DOCSLIB.ORG

Production of Acrylic Acid from Ethylene

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Production of Acrylic Acid from Ethylene University of Pennsylvania ScholarlyCommons Department of Chemical & Biomolecular Senior Design Reports (CBE) Engineering 4-2014 Production of Acrylic Acid from Ethylene Patricia Campos University of Pennsylvania Minsik Jun University of Pennsylvania Rahul Puranmalka University of Pennsylvania Follow this and additional works at: https://repository.upenn.edu/cbe_sdr Part of the Biochemical and Biomolecular Engineering Commons Campos, Patricia; Jun, Minsik; and Puranmalka, Rahul, "Production of Acrylic Acid from Ethylene" (2014). Senior Design Reports (CBE). 61. https://repository.upenn.edu/cbe_sdr/61 This paper is posted at ScholarlyCommons. https://repository.upenn.edu/cbe_sdr/61 For more information, please contact [email protected]. Production of Acrylic Acid from Ethylene Abstract A preliminary process design and economic analysis into the possible threat of ethylene- based acrylic acid manufacture is presented. Pipeline ethylene is fed at 14,000 ft2/hr to the first block of this process. The epoxidation of ethylene to ethylene oxide takes advantage of microchannel technology and eliminates the need for inerts, thus decreasing equipment sizing downstream while achieving a yield of 80% overall. The resulting ethylene oxide stream is carbonylated in a liquid phase, homogeneous reaction. The β-propiolactone is then rearranged in phosphoric acid to produce 37,000 lbs of acrylic acid per hour for a yearly rate of just over 300M pounds at greater than 99.4% mass purity. The product contains 300 ppm mono-methyl ether hydroquinone to prevent the product from polymerizing and entering the explosive limits. Using an after tax discount rate of 15%, the NPV is -$50M in December, 2014, 35 years from construction start date. The IRR is 13.84% and confirms the notion that a microchannel costs need to be further evaluated to determine the profitability. In the project, the EO plant accounts for 90% of the equipment cost and 50% of the total invested capital cost. A cost plus analysis of ethylene oxide costs was determined and IRR data was determined based on the variability of ethylene prices and the cost-plus price of producing ethylene oxide. It was determined that the project has an IRR of 42.17% with a NPV of $288M when an after tax cash flow analysis was conducted with an after tax discount rate of 15%. It was concluded that the feasibility of this project depends heavily on the cost of the microchannel reactors, and at this stage, the costs of the microchannel do not outweigh the advantages offered by the new reactor. It is recommended that further analysis be done to more accurately cost the microchannel reactor and to investigate the benefits of increasing the per pass conversion of ethylene. Further analysis on the reactor designs and rates for the carbonylation step and rearrangement step could help hone in the reality of an ethylene based acrylic acid process. Most importantly, further economics should be conducted to see if the best-case scenario assumptions used in this paper are too ideal. The new economics should be compared to the sensitivity analysis conducted in this study. Disciplines Biochemical and Biomolecular Engineering | Chemical Engineering | Engineering This working paper is available at ScholarlyCommons: https://repository.upenn.edu/cbe_sdr/61 Mr. Leonard Fabiano University of Pennsylvania School of Engineering & Applied Science 220 S 33rd Street Philadelphia, PA 19104 Dear Mr. Fabiano, Enclosed is our design for an ethylene based acrylic acid production plant in fulfillment of the design problem proposed by Mr. John Wismer. In this report, we investigate the potential for ethylene based acrylic acid to pose a threat to the propylene based business due to the natural gas boom in the US. The investigation involves designing the epoxidation of ethylene using microchannel technology, carbonylation of ethylene oxide to β-propiolactone using a homogeneous, cobalt catalyst, and acid catalyzed rearrangement of β-propiolactone. The report focuses on plant design and an economic analysis to determine the threat posed in the US by recent price changes in the cost of ethylene due to shale gas. The plant is designed to operate 24 hours a day for 350 days a year, with a yearly production rate of 300M lbs of acrylic acid. Economics were calculated based on the entire plant and based on ethylene-oxide cost plus analysis. For the entire plant, total permanent investment would entail $ $560M with profitability depending closely on the total permanent investment. Using present ICIS commodity chemical pricing, the Project has an IRR of 13.48% with a NPV of -$50M after 35 years. Using cost plus analysis, the non-EO section of the plant has a total capital investment of $120M with an IRR of 42.17% and an NPV of $288M over 35 years. Details regarding the process equipment and plant profitability are enclosed, along with safety requirements. Based on this analysis, further design work must be taken verify the assumptions that have been made for this process. Determining the price and effectiveness of the microchannel reactor is key for evaluating the benefits of using a process that is void of inerts and diluents. It is crucial that pilot plant work should be undertaken to understand the true kinetics behind the carbonylation of β-propiolactone since the kinetics determine the necessary resonance time, the reactor size, per pass conversion, and overall efficiency. Pilot plant testing should be undertaken to determine the ratio of β-propiolactone to phosphoric acid needed for rearrangement on a larger scale. Reconciling this information with the data in this project would paint a clearer picture to the profitability of ethylene-based acrylic acid using cost-plus analysis. At this stage, the group concludes the idea that ethylene based acrylic acid could be a threat to propylene based manufacturers cannot be disqualified and should be further investigated. Sincerely, Rahul Puranmalka Minsk Jun Patricia Campos Production of Acrylic Acid from Ethylene Campos, Jun, Puranmalka Table of Contents Section 1 – Abstract ........................................................................................................................ 6 Section 2 – Introduction .................................................................................................................. 8 2.1 Product .................................................................................................................................. 9 2.2 Current Methods of Production ........................................................................................... 10 2.3 Proposed Production Method .............................................................................................. 10 2.3.1 Step 1: Oxidation of Ethylene ...................................................................................... 11 2.3.2 Step 2: Carbonylation of Ethylene Oxide ..................................................................... 13 2.3.3 Step 3: Acid-Catalyzed Rearrangement of β-Propiolactone ........................................ 15 2.4 Customer Requirements ...................................................................................................... 16 2.5 Commercial Applications .................................................................................................... 16 2.6 Project Charter..................................................................................................................... 17 2.7 Innovation Map ................................................................................................................... 18 Section 3 – Process Description .................................................................................................... 19 3.1 Overview ............................................................................................................................. 20 3.2 Block 100: Epoxidation of Ethylene to Ethylene Oxide ..................................................... 21 3.2.1 Microchannel Reactor ................................................................................................... 22 3.2.2 Ethylene Oxide Scrubbing ............................................................................................ 22 3.2.3 Ethylene Oxide Purification ......................................................................................... 23 3.2.4 CO2 Separation ............................................................................................................. 23 3.3 Block 200: Carbonylation of Ethylene Oxide to β-Propiolactone ...................................... 25 3.4 Block 300: Acid Catalyzed Rearrangement of β-Propiolactone to Acrylic Acid ............... 27 3.4.1 Reactor and Purification of Acrylic Acid ..................................................................... 28 3.4.2 Acrylic Acid Storage and Handling .............................................................................. 28 1 Production of Acrylic Acid from Ethylene Campos, Jun, Puranmalka Section 4 – Flow Sheets and Stream Reports ............................................................................... 30 4.1 Section 100 - Epoxidation of Ethylene ............................................................................... 31 4.2 Section 200 - Carbonylation of Epoxide ............................................................................. 35 4.3 Section 300 - Acid Catalyzed Rearrangement ...................................................................
Load more

Recommended publications
  • Rheology Modification of Hydrogen Peroxide-Based Applications Using
    Rheology Modification of Hydrogen Peroxide-Based Applications Using Cross-Linked Polyacrylic Acid Polymers* Julie Schmucker-Castner and Dilip Desai The BFGoodrich Company 1. Key Words: Hydrogen Peroxide, Hair Bleach, Two-Part Hair Color, Rheology Modification, Thickened Hydrogen Peroxide, Hydrogen Peroxide Gels, Hydrogen Peroxide Stability, Cross-Linked Polyacrylic Acid, Carbomer, Acrylates / C10-30 Alkyl Acrylate Crosspolymer 2. Summary: A fundamental study of the stability of hydrogen peroxide-based gels, thickened using cross-linked polyacrylic acid polymers, will be presented. Recent systematic experiments will demonstrate that excellent long-term stability of such gels can be achieved. The study evaluates different types of cross- linked polyacrylic acid polymers (as well as an associative acrylic polymer), several commercial sources of hydrogen peroxide, hydrogen peroxide concentrations and the effect of pH. Resulting viscosities from combinations of these variables will be presented, as well as the effects of accelerated aging on percent active peroxide and viscosity of the thickened peroxide gels. The results of this study will enable the formulator to determine the appropriate polymer and conditions necessary for optimal stability and rheological properties for hydrogen peroxide applications. This study will demonstrate that some cross-linked polyacrylic acid polymers are very compatible and stable with H2O2 and that these polymers do not affect the H2O2 stability under certain conditions. In addition, this study will show that certain cross-linked polyacrylic acid polymers can produce very viscous gels and yield higher viscosities in typical permanent hair color formulas compared to many commercially available products. Because of the excellent compatibility and stability demonstrated, cross-linked acrylic acid polymers are ideal rheological modifiers for hydrogen peroxide-based applications.
    [Show full text]
  • Provisional Peer-Reviewed Toxicity Values for Sulfolane (Casrn 126-33-0)
    EPA/690/R-12/024F l Final 1-30-2012 Provisional Peer-Reviewed Toxicity Values for Sulfolane (CASRN 126-33-0) Superfund Health Risk Technical Support Center National Center for Environmental Assessment Office of Research and Development U.S. Environmental Protection Agency Cincinnati, OH 45268 AUTHORS, CONTRIBUTORS, AND REVIEWERS CHEMICAL MANAGER Dan D. Petersen, PhD, DABT National Center for Environmental Assessment, Cincinnati, OH DRAFT DOCUMENT PREPARED BY ICF International 9300 Lee Highway Fairfax, VA 22031 PRIMARY INTERNAL REVIEWERS Ghazi Dannan, PhD National Center for Environmental Assessment, Washington, DC Q. Jay Zhao, PhD, MPH, DABT National Center for Environmental Assessment, Cincinnati, OH This document was externally peer reviewed under contract to Eastern Research Group, Inc. 110 Hartwell Avenue Lexington, MA 02421-3136 Questions regarding the contents of this document may be directed to the U.S. EPA Office of Research and Development’s National Center for Environmental Assessment, Superfund Health Risk Technical Support Center (513-569-7300). i Sulfolane TABLE OF CONTENTS COMMONLY USED ABBREVIATIONS ................................................................................... iii BACKGROUND .............................................................................................................................1 DISCLAIMERS ...............................................................................................................................1 QUESTIONS REGARDING PPRTVS ...........................................................................................1
    [Show full text]
  • Carbonylation of Protected Or Non-Protected 2-Bromobenzaldehyde Catalyzed by Cobalt Carbonyl
    772 Bull. Korean Chem. Soc. 1994, Vol. 15, No. 9 Sang Chui Shim et al. Carbonylation of Protected or Non-protected 2-Bromobenzaldehyde Catalyzed by Cobalt Carbonyl Sang Chui S버 m*, Dong Yub Lee, Heung Jin Choi, Chil Hoon Doh1, and Keun Tai Huh* ^Department of Industrial Chemistry, Kyungpook National University, Taegu 701-702, Korea ^Department of Materials Science and Engineering Kyungsung University, Pusan 608-736, Korea Korea Electrotechnology Research Institute, Changwon, Korea Received May 11, 1994 The cobalt catalyzed carbonylation of bromobenzene having protected aldehyde group gives the corresponding ester in good yields, but 2-bromobenzaldehyde gives 3-alkoxyphthalide in the noticeable yield instead of alkyl 2-formylben- zoates. Introduction Table 1. Carbonylation of 2-Bromobenzenes Having Protected Aldehyde Groups to 2-Substituted Alkyl Benzoates Catalyzed by The metal-catalyzed carbonyl가 ion of aryl halides has ver­ Cobalt CarbonyF satile utility in the preparative organic chemistry1. Of many Run Reactant catalysts2 used in the carbonylation of aryl halides cobalt Alcohol Product Yield (%y carbonyl species have been conducted under mild conditions, 1 1 CH3CH2OH 2b 88 room temperature and one atmospheric pressure of carbon 2 1 CH3CH2OH 2b 75 。 monoxide. More recently, using dicobalt octacarbonyl at room 3 1 CH3CH2OH 2b 38d temperature under one atmospheric pressure of carbon mo­ 4 1 CH3OH 2a 80 noxide many applications were reported on the carbonylation 5 1 CH3CH2CH2OH 2c 85 of benzal halides,3-5 and halo (halomethyl)benzenes6-8. 6 (CH3)2CHOH 21 However, studies2,9-11 on the carbonylation of aryl halides 1 2d 7 CH3CH2CH2CH2OH having other reactive functional groups are rare.
    [Show full text]
  • 2. Catalysis Involving CO
    2. Catalysis Involving CO (Source: Collman / Hegedus + Chiusoli / Maitlis + original papers mentioned below) !1 General Reactivity of CO-Complexes 1 is the resonance representing the pure "-donation of CO to the metal. 3 is contributing the most when the # back donation from the metal to CO is weak. The carbon is more electrophilic here. 2 is the extreme structure that evidences the # back donation of the metal to the #* of CO. !2 – Synthesis Gas and Water Gas Shift Reaction CO / H2 as feedstock. – Hydrocarbonylation (or Hydroformylation) of Olefins / Oxo Reaction Synthesis of aldehydes and alcohols from alkenes with cobalt and rhodium catalysts. – Carbonylation of Alcohols: Monsanto’s Acetic Acid Process Preparation of acetic acid from methanol and CO. !3 Synthesis Gas (Syn Gas, CO / H2) as Feedstock Steam over coal: C + H2O → CO + H2 0 0 (!ΔH 298 K = 131 kJ/mol; !ΔG1073 K= –12 kJ/mol) Steam reforming of methane: CH4 + H2O → CO + 3 H2 0 0 (!ΔH 298 K = 206 kJ/mol; !ΔG1073 K= –24 kJ/mol) Coupled with partial oxidation to give an endothermic overall reaction: H 0 2 C + H2O + O2 → CO + CO2 + H2 (Δ 298 K = –285 kJ/mol) 1 H 0 CH4 + 2 O2 → CO + 2 H2 (Δ 298 K = –36 kJ/mol) !4 Water-Gas-Shift Reaction (WGSR) Allows adjust the CO : H2 ratio by converting CO to H2: !!⇀ CO + H2O ↽!! CO2 + H2 Drawback: CO2 as byproduct. Catalysts: Heterogeneous Cr2O3 (T = 350°C) Cu-Zn-oxide (T = 200 – 300°C) Fe3O4 Homogeneous Carbonyl complexes: [FeH(CO)4]–, [RhI2(CO)2]–, [RuCl(bipy)2(CO)]+ !5 Homogeneously Catalyzed WGSR Principle: O CO OH– – CO2 M M CO M C M H – OH – + H O – ! M H 2 M + OH + H2 !6 Catalytic WGSR ! !7 Hydroformylation or Oxo Synthesis Synthesis of aldehydes and alcohols from alkenes.
    [Show full text]
  • Groundwater and Soil  Oxygen and Nutrients (Soil Tilling, Blowers) (Biogenie, 2006)
    RemTech 2016 Brent Lennox, M.Sc., P.Geol., Senior Hydrogeologist Eric Pringle, M.A.Sc., P.Eng., Principal Hydrogeological Engineer Waterline Resources Inc. Used in Sulfinol for sour gas sweetening since 1960s Human health related guidelines Poorly adsorbed to soil High solubility in water Microbial degradation slow in typical groundwater conditions Clear, colourless, no field indicators (visual or olefactory) Microbial degradation rapid in aerobic environments and surface water (CCME, 2006) + 2- C4H8O2S + 6.5O2 4CO2 + 3H2O + 2H +SO4 Nutrients improve degradation times Low pH conditions inhibit degradation Typical degradation times: 2 to 4 days at 28°C and 8 to 12 days at 8°C (Green et al., 1998), average air temperatures during trials ranged from 6.9 to 14.1°C Groundwater and Soil Oxygen and nutrients (soil tilling, blowers) (Biogenie, 2006) Groundwater Activated Sludge Treatment System (WorleyParsons Komex, 2008) Oxidants (e.g., hydrogen peroxide) and/or UV light Mixed success (Barr Engineering, 2013; Gallegos et al., 2013; EBA, 2015) Peroxide and iron catalyst shown to be more effective than peroxide (Gallegos, 2013) No sulphate as by-product Site is an operating gas plant located in southern Alberta Constructed in 1960s Sulfolane investigation and monitoring since 1994 No active facilities Downgradient of active facilities Majority of plant waste stored here before the 1980s Potential materials disposed: alumina catalyst, filters (compressor, sulfinol, salt water, glycol, solvent receiver), zeolite, etc. Cells
    [Show full text]
  • Reactions of Alkenes and Alkynes with Formaldehyde Catalyzed by Rhodium Systems Containing Phosphine Ligands
    J. Mex. Chem. Soc. 2017, 61(2), 120-127 Article © 2017, Sociedad Química de México ISSN 1870-249X Reactions of alkenes and alkynes with formaldehyde catalyzed by rhodium systems containing phosphine ligands Merlín Rosales,1* Beatriz González,1 Jessely Molina,1 Homero Pérez,1 María Modroño-Alonso2 and Pablo J. Baricelli2 1 Universidad del Zulia (L.U.Z.), Facultad Experimental de Ciencias. Departamento de Química, Laboratorio de Química Inorgánica (LQI). Maracaibo (Venezuela). 2 Universidad de Carabobo, Facultad de Ingeniería, Centro de Investigaciones Químicas, Valencia (Venezuela). * Corresponding author: Tel +584143602104 FAX +582614127701 Ciudad Universitaria. Módulo 2. Maracaibo. Venezuela e-mail adress: merlin2002 @cantv.net; [email protected] (M. Rosales) Received October 18th, 2016; Accepted March 8th, 2017. Abstract. The reaction of alkenes (allyl alcohol, styrene and C6 Resumen. La reacción de alquenos (alcohol alílico, estireno y alquenos alkenes) with formaldehyde was efficiently performed by using Rh C6) con formaldehido se realizó eficientemente usando precatalizado- precatalysts formed in situ by the addition of triphenylphosphine res de Rh formados in situ por adición de trifenilfosfina (PPh3), (PPh3), 1,2-bis(diphenylphosphino)ethane (dppe) or 1,1,1-tris(diphen- 1,2-bis(difenilfosfino)etano (dffe) o 1,1,1-tris(difenilfosfinometil) etano ylphosphinomethyl)ethane (triphos) to the complex Rh(acac)(CO)2 at (trifos) al complejo Rh(acac)(CO)2 a 130ºC en 1,4-dioxano, produ- 130ºC in 1,4-dioxane, yielding their corresponding aldehydes; the best ciendo los correspondientes aldehídos. El mejor sistema catalítico fue 2 catalytic system was Rh(acac)(CO)2/2dppe, which generates the cat- Rh(acac)(CO)2/2dffe, el cual genera el complejo catiónico [Rh(k -P,P- 2 + + ionic complex [Rh(k -P,P-dppe)2] .
    [Show full text]
  • Direct Carboniiatiom of Aromatic Nttriles Using
    DIRECT CARBONIIATIOM OF AROMATIC NTTRILES USING DICOBALT OCTACARBONIL by JOSEPH EDMUND GERVAX B..Sc Honours, University of Montreal, Loyola College, l?6l A THESIS SUBMITTED IN PARTIAL FUIFIIMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE in the Department of Chemistry We accept this; thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA June, 1963 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that per• mission for extensive copying of this thesis for scholarly purposes may be granted by the Head of my Department or by his representatives. It is understood that copying, or publi• cation of this thesis for financial gain shall not be allowed without my written permission. Department of CHEMISTRY The University of British Columbia,. Vancouver 8, Canada. Date June 2°» W ABSTRACT A new method of synthesizing N-substituted phthalimidines is described. When benzonitrile was reacted with carbon monoxide containing about 0.0k volume percent of hydrogen and in the presence of dicobalt octacarbonyl and pyridine in benzene solution at 235° and 3U00 p.s.i. pressure the following compounds were produced: MTbenzyphthalimidine (8$), N-phenylphthalimidine (3»7%), and benzamide (3*9%)- When lj.0 p.s.i. hydrogen was added under the same reaction conditions, the yield of N-benzylphthalimidine increased (16%)., When benzonitrile was subjected to the same reaction conditions using 2U0 p.s.d* hydrogen and no pyridine, N-benzylphthalimidine (1%%) and sym-dibenzylurea (8$) were produced.
    [Show full text]
  • Green Chemistry Accepted Manuscript
    Green Chemistry Accepted Manuscript This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available. You can find more information about Accepted Manuscripts in the Information for Authors. Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the Ethical guidelines still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains. www.rsc.org/greenchem Page 1 of 21 Green Chemistry Green Chemistry RSCPublishing CRITICAL REVIEW Catalytic Routes towards Acrylic Acid, Adipic Acid and ε-Caprolactam starting from Biorenewables Cite this: DOI: 10.1039/x0xx00000x Rolf Beerthuis, Gadi Rothenberg and N. Raveendran Shiju* Received 00th January 2012, The majority of bulk chemicals are derived from crude oil, but the move to biorenewable resources is Accepted 00th January 2012 gaining both societal and commercial interest. Reviewing this transition, we first summarise the types of today’s biomass sources and their economical relevance. Then, we assess the biobased productions DOI: 10.1039/x0xx00000x of three important bulk chemicals: acrylic acid, adipic acid and ε-caprolactam.
    [Show full text]
  • CO Route Cuts Acrylic Acid Costs
    BEST INNOVATION BY AN SME since the 1980s but, to date, no one has been able to develop an economically feasible proc- ess. The thermoplastic has similar properties to polyethylene terephthalate (PET), but with significantly higher barrier properties. Novomer’s proprietary system is based on ho- mogeneous catalyst technology that was origi- nally discovered at New York-based Cornell University by Geoffrey Coates, Novomer’s co-founder and chairman of its scientific advisory board. The significance of the process is that it enables the use of a low-cost monomer, in this case carbon monoxide (CO), which is combined with ethylene oxide (EO) to make propriolactone. Novomer says that the use of inexpensive raw materials, such as CO and ethane-derived EO, and the catalyst’s selec- Superabsorbent polymer (SAP) made with Novomer’s catalyst has the same tivity, which is in excess performance as SAP made using the traditional propylene-based route of 99%, means that the Novomer “Our ultimate vision... is that low molecular weight PPL CO route could be shipped globally and converted to AA or acrylate esters upon demand” MIKE SLOWIK cuts acrylic Director of chemicals, Novomer cost of the process is potentially 40% lower than current available technologies. acid costs In addition, the process is expected to have a lower carbon and energy footprint because it operates at moderate temperatures, notably between 30-50oC. This compares with an Novomer, winner of the Best Innovation by an SME operating temperature of over 250oC in the existing AA production process. category, has widened its vision for the proprietary Novomer has raised about $30m so far in technology, which won last year’s Innovation with Best venture capital funding which it is using to part-finance construction of a continuous pi- Environmental Benefit category lot-scale process plant.
    [Show full text]
  • Chemical Intercalation of Zerovalent Metals Into 2D Layered Bi2se3 Nanoribbons † † ‡ † † † § Kristie J
    Article pubs.acs.org/JACS Chemical Intercalation of Zerovalent Metals into 2D Layered Bi2Se3 Nanoribbons † † ‡ † † † § Kristie J. Koski, Colin D. Wessells, Bryan W. Reed, Judy J. Cha, Desheng Kong, and Yi Cui*, , † Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, United States ‡ Physical and Life Sciences Directorate, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, California 94550, United States § SLAC National Accelerator Laboratory, Stanford Institute for Materials and Energy Sciences, 2575 Sand Hill Road, Menlo Park, California 94025, United States *S Supporting Information ABSTRACT: We have developed a chemical method to intercalate a variety of zerovalent metal atoms into two-dimen- sional (2D) layered Bi2Se3 chalcogenide nanoribbons. We use a chemical reaction, such as a disproportionation redox reaction, to generate dilute zerovalent metal atoms in a refluxing solution, which intercalate into the layered Bi2Se3 structure. The zerovalent nature of the intercalant allows superstoichiometric intercalation of metal atoms such as Ag, Au, Co, Cu, Fe, In, Ni, and Sn. We foresee the impact of this methodology in establishing novel fundamental physical behaviors and in possible energy applications. 1. INTRODUCTION Ni, and Sn. Some interesting effects that could arise with − 7−10 intercalation are superconductivity, such as in Cu Bi2Se3, Intercalation is the insertion of a guest species into a host 6 lattice. Intercalation into layered materials is essential to battery enhanced conductivity, or possibly opening a surface state gap electrodes, electrochromics, detergents, and solid lubricants and in topological insulator Bi2Se3. This method of zerovalent metal is important in exotic fundamental two-dimensional (2D) intercalation may also be extended to other layered materials.
    [Show full text]
  • Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc
    Metal-Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc Richard H. Duncan Lyngdoh*,a, Henry F. Schaefer III*,b and R. Bruce King*,b a Department of Chemistry, North-Eastern Hill University, Shillong 793022, India B Centre for Computational Quantum Chemistry, University of Georgia, Athens GA 30602 ABSTRACT: This survey of metal-metal (MM) bond distances in binuclear complexes of the first row 3d-block elements reviews experimental and computational research on a wide range of such systems. The metals surveyed are titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, representing the only comprehensive presentation of such results to date. Factors impacting MM bond lengths that are discussed here include (a) n+ the formal MM bond order, (b) size of the metal ion present in the bimetallic core (M2) , (c) the metal oxidation state, (d) effects of ligand basicity, coordination mode and number, and (e) steric effects of bulky ligands. Correlations between experimental and computational findings are examined wherever possible, often yielding good agreement for MM bond lengths. The formal bond order provides a key basis for assessing experimental and computationally derived MM bond lengths. The effects of change in the metal upon MM bond length ranges in binuclear complexes suggest trends for single, double, triple, and quadruple MM bonds which are related to the available information on metal atomic radii. It emerges that while specific factors for a limited range of complexes are found to have their expected impact in many cases, the assessment of the net effect of these factors is challenging.
    [Show full text]
  • Hydroformylation of Formaldehyde with Rhodium Catalyst
    Patentamt O JEuropâischesEuropean Patent Office © Publication number: 002 908 Office européen des brevets Bl @ EUROPEAN PATENT SPECIFICATION (46) Date of publication of patent spécification: 12.05.82 © Int. Cl.3: C 07 C 47/19, 8 01 J 31/°2' C 07 C 45/50 © Application number: 78300820.4 @ Date of filing: 1 4.1 2.78 © Hydroformylation of formaldehyde with rhodium cataiyst. © Priority: 16.12.77 US 861474 @ Proprietor: MONSANTO COMPANY Patent Department 800 North Lindbergh Boulevard © Date of publication of application: St. Louis, Missouri 631 66 (US) 11.07.79 Bulletin 79/14 @ Inventor: Spencer, Alwyn © Publication of the grant of the patent: Johnson Matthey Research Centre Blount's Court 1 2.05.82 Bulletin 82/1 9 Jonning Common Reading R64-9NH (GB) @ Designated Contracting States: © Representative: Lunt, John Cooper etal, BECHDEFRGBLUNLSE Monsanto House 1 0-1 8 Victoria Street London, SW1H ONQ(GB) "© References cited: DE- A- 3 940 432 DE - A - 2 741 589 GB - A - 1 335 531 US - A - 3 940 432 Chemical Abstracts vol. 87, no. 19. 1977, Columbus, Ohio, USA T. MIZOROKI "Syntheses of oxygen-containing C2-compounds using carbon monoxide" page 541, column 1, abstract no. 151 634g Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.
    [Show full text]