A necessidade de uma melhor gestão de carbono e redução das emissões de CO2 leva na direção de uma melhor gestão de carbono que inclui reciclagem (CR) em detrimento a economia de carbono linear(LCE). Isso implica na utilização de fluxos de processos gasosos e líquidos sub-utilizados até o momento, e frequentemente enviados a combustão ou descartados. Neste trabalho, quatro casos são discutidos, nomeadamente: corrente de alcanos de baixo peso molecular, CO2 industrial, resíduo ligno-celulósico e glicerol contendo água e sais. O papel da catálise na valorização de tais fontes de C é discutido e exemplos de processos inovadores são apresentados.
Reviews • J. Braz. Chem. Soc. 25
(12)
• Dez 2014 • https://doi.org/10.5935/0103-5053.20140257 linkcopiar
Catalysis for the Valorization of Low-Value C-Streams
Autoria
person Michele Aresta
*
schoolDepartment of Chemical and Biomolecular Engineering, National University of Singapore, 119077 Singapore, SingaporeNational University of SingaporeSingaporeSingaporeDepartment of Chemical and Biomolecular Engineering, National University of Singapore, 119077 Singapore, SingaporeschoolConsorzio Interuniversitario Reattività Chimica e Catalisi (CIRCC), via Celso Ulpiani 27, 70126 Bari, ItalyConsorzio Interuniversitario Reattività Chimica e CatalisiItalyBari, ItalyConsorzio Interuniversitario Reattività Chimica e Catalisi (CIRCC), via Celso Ulpiani 27, 70126 Bari, Italy
person Angela Dibenedetto
schoolConsorzio Interuniversitario Reattività Chimica e Catalisi (CIRCC), via Celso Ulpiani 27, 70126 Bari, ItalyConsorzio Interuniversitario Reattività Chimica e CatalisiItalyBari, ItalyConsorzio Interuniversitario Reattività Chimica e Catalisi (CIRCC), via Celso Ulpiani 27, 70126 Bari, ItalyschoolDipartimento di Chimica, University of Bari, 70126 Bari, ItalyUniversity of BariItalyBari, ItalyDipartimento di Chimica, University of Bari, 70126 Bari, Italy
Michele Aresta is IMM Chair at the NUS, Singapore. Expert on carbon dioxide utilization in synthetic chemistry, catalysis, biomass conversion, coordination and metallorganic chemistry. He was founder of the International Conference on Carbon Dioxide Utilization (ICCDU) and is now Honorary Chair. He received the Renoir Prize for the diffusion of scientific knowledge, the Award of the Italian Chemical Society for his work on "Carbon Dioxide Activation", was appointed Honorary Professor at the University of Tianjin, and he received the Award of the Societé Française de Chimie for Inorganic Chemistry. Author of over 250 papers published in international journals, and of several reviews on CO2utilization. Editor of seven books on CO2utilization.
Angela Dibenedetto is a Professor at the Department of Chemistry, University of Bari (UNIBA), Italy. Her scientific interests are focused on carbon dioxide utilization in synthetic chemistry, catalysis, coordination chemistry and organometallic chemistry, green chemistry, marine biomass as source of fuels and chemicals applying the biorefinery concept. She is director of the Interuniversity Consortium on Chemical Reactivity and Catalysis. She was the winner of the RUCADI Prize for "Better Carbon Management – An Intelligent Chemical Use of CO2" delivered by ACP (Belgium), Carburos Metalicos (Spain) and ENIChem (Italy). Author of over 90 scientific papers published in international journals since 1995 and several book chapters.
SCIMAGO INSTITUTIONS RANKINGS
Department of Chemical and Biomolecular Engineering, National University of Singapore, 119077 Singapore, SingaporeNational University of SingaporeSingaporeSingaporeDepartment of Chemical and Biomolecular Engineering, National University of Singapore, 119077 Singapore, Singapore
Figuras | Tabelas
Thumbnail
Thumbnail
Thumbnail
Thumbnail
Thumbnail
Thumbnail
Thumbnail
Thumbnail
Thumbnail
Thumbnail
Thumbnail
Thumbnail
Thumbnail
Thumbnail
imageScheme 1 Chemicals derived from methanol (MTBE: methyl tert-butyl ether, DME: dimethyl ether, TAME: tertiary amyl methyl ether). open_in_new
imageFigure 1 Ligands used in the partial oxidation of CH4 to CH3OH using O2. open_in_new
imageFigure 2 Reaction mechanism in the partial selective oxidation CH4 → CH3OH. open_in_new
imageScheme 2 Catalytic chlorination of CH4 to CH3Cl used as precursor of CH3OH. open_in_new
imageScheme 3 Photochemical carboxylation of acetylacetone compared with the chemical carboxylation. open_in_new
imageScheme 4 Separation media for CO2 from process gas streams. open_in_new
imageFigure 3 Profile of the entropy change in the gasification process (left) compared to the approach based on biorefinery (right) in which complex structured molecules are extracted from the raw material. open_in_new
imageScheme 5 Roadmap to the valorization of non-edible biomass. open_in_new
imageScheme 6 Use of cellulose-derived C6 for making several platform molecules (in bulk). open_in_new
imageFigure 4 Structure of lignine with the glycerol units in squares. open_in_new
imageFigure 5 Some of the products of the oxidative depolymerization of lignine. open_in_new
imageFigure 6 Transeserification of lipids in aqueous solution catalyzed by bases: free fatty acids (FFAs) are converted into soaps. open_in_new
imageFigure 7 Products derived from glycerol: pure glycerol is needed. open_in_new
imageFigure 8 Glycerol conversion. open_in_new
table_chartTable 1
Some properties of C1-C4 tail gas (values for natural gas and tail gas represent ranges)
| Property | Methane | Ethane | Propane | Propene | Butane | Natural Gas | Tail gas |
|---|---|---|---|---|---|---|---|
| Molecular mass | 16.04 | 30.07 | 44.10 | 42.08 | 58.12 | Mixture | Mixture |
| Melting point / °C | -182.4 | -182.8 | -187.6 | -185 | -138.2 | -187.6/-182.4 | -187.6/-182.4 |
| Boiling point / °C | -161.5 | -88.6 | -42.1 | -48 | -0.5 | -161.5/-6.2 | -161.5/-6.2 |
| H2O sol, 25 °C / (mg L-1) | 22 | 60.2 | 62.4 | 200 | 61.2 | 22/221 | 22/221 |
table_chartTable 2
Comparison of the physical properties of some derivatives of C1-C3 alkanes
| Property | CH3COOH | CH3CH2COOH | CH3CH(COOH)CH3 | CH3(CH2)2COOH | C5 acid |
|---|---|---|---|---|---|
| Melting point / °C | 17 | -21 | -47 | -7.9 | -34.5 |
| Boiling point / °C | 118 | 141 | 155 | 163.5 | 186 |
| CH3OH | CH3CH2OH | CH3CH2CH2OH | CH3CH(OH)CH3 | CH3(CH2)2CH2OH | |
| Boiling point / °C | 64.7 | 78.4 | 96 | 82 | 118 |
table_chartTable 3
Photocatalytic conversion of methane in the presence of CO2
| CatPhoto + hν → h+ + e- |
| CH4 + h+ → •CH3 + H+ |
| CO2 + e- → •CO2 |
| •CH3 + •CH3 → CH3-CH3 |
| CH4 + •CO2- → CH3COO- + •H |
| CH3COO- + H+ → CH3-COOH |
| •CO2- + •H → HCOO- |
| HCOO- + H+ → HCOOH |
table_chartTable 4
Separation technologies and their pros and cons
| Technology | Pros | Cons |
|---|---|---|
| Solid phases | Low loss | Energy consumption |
| Liquid phases (LP) MEA | Mature | Loss, volume |
| Membranes (M) | Reduced volume-space | Cost, life-time |
| Combined (LP/M) | Efficiency | Volume, cost |
| Cryogenic | Low emission | Cost, use of electricity |
| Issues: CAPEX, OPEX, energetic costs (energy penalty: 20-40+%) | ||
-
CAPEX: capital expenditure; OPEX: operational expenditure.
table_chartTable 5
Industrial sources of CO2 (average of several sources)
| Industrial sector | MtCO2 y-1 produced |
|---|---|
| Oil refineries | 850-900 |
| Ethene and other petrochemical processes | 155-300 |
| LNG sweetening | 25-30 |
| Ethene oxide | 10-15 |
| Ammonia | 160 |
| Fermentation | > 200 |
| Iron and steel | ca. 900 |
| Cement | > 1000 |
-
LNG: liquified natural gas.
table_chartTable 6
Utilization of CO2 in the chemical industry and in technological applications
| Compound | Actual production | CO2 used | |
|---|---|---|---|
| Urea | 155 | 114 | |
| Methanol | 50 | 8 | |
| DME | 11.4 | 3 | |
| MTBE | 30 | 1.5 | |
| CH2O | 21 | 3.5 | |
| Carbonates | 0.2 | 0.005 | |
| Polycarbonates | 4 | 0.01 | |
| Carbamates | 5.3 | 0 | |
| Polyurethanes | > 8 | 0 | |
| Acrylates | 2.5 | 0 | |
| Polyacrylates | |||
| Formic acid | 0.6 | 0 | |
| Inorganic carbonates | 200 | ca. 50 | |
| (CaCO3, | 113.9 | ||
| soda Solvay, pigments) | 50 | ||
| Total | 172 | ||
| Non-chemical uses | Amount used | 28 | |
| EOR | 50 | 10 | |
| Others | 22 | 18 | |
-
DME: dimethyl ether; EOR: enhanced oil recovery.
table_chartTable 7
Perspective feedstock for the chemical industry and energy production sector
| Short term (2030) | Medium term (2050) | Long term (> 2050) | |
|---|---|---|---|
| Chemistry | Oil and gas dominate | Oil and gas | Oil and gas |
| Biomass will grow | Coal will re-enter with clean technologies | Coal will be used with clean technologies | |
| Biomass will reach its maximum | CO2 will be recovered and used on a large scale | ||
| CO2 will be used | |||
| Energy | Mix of fossils | Switch to perennial | Substantial grow of perennial |
| Wind will grow | Solar will continue to grow and spread | Electricity will play a key role also in the transportation sector | |
| Solar will grow | Fuels produced from water and CO2 will share an important part of the market |
table_chartTable 8
Chemicals derived from cellulose derived monomers (a selection of opportunities)26
| Starting material | Product | Catalyst | Solvent | T / K | Yield / % | Selectivity / % |
|---|---|---|---|---|---|---|
| Cellulose | 5-HMF | ZrO2/TiO2 | MIK | - | 87 | 35 |
| Cellulose | Levulinic acid | H2SO4 (1.5-3%) | H2O | - | - | 70-80 |
| Glucose | 5-HMF | H+ | Water | > 373 | 30-60 | 20-50 |
| Glucose | 5-HMF | Acid resins | Water | 373-473 | 30-60 | 20-40 |
| Glucose | 5-HMF | Al/Mg hydrotalcite Amberlist-15 | Water | - | 60 | 76 |
| Fructose | 5-HMF | H-form zeolites | Water | - | 60 | 53 |
| Fructose | - | - | DMSO/MIK/BuOH | - | 90 | 89 |
| Fructose | γ-Valerolactone | Ru/C | H2O | 450 | 80 | 62 |
| 5-HMF | Furanics (HMF ethers, esters) | Various | Alcohol/organic acids | > 373 | Variable | Variable |
-
HMF: 5-hydroxymethylfurfural; MIK: methylisobutylketone.
table_chartTable 9
Catalytic oxidative cleavage of lignin: catalysts and products28
| Catalyst | Media, supports or co-catalysts | Oxidant | Products |
|---|---|---|---|
| Laccase (multi-Cu enzyme) | Associated HRP (iron protoporphyrin) | O2 (Laccase) H2O2 (HRP) | Oxidized lignine |
| Co-immobilized laccases and HPR | Clay | O2, H2O2 | Oxidized depolymerized lignine |
| Mn(TMePyP)/clay/HBT (clay-PMS). The Fe analogue can also be used | Hydroxybenzotriazole or veratrilic alcohol | H2O2 | Oxidized oligomers, and monomers |
| Co, Cu, Mn(Salen) complexes | Inorganic acids, PPh3, ethylendiamine | O2 or H2O2 | Oxidized monomers from dimers |
| Polyoxometalates Mo(VI), W(VI), V(V), Nb(V): XM'aM"12-aObm- Keggin anions | SiO2 | O2 or H2O2 | Oxidized monomers and parent oligomers |
| O3ReCH3 | Polymeric ligands: poly-4-vinylpyridine and its N-oxide | H2O2 | Oxidized monomers and parent oligomers |
-
HPR: horseradish peroxidase; HBT: 1-hydroxybenzotriazole; HRP: horseradish peroxidase.
table_chartTable 10
Comparison of the properties of H2 produced from glycerol via bio-technology (column 2) or VPR (column 3)
| Concentration of glycerol | 2-6% | 1-20% |
|---|---|---|
| Conversion of glycerol | 100% at 2% feed | 100% at 1% feed |
| Purity of H2 | > 99% | 90% |
| Presence of CO | Absent | Present |
| Presence of CO2 | Traces | Present |
| Temperature | Ambient | 500-600 K |
| Pressure | 0.6 MPa | 2.0-3.0 MPa |
| Lifetime of the catalyst | More than seven days | Less than one week |
| Co-products | Organic acids, ethanol | Organic acids and others |
Como citar
location_on
Sociedade Brasileira de Química
Instituto de Química - UNICAMP, Caixa Postal 6154, 13083-970 Campinas SP - Brazil, Tel./FAX.: +55 19 3521-3151 -
São Paulo -
SP -
Brazil
E-mail: office@jbcs.sbq.org.br
E-mail: office@jbcs.sbq.org.br
rss_feed
Acompanhe os números deste periódico no seu leitor de RSS
Versão para download de PDF
Artigos relacionados
Versões e tradução automática
Versão original do texto
Tradução automática