Building a Research Data Registry for the UK

Presentation at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

Methyl and ethyl chloride synthesis in microreactors

Methyl chloride is an important chemical intermediate with a variety of applications. It is produced today in large units and shipped to the endusers. Most of the derived products are harmless, as silicones, butyl rubber and methyl cellulose. However, methyl chloride is highly toxic and flammable. On-site production in the required quantities is desirable to reduce the risks involved in transportation and storage. Ethyl chloride is a smaller-scale chemical intermediate that is mainly used in the production of cellulose derivatives. Thus, the combination of onsite production of methyl and ethyl chloride is attractive for the cellulose processing industry, e.g. current and future biorefineries. Both alkyl chlorides can be produced by hydrochlorination of the corresponding alcohol, ethanol or methanol. Microreactors are attractive for the on-site production as the reactions are very fast and involve toxic chemicals. In microreactors, the diffusion limitations can be suppressed and the process safety can be improved. The modular setup of microreactors is flexible to adjust the production capacity as needed. Although methyl and ethyl chloride are important chemical intermediates, the literature available on potential catalysts and reaction kinetics is limited. Thus the thesis includes an extensive catalyst screening and characterization, along with kinetic studies and engineering the hydrochlorination process in microreactors. A range of zeolite and alumina based catalysts, neat and impregnated with ZnCl2, were screened for the methanol hydrochlorination. The influence of zinc loading, support, zinc precursor and pH was investigated. The catalysts were characterized with FTIR, TEM, XPS, nitrogen physisorption, XRD and EDX to identify the relationship between the catalyst characteristics and the activity and selectivity in the methyl chloride synthesis. The acidic properties of the catalyst were strongly influenced upon the ZnCl2 modification. In both cases, alumina and zeolite supports, zinc reacted to a certain amount with specific surface sites, which resulted in a decrease of strong and medium Brønsted and Lewis acid sites and the formation of zinc-based weak Lewis acid sites. The latter are highly active and selective in methanol hydrochlorination. Along with the molecular zinc sites, bulk zinc species are present on the support material. Zinc modified zeolite catalysts exhibited the highest activity also at low temperatures (ca 200 °C), however, showing deactivation with time-onstream. Zn/H-ZSM-5 zeolite catalysts had a higher stability than ZnCl2 modified H-Beta and they could be regenerated by burning the coke in air at 400 °C. Neat alumina and zinc modified alumina catalysts were active and selective at 300 °C and higher temperatures. However, zeolite catalysts can be suitable for methyl chloride synthesis at lower temperatures, i.e. 200 °C. Neat γ-alumina was found to be the most stable catalyst when coated in a microreactor channel and it was thus used as the catalyst for systematic kinetic studies in the microreactor. A binder-free and reproducible catalyst coating technique was developed. The uniformity, thickness and stability of the coatings were extensively characterized by SEM, confocal microscopy and EDX analysis. A stable coating could be obtained by thermally pretreating the microreactor platelets and ball milling the alumina to obtain a small particle size. Slurry aging and slow drying improved the coating uniformity. Methyl chloride synthesis from methanol and hydrochloric acid was performed in an alumina-coated microreactor. Conversions from 4% to 83% were achieved in the investigated temperature range of 280-340 °C. This demonstrated that the reaction is fast enough to be successfully performed in a microreactor system. The performance of the microreactor was compared with a tubular fixed bed reactor. The results obtained with both reactors were comparable, but the microreactor allows a rapid catalytic screening with low consumption of chemicals. As a complete conversion of methanol could not be reached in a single microreactor, a second microreactor was coupled in series. A maximum conversion of 97.6 % and a selectivity of 98.8 % were reached at 340°C, which is close to the calculated values at a thermodynamic equilibrium. A kinetic model based on kinetic experiments and thermodynamic calculations was developed. The model was based on a Langmuir Hinshelwood-type mechanism and a plug flow model for the microreactor. The influence of the reactant adsorption on the catalyst surface was investigated by performing transient experiments and comparing different kinetic models. The obtained activation energy for methyl chloride was ca. two fold higher than the previously published, indicating diffusion limitations in the previous studies. A detailed modeling of the diffusion in the porous catalyst layer revealed that severe diffusion limitations occur starting from catalyst coating thicknesses of 50 μm. At a catalyst coating thickness of ca 15 μm as in the microreactor, the conditions of intrinsic kinetics prevail. Ethanol hydrochlorination was performed successfully in the microreactor system. The reaction temperature was 240-340°C. An almost complete conversion of ethanol was achieved at 340°C. The product distribution was broader than for methanol hydrochlorination. Ethylene, diethyl ether and acetaldehyde were detected as by-products, ethylene being the most dominant by-product. A kinetic model including a thorough thermodynamic analysis was developed and the influence of adsorbed HCl on the reaction rate of ethanol dehydration reactions was demonstrated. The separation of methyl chloride using condensers was investigated. The proposed microreactor-condenser concept enables the production of methyl chloride with a high purity of 99%.

Studies of rotor dynamics using a multibody simulation approach

The non-idealities in a rotor-bearing system may cause undesirable subcritical superharmonic resonances that occur when the rotating speed of the rotor is a fraction of the natural frequency of the system. These resonances arise partly from the non-idealities of the bearings. This study introduces a novel simulation approach that can be used to study the superharmonic vibrations of rotor-bearing systems. The superharmonic vibrations of complex rotor-bearing systems can be studied in an accurate manner by combining a detailed rotor and bearing model in a multibody simulation approach. The research looks at the theoretical background of multibody formulations that can be used in the dynamic analysis of flexible rotors. The multibody formulations currently in use are suitable for linear deformation analysis only. However, nonlinear formulation may arise in high-speed rotor dynamics applications due to the cenrrifugal stiffening effect. For this reason, finite element formulations that can describe nonlinear deformation are also introduced in this work. The description of the elastic forces in the absolute nodal coordinate formulation is studied and improved. A ball bearing model that includes localized and distributed defects is developed in this study. This bearing model could be used in rotor dynamics or multibody code as an interface elements between the rotor and the supporting structure. The model includes descriptions of the nonlinear Hertzian contact deformation and the elastohydrodynamic fluid film. The simulation approaches and models developed here are applied in the analysis of two example rotor-bearing systems. The first example is an electric motor supported by two ball bearings and the second is a roller test rig that consists of the tube roll of a paper machine supported by a hard-bearing-type balanceing machine. The simulation results are compared to the results available in literature as well as to those obtained by measuring the existing structure. In both practical examples, the comparison shows that the simulation model is capable of predicting the realistic responses of a rotor system. The simulation approaches developed in this work can be used in the analysis of the superharmonic vibrations of general rotor-bearing systems.

Design and Simulation of High-Speed Rotating Electrical Machinery

Global energy consumption has been increasing yearly and a big portion of it is used in rotating electrical machineries. It is clear that in these machines energy should be used efficiently. In this dissertation the aim is to improve the design process of high-speed electrical machines especially from the mechanical engineering perspective in order to achieve more reliable and efficient machines. The design process of high-speed machines is challenging due to high demands and several interactions between different engineering disciplines such as mechanical, electrical and energy engineering. A multidisciplinary design flow chart for a specific type of high-speed machine in which computer simulation is utilized is proposed. In addition to utilizing simulation parallel with the design process, two simulation studies are presented. The first is used to find the limits of two ball bearing models. The second is used to study the improvement of machine load capacity in a compressor application to exceed the limits of current machinery. The proposed flow chart and simulation studies show clearly that improvements in the high-speed machinery design process can be achieved. Engineers designing in high-speed machines can utilize the flow chart and simulation results as a guideline during the design phase to achieve more reliable and efficient machines that use energy efficiently in required different operation conditions.

Minkä nuorena hallitsee sen aikuisena taitaa? Liikehallinnan pysyvyys kouluiästä aikuisikään – 24 vuoden seurantatutkimus

Tässä 24 vuoden pitkittäistutkimuksessa tutkitaan liikehallinnan kehitystä ja pysyvyyttä kouluiästä aikuisikään. Lisäksi ennustetaan ja selitetään aikuisiän liikehallintaa kouluiän liikehallinnan perusteella. Tutkimukseen osallistui 44 miestä ja 44 naista eri puolilta Suomea, joiden liikehallintaa mitattiin kouluiässä 1985 ja 1988 (9–16-vuotiaina) sekä aikuisiässä 2009 (33−39-vuotiaina). Liikehallintaa mitattiin kuudella liiketehtävämittarilla (flamingoseisonta, tarkkuusheittokiinniotto, kahdeksikkokuljetus, edestakaisinhyppely, vauhditon 5-loikka ja kärrynpyörä) sekä niistä lasketulla summamuuttujalla. Miesten ja naisten liikehallintaa vertailtiin varianssianalyysilla. Kouluiässä pojat menestyivät välineenkäsittelytehtävissä ja tytöt tasapaino- ja voimistelutehtävissä, mutta kokonaisuutena sukupuolten välillä ei ollut eroa. Aikuisena miehet olivat naisia parempia lähes kaikissa tehtävissä. Kovarianssianalyysissä havaittiin, että kehonrakenteeltaan (BMI) erilaisten ryhmien liikehallinnassa oli vain yksittäisiä eroja koulu- ja aikuisiässä. Toistettujen mittausten varianssianalyysissa ilmeni, että kouluiässä molempien sukupuolten liikehallinnan kehitys oli samanlaista. Kouluiän jälkeen kevyiden ja keskipainoisten poikien liikehallinta parani, mutta painavien tulokset eivät muuttuneet. Kevyiden tyttöjen tuloksissa ei tapahtunut muutosta, mutta keskipainoisten ja painavien tulokset heikkenivät. Koululiikunnan tehostus- ja vertailuryhmien välille kouluiässä muodostuneet erot kaventuivat tai katosivat aikuisena. Kouluiän liikehallinnaltaan eritasoisten ryhmien väliset erot kaventuivat, mutta eivät poistuneet kouluiän jälkeen. Klusterianalyysissa tutkittavat jakaantuivat kouluiässä neljään liikehallintatyyppiin (yleishyvät, tasapainoiset, pallotaitajat ja yleisheikot), jotka säilyivät myös aikuisiässä, mutta niiden väliset erot kaventuivat. Ristiintaulukointi ja khiin neliö -testi osoittivat, että tasoryhmän ja liikehallinnan monipuolisuuden pysyvyys oli vahvaa kouluiästä aikuisikään. Koulu- ja aikuisiän liikehallintatulosten välinen korrelaatio oli naisilla (0.69) vahvempaa kuin miehillä (0.48). Yksittäiset mittaustulokset kouluiässä selittivät keskimäärin 33 % aikuisiän tuloksista (korrelaation neliö). Regressioanalyysissa miesten aikuisiän liikehallintaa selittivät kouluiän muuttujista parhaiten liikehallinnan monipuolisuus sekä liikkuvuus (61 %), mutta naisilla vain liikehallinnan monipuolisuus (37 %). Miesten ja naisten erot liikehallinnassa syntyivät kouluiän jälkeen, mikä johtunee erilaisista liikuntatavoista ja -harrastuksista. Kouluiän liikehallinta määritti vahvasti varsinkin tytöillä aikuisiän liikehallintaa sekä yksilö- että ryhmätasolla, mikä korostaa monipuolisen koululiikunnan merkitystä. Yksilölliset muutokset olivat mahdollisia. Kouluiän jälkeen erityisesti naiset ja kehonrakenteeltaan painavat tarvitsisivat hermolihasjärjestelmää monipuolisesti kuormittavaa ja liikesuunniltaan moniulotteista liikuntaa liikehallinnan kehittämiseksi ja ylläpitämiseksi. Naisten liikehallinnan taantuminen varsinkin tasapainotehtävissä voi altistaa kaatumistapaturmille ja rajoittaa fyysistä toimintakykyä.

Post Scrum

The opposing team has the ball.

The Attack

A Brock player hits the ball over in this match suspected to be from 87/88 or 88/89.

The effect of literacy training on the self-concept of moderately mentally handicapped adults

In this single group, pretest/posttest design study the literacy level and self-concept of nine moderately mentally handicapped adults was assessed. The participants in the study were involved in reading lessons using the Ball-Stick-Bird reading system, a brainbased program. No significant differences were found in either literacy level or reading level after intervention. However, there were changes in reading behaviour. These changes occurred in the subskills ofdirectionality, letter-sound correspondence, wordreading, and use of reading materials.

Grantham Township Records Collection

Item one is a minute book for Grantham Township, Ontario. It records the proceedings of meetings from 1818-1854 and the names of parish and town officers from 1818 to 1842. Names include: Chisholm, Ball, Steele, TenBroeck, Shipman, Laraway, McKerney, Adams, Pawling, Merritt, Rolls, Robertson, Lampman, Phelps, Darling. Also notes the laws agreed upon for the period - mainly dealing with livestock. Item two is a report and evidence of boundary line disputes in the Township of Grantham. Includes affidavits from witnesses to the boundary dispute and a report to the Honourable the Commissioner of Crown Lands Quebec. The affadavits were recorded in 1844, and transcribed into the folio in 1852. Lewis A. Ball was the commissioner before whom the affadavits were sworn and duly recorded. Includes field notes by Frederic F. Passmore, Provincial land surveyor. The boundary lines in dispute were 1. between the 2nd and 3rd Concessions, from Lot no. 1 to Lot no. 5, 2. between the 4th and 5th concessions, from lot no. 4 to lot no. 5 and 3. between lots 14 in the 9th and 10th concession of the Township of Grantham.

Second Welland Canal - Book 2, Survey Map 6 - Locks 19, 20, 21 and 22 in Grantham

Survey map of the Second Welland Canal created by the Welland Canal Company showing south Merritton along the boundary between the Grantham and Thorold Townships. Identified structures associated with the Canal include Locks 19, 20, 21, and 22, Lock Tenders House, and the towing path. The surveyors' measurements and notes can be seen in red and black ink and pencil. Local area landmarks are also identified and include streets and roads (ex. Pine Street and Macadamized Road), J. Brown Cement Mill, W. B. Hendershot Saw Mill, W. Parnall Spoke and Sash Factory, W. Beatty Saw Mill, W. Beatty Tannery, a number of structures (possibly houses) belonging to: Mrs. Aikins, J. Battle, and E. Keefer, and a foundry, smithy, and machine shop (all of which possible belonged to J. Dobbie). Properties and property owners of note are: Concession 10 Lots 9 and 10, W. C. Loan Company, P.H. Ball, and J. Keefer. Two small properties belonging to W. B. Hendershot and W. Beatty exist and are outlined in red. A half acre property reserved for a lock lot exists and is outlined in blue. An additional property reserved for a quarry is also identified, but not outlined.

Welland Canal Survey of Lands John Martindale

Survey map and description of John Martindale's land created by The Welland Canal Company. Included is a written description of the land along with a drawing of the land. Noteable features include; property line between Martindale and Tenbroeck properties, original bed of 12 mile creek, tpw path diagram for the Welland canal on the wrong side of the diagram should be on the east side. The land was originally in the posession of William Ball when the original land survey was completed by G. Keefer in 1831. The land was also surveyed by Wm. Rykert. The description and sketch was not used in making the deed for the land. Surveyor notes are seen in pencil on the map.

Welland Canal Survey of Lands Thomas Ker 1826

Survey map and description of Thomas Ker's land created by The Welland Canal Company. Included is a written description of the land along with a drawing of the land. Noteable features include; line between Jacob I. Ball and Thomas Ker's land, line between Widow Ball and Thomas Ker's land, part of the land taken for hydraulic purposes is marked. Surveyor notes are seen in pencil on the map. The survey for the land was signed and submitted August 23, 1826. An additional piece of land was surveyed on November 28, 1834 for 2 1/4 acres. The land was used by the Welland Canal Company for both canal and hydraulic purposes in lot no.10 in the 10th concession of Grantham.

Average White Band poster, ca. 2000

The Average White Band's debut album, Show your hand, was released in 1973. The "classic funk and R & B" band included members Alan Gorrie, Owen "Onnie" McIntyre, Malcolm "Mollie" Duncan, Roger Ball, Robbie McIntosh, and Mike Rosen. Rosen was quickly replaced by Hamish Stuart. The band, comprised of Scotsmen, released a second album in 1974 that featured the US number 1/UK Top 10 single "Pick up the Pieces". That same year, Robbie McIntosh died of a heroin overdose and was replaced by Steve Ferrone. The song "Cut the Cake" from their third album made the US top 10, and subsequent releases in the late 1970s and early 1980s proved successful. The members largely pursued individual projects in the years that followed, but re-formed in 1989 (with original members Gorrie, Ball and McIntyre, and new members Alex Ligertwood and Eliot Lewis) and released the album Aftershock. Over the years, the band's members have changed, and the band is currently comprised of Onnie McIntyre, Rocky Bryant, Alan Gorrie, Fred "Freddy V" Vigdor and Klyde Jones. Their most recent album, Times Squared, was released in 2009.