DOCSLIB.ORG

Regeneration of Rhodium Hydroformylation Catalysts

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Regeneration of Rhodium Hydroformylation Catalysts Europâisches Patentamt à. European Patent Office (if) Publication number: O 015 379 Office européen des brevets Bl Kg) EUROPEAN PATENT SPECIFICATION @ Dateof publication of patent spécification: 18.05.83 © Int. Cl.3: B 01 J 31/40, c 07 c 45/50, C 07 C 47/02 @^ ApplicationA ,• @ number:k 80100446.6oMnn„«* e (22) Date offiling: 29.01 .80 (54) Régénération of rhodium hydroformylation catalysts. (§) Priority: 12.02.79 US 11604 @ Proprietor: EASTMAN KODAK COMPANY Patent Department 343 State Street Rochester, New York 1 4650 (US) (43) Date of publication of application: 17.09.80 Bulletin 80/19 @ Inventor: Dawes, John Leslie P.O. Box 7444 @ Publication of the grantof the patent: Longview Texas (US) 18.05.83 Bulletin 83/20 Inventor: Devon Jr., Thomas James P.O. Box 7444 Longview Texas (US) @ Designated Contracting States: DE FRGBNL (74) Représentative: Brandes, Jûrgen, Dipl.-Chem. Dr. et al, (56) Références cited: Thierschstrasse 8 EP - A - 0 000 685 D-8000 Munchen 22 (DE) FR - A - 2 258 357 US - A - 3 547 964 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 a. paid. (Art. 99(1) European convention). IU patent Courier Press, Leamington Spa, England This invention relates to the Oxo process for effective method for catalyst reactivation the hydroformylation of an unsaturated com- without significant loss of the valuable rhodium. pound, such as an a-olefin, by the reaction Several methods of regeneration have been of the unsaturated compound with carbon suggested in the prior art. U.S. Patent monoxide and hydrogen in the presence of a 3,555,098 described the use of water or caustic catalyst. More specifically, this invention relates as a wash for the catalyst. This method removes to a method of regenerating a rhodium catalyst such poisons as acids but has not been effective useful in such a hydroformylation reaction. for regeneration of the rhodium catalyst. In a hydroformylation reaction, which is Japanese Patent 73/43799 describes reduc- called the Oxo process, an unsaturated com- tion with hydrogen as a suitable regeneration pound, such as an a-olefin, is reacted with syn- method. Japanese Patent 74/94385 describes thesis gas which contains carbon monoxide and the use of molecular oxygen for regeneration of hydrogen to form an aldehyde of the un- the catalyst. saturated compound. For example, propylene is European patent application 0 00685 reacted with carbon monoxide and hydrogen in describes the treatment of a rhodium triaryl the presence of a suitable catalyst to form iso- phosphite complex catalyst, which comprises an butyraldehyde and n-butyraldehyde. oxidation reaction at a temperature of from 0 to Cobalt catalysts are known to be efficient 85°C until the ligand is completely oxidized. and effective catalysts for the hydroformylation French patent 22 58 357 describes a reaction. However, the cobalt catalysts produce regeneration method according to which an undesirable quantities of by-products such as organic solution containing the complex of paraffins, alcohols, acetals, aldol type products rhodium in combination with triphenylphos- and other high boiling products. In contrast, phine is submitted to a treatment with an rhodium catalysts are known to be more selec- aldehyde such as formaldehyde or isobutyralde- tive in the hydroformylation process and to hyde in presence of an acid. produce yields of the desired aldehydes as high None of these methods restores fresh as 99% and substantially less of the undesired catalyst activity without significant loss of by-products. Also, the rhodium catalysts can be rhodium. used at much lower temperatures and pres- Numerous catalyst regeneration procedures sures than the cobalt catalysts and as a result have been tried. These procedures included significantly lower equipment and utilities treating the inactive catalyst with hydrogen, requirements are needed to build and oper- carbon monoxide, synthesis gas (the combina- ate a hydroformylation facility using rhodium tion of carbon monoxide and hydrogen used in catalysts. the Oxo reaction); washing the inactive catalyst The rhodium catalysts that are used in a with water or aqueous caustic; refluxing the hydroformylation reaction are complexes of inactive catalyst with aqueous caustic or an rhodium in combination with a ligand or func- acetic acid anhydride mixture; treating the tional group that activates rhodium into a inactive catalyst with hydrochloric acid followed hydroformylation catalyst under reaction con- by a sodium isobutyrate wash; treating the ditions. There are many known ligands that can inactive catalyst with reducing agents, e.g., be used in the rhodium catalyst complex. For sodium borohydride in methanol or hydrazine in example, triaryl, trialkyl or mixed aryl alkyl ethanol; and treating the inactive catalyst with amines, phosphines, arsines or stilbines can be air in the absence of aldehyde. None of these used. The complex of rhodium and ligand reacts procedures proved adequate as a catalyst with the carbon monoxide and hydrogen in the reactivation method. synthesis gas to become even more com- The process of this invention for regenerat- plicated. For example, when rhodium and tri- ing a deactivated rhodium hydroformylation methylphosphine are reacted with carbon catalyst which has been removed from the monoxide and hydrogen, a complex material hydroformylation reaction, overcomes the whose structure is unknown is formed. problems of the prior art. The method of this During hydroformylation reactions, rhodium invention is characterized by catalysts become deactivated to a point where a) adding aldehyde to the deactivated they have insufficient activity to support an catalyst so that at least one mole of aldehyde is economical reaction. Normally a fully active present for each mole of rhodium and each rhodium catalyst complex is straw colored while mole of ligand, an inactive complex is black. Monitoring this b) oxidizing the aldehyde-containing catalyst color change is one practical method of deter- with an oxygen-containing gas at a tempera- mining if a catalyst is active or inactive. ture below the boiling point of the aldehyde The principal disadvantages of rhodium until substantially all the ligand is oxidized, catalysts for a hydroformylation reaction are the c) removing solid oxidized ligand formed extremely high capital investment needed for during the oxidation, and the initial catalyst charge and the lack of an d) adjusting the ligand to rhodium ratio of the regenerated catalyst for use in a hydroformyla- thereof. Air is then blown through the solution tion reaction. at a slow rate so the temperature of the mix- Optionally, it may be desirable to remove ture does not rise rapidly. As catalyst reactiva- some ligand from the catalyst prior to the tion proceeds the solution changes from a black adjustment of the aldehyde content. This will color to a straw color. From a few minutes (30 serve to reduce the amount of ligand lost during or less) to 48 hours or more are needed for the oxidation and to reduce the amount of alde- reactivation. Excess aldehyde and any acids hyde which must be added to achieve the formed during oxidation are then removed. The correct aldehyde/rhodium/ligand balance. In amount of aldehyde and air used in the oxida- addition, following oxidation, it may be desirable tion are controlled to minimize the formation of to treat the catalyst so as to remove any acid acid in the regeneration process. The solution is produced during the oxidation step. This then filtered to remove any solids, for example method results in a virtually complete reactiva- triphenylphosphine oxide, and returned to the tion of catalyst with minimal rhodium loss and it catalyst recycle stream with added phosphine. can be used repeatedly on the same catalyst Progress of the catalyst regeneration can be charge without the build-up of undesirable by- monitored by the change in color from the dark products. Surprisingly it has been found that deactivated form to the straw yellow of the this method is also effective in reactivating active form.. Regeneration is not complete until rhodium oxo catalysts which have been all the phosphine, etc., is oxidized to the poisoned by sulfur. phosphine oxide. When excess phosphine is The reactivation of the deactivated rhodium employed in the reaction it should be removed catalyst is carried out under mild reaction con- from the stream prior to regeneration and then ditions. Consequently, the reactivation of the replaced after the regeneration. catalyst can be accomplished in inexpensive In the following example triphenylphosphine equipment using ambient or atmospheric con- is represented by the symbol P03. ditions. An oxygen-containing gas, such as air, is used for the oxidation and the oxidation reac- Example tion is carried out at a temperature below the A sample of an oxo catalyst containing 1 boiling point of the aldehyde that is added to the mole of rhodium and 19 moles of triphenyl deactivated catalyst. Preferably, the oxidation phosphine, deactivated in propylene hydro- reaction is carried out at room temperature. formylation at 100°C. and 6792 kPa, was The aldehyde that is added to the deactivated removed from the reactor, stripped in vacuo and catalyst is preferably an aldehyde that is formed divided into four portions. The first portion was in the hydroformylation reaction. When an @- diluted with isobutyraldehyde to 55 ppm (parts olefin is being reacted in the hydroformylation per million) rhodium and tested for propylene process, a saturated aliphatic aldehyde such as hydroformylation at 100°C. and 6792 kPa. acetaldehyde, propionaldehyde, n-butyralde- Butyraldehydes were produced at a rate of 11 hyde, isobutyraldehyde or higher boiling alde- pounds per cubic foot (176 g/liter) per hour and hydes can be used.
Load more

Recommended publications
  • 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]
  • 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]
  • 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]
  • Hydroformylation of 1-Hexene Over Rh/Nano-Oxide Catalysts
    Catalysts 2013, 3, 324-337; doi:10.3390/catal3010324 OPEN ACCESS catalysts ISSN 2073-4344 www.mdpi.com/journal/catalysts Article Hydroformylation of 1-Hexene over Rh/Nano-Oxide Catalysts Maija-Liisa Kontkanen 1, Matti Tuikka 1,2, Niko M. Kinnunen 1, Sari Suvanto 1 and Matti Haukka 1,2,* 1 Department of Chemistry, University of Eastern Finland, P.O. Box 111, FI-80101 Joensuu, Finland; E-Mails: [email protected] (M.-L.K.); [email protected] (M.T.); [email protected] (N.M.K.); [email protected] (S.S.) 2 Department of Chemistry, University of Jyväskylä, P.O. Box 35, University of Jyväskylä, Finland * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +358-40-805-4666; Fax: +358-4-260-2501. Received: 26 January 2013; in revised form: 25 February 2013 / Accepted: 6 March 2013 / Published: 21 March 2013 Abstract: The effect of nanostructured supports on the activity of Rh catalysts was studied by comparing the catalytic performance of nano- and bulk-oxide supported Rh/ZnO, Rh/SiO2 and Rh/TiO2 systems in 1-hexene hydroformylation. The highest activity with 100% total conversion and 96% yield of aldehydes was obtained with the Rh/nano-ZnO catalyst. The Rh/nano-ZnO catalyst was found to be more stable and active than the corresponding rhodium catalyst supported on bulk ZnO. The favorable morphology of Rh/nano-ZnO particles led to an increased metal content and an increased number of weak acid sites compared to the bulk ZnO supported catalysts. Both these factors favored the improved catalytic performance.
    [Show full text]
  • Hydroformylation of C3 and C8 Olefins in Hydrocarbon Gas-Expanded Solvents
    HYDROFORMYLATION OF C3 AND C8 OLEFINS IN HYDROCARBON GAS-EXPANDED SOLVENTS By Dupeng Liu Submitted to the graduate degree program in Chemical & Petroleum Engineering and the Graduate Faculty of the University of Kansas in partial fulfillment of the requirements for the degree of Doctor of Philosophy. Chairperson: Bala Subramaniam Raghunath V. Chaudhari Jon Tunge Aaron Scurto Kevin Leonard Date Defended: April 30th, 2018 The dissertation committee for Dupeng Liu certifies that this is the approved version of the following dissertation: HYDROFORMYLATION OF C3 AND C8 OLEFINS IN HYDROCARBON GAS-EXPANDED SOLVENTS Chairperson: Bala Subramaniam Date Approved: May 8th, 2018 ii Abstract Hydroformylation involves the addition of syngas to the double bond of an alkene yielding aldehydes used to produce basic building blocks for myriad consumer goods. Resource-efficient technologies that conserve feedstock and energy continue to be of interest to industry. It has been shown previously by our group that the use of CO2-expanded liquids significantly enhances the Rh-catalyzed 1-octene hydroformylation rate and selectivity. This dissertation extends this concept by employing light alkanes such as propane and n-butane as compressed solvents in propylene and 1-octene hydroformylation, respectively. Phase behavior measurements demonstrate that at identical H2 or CO fugacities in the vapor phase, the H2 and CO solubilities in either propane- or propylene-expanded solvents (PXLs) are greater than those in the corresponding neat solvents by as high as 76% at 70 °C and 1.5 MPa. The H2/CO ratio in PXLs is enhanced by simply increasing the propane partial pressure. In contrast, the H2/CO in the neat solvent at a given temperature is constant at all syngas partial pressures.
    [Show full text]
  • (12) Patent Application Publication (10) Pub. No.: US 2003/0032845 A1 Han Et Al
    US 20030032845A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2003/0032845 A1 Han et al. (43) Pub. Date: Feb. 13, 2003 (54) HYDROFORMYLATION OF ETHYLENE Related U.S. Application Data OXIDE (63) Continuation-in-part of application No. 09/924,822, (76) Inventors: Yuan-Zhang Han, West Chester, PA filed on Aug. 8, 2001, now abandoned. (US); Krishnan Viswanathan, Houston, TX (US) Publication Classification Correspondence Address: (51) Int. Cl. ................................................ C07C 29/15 LYONDELL CHEMICAL COMPANY (52) U.S. Cl. ............................................ 568/862; 568/867 3801 WEST CHESTER PIKE NEWTOWN SQUARE, PA 19073 (US) (57) ABSTRACT (21) Appl. No.: 10/038,975 1,3-propanediol is formed from ethylene oxide containing formaldehyde and acetaldehyde impurities by hydroformy (22) Filed: Jan. 4, 2002 lation and hydrogenation. Patent Application Publication Feb. 13, 2003 US 2003/0032845 A1 N y so US 2003/0032845 A1 Feb. 13, 2003 HYDROFORMYLATION OF ETHYLENE OXDE wise, the procedures described in recently filed applications Ser. No. 09/882,346, 09/882,347 and 09/882,641 filed Jun. RELATED APPLICATION 15, 2001 can be employed and are incorporated herein by 0001. This application is a continuation-in-part of appli reference. cation Ser. No. 09/924,822 filed Aug. 8, 2001. 0010 Generally speaking, ethylene oxide which has been employed as feed in prior procedures is a commercial grade BACKGROUND OF THE INVENTION of ethylene oxide from which a predominance of the impu rities coproducted during ethylene oxide formation have 0002) 1. Field of the Invention been removed. Generally, the aldehyde Specifications for 0003. This invention relates to the catalytic hydroformy such commercial ethylene oxide are a maximum of 30-50 lation of ethylene oxide and especially to a process wherein ppm by weight of aldehyde expressed as acetaldehyde.
    [Show full text]
  • And Regioselective Hydroformylation of Alkenes with CO2/H2 Over a Bifunctional Catalyst
    Chemo- and Regioselective Hydroformylation of Alkenes with CO2/H2 over a Bifunctional Catalyst Kai HUA Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210 (P. R. China). Fang Liu Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210 (P. R. China). Yin Wei Low-Carbon Conversion Science and Engineering Long Shao Shanghai Advanced Research Institute, Chinese Academy of Sciences Chao Deng ShanghaiTech University Ming Zhang Shanghai Advanced Research Institute, Chinese Academy of Sciences Lin Xia Shanghai Advanced Research Institute, Chinese Academy of Sciences Liangshu Zhong Shanghai Advanced Research Institute https://orcid.org/0000-0002-4167-8630 Hui Wang ( [email protected] ) Shanghai Advanced Research Institute, Chinese Academy of Sciences Yuhan Sun Shanghai Advanced Research Institute, Chinese Academy of Sciences Article Keywords: CO2, H2, chemo- and regioselective hydroformylation of alkenes, bifunctional catalyst Posted Date: October 7th, 2020 DOI: https://doi.org/10.21203/rs.3.rs-85641/v1 License: This work is licensed under a Creative Commons Attribution 4.0 International License. Read Full License Version of Record: A version of this preprint was published at Green Chemistry on January 1st, 2021. See the published version at https://doi.org/10.1039/D0GC03913F. Chemo- and Regioselective Hydroformylation of Alkenes with CO2/H2 over a Bifunctional Catalyst Kaimin Hua1,2, Xiaofang Liu1,* Baiyin Wei1,3, Zilong Shao1, Yuchao Deng1,3, Jianming Zhang1, Lin Xia1, Liangshu Zhong1,3, Hui Wang1,* Yuhan Sun1,3,4* Abstract: Combining CO2 and H2 to prepare building blocks for high-value-added products is an attractive yet challenging approach. A general and selective rhodium- catalyzed hydroformylation of alkenes using CO2/H2 as a syngas surrogate is described here.
    [Show full text]
  • Preparation and Characterization of Rh/Mgsnts Catalyst for Hydroformylation of Vinyl Acetate: the Rh0 Was Obtained by Calcination
    Article Preparation and Characterization of Rh/MgSNTs Catalyst for Hydroformylation of Vinyl Acetate: The Rh0 was Obtained by Calcination Penghe Su 1, Ya Chen 1, Xiaotong Liu 1, Hongyuan Chuai 1, Hongchi Liu 1, Baolin Zhu 1,2, Shoumin Zhang 1,2 and Weiping Huang 1,2,3,* 1 College of Chemistry, Nankai University, Tianjin 300071, China; [email protected] (P.S.); [email protected] (Y.C.); [email protected] (X.L.); [email protected] (H.C.); [email protected] (H.L.); [email protected] (B.Z.); [email protected] (S.Z.) 2 The Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China 3 Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300071, China * Correspondence: [email protected]; Tel.: +86-138-2009-6974 Received: 01 February 2019; Accepted: 18 February 2019; Published: 26 February 2019 Abstract: A simple and practical Rh-catalyzed hydroformylation of vinyl acetate has been synthesized via impregnation-calcination method using silicate nanotubes (MgSNTs) as the supporter. The Rh0 (zero valent state of rhodium) was obtained by calcination. The influence of calcination temperature on catalytic performance of the catalysts was investigated in detail. The catalysts were characterized in detail by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectrometer (XPS), atomic emission spectrometer (ICP), and Brunauer–Emmett–Teller (BET) surface-area analyzers. The Rh/MgSNTs(a2) catalyst shows excellent catalytic activity, selectivity and superior cyclicity. The catalyst could be easily recovered by phase separation and was used up to four times. Keywords: silicate nanotubes; Rh; hydroformylation; vinyl acetate 1.
    [Show full text]
  • Resource-Efficient Catalytic Technologies for Shale Gas Upgrading
    Resource-Efficient Catalytic Technologies for Shale Gas Upgrading Bala Subramaniam, Christopher J. Lyon and Darryl Fahey Center for Environmentally Beneficial Catalysis Department of Chemical and Petroleum Engineering University of Kansas, Lawrence, KS Shale Gas Monetization Workshop Montgomery, TX March 27, 2014 Outline • The global chemical industry • Emerging feedstocks for making chemicals • The need for resource-efficient technologies • Examples with LCA analyses • Concluding remarks The Center for Environmentally Beneficial Catalysis Growth of Global Chemical Industry [Global Chemical Outlook, UN Environment Programme, 2012] The Center for Environmentally Beneficial Catalysis Petrochemicals Chemical intermediates (building blocks) Consumer goods • <10% of crude oil used to make chemicals • Chemicals more profitable than fuels The Center for Environmentally Beneficial Catalysis Natural Gas and Biomass as Alternate Feedstocks Chemical intermediates Biomass (building blocks) and Shale Gas Consumer goods - US natural gas production up ~28% since 2006, thanks to increased shale gas production [EIA, 2013] - Biomass abundant for making chemical intermediates The Center for Environmentally Beneficial Catalysis Natural Gas Typical Shale Gas Production by Source Composition [Energy Information Administration, 0383-2013] The Center for Environmentally Beneficial Catalysis Proposed Expansion of U.S. Ethylene Production Capacity, 2013-2020 Company Location Proposed capacity, MMTY Chevron Phillips Baytown, TX 1.5 Exxon Mobil Baytown, TX 1.5 Sasol
    [Show full text]
  • Forty-Five Years of Progress for the LP Oxosm Process
    https://doi.org/10.1595/205651317X695875 Johnson Matthey Technol. Rev., 2017, 61, (3), 246–256 JOHNSON MATTHEY TECHNOLOGY REVIEW www.technology.matthey.com Industrial Low Pressure Hydroformylation: Forty-Five Years of Progress for the LP OxoSM Process A long standing collaboration between Johnson Matthey and Dow continues to sustain the high standing of their oxo technology through innovative solutions to address the changing needs of the global oxo alcohol market By Richard Tudor Introduction Retired, Reading, UK The LP OxoSM Process is the rhodium-catalysed Atul Shah* hydroformylation process in wide use today in a variety Johnson Matthey, 10 Eastbourne Terrace, London, W2 of industrial applications. These applications have been 6LG, UK developed, co-marketed and licensed as a cooperation between affiliates of The Dow Chemical Company *Email: [email protected] (‘Dow’) and Johnson Matthey or their predecessors, for over 45 years. The LP OxoSM Process first made an impact in the 1970s when its technical elegancy, environmental Since the mid-1970s when the ‘Low Pressure Oxo’ footprint and economics attracted huge attention by process (LP OxoSM Process) was first commercialised, the world’s producers of normal butyraldehyde for it has maintained its global position as the foremost conversion to the plasticiser alcohol 2-ethylhexanol oxo process, offering particular appeal to independent (2EH). producers of commodity plasticisers facing increasing regulatory pressure. The story of this important The Early Dominance of Cobalt Catalysis industrial process is told from its early beginnings when laboratory discoveries by independent groups of Hydroformylation is the reaction of an unsaturated researchers in USA and UK revealed the remarkable olefinic compound with hydrogen and carbon ability of organophosphine containing rhodium monoxide to yield an aldehyde.
    [Show full text]
  • Organometallic Chemistry and Applications
    Chemistry 462 Fall 2017 MYD Organometallic Chemistry and Applications Note: Organometallic Compounds and Complexes Contain a M-C Bond. Organometallic chemistry timeline 1760 Louis Claude Cadet de Gassicourt investigates inks based on cobalt salts and isolates Cacodyl from cobalt mineral containing arsenic 1827 William Christopher Zeise produces Zeise's salt; the first platinum / olefin complex 1848 Edward Frankland discovers diethylzinc 1863 Charles Friedel and James Crafts prepare organochlorosilanes 1890 Ludwig Mond discovers nickel carbonyl 1899 Introduction of Grignard reaction 1899 John Ulric Nef discovers alkylation using sodium acetylides. 1900 Paul Sabatier works on hydrogenation of organic compounds with metal catalysts. Hydrogenation of fats kicks off advances in food industry; see margarine! 1909 Paul Ehrlich introduces Salvarsan for the treatment of syphilis, an early arsenic based organometallic compound 1912 Nobel Prize Victor Grignard and Paul Sabatier 1930 Henry Gilman works on lithium cuprates, see Gilman reagent 1951 Walter Hieber was awarded the Alfred Stock prize for his work with metal carbonyl chemistry—(but not the Nobel Prize). 1951 Ferrocene is discovered 1963 Nobel prize for Karl Ziegler and Giulio Natta on Ziegler-Natta catalyst: Polymerization of olefins 1965 Discovery of cyclobutadieneiron tricarbonyl 1968 Heck reaction 1973 Nobel prize Geoffrey Wilkinson and Ernst Otto Fischer on sandwich compounds 1981 Nobel prize Roald Hoffmann and Kenichi Fukui for expression of the Woodward-Hoffman Rules 2001 Nobel prize W. S. Knowles, R. Noyori and Karl Barry Sharpless for asymmetric hydrogenation 2005 Nobel prize Yves Chauvin, Robert Grubbs, and Richard Schrock on metal-catalyzed alkene metathesis 2010 Nobel prize Richard F. Heck, Ei-ichi Negishi, Akira Suzuki for palladium catalyzed cross coupling reactions The following slides are meant merely as examples of the catalytic processes we will explore later this semester.
    [Show full text]
  • 1 IG. Palladium I I. Basic Principles
    P. Wipf 1/30/2007 I. Basic Principles IG. Palladium I - Heck Reactions - Stille, Suzuki, Negishi, Sonogashira etc Cross Couplings - π-Allyl Palladium Chemistry - Heteroatom Couplings - Applications in Natural Product Synthesis 1 P. Wipf 1/30/2007 The Heck Reaction Herbert C. Brown Award for Creative Research in Synthetic Methods (sponsored in part by Sigma-Aldrich since 1998). Richard F. Heck (retired) – University of Delaware (USA) Professor Heck, of “Heck Reaction/Coupling” fame, has had a long and distinguished career in chemistry. Beginning with Co- mediated hydroformylation, Heck was one of the first to apply transition metal catalysis to C-C bond formation. His studies of the mechanisms of transition metal catalyzed reactions led to Pd-mediated couplings that have had a profound impact in many areas of chemistry and materials science. 2 P. Wipf 1/30/2007 Reviews: Shibasaki, M.; Vogl, E. M.; Ohshima, T. "Asymmetric Heck reaction." Advanced Synthesis & Catalysis 2004, 346, 1533-1552. Dounay, A. B.; Overman, L. E. "The asymmetric intramolecular Heck reaction in natural product total synthesis." Chem. Rev. 2003, 103, 2945-2963. Beletskaya, I. P.; Cheprakov, A. V. "The Heck reaction as a sharpening stone of palladium catalysis." Chem. Rev. 2000, 100, 3009-3066. The Complex. Among Pd(0) and Pd(II) complexes commonly used are Pd(PPh3)4, Pd2(dba)2, and Pd2(dba)2CHCl3. Pd(PPh3)4 should be stored cold and under inert gas; the dibenzylideneacetone complexes are more stable catalyst precursors. Both phosphine structure and phosphine/Pd ratio effect catalyst structure and reactivity (the lower the phosphine/Pd ratio, the more reactive the catalyst).
    [Show full text]