PT103684A - LIQUID BIOFUELS CONSTITUTED BY DIHYDROXYMETHYLFURAN, PROPANOL AND ITS PRODUCTION PROCESS FROM POLYOLES OF AGRICULTURAL ORIGIN - Google Patents

LIQUID BIOFUELS CONSTITUTED BY DIHYDROXYMETHYLFURAN, PROPANOL AND ITS PRODUCTION PROCESS FROM POLYOLES OF AGRICULTURAL ORIGIN Download PDF

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PT103684A
PT103684A PT103684A PT10368407A PT103684A PT 103684 A PT103684 A PT 103684A PT 103684 A PT103684 A PT 103684A PT 10368407 A PT10368407 A PT 10368407A PT 103684 A PT103684 A PT 103684A
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hydrogenation
dehydration
ionic liquid
products
process according
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PT103684A
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Pedro Manuel Brito Da Silva Correia
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Pedro Manuel Brito Da Silva Correia
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Priority to PT103684A priority Critical patent/PT103684A/en
Priority to EP07734420A priority patent/EP2144977A1/en
Priority to PCT/IB2007/001102 priority patent/WO2008053284A1/en
Publication of PT103684A publication Critical patent/PT103684A/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Furan Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

O DIHIDROXIMETILFURANO PURO OU MISTURADO COM OUTROS SUBPRODUTOS DA HIDROGENAÇÃO DO HIDROXIMETILFURFURAL OBTIDO POR DESIDRATAÇÃO DE HIDRATOS DE CARBONO TEM BOAS QUALIDADES COMO COMPONENTE DE COMBUSTÍVEL AUTOMÓVEL E UM CUSTO DE PRODUÇÃO COMPETITIVO SEGUNDO O PROCESSO AGORA REIVINDICADO. OS HIDRATOS DE CARBONO PODEM SER O AÇÚCAR, A CELULOSE OU O AMIDO. PARTICULARMENTE INTERESSANTE É A UTILIZAÇÃO DE CANA DE AÇÚCAR SOB FORMA DE SERRADURA DESHIDRATADA. ESTA SERRADURA VERIFICOU-SE SER HIDROLISADA EM FRUTOSE E GLUCOSE NOS LÍQUIDOS IÓNICOS E ÀS TEMPERATURAS AGORA APRESENTADAS. O PROPANOL OBTIDO POR DESIDRATAÇÃO DA GLICERINA, SEGUIDA DE HIDROGENAÇÃO TAMBEM É UM BOM COMPONENTE. A GLICERINA É UM SUBPRODUTO DA PRODUÇÃO DO BIODIESEL, PRODUZIDO A PARTIR DE ÓLEOS VEGETAIS. O PROCESSO DE PRODUÇÃO EM AMBOS OS CASOS CONSISTE EM REALIZAR UMA DESIDRATAÇÃO EM LÍQUIDOS IÓNICOS, E EFECTUAR A HIDROGENAÇÃO DO INTERMEDIÁRIO OBTIDO DEPOIS DE O SEPARAR OU SEM O SEPARAR DO LIQUIDO IÓNICO. O LIQUIDO IÓNICO FUNCIONA DE EXCELENTE SOLVENTE E TAMBEM DE CATALISADOR, QUE PERMITE BAIXAR A TEMPERATURA DE DESIDRATAÇÃO CONSIDERÁVELMENTE. A SEPARAÇÃO ENTRE O DHF E O LIQUIDO IÓNICO E A ÁGUA É FEITA POR DESTILAÇÃO OU DE PREFERÊNCIA POR EXTRACÇÃO COM ÉTER ETÍLICO OU COM ANIDRIDO CARBÓNICO SUPERCRITICO.PURE OR MIXED DIHYDROXYMETHYLFURANE WITH OTHER BY-PRODUCTS OF THE HYDROXYMETHYLFURFURAL HYDROGENATION OBTAINED BY CARBON HYDRATE DEHYDRATION HAS GOOD QUALITIES AS A COMPOUND OF AUTOMOBILE FUEL AND A COST OF COMPETITIVE PRODUCTION ACCORDING TO THE PROCEDURE NOW CLAIMED. CARBON HYDRATES CAN BE SUGAR, CELLULOSE OR STARCH. PARTICULARLY INTERESTING IS THE UTILIZATION OF SUGAR CANE IN THE FORM OF DEHYDRATED SERRADURA. THIS SERRADURE IS VERIFIED TO BE HYDROLYSISED IN FRUIT AND GLUCOSE IN THE IONIC LIQUIDS AND THE TEMPERATURES NOW PRESENTED. PROPANOL OBTAINED BY GLYCERIN DEHYDRATION, FOLLOWED BY HYDROGENATION IS ALSO A GOOD COMPONENT. GLYCERIN IS A BY-PRODUCTS OF BIODIESEL PRODUCTION, PRODUCED FROM VEGETABLE OILS. THE PRODUCTION PROCESS IN BOTH THE CASES CONSISTS IN CONDUCTING A DEHYDRATION IN IONIC LIQUIDS, AND PERFORMING THE HYDROGENATION OF THE INTERMEDIATE OBTAINED AFTER SEPARATING OR SEPARATING THE IONIC LIQUID. THE IONIC LIQUID WORKS OF EXCELLENT SOLVENT AND ALSO OF CATALYST, WHICH ALLOWS TO LOWER THE DEHYDRATION TEMPERATURE CONSIDERABLY. SEPARATION BETWEEN DHF AND IONIC LIQUID AND WATER IS MADE BY DISTILLATION OR PREFERENCE BY EXTRACTION WITH ETHYL ESTER OR WITH SUPERCRYTICAL CARBON ANCILLUS.

Description

11

Descriçãodescription

Biocombustiveis líquidos constituídos por dihidroximetil furano, propanol e seu processo de produção a partir de poliois de origem agricola 1. Domínio técnico da invençãoLiquid biofuels consisting of dihydroxymethyl furan, propanol and their production process from polyolefins of agricultural origin 1. Technical domain of the invention

Biocombustiveis, líquidos iónicos, extracção supercritica com anidrico carbónico. 2 . Estado da técnica anterior A utilização da madeira como fonte de energia sempre existiu, mas a sua utilização em meios de transporte modernos exige a sua conversão em combustiveis líquidos. A glicerina obtida como subproduto da industria de biodiesel tornou-se também numa matérias prima possível para combustível automóvel.Biocombustiveis, ionic liquids, supercritical extraction with carbonic anhydride. 2 . BACKGROUND ART The use of wood as an energy source has always existed, but its use in modern means of transport requires its conversion into liquid fuels. Glycerin obtained as a by-product of the biodiesel industry has also become a possible raw material for automotive fuel.

Tanto a glicerina como os hidratos de carbono são quimicamente poliois.Both glycerin and carbohydrates are chemically polyolefins.

Os combustiveis líquidos para meios de transporte obtidos a partir de produtos agrícolas são principalmente os seguintes: 2.1. Produção de hidrocarbonetos via gás de sintese A tecnologia para converter materiais contendo carbono em hidrocarbonetos é conhecida desde os anos 40, sendo o processo mais usado o de Fischer Tropsch, que permite transformar qualquer matéria contendo carvão em gás de síntese, por conversão com vapor de água (steam reforming) seguida de conversão da mistura de monóxido de carbono e hidrogénio em hidrocarbonetos. 0 processo Fischer Tropsch a partir de carvão foi muito usado na Alemanha durante a 2a guerra mundial e na África do Sul durante o bloqueio por questões raciais. O processo 2Liquid fuels for means of transport obtained from agricultural products are mainly the following: 2.1. Production of hydrocarbons via synthesis gas The technology for converting carbon-containing materials into hydrocarbons has been known since the 1940s, with Fischer Tropsch being the most widely used process for converting any carbon-containing material into synthesis gas by conversion with steam steam reforming followed by conversion of the mixture of carbon monoxide and hydrogen into hydrocarbons. The Fischer Tropsch process from coal was widely used in Germany during World War II and in South Africa during the racial blockade. Process 2

Fischer Tropsch também é aplicável à conversão de madeira, contendo celulose e lenhina, em hidrocarbonetos.Fischer Tropsch is also applicable to the conversion of wood, containing cellulose and lignin, into hydrocarbons.

As reacções químicas, tomando como exemplo o hexano, são: C + H20 -> CO + H2 C + 2H20 -> C02 + 4H2 6C0 + 14H2 -> C6H14 + 6H20 A reacção global é 9,5 C + 7H20 C6Hi4 + 3,5 C02 A formação de hidrocarbonetos exige para cada 6 átomos de carbono 14 átomos de hidrogénio o que obriga a que uma parte do carbono seja perdida como anidrido carbónico, na segunda reacção, visto que a primeira reacção não produz o hidrogénio suficiente.The chemical reactions, taking the hexane as an example, are: C + H20 - > CO + H2 C + 2H20 - > C02 + 4H2 6CO + 14H2 -> C6 H14 + 6 H2 O The overall reaction is 9.5 C + 7 H20 C6 H14 + 3.5 CO2 The formation of hydrocarbons requires for every 6 carbon atoms 14 hydrogen atoms which forces one part of the carbon to be lost as carbon dioxide, second reaction, since the first reaction does not produce sufficient hydrogen.

Por cada 9,5 átomos de carbono há 3,5 que não aparecem no combustível final. 2.2. Produção de etanol via fermentação de açúcarFor every 9.5 carbon atoms there are 3.5 that do not appear in the final fuel. 2.2. Production of ethanol via sugar fermentation

Um processo muito usado nos países produtores de cana de açúcar é a extracção do açúcar, que representa 12% da cana, e fermentação enzimática em etanol.A process widely used in sugarcane producing countries is the extraction of sugar, which accounts for 12% of sugarcane, and enzymatic fermentation in ethanol.

Mais recentemente está a ser estudada a conversão da própria celulose da cana em açúcar para aumentar a quantidade de etanol por tonelada de cana de açúcar. Esta conversão é feita por hidrólise ácida ou por fermentação. A cana de açúcar permite uma produção de 80 toneladas por hectar, sendo porventura a cultura agrícola que mais combustível por hectar e por ano produz. A reacção química é: C6Hi206 -> 2C2H5OH + 2C02More recently, the conversion of sugarcane pulp into sugar is being studied to increase the amount of ethanol per ton of sugarcane. This conversion is by acidic hydrolysis or by fermentation. The sugar cane allows a production of 80 tons per hectare, being perhaps the agricultural crop that more fuel per hectare and per year produces. The chemical reaction is: C 6 H 20 O - > 2C 2 H 5 OH + 2CO 2

Por cada 6 átomos de carbono há 2 que saem para a atmosfera e são perdidos para o combustível final. 3For every 6 carbon atoms there are 2 that go out into the atmosphere and are lost to the final fuel. 3

Depois do aumento do preço do petróleo nos últimos anos, considerando os conflitos nos países produtores de petróleo e considerando a expectativa da continuação dos conflitos e do aumento de preço do petróleo, faz-se intensa investigação de alternativas baseadas em fontes renováveis, não poluentes e de baixo custo, como é o caso da cana de açúcar. A obtenção de etanol por fermentação é demorada e tem custos elevados, pois a separação da água por destilação é limitada pela existência dum azeotropo. 2.3. Produção de hidrocarbonetos a partir de gás de síntese via metanol 0 metanol é produzido a partir de gás de síntese, uma mistura de hidrogénio com monóxido de carbono, que pode ser obtida a partir de gás natural, de carvão ou de fuel obtido como resíduo da destilação do petróleo. 0 gás de síntese também pode ser obtido a partir de resíduos vegetais, mas este processo consome muita energia na conversão e tem um custo elevado.Following the rise in oil prices in recent years, considering the conflicts in the oil-producing countries and considering the prospect of continued conflict and rising oil prices, there is a strong investigation of alternatives based on renewable, non-polluting and of low cost, as is the case of sugar cane. Obtaining ethanol by fermentation is time-consuming and expensive, as the separation of water by distillation is limited by the existence of an azeotrope. 2.3. Production of hydrocarbons from synthesis gas via methanol Methanol is produced from synthesis gas, a mixture of hydrogen with carbon monoxide, which can be obtained from natural gas, coal or fuel oil obtained as a residue from distillation. The synthesis gas can also be obtained from plant residues, but this process consumes a lot of energy in the conversion and has a high cost.

As patentes (1-8) descrevem a conversão de metanol em éter metílico e a conversão deste em hidrocarbonetos na presença de zeolitos a pressões e temperaturas elevadas.Patents (1-8) describe the conversion of methanol to methyl ether and conversion thereof into hydrocarbons in the presence of zeolites at elevated temperatures and pressures.

As reacções químicas, tomando como exemplo o hexano, são: CH4 + H20 -> CO + 3H2 CO + 2H2 -> CH3OH 2CH3OH -> CH3OCH3 + H20 3CH3OCH3 + H2 -» C6H14 + 3H20The chemical reactions, using hexane as an example, are: CH 4 + H 2 O - > CO + 3H 2 CO + 2H 2 - > CH3OH 2CH3OH -> CH3OCH3 + H20 3CH3OCH3 + H2 -> C6 H14 + 3H20

Reacção global 6CH4 C6Hi4 + 5H2 4 O processo é um produtor liquido de hidrogénio e todos os átomos de carbono do metano vão aparecer nos hidrocarbonetos finais.The process is a liquid hydrogen producer and all the carbon atoms in the methane will appear in the final hydrocarbons.

Este processo tem o inconveniente, em relação à celulose, de exigir uma quase total decomposição dos hidratos de carbono em CO e H2 e a síntese química a partir destes compostos simples de hidrocarbonetos. 2.4. Produção de hidroximetilfurfural a partir de açucaresThis process has the disadvantage, in relation to cellulose, of requiring almost complete decomposition of the carbohydrates into CO and H2 and the chemical synthesis from these simple hydrocarbon compounds. 2.4. Production of hydroxymethylfurfural from sugars

Existem numerosas publicações sobre a deshidratação de açucares, que referem sempre a mesma dificuldade de valorização comercial do processo devido à sua baixa selectividade. 0 açucares são muito solúveis em água mas muito pouco solúveis em solventes orgânicos mesmo polares. A temperatura de deshidratação nestes solventes e com os catalisadores utilizados é sempre superior à temperatura de degradação dos intermediários deshidratados formados, principalmente o hidroximetilfurfural. Este composto polimeriza muito facilmente. (9) 0 hidroximetil furfural não pode ser directamente usado como combustível devido à instabilidade causada pela função aldeido. 2.5. A eterificação de açucares seguida de fragmentação da molécula (cracking) A eterificação de açucares com metanol ou etanol foi ensaiada com numerosos catalisadores e solventes. Antes de se dar qualquer eterificação, verifica-se a formação de hidroximetil furfural que polimeriza e forma uma massa escura acastanhada. 5 2.6. Deshidratação de hidratos de carbono com ácido sulfurico A eliminação de água por acção, por exemplo, de ácido sulfúrico concentrado conduz à formação de carvão. De facto, quimicamente o hidrogénio e o oxigénio nos hidratos de carbono estão exactamente nas proporções da água. Se a água sai fica carvão. A utilização duma solução aquosa diluída de ácido sulfúrico condus a tempos de reacção muito longos. Entretanto, os intermediários formados, designadamente o hidroximetil furfural polimerizam. A água é normalmente um mau solvente para reacções em que a molécula principal se pretende que perca água. 2.7. Fragmentação com hidrogenação de hidratos de carbono (Hydro cracking)There are numerous publications on the dehydration of sugars, which always refer to the same difficulty of commercial valorization of the process due to its low selectivity. The sugars are very soluble in water but very little soluble in even polar organic solvents. The dehydration temperature in these solvents and with the catalysts used is always higher than the degradation temperature of the dehydrated intermediates formed, especially hydroxymethylfurfural. This compound polymerizes very easily. (9) Hydroxymethyl furfural can not be directly used as fuel due to instability caused by the aldehyde function. 2.5. The etherification of sugars followed by fragmentation of the molecule (cracking) The etherification of sugars with methanol or ethanol was tested with numerous catalysts and solvents. Before any etherification takes place, hydroxymethyl furfural formation is formed which polymerizes and forms a dark brown mass. 5 2.6. Dehydration of carbohydrates with sulfuric acid Removal of water by the action of, for example, concentrated sulfuric acid leads to the formation of coal. In fact, chemically hydrogen and oxygen in carbohydrates are exactly in the proportions of water. If the water comes out, coal remains. The use of a dilute aqueous sulfuric acid solution at very long reaction times. However, the intermediates formed, namely hydroxymethyl furfural polymerize. Water is usually a poor solvent for reactions where the main molecule is intended to lose water. 2.7. Hydrogenation of carbohydrates (Hydro cracking)

Este processo tem o inconveniente da temperatura de desidratação dos hidratos de carbono ser inferior à temperatura de hidrogenação da cadeia de átomos de carbono, o que implicaria uma hidrogenação do próprio carvão a elevada temperatura, a qual não é possível em condições económicas. 2.8. A conversão de glicerina em propanolThis process has the disadvantage that the dehydration temperature of the carbohydrates is lower than the hydrogenation temperature of the carbon chain, which would imply a hydrogenation of the coal itself at elevated temperature, which is not possible under economical conditions. 2.8. Conversion of glycerin to propanol

Esta reacção é conhecida da química há muito tempo. No entanto, passa por um intermediário, a acroleina, que se forma ao mesmo tempo que muitos outros subprodutos, o que baixa a selectividade e interesse comercial dos processos até agora conhecidos.This reaction has long been known in chemistry. However, it passes through an intermediate, acrolein, which forms at the same time as many other by-products, which lowers the selectivity and commercial interest of the processes hitherto known.

Converter a acroleina por hidrogenação em propanol é uma reacção conhecida que se realiza com bom rendimento. 6 A utilização da acroleina directamente como combustível não é possível devido à sua dupla ligação e à função aldeido que tornam a molécula instável. 2.9. Os custos de produçãoConverting the acrolein by hydrogenation in propanol is a known reaction which is carried out in good yield. 6 The use of acrolein directly as a fuel is not possible because of its double bonding and the aldehyde function that make the molecule unstable. 2.9. The costs of production

Os conbustiveis líquidos de origem vegetal como o bioetanol e o biodiesel de oleaginosas, produzidos actualmente, são competitivos quando o petróleo bruto está a cerca de 80 USD/barril. O processo agora apresentado é competitivo com o petróleo bruto a cerca de 30 USD/barril. 3. Exposição da invenção O biocombustivel agora apresentado contendo dihidroximetil furano (DHF) e subprodutos da hidrogenação do hidroximetil furfural (subprodutos que também vamos designar como DHF), assim como o biocombustivel contendo propanol, só passou a ter interesse a partir do momento em que se desenvolveram processos de produção com custos competitivos. O processo agora apresentado parte de açucares, amido ou celulose ou de glicerina, todos poliois de origem vegetal e usa líquidos iónicos como solventes e catalisadores numa deshidratação parcial a qual é seguida duma hidrogenação e finalmente uma extracção supercritica com anídrido carbónico.Liquid fuels of vegetable origin such as bioethanol and biodiesel from oilseeds currently produced are competitive when crude oil is about $ 80 / barrel. The process now being filed is competitive with crude at about $ 30 / barrel. 3. PRESENTATION OF THE INVENTION The biofuel now introduced containing dihydroxymethyl furan (DHF) and byproducts of hydroxymethyl furfural hydrogenation (by-products which we will also designate as DHF), as well as the propanol-containing biofuel, only became of interest as soon as competitive production processes have been developed. The process now shown comprises sugars, starch or cellulose or glycerol, all vegetable polyols and uses ionic liquids as solvents and catalysts in a partial dehydration which is followed by hydrogenation and finally supercritical extraction with carbonic anhydride.

Verificamos que a celulose ou o amido hidrolisam no liquido iónico às temperaturas em que se realiza a deshidratação dos açucares. Esta descoberta facilita naturalmente o processo.We verified that the cellulose or starch hydrolyzes in the ionic liquid at the temperatures in which the dehydration of the sugars is carried out. This discovery naturally facilitates the process.

No caso da celulose ser pura, como algodão em rama, como exemplo laboratorial, a hidrólise e solubilização é total à temperatura da deshidratação. 7 A cana de açúcar pulverizada em serradura e deshidratada por aquecimento em vácuo é a matéria prima ideal para o processo, considerando que a cana de açúcar é produzida com o elevado rendimento de 80 ton por ano e por hectar e considerando que a cana de açúcar tem cerca de 30% de hidratos de carbono e 70% de água. Desta forma, o DHF corresponde a uma produção de cerca de 20 ton por ano e por hectar.In the case of cellulose being pure, as raw cotton, as laboratory example, the hydrolysis and solubilization is complete at the temperature of dehydration. 7 Sugar cane powdered in sawdust and dehydrated by vacuum heating is the ideal raw material for the process, considering that sugar cane is produced with the high yield of 80 tons per year per hectare and considering that sugar cane has about 30% carbohydrate and 70% water. In this way, the DHF corresponds to a production of around 20 tons per year and per hectare.

Para comparação, o bioetanol obtido de cana de açúcar corresponde a uma produção de 6 ton por hectar e por ano e o biodiesel de oleaginosas de soja e girassol corresponde a 1-2 ton/hectar e por ano e o biodiesel de oleaginosas como a mamona (rícino) corresponde a 0,6 ton por ano e por hectar. A serradura deshidratada de cana de açúcar, após tratamento com liquido iónico, deixa um resíduo de cerca de 3-4% do peso da serradutra deshidratada, que se separa fácilmente por filtração e se verificou ser lenhina.For comparison, bioethanol obtained from sugarcane corresponds to a production of 6 tons per hectare per year and biodiesel of soybean and sunflower oilseeds corresponds to 1-2 ton / hectare per year and biodiesel from oilseeds such as castor bean (castor) corresponds to 0.6 tons per year per hectare. The dehydrated sugarcane sawdust, after treatment with ionic liquid, leaves a residue of about 3-4% by weight of the dehydrated serradutra, which is readily separated by filtration and found to be lignin.

Por hidrólise da celulose ou amido forma-se uma mistura de glucose e frutose. A frutose e a glucose podem ser deshidratadas a uma temperatura de cerca de 140°C duma forma muito selectiva e com bom rendimento se o solvente for constituido por certos líquidos iónicos que se mantém líquidos à temperatura ambiente.By hydrolysis of the cellulose or starch a mixture of glucose and fructose is formed. The fructose and glucose may be dehydrated at a temperature of about 140 ° C in a very selective manner and in good yield if the solvent is made up of certain ionic liquids which remain liquid at room temperature.

Esta deshidratação parcial das hexoses é possível porque se forma como intermediário um derivado do furano que é estável devido à existência dum anel com características aromáticas.This partial dehydration of the hexoses is possible because a furan derivative which is stable due to the existence of a ring with aromatic characteristics forms as the intermediate.

Estes líquidos iónicos ensaiados foram derivados do N metil imidazol, que contem um anel com características aromáticas, mais resistente á hidrogenação do que o grupo aldeido do hidroximetil furfural. 8These tested ionic liquids were derived from N-methyl imidazole, which contains a ring with aromatic characteristics, more resistant to hydrogenation than the aldehyde group of hydroxymethyl furfural. 8

Esta reacção de deshidratação da glucose e da frutose vem descrita numa publicação cientifica recente (10). O liquido iónico alem de ser um bom solvente, funciona de catalisador.This dehydration reaction of glucose and fructose is described in a recent scientific publication (10). The ionic liquid, besides being a good solvent, works as a catalyst.

No entanto, nestas publicações procura-se isolar o hidroximetil furfural em condições de baixo rendimento e elevado custo.However, in these publications it is sought to isolate the hydroxymethyl furfural under conditions of low yield and high cost.

Por este motivo propomos agora realizar a hidrogenação do hidroximetil furfural no próprio liquido iónico, e só depois efectuar a separação, por destilação em vazio ou por extracção. O hidroximetil furfural polimeriza muito fácilmente formando poliacetal. Por outro lado, o liquido iónico é muito viscoso, o que dificulta a reacção de hidrogenação com catalizadores sólidos, pois a difusão de líquidos viscosos é difícil.For this reason we propose now to carry out the hydrogenation of the hydroxymethyl furfural in the ionic liquid itself, and only then to carry out the separation by vacuum distillation or by extraction. Hydroxymethyl furfural polymerizes very readily to form polyacetal. On the other hand, the ionic liquid is very viscous, which hinders the hydrogenation reaction with solid catalysts, since the diffusion of viscous liquids is difficult.

Propomos por isso a adição ao liquido iónico de metanol, etanol ou propanol, que tem assim uma dupla função : evita a formação de poliacetal, graças à formação de acetal de baixa massa molecular, que também utilizável como componente de combustível liquido. por outro lado o álcool adicionado ao liquido iónico baixa a viscosidade da mistura reaccional. A hidrogenação dos produtos da deshidratação é feita na presença de hidrogénio a uma pressão de cerca de 40-50 bar, a uma temperatura de cerca de 140 - 150°C e usando como catalisadores paládio ou platina sobre carvão activado, ou Raney níquel, ou crómio-molibdénio ou níquel-molibdénio sobre oxido de alumínio, ou de preferencia cromite de cobre misturado com óxido de bário, que é particularmente especifico para a hidrogenação de aldeídos a álcoois.We propose, therefore, the addition to the ionic liquid of methanol, ethanol or propanol, which thus has a double function: it avoids the formation of polyacetal, thanks to the formation of acetal of low molecular mass, which also usable as liquid fuel component. on the other hand the alcohol added to the ionic liquid lowers the viscosity of the reaction mixture. Hydrogenation of the dehydration products is carried out in the presence of hydrogen at a pressure of about 40-50 bar, at a temperature of about 140-150 ° C and using as catalysts palladium or platinum on activated carbon, or Raney nickel, or chromium-molybdenum or nickel-molybdenum on aluminum oxide, or preferably copper chromite mixed with barium oxide, which is particularly specific for the hydrogenation of aldehydes to alcohols.

Os líquidos ionicos ensaidos não vaporizam abaixo da temperatura de decomposição, que é cerca de 200ac. 9 A separação por destilação do DHF e do liquido iónico é possível, mas exige um vácuo elevado, pois a temperatura de ebulição do DHF à pressão atmosférica é superior à temperatura de decomposição do liquido iónico.The tested ionic liquids do not vaporize below the decomposition temperature, which is about 200Â ° C. 9 Separation by distillation of DHF and ionic liquid is possible but requires high vacuum since the boiling temperature of DHF at atmospheric pressure is higher than the decomposition temperature of the ionic liquid.

Preferimos por isso a separação entre o DHF e o liquido iónico por extracção, sendo particularmente interessante a extracção com anidrido carbónico supercritico. Esta extracção exige sómente um consumo de energia para comprimir o anidrido carbónico reciclado, pois a entalpia de vaporização de fluidos supercriticos é nula, visto que o estado liquido e gasoso não se distinguem. É possível trabalhar em continuo ou descontinuo, com ou sem separação do hidroximetil furfural do liquido iónico entre a deshidratação e a hidrogenação.We therefore prefer the separation between DHF and the ionic liquid by extraction, and the extraction with supercritical carbonic anhydride is particularly interesting. This extraction requires only an energy consumption to compress the recycled carbonic anhydride, since the enthalpy of vaporization of supercritical fluids is zero, since the liquid and gaseous state can not be distinguished. It is possible to work continuously or discontinuously with or without the hydroxymethyl furfural separation of the ionic liquid between dehydration and hydrogenation.

Em escala piloto e industrial, preferimos no entanto trabalhar em continuo e sem separação dos produtos da mistura reaccional até final da hidrogenação.On a pilot and industrial scale, however, we prefer to work continuously and without separation of the products from the reaction mixture until the end of the hydrogenation.

ExemploExample

Neste exemplo trabalhamos em descontinuo. Num reactor de 440 ml com agitador com acoplamento magnético PARR, foram carregados:In this example we work discontinuously. In a 440 ml reactor with PARR magnetic coupling stirrer were charged:

Cloreto de l-H-3 metil imidazolium 100 g1 H-3-methyl imidazolium chloride 100 g

Etanol 40 gEthanol 40 g

Celulose (algodão em rama) 60 g carvão activado contendo 0,05 g/g de paládio 1,2 gCellulose (cotton wool) 60 g activated carbon containing 0.05 g / g palladium 1.2 g

Fechou-se o reactor, inertizou-se com azoto. Carregou-se hidrogénio a 40 bar e aqueceu-se a 140°C mantendo uma corrente de hidrogénio durante uma hora que corresponde a uma quantidade de um mole de hidrogénio para um mole de Hexose contida na celulose. 10The reaction vessel was quenched, and quenched with nitrogen. Hydrogen was charged at 40 bar and heated to 140 ° C maintaining a stream of hydrogen for one hour corresponding to an amount of one mole of hydrogen to one mole of Hexose contained in the cellulose. 10

Arrefeceu-se, filtrou-se o carvão activado, fez-se uma extracção supercritica com anidrido carbónico por um processo conhecido e descontinuo. A análise por HPLC com columa Biorad Aminex permitiu determinar uma quantidade de DHF de 0,91 mol por mole de hexose.The activated carbon was cooled, filtered, supercritical extracted with carbonic anhydride by a known and discontinuous process. Analysis by HPLC with Biorad Aminex column allowed to determine an amount of DHF of 0.91 mol per mole of hexose.

Bibliografia 1 . USP 4431856(1982) , 2 . USP 4423274 (1982), 3 . USP 4379123 (1980), 4 . USP 4328384 (1980), 5 . USP 4251484 (1979), 6 . USP 4238631 (1979), 7 . USP 4138440 (1974), 8 . USP 4071573), 9 . Synthesis, Chemistry and Applications of 5-Bibliography 1. USP 4431856 (1982), 2. USP 4423274 (1982), 3. USP 4379123 (1980), 4. USP 4328384 (1980), 5. USP 4251484 (1979), 6. USP 4238631 (1979), 7. USP 4138440 (1974), 8. USP 4071573), 9. Synthesis, Chemistry and Applications of 5-

Hydroxymethyl - furfural and its derivatives, Jaroslaw Lewkowski, Arkivoc, 2001, 17-54 10 . Dehydration of fructose and sucrose into 5 hydroxymethyelfurfural in the presence of l-H-3-methyl imidazolium chloride acting both as solvent and catalyst, Claude Moreau, Annie Finiels, Laurent Vanoye, journal of Molecular catalysis A, Chemical 253 , 2006, 165-169 Estoril , 9 de Março de 2007Hydroxymethyl-furfural and its derivatives, Jaroslaw Lewkowski, Arkivoc, 2001, 17-54 10. Dehydration of fructose and sucrose into 5 hydroxymethyelfurfural in the presence of lH-3-methyl imidazolium chloride acting both as solvent and catalyst, Claude Moreau, Annie Finiels, Laurent Vanoye, journal of Molecular catalysis A, Chemical 253, 2006, 165-169 Estoril , March 9, 2007

Pedro Brito CorreiaPedro Brito Correia

Claims (8)

1 Reivindicações : 1 . Biocombustiveis caracterizados por conterem na sua composição dihidroximetilfurano (DHF) ou outros produtos da hidrogenação do hidroximetilfurfural (subprodutos designados a seguir também como DHF) , ou propanol obtido a partir da glicerina, ou misturas destes compostos entre si com ou sem hidrocarbonetos.Claims: 1. Biofuels characterized in that they contain in their composition dihydroxymethylfuran (DHF) or other hydrogenation products of hydroxymethylfurfural (by-products hereinafter also as DHF), or propanol obtained from glycerol, or mixtures thereof with or without hydrocarbons. 2 . Processo de produção de DHF caracterizado por usar como matérias primas celulose, amido ou açucares, em que primeiro se dá, no caso dos polisacaridos (celulose ou amido) , uma reacção de hidrólise convertendo-se em açucares, e em que os açucares são depois deshidratados, tendo lugar ambas as reacções de hidrólise e deshidratação por aquecimento num solvente constituído por um liquido iónico, realizando-se depois da deshidratação uma reacção de hidrogenação seguida de destilação, ou extracção com eter dietílico ou anidrido carbónico supercritico, para isolar o DHF , separar a água formada e reciclar o liquido iónico2 . A process for the production of DHF characterized by using as starting materials cellulose, starch or sugars, in which, in the case of polysaccharides (cellulose or starch), there is a hydrolysis reaction converting to sugars, and wherein the sugars are then both hydrolysis and dehydration reactions occurring by heating in a solvent consisting of an ionic liquid, a hydrogenation reaction followed by distillation followed by dehydration followed by extraction with diethyl ether or supercritical carbonic anhydride to isolate the DHF, separate the formed water and recycle the ionic liquid 3 . Processo segundo a reivindicação 2 caracterizado por o liquido iónico ser constituído por derivados 1-substituidos do 3 metil imidazol ou do 3 butil imidazol, tendo como anião o cloreto ou o anião tetrafluoreto de boro, e por o liquido iónico estar misturado com metanol, etanol, propanol ou suas misturas em proporções que podem variar entre 20% - 80% de liquido iónico sendo o restante álcool, em que a função do álcool é estabilizar o grupo aldeido por formação de acetal e evitar a polimerização em poliacetal do intermediário hidroxi metil furfural. 23. A process according to claim 2, characterized in that the ionic liquid consists of 1-substituted derivatives of 3-methyl imidazole or 3-butyl imidazole, having as anion the chloride or anion boron tetrafluoride, and the ionic liquid being mixed with methanol, ethanol , propanol or mixtures thereof in proportions ranging from 20% -80% ionic liquid with the remainder being alcohol, wherein the function of the alcohol is to stabilize the aldehyde group by acetal formation and avoid the polyacetal polymerization of the hydroxy methyl furfural intermediate . 2 4 . Processo segundo a reivindicação 2 caracterizado por a deshidratação e a hidrogenação se realizarem num único reactor em continuo, sendo a temperatura de 50 - 200°C .4. A process according to claim 2, characterized in that the dehydration and the hydrogenation are carried out in a single continuous reactor, the temperature being 50-200Â ° C. 5 . Processo segundo a reivindicação 2 caracterizado por se realizar em descontinuo uma hidrogenação dos produtos da deshidratação após sua separação do liquido iónico e da água.5. A process according to claim 2 characterized in that a hydrogenation of the products of the dehydration is carried out in a discontinuous manner after its separation from the ionic liquid and water. 6 . Processo segundo a reivindicação 2 caracterizado por se realizar em descontinuo uma hidrogenação dos produtos da deshidratação sem a sua separação do liquido iónico e da água, sendo a separação posterior à hidrogenação6. A process according to claim 2 characterized in that hydrogenation of the dehydration products is carried out in a non-continuous manner without their separation from the ionic liquid and water, the post-hydrogenation separation 7 . Processo segundo as reivindicações 4, 5 e 6 caracterizado por se realizar uma hidrogenação dos produtos da deshidratação na presença de hidrogénio a uma pressão de 2 a 50 bar, a uma temperatura de 50 a 200°C e usando como catalisadores 0,01 a 10% de paládio ou platina sobre carvão activado, Raney níquel, ou crómio-molibdénio ou níquel-molibdénio sobre oxido de alumínio, ou de preferencia cromite de cobre misturada com óxido de bário, que é particularmente especifico para a hidrogenação de aldeidos a álcoois.7. A process according to claims 4, 5 and 6 characterized in that hydrogenation of the dehydration products in the presence of hydrogen is carried out at a pressure of 2 to 50 bar, at a temperature of 50 to 200 ° C and using as catalysts 0.01 to 10 % of palladium or platinum on activated carbon, Raney nickel, or chromium-molybdenum or nickel-molybdenum on aluminum oxide, or preferably copper chromite mixed with barium oxide, which is particularly specific for the hydrogenation of aldehydes to alcohols. 8 . Processo segundo a reivindicação 2 caracterizado por o poliol ser glicerina que se submete às mesmas reacções e operações de separação que os açucares. Estoril , 9 de Março de de 2007 Pedro Brito Correia8. A process according to claim 2 characterized in that the polyol is glycerin which undergoes the same reactions and separation operations as the sugars. Estoril, March 9, 2007 Pedro Brito Correia
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