BR102018076206A2 - production processes of carbon nanostructures with acidic and magnetic properties, from bio-oil, products and use - Google Patents
production processes of carbon nanostructures with acidic and magnetic properties, from bio-oil, products and use Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
A presente tecnologia descreve um processo de transformação do bio-óleo em nanoestruturas de carbono com propriedades ácidas, podendo ser magnéticas. Esse processo envolve a reação de sulfonação do bio-óleo em uma faixa de temperatura entre 80 e 120 °C, podendo ser impregnado com 8 a 24% de ferro, e pirolisado a 400-600 °C, o que leva à formação de nanoestruturas de carbono funcionalizadas com grupos sulfônicos ácidos, que apresentam aplicações em diversos campos da ciência, como adsorção e catálise.
Description
[001] A presente tecnologia descreve um processo de transformação do bio-óleo em nanoestruturas de carbono com propriedades ácidas, podendo ser magnéticas. Esse processo envolve a reação de sulfonação do bio-óleo em uma faixa de temperatura entre 80 e 120 °C, podendo ser impregnado com 8 a 24% de ferro, e pirolisado a 400-600 °C, o que leva à formação de nanoestruturas de carbono funcionalizadas com grupos sulfônicos ácidos, que apresentam aplicações em diversos campos da ciência, como adsorção e catálise.[001] The present technology describes a process of transforming bio-oil into carbon nanostructures with acidic properties, which can be magnetic. This process involves the sulfonation reaction of the bio-oil in a temperature range between 80 and 120 ° C, which can be impregnated with 8 to 24% iron, and pyrolysed at 400-600 ° C, which leads to the formation of nanostructures of carbon functionalized with acidic sulfonic groups, which have applications in several fields of science, such as adsorption and catalysis.
[002] O bio-óleo é um material muito promissor em processos de biorrefinaria. Geralmente é produzido a partir da pirólise rápida de qualquer rejeito constituído de biomassa. Ele é uma mistura complexa de compostos orgânicos de alta massa molecular que apresenta alta viscosidade, baixa volatilidade, alta acidez, instabilidade térmica e não é miscível em combustíveis fósseis, características que dificultam sua utilização.[002] Bio-oil is a very promising material in biorefinery processes. It is usually produced from the rapid pyrolysis of any biomass waste. It is a complex mixture of organic compounds of high molecular weight that has high viscosity, low volatility, high acidity, thermal instability and is not miscible in fossil fuels, characteristics that hinder its use.
[003] A síntese de biodiesel em escala industrial ocorre a partir da catálise básica em meio homogêneo. Após a síntese, o biodiesel deve passar por uma etapa de lavagem e secagem, o que aumenta o tempo, o custo do processo e a geração de grande quantidade de resíduo básico. Além disso, o óleo utilizado nesse processo, que corresponde a quase 80 % do custo total da produção de biodiesel, deve ser refinado, para evitar a formação de sabão.[003] The synthesis of biodiesel on an industrial scale occurs from basic catalysis in a homogeneous environment. After synthesis, biodiesel must go through a washing and drying step, which increases the time, the cost of the process and the generation of a large amount of basic waste. In addition, the oil used in this process, which corresponds to almost 80% of the total cost of biodiesel production, must be refined to avoid the formation of soap.
[004] Muitos esforços têm sido realizados para a utilização do bio-óleo. O documento de patente CN101298566A, intitulado “Method for preparing biocarbon solid acid catalyst and biodiesel”, de 2008, descreve um carvão sulfonado obtido através de duas etapas (pirólise e sulfonação), a partir de substâncias biológicas naturais puras.[004] Many efforts have been made to use bio-oil. The patent document CN101298566A, entitled “Method for preparing biocarbon solid acid catalyst and biodiesel”, of 2008, describes a sulfonated coal obtained through two steps (pyrolysis and sulfonation), from pure natural biological substances.
[005] O documento de patente CN107954626 (A), intitulado “Preparation method of biomass-based water reducer”, de 2017, refere-se a um método de preparação do redutor de água baseado na biomassa, onde os fenóis misturados extraídos do bio-óleo de pirólise são submetidos a uma reação de sulfonação, o solvente é removido e um derivado sulfonado dos fenóis é obtido. O derivado sulfonado e aldeídos extraídos do bio-óleo de pirólise são submetidos a uma reação de condensação de aldeído fenólico sob a ação de um catalisador ácido e obtém-se uma solução de polímero de condensação de aldeído fenólico sulfonado do composto; o valor de pH da solução é ajustado para 6-9, e o redutor de água à base de biomassa é obtido.[005] The patent document CN107954626 (A), entitled “Preparation method of biomass-based water reducer”, of 2017, refers to a method of preparing the water reducer based on biomass, where the mixed phenols extracted from the bio -pyrolysis oil is subjected to a sulfonation reaction, the solvent is removed and a sulfonated derivative of the phenols is obtained. The sulfonated derivative and aldehydes extracted from the pyrolysis bio-oil are subjected to a condensation reaction of phenolic aldehyde under the action of an acid catalyst and a solution of condensation polymer of sulfonated phenolic aldehyde of the compound is obtained; the pH value of the solution is adjusted to 6-9, and the biomass water reducer is obtained.
[006] O documento de patente US12742209, de 2007, intitulado “Integrated Process for Producing Diesel Fuel from Biological Material and Products, Uses and Equipment Relating to Said Process”, descreve o processo para produção do diesel e aditivos de um material biológico através da produção de parafinas utilizando a reação Fischer Tropsch e a hidrodeoxigenação do bio-óleo e gorduras. Os dois hidrocarbonetos são combinados e destilados juntos. A invenção também se refere à utilização de material lignocelulósico, para a produção de combustível diesel.[006] The patent document US12742209, 2007, entitled “Integrated Process for Producing Diesel Fuel from Biological Material and Products, Uses and Equipment Relating to Said Process”, describes the process for producing diesel and additives from a biological material through paraffin production using the Fischer Tropsch reaction and the hydrodeoxygenation of bio-oil and fats. The two hydrocarbons are combined and distilled together. The invention also relates to the use of lignocellulosic material, for the production of diesel fuel.
[007] O documento de patente CN101314138A, de 2008, intitulado “Carbonaceous solid acid catalyst prepared by direct sulphonation of biomass”, descreve o processo de produção de um sólido carbonáceo a partir da reação da biomassa com ácido sulfúrico concentrado e utilização desse material para produção de biodiesel a partir de ácidos graxos e álcoois de cadeia curta. Nesse caso o bio-óleo não foi utilizado para a produção de um material carbonáceo organizado.[007] The patent document CN101314138A, of 2008, entitled “Carbonaceous solid acid catalyst prepared by direct sulphonation of biomass”, describes the process of producing a carbonaceous solid from the reaction of biomass with concentrated sulfuric acid and the use of this material for biodiesel production from fatty acids and short-chain alcohols. In this case, bio-oil was not used to produce an organized carbonaceous material.
[008] No artigo “Facile synthesis of highly efficient and recyclable magnetic solid acid from biomass waste”, a biomassa impregnada com ferro e pirolisada para a síntese de um carvão com propriedades magnéticas. Posteriormente o carvão magnético foi sulfonado, produzindo um catalisador ácido heterogêneo. O bio-óleo produzido não foi utilizado como o precursor dos materiais ácidos (LIU, W. et al. Scientific reports, v.3, p.2419, 2013).[008] In the article “Facile synthesis of highly efficient and recyclable magnetic solid acid from biomass waste”, biomass impregnated with iron and pyrolyzed for the synthesis of a coal with magnetic properties. Subsequently, the magnetic charcoal was sulfonated, producing a heterogeneous acid catalyst. The bio-oil produced was not used as the precursor to acidic materials (LIU, W. et al. Scientific reports, v.3, p.2419, 2013).
[009] No artigo “Production of carbon nanostructures in biochar, bio-oil and gases from bagasse via microwave assisted pyrolysis using Fe and Co as susceptors”, a biomassa foi impregnada com Fe e Co, e pirolisada para a síntese de um carvão magnético. Posteriormente, o carvão magnético foi sulfonado. Foi realizado um balanço de massa do bio-óleo produzido, mas ele não foi utilizado como o precursor dos materiais ácidos (Debalina, B.; Rajasekhar B.; Vinu, R. Journal of Analytical and Applied Pyrolysis, v.124, p. 310-318, 2017).[009] In the article “Production of carbon nanostructures in biochar, bio-oil and gases from bagasse via microwave assisted pyrolysis using Fe and Co as susceptors”, the biomass was impregnated with Fe and Co, and pyrolyzed for the synthesis of a magnetic coal . Later, the magnetic coal was sulfonated. A mass balance of the produced bio-oil was performed, but it was not used as the precursor to acidic materials (Debalina, B .; Rajasekhar B .; Vinu, R. Journal of Analytical and Applied Pyrolysis, v.124, p. 310-318, 2017).
[010] Na presente tecnologia, o bio-óleo, um material viscoso de baixo valor agregado, foi utilizado como precursor para a síntese de materiais nanoestruturados de carbono com propriedades ácidas. Os materiais nanoestruturados são produzidos em apenas uma etapa (sulfonação). A presente tecnologia também descreve um processo de produção de nanomateriais ácidos com propriedades magnéticas, envolvendo a impregnação do bio-óleo com Fe e pirólise, onde é formado um carvão magnético sólido, que é posteriormente sulfonado. A tecnologia permite a utilização do bio-óleo como um precursor para a síntese de materiais nanoestruturados de carbono com propriedades ácidas, podendo apresentar propriedades magnéticas, gerando produtos que podem ser utilizados em reações de esterificação e outras reações.[010] In the present technology, bio-oil, a viscous material with low added value, was used as a precursor for the synthesis of nanostructured carbon materials with acidic properties. Nanostructured materials are produced in just one step (sulfonation). The present technology also describes a process for producing acidic nanomaterials with magnetic properties, involving the impregnation of the bio-oil with Fe and pyrolysis, where a solid magnetic carbon is formed, which is subsequently sulfonated. The technology allows the use of bio-oil as a precursor for the synthesis of nanostructured carbon materials with acidic properties, which can have magnetic properties, generating products that can be used in esterification reactions and other reactions.
[011] No estado da técnica não foi encontrado nenhum trabalho sobre utilização do bio-óleo para produção de nanoestruturas de carbono com características ácidas. A modificação do bio-óleo, formação de materiais nanoestruturados de carbono e sua aplicação como catalisador são objeto da presente tecnologia, onde o bio-óleo, um rejeito proveniente da pirólise de biomassa, quando submetido à reação de sulfonação, tem sua estrutura totalmente alterada, produzindo nanoestruturas de carbono com grupos ácidos superficiais.[011] In the state of the art, no work has been found on the use of bio-oil for the production of carbon nanostructures with acidic characteristics. The modification of the bio-oil, formation of nanostructured carbon materials and its application as a catalyst are the object of the present technology, where the bio-oil, a waste from the biomass pyrolysis, when submitted to the sulfonation reaction, has its structure totally altered , producing carbon nanostructures with superficial acid groups.
[012] A tecnologia proposta permite a produção de nanoestruturas ácidas baseadas em carbono por um método rápido, fácil e de baixo custo. Além disso, os materiais obtidos podem ser utilizados como catalisadores heterogêneos em reações de esterificação e hidrólise, e podem ser recuperados do meio reacional mais facilmente, evitando a lavagem, por exemplo, do biodiesel. Os materiais sintetizados também podem ser utilizados como adsorventes.[012] The proposed technology allows the production of carbon-based acid nanostructures by a fast, easy and low cost method. In addition, the materials obtained can be used as heterogeneous catalysts in esterification and hydrolysis reactions, and can be recovered from the reaction medium more easily, avoiding washing, for example, biodiesel. The synthesized materials can also be used as adsorbents.
[013] A presente tecnologia trata de um processo para a modificação química do bio-óleo, através da sulfonação para produção de materiais nanoestruturados de carbono, com propriedades ácidas, que apresentam aplicações em diversos campos da ciência, como adsorção e catálise.[013] The present technology deals with a process for the chemical modification of bio-oil, through sulfonation to produce nanostructured carbon materials, with acidic properties, which have applications in several fields of science, such as adsorption and catalysis.
[014] Os materiais produzidos podem ser reutilizados ou facilmente separados com ímãs do meio reacional, não contaminam as fases de biodiesel e podem ser utilizados em reações com óleos de alta acidez para produção do biocombustível, diminuindo os custos do processo.[014] The produced materials can be reused or easily separated with magnets from the reaction medium, do not contaminate the biodiesel phases and can be used in reactions with high acid oils for the production of biofuel, reducing the process costs.
[015] A Figura 1 apresenta difratogramas de raios-X dos materiais sulfonados com razões em massa H2SO4: bio-óleo 1,8, 3,7, 9,2 e 18,4 a 120 °C por 2 h.[015] Figure 1 shows X-ray diffractograms of sulfonated materials with mass ratios H2SO4: bio-oil 1.8, 3.7, 9.2 and 18.4 at 120 ° C for 2 h.
[016] A Figura 2 apresenta espectro Raman dos materiais sulfonados (BS1.8, BS3.7,BS9.2 e BS18.4) com razões em massa H2SO4: bio-óleo 1,8, 3,7, 9,2 e 18,4 a 120 °C por 2 h.[016] Figure 2 shows the Raman spectrum of sulfonated materials (BS1.8, BS3.7, BS9.2 and BS18.4) with H2SO4 mass ratios: bio-oil 1.8, 3.7, 9.2 and 18.4 to 120 ° C for 2 h.
[017] A Figura 3 apresenta imagens de microscopia eletrônica de transmissão das nanoestruturas de carbono (1-grafeno, 2-grafite, 3-carbono amorfo e 4-estruturas fechadas) sulfonadas com razão em massa H2SO4: bio-óleo 1,8, a 120 °C por 2 h.[017] Figure 3 shows electron microscopy images of the transmission of carbon nanostructures (1-graphene, 2-graphite, 3-amorphous carbon and 4-closed structures) sulfonated with mass ratio H2SO4: bio-oil 1.8, at 120 ° C for 2 h.
[018] A Figura 4 apresenta a densidade dos sítios ácidos em mmol.g-1 dos materiais sulfonados com razões em massa H2SO4: bio-óleo 1,8, 3,7, 9,2 e 18,4, obtidos por titulação potencimétrica com n-butilamina.[018] Figure 4 shows the density of acidic sites in mmol.g-1 of sulfonated materials with mass ratios H2SO4: bio-oil 1.8, 3.7, 9.2 and 18.4, obtained by potentiometric titration with n-butylamine.
[019] A Figura 5 apresenta os valores de conversão de reações de esterificação utilizando 7,5 % dos catalisadores BS1,8, BS3,7, BS9,2, e BS18,4, 1:10 ácido oleico: metanol, 100 °C e 3 h de reação.[019] Figure 5 shows the conversion values of esterification reactions using 7.5% of the catalysts BS1,8, BS3,7, BS9,2, and BS18,4, 1:10 oleic acid: methanol, 100 ° C and 3 h of reaction.
[020] A Figura 6 apresenta difratogramas de raios-X dos materiais com 8% em massa de ferro, pirolisados entre 400-600 °C e sulfonados com razão em massa H2SO4: bio-óleo 9,2 a 120 °C por 2 h.[020] Figure 6 shows X-ray diffractograms of materials with 8% by weight of iron, pyrolysates between 400-600 ° C and sulfonated with mass ratio H2SO4: bio-oil 9.2 at 120 ° C for 2 h .
[021] A Figura 7 apresenta o espectro Mӧssbauer a 30K dos materiais impregnados com 8% em massa de ferro, pirolisados entre 400-600 °C e sulfonados com razão em massa H2SO4: bio-óleo 9,2 a 120 °C por 2 h.[021] Figure 7 shows the Mӧssbauer spectrum at 30K of materials impregnated with 8% by weight of iron, pyrolyzed between 400-600 ° C and sulfonated with mass ratio H2SO4: bio-oil 9.2 at 120 ° C for 2 H.
[022] A Figura 8 apresenta imagens de microscopia eletrônica de transmissão dos materiais impregnados com 8 % em massa de ferro, pirolisados a 450°C (Quadrante 1 e 2) e sulfonados com razão em massa H2SO4: bio-óleo 9,2 a 120 °C por 2 h (Quadrante 3 e 4).[022] Figure 8 shows electron microscopy images of the transmission of materials impregnated with 8% by weight of iron, pyrolyzed at 450 ° C (
[023] A Figura 9 apresenta valores de conversão de reações de esterificação utilizando 10 % dos catalisadores (B8Fe)400S, (B8Fe)450S, (B8Fe)500S, e (B8Fe)600S, 1:10 ácido oleico: metanol, 100 °C e 6 h de reação.[023] Figure 9 shows conversion values for esterification reactions using 10% of the catalysts (B8Fe) 400S, (B8Fe) 450S, (B8Fe) 500S, and (B8Fe) 600S, 1:10 oleic acid: methanol, 100 ° C and 6 h of reaction.
[024] A presente tecnologia descreve um processo de transformação do bio-óleo em nanoestruturas de carbono com propriedades ácidas, podendo ser magnéticas. Esse processo envolve a reação de sulfonação do bio-óleo em uma faixa de temperatura entre 80 e 120 °C, podendo ser impregnado com 8 a 24% de ferro, e pirolisado a 400-600 °C, o que leva à formação de nanoestruturas de carbono funcionalizadas com grupos sulfônicos ácidos, que apresentam aplicações em diversos campos da ciência, como adsorção e catálise.[024] The present technology describes a process of transforming bio-oil into carbon nanostructures with acidic properties, which can be magnetic. This process involves the sulfonation reaction of the bio-oil in a temperature range between 80 and 120 ° C, which can be impregnated with 8 to 24% iron, and pyrolysed at 400-600 ° C, which leads to the formation of nanostructures of carbon functionalized with acidic sulfonic groups, which have applications in several fields of science, such as adsorption and catalysis.
[025] O processo de produção de nanoestruturas de carbono compreende a sulfonação direta de amostras de bio-óleo, através das seguintes etapas:
- a. Misturar o bio-óleo e ácidos inorgânicos ou sais com grupos sulfônicos, na proporção entre 1:2 e 1:20 (m/m);
- b. Homogeneizar a mistura obtida na etapa “a”, por tempo entre 30 e 360 minutos, e aquecer entre 80 e 160 °C, preferencialmente a 80 °C;
- c. Lavar o material esponjoso obtido na etapa “b” com água destilada até o valor de pH encontrar-se na faixa de 5,5 a 6,0;
- d. Secar o sólido obtido entre 60 a 100 °C, por um período entre 6 e 12 horas.
- The. Mix the bio-oil and inorganic acids or salts with sulfonic groups, in the proportion between 1: 2 and 1:20 (m / m);
- B. Homogenize the mixture obtained in step "a", for a time between 30 and 360 minutes, and heat between 80 and 160 ° C, preferably at 80 ° C;
- ç. Wash the spongy material obtained in step “b” with distilled water until the pH value is in the range of 5.5 to 6.0;
- d. Dry the solid obtained at 60 to 100 ° C, for a period between 6 and 12 hours.
[026] Os ácidos inorgânicos descritos na etapa “a” podem ser selecionados do grupo compreendendo H2SO4, H2SO4 fumegante, HCIO3S, e H2SO3. Os sais com grupos sulfônicos descritos na etapa “a” podem ser selecionados de quaisquer sais ou reagentes contendo os grupos SO3, SO2, R2SO3 ou C2H6SO4, onde R é CnHx.[026] The inorganic acids described in step "a" can be selected from the group comprising H2SO4, fumigating H2SO4, HCIO3S, and H2SO3. The salts with sulfonic groups described in step “a” can be selected from any salts or reagents containing the groups SO3, SO2, R2SO3 or C2H6SO4, where R is CnHx.
[027] O processo de produção de nanoestruturas de carbono compreende a impregnação de bio-óleo com sais de metais, através das seguintes etapas:
- a. Misturar o bio-óleo com sais inorgânicos contendo Fe, Co e Ni, na proporção entre 8 e 24 % em massa;
- b. Homogeneizar a mistura obtida na etapa “a”, por tempo entre 30 e 120 minutos, à temperatura ambiente;
- c. Secar o material obtido na etapa “b” entre 80 e 120°C;
- d. Secar o sólido obtido em estufa entre 60
e 100°C, por um período entre 6 e 12 horas; - e. Aquecer o material obtido na etapa “d” entre 400 a 600 °C em um forno tubular horizontal, com fluxo de N2, argônio ou outro gás inerte por 1 a 3 horas para ocorrer a reação de pirólise;
- f. Misturar o material obtido na etapa “e” com ácidos inorgânicos ou sais com grupos sulfônicos, na proporção entre 1:2 e 1:20 (m/m).
- The. Mix the bio-oil with inorganic salts containing Fe, Co and Ni, in the proportion between 8 and 24% by mass;
- B. Homogenize the mixture obtained in step “a”, for a time between 30 and 120 minutes, at room temperature;
- ç. Dry the material obtained in step “b” between 80 and 120 ° C;
- d. Dry the obtained solid in an oven between 60 and 100 ° C, for a period between 6 and 12 hours;
- and. Heat the material obtained in step "d" between 400 to 600 ° C in a horizontal tubular oven, with a flow of N2, argon or other inert gas for 1 to 3 hours to occur the pyrolysis reaction;
- f. Mix the material obtained in step “e” with inorganic acids or salts with sulfonic groups, in the proportion between 1: 2 and 1:20 (m / m).
[028] Os sais inorgânicos descritos na etapa “a” podem ser selecionados do grupo compreendendo FeCI3, Fe(NO3)3, CoCI2, Co(NO3)2, NiCI2, Ni(NO3)2, NiSO4, CoSO4 e FeSO4.[028] The inorganic salts described in step “a” can be selected from the group comprising FeCI3, Fe (NO3) 3, CoCI2, Co (NO3) 2, NiCI2, Ni (NO3) 2, NiSO4, CoSO4 and FeSO4.
[029] Os ácidos inorgânicos descritos na etapa “f՚՚ podem ser selecionados do grupo compreendendo H2SO4, H2SO4 fumegante, HCIO3S, e H2SO3. Os sais com grupos sulfônicos descritos na etapa “f'' podem ser selecionados do grupo compreendendo SO3, SO2, R2SO3 e C2H6SO4.[029] The inorganic acids described in step “f ՚՚ can be selected from the group comprising H2SO4, fumigating H2SO4, HCIO3S, and H2SO3. The salts with sulfonic groups described in step “f '' can be selected from the group comprising SO3, SO2, R2SO3 and C2H6SO4.
[030] As nanoestruturas de carbono da presente tecnologia apresentam propriedades ácidas, podendo ser magnéticas, e são produzidas a partir do bio-óleo, conforme os processos definidos acima.[030] The carbon nanostructures of the present technology have acidic properties, which can be magnetic, and are produced from bio-oil, according to the processes defined above.
[031] As nanoestruturas de carbono descritas acima podem ser utilizadas em reações de catálise e adsorção.[031] The carbon nanostructures described above can be used in catalysis and adsorption reactions.
[032] A presente invenção pode ser mais bem compreendida através dos exemplos, não limitante.[032] The present invention can be better understood through the examples, not limiting.
[033] As amostras de bio-óleo foram sulfonadas com diferentes ácidos nas razões ácido:bio-óleo entre 1,8 e 18,4 (m/m), a 120 °C, durante 2 h. Após esse tempo, os materiais foram lavados até pH da água destilada (pH=6,0) e secos em estufa. Os materiais obtidos foram caracterizados por difração de raios-X, microscopia eletrônica de varredura e espectroscopia Raman.[033] The bio-oil samples were sulfonated with different acids in the acid: bio-oil ratio between 1.8 and 18.4 (m / m), at 120 ° C, for 2 h. After that time, the materials were washed to pH of distilled water (pH = 6.0) and dried in an oven. The materials obtained were characterized by X-ray diffraction, scanning electron microscopy and Raman spectroscopy.
[034] Os difratogramas de raios-X mostraram que após a sulfonação, formou-se um material com fases amorfas de carbono (Figura 1). O aumento da razão ácido:bio-óleo, causou o deslocamento dos sinais, mostrando que a distância entre as camadas de carbono diminuiu. Além disso, foi observado também o afinamento dos picos.[034] X-ray diffractograms showed that after sulfonation, a material with amorphous carbon phases was formed (Figure 1). The increase in the acid: bio-oil ratio caused the signals to shift, showing that the distance between the carbon layers decreased. In addition, the thinning of the peaks was also observed.
[035] Os espectros Raman dos materiais (Figura 2) mostraram a presença de duas bandas características de materiais de carbono, a banda D em 1380 cm-1 e a D em 1580 cm-1. É importante salientar que intensidade da banda G maior que a D, mostra que as estruturas formadas são organizadas e apresentam poucos defeitos.[035] The Raman spectra of the materials (Figure 2) showed the presence of two characteristic bands of carbon materials, the D band at 1380 cm-1 and the D band at 1580 cm-1. It is important to note that the intensity of the G band greater than that of D shows that the structures formed are organized and have few defects.
[036] As imagens de microscopia eletrônica de varredura mostraram que os materiais estão organizados na forma de camadas e o mapeamento mostrou que o enxofre está distribuído sobre toda a superfície do material. As imagens de microscopia eletrônica de transmissão (Figura 3) mostraram a presença de nanoestruturas de carbono, grafite, folhas de grafeno, estruturas circulares fechadas assim como carbono amorfo.[036] Scanning electron microscopy images showed that the materials are organized in the form of layers and the mapping showed that the sulfur is distributed over the entire surface of the material. Transmission electron microscopy images (Figure 3) showed the presence of carbon nanostructures, graphite, graphene sheets, closed circular structures as well as amorphous carbon.
[037] A acidez dos materiais após a sulfonação também foi analisada (Figura 4). Para a análise de acidez os materiais obtidos foram colocados sob agitação, em contato com acetonitrila. Após 24 horas, o material foi titulado com uma solução de n-butilamina 0,025 mol.L-1. O número de sítios ácidos dos materiais foram 0,03, 0,18, 0,26 e 0,32 mmol.g-1. Esses valores mostram que ao aumentar a razão H2SO4:bio-óleo, o número de sítios ácidos aumenta. Esses sítios podem ser atribuídos à presença dos grupos -OH, -CO2H e -SO3H[037] The acidity of the materials after sulfonation was also analyzed (Figure 4). For the analysis of acidity the materials obtained were placed under agitation, in contact with acetonitrile. After 24 hours, the material was titrated with a 0.025 mol.L-1 n-butylamine solution. The number of acidic sites of the materials were 0.03, 0.18, 0.26 and 0.32 mmol.g-1. These values show that by increasing the H2SO4: bio-oil ratio, the number of acidic sites increases. These sites can be attributed to the presence of the groups -OH, -CO2H and -SO3H
[038] As amostras dos catalisadores ácidos sulfonados (BS1,8, BS3,7, BS9,2 e BS-18,4) foram testadas como catalisadores para a síntese de biodiesel. Foi utilizado ácido oleico e metanol 1:10 (razão molar); a 100 °C, 3 h de reação; massa de catalisador 7,5 % em relação à massa do ácido oleico e agitação magnética. As reações apresentaram conversões de óleo em biodiesel (ésteres) acima de 90 % (Figura 5).[038] Samples of the sulfonated acid catalysts (BS1.8, BS3.7, BS9.2 and BS-18.4) were tested as catalysts for the synthesis of biodiesel. Oleic acid and methanol 1:10 (molar ratio) were used; at 100 ° C, 3 h of reaction; mass of catalyst 7.5% in relation to the mass of oleic acid and magnetic stirring. The reactions showed oil to biodiesel conversions (esters) above 90% (Figure 5).
[039] As amostras de bio-óleo foram impregnadas com 8 % em massa de ferro, agitadas durante 1 h e secas entre 80 e 120 °C. Em seguida, as amostras foram pirolisadas a 400 °C por 1 h em atmosfera de N2. As amostras foram então tratadas com diferentes ácidos nas razões ácido:bio-óleo entre 1,8 a 18,4 (m/m), a 120 °C, durante 2 h. Após esse tempo, os materiais foram lavados até pH da água destilada (pH=6,0) e secos em estufa. Os materiais obtidos foram caracterizados por difração de raios-X, microscopia eletrônica de varredura, espectroscopia Mӧssbauer e titulação potenciométrica.[039] The bio-oil samples were impregnated with 8% by weight of iron, stirred for 1 h and dried between 80 and 120 ° C. Then, the samples were pyrolyzed at 400 ° C for 1 h in an N2 atmosphere. The samples were then treated with different acids in the acid: bio-oil ratio between 1.8 to 18.4 (w / w), at 120 ° C, for 2 h. After that time, the materials were washed to distilled water pH (pH = 6.0) and dried in an oven. The materials obtained were characterized by X-ray diffraction, scanning electron microscopy, Mӧssbauer spectroscopy and potentiometric titration.
[040] Os difratogramas de raios-X mostraram que após pirólise e sulfonação, formou-se um material com fases amorfas de carbono e fases cristalinas relacionadas à magnetita Fe3O4 (Figura 6). Além disso, com o aumento da temperatura da pirólise, houve uma diminuição significativa da fase amorfa.[040] X-ray diffractograms showed that after pyrolysis and sulfonation, a material was formed with amorphous carbon phases and crystalline phases related to Fe3O4 magnetite (Figure 6). In addition, with the increase in pyrolysis temperature, there was a significant decrease in the amorphous phase.
[041] A partir dos espectros Mӧssbauer obtidos a 30K (Figura 7), observa-se que em todos os materiais pirolisados e sulfonados ocorreu a redução do Fe3+ para Fe2+, possivelmente devido à oxidação do carbono.[041] From the Mӧssbauer spectra obtained at 30K (Figure 7), it is observed that in all pyrolyzed and sulfonated materials there was a reduction in Fe3 + to Fe2 +, possibly due to the oxidation of carbon.
[042] As imagens de microscopia eletrônica de varredura mostraram que os materiais estão organizados e a partir do mapeamento observou-se que o enxofre e ferro estão distribuídos sobre toda a superfície do material. As imagens de microscopia eletrônica de transmissão dos materiais B8Fe450 e B8Fe450S (Figura 8) mostraram carbono amorfo e algumas nanoestruturas. Além disso, os materiais apresentaram Fe em sua composição. No geral, quando o material foi sulfonado, o teor de Fe diminuiu no material, devido à lixiviação.[042] Scanning electron microscopy images showed that the materials are organized and from the mapping it was observed that sulfur and iron are distributed over the entire surface of the material. Transmission electron microscopy images of materials B8Fe450 and B8Fe450S (Figure 8) showed amorphous carbon and some nanostructures. In addition, the materials presented Fe in their composition. In general, when the material was sulfonated, the Fe content decreased in the material, due to leaching.
[043] A análise da acidez dos materiais por titulação mostrou que as amostras pirolisadas a temperaturas maiores que 500 °C não apresentaram acidez significativa, devido à estrutura organizada do carvão formado.[043] The analysis of the acidity of the materials by titration showed that the pyrolysed samples at temperatures above 500 ° C did not show significant acidity, due to the organized structure of the formed coal.
[044] As amostras dos materiais carbonáceos magnéticos (B8Fe)400S, (B8Fe)450S, (B8Fe)500S e (B8Fe)600S foram testadas como catalisadores para a síntese de biodiesel. Foi utilizado ácido oleico e metanol 1:10 (razão molar); a 100 °C, 6 h de reação; massa de catalisador 10 % em relação à massa do ácido oleico e agitação magnética. As reações utilizando os catalisadores (B8Fe)400S e (B8Fe)450S apresentaram conversões de óleo em biodiesel (ésteres) acima de 90 % (Figura 9).[044] Samples of the carbonaceous magnetic materials (B8Fe) 400S, (B8Fe) 450S, (B8Fe) 500S and (B8Fe) 600S were tested as catalysts for the synthesis of biodiesel. Oleic acid and methanol 1:10 (molar ratio) were used; at 100 ° C, 6 h of reaction; mass of
Claims (10)
- a) Misturar o bio-óleo e ácidos inorgânicos ou sais com grupos sulfônicos, na proporção entre 1:2 e 1:20 (m/m);
- b) Homogeneizar a mistura obtida na etapa “a”, por tempo entre 30 e 360 minutos, e aquecer entre 80 e 160 °C;
- c) Lavar o material esponjoso obtido na etapa “b” com água destilada até o valor de pH encontrar-se na faixa de 5,5 a 6,0;
- d) Secar o sólido obtido entre 60 a 100 °C, por um período entre 6 e 12 horas.
- a) Mix bio-oil and inorganic acids or salts with sulfonic groups, in the proportion between 1: 2 and 1:20 (w / w);
- b) Homogenize the mixture obtained in step “a”, for a time between 30 and 360 minutes, and heat between 80 and 160 ° C;
- c) Wash the spongy material obtained in step “b” with distilled water until the pH value is in the range of 5.5 to 6.0;
- d) Dry the solid obtained at 60 to 100 ° C, for a period between 6 and 12 hours.
- a) Misturar o bio-óleo e sais inorgânicos contendo Fe, Co e Ni, na proporção entre 8 e 24 % em massa;
- b) Homogeneizar a mistura obtida na etapa “a”, por tempo entre 30 e 120 minutos à temperatura ambiente;
- c) Secar o material obtido na etapa “b” entre 80 e 120°C;
- d) Secar o sólido obtido em estufa entre 60 e 100°C por um período entre 6 e 12 horas;
- e) Aquecer o material obtido na etapa “d” entre 400 a 600°C em um forno tubular horizontal, com fluxo de gás inerte (50-100 mL.min-1) por 1 a 3 horas para ocorrer a reação de pirólise;
- f) Misturar o material obtido na etapa “e” com ácidos inorgânicos ou sais com grupos sulfônicos, na proporção entre 1:2 e 1:20 (m/m).
- a) Mix the bio-oil and inorganic salts containing Fe, Co and Ni, in the proportion between 8 and 24% by weight;
- b) Homogenize the mixture obtained in step “a”, between 30 and 120 minutes at room temperature;
- c) Dry the material obtained in step “b” between 80 and 120 ° C;
- d) Dry the obtained solid in an oven between 60 and 100 ° C for a period between 6 and 12 hours;
- e) Heat the material obtained in step “d” between 400 to 600 ° C in a horizontal tubular oven, with an inert gas flow (50-100 mL.min-1) for 1 to 3 hours to occur the pyrolysis reaction;
- f) Mix the material obtained in step “e” with inorganic acids or salts with sulfonic groups, in the proportion between 1: 2 and 1:20 (m / m).
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