text:
Sandra (8) cont.Mature
Sandra rose to her feet, took the blazer from him and put it on. She followed him as he walked to the kitchen to grab a drink, where the pair received a slightly worried look from Rhyley's mother who was chatting there with Mrs Steelfang. They came back out and walked through the dining room off the side of the hallway - which adjoined the living room, separated by a door with frosted glass panes in a light-coloured wood frame - and provided a side exit to the house. Rhyley led her around to the back of the house, stopping a short distance away from the French windows of the conservatory where the other adults were congregated. Sandra suddenly remembered what Roger had said about Rhyley taking girls outside... and decided not to think about it.
He leant against the back wall of the house and said "You came then."
Sandra was confused. Had he been expecting her not to turn up?
"Well, I said I would," she said.
"Everyone will know now," Rhyley commented. He sighed, taking a sip from the can of beer he had picked up. He looked ... bothered.
"Well, I don't know what you want me to do. Should I go back inside and kiss Roger?" Sandra asked.
Rhyley looked at her, startled.
"No. I said I wouldn't let him have you. And why would you kiss him? Would you even kiss me?"
"I'm saving my virginity, not staying abstinent from all physical contact," Sandra replied, cross and incredulous that he could think something like that.
Rhyley looked at the ground. He seemed slightly ashamed. The grass was yellowing in the shade of the house.
"Okay. But would you kiss me?"
Sandra sighed.
"Not right this minute, no."
"That's understandable." His tone wasn't self-pitying or self-mocking; he was just making a statement of fact.
"You don't get me, do you?" Sandra asked him.
"Not at all."
"Why am I here?"
"Tradition," Rhyley said simply. He sipped more of his beer. He offered it to her. "Want some?" Sandra had left her squash in the living room.
"No, thanks."
"All right." Rhyley drank some more.
"Why are we just standing here?" Sandra asked, confused.
Rhyley sighed.
"I don't really know. Perhaps I was hoping that you would kiss me."
Something shivered inside Sandra, seeming to focus on the fact that Rhyley and she were alone out here.
"I'd like to get back in now." She turned to go back the way they came, not wanting to face a sea of potentially disapproving faces by going through the conservatory, but Rhyley reached out to touch her hand.
"Just a few more minutes?"
Sandra turned back.
"For what?" she asked, even more confused.
"What d'you like to do at parties?" he asked, seeming to want to have a conversation with her.
"Um..." Sandra decided that she might as well answer him. "Chat, sing along to the music. If I'm really comfortable and there's not much light, I'll dance."
Rhyley sighed, looking disappointed.
"Let's chat, then."
"What about?" Sandra asked, raising an eyebrow. "All our differences?"
"Well, how about the things that you like?" Rhyley suggested patiently. "I'm guessing you won't like to hear about what I like."
"Why are you even bothering?" Sandra asked, puzzled.
Rhyley frowned and looked straight through the air in front of him as he spoke.
"You deserve that, don't you? It's not your fault that you're my soulmate; it's not your fault that I don't understand why you make everything so complicated for yourself... I have to try to have some sort of a relationship with you. I'll be damned if I let Roger bloody Steelfang steal you from me."
Sandra was amazed. Beyond the fact that he had said she complicated things for herself, beyond the fact that he had insulted her best friend, she had read a message in Rhyley's words - a message that told her that he wasn't actually a bad person and that he felt he owed it to her to make an effort, even though he found her hard to understand. And perhaps, in the end, that was what love and relationships came down to: the willingness to try at another level when the preferred outcome seemed impossible. In other words, compromise. She suddenly found herself closing the space between them and rising onto her tiptoes to kiss Rhyley.
Rhyley dropped his beer can in shock - Sandra heard it hit the ground and the liquid sloshing around inside it. She was intending to pull back after the first few seconds but Rhyley held her waist and kissed back, sending a wave of pleasure through Sandra, who had never kissed a boy before, and who had certainly not expected to be kissed back. Rhyley pushed her against the wall, causing her to feel the thrill of doing something forbidden as well as evoking what she could only describe as 'excited reaction'. A distant part of her thought 'All right, a little bit longer, but not too much - first kiss, remember?' but she was so engulfed in how much she was enjoying being kissed and the novelty of that enjoyment that she barely listened to it. Rhyley's hands were moving down her sides a little, stroking the top of her hips - which was really delightful - and her arms were around his neck, holding onto him as her mouth moved against his.
Surprisingly, Rhyley was the one to stop first. He ducked his head slightly and said, "I think that's enough now, Sandra."
She noticed that his grip on her hips had tightened slightly.
"Um, yeah," she muttered, embarrassed, unwinding her arms.
Rhyley stepped backwards, gazing at her. Sandra saw that his eyes were darkened slightly. She guessed how she must look: flushed, chest rising and falling quickly, eyes slightly wide. She wondered whether that made her look beautiful or desperately scared.
"That ... was unexpected," he said. "I ... Was it something I said or did you just suddenly find me attractive?"
Sandra looked away, the intensity of his gaze starting to make her feel slightly unbalanced.
"What you said," she murmured. "You saying that I deserved it ... I felt like I understood you better. But I don't want a long discussion on why I kissed you - I'm caught up in how it felt and I don't want that to end." She paused. "I want to hold you."
Rhyley sat down, avoiding the beer can.
"Come sit and I'll hold you."
Sandra slowly lowered herself to the ground, sitting on his lap. Rhyley's arms came around her and Sandra felt... wanted. Emotionally, and in a strange sort of physical way too. Rhyley's body wanted hers against it in the same way that she wanted to be against it.
"I liked that, I really did," Sandra murmured, more speaking her feelings out loud than talking to Rhyley. "I'm so glad I kissed you."
Rhyley was silent. Sandra worried about what that meant.
"Oh, sorry," Rhyley said, sounding a bit like she'd woken him up. "I've just got to stay... a bit distracted. Because I want you, you know? That's why I stopped kissing you."
"Oh, but it must be tempting with me sitting so close," Sandra said, trying to move to get off him. Rhyley held onto her.
"Sandra, stop. You can stay there." Sandra stopped moving. "It's very tempting. But it's kind of a nice pain."
"Oh," said Sandra, surprised. She was unsure was to whether 'nice pain' was good or bad. "Okay then."
Rhyley was quiet for a few minutes. Then, he murmured, "I wish you would do it with me, Sandra."
Sandra tensed.
"Look, Rhyley, I think I should move off you."
"No, I'd rather you didn't, Sandra. Listen... if we're soulmates, then isn't it kind of guaranteed that we're going to get married?"
Sandra saw where he was going and she didn't like it.
"Rhyley, please. Even if I weren't chaste, I wouldn't right now. I don't feel ready, that was just our first kiss... If you pester me about it, I will go to Roger." Sandra regretted that instantly. The words had come automatically, as though they hadn't been her idea at all.
Rhyley abruptly let go. Sandra stood up, feeling guilty.
"I'm sorry... You were scaring me," she confessed.
Rhyley looked irritated.
"Is this how it's going to be? Every time I mention sex you're going to threaten to run to Roger?"
Sandra looked at her feet in shame.
"No," she mumbled. "Sorry."
Rhyley stood up and closed the small gap between them. He tilted her chin up so she was looking at him. His eyes showed annoyance and incomprehension.
"Did you not want me? Even just a little?"
"I did," Sandra whispered. "But if I betray myself..." She trailed off, not even wanting to contemplate it.
Rhyley stepped back, giving her some space.
"How far would you go before marriage?" he asked bluntly.
Sandra blushed at the question.
"I - I don't know much," she confessed hesitantly. "But ... I'd take my clothes off."
Rhyley sighed slightly, nodding.
"I'm sorry - for scaring you. I'll try to go at your speed. But you have to understand that I don't normally have to restrain myself when I want it. Just a warning."
Sandra nodded slowly.
"I'll try not to arouse you," she told him quietly.
Rhyley smiled wryly.
"Good luck with that one. Shall we go back indoors then?"
Before Sandra turned for the door, Rhyley reached out and stroked her face. He kissed her gently and briefly.
"I'm glad you kissed me too."


text: A show with 4 singers performed while you are eating. I'm far from an expert, but the quality of singing was very good. The songs where often in English and ranged from the 50's until 2000. So also ideal for visitors like myself and they covered every music genre. The food was of good quality and a welcome surprise. Respect... More

subset: commoncrawl


text:
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text:
|Publication number
|Publication type
|Application number
|Publication date
|Mar 9, 2004
|Filing date
|Dec 3, 2001
|Priority date
|Dec 3, 2001
|Fee status
|Publication number
|James F. McGehee, Giuseppina R. Boveri, Paul A. Sechrist
|Original Assignee
|Uop Llc
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (13), Non-Patent Citations (3), Referenced by (8), Classifications (13), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
The present invention relates to a process for cooling or heating polymer in a polymerization reactor. The invention specifically relates to cooling polymerized solids in a polycondensation reactor. The invention particularly relates to cooling polyester, polyamide or polycarbonate chips in a solid-state polycondensation (SSP) reactor.
Polymer resins are molded into a variety of useful products. One such polymer resin is polyethylene terephthalate (PET) resin. It is well known that aromatic polyester resins, particularly PET, copolymers of terephthalic acid with lower proportions of isophthalic acid and polybutylene terephthalate are used in the production of beverage containers, films, fibers, packages and tire cord. U.S. Pat. No. 4,064,112 B1 discloses a solid-state polycondensation or polymerization (SSP) process for the production of PET resins.
While for fibers and films the intrinsic viscosity of the resin must generally be between 0.6 and 0.75 dl/g, higher values are necessary for molding materials such as containers and tire cord. Higher intrinsic viscosity such as greater than 0.75 dl/g can only with difficulty be obtained directly through polycondensation of molten PET, commonly called the melt phase process. The SSP process pushes polymerization to a higher degree thereby increasing the molecular weight of the polymer by the heating and removal of reaction products. The polymer with higher molecular weight has greater mechanical strength and other properties useful for production of containers, fibers and films, for example.
The SSP process starts with polymer chips that are in an amorphous state. U.S. Pat. No. 4,064,112 B1 teaches crystallizing and heating the chips in a crystallizer vessel under agitation to a density of 1.403 to 1.415 g/cm3 and a temperature ranging between 230� and 245� C. (446� and 473� F.) before entering into the SSP reactor. Otherwise the tacky chips tend to stick together.
The SSP reactor may consist of a cylindrical reactive section containing a vertical mobile bed into which the polymer chips are introduced from above and a frusto-conical portion of a dispensing section at the base for dispensing the product chips. The polycondensation reactor typically operates at temperatures between 210�. and 220� C. (410� and 428� F.).
The polyester chips move through the cylindrical reactive section of the polycondensation reactor by gravity in plug-flow. However, when the chips enter the frusto-conical portion of the dispensing section at the base of the polycondensation reactor, they enter into a non-flat velocity profile which interjects a non-uniformity in the amount of time that the chips are in the polycondensation reactor. Accordingly, a chip-to-chip variation in the degree of polymerization occurs due to the variation in residence time. Moreover, at the transition from the cylinder to the cone, the chips are subjected to a consolidation pressure that may be several times the normal radial axial pressure to which the chip had previously been subjected. The chips that are in a glassy region have a strong sticking tendency. Hence, the consolidation pressure can cause lumping of chips and interruption of flow.
Various reactions occur during polycondensation of PET. The main reaction that increases the molecular weight of PET is the elimination of the ethylene glycol group:
Inert gas such as nitrogen is introduced into the crystallizer vessel and the polycondensation reactor to strip the developing polymer of volatile impurities generated by the polycondensation reaction. Impurities include ethylene glycol and acetaldehyde if PET is produced. U.S. Pat. No. 5,708,124 B1 discloses maintaining the ratio of the mass flow rate of inert gas to the mass flow rate of PET polymer solids to below 0.6 in an SSP reactor.
The conventional method used for the purification of an inert gaseous stream recycled from an SSP process includes an oxidation step for converting the organic impurities to CO2 and a drying step to eliminate the water formed in the polymerization process and the oxidation step. The oxidation step is carried out with gas containing oxygen by using an oxygen concentration of no more than in slight excess of the stoichiometric quantity with respect to the organic impurities. The oxidation step is controlled according to U.S. Pat. No. 5,612,011 B1 so that the inert gaseous stream at the outlet contains an oxygen concentration of not more than 250 ppm and preferably according to U.S. Pat. No. 5,547,652 B1 so that the inert gaseous stream at the outlet contains an oxygen concentration of not more than 10 ppm. These patents taught that a previously required deoxidation step of reducing the oxygen with hydrogen between the oxidation and drying steps was not required. Typically, the inert gaseous stream must be heated before it is recycled to the polycondensation reactor requiring additional utility cost.
It is also well known that polyamide resins, and among them particularly PA6, PA6,6, PA11, PA12 and their copolymers, find wide application both in the fiber and flexible packaging sectors, and in the manufactured articles production by blow and extrusion technology. While the resin relative viscosity for fibers is low at about 2.4 to 3.0, higher relative viscosities of 3.2 to 5.0 are needed for articles produced by blow and extrusion technologies. The relative viscosity is increased to above 3.0 by means of an SSP process operating at temperatures of between 140� and 230� C. (284� and 446� F.), depending on the polyamide types used. U.S. Pat. No. 4,460,762 B1 describes an SSP process for a polyamide and different methods to accelerate this reaction.
An SSP process for polyamide resins is also described in the article "Nylon 6 Polymerization in the Solid State," R. J. Gaymans et al., Journal of Applied Polymer Science, Vol. 27, 2515-2526 (1982) which points out the use of nitrogen as a heating and flushing aid. The reaction is carried out at 145� C. (293� F.).
It is also known that the molecular weight of polycarbonate can be increased through an SSP process.
The polymer chips exiting from an SSP reactor must be cooled to below the glass transition temperature for packaging purposes, especially to avoid heat damage to packaging containers, such as sacks and boxes. The desired packaging temperature is below 80� C. (176� F.) for PET chips. U.S. Pat. No. 5,817,747 B1 teaches two-stage cooling of the polymer chips after exiting the polycondensation reactor. The first cooling stage is a bed fluidized with nitrogen used for purging impurities from the SSP process after the nitrogen has been purified. The fluidizing gas entrains and separates the polymer dust from the polymer chips while cooling them to 160� to 180� C. (320� to 356� F.). The polymer dust is formed in the processing apparatuses by the action of rotating parts of an agitator in contact with the polymer chips in the crystallizer vessel and the sliding friction between the chips and the walls of the polycondensation reactor. The second cooling stage is a shell and tube or wall-type heat exchange cooler which uses water as the cooling fluid to cool the chips to between 40� and 60� C. (104� and 140� F.).
U.S. Pat. No. 5,662,870 B1 discloses a fluidized bed with two chambers for cooling polymer chips exiting the SSP reactor in a single stage. Fluidizing gas from the hotter chamber into which hot chips enter from the SSP reactor is recycled to heat the SSP reactor after it is de-dusted through a cyclone. Fluidizing gas from the cooler chamber is also de-dusted through a cyclone and recycled to the fluidizing bed. The amount of dust collected in the fluidizing gas from a fluidized bed is significant and must be removed.
JP 5-253468 A1 teaches introducing a nitrogen gas into a vessel surrounding a dispensing cone at the bottom of a reaction chamber to indirectly cool a product, solid-gas mixture in the cone without causing turbulence within the cone.
A thesis by G. Ghisolfi entitled "Impianto di Postpolicondensazione di Polietilentereftalato" (1984-85) discloses an SSP reactor with nitrogen gas distributors located along the height of the reactor of which the bottom nitrogen distributor cools polyester chips to below a temperature at which oxidation can occur such as to 177� C. (351� F.). The chips would have to be subsequently cooled to lower temperatures to permit packaging. A presentation by A. Christel entitled "Advanced PET Bottle-to-Bottle Recycling" given at the Polyester 2000 World Congress discloses directly cooling recycled PET flakes at an outlet of a hopper of an SSP reactor with cold nitrogen.
Cooling the polymer chips after exiting the polycondensation reactor requires at least one cooling device, a gas mover such as a fan and a dust removal device. Either this equipment has to be located beneath the reactor or a pickup point and pneumatic conveying means has to be used to carry the hot chips to the top of a cooling section. Each approach involves additional equipment and building costs. Moreover, the former approach requires a taller overall SSP complex.
U.S. Pat. No. 4,255,542 B1 discloses an exothermic gas phase polymerization process in a fluidized bed reactor which is cooled by indirect cooling within the reactor. U.S. Pat. No. 3,227,527 B1 discloses a catalytic reactor vessel in which product gas permeates a truncated cone section at the base of the reactor to be cooled by quench liquid before exiting the reactor. These patents do not involve direct cooling of polymer solids in a packed bed with a gas.
Accordingly, an object of the present invention is to eliminate the additional cooling equipment required to cool the chips to a packaging temperature after exiting the SSP reactor. An additional object of the present invention is to consolidate the equipment used for cooling polymer solids and for introducing purge gas to the SSP reactor for the purging of impurities. An additional object of the present invention is to cool the polymer chips entering the dispensing section of the SSP reactor and therefore make the dispensing section a non-reactive region and to prevent the hot, tacky polymer chips from lumping when they are subjected to the consolidation pressure upon entering the frusto-conical portion of the dispensing section. An even further object of the present invention is to be able to eliminate the need for expensive dust removal equipment required with post-polycondensation reactor cooling equipment.
We have found that it is possible to cool the polymer chips from the SSP reactor temperature of 185� to 240� C. (365� to 464� F.) down to below 175� C. (347� C.) in a dispensing section of the polycondensation reactor. Moreover, we have found that we can cool the pellets to below 80� C. (176� F.) which is below the glass transition temperature for normal packaging and transport of PET chips. It was surprisingly learned that the heat transfer from gas to solids is rapid enough to allow the upper part of the dispensing section to be used for efficient cooling if particular mass ratios are used.
Accordingly, in one embodiment, the present invention relates to an apparatus for conducting a polymerization process. The apparatus comprises a reactor including a heated reactive section in which substantial polymerization of polymer solids therein occurs and a dispensing section for dispensing polymer solids from the reactor. The dispensing section defines an interior volume. A gas inlet connective with the interior volume of the dispensing section delivers gas to the dispensing section to heat or cool polymer solids traveling through the dispensing section. A gas outlet connective with the reactor proximate the dispensing section withdraws gas from the dispensing section.
In another embodiment, the present invention relates to a process for cooling polymer solids in a reactor comprising a reactive section and a dispensing section. The process comprises delivering polymer solids to the top of the reactive section. The polymer solids are polymerized as they flow downwardly in the reactive section so as to increase the molecular weight of the polymer solids. The polymer solids are dispensed from the dispensing section of the reactor. Gas is delivered to the dispensing section to flow countercurrently to the polymer solids and contact and heat or cool the polymer solids in the dispensing section. Some of the gas is withdrawn at an outlet proximate to the dispensing section.
In a further embodiment, the present invention relates to a process for adjusting the temperature of moving solids in a vessel by direct heat exchange with a gas. The process comprises delivering solids to a first section of the vessel. The solids are dispensed from a second section of the vessel. Gas is flowed through the vessel to effect direct heat exchange between the gas and the solids. A ratio of a mass flow rate of the gas multiplied by the heat capacity of the gas to a mass flow rate of solids multiplied by the heat capacity of the solids over a temperature range in the reactor is at least one.
Additional objects, embodiments and details of this invention can be obtained from the following detailed description of the invention.
FIG. 1 is a schematic view of a polymerization flow scheme of the present invention.
FIG. 2 is a partial, enlarged view of a reactor dispensing section and cooling apparatus of FIG. 1.
FIG. 3 is a partial, enlarged view of an alternative reactor dispensing section and cooling apparatus of FIG. 1.
FIG. 4 plots a temperature profile through the dispensing section of a reactor.
A detailed description of a preferred process and apparatus of the present invention is given in the context of a solid-state polycondensation (SSP) process. The SSP process can be used to increase the intrinsic viscosity of polyester, polyamide and polycarbonate components. However, the present invention may be used with other types of polymerization processes in which cooling of the polymer solid product is necessary.
Polyester resins usable in the SSP process are products of polycondensation of aromatic bicarboxylic acid, particularly terephthalic acid or its esters with diols with 1 to 12 carbon atoms such as ethylene glycol, 1,4-dimethylolcyclohexane and 1,4-butanediol. Polyethylene terephthalate (PET) and polybutylene terephthalate are the preferred resins. Polyester resins usable in the SSP process also may include elastomeric polyester resins, including segments deriving from polyethylene glycol, and copolyesters containing up to 20% of units deriving from aromatic bicarboxylic acids different from terephthalic acid, such as isophthalic acid. PET resins to be subjected to SSP can contain a resin-upgrading additive to accelerate the SSP reaction. The preferred upgrading compounds are the dianhydrides of tetracarboxylic aromatic acids, and particularly pyromellitic dianhydride. The upgrading agent is generally used in a quantity of about 0.05 to 2% by weight. Conventional additives, like stabilizers, dyes, flame-retardants and nucleants can also be present in the resin. Polyester resins useful for upgrading in SSP processes can also be material produced from recycled containers which have been washed, shredded and dried. Typically, the recycled material is remelted and pelletized before being sent to the SSP process.
Polyamide resins usable in the process of the invention include polyamide 6 derived from caprolactam, polyamide 6,6 obtained from hexamethylenediamine and adipic acid, polyamide 11 obtained from aminoundecanoic acid, and 12 polylaurilacetone copolyamides 6/10 and 10/12 and also polyamides of metaxylene diamine.
FIG. 1 is an example of an SSP process for upgrading PET chips to which the present invention can be applied. However, the present invention can be applied to other polymerization processes in which the polymer solids must be cooled and/or heated. The SSP process in FIG. 1 can process up through 100 metric tons/day and typically 300 to 500 metric tons/day of polymer solids. The polyester SSP process comprises feeding amorphous, clear polyester chips having an intrinsic viscosity usually ranging from about 0.57 to 0.65 dl/g to a hopper 12 through a line 10. The intrinsic viscosity or molecular weight of the starting material is immaterial to the practice of the invention. Generally, the SSP process can be successfully performed with feeds across a wide range of values. For example, techniques are disclosed for using a starting material having a degree of polymerization as low as 2-40 by U.S. Pat. No. 5,540,868 B1, U.S. Pat. No. 5,633,018 B1 and U.S. Pat. No. 5,744,074 B1 which contemplate eventually undergoing SSP processing to raise the molecular weight sufficient to make useful resins. Also, the starting intrinsic viscosity in the case of post-consumer recycle material can be at levels of above 0.65 dl/g. The hopper 12 feeds the chips through a line 14 and a control valve 16 to a fluidized bed pre-crystallizer 18. The pre-crystallizer 18 operates at about 170� C. (338� F.) and 10.3 kPa gauge (1.5 psig) to achieve about 35% crystallinity of the polyester chips. The polyester chips are then fed from the pre-crystallizer 18 through a line 20 and a control valve 22 into a first crystallizer 24. If more capacity is necessary, a second crystallizer 28 may be utilized which the first crystallizer 24 feeds through a line 26. In the crystallizers 24, 28, the chips are eventually preheated or cooled in some cases to an SSP reaction temperature while being subjected to mechanical agitation to prevent the chips from sticking to each other. The chips leaving the crystallizer will exhibit about 45% crystallinity. Crystallizing PET granules prior to polycondensation prevents the granules from sticking during the SSP reaction.
The chips leaving the crystallizer(s) are then fed through a line 30 and a control valve 32 to a moving packed bed SSP reactor 34 operated suitably at 150� to 240� C. (302� to 464� F.) and preferably at 210� to 220� C. (410� to 428� F.) for PET. chips move by gravity through a heated reactive section 70 in which polymerization occurs for about 12 to 36 hours to yield crystalline, opaque pellets with an intrinsic viscosity of 0.75 dl/g or greater depending upon the application to which the polyester pellets will be put. The chips are withdrawn from the reactor 34 through a line 36.
An oxygen-free inert gas, typically nitrogen, purges the polymerization reactor, the crystallizers and the precrystallizer to remove impurities given off by the chips. The inert gas is delivered through a line 38 into the reactor 34. A gas line 42 removes inert gas with impurities from the reactor 34 and splits into a recycle line 44 and a crystallizer line 46. The crystallizer line 46 delivers the inert gas to the second crystallizer 28 and a line 48 delivers inert gas from the second crystallizer 28 to the first crystallizer 24. A line 50 delivers inert gas with impurities to the pre-crystallizer 18 and a line 52 delivers inert gas with impurities to join the recycle line 44. The inert gas recycled in a combined recycle line 53 is preferably at a temperature between 200� and 220� C. (392� and 428� F.).
The combined recycle line 53 runs the inert gas with impurities through a filter 54. After the recycled inert gaseous stream is filtered, air is injected by a line 57 into a line 56 exiting the filter 54. The air/inert gaseous mixture is carried by a line 59 through a heater (not shown), if necessary to achieve the desired oxidation reaction temperature, into an oxidation reactor 58 where the organic impurities are combusted by circulating the stream over a catalyst bed including an oxidation catalyst. Oxygen is injected by the line 57 in substantially stoichiometric quantities to assure the complete combustion of the organic impurities in the oxidation reactor 58. Preferably no greater than about 10 ppm of oxygen is present in the effluent of the reactor 58. The oxidation reactor 58 can be operated with these conversions at temperatures ranging from 200� to 350� C. (392� to 662� F.) depending on the catalyst. A line 60 withdraws the effluent from the oxidation reactor 58 that contains only nitrogen, carbon dioxide, water and traces of oxygen. The carbon dioxide content stabilizes at a certain level due to the losses through the SSP plant and acts like an inert gas due to its chemical inertia. The exiting gaseous stream in the line 60 may be circulated through a heat exchanger (not shown) for heat recovery or to condense and dispose of part of the water by cooling the oxidation reactor effluent. No optional condensation collection equipment is shown in the drawings. The gaseous stream is delivered by the line 60 to a dryer 62 preferably operating at 200� C. (392� F.). The dryer 62 preferably contains molecular sieves for adsorbing the water. The effluent of the dryer 62 is transported through a line 64 after having been filtered (not shown) of possible particles deriving from the molecular sieves. The line 64 is combined with a line 74 to form the line 38. The line 38 recycles the gaseous stream to the reactor 34. The regeneration of the molecular sieves bed is performed according to known methods, operating for example on a closed circuit with a hot nitrogen stream (not shown).
The reactor 34 includes the heated cylindrical active or reactive section 70 that is preferably heated by a circulating oil jacket. The reactor 34 also includes a dispensing or inactive section 72 comprising a cylindrical disengaging portion 88 and an inverted, generally frusto-conical consolidating portion 90. The inert gas, preferably nitrogen, enters an interior volume 91 defined by the dispensing section 72 through the line 38. The inert gas directly cools the polymer solids in the dispensing section down to below 175� C. (347� F.), suitably below 100� C. (212� F.), preferably down to below 80� C. (176� F.) and perhaps to below 50� C. (122� F.) if desired. The cooled polymer solids can then be transported to storage through the line 36 without the need for any additional cooling equipment. A portion of the inert gas is withdrawn from the reactor 34 proximate to the dispensing section 72 by a line 76 and enters a dust removal device 78. Proximate to the dispensing section 72 means, the withdrawal point of the line 76 is either in the dispensing section 72 or not above the lower quarter of the reactive section 70 and preferably not above the lower tenth of the reactive section 70. The de-dusted gas is transported from the dust removal device 78 through a line 80 and is moved by a fan 82 through a line 84 to a cooler 86 and is combined with the line 64 to be recycled to the dispensing section 72 of the reactor 34 by the line 38.
The cooling apparatus is illustrated in more detail in FIG. 2. FIG. 2 gives a partial view of the reactor 34. The cylindrical disengaging portion 88 has an inner diameter that is greater than the inner diameter of the reactive section 70. Gas is withdrawn from the reactor 34 through at least one outlet nozzle 92 through the line 76 for recycling. The outlet nozzle is preferably disposed in the disengaging portion 88 of the dispensing section 72. Although only one outlet nozzle 92 is shown in FIG. 2, a plurality of the radially disposed outlet nozzles 92 is contemplated. The remaining gas will ascend through the reactive section 70 of the reactor 34 and purge impurities stripped from the developing polymer. Because the polymer solids exchange heat with the cooling gas, the gas now withdrawn through the outlet nozzles 92 and that ascends through the reactive section 70 will have a temperature that is not substantially different from polymer solids in the reactive section 70 of the reactor 34. Therefore, the gas that ascends into the reactive section 70 will not impede the polycondensation reaction by cooling.
The dust removal device 78 is either a dust-removing cyclone or a filter, which can operate continuously. The dust removed by the cooling gas flowing through the moving packed bed of polymer solids is low because it is only taken from the top-most layer of the polymer. Therefore, the cooling of circulating gas can be performed with a simple filter or dust removal cyclone which is more compact and less expensive than the equipment required to remove dust from a conventional fluidized bed. The fan 82 pumps cooling gas from the dust removal device 78 through the lines 80 and 84 to the cooler 86. The cooler 86 removes the heat gained by the gas in the dispensing section 72 by indirect heat exchange with a cooling medium such as water. The line 74 combines the cooled gas from the cooler 86 with recycled purge gas in the line 64 to form the line 38. The flow rate of the gas removed proximate to the dispensing section 72 may be set by a variable capacity characteristic of the fan or by a control valve (not shown) in FIG. 2. Thus, the excess inert gas, equal to the flow of gas from the dryer 62 in the line 64, ascends into the reactive section 70 from the dispensing section 72. The flow of gas through the line 64 is regulated by a control valve 40. It is preferred that the control valve 40 be regulated to ensure that the mass flow ratio of gas to solids be less than 0.6, taking into account the gas removed from the reactor for cooling and recirculation. The temperature of the ascending and withdrawn gas is set by the temperature of the gas fed to the dispensing section 72 plus the temperature rise caused by the removal of heat from the polymer solids.
The variable capacity fan 82 or control valve regulates the temperature of the polymer solids exiting the outlet 100 of the reactor 34. For example, if the fan 82 or the control valve is set to allow a very low flow rate or no flow at all, the temperature of the gas in the line 38 will be higher because it would not be mixed with as much cooled gas from the line 74. Hence, if desired, the polymer solids exiting the outlet 100 will not be cooled as much and can be sent directly to a molding process such as injection molding which requires the polymer solids to be at a temperature above the glass transition temperature for moldability. Moreover, the temperature of solids is exiting the reactor may be regulated based on the flow rate of coolant circulated through the cooler 86, without affecting the flow rate of gas withdrawn through the outlet nozzle 92 and recirculated through an inlet nozzle 96.
The inlet nozzle 96 distributes the gas to a ring distributor 98 that is an annulus around the inside diameter of the dispensing section 72. The ring distributor 98 has openings distributed radially around its circumference for distributing gas into the dispensing section 72. It is preferred that the distributor not extend into the reactor 34 to avoid obstructing the flow of polymer solids.
FIG. 3 is similar to FIG. 2 with the exception that it has a different device for injecting the inert gas into the dispensing section 72 and that it includes a control valve 94 in a bypass line 68. The elements in FIG. 3 that differ from corresponding elements in FIG. 2 are designated with a prime symbol (′). Otherwise, the elements have essentially the same function and structure in FIG. 3 as in FIG. 2. A distributor 98′ in FIG. 3 injects cooling gas around the periphery of the dispensing section 72 of the reactor 34. The distributor 98′ has a closed outer surface but the inner surface is contiguous with the wall of the dispensing section 72 and includes perforations for injecting the cooling gas into the dispensing section 72. The perforations in the distributor 98′ may be defined by slots or bands or may comprise a profile wire screen. The distributor 98′ does not extend substantially into the reactor 34.
Another difference from FIG. 2 is that the control valve 94 in FIG. 3 is used to control the temperature of the polymer solids leaving the outlet 100. A line 84′ splits into a line 102 that goes to the cooler 86 and the line 68 that bypasses the cooler 86 via the control valve 94 and joins the effluent of the cooler 86 in a line 74′. A combined line 104 joins the line 64 from the dryer 62 to form the line 38 in communication with the inlet nozzle 96. The amount of gas in the line 68 that bypasses the cooler 86 regulated by the control valve 94 affects the temperature of the gas in the line 104 which affects the temperature in the line 38 which contacts the polymer solids. If the exiting polymer solids are too cool, the control valve 94 will be opened more so less of the recirculated gas will be cooled in the cooler 86 and vice versa. The control valve 94 can be hooked up to a temperature indicator controller (not shown) which could control the operation of the control valve 94 automatically based on desired temperature of the solids exiting the outlet 100. The flow scheme in FIG. 3 is advantageous because the temperature of polymer solids can be controlled while keeping the gas withdrawn through the outlet nozzle 92 and recirculated through the inlet nozzle 96 constant. Hence, the flow rate of gas that ascends through the reactive section 70 to purge the impurities will not be affected.
Other types of cooling gas injection and collection equipment may be used according to the teaching of the present invention. Moreover, it is contemplated that warm inert gas could be fed to the reactor for heating the solids if desired with the same equipment with the exception of using a heater instead of the cooler 86. For example, this flow scheme could be used to heat the polymer solids to make it suitable for injection molding after polycondensation.
It is preferable that the local actual velocity of the cooling gas in all sections of the dispensing section not exceed 75% of the minimum fluidization velocity of polymer solids. This preference is primarily to avoid agitation of the solids which may lead to flow mal-distribution and subsequent loss of cooling efficiency. Secondly, fluidization of the polymer solids may upset the mass flow of solids through disturbances in the bed which could lead to wider residence time distribution and variability in intrinsic viscosity.
In order to ensure temperature uniformity of the polymer solids, it is important that a thermal mass ratio "R" be greater than or equal to 1. The thermal mass ratio is as follows:
With R≧1 and plugging in the heat capacities of the inert gas and the solids, equation (1) can be reworked as follows:
With nitrogen as the inert gas and polyester, polyamide or a polycarbonate as the solids, a suitable ratio of upward mass flow rate for gas to downward mass flow rate for solids is 1.6 and 1.9 is a preferred ratio which accounts for any flow nonuniformity.
Cooling is accomplished efficiently in the dispensing section 72 of the reactor 34 without wasting extra space or using additional equipment. Typically, the cooling equipment is below the reactor 34. By removing the conventional cooling equipment, capital cost is reduced and the overall height of the SSP complex is reduced. Alternatively, no pickup point is required to convey hot polymer solids to a cooling zone which is not situated below the polycondensation reactor.
Solid flow mechanics indicate that through the cylindrical active section of the reactor 34, the polymer solids are in plug flow. However, when the polymer solids enter the frusto-conical portion 90 of the dispensing section 72, they begin to flow non-uniformly to some extent. By cooling the polymer solids to below the reaction temperature, the dispensing section ceases to be an active section and the solid-to-solid variation in intrinsic viscosity or molecular weight is lower because the effective residence time along the solids has a tighter distribution. Additionally, when the solids transition from the cylindrical reactive section 70 to the frusto-conical portion 90 of the dispensing section 72 and the polymer solids are subjected to a consolidation pressure, the polymer solids are prevented from sticking together which can cause lumping of the solids and flow interruption. By maintaining the transition between the reactive section 70 and dispensing section 72 of the polycondensation reactor at a lower temperature, the stickiness can be reduced resulting in ease of operation. Therefore, materials more prone to sticking can be processed by cooling in the dispensing section. Moreover, the temperature of the reactor 34 can be increased to cause higher reactivity of the polymer with a concomitant higher production rate and increase in intrinsic viscosity or molecular weight.
The high thermal conductivity of polymer resins such as PET is such that the inert gas ascending above the dispensing section is closely approaching the temperature of the downwardly flowing polymer solids. If this ascending gas from the dispensing section were too cool, it would have to be subjected to intermediate heating to prevent the cooler gas from negatively impacting the polycondensation reaction. However, the efficient recuperation of what would otherwise be waste heat from the polymer solids allows the excess cooling gas to flow through the active section of the polycondensation reactor and serve to purge the polymer solids of impurities. Hence, only one inert gas stream must be fed to the reactor which serves both cooling and purging functions. Additionally, the polymer solids in the dispensing section serve to distribute the gas across the cross-section of the reactor, thereby obviating the need for distribution equipment which is more expensive and can obstruct the flow of solids.
The following example is given to illustrate and not to limit the invention.
The dispensing section of the present invention was tested in a pilot reactor of 618 mm inside diameter. Nitrogen cooling gas was injected radially at a point in the frusto-conical portion of the dispensing section corresponding to a gas velocity of approximately 0.6 m/sec. The cooling gas was withdrawn at the top of the frusto-conical portion of the dispensing section. PET copolymer having an intrinsic viscosity of 0.6 dl/g was raised to 0.8 dl/g in the reactor and the product leaving the frusto-conical portion of the dispensing section had a temperature of approximately 45� C. (113� F.). The mass flow rate ratio of gas to solids in the dispensing section was 2.0 and the gas was injected at approximately 42� C. (108� F.). Pellet temperatures were measured by sliding a thermocouple approximately at centerline and the results were that the heat transfer was accomplished at slightly higher than 1 reactor diameter. A plot of the temperature profile is shown in FIG. 4. Because it was believed that the thermocouple was in contact with the PET pellets, the temperature of the gas was estimated by a heat balance.
The dust in the stream leaving the reactor was collected by a filter and amounted to less than 5 ppmw of the gas stream. A cooling gas stream with such a low dust concentration is suitably moved by a normal gas mover.
|Cited Patent
|Filing date
|Publication date
|Mar 4, 1963
|Jan 4, 1966
|Universal Oil Prod Co
|High temperature reactor
|Apr 15, 1976
|Dec 20, 1977
|Zimmer Aktiengesellschaft
|Process for the continuous production of high molecular weight polyethylene terephthalate
|Nov 30, 1978
|Mar 10, 1981
|Union Carbide Corporation
|Exothermic polymerization in a vertical fluid bed reactor system containing cooling means therein and apparatus therefor
|Mar 25, 1981
|Jul 17, 1984
|Stamicarbon B.V.
|Preparation of high molecular polytetramethylene adipamide
|Jan 20, 1995
|Jul 30, 1996
|E. I. Du Pont De Nemours And Company
|Process for pellet formation from amorphous polyester
|Nov 8, 1993
|Aug 20, 1996
|Sinco Engineering S.P.A.
|Process for the purification of inert gases
|Nov 16, 1995
|Mar 18, 1997
|Sinco Engineering S.P.A.
|Process for the purification of inert gases
|Jan 20, 1995
|May 27, 1997
|E. I. Du Pont De Nemours And Company
|Apparatus for forming crystalline polymer pellets
|Nov 27, 1995
|Sep 2, 1997
|Hosokawa Bepex Corporation
|Fluid bed cooling system for polymer processing
|Dec 7, 1995
|Jan 13, 1998
|Sinco Engineering S.P.A.
|Process for the solid state polycondensation of polyester resins
|Aug 8, 1996
|Apr 28, 1998
|E. I. Du Pont De Nemours And Company
|Process for forming crystalline polymer pellets
|Oct 16, 1997
|Oct 6, 1998
|Sinco Engineering S.P.A.
|Cooling process for polyester and/or polymide resins
|Title not available
|Article "Nylon 6 Polymerization in the Solid State" by R.J. Gaymans et al, Journal of Applied Polymer Science, vol. 27, 2513-2526 (1982).
|Presentation "Advanced PET Bottle-to-Bottle Recycling" by A. Christel, Polyester 2000 World Congress, Nov. 28-Dec. 1, 2000, Zurich, Switzerland.
|Thesis "Impianto di Postpolicondensazione di Polietilentereftalato" G. Ghisolfi (1984-85).
|Citing Patent
|Filing date
|Publication date
|Sep 14, 2001
|Nov 22, 2005
|Mitsubishi Gas Chemical Company, Inc.
|Crystallization process and apparatus therefor
|Feb 10, 2011
|Sep 22, 2015
|Krones Ag
|Method and plant for the manufacture of container preforms
|Sep 14, 2001
|Sep 25, 2003
|Takahisa Furuya
|Crystallization process and apparatus therefor
|May 19, 2005
|Mar 2, 2006
|Parker Joseph L
|Waste treatment system for PTA and PET manufacturing plants
|Oct 27, 2008
|Apr 9, 2009
|Wellman, Inc.
|Methods for Making Polyester Resins in Falling Film Melt Polycondensation Reactors
|Feb 10, 2011
|Aug 18, 2011
|Krones Ag
|Method and plant for the manufacture of container preforms
|Feb 17, 2011
|Sep 21, 2011
|Device and method for manufacturing container preforms
|Jan 5, 2011
|Feb 1, 2012
|Krones AG
|Device and method for manufacturing container preforms
|U.S. Classification
|528/503, 528/492, 422/251, 422/253, 422/245.1
|International Classification
|Cooperative Classification
|European Classification
|Aug 25, 2003
Owner name: UOP LLC, ILLINOIS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MCGEHEE, JAMES F.;BOVERI, GIUSEPPINA R.;SECHRIST, PAUL A.;REEL/FRAME:013905/0129;SIGNING DATES FROM 20020124 TO 20020129
|Aug 20, 2007
|Fee payment
Year of fee payment: 4
|Oct 24, 2011
|Maintenance fee reminder mailed
|Mar 9, 2012
|Lapse for failure to pay maintenance fees
|May 1, 2012
|Expired due to failure to pay maintenance fee
Effective date: 20120309


text:
Harry Redknapp hopes to return to manage at the top level in England after starting the Premier League season without a club.
The 65-year-old was sacked by Tottenham in June after four years in charge at White Hart Lane.
While insisting he is not rushing to return, Redknapp admits he would come back for the "right job" which would most likely be in England.
He said: "I've managed good players at Tottenham and at Portsmouth and at West Ham.
"When you've been working with top players it's very difficult to work with inferior players if you like. I think I am capable of managing at the very top level so we'll see what comes up."Reuse content


text:
Tatarko gets reacquainted with school board procedures
When the USD 383 school board selected Beth Tatarko as its newest board member, she stepped into a different situation than her first board stint.
Among other things, Tatarko, a board member from 2005 to 2009, returns to a shakier financial situation.
When she left, the district had just experienced its initial decrease in state funding when the nationwide recession hit during the 2008-09 school year. The base state aid per pupil (BSAPP) has decreased from $4,400 in 2008-09 to $3,780 this school year. The state legislature approved a fiscal year 2013 budget Sunday that increases the BSAPP by $60 as a start to making up for the $620 per pupil cut.
"Since I left, there has been a 17-percent reduction in state funding. That's very difficult for a school district to handle," Tatarko said.
Tatarko said she is concerned about the impact of the tax bill signed by Gov. Sam Brownback to reduce personal income tax rates and eliminate taxes on non-wage income. The bill cuts state income taxes by around $3.7 billion over five years.
Tatarko said reducing that revenue would put more pressure on local property taxes to fund education. "Basically, the state is pushing its responsibility down to local government for more funding," she said.
Tatarko said this is a bad situation because some districts can raise money — those in Johnson County, for example, and some western Kansas counties with oil fields — while others would struggle.
Tatarko said she read through materials concerning the district's needs for the next school year, and mentioned that the teachers needed would be of the most importance.
"The big one would be to maintain class size that is sustainable according to funding levels and is good for teachers and students as far as learning," she said.
Other than the financial situation, Tatarko said the big topics on the agenda are maintaining the quality of the district's buildings and possible changes in school schedules.
Tatarko served as the board president when the board approved the bond issue in 2008, but mostly she has viewed the construction process as a taxpayer. She said the project has gone well from afar.
"With a couple of minor exceptions, it has been very phenomenal for the district," she said. "Our buildings were in dire need and they needed a facelift."
Tatarko said trips to facilities are being arranged as well as talks with principals and parents.
She said she has received positive feedback for the most part, calling Woodrow Wilson Elementary a high priority based on previous stories of the district's struggles.
Tatarko emphasized the importance of capital outlay funds being used to maintain the buildings in the long-term. She said proper staffing of maintenance personnel will help that process, although it won't be easy.
"It's going to be a big challenge if the state doesn't provide the funding that it should," she said.
Tatarko said she likes how the board has handled looking into senior early release, start time for all schools, open and closed lunch at MHS, and the elementary and high school schedules. The board has approved the assembling of committees with district, board and community representatives to develop proposals for the topics first discussed at the board's winter retreat.
Tatarko said the communities of Manhattan and Ogden are very involved in the education process.
"We've always tried to include multiple stakeholders in the process, and that's something I like and value," she said. Tatarko said the process will involve getting feedback, determining the pros and cons of the pathways, and looking at other model programs.
Tatarko admits that despite keeping up with the board's activities, she has bit of a learning process ahead. She said she expects to meet with Supt. Bob Shannon soon.
"I'm sure Dr. Shannon has a to-do list for me," she said.
However, Tatarko will rely on her previous experience to help in the transition. She said a new board member goes through a two-day, six- to eight-hour orientation that covers topics including budgets, negotiations, policies and facilities.
"A lot of those things I've already done, so I think the refresher course will be a lot shorter," she said.
Tatarko said she doesn't have a personal agenda or platform she's looking to promote. She has said she intends to serve only the remainder of former president Doug Messer's term, which ends in June 2013.
"I just want to make sure I can contribute as a steward and be a leader in the process," she said.
Tatarko described the style she brings as a board member as collaborative, accessible, open to new ideas and energetic.
"I like to get things done," she said.


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Popular property highlights
Located in Cadore, Belvedere is within a 5-minute walk of Eyeglass Museum. This 19-room, 4-star hotel has free in-room WiFi along with free self parking and a fitness center. It's in central Pieve di Cadore and also within a 20-minute drive of Church of Sant'Orsola and Cibiana di Cadore Town Hall.
Free buffet breakfast is included with your stay and awaits you each morning from 7:30 AM to 10:00 AM. Savor a meal from the comfort of your room with room service, or grab a bite to eat at the onsite restaurant.
The 19 accommodations feature furnished balconies and afford space to spread out with dining areas. 20-inch LCD TVs come with digital channels, and guests can stay connected with free WiFi. Beds sport down comforters and bathrooms offer rainfall showers, hair dryers, and free toiletries. Sofa beds, minibars, and safes are also standard.
Guests of Belvedere enjoy a fitness center, free WiFi in public areas, and a kids' club. You can take advantage of free parking if you drive. Front-desk staff can assist with concierge services and luggage storage. Other amenities at this family-friendly hotel include coffee/tea in a common area and a TV in a common area.
Property features
- Free buffet breakfast
- Free WiFi in rooms and public areas
- Free parking
- Onsite dining
Hotel Amenities
Hotel Amenities
The hotel offers a restaurant. A complimentary breakfast is offered each morning. Wireless Internet access is complimentary. This family-friendly hotel also offers a fitness center, ski storage, and coffee/tea in a common area. Limited complimentary onsite parking is available on a first-come, first-served basis.
- Children's club (surcharge)
- Total number of rooms - 19
- Number of floors - 3
- Babysitting or childcare
- Coffee/tea in common areas
- Free breakfast
- Concierge services
- Elevator/lift
- Fitness facilities
- Front desk (limited hours)
- Free WiFi
- Parking (limited spaces)
- Luggage storage
- Restaurant
- Year Built 1920
- Free RV, bus, truck parking
- Free self parking
- Ski storage
- Number of buildings/towers - 1
- Television in common areas
- Use of nearby fitness center (discount)
Family Friendly Amenities
- Family Hotel
- Free Wi-Fi
- Babysitting or childcare
- Separate dining area
- Sofa bed
- Cribs/infant beds (complimentary)
Available in all rooms: Free WiFi
Available in some public areas: Free WiFi
Free self parking, Free RV, bus, truck parking, Parking (limited spaces)
Room Amenities
Belvedere offers 19 accommodations with minibars and safes. Rooms open to furnished balconies. Accommodations have separate dining areas and are furnished with double sofa beds. Beds feature down comforters. 20-inch LCD televisions come with digital channels. Bathrooms include shower/tub combinations with rainfall showerheads, bidets, complimentary toiletries, and hair dryers.
Guests can surf the web using the complimentary wireless Internet access. Business-friendly amenities include desks and phones. Housekeeping is provided daily.
- Furnished balcony
- Phone
- Minibar
- Daily housekeeping
- Private bathroom
- Free toiletries
- Hair dryer
- Shower/tub combination
- Bidet
- Rainfall showerhead
- In-room safe
- Desk
- Sofa bed
- Digital TV service
- Free WiFi
- Separate dining area
- Blackout drapes/curtains
- Room service (limited hours)
- Sofa bed size
- Free cribs/infant beds
- Down comforter
Where to Eat
Belvedere has a restaurant on site.
Room service (during limited hours) is available.
A complimentary buffet breakfast is served each morning between 7:30 AM and 10:00 AM.
Nearby Things to Do
Recreational amenities at the hotel include a fitness center.
The recreational activities listed below are available either on site or nearby; fees may apply.
- Golfing nearby
- Downhill skiing nearby
- Cross-country skiing nearby
- Snowboarding nearby
- Snowshoeing nearby
- Snowmobiling nearby
- Mountain biking nearby
- Skydiving nearby
- Ski lessons available nearby
- Ski equipment rental shops nearby
- Golf lessons available nearby
- Sledding nearby
- Snow tubing nearby
- Bicycle rentals on site
- Free bicycles nearby
- Hiking/biking trails on site
If you have requests for specific accessibility needs, please note them at check-out when you book your room.
- In-room accessibility
Hotel Policies
Check-in time starts at 2:30 PM
Check-in time ends at 10 PM
Special check-in instructions:
Check-out time is 10:30 AM
Payment types
Children and extra beds
- Children are welcome.
- Kids stay free! Children 3 years old and younger stay free when using existing bedding.
- Free cribs (infant beds)!
- Pets allowed
- 1 per room (up to 5 kg)
You need to know
Extra-person charges may apply and vary depending on property policy.
Government-issued photo identification and a credit card or cash deposit are required at check-in for incidental charges.
Special requests are subject to availability upon check-in and may incur additional charges. Special requests cannot be guaranteed.
Service animals exempt from fees/restrictions
Noise-free rooms not guaranteed
Parking height restrictions apply
- Resort fee
Hotel Name
- Belvedere Hotel Pieve di Cadore
- Belvedere Pieve di Cadore
We should mention
All guests, including children, must be present at check-in and show their government-issued photo ID card or passport. Cash transactions at this property cannot exceed EUR 2999.99, due to national regulations. For further details, please contact the property using information in the booking confirmation. A resort fee is included in the total price displayed. Children 3 years old and younger stay free when occupying the parent or guardian's room, using existing bedding.


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Iphone 6/6S Plus Hard-Shell Case In Hydrangea Embossed Python
Our popular hard-shell case now designed for iPhone 6/6s Plus. Crafted from embossed python leather. This case will be an essential item for those who appreciate craftsmanship as much as on-the-go style.
- Full-Grain Embossed Python Leather
- For iPhone 6 Plus and iPhone 6s Plus
- Color case ships as pictured
- Cutouts that allow access to controls and ports
- Personalization available up to three initials
- Size: 3" x 6 1/4" L x 1/4" D
Product code: I6P-PYY-HYD
Order Processinggigi-new-york orders are processed within 3-4 Business Days. *Processing times may be delayed during sale and holiday seasons.
ShippingFree ground shipping is available on all orders shipped within the U.S., shipping costs are non-refundable.
Returngigi-new-york want you to be completely happy with your purchase. If you are not satisfied for any reason, gigi-new-york will gladly accept your return of unwashed, unworn, unaltered or defective merchandise within 21 days (Items must be returned in their original packing so please keep the box and other packing materials until you have decided on your purchase. Personalized items are not available for returns or exchanges, unless in the event there is an error on the part of GiGi New York i.e; misspelling). Merchandise must have all tags attached. All returns must be accompanied by a copy of the packing slip included with your shipment. Failure to include this form will result in prolonged processing of your return. All items marked FINAL SALE cannot be returned and exchanged at any time.
To return a gigi-new-york item, we kindly ask you to Login to your Orchard Mile account, and select the order you would like to return. Within the order details page, click "Request Return" for each item you would like to return..
gigi-new-york reserves the right to deny a refund if the merchandise does not meet the return policy requirements. Any merchandise received outside of the return window will be returned to the customer.
Please note: We cannot confirm delivery of your return but we will send a confirmation email that your credit card has been refunded within approximatly 10-14 business days of receiving your returned merchandise.


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anti-Human RORA Antibodies:
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Association between RORA gene polymorphisms and the DSM-5 posttraumatic stress disorder symptoms in male earthquake survivors in China.
The RORA intronic SNP rs11632098 was associated with greater odds of reporting depressive symptoms in older adults.
A common SNP in the RORA gene (rs2899663) was associated with a 21% reduced odds of placental abruption.
In a Han Chinese population, an association between RORA gene variation and depression personality trait was found.
associations between NR1D1 (show NR1D1 Antibodies), RORA and RORB (show RORB Antibodies) genes and bipolar disorder.(
the data presented in this report are that RORA is linked in important ways to molecules that could be playing important roles in the AD etiology.
Retinoic acid receptor-related orphan receptor-alpha (RORalpha) may be a potential risk gene for chronic obstructive pulmonary disease (COPD (show ARCN1 Antibodies)).
RORA variants were associated with dyslipidemia and obesity in Mexicans.
RORA rs12912233 alone might be a possible risk variant for epilepsy in Malaysian Chinese, but that, together with RORA rs880626 and SCN1A (show SCN1A Antibodies) rs3812718, this polymorphism may have a synergistic effect in the epilepsy risk in Malaysians.
A cluster of RORA SNPs around rs2083074 showed an effect on psychic adverse drug reactions in the bipolar disorder.
RORalpha regulates pathologic retinal angiogenesis by modulating SOCS3 (show SOCS3 Antibodies)-dependent inflammation
This study showed that spontaneous Rora mutations causing cerebellar pathology are impaired in motor functions during the neonatal period.
the inhibition of NF-kappaB (show NFKB1 Antibodies) by melatonin, but not that of NLRP3 (show NLRP3 Antibodies), was blunted in RORalpha (sg/sg) mice, indicating that functional RORalpha transcription factor is necessary for the initiation of the innate immune response against inflammation.
Rora induces the mRNA level of antioxidant enzymes, superoxide dismutase 2 (show SOD2 Antibodies) and glutathione peroxidase 1 (show GPX1 Antibodies), through the Rora response elements located in the upstream promoters of Sod2 (show SOD2 Antibodies) and Gpx1 (show GPX1 Antibodies).
The nuclear receptors retinoic acid receptor (show RARA Antibodies)-related orphan receptors-alpha and gammat (RORalpha and RORgammat) play critical roles in the development of TH17 cells.
RORalpha is a transcriptional activator of insulin (show INS Antibodies).
Corl2/Skor2 (show SKOR2 Antibodies) has a role in regulating cerebellar Purkinje cell differentiation in a pathway involving RORalpha
RORalpha is a key regulator of diurnal rhythm and fasting induction of CYP8B1 (show CYP8B1 Antibodies), which regulates bile acid composition and serum and liver cholesterol levels.
This study suggests an autocrine Wnt5a (show WNT5A Antibodies)-Ror signaling pathway that directs sympathetic axon branching during target innervation.
Disruption of Roralpha1 and cholesterol 25-hydroxylase (show CH25H Antibodies) expression attenuates phagocytosis in male Roralphasg/sg mice.
The protein encoded by this gene is a member of the NR1 subfamily of nuclear hormone receptors. It can bind as a monomer or as a homodimer to hormone response elements upstream of several genes to enhance the expression of those genes. The specific functions of this protein are not known, but it has been shown to interact with NM23-2, a nucleoside diphosphate kinase involved in organogenesis and differentiation, as well as with NM23-1, the product of a tumor metastasis suppressor candidate gene. Four transcript variants encoding different isoforms have been described for this gene.
, nuclear receptor ROR-alpha
, nuclear receptor RZR-alpha
, nuclear receptor subfamily 1 group F member 1
, retinoic acid receptor-related orphan receptor alpha
, retinoid-related orphan receptor alpha
, thyroid hormone nuclear receptor alpha variant 4
, transcription factor RZR-alpha
, retinoid-related orphan receptor-alpha


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Over the past two years Mark has been working on a case for my company with regards to an Intellectual Property dispute. I can only say that he and his firm are the most ethical, professional, and competent lawyers I have had to work with. If anyone needs IP law firm then I would highly recommend Weatherly, Kerven, and Seigel.


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|Criticism, interpretation, etc
|Additional Physical Format:
|Online version:
Smith, Paul Julian.
Television in Spain.
Woodbridge : Tamesis, 2006
|Named Person:
|Pedro Almodóvar; Pedro Almodóvar
|Document Type:
|All Authors / Contributors:
Paul Julian Smith
|9781855661363 1855661365
|OCLC Number:
|176 pages : illustrations ; 24 cm.
|1. The Approach to Spanish Television Drama of the New Golden Age: Remembering, Repeating, Working Through [Cuéntame cómo pasó --
Tell Me How it Happened, 2001-] --
2. The Classic Serial: Public Service, Literarity, and the Middle-brow [Fortunata y Jacinta, 1980 and La Regenta, 1995] --
3. Chronicles of a Village: Francoist Newsreel, Feature Film and Television [Crónicas de un pueblo --
Chronicles of a Village, 1971-4; Cine de barrio --
Neighbourhood Cinema --
4. The Urban Sitcom: Community, Consumption, Comedy [Aquí no hay quien viva --
No one Can Live Here, 2003-] --
5. Telebasura: Trash, Talk, and Reality [Crónicas marcianas, 1997-2005] --
6. Almodóvar on Television: Industry, Thematics, Theory --
7. Conclusion: A Day in the Life of Spanish Television.
|Series Title:
|Colección Támesis., Serie A,, Monografías ;, 232.
|Paul Julian Smith.
|More information:
Any follower of Spanish cinema who turns to television finds that the locally produced programs are as creative and original as any feature film. This book gives close readings of TV programmes broadcast since the 1970s. It examines TV channels, production companies, governments, and the role of the press, academy, and audience. Read more...
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Essential reading for anyone working in the field. SCREEN
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Related Subjects:(11)
- Almodóvar, Pedro -- Criticism and interpretation.
- Television programs -- Spain.
- Motion pictures and television -- Spain.
- Almodóvar, Pedro.
- Motion pictures and television.
- Television programs.
- Spain.
- Televisie.
- Spanje.
- Film.
- Spanien.
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by fadedreq updated 2009-04-16


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51 7th AvenueApt. 1
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Additional features of this building include: Basement storage, Stroller Parking on Garden Level.
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Question about facial fat transfer. Any suggestions?
How is that usually done? Is the fat taken out with a syringe, no sugery required? Or, does the patient need to lipo? I'm skinny, and have no areas to lipo but have enough to suck out with a syringe. I'm interested in cheek/nasal labia fold augmentation. I'm fairly young (35), and want something a little more permanent. Thanks!
Doctor Answers 7
Fat Facilitates Phenomenal Improvement
Great question. For no surgery to occur, you may consider injectable fillers "off the shelf" such as Juvederm, VOLUMA, Restylane and/or Radiesse. While they help fill and stimulate collagen, they do not have the same effect as fat grafting. Fat contains stem cells which helps improve the quality and texture of your skin as well as provide volume. To obtain the fat, liposuction is performed. Common areas from which fat may be obtained include the abdomen, love handles and thighs. Fat can not only be used to help augment cheeks and the nasolabial folds but may also be used to enhance the breast (autoaugmentation) and buttocks (Brazilian butt lift aka BBL). I recommend that you schedule a consultation to have an in-depth discussion on what options may be best for you.
Facial fat transfer
I perform all my facial fat transfers under local anesthesia with oral medications to relax you. Fat is usually obtained from the lower abdomen, flanks or thigh areas. No 'surgery' per se is performed- as small openings are made around the areas that the fat will be taken from and a harvesting cannula is uses to suck out the fat with a small syringe. Its all performed manually, meaning that there are no machines used to obtain the fat.
Once the fat is obtained. It is cleaned and then injected into the areas of the face that need the augmentation. More fat is placed than is needed to ensure the longevity of results.
Patients appear 'restaurant' ready by about 7days after the procedure. The benefits of the fat transfer also extend a little further than just volume replacement. There are stem cells in the transferred fat that tends to rejuvenate the overlying skin on the face, resulting in improved skin texture as well.
Once the fat is obtained. It is cleaned and then injected into the areas of the face that need the augmentation. More fat is placed than is needed to ensure the longevity of results.
Patients appear 'restaurant' ready by about 7days after the procedure. The benefits of the fat transfer also extend a little further than just volume replacement. There are stem cells in the transferred fat that tends to rejuvenate the overlying skin on the face, resulting in improved skin texture as well.
Web reference: http://www.drmadnani.com/4-facts-you-need-to-know-about-fat-transfer/
Fat Grafting To Face
Fat transfer from the tummy or thighs to the face is an excellent option for people of all ages. Younger patients can enhance their cheekbones or lips with fat that is natural and long lasting. As we age, our face deflates, losing fat, causing sagging skin to look more obvious. Fat grafting to the face rejuvenates the face with biological filler, your own fat! I frequently use fat transfer to my facelift patients to enhance and prolong the result. Depending on the individual, one treatment does the trick, but sometimes secondary touch ups are needed. Be sure to consult with a board certified plastic surgeon. Good luck!
You might also like...
Fat Grafting Techniques
The technique for fat grafting depends on the area(s) being grafted and the amount of fat needed. In all cases, fat needs to be harvested from other areas of the body. For example if you want fat grafting for your face, the face can be harvested from around your belly button or your thigh. The amount of fat harvested will likely not make a difference in those areas as a minimal amount of fat is needed for the face. However, if you are having a BBL, then a considerable amount of fat is required - usually from abdomen, flanks, lower back and even the thighs. In this case, there will be a difference in the areas harvested as the fat removed will lead to a thinner contour. The best option is to set up an in-person consultation to discuss your options.
Good Luck.
Good Luck.
Web reference: http://www.ShaferPlasticSurgery.com
Facial fat grafting
Facial fat grafting can be done in various ways. The fat is usually harvested by hand with a syringe and canula after numbing the area with tumescent lidocaine saline solution. I use a microcanula to avoid large pieces of fat transfered around especially delicate areas of the face. The fat is then centrifuged and the pure fat is transferred to a very small syringe and a microcanula is is used to inject it into the desired areas. The fat then must attain a blood supply and usually not all the fat does this, the fat that doesn't get a blood supply doesn't stick around and is metabolized by your body naturally.
Thank you
Dr. Schwarcz
Thank you
Dr. Schwarcz
Facial fat transfer
Fat can be harvested usually from the abdomen, waist or thigh through a small incision using a syringe. It can be done under local.
Web reference: https://www.stevenwallachmd.com/non-invasive-procedures/fat-injections/
Facial fat grafting
Hello and thank you for your question. Fat grafting to the face can add permanent volume to the face in favorable areas in the appropriate patient. Harvesting the fat for grafting is very easy and can be performed with a hand held syringe in the office. The most important aspect is to find a surgeon you are comfortable with. I recommend that you seek consultation with a qualified board-certified plastic surgeon who can evaluate you in person.
Best wishes and good luck.
Richard G. Reish, M.D.
Harvard-trained plastic surgeon
Best wishes and good luck.
Richard G. Reish, M.D.
Harvard-trained plastic surgeon
These answers are for educational purposes and should not be relied upon as a substitute for medical advice you may receive from your physician. If you have a medical emergency, please call 911. These answers do not constitute or initiate a patient/doctor relationship.


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Evidence to the Fourth Independent Review of the Work Capability Assessment
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For the first five years of Employment and Support Allowance, the government has to hold an independent review of the test used (the Work Capability Assessment). They have appointed Dr Paul Litchfield to carry out the latest review. We asked people to tell us about their experiences of undergoing the Work Capability Assessment and have written our response based on what they said.


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Customization information
Please include requests, questions, color or size information or gift card message.
Be sure to check out our guitar pick earrings and necklaces. Bamboo bead with a segment of Origami paper. We added a purple Swarovski crystal. A durable finish was added to protect the paper. Hand wire wrapped, the bamboo bead is 1 5/8" long x 3/4" wide x 1/4" thick. Overall this pendant is approximately 2 1/4" long.The pendant will arrive on an adjustable waxed cotton cord necklace unless otherwise specified. All of our items are individually handcrafted in our studio in Albuquerque, New Mexico We try to honor your special requests. Email for more details. We do not offer engraving.All designs, text and photos copyright Eclectic Elements 2002-2009 and may not be reproduced in whole or in part without prior, express written permission. All rights reserved.


text:
Around the Nation
Iowa Residents Hope New Levee Will Save Hamburg
In southwest Iowa, crews have been working to save a tiny town from the rising Missouri River. Hamburg, Iowa, is of particular concern, following the breach of a nearby levee. Crews are building up another earthen levee just outside of town.
RENEE MONTAGNE, host:
In Iowa, crews have been working through the night, racing against the clock to save a tiny town along the rising Missouri River. Communities in several states are being threatened by heavy rains and melting snow that have swelled the river this year. Hamburg, Iowa is of particular concern this week, following the breach of a nearby levee. And now officials are working to build up a second earthen levee just outside of town. From Hamburg, Iowa Public Radio's Sarah McCammon reports.
SARAH MCCAMMON: Dave Ray's voice is hoarse. Yours would be too if you'd been shouting over noisy earth-moving equipment at sites all along the Missouri River all month. Ray is a geotechnical engineer with the U.S. Army Corps of Engineers in Omaha. He says crews have been racing to build up the earthen levee.
Mr. DAVE RAY (Army Corps of Engineers): They're raising it up another three feet from the original design. And they've got good clean material close to the site, so that cuts down on haul distance and time. And he's working 24 hours to raise the thing up.
MCCAMMON: So I'm on the western side of Hamburg, about a quarter mile or so maybe west of town, surrounded by kind of a soybean field, looks like, and a lot of earth movers, just moving dirt, kind of digging up this field and turning it in - the dirt into a wall that hopefully will hold back the floodwaters.
Mr. RAY: So we've got every confidence that we'll get ahead of it enough to stop the water from coming into Hamburg and flooding the area. So...
MCCAMMON: How confident are you that this flooding will hold?
Mr. RAY: Real confident. They're placing it as well as we can with the equipment and time we have.
MCCAMMON: Melting snowpack in the Rocky Mountains way above normal has prompted the Corps to release water from upstream reservoirs. And that's causing flooding headaches downstream, in the Dakotas, Nebraska, Iowa and Missouri. Recent heavy rains in Montana and North Dakota aren't helping either. Throw in this levee breach, and the town of Hamburg could be in trouble.
Twenty-two-year-old Nathan Beach drove here from Lincoln, Nebraska, where he's attending college. He came to see the town for what he fears will be the last time. Beach has lots of memories traveling here from his childhood home in eastern Iowa.
Mr. NATHAN BEACH: I'm here to visit Hamburg because I think it might be flooding soon and I want to see the place where I came here as a child. My grandparents used to live here. My grandfather used to have a watch shop here. So I want to visit the town, see where their house used to be, and maybe see it before it all got inundated.
MCCAMMON: The town is mostly quiet now. At least half of its 1,200 or so residents have already left. But down the road at the elementary school, volunteers are chipping away at a mountain of sand in the parking lot, filling burlap bags one shovelful at a time.
Tyler Woodward says many of those who remain say their homes are safe, but they want to do something to help their neighbors.
Mr. TYLER WOODWARD: We live up on the hill, so we're fine there. We evacuated our business down there on the bottom. Most farmers moved out all their equipment and stuff out of their shops. And now all the homes are evacuated down there. Behind the levee and the south end of town is evacuated pretty much too, so...
MCCAMMON: It's not clear how long this town will stay largely empty. Predictions are that Missouri River levels will remain unusually high well into August.
For NPR News, I'm Sarah McCammon, in Hamburg, Iowa.
Copyright © 2011 NPR. All rights reserved. Visit our website terms of use and permissions pages at www.npr.org for further information.
NPR transcripts are created on a rush deadline by Verb8tm, Inc., an NPR contractor, and produced using a proprietary transcription process developed with NPR. This text may not be in its final form and may be updated or revised in the future. Accuracy and availability may vary. The authoritative record of NPR's programming is the audio record.


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Ad ID: 54519
Buffet Restaurant for Sale Auckland Central
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Buffet Restaurant for Sale Auckland CentralHuge restaurant in a prime Central location licensed for 120 people with two separate rooms for conference & VIP meetings
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Ron Vazirani - DDI: (09) 555 6036 or MOB: 021 294 2978
Ref: EL00113
Timestamp: 20170111054510
Business Resources
- Anil Vazirani
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|+64 21 0277 8149|Phone Anil Vazirani
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text:
307 Iowa Street, Whitehall 49461
See more homes for sale in Whitehall, MI
This property has been Sold!
04/25/2016 at $145,000
Lovely Whitehall four bedroom 2 bath home has spacious rooms throughout. Home offers an open kitchen with pantry and breakfast nook, formal dining, and a main floor family room with fireplace. Huge living room with field stone fireplace, 21x16 master bedroom with an extra storage room that could easily be converted to a master bath. Entertaining out doors is a snap with spacious decks, play set and private fenced in back yard. Close to Schools and just minutes to the ball park. Peaceful setting on this large lot in a quiet neighborhood
Property Information
- Status
- Sold
- Address
- 307 Iowa Street
- City
- Whitehall
- Zip
- 49461
- County
- Muskegon
- Township
- Whitehall City
- Total Finished SqFt
- 2,430
- Above Grade SqFt
- 2,430
- Garage
- 2.0
- Garage Desc.
- 2, Attached
- Water
- Public
- Sewer
- Public
- Year Built
- 1952
- Taxes
- $2,596
Rooms and Land
- MasterBedroom
- 16X21 2nd Floor
- Bedroom2
- 10X13 1st Floor
- Bedroom3
- 10X12 1st Floor
- Bedroom4
- 17X18 2nd Floor
- Family
- 13X23 1st Floor
- FormalDining
- 10X12 1st Floor
- Kitchen
- 13X16 1st Floor
- Living
- 13X19 1st Floor
- Basement
- Full Basement
- Cooling
- Window Unit
- Heating
- Forced Air, Natural Gas
- Acreage
- 0.5
- Lot Dimensions
- 120x180
- Appliances
- Dishwasher, Dryer, Garbage Disposal, Range, Refrigerator, Washer
- Fireplace Desc.
- Family, Living
- Features
- Ceiling Fans, Ceramic Floor, Garage Door Opener, Humidifier, Laminate Floor, Wood Floor
- Exterior Materials
- Brick, Vinyl
- Exterior Features
- Deck(s), Fenced Back, Play Equipment, Porch(es)
Listing Video for 307 Iowa Street, Whitehall MI 49461
Mortgage Calculator
Listing Broker
Listing Courtesy of Coldwell Banker Woodland Schmidt Whitehall
Office Address 202 E Colby St.
Listing Agent Sandra Morningstar
Listings last updated: . Some properties that appear for sale on this web site may subsequently have been sold and may no longer be available.
Our Michigan real estate agents can answer all of your questions about 307 Iowa Street, Whitehall MI 49461. Real Estate One, Max Broock Realtors, and J&J Realtors are part of the Real Estate One Family of Companies and dominate the Whitehall, Michigan real estate market. To sell or buy a home in Whitehall, Michigan, contact our real estate agents as we know the Whitehall, Michigan real estate market better than anyone with over 100 years of experience in Whitehall, Michigan real estate for sale.
The data relating to real estate for sale on this web site appears in part from the IDX programs of our Multiple Listing Services. Real Estate listings held by brokerage firms other than Real Estate One includes the name and address of the listing broker where available.
IDX information is provided exclusively for consumers personal, non-commercial use and may not be used for any purpose other than to identify prospective properties consumers may be interested in purchasing.
All information deemed materially reliable but not guaranteed. Interested parties are encouraged to verify all information. Copyright© 2017 MichRIC LLC, All rights reserved.