Anyone know what it's for? We're not getting our TBR - Abbey Street pedestrian crossing are we? Too much to hope for?!
I wonder how the C10 will be diverted.
My guess would be, right into Druid St., (if Abbey St. is open as far as the rail bridge), then left into TBR, right into Decima St./Bermondsey St., left into Long Lane.
If Abbey St. is closed at Jamaica Rd., then bear left into Tanner St. from Jamaica Rd., follow Druid St. to the right, then left into TBR and as before.
Does anybody know why Abbey St is being closed?
If it IS only the part of the road under the bridge that is closed then there are a multitude of ways to get around it, maybe not for a bus, but certainly cars etc.
e.g. L. into St. James, R. Dockley, R. Thurland, L. Spa, R. Enid, L. into Abbey.
Alternatively, R. Druid, L. Tanner, L. Riley, R. Abbey.
"I am writing to let you know that from Monday 8 April, bus route C10 will be diverted for about three months. This is due to the closure of Abbey Street at the Old Jamaica Road junction, as a result of railway bridge works being carried out on behalf of Southwark Council and Network Rail.
Buses will be diverted in both directions via Southwark Park Road, Grange Road, Tower Bridge Road, Bricklayers Arms and Great Dover Street, and will not serve Jamaica Road (between Southwark Park Road and Abbey Street), Bermondsey Station, Abbey Street and Long Lane.
Could push a fair bit more traffic onto the other east - west routes, especially Grange Road and Jamaica Road / Tanner Street. The routes of the 1 and 188 worryingly (though the latter is fairly hopeless). Abbey Street'll be a nice, quiet place to live for the next couple of months though.
It's going to be horrendous for those of us who live down these alternative roads. Every morning and evening these roads are clogged up anyway, the roads have all been narrowed which already causes jams.


text:
Afterhouse: Bringing hope to a Detroit neighborhood
Tags: Economic Development, Taubman College of Architecture and Urban Planning
Afterhouse participants work to repurpose a burned-out house
In a Detroit neighborhood shared by Bangladeshi, Polish immigrants, longtime African-American residents and young artists, something is happening.
"I didn't think it would be so powerful," U-M's Steven Mankouche says of the Archolab-Afterhouse project he and his partner, artist Abigail Murray, are leading. Its goal is to repurpose a burned-out house as a semi-subterranean, passive geothermal greenhouse that will serve the neighborhood.
The project at 3347 Burnside Street, just north of Hamtramck, has been creating excitement among residents — and hope – all year.
"We see Afterhouse as a provocative/proactive response to blight and community grown food."
– Steven Mankouche, Associate Professor of Architecture
"They see people fixing up houses, painting, but nobody here builds something new. I think it shows a certain investment, a commitment to the place," says Mankouche, associate professor of architecture, Taubman College of Architecture and Urban Planning.
In contrast to urban agriculture projects that require lots of space, Afterhouse is discreet, almost hidden, because it maintains the scale of the original house. Further, the growing climate in the house does not require the expense of active heating in the winter or cooling in the summer.
Hand demolition work began in spring 2014. The cement-steadied foundation serves as the base for an upright frame of repurposed structural lumber. The sturdy wood studs were salvaged from the 1920s home, then de-nailed this past summer. The frame was covered with clear polycarbonate plastic sheeting this fall. The basement is filled with dirt for planting. Current floor drains are perfect to serve the greenhouse project, Mankouche says.
"The idea is to grow crops in a climate comparable to a northern Mediterranean climate. Olive trees, pomegranates, rosemary, certain citrus, kiwi, pistachio — we may try mangoes," he says.
Their Archolab group, which oversees Afterhouse, raised $14,838 through Hatchfund, a non-profit, crowd-source funding organization. The group also won $7,500 through a joint U.S. Department of Economic Development-Michigan State University Regional Economic Innovation grant, Taubman College seed funding as well as support from Undergraduate Research Opportunity Program students. They include Travis Williams, senior architecture major from Detroit and Eddie Sachs, a Taubman College senior and Detroit native who grew up near the project site.

redpajama_set_name: RedPajamaCommonCrawl


text:
multiplication >
Para vs. Por Sun May 04 2008 11:38:34 GMT+0000 (Coordinated Universal Time)
Vocab words 1-16 Mon Jan 19 2009 21:49:58 GMT+0000 (Coordinated Universal Time)
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Spanish 311 verbs that mean to run Mon May 14 2018 16:36:55 GMT+0000 (Coordinated Universal Time)
Microbiology/Infectious Diseases II Mon May 14 2018 16:37:19 GMT+0000 (Coordinated Universal Time)
Latin Vocabulary Words: dulcis - evoco Mon May 14 2018 16:36:16 GMT+0000 (Coordinated Universal Time)
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Geometry - Deductive Reasoning Mon May 14 2018 16:36:26 GMT+0000 (Coordinated Universal Time)
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spelling cs Mon May 14 2018 16:36:39 GMT+0000 (Coordinated Universal Time)
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nat boards I b Mon May 14 2018 16:36:44 GMT+0000 (Coordinated Universal Time)
Exercise sur le Subjontif Mon May 14 2018 16:36:48 GMT+0000 (Coordinated Universal Time)
subjontif
subjuctif
subjunctif
Microbiology test # 3 (readings F.C) Mon May 14 2018 16:36:48 GMT+0000 (Coordinated Universal Time)
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Flemmish words 7 Mon May 14 2018 16:36:50 GMT+0000 (Coordinated Universal Time)
flemmish
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Fourth Grade Math Vocabulary Mon May 14 2018 16:36:54 GMT+0000 (Coordinated Universal Time)
Renal and GI Mon May 14 2018 16:36:56 GMT+0000 (Coordinated Universal Time)
VTMC 236 Epidemiology Midterm Mon May 14 2018 16:36:59 GMT+0000 (Coordinated Universal Time)
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affixes
gsl43 Mon May 14 2018 16:37:03 GMT+0000 (Coordinated Universal Time)
Deutsch Heute Einführung Mon May 14 2018 16:37:07 GMT+0000 (Coordinated Universal Time)
einfã¼hrung
8k to end 02-03 second half Mon May 14 2018 16:37:08 GMT+0000 (Coordinated Universal Time)
Module 2 Pharmacology Mon May 14 2018 16:37:08 GMT+0000 (Coordinated Universal Time)
anti-fungals
German Other Words Chapter Einführung Mon May 14 2018 16:37:10 GMT+0000 (Coordinated Universal Time)
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PDBE Growth & Development Mon May 14 2018 16:37:11 GMT+0000 (Coordinated Universal Time)
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Deutsch Heute - Einführung - Andere Wörter Mon May 14 2018 16:37:15 GMT+0000 (Coordinated Universal Time)
vocab - book Mon May 14 2018 16:37:18 GMT+0000 (Coordinated Universal Time)
Esperanto - Vere aux Fantazie Mon May 14 2018 16:37:21 GMT+0000 (Coordinated Universal Time)
vortoj
Altered Genitourinary Function Tue Oct 09 2012 13:23:59 GMT+0000 (Coordinated Universal Time)
roselyn setMNO Tue Nov 20 2007 06:43:00 GMT+0000 (Coordinated Universal Time)
AP Biology Terms Mon Dec 03 2007 01:32:03 GMT+0000 (Coordinated Universal Time)
Geometry Vocab. Ch. 2≠ Sat Dec 15 2007 04:35:18 GMT+0000 (Coordinated Universal Time)
Apex Spanish 1 - 4.3 Sun Dec 30 2007 20:56:16 GMT+0000 (Coordinated Universal Time)
SAT Vocab Most Common Words Part 2- I to Z Wed Jan 02 2008 11:43:25 GMT+0000 (Coordinated Universal Time)
Por vs Para Wed Jan 30 2008 03:41:21 GMT+0000 (Coordinated Universal Time)
Pathophysiology Sun Feb 10 2008 10:52:58 GMT+0000 (Coordinated Universal Time)
Japanese 4 Xatu Thu Mar 06 2008 14:32:28 GMT+0000 (Coordinated Universal Time)
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Spanish II Exams: Por vs Para Fri May 16 2008 17:29:24 GMT+0000 (Coordinated Universal Time)
Review for Spanish final Tue May 08 2007 07:12:32 GMT+0000 (Coordinated Universal Time)
Por V. Para Thu May 22 2008 23:38:56 GMT+0000 (Coordinated Universal Time)
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EDM Unit 6 Vocabulary Tue Jun 24 2008 17:30:16 GMT+0000 (Coordinated Universal Time)
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Numbers Thu Jul 24 2008 20:25:54 GMT+0000 (Coordinated Universal Time)
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CHM1000 Fri Aug 29 2008 00:34:20 GMT+0000 (Coordinated Universal Time)
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le temps Sun Jun 03 2007 23:39:44 GMT+0000 (Coordinated Universal Time)
My flashcard Mon Oct 13 2008 06:57:52 GMT+0000 (Coordinated Universal Time)
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3620 Chapter 8 Sun Nov 02 2008 19:15:18 GMT+0000 (Coordinated Universal Time)
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Esperanto Affixes Wed Nov 26 2008 11:53:19 GMT+0000 (Coordinated Universal Time)
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I've been in the Lab and now it's time!!
This is the mantra of Team Achieve. My team works hard at improving themselves and their bodies. Everyday I try to help the team members to learn that they can achieve things they never thought they we capable of the day before. So when they face a challenge they respond "Say I can't...and I'll do it..."


looks alright, but the screen, its too dull! the lighting on it is v. bad!!! brighten up for fucks sake!
hey guyz canany 1 of tell me where can i get free games for 3510i "FREE" via wap o gprs thank you!!!!!
Ro: Am crezut ca pot salva 150 de sms-uri cu memoria lui "mare" ca la alte mobile Nokia mistoace, (6210, 6510, 6310 etc)dar am constatat ca nu pot salva decat 50 de sms-uri. Poate ma anunta si pe mine cineva daca telefonul lui se comporta la fel.
i've just bought the phone and i think its great, colour is ok, but its cool in the dark.
The list goes on. My friends are VERY jealous bcus of my phone but I simply don't think it's a reliable phone. I'm switching to a Samsung which I really like.
I have this model about a week and i think so far is good. I had before 6210, 6150, 6510, Z5, 2618, 3210, 511. So i must say that i know telephons. No major soft problems, but i recomand you that you should wait a few mounth until you by it, because until then he will have a good soft. Polifonics tones are acceptable but total inferiors compare to others phones. It's rong about one thing: Why you have the meniu "Phone book"? Because in principal screen when you press names you enter in the phone book. It's a shity thing...Anyway, because my english is shity too, i say thats so far is a good model at low price.
well... i decided to but this phone, it's nice, almost cheap and.... it has a color screen.
i hope it will have satisfing options for backgroud etc.
Hey Ven seems as though u got a faulty one as mine doesn't do that and i've downloaded games etc.
I just bought this fone yesterday & i am pretty happy with it.The color screen is amazing.considering the price u pay the features u get r amazing.the only thing i found wierd is that once u play the games (java!)& close it,the fone gets switched off for 3-5 sec & then switches back on!Is it only with my piece or is it common?
Great phone! We hope to sell it soon in our Dutchtone Shop! Good price Vs. quality! Please keep me informed about your website?! Is there something as a newsletter, I can receive?! Thanks!
yeah Excellent phone, has many features, overall itz a gr8 phone, ut is there any Wapsite which offers free j2me games for this cell.
I'm about to buy this phone, looks very funky and the color-display rules.
Do you know how hard to get money in this year?? I think u should make good product with price around 1-5 dollar baka!
good phone have a samsung t100 . but it is feature less compared to this little number . any wap sites for funky wallpaper .
Yeh this cell phone really Rox, To many fatures..Excellent phone..
Total of 384 user reviews and opinions for Nokia 3510i.


text:
Changing Pace: Other Attributes of the Main Line Project
As the main line tour progresses I have been doing a lot of thinking about the direction of my blog posts during my seemingly endless research on the physical plant of the former Pennsylvania Railroad. In the process of producing this tour I have been ignoring a large part of the project, the towns the railroad traveled through. These places large and small developed around natural resources and manufacturing, much of which revolved around iron and steel production. The landscape of Pennsylvania, Eastern Ohio and West VA first began expanding because of natural and man-made waterways, which provided industry with a means of transportation to expand their markets. Though a major advancement, canals and rivers were subject to seasonal changes shutting down shipping with the winter freeze and summer droughts. It quickly became evident that a better mode of transportation was needed and the railroad was the answer. Politicians, lobbyists and industrial magnates fought for access to prime locations, rail lines were chartered, built and continually improved through the late 19th Century. As a result towns along the railroad boomed, people were no longer in isolated communities but part of an industrial chain that drove the American economy. With the new ability to move large quantities of raw material and finished product across the country the steel industry expanded and so did the need for labor. Immigrants came by the thousands to places scattered across the region to work the mills, mines and for the railroads. The ethnic diversity was reflected in the various churches, neighborhoods and shops that brought the familiar comforts of the old country to this new place of work. Throughout the years there have been high times and lows in many of these towns, rocked by labor disputes, natural disasters and the eventual decline of the American steel industry.
The view from Singer Street in Johnstown, Pennsylvania exemplifies the somber beauty of mill towns across Pennsylvania. Homes cling to the hillsides and business districts look toward the mill, once the focal point to the local economy. Today countless places like Johnstown are a quiet memorial to the era of steel and manufacturing across the region.
Today many of these places serve as a monument to industry and a way of life that has disappeared. The villages, company towns and entire sections of cities often look onto the mill, celebrating the pride and prosperity these now abandoned places once provided for many hard working families. I have found myself completely entranced by places like Johnstown and Braddock, places that are a fraction of their former self, wondering what it was like when these places were in their prime. In residential areas there is little uniformity from house to house with the exceptions of clusters of company housing yet all of these places look oddly the same. Frame houses on hill sides, all slightly modified over the years or just plain neglected, empty streets and brown fields, virtually deserted town squares flanked with grand commercial buildings constructed of stone and terracotta, town by town the theme repeats.
East Conemaugh was situated across from the Franklin Works of Cambria Iron, later Bethlehem Steel. The mills are gone and the rail yards empty, the Main Line of the Pennsylvania Railroad still enters town on the far side of the Conemaugh River, the final resting place of engineer John Hess who used his locomotive whistle to warn the townspeople of the impending destruction of the great flood of 1889.
Like much of my work, this imagery is an observation, part of connecting the dots to understand a particular place or landscape. To many its a bleak and depressing place, I am often asked why bother visiting let alone taking pictures, some locals even get mad that an outsider would objectify their struggling community. To me the typical mill town is a comforting and familiar place, one of repetition and rhythm. You can find something different in every visit, grand and ornate homes in a row of company buildings, five story apartment houses in a town that doesn't even rate a gas station, and the rail line that once fed this industrial giant snaking along from town to town. This is where the Main Line of the Pennsylvania Railroad once travelled, the towns it built, nurtured and its predecessors served until the industry dried up. The railroad still thrives but like many places, the trains don't stop here anymore. The mill town is a place of beauty in its own right, and I am happy to have experienced every one of them and look forward to sharing a different viewpoint of the built landscape that came as result of the railroads and industry. Over the coming months you can expect images celebrating these places as work continues on understanding the late Pennsylvania Railroad and the landscape it travelled. Enjoy!
Categories: Architecture, Railroads, The Mainline Tags: Conemaugh River, from the mainline, historic documentation, large format photography, michael froio, Mill towns, Ohio River, Pennsylvania, Pennsylvania Railroad, rail transportation, Rust Belt, Steel, Vernacular architecture
January 16, 2014 by Michael Froio


November 6, 2016 • Far down the ballot, district attorney races could reshape the criminal justice system for millions of Americans by electing a more diverse slate of prosecutors.
October 26, 2016 • The Centers for Disease Control and Prevention now urges pregnant women to "consider postponing travel to all parts of Miami-Dade County." Zika is on the way to becoming an endemic disease in the U.S.
October 21, 2016 • As part of Morning Edition's election-year project Divided States, four voters in Florida, a battleground state, share their thoughts on the presidential candidates and the final debate.
October 14, 2016 • Florida "effectively has no death penalty," leaving the legal standing of some 390 death row inmates in doubt, as member station WLRN reports.
October 13, 2016 • Florida health officials say they have identified five cases in which people appear to have contracted Zika through mosquitoes in an area that includes Miami's Little Haiti neighborhood.
October 7, 2016 • The National Hurricane Center says Matthew is a Category 3 storm with maximum sustained winds of 105 mph. The strongest winds are so far staying offshore, but forecasters warn that could change.
October 5, 2016 • Hurricane Matthew killed at least 11 people in Haiti before it barreled north toward the Bahamas. Florida, Georgia and the Carolinas all declared states of emergency as they prepared for the storm.
September 20, 2016 • Pregnant women in South Florida can get free Zika tests through the state's health department. But delays in getting back the results are heightening worries and may affect medical options.
September 2, 2016 • The Category 1 hurricane hit Florida, then weakened to a tropical storm as it moved inland. Hermine is expected to drop heavy rain in Georgia and the Carolinas before tracking out over the Atlantic.


Response: Congenital cytomegalovirus (CMV) infection can cause long-term neurological sequelae, such as hearing difficulties and mental retardations, in affected children. Some investigators reported that early diagnosis and antiviral therapy can improve neurological outcomes in symptomatic congenital infected infants. However, universal screening of newborns for congenital CMV infection is not yet available. Therefore, the development of non-invasive methods for prenatal detection of mothers and newborns at high risk for congenital CMV infection has been desired.
We aimed to determine maternal clinical, laboratory, and ultrasound findings that effectively predict the occurrence of congenital CMV infection in high-risk pregnant women, who were positive for CMV IgM.
We performed maternal blood screening for CMV IgG and IgM, and 300 IgM-positive pregnant women, including 22 with congenital CMV infection, received series of examinations. We evaluated maternal clinical and laboratory findings, including serum CMV IgM and IgG, IgG avidity index, antigenemia testing, and CMV-DNA PCR for the maternal serum, urine, and uterine cervical secretion, and prenatal ultrasound findings.
Response: We demonstrate, for the first time, that the presence of CMV-DNA in the maternal uterine cervical secretion and ultrasound fetal abnormalities was predictive of the occurrence of congenital CMV infection in high-risk mothers.
Response: Our findings may enable congenital CMV-infected newborns to receive early antiviral therapies and may contribute to improve their neurological outcomes.
This entry was posted in Author Interviews, OBGYNE and tagged birth defects, CMV, pregnancy by Marie Benz MD FAAD. Bookmark the permalink.


text:
Enantiocomplementary Preparation of (S)- and (R)-Arylalkylcarbinols by Lipase-Catalysed Resolution and Mitsunobu Inversion: Impact of Lipase Amount
Effect of Ce and Zr Addition to Ni/SiO2 Catalysts for Hydrogen Production through Ethanol Steam Reforming
Baker's Yeast Mediated Reduction of 2-Acetyl-3-methyl Sulfolane
Inhibition of a Gold-Based Catalyst in Benzyl Alcohol Oxidation: Understanding and Remediation
10.3390/catal4020196
Trunfio, G.
Arena, F.
Open AccessReview
Deactivation Pattern of a "Model" Ni/MgO Catalyst in the Pre-Reforming of n-Hexane †
Giuseppe Trunfio
Francesco Arena
1,2,*
Dipartimento di Ingegneria Elettronica, Chimica e Ingegneria Industriale, Università degli Studi di Messina, Viale F. Stagno D'Alcontres 31, I-98166 Messina, Italy
Istituto CNR-ITAE "Nicola Giordano", Salita S. Lucia 5, I-98126 Messina, Italy
Dedicated to Professor Adolfo Parmaliana, who died five years ago (2 October 2008), for his passionate contribution to the research topic of hydrocarbon reforming.
Catalysts 2014, 4(2), 196-214; https://doi.org/10.3390/catal4020196
Received: 14 August 2013 / Revised: 20 January 2014 / Accepted: 5 June 2014 / Published: 19 June 2014
(This article belongs to the Special Issue Advances in Catalyst Deactivation)
The deactivation pattern of a "model" Ni/MgO catalyst in the pre-reforming of n-hexane with steam (T, 450 °C; P, 5–15 bar) is reviewed. The influence of the steam-to-carbon ratio (S/C, 1.5–3.5) on the rate of catalyst fouling by coking is ascertained. Catalyst fouling leads to an exponential decay in activity, denoting 1st-order dependence of the coking process on active sites availability. Hydrogen hinders the coking process, though slight activity decay is due to sintering of the active Ni phase. Deactivation by thiophene causes a sharp, almost linear, drop to nearly zero activity within only 6 h; this deactivation is likely due to dissociative adsorption of thiophene with subsequent strong, irreversible chemical adsorption of S-atoms on active Ni sites, i.e., irreversible poisoning. Modeling of activity decay curves (α, at/a0) by proper kinetic equations allows assessing the effects of temperature, pressure, S/C, H2 and thiophene feed on the deactivation pattern of the model Ni/MgO catalyst by coking, sintering, and poisoning phenomena.
pre-reforming; activity decay; poisoning; sintering
There is a strong commitment worldwide to enhance the practical and economical feasibility of the steam reforming (SR) technology through efficiency improvement and feedstock versatility, which could result in significant improvements in fuel processing economy [1,2,3,4,5,6,7]. In this context, pre-reforming constitutes an established technology with economic and operational benefits on the overall syngas production, representing an important tool, especially for the revamping of older SR plants [2,3,4,8,9,10]. A pre-reforming unit consists in a tubular adiabatic reformer, allowing whatever hydrocarbon feed (NG, LPG, VN) be converted to CH4 and COx at low temperature, typically in the 450–550 °C range, with many practical advantages consisting of [2,3,4]:
an increased production capacity with smaller reformer furnaces;
a higher feedstock flexibility;
enhanced SR tube and catalyst lifetime;
design of innovative process configuration for low energy consumption and investment costs.
Furthermore, the pre-reforming unit drastically limits the risk of carbon formation inside tubular reformers, ensuring a total conversion of higher hydrocarbons, and allowing, then, SR operations at lower steam-to-carbon (S/C) ratio, with a higher preheat temperature and heat flux and capacity [9,10,11]. Moreover, the pre-reforming catalyst ensures the total elimination of S-containing impurities, contributing to enhance SR catalysts' lifetime [2,3,4,5,8,11,12,13,14].
Considering the importance for the improvement of syngas producing plants, little previous literature deals with the basic aspects of the steam reforming of higher hydrocarbons reaction under low temperature and high pressure conditions [12,14,15,16,17]. In fact, only after the pioneering work of Rostrup-Nielsen on the steam reforming of C1-C7 alkanes on magnesia-supported metal catalysts, which led to the development of the SPARG process [2,10,14], has light been shed on the reaction mechanism and kinetics, leading to further improvements in catalysts' performance [11,14,16,17].
Although noble-metal-based systems feature a high reactivity in the reforming of superior hydrocarbons to methane and carbon oxides, typical formulations of pre-reforming catalysts include nickel as the active phase [6,7,8,16,17]. Due to different operating conditions, pre-reforming catalysts are generally richer in Ni loading (50–70 wt%), with the addition of rare earth elements (e.g., La, Sm, Ce, Y, Zr, etc.) as promoters, and are characterized by larger total (SA) and metal surface area (MSA) than SR counterparts [6,16]. Loading of the active phase and type of promoters, however, depend upon process characteristics and targets [6,16].
Generally, coking processes on Ni-based catalysts in steam reforming and methanation reactions proceed through common carbon intermediates leading to the formation of several types of deposits depending on operating conditions [2,8,12,13,14,15,18,19,20,21,22,23,24]. Moreover, effects of metal sintering on the active surface area of typical pre-reforming catalysts have been assessed [25]. Catalyst poisoning is generally caused by strong chemisorption of sulfur impurities present in the feed stream as inorganic and/or organic sulfides in most naturally occurring feedstock; sulfur poisoning depends on many variables including the kind of sulfur compound, nature of the catalyst and operating conditions [7,26,27].
In earlier papers, we documented that Ni/MgO catalysts obtained by an original non-aqueous preparation route exhibit a remarkable performance in both "steam" and "dry" reforming of methane [28,29,30]. Hindering the formation of the NiMgOx solid solution, indeed, such a preparation procedure allows tuning both physico-chemical and catalytic properties through a proper selection of Ni loading, calcination and reduction treatments [28,29,31].
This review provides an overview of reaction and deactivation networks occurring early (i.e., during the first 17 h) on a "model" Ni/MgO catalyst in the steam reforming of n-hexane under pre-reforming conditions (T, 450 °C; P, 5–15 atm). Rates, selectivities, rate constants, and equilibrium constants of important reaction paths as a function of time and rate constants for deactivation by sintering, coking, and poisoning from the previous literature (with an emphasis on the authors' previous works) are presented, and the effects of catalyst deactivation on activity, selectivity, and stability are analyzed and discussed.
2.1. Effects of the Experimental Conditions on the Activity-Selectivity-Stability Pattern
Activity data of the "model" Ni/MgO catalyst in the pre-reforming of n-hexane at standard reaction conditions (T, 450 °C; P, 10 bar; PC6H14, 0.18 bar; PH2O, 3.0 bar; S/C, 2.8) are shown in Figure 1 in terms of n-hexane conversion (χ) and product selectivity vs. reaction time (t.o.s.). The only detected products are CH4, CO2, and CO [11,12,13,14,15,16,17] with a relative distribution which depends on the conversion level. After 30 min, taken as the initial reaction time (t0, a0), the hexane conversion is ≈70% with CH4, CO2 and CO selectivities of ca. 55, 43 and 2%, respectively. A drop in conversion of about 50% over a period of only 17 h involves a SCH4 decrease from 55 to 30%, counterbalanced by a rise in SCO2 from 45 to 70%, although no significant changes in SCO (2–3%) are observed.
Figure 1. n-hexane conversion (χ) and product selectivity (Sχ) vs. t.o.s. at standard reaction conditions (adapted from ref. [11] with the kind permission of Elsevier, copyright 2004).
Activity data at 450 °C with varying space velocity (GHSV), feed stream composition (PH2O and PH2) and pressure are summarized in Table 1 in terms of initial and final hexane conversion (χ, %), reactor output (molC6H14∙h−1∙gcat−1), product selectivity (Sχ, %) and weight gain of the "used" catalyst samples (WC, g∙gcat−1) due to carbon deposition and/or coke formation, determined by TGA-DSC measurements. In addition, the influence of experimental conditions on the "relative activity" (α = χ/χ0, the ratio between conversion at the time "t" and "t0" respectively) is shown in Figure 2.
Table 1. Initial and final (17 h) activity data and amount of carbon on the "used" catalyst samples under different reaction conditions (T, 450 °C; pC6H14/p0, 0.018).
P (atm)
GHSV a (h−1)
χC6H14 (%)
Reactor output (molC6H14 h−1 gcat−1)
SCH4 (%)
SCO2 (%)
SCO (%)
SC2–C5 (%)
WC b (g gcat−1)
a 10 1.5 12,000 53–08 0.26 – 0.04 55–9 43–88 2–3 - 1.32
b 10 2.8 12,000 71–25 0.35–0.12 56–28 42–69 2–3 - 0.96
c 10 3.5 12,000 76–34 0.38–0.17 56–42 43–57 1–1 - 0.89
d 10 2.8 24,000 38–11 0.38–0.11 39–5 59–93 2–2 - 1.23
e c 10 2.8 24,000 77–73 0.77–0.73 98–97 1–2 0–0 1–1 0.03
f 15 2.8 12,000 69–37 0.51–0.27 60–50 39–49 1–1 - 0.75
g 5 2.8 12,000 67–21 0.17–0.05 49–25 49–73 1–2 - 1.02
h d 10 2.8 24,000 65–00 0.65–0.00 97–97 2–2 1–1 - 0.21
a FC6H14/Vcat; b weight gain due to carbon deposition and/or coke formation; c hydrogen (H2/C, 1) in the feed; d hydrogen (H2/C, 1) and thiophene (50 ppm on C6H14) in the feed.
Data in Table 1 indicate that feed composition and operating conditions affect both hexane conversion and CH4, CO2 and CO selectivities, while trace amounts of C2-C5 hydrocarbons (SC2-C5 ≈ 1%) are detected only in presence of hydrogen (run e).
Figure 2. Relative activity vs. t.o.s. at different experimental conditions (see Table 1).
At a constant pressure of 10 atm, the most obvious effects of the S/C ratio increase from 1.5 to 3.5 (runs a–c) consist in a progressive increase of hexane conversion (from 53 to 76%), indicating a positive effect of water pressure on the reactor output, and a better catalyst stability (Figure 2) coupled to a relative influence on product selectivity during reaction time (Table 1). The pressure increase from 5 to 15 atm (S/C, 2.8) has no significant effect on the conversion level (runs b, f, g), as an increase from 0.17 to 0.51 mmolC6H14·h−1·gcat−1 (Table 1) mirrors a fairly constant pressure-normalized reactor output (0.035 molC6H14·h−1·gcat−1/atm).
Figure 3. Overall conversion-selectivity (Sχ) data and H/Oout ratio at different conditions (see Table 1) and reaction times (adapted from ref. [15] with the kind permission of Wiley, copyright 2006).
In addition, an enhancement of SCH4 (49–60%) and, even more so, of catalyst stability are evident, especially at 15 atm (run f).
Furthermore, a twofold increase of GHSV from 12,000 to 24,000 h−1 (runs b, d) causes an almost proportional decrease of the initial conversion (38%) according to an unchanging reactor output (0.35–0.38 molC6H14·h−1·gcat−1), a drop in SCH4 from 55 to 39% with a corresponding growth of SCO2 (Table 1), and a considerably stronger activity decay (Figure 2).
In all the cases, a decreasing trend of the relative activity curves denotes noticeable deactivation phenomena, the extents of which depend on S/C ratio, P, and GHSV (Figure 2). The observed loss of activity can be largely accounted for by the weight loss recorded by TGA-DSC analysis of "used" catalyst samples (Table 1) during combustion of the carbonaceous deposits. This points to carbon formation and coking as the main causes of catalyst deactivation [11,15]. However, such experiments did not allow to differentiate between carbon and coke nor quantitatively measure CO2 and H2O.
Under simulated pre-reforming conditions (run e) with H2 in the feed [3,4,5,6,16,17,18], a markedly higher initial conversion (77%) and a two-fold higher reactor output are observed relative to the standard tests (runs b, d). Moreover, the addition of hydrogen (H2/C = 1) to the feed increases SCH4 to 97–98% and greatly improves catalyst stability, with only a minor (ca. 5%) activity loss during 17 h of t.o.s. (Figure 2, run e).
All the conversion-selectivity data at different conditions (see Table 1) and reaction times provide some general relationships showing that the selectivity pattern depends only on the activity level (Figure 3). Thus, SCH4 increases steadily with increasing conversion, reaching an asymptotic value of 55% in the conversion range of 60–80%, while SCO2 decreases from 90 to 45% and SCO from 2 to 0.5% over the full range of measured conversion (8–75%). Changes in CO/CO2 are consistent with the equilibrium composition predicted from the WGS reaction [11,15,16,18,19,32,33,34,35,36,37]. The overall result of these changes in product selectivities is a trend of increasing output hydrogen/oxygen atomic ratio (H/Oout) from zero at 8% conversion to a maximum value of 2.4 at 67% conversion (Figure 3), which is essentially the same as the H/C ratio of the hexane molecule of 2.33. The apparent increase in the "hydrogenation" functionality with increasing conversion level is consistent with a reaction network involving (1) cracking of hexane; (2) water dissociation; (3) primary formation of CO, which is further transformed to CO2 via the water-gas-shift (WGS); and (4) CH4 via methanation (MET) paths respectively [11,15], according to the following surface reaction network, which includes two irreversible (1 and 8) and six reversible (2–7) steps [11,13,14,15,16,19,21,33,35].
The above reaction scheme explains the inhibition of the methanation path (5) at low PCO and PH2, that is the case at low conversion, while the excess of steam favors the formation of CO2 via the WGS path (6). Thus, hydrogen "availability", determined by the extent of hexane conversion, is the key-parameter controlling the CH4/CO2 distribution [38]. Therefore, enabling the gasification of coke-precursor species [11,15,16,17,21,22,35,36], the methanation step is the "competitor" process of coking, explaining the high catalyst stability and the negligible weight gain of the used catalysts under H2 co-feeding (Table 1). In fact, the same carbon-intermediate (Cα) can undergo methanation at high H2 concentrations or, at low H2 concentrations, generate the following less reactive carbon species, precursors of C-deposit buildup [19,20,21,22,35,36], by ageing
amorphous carbon (Cβ),
vermicular carbon (CV),
bulk Ni carbide (Cγ), and
crystalline, graphitic carbon (CC).
2.2. Modeling of Deactivation Phenomena
From a mechanistic point of view, the coking process can be viewed as a consequence of the surface accumulation of carbon moieties due to a lower gasification rate relative to the accumulation rates of Calpha, polymeric carbon and coke, by the CO decomposition (Scheme 1a) or hexane cracking (Scheme 1b).
Scheme 1. Carbon formation by CO decomposition (a) or hexane cracking (b).
TEM pictures of the used catalyst samples in Figure 4 confirm that catalyst deactivation, feeding or not hydrogen, proceeds by different paths to form different inactive carbon or coke species. According to previous TGA results, under standard reaction conditions (run b) the catalyst grains (Figure 4B) appear embedded into an array of large carbon fibers (dfiber = 20–50 nm), while no carbon deposits are apparent on the used catalyst in presence of H2 (Figure 4C) [11,15,17,35], although halos surrounding several crystallites may be due to films of coke precursors.
Figure 4. TEM views (A–C) and PSD (D) of the "fresh" and "used" catalyst samples: (A) "fresh"; (B) "used" (run b); (C) "used" (run e); (D) CSD's of samples reproduced in panels A–C.
It should be emphasized that the principal cause of deactivation in prereforming or reforming of C2+ hydrocarbons at relatively low reaction temperatures is the formation of a hydrocarbonaceous film on the nickel surface [19] which poisons nickel sites. This work establishes that deactivation is minimized at high H2 concentrations.
In both Runs b and e, an observed "smoothing" of the cubic habit of the magnesia carrier (Figure 4B,C) is consistent with moderate restructuring of the support, probably due to reaction with steam [15,16]; this is likely the origin of very modest metal sintering, apparent from minor changes in Ni crystallite size distributions (Figure 4D), accounting for ca. a 10% decrease in metal dispersion in agreement with H2 uptake data [11].
As might be expected, thiophene co-feeding causes the most rapid decrease in reaction rate with a linear drop during the first 6 h, (Figure 2, run h) [7]. The amount of C5H5S fed during this time (0.05 g/kg hexane) corresponds to ca. 3 μmol (0.51 μmol/h), while the H2 uptake of the fresh catalyst (120 µmol/gcat) corresponds to a surface Ni atom concentration for a 0.025 g sample of 6.0 µmol (i.e., 240 µmol/gcat of surface Ni sites assuming a H/Ni adsorption stoichiometry of 1 [7,15]). Thus, during pre-reforming with the above specified feed of thiophene (run h), the maximum S/Ni surface atomic ratio (i.e., average chemisorption stoichiometry) would be 0.5, assuming complete and irreversible adsorption of sulfur atoms, which is likely under these conditions; in other words, each thiophene molecule deactivates two Ni atoms. However, due to the rapid and irreversible adsorption of S atoms on surface Ni atoms, the rate of poisoning could be influenced by pore diffusional resistances; thus the amount of adsorbed S in the catalyst sample would drop off sharply at the front of the bed and the sharp interface of sulfur saturated nickel would travel slowly, similar to a chromatographic wave, through the catalyst bed. Hence, the equations modeling thiophene adsorption are very complex and by necessity would include expressions for diffusion into the pores, adsorption, dissociation, and the slowly moving axial concentration gradient through the bed, as illustrated by the sophisticated two-dimensional model of H2S adsorption on a Ni steam reforming catalyst described by Rostrup-Nielsen [39].
From the previous discussion, the deactivation pattern of the Ni/MgO catalyst can be assessed taking into account the overall effects of coking, sintering, and poisoning. However, other than Run h, the behavior of deactivation versus time observed in Figure 2 and Figure 5 is due primarily to the formation of carbon and coke, since negligible sulfur was present and effects of sintering were negligibly small. With the exception of Run h, in the presence of thiophene, deactivation was log-linear (see Figure 5), consistent with an exponential activity decay
α = exp[-kdeact·t]
Accordingly, the first order deactivation rate equation is
These can be also expressed in terms of active sites availability (Csite), assuming that activity is directly proportional to the concentration of surface sites [20],
and, thus
where Csite and C°site are the instantaneous and initial concentrations of active sites, respectively. Hence, the exponential decay of activity by coking is described by the equation
which accounts for the general exponential-decay of catalytic activity for each of the runs in Figure 2. From the slopes of the linear fits of the deactivation rate data in Figure 5, the deactivation rate constants (kdeact) listed in Column 3 of Table 2 are obtained. It is further assumed that the rate of sintering (which depends mainly on temperature) is negligibly small for all runs given the very small change in crystallite diameter during reaction.
Figure 5. Plot of the relative activity at different experimental conditions (see Table 1) vs. t.o.s..
Table 2. Deactivation kinetic constants for coking.
kcok a (h−1)
a 1.00 1.1 × 10−1 ± 2 × 10−3
b 1.00 5.5 × 10−2 ± 6 × 10−4
c 0.99 7.0 × 10−2 ± 1 × 10−3
d 0.97 7.7 × 10−2± 5 × 10−3
e 0.96 -
f 0.98 3.0 × 10−2 ± 1 × 10−3
g 0.97 6.3 × 10−2 ± 3 × 10−3
a kcok = kdeact.
It is emphasized that the calculation of rate constants in Table 2 (Run h involving sulfur poisoning excepted) relies on the following assumptions:
The rates of deactivation by coking and sintering are small relative to the rate of the main reaction. Hence the pseudo steady-state approximation can be made. This is a reasonable assumption in view of 2–3 orders of magnitude differences between reaction and coking rates at any condition and t.o.s. [15];
The rate of coking is slow enough that it is not influenced by a pore diffusional resistance for the deactivation process;
Pore diffusion resistance for the main reaction is neglected which, at high reaction rates and conversions, would lower the concentration of hydrocarbon coke precursors into the pores, then lowering coking rates along the pores; similarly concentration gradients through the bed due to high conversions should cause a decrease in adsorbed carbon concentration through the bed. This is probably a poor assumption in view of the high conversions of this study. Thus, the rate constants could be significantly in error due to differences in pore diffusional resistance between runs and represent at best rough averages across pellets and bed.
Figure 6. Log-plot of the kinetic constant of coking vs. water partial pressure (A); and Relationship between the weight gain of the used samples (Table 1) and the kinetic constant of coking (Table 2) at different reaction conditions (B).
Values of kcok in Table 2 are not constant as predicted by the simple first order deactivation model; indeed, they vary by a factor of 20. In fact, the log-plot of kcok (Figure 6A) discloses an inverse dependence (−1.10 ± 0.05) on PH2O, confirming that water concentration is a key-factor in controlling coking rate at low H2 concentrations (typical of steady-state), a logical result given that water is also a gasifying agent for carbon. The straight-line relationship between kcok and weight gain in the used samples in Figure 6B supports a link between deactivation at low H2 concentrations to fouling by C-deposits for a range of typical prereforming conditions.
2.3. Effect of Deactivation on Product Selectivity and Surface Functionalities
Thermodynamic and kinetic evaluations of the outlet stream composition [2,9,15,21,22,23] shed light on driving force for carbon deposition and, in turn, how carbon deposits influence selectivity. In particular, assuming hexane cracking to be irreversible [9,15,22], a rough estimate of the outlet stream composition can be made from a thermodynamic analysis of gasification (GAS), water-gas-shift (WGS), and methanation (MET) reactions (Table 3) [9,10,11,15]. However, also the Boudouard reaction has been considered to evaluate the incidence of CO dismutation on carbon formation and coking [11]. Specifically, Px values obtained from conversion-selectivity data were substituted in the equilibrium expressions to calculate experimental Kexp values of MET, GAS, WGS and DISP reactions as a function of t.o.s. [11].
Table 3. Thermodynamic constants of the various reactions of the steam reforming network (adapted from ref. [11] with the kind permission of Elsevier, copyright 2004).
KP a
CRK C6H14 ➞ 6 C + 7 H2 -
GAS C + H2O ⇆ CO + H2 5.09 × 10−4
WGS CO + H2O ⇆ CO2 + H2 7.47 × 100
MET C + 2H2 ⇆ CH4 5.41 × 101
DISP 2 CO ⇆ C + CO2 1.47 × 104
Equilibrium pressure constant values at 450 °C with Px values in MPa.
The ratio (β) of Kexp to the corresponding calculated value of the equilibrium constant Keq at 450 °C (from Table 3) provides a measure of the distance from equilibrium for each reaction, allowing a reliable assessment of the effects of the S/C ratio (Figure 7A–C) and H2 feeding (Figure 7D) on activity versus time patterns. Figure 7 shows that irrespective of t.o.s. and S/C ratio, the WGS reaction is always near thermodynamic equilibrium conditions, given that βWGS values vary between 0.6 and 1.0. In contrast, gasification (βGAS ≈ 0.5) and, even more so, methanation (βMET, 0.2–0.05) reactions operate far from equilibrium and are thus kinetically controlled. It follows from the previous discussion that lower rates of GAS and MET relative to hexane cracking constitutes a major driving force to carbon deposits build-up [17,19,20,35]. Furthermore, the observation that βDISP is always larger than one implies a [PCO2/(PCO)2] ratio greater than that allowed by thermodynamics, indicating that under prereforming conditions on Ni/MgO, the forward reaction, which also contributes to carbon formation, is more kinetically favorable than the reverse gasification of carbon by CO2. However, this deviation could also be an artifact of the approximate reaction model.
It is interesting that while βGAS and βMET decrease with trends similar to that of the relative activity (α), βDISP increases progressively with t.o.s. (almost exponentially under the conditions of Figure 7A), suggesting that carbon and coke reactivity decrease accordingly by ageing (i.e., by conversion of coke precursors to highly polymerized coke and by conversion of Cα→Cβ, CV, Cγ, CC) [16,17,19,21,36]. In fact, the changes in product selectivity with the activity level (Figure 3) mirror the different influences of coke and carbon on different functionalities of Ni catalysts, consistent with the 14CO and 14CO2 isotopic labeling experiments of Jackson et al. who found that Ni/Al2O3 catalyst retains high activity towards the scrambling of C-atoms and surface carbon gasification, despite a considerable decrease in the availability of metal surface area due to growth of gum-like carbonaceous deposits [35].
Figure 7. Pre-reforming of the n-hexane (T, 450 °C; P, 10 bar). Effect of S/C ratio and H2 feeding on α and β values of GAS, WGS, MET and DISP reactions vs. t.o.s.: (A) S/C, 1.5; H2/C, 0; (B) S/C, 2.8; H2/C, 0; (C) S/C, 3.5; H2/C, 0; (D) S/C, 2.8; H2/C, 2. Legend: (●) α; ( ) βWGS; (○) βDISP; ( ) βGAS; ( ) βMET (reproduced from ref. [11] with the kind permission of Elsevier, copyright 2004).
In the present paper, the role of the methanation reaction in modeling of prereforming has been emphasized. Bartholomew emphasized that methanation and steam reforming functionalities of Ni catalysts are closely related on the basis of the activation energy values [22]. Furthermore, Rostrup-Nielsen stressed that hydrogenolysis and steam reforming reactions share many surface steps, requiring also analogous ensembles (n, 2.5–2.7) of active sites [17]. Hence, effects of deactivation on prereforming catalyst functionalities can be assessed by inspecting the trends of the relative rates of MET, GAS, and WGS reactions (αx = α·Sχ), as shown in Figure 8. The semi-log plot of the relative rates of CH4 (αCH4), CO (αCO), and CO2 (αCO2) formation provides satisfactory linear trends (Figure 8), the slopes of which (kMET, kGAS, kWGS) represent the decay constants for the above functionalities, listed in Table 4.
These figures reveal the following trends:
MET rate (αCH4) decreases much more steeply than relative activity;
GAS rate (αCO) decreases similar to relative activity;
WGS rate (αCO2) decreases less than relative activity.
Figure 8. Relative rates of hexane conversion (α, ●), CH4 (αCH4, ▲), CO2 (αCO2, ♦) and CO (αCO, ▼) formation vs. t.o.s. at different reaction conditions (see Table 1) (adapted from ref. [15] with the kind permission of Wiley, copyright 2006).
Indeed, direct relationships between kMET, kGAS, and kWGS decay and that of activity loss (kdeact) result in straight-line correlations (Figure 9) with slopes equal to 2.7 ± 0.3, 1.1 ± 0.2 and 0.6 ± 0.1, respectively. From this and similar figures it can be shown that MET, GAS, and WGS functionalities depend on different ensembles of active sites [11,15,17,19,20,21,36]; thus, a slope of 1 for kGAS/kdeact suggests that hexane conversion involves single sites leading to CO, while MET and WGS require larger and smaller ensemble of active sites for methane and carbon dioxide formation, respectively.
Table 4. Deactivation constants of the various functionalities (T, 450 °C): hexane conversion (kdeact), methanation (kMET), gasification (kGAS), water-gas-shift (kWGS).
kdeact a (h−1)
kMET (h−1)
kGAS (h−1)
kWGS (h−1)
a 1.1 × 10−1 1.1 × 10−1 2.2 × 10−1 1.1 × 10−1 6.6 × 10−2
b 5.9 × 10−2 5.6 × 10−2 9.7 × 10−2 2.7 × 10−2 3.2 × 10−2
c 4.4 × 10−2 4.0 × 10−2 6.0 × 10−2 2.8 × 10−2 2.7 × 10−2
d 8.1 × 10−2 7.7 × 10−2 2.2 × 10−1 7.1 × 10−2 6.1 × 10−2
e 3.5 × 10−3 0.000 3.5 × 10−3 1.2 × 10−2 1.9 × 10−2
f 3.4 × 10−2 3.0 × 10−2 4.4 × 10−2 2.8 × 10−2 2.2 × 10−2
a data taken from Table 2.
In fact, according to Beeckman et al. who adopted a stochastic approach to describe deactivation by coking under different mechanisms [34], MET functionality is affected to the maximum extent by the fouling of active sites because of its high number of metal atoms required for each site (e.g., formal site molecularity) in comparison to GAS and WGS ones [11,15,17,19,40,41].
Therefore, in agreement with literature data, kinetic and thermodynamic findings confirm that surface carbon (i.e., Cα) hydrogenation is the crucial step controlling activity, selectivity, and stability against coking in the pre-reforming process. Activity decay is more pronounced at low conversion, mostly under the occurrence of GAS and WGS reactions, as CO formation-decomposition is mainly responsible for carbon build-up via an adsorbed Cα intermediate [19,35].
Figure 9. Relationships between kMET (●), kGAS (▼), kWGS (♦) and kdeact (see Table 4) (adapted from ref. [15] with the kind permission of Wiley, copyright 2006).
However, with addition of high concentrations of H2, similar values of kdeact and kMET (Table 4), and a much steeper decay of gasification (kGAS/kdeact ≈ 3.5) and WGS (kWGS/kdeact ≈ 5) functionalities [11,17,19] evidence that different reaction and deactivation paths are favored.
3. Experimental Section
3.1. Catalyst Preparation
The 19.1 wt% Ni/MgO catalyst was prepared by incipient wetness impregnation of "smoke" MgO powder (UBE Ltd., Yamaguchi, Japan SABET, 30 m2·g−1) with an ethanolic solution of the Ni(NO3)2 salt [28,29,30,31]. The catalyst was dried at 80 °C, calcined at 400 °C (16 h) and pre-reduced for 6 h at 650 °C under H2 flow.
3.2. Catalyst Testing
Catalytic tests in the pre-reforming of n-hexane were performed at 450 °C and a pressure of 5–15 bar, using an isothermal "fixed bed" stainless steel microreactor (i.d., 6 mm), loaded with 25 mg of catalyst (40–70 mesh), diluted with same-sized SiC in a 1/30 weight ratio [11,15]. Before tests, the catalyst was heated at 450 °C and further reduced in situ for 1 h in H2 flow (100 STP mL min−1; P, 1 bar). The reaction mixture including n-C6H14 (1.8%), N2 (8.0%), H2O (16.2–37.8%) and He (rest) for a variation of the S/C ratio between 1.5 and 3.5 respectively, was fed at the rate of 283 (GHSV, 12,000 h−1) or 566 (GHSV, 24,000 h−1) STP mL min−1. The effects of H2 (11.0%; H2/C, 1.0) and thiophene (50 ppm in n-hexane) were probed at the highest GHSV and a S/C ratio of 2.8. Both water and n-hexane were fed as liquid by HPLC pumps. The reaction temperature was controlled by a thermocouple in contact with the catalytic bed, while the reactor stream was analyzed by a GC equipped with a three-columns analytical system connected to both TCD and FID detectors for permanent gases and hydrocarbons analyses, respectively [11,15].
3.3. Catalyst Characterization
TEM analyses were performed using a PHILIPS CM12 Transmission Electron Microscope (point-to-point resolution, 0.3 nm) on "fresh" and "spent" catalyst samples, dispersed ultrasonically in ethanol and deposited over a thin carbon film supported on a standard copper grid. The Ni particle size distribution (PSD) was obtained from an average of 150–200 particles, and the average volume-area particle size calculated by the conventional statistical formula [29,30,31]:
The H2 uptake of "fresh" and "used" catalyst was evaluated by TPD measurements in the range −80–620 °C using Ar as carrier gas (30 stp cm3·min−1) after in situ reduction of the samples in H2 flow at 450 °C for 1 h and subsequent saturation at r.t. (room temperature) and further at −80 °C. The fraction of reduced Ni was evaluated by titration at 450 °C with O2 pulses (Ni + ½ O2 → NiO) after TPD analysis [31].
TGA-DSC measurements of the "used" catalyst samples (5 mg) in the range of 20–400 °C were performed using a Simultaneous Thermal Analyser (STA 409C, Netzsch), operating in air with a heating rate of 10 °C/min and an accuracy of 0.01 mg.
This review summarizes highlights of previous studies (mainly in our laboratory) of reaction and deactivation paths on a "model" Ni/MgO catalyst in the pre-reforming of n-C6H14 with steam at 450 °C. A kinetic and thermodynamic analysis of the data from these studies provides (1) new deactivation rate parameters for carbon deposition and coke formation and (2) insights into the surface reaction network of the pre-reforming process, including hexane cracking, water-gas-shift, and methanation reactions.
Important conclusions from this work can be summarized as follows:
Deactivation of Ni/MgO by carbon deposition and coking follows a pseudo 1st-order dependence on active site concentration, consistent with an exponential decay with t.o.s. That deactivation by coke and carbon formation is not simple first order in site concentration, is evident from observed decreases in deactivation rate constants with increasing S/C ratio, P, and contact time.
Comparison of thermodynamic predictions with experimental values of outlet stream composition leads to the conclusion that the kinetics of hexane cracking/reforming, carbon gasification and methanation reactions control the rate of coking; methanation is the critical, rate limiting step responsible for coke deposition in the near absence of H2. Carbon formation via the Boudouard reaction is apparently thermodynamically and kinetically favored.
Under simulated industrial pre-reforming conditions at a high H2 concentration, hydrogen substantially increases reaction throughput by speeding up hydrogenolysis, CO formation via the water-gas-shift, and methanation reactions. H2 at high concentrations gasifies coke and carbon precursors, thereby largely preventing formation of coke and inactive carbons.
S-poisoning by thiophene co-feeding causes a sharp drop in catalytic activity due to irreversible poisoning; however, strong pore diffusional resistances in catalyst pellets and bed prevent an accurate analysis of the poisoning mechanism and kinetics.
This work was conceived by Francesco Arena, who arranged the manuscript, and Giuseppe Trunfio, who carried out the experiments and also conceived and revised the manuscript.
Piel, W.J. Transportation fuels of the future? Fuel Process. Tech. 2001, 71, 167–179. [Google Scholar] [CrossRef]
Nagase, S.; Takami, S.; Hirayama, A.; Hirai, Y. Development of a high efficiency substitute natural gas production process. Catal. Today 1998, 45, 393–397. [Google Scholar] [CrossRef]
Cromarty, B.J.; Hooper, C.W. Increasing the throughput of an existing hydrogen plant. Int. J. Hydrogen Energy 1997, 22, 17–22. [Google Scholar] [CrossRef]
Aitani, A.M. Processes to enhance refinery-hydrogen production. Int. J. Hydrogen Energy 1996, 21, 267–271. [Google Scholar] [CrossRef]
Fierro, J.L.G.; Peña, M.A.; Gómez, J.P. New catalytic routes for syngas and hydrogen production. Appl. Catal. A 1996, 144, 7–57. [Google Scholar] [CrossRef]
Rostrup-Nielsen, J.; Christiansen, L.J. Concept in Syngas Manufacture. In Catalytic Science Series; Imperial College Press: London, UK, 2011; Volume 10. [Google Scholar]
Bartholomew, C.H.; Farrauto, R.G. Fundamental of Industrial Catalytic Processes, 2nd ed.; J. Wiley & sons, Inc.: Hobken, NJ, USA, 2006; pp. 339–371. [Google Scholar]
Wang, X.; Gorte, R.J. A study of steam reforming of hydrocarbon fuels on Pd/ceria. Appl. Catal. A 2002, 224, 209–218. [Google Scholar] [CrossRef]
Zou, X.; Wang, X.; Li, L.; Shen, K.; Lu, X.; Ding, W. Development of highly effective supported nickel catalysts for pre-reforming of liquefied petroleum gas under low steam to carbon molar ratios. Int. J. Hydrogen Energy 2010, 35, 12191–12200. [Google Scholar] [CrossRef]
Shen, K.; Wang, X.; Zou, X.; Wang, X.; Lu, X.; Ding, W. Pre-reforming of liquefied petroleum gas over nickel catalysts supported on magnesium aluminum mixed oxides. Int. J. Hydrogen Energy 2011, 36, 4908–4916. [Google Scholar] [CrossRef]
Arena, F.; Trunfio, G.; Alongi, E.; Branca, D.; Parmaliana, A. Modeling the activity-stability pattern of Ni/MgO catalysts in the pre-reforming of n-hexane. Appl. Catal. A 2004, 266, 155–162. [Google Scholar] [CrossRef]
Ayabe, A.; Omoto, H.; Utaka, T.; Kikuchi, R.; Sasaki, K.; Teraoke, Y.; Educhi, K. Catalytic autothermal reforming of methane and propane over supported metal catalysts. Appl. Catal. A 2003, 241, 261–269. [Google Scholar] [CrossRef]
Rostrup-Nielsen, J. Activity of nickel catalysts for steam reforming of hydrocarbons. J. Catal. 1973, 31, 173–181. [Google Scholar] [CrossRef]
Rostrup-Nielsen, J. Catalysis, Science and Technology; Springer: Berlin, Germany, 1983. [Google Scholar]
Arena, F. Basic Relationships in the Pre-Reforming of n-Hexane on Ni/MgO Catalyst. AIChE J. 2006, 52, 2823–2831. [Google Scholar] [CrossRef]
Christensen, T.S. Adiabatic prereforming of hydrocarbons—An important step in syngas production. Appl. Catal. A 1996, 138, 285–309. [Google Scholar] [CrossRef]
Rostrup-Nielsen, J.; Alstrup, I. Innovation and science in the process industry: Steam reforming and hydrogenolysis. Catal. Today 1999, 53, 311–316. [Google Scholar] [CrossRef]
Sperle, T.; Chen, D.; Lødeng, R.; Holmen, A. Pre-reforming of natural gas on a Ni catalyst. Criteria for carbon free operation. Appl. Catal. A 2005, 282, 195–204. [Google Scholar] [CrossRef]
Bartholomew, C.H. Carbon deposition in methanation and steam reforming. Catal. Rev. Sci. Eng. 1982, 24, 67–112. [Google Scholar] [CrossRef]
Butt, J.B.; Petersen, E.E. Activation, Deactivation and Poisoning of Catalysts; Academic Press; Inc.: San Diego, CA, USA, 1998. [Google Scholar]
Forzatti, P.; Lietti, L. Catalyst deactivation. Catal. Today 1999, 52, 165–181. [Google Scholar] [CrossRef]
Bartholomew, C.H. Mechanism of catalyst deactivation. Appl. Catal. A 2001, 212, 17–60. [Google Scholar] [CrossRef]
Kroll, V.C.H.; Swaan, H.M.; Mirodatos, C. Methane Reforming Reaction with Carbon Dioxide Over Ni/SiO2 Catalyst. Deactivation Studies. J. Catal. 1996, 161, 409–422. [Google Scholar] [CrossRef]
Tailleur, R.G.; Davila, Y. Optimal Hydrogen Production through Revamping a Naphtha-Reforming Unit: Catalyst Deactivation. Energy Fuels 2008, 22, 2892–2901. [Google Scholar] [CrossRef]
Sehested, J.; Carlsson, A.; Janssens, T.V.W.; Hansen, P.L.; Datye, A.K. Sintering of nickel steam-reforming catalysts on MgAl2O4 spinel supports. J. Catal. 2001, 197, 200–209. [Google Scholar] [CrossRef]
Ashrafi, M.; Pfeifer, C.; Pröll, T.; Hofbauer, H. Experimental Study of Model Biogas Catalytic Steam Reforming: 2. Impact of Sulfur on the Deactivation and Regeneration of Ni-Based Catalysts. Energy Fuels 2008, 22, 4190–4195. [Google Scholar] [CrossRef]
Gallego, J.; Batiot-Dupeyrat, C.; Barrault, J.; Mondragón, F. Severe Deactivation of a LaNiO3 Perovskite-Type Catalyst Precursor with H2S during Methane Dry Reforming. Energy Fuels 2009, 23, 4883–4886. [Google Scholar] [CrossRef]
Arena, F.; Parmaliana, A. Strategies of design of Ni/MgO catalysts for the reforming of hydrocarbon to hydrogen/syngas. Curr. Top. Catal. 2006, 5, 69–88. [Google Scholar]
Parmaliana, A.; Arena, F.; Frusteri, F.; Coluccia, S.; Marchese, L.; Martra, G.; Chuvilin, A. Magnesia Supported Nickel Catalysts. Part II: Surface properties and reactivity in CH4 steam reforming. J. Catal. 1993, 141, 34–47. [Google Scholar] [CrossRef]
Frusteri, F.; Spadaro, L.; Arena, F.; Chuvilin, A. TEM evidence for factors affecting the genesis of carbon species on bare and K-doped Ni/MgO catalysts during the dry-reforming of methane. Carbon 2002, 40, 1063–1070. [Google Scholar] [CrossRef]
Arena, F.; Horrell, B.A.; Cocke, D.L.; Parmaliana, A.; Giordano, N. Magnesia-Supported Nickel Catalysts. I: Structure and morphological properties. J. Catal. 1991, 132, 58–67. [Google Scholar] [CrossRef]
Suzuki, T.; Iwanami, H.; Yoshinari, T. Steam reforming of kerosene on Ru/Al2O3 catalyst to yield hydrogen. Int. J. Hydrogen Energy 2000, 25, 119–126. [Google Scholar] [CrossRef]
Ming, Q.; Healey, T.; Allen, L.; Irving, P. Steam reforming of hydrocarbon fuels. Catal. Today 2002, 77, 51–64. [Google Scholar] [CrossRef]
Beeckman, J.W.; Nam, I.-S.; Froment, G.F. Stochastic modeling of catalyst deactivation by site coverage. Stud. Surf. Sci. Catal. 1987, 34, 365–379. [Google Scholar] [CrossRef]
Jackson, S.D.; Thomson, S.J.; Webb, G. Carbonaceous deposition associated with the catalytic steam-reforming of hydrocarbons over nickel alumina catalysts. J. Catal. 1981, 70, 249–263. [Google Scholar] [CrossRef]
Snoeck, J.-W.; Froment, G.F.; Fowles, M.J. Filamentous carbon formation and gasification: thermodynamics, driving force, nucleation, and steady-state growth. J. Catal. 1997, 169, 240–249. [Google Scholar] [CrossRef]
Chen, F.; Zha, S.; Dg, J.; Liu, M. Pre-reforming of propane for low-temperature SOFCs. Solid State Ionics 2004, 166, 269–273. [Google Scholar] [CrossRef]
Sughrue, E.L.; Bartholomew, C.H. Kinetics of carbon monoxide methanation on nickel monolithic catalysts. Appl. Catal. 1982, 2, 239–256. [Google Scholar] [CrossRef]
Rostrup-Nielsen, J. Sulfur Poisoning. In Progress in Catalyst Deactivation; Figuerido, J.L., Ed.; Martinus Nijhoff Publisher: The Hague, The Netherlands, 1982; pp. 209–227. [Google Scholar]
Sidjabat, O.; Trimm, D.L. Nickel-magnesia catalysts for the steam reforming of light hydrocarbons. Top. Catal. 2000, 11/12, 279–282. [Google Scholar] [CrossRef]
Fujita, S.; Terenuma, H.; Nakamura, M.; Takezawa, N. Mechanisms of methanation of CO and CO2 over Ni. Ind. Eng. Chem. Res. 1991, 30, 1146–1151. [Google Scholar] [CrossRef]
Trunfio, G.; Arena, F. Deactivation Pattern of a "Model" Ni/MgO Catalyst in the Pre-Reforming of n-Hexane. Catalysts 2014, 4, 196-214. https://doi.org/10.3390/catal4020196
Trunfio G, Arena F. Deactivation Pattern of a "Model" Ni/MgO Catalyst in the Pre-Reforming of n-Hexane. Catalysts. 2014; 4(2):196-214. https://doi.org/10.3390/catal4020196
Trunfio, Giuseppe, and Francesco Arena. 2014. "Deactivation Pattern of a "Model" Ni/MgO Catalyst in the Pre-Reforming of n-Hexane" Catalysts 4, no. 2: 196-214. https://doi.org/10.3390/catal4020196
Catalysts, EISSN 2073-4344, Published by MDPI


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Rivian electric 'rally car' planned as third model in range
Electric-car startup already working on follow-up to pickup and SUV
Rivian, the US electric-car startup that revealed pickup truck and SUV models at this year's Los Angeles Auto Show (above), is working on a rally-car-like hatchback for its third product.
Speaking to our sister brand Auto Express at the show, company founder Robert Scaringe said "The products we're working on all speak to the version of adventure where you have a combination of on and off-road capability, and a level of functionality that's unique and different from other vehicles in its space.
"The third, fourth and fifth vehicles may have different form factors; the third vehicle is smaller in wheelbase than what you see here in LA, but think of it as Rivian's interpretation of what you would see as a rally car. With a lot of ground clearance."
California-based Rivian has 600 employees currently, and is in the process of renovating an old Mitsubishi factory in Illinois to put its cars into production from 2020.
In addition to building its own models, Scaringe added, the company is also open to licensing its technology or producing components for other brands. The founder said Rivian was actively discussing the possibility with several established and newcomer car brands.


We were hired in August of 2017 to do a minor upgrade of the Port Coquitlam Council Chamber. The job consisted of rewiring the televisions in the chamber so that an HDMI signal could be fed to the new televisions. The existing TVs appeared to be original, and were old plasma TVs, with VGA signal connectors, and no HDMI inputs. The new replacement TVs had HDMI inputs, but no VGA inputs. A rewiring had to be done, and the televisions were wall rather than ceiling mounted.
We were also asked to move one of their desktop computer locations with associated wiring to a different council desk, so that the line of sight for people in the gallery as well as the online stream would be improved.
The retrofit consisted of installing several HDMI to CAT5 receiver/transmitter units, that would allow an HDMI signal to be run over CAT5 cabling over significant distances reliably. To re-route the computer a nd control wires, we had to re-route cables through the floor, and then reconnect them. The existing connections had some loose ends, so these were cleaned up and terminated. We also cleaned up some of the wiring in the main audio/video rack, to reduce the rat's nest of cabling.
Finally, we relabeled and added an HDMI input in the public gallery, so that a laptop could be plugged in, and be shown on the council TVs as well as on the streaming online.


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Such sort of Correspondence comprises a number of Advantages, Nevertheless You Will Find Likewise some risks involved inside. The professional strategy is vital even in the event the identification letter is linked to some personal problems. If it's personal authorization letter then you ought to mention that your connection with the person to whom you wish to provide a few authorities.
The authorization letter must Stay simple and brief so as to Prevent any sort of misinterpretations. In the event of any misdoing, it may be used as legal evidence. An Authorization letter to file for cash is composed by way of someone that wishes to authorize another guy to file for cash in their behalf.
Until now, you should have known what an authorization Letter is all about. In cases such as this, you must write an authorization letter so as to publish the info. An authorization letter is a significant document and you'll need to be certain that it is a tightly worded document that can't be negotiated or misconstrued in any manner. Creating an authorization letter for files is sometimes one of the prerequisites you should submit before you're likely to be permitted to be represented by someone else.
A letter of consent could be used for many reasons. It Is an extremely straightforward but necessary legal document that is required in case of many events. The authorization letter to acquire files must have content that is first and match for the transaction where it is going to be used. It must contain all of the contact information that may be used by the letter recipient if they would like to gather additional info or if they would like to raise anyA points of clarification.
It's likely to send them a letter employing the addresses Provided below or you can view their website and complete the acceptable form. Authorization letters have to be verified carefully. An authorization letter is used when you want to give someone the ability to perform a task for your advantage. Some folks believe it is not required to make an authorization letter to acquire documents anymore. Should you wish to generate a productive authorization letter to acquire documents, you have got to make certain that you will begin looking into quality criteria that will allow you to come up with a letterA that is presentable, appropriate to be used for a certain trade, and finish with all the particulars which you would love to present.
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If you're feeling a letter to authorize the Delivery person to depart Bundle at your house, it is quite straightforward. Such a letter might also be required when authorizing an individual to collect some essential records for your benefit. Authorization letters are necessary for authorizing a person to execute your legal, business, medical, and other relevant transactions for your advantage. It is usually used for business purposes. Authorization letters are very simple to write but you must format them properly. An authorization letter is issued by somebody, company or company concern to have the ability to spend the receiver with certain powers that can be anything from withdrawing cash from a financial institution account to making a business deal. You have to give them a written letter of authorization to your advantage.
Your letter may be redeemed in the event the words given by you've Got the double significance. It is essential that before you draft the letter and you get in touch with somebody who has completed passport work before, who will be able to assist you with the procedure. The letter is also utilized for insurance and healthcare variables. Traveling Length of Authorization A travel letter of consent is among the sorts of consent letters which are written by people who want to give authority to someone else.
The renter credit report enables you to find a tenant's fiscal history. You only have to understand why the two files are necessary. In paragraph two, spell out exactly what the letter is supposed to pay. A letter giving another person permission to watch on your child can save yourself a whole lot of harm and hassle when you want a person to pick him up in school, get him into the doctor or become the principal caregiver for over a couple of hours. You've also asked they produce each of those receipts for every single transaction which you engaged in during the full life of their usage of that credit rating card. To start with, an e-KTP card is put on the gadget.
Back in the Outline Manager, you may also add different keys. Your customers must dance with you whenever they wish to understand that value it is possible to deliver. If they are not prepared, willing and able to execute the value you leave, then nothing will occur. Thus, to achieve your company aims, you need great clients with whom you are able to produce great price and lasting outcomes. When an individual creates a purchase, he might buy more than 1 product.
Possibly the Most essential function in a company is the Constraint of company purchases. Because you're not in control of the companies. As soon as you have decided what type of energy of Attorney you need, you have got to read it carefully once and twice to ensure that's clarify and state the exact same function that you're looking for.
For the group organization to say that it had an Agreement on youpersonally, it has to demonstrate the manner that it was likely to do great for you. It's accurate, you signed an agreement by way of your charge card business, but you didn't sign one with the companies that purchased your debt out of the credit card company. Doing this produces a contract which could be binding. Try to recall, you have a lease. Needing to evict a tenant can be unbelievably stressful. When you are browsing for new tenants, then you need to make certain you pick tenants that will handle your assumptions and pay rent punctually.
During trades, it is not uncommon for sellers to ship Orders prior payment. Purchasing is the process of purchasing goods and alternatives. Secondly, there is a rate cost to using a VPNit is not terrible, but it is noticeable.
When you understand a renter's income and the sum of obligations, you can Find out in the event the renter can afford rent, contemplating her or his other financial obligations. People investment simply suggests that customers must give an executing staff to do the job. The airline provider notifies the client that the refund amount was moved into a pocket, and might be used for a booking in the future. A collection company can not collect any amount of money that is not permitted by law or by arrangement. What's more, it would be required to show the terms of the arrangement in court. Most collection agencies aren't going to respond to your correspondence, since they cannot furnish the proof nor the information that you request. For instance, the collection agency and collection agentas license is a thing that no collection agency wants to provide, as you may know the agencyas and agentas information.
The plaintiff is waving a blank bit of paper facing you. If it's A increased court, then you have to retain an attorney. If you choose to retain an lawyer, you do not demand a high-priced one. If you have decided you don't need a lawyer and that you will prepare your Power of Attorney by yourself, it's necessary for you to pay full attention whilst performing it so as to make any error that cost you a lot later. Back in Texas, the law permits you to change the lock of the doors, but you've got to extend the tenant a key instantly if they ask for one. With various information regarding its citizens collected via the e-KTP system, the government was (supposedly be) able to create an exhaustive database of each citizen. Firstly, citizens do not have to remember a variety of credentials for various sites.
The purchasing procedure can vary from 1 organization to Another, but there are a few common denominators. The company process is very similar to that clarified in the mentioned article, we'll clarify only factors. Following that, the installation procedure will operate for about two minutes. The entire procedure takes approximately ten minutes. The civil government process were rather bureaucratic and slow, folks would only ask a new identity card every time they moved to a brand new municipality. In case you haven't been a part of thepurchasing process, it's likely that you won't know what a buy order is or exactly what a shipping order is. The very first step in the funnel production technique is naming your own funnel.
Doing this will cause a product to be habit-forming. ProductsSelect specific goods on that you want the upsell funnel to go triggered. A customer must cancel a flight reservation, but it will incur a steep punishment because there isn't any cancellation window left. There are many services out there which run VPNs it's possible to buy access to.
Job abandonment is typically Once a worker doesn't Appear for work for numerous days without calling in or providing any kind of notification. Unemployment generally, it is considered to be voluntarily leaving work. The second sort of contract abandonment happens when a contractor is no more able to do the job on a project. 4 Abandonment of job ahead of the conclusion of the contract period needs to be voluntary.
Seek consultation Your job abandonment policy Has to Be written With the assistance of HR. Employment agreements can also provide for forfeiture of wages in the event the employee abandons their occupation and doesn't offer you the mandatory amount of notice. A superb employment agreement should incorporate an abandonment clause. In precisely the exact same way, a contract of employment or office policy might also have a set period of time stipulated.
Employers are often reluctant to produce direct contact with an Employee who's absent without reason, but it is crucial to clarify and confirm what's going on with your worker. For a company to safely deem an employee to have abandoned their employment, the employer must make several real attempts to speak to the worker on a fair time framework to comprehend the reason for their absence. To handle the employee's absence, employers must run many processes for every circumstance. They must ensure that workers receive policy handbooks when they are first employed and following each time that the manual is updated.
Usually, employers would be prudent to document the Circumstance, keep routine contact and issue warnings as appropriate. Employers should assess the relevant contemporary award, agreement or policy to see whether it offers information about what to do in the event of abandonment. The employer provided the employee with one last chance to submit the necessary medical details. Rather they must investigate into the conditions of the worker's absence. Employers suffer as they are not obtaining each one of the talent attempting to reach them. When the employer is apprised of the advice concerning the employee's absence, it is going to be difficult for the employer to set up abandonment. For hired individuals unable to go back to place of dwelling in the exact same day he or she supplies housing at no cost.
You might even look at Trying to get connected with all the Worker through other people like work colleagues, family or treating professionals or even to pay a visit to the worker's house. Over the course of this forthcoming several weeks, the employee appealed the refusal of benefits. Regardless of the primary reason for abandoning job, employees should make every endeavor to get in touch with their company or entrust somebody else to do it on their own behalf. The employee might have simply disappeared. If he subsequently turns up disciplinary action needs to be taken. Consequently, he couldn't pursue his unfair dismissal case. Workers represented by a union may be governed by the appropriate bargaining unit agreement.
You Have to Attempt to communicate in writing to the employee prior to Creating a choice to separate or dismiss. In this kind of situation, the employee is treated as if they had terminated the job and there is no dismissal. In order to terminate the job, you'd want to demonstrate that the worker has failed to comply by a legal and reasonable direction of the enterprise. The moment it is not always legally essential to generate an attempt to consult with a worker before starting the finishing procedure, it's considerate and will help steer clear of legal snafus if there was a genuine misunderstanding. You ought to confirm the worker's employment agreement and try to track her down before it's possible to choose to begin a disciplinary procedure.
You can find an infinite number of reasons why workers are not Able to attend occasion. When an employee will be late or unable to report to work, the employee must notify her or his supervisor when possible. If he's not able to report to work because of illness or circumstances out of her hands, she must notify the right person with a phone call. So if he fails to turn up, you have to try and get in contact with them. Occasionally he will have a fantastic reason for being absent from work and unable to contact their company. A worker might be regarded as abandoning their occupation whenever they are absent from work for a lengthy period without having given any notice. Sometimes he just did not know all of their options.
In case the worker does not respond to you in the interval Specified in the letter and you are in a position to be sure they've received it then you're able to assume that they've abandoned their employment and can proceed at any termination payments. He simply didn't come to work. An employee with a disability may require a prolonged absence from work because of their medical condition.
A document could possibly be mandatory if an individual wishes To work after a family crisis. Indeed, a recent report indicates that, each year, Chicago is one of the most financially disadvantaged urban districts in the nation. A health report may be an exceptionally valuable device that can pardon you from a whole lot of life bothers.
When it Regards fraudulent justification letters, you have to be very careful. To create your imitation excuse convincing, you need to be certain the letter or notice you gift to your boss seems real. The conventional medicinal excuse is sufficient to escape school or work. No matter the case, keep in mind which you needn't bother using a standard fake medical justification, you need the ideal excuse. For instance, you might start the sentence, " I believe the new working hours would have the following positive effects on the business" You might truly feel the need to guarantee your supervisor your program change will not negatively impact the department's operations or your own capacity to control the workload.
A Comprehensive approach to managing a top Excellent note is to Receive it from a respectable website which offers premium dr. notes. There is truly not anything wrong with utilizing notes repeatedly. A dentist's note is a little paper that might have a watermark on it, and it might cover a huge variety of procedures. You need a strong note your higher-ups will not address. A bogus note from a physician or a clinic gives you the reason you require.
That the employee has missed work to get a certain number of times. The letter have some components inside them folks can cut and paste, also. It should be prepared and delivered once the employee or student is aware of the duty to be in court. Letters of explanation are similarly employed by people who have been picked, however, can't pay a visit to the prosecution obligation.
The doctor may ask the employer or instructor to Supply you A bit of time-off to recover. At length, the professor walked . As a parent, you're in a position to completely anticipate the teachers and college to at least keep a watch out for your kid and permit you to know whether they see any issues. Parents continue to be perfectly free to excuse or ignore their children' presence difficulties, but knowing their child is falling behind peers may be all they need to behave. There are obviously many very good parents who despite the never-ending obligations of a parent, so make sure their child is on the proper path. My relationships with every relative proved very strained. Parental participation in schools can create the difference between an awful school and a fantastic school and an excellent school and fantastic school.
Your job demands full time commitment! Feel enthusiastic when performing work. If you don't have to lose your job due to a poorly forged notice, get the best one here. Your job starts annoying you and you will need to eradicate it. When you are accepted for work, you have to attend orientation training in case you are not a certified instructor. Or it's not going to be simple for them to deal with the job you were doing.
A back to work note is sometimes essential for the employer To permit the worker to return to perform the job. From the example of attendance letters, the more personalized, relative correspondence makes a decision based on new information and provides a different social context to your choice. Occasionally, the reasons are extremely personal and don't will want to go shared. My situation was not unknown. When it's to do with an issue as complex as absenteeism, the potential for the 2 prizes and penalties are able to really make a difference. Consequently, nobody will intervene on your personal matter. For this reason, you could have a couple problems, irrespective of the risk your explanation is accepted.
Allocating funds for letters could possibly be a harder task. The website has plenty of packages out there. There are rather a lot of Sites which seem to provide these fake note designs free of price. Hold on to The certified mail receipt so you can check on the internet to see when The letter has been sent. Although, there are many websites online Offering fake letters and documents, you will have to choose the perfect one For you. Regardless of whether you are going to be checking your email.


The American housing stock continues to age; a trend that represents an opportunity for remodelers and over the long term may signal a future increased demand for new home construction.
The 2011 AHS also found that 41% of the owner-occupied housing stock in the U.S. was built prior to 1969. Homes built from 2000 to 2009 account for 15% of the owner-occupied housing stock.
The share of the housing stock at least 40 years old, 41%, represents a significant increase over prior years. The share in 2001 was 35% and only 27% in 1991. The share of the housing stock at least 20 years old also increased significantly over the time period.


Is the anxiety that you suffer from more than just the standard worries and everyday stress? It is possible that you are facing a more serious anxiety condition and require the services of a professional. In the article that follows, you will learn tips on how you can relieve anxiety.
Think of your worst fear and tell a trusted person about it, exaggerating as much as possible when you tell them. After hearing how ridiculous you sound out loud, often people see their fear from a different perspective.
As soon as you wake up each morning, you should take some time to tell yourself some positive affirmations. Voice what you wish to accomplish that day and how you want to spend it. Then, do the best that you can to ensure that it happens that way.
Stay busy; stay active. These are keys to success with anxiety. If you spend your entire day sitting on the sofa and focusing on nothing at all, you just might find that your mind wanders to anxious thoughts. Simple things such as cleaning the house or washing your car can be really effective.
Keep a diary. Many find this especially useful, not realizing that they are harboring anxious thoughts. When using a diary to let go of the stress in your mind, your brain is free to think about what is going on right now.
Talk to someone about your feelings, whether it's a friend, family member or a doctor or therapist. Holding all of your feelings in will only make your feelings worsen. Sharing your feelings can help you feel a lot better and lower anxiety levels.
If you have a hard time relaxing and cutting down racing thoughts when you are trying to sleep, try keeping a journal or a diary. Just a few minutes spent writing your problems down on paper can assist you in getting your thoughts out, helping you with sleep. Be sure to work on your journal as often as necessary.
A lot of people that have stress and anxiety don't relax enough. Make time daily to relax and quiet your mind. By just relaxing for half an hour or less every day, you're anxiety levels will begin to decrease.
If you are worried about something, talk it out with someone. A good support system is crucial to anyone dealing with anxiety. Talking things over can reduce the stress and anxiety you feel every day.
Practice being aware of the present. Some of the worst things anxious folks can do is focusing too much on past events and future obligations. This creates worry, and causes you to feel overwhelmed which leads to other feelings that can trigger an anxiety attack. Minimize anxiety by thinking only about your current activity.
It will be apparent to you by now that effective treatments are required to deal with anxiety issues. Anxiety is not something you should ignore or try to get over alone. Luckily, there are treatments that can assist you out there. By using the excellent information that you read here, you will be able to decrease your symptoms of anxiety.


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Hurtigruten to Do Total Makeover of Four Ships in 2016
Hurtigruten Announces Total Makeover of Four of its Ships. Follows the Purchase and Major Upgrade of Hurtigruten's Newest Ship – MS Spitsbergen
Renovation costs budgeted at more than 550 million NOK ($64M US)
Seattle, November 2015 – Hurtigruten has announced a major renovation initiative for 2016. All four of their mid-1990s-built ships are being upgraded with new interiors and furnishings – reflecting a modern Scandinavian design inspired by the scenery of "the world's most beautiful voyage," so named by several leading publications when describing Norway's fjord-indented west coast. The Norwegian shipyard Fosen Yards has won the contract in an international tender and the work will be done around the clock.
The four ships will be rotated through the shipyard with work expected to take a little over three weeks for each of the four ships: the MS Polarlys (completed by Feb. 2); MS Kong Harald (Feb. 7); MS Nordkapp (April 19); and MS Nordnorge (Nov. 18). The new MS Spitsbergen, undergoing a more major upgrade to fit in with the current fleet, will launch in the Spring.
Established more than 120 years ago to serve as a lifeline for the cities, towns and villages along the Norway coast, the pioneer explorer company from the country of Amundsen and Nansen has been a leader in the fast growing global adventure cruise tourism market. "As we continue to reinvent the Hurtigruten experience by combining tradition, innovation and sustainability, our ship upgrades aim to ensure our position as an innovator and leading force in nature-based explorer travels in polar waters," says Hurtigruten CEO Daniel Skjeldam.
The updated look for these ships has been named New Arctic Interior and will reflect the breath-taking coastal landscapes in a stylish and yet unpretentious manner. All of the ship's common areas, reception foyers, cafes and bistro areas and the aft deck will be renovated. The colors will be earthy and derived from the coast and the sea, while making use of many natural materials, such as wood, slate and leather. Designs and shapes are expected to bear a resemblance to those found in nature - such as the flow of the waves or the strength of the majestic fjords.
In addition, the ongoing transformation of the restaurants and the food served will continue. With more than 100,000 foreign guests sailing annually, Hurtigruten has partnered with dozens of local food suppliers to develop the Coastal Kitchen concept. With seasonal ingredients, often harvested the same day, guests are able to enjoy the freshest and best Norwegian food available. A range of fresh pastries from the ship's own bakeries will be offered and barbeque stands are being added to the outside decks. The all-important bar will be moved to the panoramic lounge, offering incredible views as guests enjoy an afternoon or evening cocktail. And fitness rooms will now have the world's best views.
Hurtigruten is a world leader in exploration travel, sailing to the most remote of destinations – Antarctica, Spitsbergen, Greenland and Iceland - as well as year-round along Norway's coast. The company's fleet of intimate ships, each of which carry 100 to 646 guests, allows travelers to enjoy the scenery and culture of the destination in a relaxed atmosphere.
Additional information, brochures and reservations can be obtained from travel agents or Hurtigruten's visitor-friendly website, www.hurtigruten.us; by phone at 877-301-3117; or fax at 888-524-2145. To order brochures 24 hours a day, call 800-582-0835.


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Elevation 27 and Aidnow present: An Evening with Mac McAnally
Performance Date
Performance Name
Performance Info
Performance Tickets
Elevation 27 and Aidnow present: An Evening with Mac McAnally8:00 PM | Doors: 7:00 PM
Elevation 27Virginia Beach, VA
Buy Tickets $40.00 - $75.00
Elevation 27 and Aidnow are proud to present - an evening with the record-breaking 10-time CMA Musician of the Year, a longtime and current member of Jimmy Buffett's Coral Reefer Band - MAC MCANALLY!
FRIDAY, AUGUST 2nd at 8:00 PM, 7:00 PM Doors
Tickets: General Admission - $40.00
Reserved Dining - $55.00
Reserved Dining with Meet and Greet - $75.00
* Aidnow is a Virginia Beach non-profit that provides educational resources and services for local homeless students and children living in poverty locally and throughout the world *
General Admission tickets are standing room only.
Reserved Seating Tickets at Dining Tables and Booths include admission to the show. If your party does not occupy all the seats at a Table or Booth, you may be seated with other guests. You must arrive at or before the time assigned to your table or booth, or your seat may be given away. Waitress service will be available approximately 30 minutes after you are seated. Please allow an additional 30 minutes for your food to arrive. *All Reserved Seating Tickets are subject to a requested food minimum of $9.00 per guest.
Please note: If our parking lot is full, please park in the Walmart parking lot closest to Advance Auto.
A record-breaking 10-time CMA Musician of the Year, Mac McAnally is a NashvilleSongwriters Hall of Fame, Mississippi Musicians Hall of Fame, and Alabama MusicHall of Fame inductee. The renowned songwriter, singer, and instrumental virtuoso has authored dozens of hit records for other artists, several of which peaked at No. 1. His own recording career began with a debut hit single "It's a Crazy World" (1977) and continues most recently with this 14th album relaseSouthbound(2017), an ambitious orchestral adaptation of many of his best-known songs. He has written hits for Alabama, Jimmy Buffett, Kenny Chesney, and Sawyer Brown, and has studio credits that include albums by Toby Keith, Linda Ronstadt, George Strait, Dolly Parton, Brad Paisley, and Amy Grant, among many others.