Lopes de Miranda, Jussara

English

Engineering Conferences International

JLMirandaAuthors: Aurea A. Barbosa, Heitor B. Pereira Ferreira, Claudio J A Mota and CO2 Conversion to Organic Compounds and Polymeric Precursors1JLMiranda Jussara Lopes de Miranda*Institute of ChemistryFederal University of Rio de Janeiro (UFRJ)  Rio de JaneiroBrazilJLMirandaOutline- Energy Supply in Brazil - Presentation of the Lacqua’s projets- Motivation for CO2 conversion- Industrial uses of CO2JLMiranda2- Challenges for CO2 conversion- CO2 Conversion by heterogeneous catalysis- CO2 Conversion by Homogenous catalysis- CO2 Capture using metal organic frameworks- Future GoalsEnergy Supply in Brazil3CO2, LACQUA –IQ/UFRJI /Laboratory of Catalysis and Environmental Chemistry CO2 Capture with MOFs(Metal Organic Frameworks)CAPTURECO24CO2, JLMirandaCONVERSIONConversion of CO2 into Organic Products METHANOL, FORMIC ACID, FORMALDEHYDE POLYMERS PRECURSORSMotivation for CO2 ConversionCO2, CO2, JLMiranda5IPCC reportsCO2, Main Sources of CO2CO2, JLMiranda6IPCC - Third Assessment Report (TAR)Current Industrial Uses of CO2CO2, Industrial Processes that use CO2Global Capacity /yearQuantitity of CO2 fixedUrea 95 Mt 54 MtCO2, JLMiranda7Salicylic Acid 70 Mt 25 MtMethanol 20 Mt 2 MtCyclic Carbonates 80 Mt ~ 40 ktPolypropilenocarbonate 70 Mt ~30 ktAresta, M. , Carbon Dioxide Recovery and Utilization, Kluwer Academic Publishers, Netherlands, 2003CO2, Expected Benefits from CO2 ConversionEnvironmentalEconomicalContribution to the reduction in CO2 emissionsCO2 conversion into products of economical valueCO2, JLMiranda8SocialScientificalContribution to a better human health & better climate conditionsSynthesis of new designed catalysts and the study of C1 chemistry Fossil Fuel Non-fossilEnergyConversion of CO2 into Organic Products MotivationCO2, 9Energy CO2ReuseCO2 reductionFuel UtilisationsEnergyBiomassCO2, JLMirandaCO2, Challenges to CO2 Conversion- Use of CO2 as the starting material for the synthesisof organic chemical products, carbohydrates andpolymers- Need of pure and concentrated CO2 for conversionprocesses – implies the costs of capture andCO2, JLMiranda10transportation-Energy demand for CO2 conversion – use of energeticreagents and good catalysts- Global market context for the products that aresynthesized from CO2Examples of Industrial Processes That Use CO2CO2, CO2 + 2 NH3 H2N-CO-NH2 + H2OUrea ProductionT= 185-190oC, P=150-220 atmIt occurs in two stepsCO2, JLMiranda11CO2 + 2 NH3            H2N-COO-NH4+H2N-COO-NH4+ H2NCONH2 + H2O- It is the product that uses the greatest amount of CO2- Global production in 2002 – 100 millions of tons/year = 22 millions of tons CO2- More than 54 % of global capacity is in Southeast Asia - Urea can be used as a fertilizer 46%) or raw material for carbonates- It can be associated with CO2 CaptureCO2, Production of Dimethyl Carbonate (DMC) without phosgene and chlorine- The usual route for DMC synthesisCO + Cl2 COCl2COCl2 + 2 CH3OH        CH3OCOOCH3 + 2 HClCO2, JLMiranda12Industrial Process fromAsahi Chemical Industry:Polymers synthesis since 2002Production50.000 ton/yearRemoval of CO2 1730 ton/10.000 ton PC , JLMirandaCO2Some Features of CO2 ConversionIn ResearchMethanolFormic Acid, Formiatesand amidesDimethylcarbonatee polycarbonatesJLMiranda13PetrochemicalsMetal catalysts : Ru, Rh, Ni, Pd, PtHomogenous  and Heterogenous Catalysis.Capture and Conversion of CO2 into Organic Carbon Products and Polymeric PrecursorsSynthesis of catalysts able to aid CO2 conversionConversion of CO2 into organic productsCO2CO2, 14CONVERSIONFixation of CO2 into Organic ProductsMETHANOL, FORMIC ACID, FORMALDEHYDEPRECURSORS OF POLYMERSCO2, JLMirandaJLMiranda1- Heterogenous Catalysis- Hydrogenation of CO2Ni, Ru catalystsCO + H Organic productsEXPERIMENTALJLMiranda152 22- Homogeneous Catalysis – CO2 reaction with                            methanolSn catalystsCO2 + H3C-OH                    Organic productsExperimental Steps: Part I - Heterogenous Catalysis-Hydrogenation of CO2 - Synthesis of Catalystsh Synthesis of catalysts based on complexes of nickel and ruthenium – eleven catalysts were synthesized.hSynthesis of the mesoporous (silicate)CO2, 16hIntercalation of the cationic complexes of nickel and ruthenium into the mesoporoushCharacterization of the catalysts:- Elemental Analysis                - Nuclear Magnetic Resonance                - Infrared Spectroscopy          - Thermogravimetric Analysis- X-ray diffraction                  - Electronic analysisCO2, JLMirandaIntercalation resultsCO2, Sample Distance d (Å) ∆ d (Å)Sodium mesoporous 15.21 -mesoporous+surfactant/ButOH20.67 5.46CO2, JLMiranda17Ni2+ intercalated 15.17 5.50Ru3+ intercalated 15.28 5.39Cat Ni1 intercalated 18.21 2.46Cat Ni2 intercalated 18.92 1.75Cat Ru1 intercalated 18.21 2.46Conversion Results of Heterogeneous CatalysisCatalyst Product Temp (oC)Cat 1 Formaldehyde 14911 Catalysts synthesized – 7 were active – 20 to 30 % of conversion, pressure = 1 atm CO2 18Cat 2 Formaldehyde 111-124Cat 3 Methanol, Formic acid, formaldehyde150-152Cat 4 Methanol 152Cat 5 Formic acid 152Cat 6 Methanol 150-152CO2 , JLMirandaConclusions from Conversion of CO2 into Organic Products by Heterogeneous Catalysis♦11 Catalysts were synthesized and characterized♦Seven catalysts were able to convert CO2        30 % of total conversion♦The main products of the conversion were: methanol, formic CO2, 19ac. and formaldehyde♦Mild conditions for conversion : P= 1 atm and ∆T = 120 to 150 oC♦ 1 Patent submitted.CO2, JLMiranda2- CO2 Conversion by Homogeneous Catalysis CO2 reaction  with  methanolcatalytic test in a Parr reactorSn alcoxide CO2 + H3C-OH                    Organic productsSn modified alcoxide catalystCO2, JLMiranda20catalystMethanol CO22 h 423 KGCMS AnalysisLiquidSolidJLMirandaData from near infrared spectrum and far infrared spectrum of the catalyst before and after the catalytic test showed that The  Sn catalyst before and afterthe Conversion TestJLMiranda21The catalystis stableJLMirandaGCMS  Spectrum of the obtained product350040004500AbundanceScan 457 (2.695 min): 2.D73MeMeOMeOMeCJLMiranda2250 100 150 200 250 300 350 400 450050010001500200025003000m/ z-->5689147 207 254 354 406 446 504JLMiranda3000350040004500AbundanceScan 647 (3.780 min): 2.D74Pr-nMeO COGCMS  Spectrum of the obtained productJLMiranda2360 80 100 120 140 160 180 200 220 240 260 28005001000150020002500m/z-->515987102 165175 187 207 275 288JLMirandaConclusions from  Homogeneous Catalysis Conversion of CO 2 into Organic Products 24-CO2 insertion into Sn-O bond of the catalyst- Formation of Oxygenated organic productsPetroleum DerivativesNatural GasBiomassCO2REUSECO2FIXATIONIndustrial Processes+Carbon Capture & ReuseConversion of CO2 into Organic Products CO2, 25CHEMICALSMethanol,Formic AcidFormaldehydeCURRENT INDUSTRIAL PROCESSESCO2eq emissions XCO2, JLMirandaJ L MirandaProjects on CO2 Capture-Synthesis of new metal organic frameworks :chromium, copper and zirconiumJ L Miranda26- Synthesis of MOFs with lower cost- Collaboration with Professor Christian Serre-Institute Lavoisier, Université de Versaillles Saint-Quentintin-En-Yvelines.JLMirandaFuture Goals- Study of the recycle of the catalysts- Comparison between nickel and rutheniumcatalystsJLMiranda27- Use of zinc catalysts in homogeneous catalysis- Synthesis of new MOFs with lower cost andgreater selectiveness- Use of ethanol to react with CO2AcknowledgmentsBrazilian Agency of Petroleum, Natural Gas and Biofuels -Human Resource ProgramBrazilian Council for Scientific28Federal University of Rio de Janeiro PRH 01-Petroleum Chemist ProgramAnd Technological Development Prof Jussara L Miranda – IQ/UFRJProf  Luiza C Moura- IQ/UFRJ Prof Marco Barreto – IQ/UFRJMarcio G. Franco (Msc)Áurea A. Barbosa (phD)Heitor Breno Ferreira (phD)Elisângela Souza (Msc)LACQUA’ S TEAM29Sueli Akemi (Msc)Francisca  Sobral (Msc)Fernanda Luna da Silva (Grad.)Lorraine Greco (Grad.)CollaborationsChirstian Serre- Université Yves-Saint-Quentin- FranceProf. Claudio Mota – IQ/UFRJ - BrazilProf. Heloise Pastore- Unicamp – BrazilProf. Diana Azevedo- UFC- BrazilThank you for your attentionjussara@iq.ufrj.br30Cristo Redentor – Rio de Janeiro One of the Ten New World Wonders

CO2 Conversion to Organic Compounds and Polymeric Precursors

https://dc.engconfintl.org/cgi/viewcontent.cgi?article=1013&amp;context=co2_summit

CO2 Conversion to Organic Compounds and Polymeric Precursors

Abstract

Similar works

Full text

Available Versions

Engineering Conferences International