny but i know it from somewere on youtube
what a cute headcrab can you add pet mod :D hi lammar here some food
i whas saying no mounting needed before you said it 2 times so dont be ****** :D just kidding like the image
wow nice
not working damn
why this is in addons>models :P
like that but could show some more weapons etc.
DOWNLOAD DOWNLOAD DOWNLOAD! lol i wanna play this awesomeness
lol posted on every single image here :P
nice made like the name endless no same barney calhoun
like it
you guys make nice mods and this group whas settedup 2 days before my birthday :P keep on going cat-life i love cats
:O this is looking so good (i want to be such good mapper too)
on my map it says every single entitie is leakt!!!!
i hate dragonball not the mod but the rest of it not vs you but just i hate dragonball
this need a serial why?


text:
BEST WESTERN PLUS Buckingham International
No availability found through our partners. Please contact the business directly or check some of our recommended alternatives.
- Free High-Speed Internet
- Room service
- Swimming pool
- Restaurant
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To infinity and Nipon
... flying =D. He got use to it really quickly and settled down.
After getting 4 hours of sleep in the last 30ish hours, I found out the sleeping tablets I got have zero effect on me and got maybe a total of 1 to 2 hours sleep on the plane.
Vic. Markets, Super Nan, Taylor Family.
... kids- Amy, Katie and Lochie were heaps of fun with our 4 lads and so us adults actually got to do loads of talking and tell stories from our childhood when Mason and I grew up on neighbouring farms. Dinner was a delicious sharing of resources and fellowship. We all had lots of fun and felt happy to share this time together. Feeling UP. Another incredible day as we edge closer towards home.
Conclusion .... All good things must end
... vegetables dwindle and carried a little supply of frozen and canned items to last us over until we reached the next larger supermarket....for us that was one overnight stay at Eucla and we shopped, with massive savings, at IGA Kalgoorlie the next day. Not a huge imposition......and why would you carry honey when you know it's going to be confiscated? And so..... What did go wrong? I forgot to apply insect repellent before heading into sand dunes one day and was bitten ...
Riddle Creek Scout Camp
... would like to go. Trouble was we were approaching it from the opposite direction. Still and all it looks achievable.
Next we tried to get the mail, but it wasn't in yet. Come back at 2pm we were advise.
To the Mill Park to pickup the suitcases. They are beaut cases cost $90 and we should be able to sell them on Gumtree for the same amount. One is the biggest you can get the other is 'on board luggage'.
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Our time in Japan
... variety is vast. Stephen however cannot cope with shopping, and would moan endlessly while sulking until I stopped shopping. I would thoroughly like to go back to japan on a shopping trip without my shopping grinch husband and I would have a blast. We had about 10kg extra in weight to take back which was handy. I had no problem filling that quota : ) The best bit? I'm not sure I can choose one! But I loved the time of year - it wasn't hot, it was quite cool. Cold enough I didn't ...


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A process is provided for the concentration and recovery of ethylene and heavier components from an oxygenate conversion process. A separation process such as a pressure swing adsorption (PSA) process is used to remove hydrogen and methane from a demethanizer overhead stream comprising hydrogen, methane, and C
1. A process for the production of an ethylene product stream from an oxygenate conversion effluent stream comprising hydrogen, carbon dioxide, water, methane, ethylene, ethane, propylene, propane, and C4-plus olefins said process comprising:
a) passing the oxygenate conversion effluent stream to a carbon dioxide removal zone to remove at least a portion of the carbon dioxide to produce a carbon dioxide depleted stream;
b) passing the carbon dioxide depleted stream to a dryer zone containing a solid desiccant to remove water to produce a dry deethanizer feed stream;
c) passing the dry deethanizer stream to a deethanizer zone to provide a light hydrocarbon feedstream comprising hydrogen, methane, ethylene and ethane, and a deethanized stream comprising propylene, propane, and C4-plus olefins;
d) passing the light hydrocarbon stream to a demethanizer zone operating at a demethanizing temperature greater than about −45� C. to provide a bottom stream comprising ethylene and ethane and an overhead stream comprising hydrogen, methane, and ethylene;
e) passing the overhead stream at effective adsorption conditions to an adsorption zone containing at least two adsorption beds, each of said adsorption beds containing a selective adsorbent to adsorb the ethylene on adsorption to produce an adsorber effluent stream comprising hydrogen and methane, and on desorption to produce a desorbed stream comprising ethylene and immediately following adsorption withdrawing a vent stream comprising hydrogen and methane in a cocurrent depressurization step which is terminated prior to the breakthrough of ethylene;
f) regenerating the dryer zone with at least a portion of the adsorber effluent stream and at least a portion of the vent stream;
g) passing the bottom stream to a C2 splitter zone to produce the ethylene product stream and an ethane stream; and
h) combining the desorbed stream with the oxygenate conversion effluent stream prior to passing the oxygenate conversion effluent stream to the deethanizer zone.
2. The process of claim 1 wherein said vent stream is withdrawn at a vent pressure comprising a pressure greater than about 700 kPa (100 psia).
3. The process of claim 1 wherein the oxygenate conversion effluent stream further comprises oxygenates including methanol and dimethyl ether and the oxygenate conversion effluent stream is passed to an oxygenate removal zone prior to passing the oxygenate conversion effluent stream to the deethanizer zone.
4. The process of claim 1 wherein the light hydrocarbon stream comprises trace amounts of acetylene and said light hydrocarbon stream is passed to a selective saturation zone containing a selective saturation catalyst to saturate the acetylene in the presence of hydrogen prior to passing the light hydrocarbon stream to the demethanizer zone.
The present invention relates to a process for the production of light olefins from the effluent of an oxygen conversion process. More particularly, the present invention relates to a process for the recovery of high purity ethylene from the reactor effluent of an oxygenate conversion process.
Light olefins serve as the building blocks for the production of numerous chemicals. Light olefins have traditionally been produced through the process of steam or catalytic cracking. The search for alternative materials for light olefin production has led to the use of oxygenates such as alcohols, and more particularly to the use of methanol, ethanol, and higher alcohols or their derivatives wherein these compounds are converted to light olefins. The alcohols may be produced by fermentation or from synthesis gas. Synthesis gas can be produced from natural gas, petroleum liquids, and carbonaceous materials including coal, recycled plastics, municipal wastes, or any organic material. Thus, alcohol and alcohol derivatives may provide non-petroleum based routes for the production of olefin and other related hydrocarbons.
Molecular sieves such as the microporous crystalline zeolite and non-zeolitic catalysts, particularly silicoaluminophosphates (SAPO), are known to promote the conversion of oxygenates to hydrocarbon mixtures. Numerous patents describe this process for various types of these catalysts: U.S. Pat. Nos. 3,928,483, 4,025,575, 4,052,479 (Chang et al.); U.S. Pat. No. 4,496,786 (Santilli et al.); U.S. Pat. No. 4,547,616 (Avidan et al.); U.S. Pat. No. 4,677,243 (Kaiser); U.S. Pat. No. 4,843,183 (Inui); U.S. Pat. No. 4,499,314 (Seddon et al.); U.S. Pat. No. 4,447,669 (Hamon et al.); U.S. Pat. No. 5,095,163 (Barger); U.S. Pat. No. 5,191,141 (Barger et al.); U.S. Pat. No. 5,126,308 (Barger et al.); U.S. Pat. No. 4,973,792 (Lewis et al.); and U.S. Pat. No. 4,861,938 (Lewis et al.). U.S. Pat. No. 4,861,938 and 4,677,242 particularly emphasize the use of a diluent combined with the feed to the reaction zone to maintain sufficient catalyst selectivity toward the production of light olefin products, particularly ethylene. The above U.S. patents are hereby incorporated by reference.
The product produced by the oxygenate conversion process is a light gas stream containing lighter components (e.g. hydrogen, nitrogen, etc.) methane, ethane and a substantial quantity of hydrocarbons of higher molecular weight, for example, propane, butane, pentane and often their unsaturated analogs. Separation of these components to recover ethylene requires a complex energy intensive scheme, thus creating a need for more efficient separation processes which yields higher recovery levels of ethylene. In typical ethylene plant recovery sections, where the ethylene production is based on the pyrolysis of naphtha or gas oil, the use of cryogenic processes utilizing the principle of gas expansion through a mechanical device to produce power while simultaneously extracting heat from the system have been employed. The use of such equipment varies depending upon the pressure of the product gas stream, the composition of the gas, and the desired end results. In the typical cryogenic expansion-type recovery processes used in the prior art, a gas stream is withdrawn from the pyrolysis furnace, compressed, and cooled. The cooling is accomplished by heat exchange with other streams of the process and/or external sources of cooling are employed such as refrigeration systems. As the product gas is cooled, liquids are condensed, collected, and separated so as to thereby obtain desired hydrocarbons. The high-pressure liquid stream so recovered is typically transferred to a demethanizer column after the pressure is adjusted to the operating pressure of the demethanizer. In such a fractionating column, the high-pressure liquid stream is fractionated to separate the residual methane and lighter components from the desired products of ethylene and heavier hydrocarbon components. In the ideal operation of such separation processes, the vapors, or light cut, leaving the process contain substantially all of the methane and lighter components found in the feed gas and substantially no ethylene and heavier hydrocarbon components remain. The bottom fraction, or heavy cut, leaving the demethanizer typically contains substantially all of the ethylene and heavier hydrocarbon components with very little methane or lighter components which are discharged in the fluid gas outlet from the demethanizer. A typical combined gas expansion and fractionation process for the separation of hydrocarbon gas stream comprising components ranging from nitrogen through C
Pressure swing adsorption (PSA) provides an efficient and economical means for separating a multi-component gas stream containing at least two gases having different adsorption characteristics. The more strongly adsorbable gas can be an impurity which is removed from the less strongly adsorbable gas which is taken off as product; or, the more strongly adsorbable gas can be the desired product, which is separated from the less strongly adsorbable gas. For example, it may be desired to remove carbon monoxide and light hydrocarbons from a hydrogen-containing feedstream to produce a purified (99+%) hydrogen stream for a hydrocracking or other catalytic process where these impurities could adversely affect the catalyst or the reaction. On the other hand, it may be desired to recover more strongly adsorbable gases, such as ethylene from a feedstream to produce an ethylene-rich product.
In PSA, a multi-component gas is typically fed to at least one of a plurality of adsorption zones at an elevated pressure effective to adsorb at least one component, while at least one other component passes through. At a defined time, the feedstream to the adsorber is terminated and the adsorption zone is depressurized by one or more cocurrent depressurization steps wherein pressure is reduced to a defined level which permits the separated, less strongly adsorbed component or components remaining in the adsorption zone to be drawn off without significant concentration of the more strongly adsorbed components. Then, the adsorption zone is depressurized by a countercurrent depressurization step wherein the pressure on the adsorption zone is further reduced by withdrawing desorbed gas countercurrently to the direction of the feedstream. Finally, the adsorption zone is purged and repressurized. The combined gas stream produced during the countercurrent depressurization step and the purge step is typically referred to as the tail gas stream. The final stage of repressurization is typically performed by introducing a slipstream of product gas comprising the lightest gas component produced during the adsorption step. This final stage of repressurization is often referred to as product repressurization. In multi-zone systems, there are typically additional steps, and those noted above may be done in stages. U.S. Pat. No. 3,176,444 issued to Kiyonaga, U.S. Pat. No. 3,986,849 issued to Fuderer et al., and U.S. Pat. No. 3,430,418 and U.S. Pat. No. 3,703,068 both issued to Wagner, among others, describe multi-zone, adiabatic PSA systems employing both cocurrent and countercurrent depressurization, and the disclosures of these patents are incorporated by reference in their entireties.
Various classes of adsorbents are known to be suitable for use in PSA systems, the selection of which is dependent upon the feedstream components and other factors generally known to those skilled in the art. In general, suitable adsorbents include molecular sieves, silica gel, activated carbon, and activated alumina. When PSA processes are used to purify hydrogen-containing streams, the hydrogen is essentially not adsorbed on the adsorbent. However, when purifying methane-containing streams, methane is often adsorbed on the adsorbent along with the impurity.
Numerous patents disclose the use of PSA in combination with fractionation to separate hydrogen and methane from heavier hydrocarbons. U.S. Pat. No. 5,245,099, which is hereby incorporated by reference, discloses a process for the concentration and recovery of ethylene and heavier components from a hydrocarbon feedstream. A PSA process is used to remove from hydrocarbon feedstream light cut comprising hydrogen, carbon monoxide, and methane and subsequently concentrate a heavy cut comprising the ethylene and heavy components in the PSA tail gas. In one aspect of the invention, an FCC off gas is separated into a light cut and a heavy cut and the heavy cut is routed to an ethylene plant.
U.S. Pat. No. 5,332,492 discloses a process for recovering hydrogen-rich gases and increasing the recovery of liquid hydrocarbon products from a hydrocarbon conversion zone effluent by the particular arrangement of refrigeration and PSA steps and two vapor-liquid, or flash, separation zones.
U.S. Pat. Nos. 5,365,011, 5,470,925, and 5,744,687 disclose a process for the integration of a PSA zone containing an adsorbent selective for the adsorption of ethylene and propylene from a catalytic cracking process at an adsorption temperature above 50� C. to about 250� C. The adsorbent is selected from the group consisting of zeolite 4A, zeolite 5A, zeolite 13X, and mixtures thereof.
The existing cryogenic and fractionation system in a typical ethylene recovery scheme can be employed in an oxygenate conversion process to recover ethylene, but the penalties of this operation are significant. The low level of light components such as hydrogen and methane relative to ethylene plant product compositions still are high enough to significantly raise the compression and refrigeration requirements in the recovery section of the oxygenate conversion plant for the incremental amount of ethylene recovered. Thus, recovering ethylene from oxygenate conversion effluent is an expensive and complex process involving extensive compression and fractionation to separate the light gases such as hydrogen and methane from the ethylene. Processes are sought which enable the concentration and recovery of the ethylene and heavier components from oxygenate conversion effluent without expensive compression and cryogenic separation steps to remove the lighter components.
The use of conventional methods developed for ethylene separation when applied to separate ethylene produced from an oxygenate conversion process effluent stream will result in a separation zone of higher capital cost and higher operating cost than required. It was discovered that the unique character of the oxygenate conversion process effluent stream allowed the use of a separation process to further concentrate and recover ethylene. For example, when a separation zone which employed a demethanization zone as an initial separation followed by a demethanization zone to recover a C
In one embodiment, the present invention is a process for the production of ethylene from an oxygenate conversion effluent stream. The oxygenate conversion effluent stream comprises hydrogen, methane, ethylene, ethane, propylene, propane, and C
FIG. 1 is a schematic process flow diagram illustrating the process of the prior art for recovering light olefins from an oxygenate conversion process.
FIG. 2 is a schematic process flow diagram illustrating the process of the present invention.
FIG. 3 is a chart of adsorption isotherms for components of demethanizer overhead on silica gel.
FIG. 4 is a chart of adsorbent delta loadings comparing silica gel and zeolite 4A over a range of adsorption temperatures.
FIG. 5 is a chart of the relative ethylene recovery required in a PSA and in the demethanizer for a range of demethanizer overhead composition.
FIG. 6 is a chart of the ratio of ethylene recycled to the ethylene recovered over a range of demethanizer overhead composition.
This invention relates to recovery schemes used in conjunction with a process for the catalytic conversion of a feedstock comprising one or more aliphatic hetero compounds comprising alcohols, halides, mercaptans, sulfides, amines, ethers, and carbonyl compounds or mixtures thereof to a hydrocarbon product containing light olefinic products, i.e., C
The oxygenate conversion step of the present invention is preferably conducted in the vapor phase such that the oxygenate feedstock is contacted in a vapor phase in a reaction zone with a molecular sieve catalyst at effective process conditions to produce hydrocarbons, i.e., an effective temperature, pressure, weight hourly space velocity (WHSV) and, optionally, an effective amount of diluent, correlated to produce hydrocarbons. The process is affected for a period of time sufficient to produce the desired light olefin products. In general, the residence time employed to produce the desired product can vary from seconds to a number of hours. It will be readily appreciated that the residence time will be determined to a significant extent by the reaction temperature, the molecular sieve selected, the WHSV, the phase (liquid or vapor) and process design characteristics selected. Reaction conditions for the conversion of aliphatic hetero compounds can be determined by those skilled in the art and preferably, in accordance with the present invention, comprise a temperature of from about 200� to 600� C., more preferably from about 300� to 500� C., and a pressure of from about 7 kPa to about 1.4 Mpa (1 to 200 psia), more preferably from about 140 kPa to about 700 kPa (20 to 100 psia). Typical processes for producing light olefins are described U.S. Pat. No. 4,499,327 and 4,873,390 cited above and hereby incorporated by reference.
The selection of a particular catalyst for use in the oxygenate conversion step depends upon the particular oxygenate conversion desired but in a preferred aspect of the present invention where the oxygenate feedstock is converted into light olefins, it is preferred that the catalysts have relatively small pores. Certain of the catalysts useful in the present invention have pores with an average effective diameter of less than 5 Å. The average effective diameter of the pores of preferred catalysts is determined by measurements described in D. W. Breck, ZEOLITE MOLECULAR SIEVES by John Wiley & Sons, New York (1974), hereby incorporated by reference in its entirety. The term �effective diameter� is used to denote that occasionally the pores are irregularly shaped, e.g., elliptical, and thus the pore dimensions are characterized by the molecules that can be adsorbed rather than the actual dimensions. Preferably, the small pore catalysts have a substantially uniform pore structure, e.g., substantially uniformly sized and shaped pore. Suitable catalyst may be chosen from among layered clays, zeolitic molecular sieves, and non-zeolitic molecular sieves.
Zeolitic molecular sieves in the calcined form may be represented by the general formula:
where Me is a cation, x has a value from about 2 to infinity, n is the cation valence, and y has a value of from about 2 to 10. Typically, well-known zeolites which may be used include chabazite�also referred to as Zeolite D, clinoptilolite, erionite, faujasite�also referred to as Zeolite X and Zeolite Y, ferrierite, mordenite, Zeolite A, Zeolite P, ZSM-5, ZSM-11, and MCM-22. Other zeolites include those having a high silica content, i.e., those having silica-to-alumina ratios greater than 10 and typically greater than 100 can also be used. Detailed descriptions of some of the above-identified zeolites may be found in D. W. Breck, supra.
Non-zeolitic molecular sieves include molecular sieves which have the proper effective pore size and are embraced by an empirical chemical composition, on an anhydrous basis, expressed by the empirical formula:
where EL is an element selected from the group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and mixtures thereof, x is the mole fraction of EL and is at least 0.005, y is the mole fraction of Al and is at least 0.01, z is the mole fraction of P and is at least 0.01 and x+y+z=1. When EL is a mixture of elements, x represents the total amount of the metal mixture present. Preferred elements (EL) are silicon, magnesium, and cobalt with silicon being especially preferred. The preparation of various ELAPOs is well-known in the art and may be found in U.S. Pat. No. 5,191,141 (ELAPO); 4,554,143 (FeAPO); 4,440,871 (SAPO); 4,853,197 (MAPO, MnAPO, ZNAPO, CoAPO); 4,793,984 (CAPO), 4,752,651 and 4,310,440 all of which are incorporated by reference. A preferred embodiment of the invention is one in which the element (EL) content varies from about 0.005 to about 0.05 mole fraction. If EL is more than one element, then the total concentration of all the elements is between about 0.005 and 0.05 mole fraction. An especially preferred embodiment is one in which EL is silicon (usually referred to as SAPO). The SAPOs which can be used in the instant invention are any of those described in U.S. Pat. Nos. 4,440,871; 5,126,308, and 5,191,141. Of the specific crystallographic structures described in the '871 patent, the SAPO-34, i.e., structure type 34, is preferred. The SAPO-34 structure is characterized in that it adsorbs xenon but does not adsorb isobutane, indicating that it has a pore opening of about 4.2 Å. Another SAPO, SAPO-17, as exemplified in Examples 25 and 26 of the '871 patent, is also preferred. The SAPO-17 structure is characterized in that it adsorbs oxygen, hexane, and water but does not adsorb isobutane, indicating that it has a pore opening of greater than about 4.3 Å and less than about 5.0 Å.
The molecular sieve catalyst for the oxygenate conversion zone preferably is incorporated into solid particles in which the catalyst is present in an amount effective to promote the desired hydrocarbon conversion. In one aspect, the solid particles comprise a catalytically effective amount of the catalyst and at least one matrix material, preferably selected from the group consisting of binder materials, filler materials, and mixtures thereof to provide a desired property or properties, e.g., desired catalyst dilution, mechanical strength, and the like to the solid particles. Such matrix materials are often, to some extent, porous in nature and may or may not be effective to promote the desired hydrocarbon conversion. Filler and binder materials include, for example, synthetic and naturally occurring substances such as metal oxides, clays, silicas, aluminas, silica-aluminas, silica-magnesias, silica-zirconias, silica-thorias, silica-berylias, silica-titanias, silica-alumina-thorias, silica-alumina-zirconias, aluminophosphates, mixtures of these and the like. The preparation of solid particles comprising catalyst and matrix materials is conventional and well known in the art and, therefore, need not be discussed in detail herein.
The oxygenate conversion reaction is preferably carried out in a bubbling bed or a fluidized bed reaction zone wherein feed and catalyst are contacted at effective oxygenate conversion conditions. During the oxygenate conversion reaction, a carbonaceous material�i.e., coke�is deposited on the catalyst. The carbonaceous deposit material has the effect of reducing the number of active sites on the catalyst which thereby affects the extent of the conversion. During the conversion process, a portion of the coked catalyst is withdrawn from the reaction zone and regenerated to remove at least a portion of the carbonaceous material and returned to the oxygenate conversion reaction zone. Depending upon the particular catalyst and conversion, it can be desirable to substantially remove the carbonaceous material e.g., to less than 1 wt-%, or only partially regenerate the catalyst, e.g., to from about 2 to 30 wt-% carbon. Preferably, the regenerated catalyst will contain about 0 to 20 wt-% and more preferably from about 0 to 10 wt-% carbon. Additionally, during regeneration, there can be oxidation of sulfur and in some instances nitrogen compounds along with the removal of metal materials from the catalyst. Moreover, regeneration conditions can be varied depending upon catalyst used and the type of contaminant material present upon the catalyst prior to its regeneration.
The oxygenate conversion effluent which comprises products obtained from the conversion process will, of course, depend, for example, on the feedstream, catalyst and conditions employed. Preferably, the desired product is organic. The organic product or products are preferably hydrocarbons in the C
In the present invention, the oxygenate conversion effluent stream comprising hydrogen, carbon dioxide, water, C
The separation zone which can comprise a solvent absorption zone, a temperature swing adsorption zone, a pressure swing adsorption zone, a vacuum swing adsorption zone, or a membrane separation zone and combinations thereof which selectively separates ethylene and heavier components from a separation zone effluent stream comprising hydrogen, methane, and carbon monoxide which is withdrawn as a first fuel gas stream. The ethylene-rich stream is recycled to the product compressor to be combined with the oxygenate conversion effluent stream. When the separation zone comprises a PSA zone, the adsorbent comprises a selective adsorbent such as silica gel, activated carbon, alumina, zeolite, and mixtures thereof for the adsorption of ethylene and ethane. Such zeolites may include zeolite type X and zeolite type Y, ion exchanged forms thereof, and mixtures thereof. The zinc exchanged form of zeolite of zeolite X and the calcium exchanged form of zeolite Y may be included in the selective adsorbent. It is particularly preferred that the selective adsorbent for the PSA process comprise silica gel and that the adsorption temperature ranges between about −18� C. and about 100� C. More preferably, the adsorption temperature ranges between about −18� C. and about 50� C. And most preferably, the adsorption temperature comprises less than about 49� C. It is believed that at adsorption temperatures above about 100� C., and especially at adsorption temperatures above about 50� C., silica gel becomes less selective for the adsorption of hydrogen and methane relative to C
The PSA process is an essentially adiabatic process for separating a multi-component fluid containing at least one selectively adsorbable component. The PSA process of the invention relates to conventional PSA processing in which each bed of an adsorption zone undergoes, on a cyclic basis, high-pressure adsorption, optional cocurrent depressurization to intermediate pressure level(s) with release of void space gas from the product end of the bed, countercurrent depressurization to lower desorption pressure with the release of desorbed gas from the feed end of the bed, with or without purge of the bed, and repressurization to higher adsorption pressure. The process of the present invention adds to this basic cycle sequence the use of a cocurrent depressurization, or vent step, in the adsorption zone in which the less readily adsorbable component is further and preferably essentially completely removed therefrom. The adsorption zone is then countercurrently depressurized to a desorption pressure that is at or above atmospheric pressure with the more adsorbable component(s) being discharged from the feed end thereof as a product of desired purity. Those skilled in the art will appreciate that the high-pressure adsorption step of the PSA process comprises introducing the PSA feedstream, or the demethanizer overhead stream, to the feed end of the adsorbent bed at a high adsorption pressure. The less readily adsorbable components (hydrogen and methane) pass through the bed and are discharged from the product end thereof. An adsorption front or fronts are established in the bed with said fronts likewise moving through the bed from the feed end toward the product end thereof. When the feedstream contains a less readily adsorbable component and a more readily adsorbable component, a leading adsorption front of the more readily adsorbable component will be established and move through the bed in the direction of the product or discharge end thereof.
The PSA feedstream or demethanizer overhead stream of this invention comprises from about 10 to about 60 mol-% hydrogen, from about 5 to 50 mol-% methane, and from about 10 to 60 mol-% ethylene and heavier components. In the adsorption zone, the more readily adsorbable components are adsorbed at an adsorption pressure and adsorption temperature and the less readily adsorbable components are passed through the adsorption zone. The adsorption zone pressure ranges from about 350 kPa to about 3.5 MPa (about 50 to about 500 psia). The adsorption zone temperature is any temperature effective to adsorb the more readily adsorbable components in the feedstream, and preferably from about −18� C. to less than about 50� C. (about 0� to about 120� F.). It is to be understood that the adsorption zones of the present invention contain adsorber beds containing adsorbent suitable for adsorbing the particular components to be adsorbed therein. As the capacity of the adsorber bed for the more readily adsorbable component is reached, that is, preferably before a substantial portion of the leading adsorption front has passed through the first adsorber bed, the PSA feedstream is directed to another bed in the adsorption zone. It is to be also understood that the term �countercurrent� denotes that the direction of gas flow through the adsorption zone, i.e., adsorber bed, is countercurrent with respect to the direction of PSA feedstream flow. Similarly, the term �cocurrent� denotes flow in the same direction as the PSA feedstream flow. The purge gas is at least partially comprised of an effluent stream, e.g., the adsorption effluent stream or the cocurrent displacement effluent stream, from the adsorption zone, as hereinafter described, which comprises the less readily adsorbable component. When hydrogen is the less readily adsorbable component, the purge gas is preferably rich in hydrogen at a higher concentration than available in the PSA feedstream. The term �enriched� is intended to be with reference to the PSA feedstream composition unless otherwise noted. Following the adsorption step, the bed undergoes a vent step wherein the bed is allowed to depressurize concurrently to a vent pressure in a direction cocurrent to the feeding step. By the use of this cocurrent depressurization step, or vent step, the effluent gas stream is substantially reduced and preferably essentially free of the less readily adsorbable component, thus having a molar concentration of more readily adsorbable components. The less readily adsorbable component that remains in the void spaces of the adsorbent bed ahead of the leading adsorption front can be essentially completely displaced from the bed and can enrich the more readily adsorbed component behind the adsorption front. This enables the more readily adsorbable component to be thereafter discharged from the feed end of the bed as a product of desired purity by countercurrently depressurizing the bed. The cocurrent depressurization step can be performed in conjunction with one or more cocurrent depressurization, or equalization, steps wherein the equalization gas is not vented, but passed to another bed. When a cocurrent depressurization step is used, it can be performed either before, simultaneously with, or subsequent to the vent step. The effluent stream from the cocurrent depressurization step, which is comprised primarily of less readily adsorbable components, can be used to partially repressurize or purge another adsorber bed. The combination of the desorption effluent resulting from the countercurrent depressurization step and the purge step are combined to have ethylene and heavier product purity of from about 20 to about 95 mol-%.
After the termination of the vent step and any desired cocurrent depressurization step(s), the adsorber bed is desorbed by reducing the pressure in a direction countercurrent to the PSA feed direction to a desorption pressure that is preferably from about atmospheric pressure to about 3.5 kg/cm2 absolute (about 50 psia). A portion of the desorption effluent stream recovered from the adsorption zone could be utilized as feed for the cocurrent displacement step following recompression.
A PSA cycle for a six-bed adsorption zone employing the vent, or cocurrent depressurization step following the adsorption step is shown in Table 1 below:
Although any suitable PSA cycle known to those skilled in the art and incorporating the steps of adsorption, equalization, provide purge, purge, and repressurization may be employed in the PSA operation, it is preferred to operate the PSA zone with a cocurrent desorption step, or vent step, immediately following the adsorption step to provide a second fuel gas stream which is employed to regenerate the dryer zone. Preferably, the vent step is terminated at a vent pressure which is at least about 700 kPa (about 100 psia).
When the separation zone comprises a membrane separation zone, the membrane employed is selective for the permeation of ethylene and heavier components and the non-permeate stream comprises hydrogen and methane. U.S. Pat. No. 5,879,431, which is herein incorporated by reference, discloses the application of a rubbery and super glassy membrane at separation conditions which include a separation temperature between about 0� C. and about −100� C. for similar separations.
The process of the present invention is hereinafter described with reference to FIGS. 1 and 2 which illustrate various aspects of the process. It is to be understood that no limitation to the scope of the claims which follow is intended by the following description. Those skilled in the art will recognize that these process flow diagrams have been simplified by the elimination of many necessary pieces of process equipment including some heat exchangers, process control systems, pumps, fractionation systems, etc. It may also be discerned that the process flow depicted in the figures may be modified in many aspects without departing from the basic overall concept of the invention.
FIG. 1 illustrates the typical light olefins recovery scheme of the prior art. Referring to FIG. 1, an oxygenate conversion effluent stream in line 1 is passed to a compression zone 18 to raise the pressure of the oxygenate conversion effluent stream in line 1 to a demethanizer pressure of between about 1050 kPa (150 psia) and about 2860 kPa (400 psia) to produce a compressed effluent stream in line 5. More preferably, the compression zone raises the pressure of the oxygenate conversion effluent stream to produce a compressed effluent stream at a demethanizer pressure between about 1750 kPa (250 psia) and about 2450 kPa (350 psia). Generally, the compression zone 18 comprises a multi-stage compressor that, at a low interstage pressure, comprises a first interstage flash drum to remove a condensate stream in line 3 comprising primarily water and unconverted methanol that is returned to the oxygenate conversion reaction zone (not shown), and a second interstage flash drum to remove a C
The present invention recognizes the unique character of the oxygenate conversion effluent stream, in particular that the light hydrocarbon stream comprises a non-adsorbable molar ratio of hydrogen and methane to C
Referring to FIG. 2, the oxygenate conversion effluent stream in line 100 is passed to a compression zone 118 to raise the oxygenate conversion effluent stream to the demethanizer pressure and produce a compressed effluent stream in line 105. As in FIG. 1, the compression zone 118 comprises a multi-stage compressor which recovers a condensate stream in line 103 comprising primarily water and methanol that is returned to the oxygenate conversion reaction zone (not shown), and a C
The following examples are only used to illustrate the present invention and are not meant to be limiting.
In a conventional process arrangement as depicted in FIG. 1 (Prior Art), the demethanizer is operated with a condenser temperature of about −95� C. (−140� F.) and a pressure of about 3200 kPa (465 psia) in order to recover at least 99.6 mol-% of the ethylene in the demethanizer bottoms product. A cooling system for operating the demethanizer in the above manner is required to provide cooling for the demethanizer condenser and to provide for chilling the demethanizer feed to a temperature of about −68� C. (−90� F.). Pure ethylene refrigeration which can provide a cooling temperature of about −101 � C. (−150� F.) and is generally used in this service. For an ethylene production rate of about 500,000 metric tonnes per year, the ethylene refrigeration system requires a centrifugal compressor with a capacity of about 4350 Nm3/hr (2700 actual cubic feet per minute-inlet) at a capital cost of about 3.9 million dollars. For an ethylene production rate of about 120,000 metric tonnes per year, the ethylene refrigeration system requires two reciprocating compressors, each with a capacity of about 1030 Nm3/hr (640 actual cubic feet per minute-inlet) at a capital cost of about 1.9 million dollars. Thus, the ethylene refrigeration system represents a significant capital cost, a large portion of which is directly related to simply compressing the ethylene.
An engineering simulation of the demethanizer operating as shown in FIG. 2 according to the present invention indicates that the demethanizer can be operated at an overhead temperature of about −40� C. (−40� F.) to provide about an 85 mol-% ethylene recovery and that this operation can be combined with a PSA zone containing silica gel as the selective adsorbent for the recovery of ethylene and ethane. The PSA zone recovers about 97.8 mol-% ethylene and about 20.5 mol-% methane. The ethylene-rich PSA tail gas is returned to the first stage of the oxygenate conversion compressor zone at a desorption pressure of about 117 kPa (17 psia). The overall recovery of the ethylene from the complex is greater than about 99.6 percent. The demethanizer bottoms comprises ethylene and ethane which is passed to an appropriate C
A comparison is shown in Table 1 of the relative equipment size or capacity for the prior art scheme of FIG. 1 and the scheme of the present invention as depicted in FIG. 2. The relative size is expressed in term as a percent larger or smaller than the base case. Although the PSA inclusive scheme of the present invention required small increases in the compression capacity and process compressors, the ethylene compressor is completely eliminated. The capacity of the compressors is expressed in energy requirements and the size differences are expressed in terms of relative column inside diameter. The PSA case represents an overall capital cost savings of about 3.2 million dollars for a 120,000 metric tonnes per year ethylene production and about a 73,000 dollars per year utility savings.
Adsorption isotherms for the individual components typically found in the overhead stream withdrawn from a demethanizer operating according to the present invention are shown in FIG. 3 for adsorption on silica gel at an adsorption temperature of about 15� C. (60� F.). Isotherm data is shown for the following components: hydrogen(a), carbon monoxide(b), methane(c), ethane(d), ethylene(e), and nitrogen(f). In FIG. 3, the ethylene and ethane isotherms indicate a high selectivity over hydrogen, methane, and carbon monoxide over the silica gel adsorbent. This adsorption isotherm data were developed using standard high-pressure Sartorius microbalance techniques well known to those skilled in the art.
Based on adsorption isotherm data developed from standard high-pressure Sartorius microbalance techniques for ethylene adsorption over silica gel and a zeolite 4A adsorbent, delta loadings expressed in grams/100 grams of adsorbent for the silica gel (a) and the 4A zeolite (b) at temperatures ranging from about 0� C. to about 100� C. were calculated and are presented in FIG. 4. Of note is the greater delta loading or adsorption capacity for silica gel relative to the delta loading of the zeolite 4A at adsorption temperatures less than about 100� C. Surprisingly, the delta loading of ethylene on the silica gel increases at adsorption temperatures less than about 100� C., while the delta loading values for the zeolite 4A are initially lower than that of the silica gel at 100� C. and gradually decrease for temperatures below 100� C.
The operation of the demethanizer of the present invention operating at a demethanizer temperature of about −40� C. as shown in FIG. 2 can be carried out over a range of recoveries according to the ratio of hydrogen and methane to C
Patent Citations
Non-Patent Citations
Referenced by
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text:
Today I made my third brew but it is the first time I have used my hydrometer. Does the reading you get from it provide any data other than potential ABV? What does the change in the readings from pre to post fermentation tell you?
Should I be researching this elsewhere.....?
OK nevermind - I just read the section on www.howtobrew.com on - duh - using a hydrometer.
History lesson on the importance of an hydrometer. It's your friend.
Simply put: a hydrometer is the only way to know your batch is done fermenting and it lets an AG brewer know how well their mashing system works.
Remember one unassailable statistic, as explained by the late, great George Carlin: "Just think of how stupid the average person is, and then realize half of them are even stupider!"
"I would like to die on Mars, just not on impact." Elon Musk
Yeah, what Dave said...


text:
was a little lame today not many deals and few buyers
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i was debating going to it or the Dothan show but after working all night the extra hour drive to see either wasn't that appealing .
the north had us outnumbered and outgunned but we had them outmanned .......................................... join the NRA


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sp 1.3.4-1.2.1-47build1 (powerpc binary) in ubuntu hardy
This package is a collection of SGML/XML tools called SP.
These tools are used to parse, validate, and normalize SGML and XML
files. The central programs included in this package are 'nsgmls',
which replaces sgmls, 'spam', 'spent', 'sgmlnorm', and 'sgml2xml'.
Author: James Clark <firstname.lastname@example.com>
Homepage: http://
- Package version:
- 1.3.4-1.2.1-47build1
- Status:
- Published
- Component:
- main
- Priority:
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Downloadable files
powerpc build of jade 1.2.1-47build1 in ubuntu hardy RELEASE produced these files:
- sp_1.3.4-1.2.1-47build1_powerpc.deb (182.7 KiB)


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Winnipeg Free Press - ONLINE EDITION
Feds say they will try to keep Lake St. Martin students together
The federal government issued a statement late Wednesday saying Ottawa is negotiating with Lake St. Martin First Nation to find a way to keep evacuated students together in school.
An estimated 85 Lake St. Martin students lost their school in Winnipeg when the Winnipeg Fire Department shut down the building for fire code infractions.
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Originally, Aboriginal Affairs Minister John Duncan in Ottawa told the community that the department would take over the schooling responsibilities from the First Nation and split the students up among different Winnipeg schools.
Late Wednesday, Ottawa suggested it was shifting its stand.
"Our priority remains ensuring that the students are able to continue with their studies with minimal interruptions, and in a safe environment," a regional departmental spokeswoman said by email.
"To that end we are in active discussions with the province to present the students, their parents, and the First Nation with options that would allow the students to remain together in a provincial school."
The department said it will now communicate directly with parents, who are among 2,000 First Nation flood evacuees in the province, for a solution to keep the students together in school.
There was no mention, however, of reopening the school that was shut down. Community leaders, meanwhile report that the repairs are being completed and arrangements are being made for fire officials to conduct another inspection, with a view to reopening the school.
The Assembly of Manitoba Chiefs weighed into the political debate around the issue earlier Wednesday.
Manitoba's chiefs want 85 Lake St. Martin school children back in the classroom and they're asking Ottawa to stop using them as political pawns in a battle over who controls the community's off-reserve school.
Manitoba's chiefs summoned federal officials to a meeting to reopen the school Lake St. Martin operates for its school-age evacuee students.
"I find it appalling that your solution to a building code issue is forced separation for these school-age children," Assembly of Manitoba Chiefs leader Derek Nepinak wrote the federal Aboriginal Affairs Minister John Duncan in a letter Tuesday.
Updated on Wednesday, November 7, 2012 at 12:44 PM CST: Adds link to letter.
6:33 PM: Updates with Ottawa response
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A$AP Rocky feat. Florence Welch, "I Come Apart"
A$AP Rocky ends the album with another surprise collaboration, this time linking with rock chanteuse Florence Welch from Florence and the Machine. It's yet another genre mash-up on an album full of them, and it's perhaps its best chance for a crossover hit. But it also shows off Rocky's biggest strengths: He's created his own lane, one where boundaries geographical (New York, Houston, Midwest), musical (trap, boom-bap, electronica) and even choronlogical (golden-age meets the future) matter little. It's not an earth-shaking album, but it's a damn good one, and a confident, charismatic mission statement from a rapper who isn't going anywhere anytime soon.
(Photos from left: Derek Reed / Picture Group Promo, Simone Joyner/Getty Images)
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Location:Birmingham, AL Job Code:811 # of openings:1 Description Recently ranked by Healthcare Informatics as one of the Top 100 Healthcare IT companies, SourceMedical provides outpatient information solutions and services for ambulatory surgery centers, surgical hospitals, and3/30/2015 Birmingham, AL Save This Job
DESCRIPTION Be Part of The Next Generation of Flight Aurora Flight Sciences is a leader in unmanned aerial systems, with a fleet of innovative aircraft designed to empower small tactical units, and safeguard our borders. Aurora provides the capabilities and process controls of2/10/2015 Manassas, VA Save This Job
LegalZoom is currently seeking a Director of Technical Accounting and Financial Reporting. This position will serve as the subject matter expert on US Generally Accepted Accounting Principles (GAAP) and will be responsible for identifying and addressing new or emerging issues or3/10/2015 Glendale, CA Save This Job
Location: Princeton, NJ NIKSUN is the recognized worldwide leader in making the Unknown Known, by using next generation technology that revolutionizes the way networks and services are secured, protected and managed. The company develops and deploys a complete range of2/15/2015 Princeton, NJ Save This Job


text: 'Rodham,' Hillary Clinton screenplay by South Korean, follows life as young woman Hollyworld Hollyworld Living Pop Culture South Korea United States Sarah Wolfe on Dec 31, 1969 @ 7:33 PM US Secretary of State Hillary Clinton pictured in Hanoi, Vietnam on July 10, 2012, a day before flying to Laos. Who knows Hillary Clinton best? It may be South Korean screenwriter Young Il Kim. Kim brings the secretary of state to Hollywood in his screenplay, "Rodham," which is generating a lot of Tinsel Town buzz. More from GlobalPost: Hillary Clinton to testify on Benghazi Kim reportedly wrote the screenplay in four months, while in and out of New Jersey coffee shops. "Rodham" follows a 20-something Hillary Rodham as she tries to choose between a career and her boyfriend, Politico reported. Her profession? The youngest attorney on the House Judiciary Committee, working to impeach President Richard Nixon. More from GlobalPost: Hillary Clinton most admited woman in US for 17th time Her boyfriend is none other than Bill Clinton, who's trying to launch his political career in Arkansas. According to Jezebel, the screenplay appeared at No. 4 on this year's Black List, an annual poll of nearly 300 film executives on their favorite scripts. Kim told Politico he was inspired to write the film after seeing the now-infamous photo of Clinton in the Situation Room during the 2011 Osama bin Laden raid. Of course, this isn't the first talk of a Hillary movie. In May, Bill Clinton told CNN's Piers Morgan he'd like Meryl Streep to play his wife on screen. But this one is certainly generating the most buzz.