WO2024036390A1 - Process for producing a renewable additive for use in marine diesel containing partial glycerides and product thus obtained - Google Patents

Process for producing a renewable additive for use in marine diesel containing partial glycerides and product thus obtained Download PDF

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Publication number
WO2024036390A1
WO2024036390A1 PCT/BR2023/050266 BR2023050266W WO2024036390A1 WO 2024036390 A1 WO2024036390 A1 WO 2024036390A1 BR 2023050266 W BR2023050266 W BR 2023050266W WO 2024036390 A1 WO2024036390 A1 WO 2024036390A1
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product
fatty acid
glycerin
renewable
marine diesel
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PCT/BR2023/050266
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French (fr)
Portuguese (pt)
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Setsuo Sato
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Brasil Bio Fuels S.A
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Publication of WO2024036390A1 publication Critical patent/WO2024036390A1/en

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    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/02—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with glycerol
    • 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

Definitions

  • This invention concerns a process for producing renewable additive for use in marine diesel containing partial glycerides and product thus obtained, belonging to the technical chemistry sector, more particularly the invention is based on the development of additives containing high energy power with renewable materials to be used and/or mixed in marine diesel and in other applications replacing traditional materials of petrochemical origin.
  • Such additives have the main benefits of being sulfur-free, high calorific value, multiple performances, providing energy and acting as lubricity agents at a competitive cost and can be mixed with petrochemical materials in numerous proportions.
  • FUNDAMENTALS OF THE TECHNIQUE [0002] The current market is regulated by the National Petroleum Agency (ANP) and there is a specific standard that regulates its use through the ANP Resolution no 51/2010.
  • ANP National Petroleum Agency
  • One of the biggest impacts on marine diesel is the sulfur content, which in the past had a limit of 3% and was reduced to 0.5% from 2020 onwards. Even with this reduction in the limit, this still means 10 times more compared to road diesel which is 0.05%.
  • the present invention exactly fills this gap in the market and provides a process for producing a renewable additive for use in marine diesel containing partial glycerides and the product thus obtained, which aims to: - Use fatty materials from renewable sources, and waste materials that do not compete with the food chain; - Use a simple esterification and transesterification process; - Use alkaline catalyst, more specifically potassium hydroxide; - Use SAFREE glycerin of high purity and competitive cost; - Use SAFREE glycerin concentration; - Obtain with this product with high calorific value; - Obtain concentration-free sulfur content, guaranteeing very low emissions compared to conventional diesel; - Obtain products with a flash point that guarantees greater safety in handling and storing products; - Obtain additives that can be mixed with petrochemical marine diesel.
  • the process of producing a renewable additive for use in marine diesel containing partial glycerides comprises the steps of: charging a reactor with residual palm fatty acid with an oleic acidity index of 45%; SAFREE glycerin 97% purity; and potassium hydroxide 85%; stirring and heating the product by applying a vacuum; resting the product at a controlled temperature and cooling the product at a controlled temperature.
  • the process of producing a renewable additive for use in marine diesel containing partial glycerides comprises the following steps: 1 - It is loaded into a reactor with the following materials by weight: 80 – 90% acid residual palm fat with an oleic acid value of 45%; 10 – 15% SAFREE glycerin 97% purity; and 0.2 – 1.0% potassium hydroxide 85%; where the partial fatty acid glycerides are: palm, palm kernel, tallow, soy, sunflower, canola, peanut, produced from oils and/or residual fatty acids, with a composition of 5% to 20% combined glycerin and free glycerin below 3% to guarantee a homogeneous product, without separation; 2 - Stirring is switched on at 50 to 70 rpm and heating begins to a temperature between 200 and 220oC (Degrees Celsius) by applying a vacuum between 90 and 110 mmHg; 3 – Keep the product at rest for between 1 and 2
  • the product obtained through the production process of a renewable additive for use in marine diesel containing partial glycerides comprises the following characteristics: Calorific value and sulfur content of the products: 6800 kcal/kg, sulfur free; 7200 to 7800 kcal/kg, sulfur with 4 to 12ppm; Flash point of products: 190 to 197oC Degrees Celsius; Acidity value of 0.8%; and Combined glycerin content of 12.8%.
  • Example 2 [0017] In a 2000ml reactor, 1000g of palm oil with an oleic acid value of 3%, 50g of SAFREE glycerin 97% purity and 3g of potassium hydroxide 85% were loaded; [0018] Stirring was switched on at 60 rpm and heating began to 215oC Degrees Celsius by applying a vacuum of 100 mmhg; [0019] After 2 hours at 215oC Celsius, the acidity value was measured and the value was 0.8% and free glycerin 2.1%; [0020] Product was cooled to 80oC Celsius and the combined glycerin content obtained was 30%; [0021] A product with the following characteristics was obtained: Calorific value and sulfur content of products: 7800 kcal/kg, sulfur 8ppm; Flash point of products: 182oC Celsius.
  • Example 3 [0022] In a 2000ml reactor, 1000g of hydrolyzed soy sludge fatty acid with an oleic acid value of 65%, 140g of SAFREE glycerin 97% purity and 3g of potassium hydroxide 85% were loaded; [0023] Stirring was switched on at 60 rpm and heating began to 215oC Degrees Celsius by applying a vacuum of 100 mmhg; [0024] After 2 hours at 215oC Celsius, the acid value was measured and the value was 1.2% and free glycerin was 3.2%; [0025] Product was cooled to 80oC Celsius and the combined glycerin content obtained was 14.1%; [0026] A product with the following characteristics was obtained: Calorific value and sulfur content of the products: 7200 kcal/kg, sulfur 12ppm; Flash point of products: 192oC Celsius.
  • Example 4 [0027] In a 2000ml reactor, 1000g of crude soybean oil with an oleic acid value of 4%, 70g of SAFREE glycerin 97% purity and 3g of potassium hydroxide 85% were loaded; [0028] Stirring was switched on at 60 rpm and heating began to 215oC Degrees Celsius by applying a vacuum of 90 mmHg; [0029] After 2 hours at 215oC Celsius, the acidity value was measured and the value was 1.6% and free glycerin 2.0%; [0030] Product was cooled to 80oC Celsius and the combined glycerin content obtained was 15.2%; [0031] A product with the following characteristics was obtained: Calorific value and sulfur content of the products: 6800 kcal/kg, sulfur free; Flash point of products: 197oC Celsius.
  • ADVANTAGES OF THE INVENTION offers the following advantages: - Provides an additive to be mixed in petrochemical diesel, reducing its environmental impacts; - Uses partial fatty acid glycerides such as: palm, palm kernel, tallow, soy, sunflower, canola, peanut, produced from oils and/or residual fatty acids, with a composition of 5% to 20% combined glycerin and free glycerin below 3% to guarantee a homogeneous product, without separation; - These chemical characteristics provide multiple performances to the product, the most relevant of which are high calorific value, lubricity, sulfur-free and extremely competitive cost; - Additionally, the glycerin used in these compositions is free of salts, but without the need for distillation, an expensive process that generates environmental waste; It is - This is glycerin produced by SAFREE (salt free) technology, which uses the liquid
  • the present invention deals with one of the most sensitive topics today because it is directly linked to climate change that directly affects our daily lives. Emissions of various gases have changed our planet's climate in a very negative way. [0034]
  • the scope of the present invention patent therefore, should not be limited to the examples of obtaining, but rather, only to the terms defined in the claims and their equivalents.

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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

The present invention relates to a process for producing a renewable additive for use in marine diesel containing partial glycerides and a product thus obtained, and pertains to the technical field of chemistry. More particularly, the invention is based on developing additives with a high energy value from renewable materials for use and/or mixing with marine diesel and for other uses substituting traditional petrochemical materials. The main benefits of said additives are that they are sulfur-free, high in calorific power, have multiple performance properties, provide energy and act as lubricating agents at a competitive cost and can be mixed with petrochemical materials in various proportions. The process comprises steps of: loading a reactor with residual palm fatty acid with an oleic acid value of 45%, 97% pure SAFREE glycerin, and potassium hydroxide 85%; stirring and heating the product in a vacuum; resting the product at a controlled temperature and cooling the product at a controlled temperature.

Description

“PROCESSO DE PRODUÇÃO DE ADITIVO RENOVÁVEL PARA USO EM DIESEL MARITIMO CONTENDO GLICERIDEOS PARCIAIS E PRODUTO ASSIM OBTIDO” CAMPO DE APLICAÇÃO [0001] Trata-se a presente invenção de um processo de produção de aditivo renovável para uso em diesel marítimo contendo glicerídeos parciais e produto assim obtido, pertencente ao setor técnico de química, mais particularmente a invenção se baseia no desenvolvimento de aditivos contendo alto poder energético com materiais renováveis para ser usado e/ou misturado em diesel marítimo e em outras aplicações substituindo os tradicionais materiais de origem petroquímica. Tais aditivos tem como principais benefícios serem isentos de enxofre, alto poder calorifico, múltiplas performances fornecem energia e atuam como agentes de lubricidade com custo competitivo e podem ser misturados nos materiais petroquímicos em inúmeras proporções. FUNDAMENTOS DA TÉCNICA [0002] O mercado atual é regulamentado pela Agência Nacional de Petróleo (ANP) e existe uma norma específica que regula o seu uso através da portaria Resolução ANP nº 51/2010. Um dos grandes impactos no diesel marítimo é o teor de enxofre que no passado tinha como limite 3% e foi reduzido para 0,5% a partir de 2020. Mesmo com esta redução no limite isto ainda significa 10 vezes mais comparado ao diesel rodoviário que é de 0,05%. O uso de materiais não petroquímicos como, por exemplo biodiesel ainda não é permitido devido ao seu impacto no custo, porém existe na própria portaria que é periodicamente revisada e a permissão deve ser dada quando o seu custo for viabilizado. [0003] Globalmente existe uma pressão muito forte para reduzir os impactos ambientais devido à emissão de gases tóxicos como o SO3, CO2 e outros nocivos à saúde humana. [0004] Diversos estudos estão sendo conduzidos para viabilizar o uso de novos materiais. A empresa Quadrise Fuels desenvolveu uma mistura de combustível pesado com glicerina denominada bioMSAR, o combustível pesado é o resíduo do refino de petróleo. [0005] A patente US810105399B2 descreve a produção de um diesel renovável composto de ácidos graxos, glicerídeos de ácidos graxos, glicerina com baixo teor de enxofre e glicerina livre. [0006] A empresa Maine Maritime Academy (MMA) desenvolveu uma formulação contendo alto teor de glicerina chamado Eco-Hybride e submeteram uma patente que deve estar pendente. [0007] Publicações, citações, projetos de pesquisa, revisões bibliográficas vem se intensificando de uma forma exponencial em sites de domínio público demonstrando a pressão e o interesse público e privado sobre o assunto. Muito provavelmente novos materiais feitos a partir de fontes renováveis estarão disponíveis em um futuro bem próximo. OBJETIVO DA INVENÇÃO [0008] Com base no acima descrito, a presente invenção vem exatamente preencher essa lacuna no mercado e proporcionar um processo de produção de aditivo renovável para uso em diesel marítimo contendo glicerídeos parciais e produto assim obtido que tem como objetivos: - Utilizar materiais graxos de fontes renováveis, e materiais residuais que não competem com a cadeia alimentícia; - Utilizar processo simples de esterificação e transesterificação; - Utilizar catalizador alcalino, mais especificamente o hidróxido de potássio; - Utilizar glicerina SAFREE de alta pureza e custo competitivo; - Utilizar concentração da glicerina SAFREE; - Obter com isto produto com alto poder calorífico; - Obter teores de enxofre isento de concentração, garantindo baixíssimas emissões comparado ao diesel convencional; - Obter produtos com flash point que garanta uma maior segurança no manuseio e estocagem dos produtos; - Obter aditivos que possam ser misturados com o diesel marítimo petroquímico. DESCRIÇÃO RESUMIDA DA INVENÇÃO [0009] O processo de produção de aditivo renovável para uso em diesel marítimo contendo glicerídeos parciais compreende as etapas de: carregamento de um reator com ácido graxo de palma residual com índice de acidez oleica de 45%; glicerina SAFREE 97% de pureza; e hidróxido de potássio 85%; agitação e aquecimento do produto aplicando-se um vácuo; repouso do produto com temperatura controlada e resfriamento do produto com temperatura controlada. DESCRIÇÃO DETALHADA DA INVENÇÃO [0010] O processo de produção de aditivo renovável para uso em diesel marítimo contendo glicerídeos parciais compreende as seguintes etapas: 1 - Em um reator carrega-se o mesmo com os seguintes materiais em peso: 80 – 90% de ácido graxo de palma residual com índice de acidez oleica de 45%; 10 – 15% de glicerina SAFREE 97% de pureza; e 0,2 – 1,0% de hidróxido de potássio 85%; onde os glicerídeos parciais de ácido graxo são: de palma, palmiste, sebo, soja, girassol, canola, amendoim, produzidos a partir de óleos e/ou ácidos graxos residuais, com composição de 5% a 20% de glicerina combinada e glicerina livre abaixo de 3% para garantir um produto homogêneo, sem separação; 2 - Liga-se a agitação com 50 a 70 rpm e inicia-se o aquecimento para uma temperatura entre 200 e 220ºC (Graus Celsius) aplicando um vácuo entre 90 e 110 mmhg; 3 – Mantém o produto em repouso entre 1 e 2 horas a uma temperatura entre 200 e 220ºC; 3 – Resfria-se o produto a uma temperatura entre 70 e 90ºC. [0011] O produto obtido através do processo de produção de aditivo renovável para uso em diesel marítimo contendo glicerídeos parciais compreende as seguintes características: Poder calorifico e teor de enxofre dos produtos: 6800 kcal/kg, enxofre isento; 7200 a 7800 kcal/kg, enxofre com 4 a 12ppm; Flash point dos produtos: 190 a 197ºC Graus Celsius; Índice de acidez de 0,8%; e Teor de glicerina combinado de 12,8%. EXEMPLOS DE OBTENÇÕES Exemplo 1: [0012] Em um reator de 2000ml carregou 1000grs de ácido graxo de palma residual com índice de acidez oleica de 45%, 150grs de glicerina SAFREE 97% de pureza e 3grs de hidróxido de potássio 85%; [0013] Ligou-se a agitação com 60 rpm e iniciou-se o aquecimento para 215ºC Graus Celsius aplicando um vácuo de 100 mmhg; [0014] Após 1hora a 215ºC Graus Celsius mediu-se o índice de acidez e obteve-se o valor de 0,8%; [0015] Produto foi resfriado a 80ºC Graus Celsius e o teor de glicerina combinado obtido foi de 12,8%; [0016] Obteve-se um produto com as seguintes características: Poder calorifico e teor de enxofre dos produtos: 7400 kcal/kg, enxofre 4ppm; Flash point dos produtos: 190ºC Graus Celsius. Exemplo 2: [0017] Em um reator de 2000ml carregou 1000grs de óleo de palma com índice de acidez oleica de 3%, 50grs de glicerina SAFREE 97% de pureza e 3grs de hidróxido de potássio 85%; [0018] Ligou-se a agitação com 60 rpm e iniciou-se o aquecimento para 215ºC Graus Celsius aplicando um vácuo de 100 mmhg; [0019] Após 2 horas a 215ºC Graus Celsius mediu-se o índice de acidez e obteve-se o valor de 0,8% e glicerina livre 2,1%; [0020] Produto foi resfriado a 80ºC Graus Celsius e o teor de glicerina combinado obtido foi de 30%; [0021] Obteve-se um produto com as seguintes características: Poder calorifico e teor de enxofre dos produtos: 7800 kcal/kg, enxofre 8ppm; Flash point dos produtos: 182ºC Graus Celsius. Exemplo 3: [0022] Em um reator de 2000ml carregou 1000grs de ácido graxo de borra de soja hidrolisado com índice de acidez oleica de 65%, 140grs de glicerina SAFREE 97% de pureza e 3grs de hidróxido de potássio 85%; [0023] Ligou-se a agitação com 60 rpm e iniciou-se o aquecimento para 215ºC Graus Celsius aplicando um vácuo de 100 mmhg; [0024] Após 2 horas a 215ºC Graus Celsius mediu o índice de acidez e obteve se o valor de 1,2% e glicerina livre 3,2%; [0025] Produto foi resfriado a 80ºC Graus Celsius e o teor de glicerina combinado obtido foi de 14,1%; [0026] Obteve-se um produto com as seguintes características: Poder calorifico e teor de enxofre dos produtos: 7200 kcal/kg, enxofre 12ppm; Flash point dos produtos: 192ºC Graus Celsius. Exemplo 4: [0027] Em um reator de 2000ml carregou 1000grs de óleo de soja bruto com índice de acidez oleica de 4%, 70grs de glicerina SAFREE 97% de pureza e 3grs de hidróxido de potássio 85%; [0028] Ligou-se a agitação com 60 rpm e iniciou-se o aquecimento para 215ºC Graus Celsius aplicando um vácuo de 90 mmhg; [0029] Após 2 horas a 215ºC Graus Celsius mediu-se o índice de acidez e obteve-se o valor de 1,6% e glicerina livre 2,0%; [0030] Produto foi resfriado a 80ºC Graus Celsius e o teor de glicerina combinado obtido foi de 15,2%; [0031] Obteve-se um produto com as seguintes características: Poder calorifico e teor de enxofre dos produtos: 6800 kcal/kg, enxofre isento; Flash point dos produtos: 197ºC Graus Celsius. VANTAGENS DO INVENTO [0032] O processo de produção de aditivo renovável para uso em diesel marítimo contendo glicerídeos parciais e produto assim obtido, oferece as seguintes vantagens: - Proporciona um aditivo para ser misturado no diesel petroquímico reduzindo seus impactos ambientais; - Utiliza glicerídeos parciais de ácido graxo como: de palma, palmiste, sebo, soja, girassol, canola, amendoim, produzidos a partir de óleos e/ou ácidos graxos residuais, com composição de 5% a 20% de glicerina combinada e glicerina livre abaixo de 3% para garantir um produto homogêneo, sem separação; - Estas características químicas conferem múltiplas performances para o produto sendo as mais relevantes o alto poder calorifico, lubricidade, isenção de enxofre e custo extremamente competitivo; - Adicionalmente a glicerina utilizada nestas composições é isenta de sais, porém sem a necessidade de destilação um processo caro e que gera resíduos ambientais; e - Trata-se da glicerina produzida pela tecnologia SAFREE (salt free) que utiliza o processo extração líquido/líquido. [0033] A presente invenção trata de um dos temas mais sensível na atualidade porque está diretamente ligado ás mudanças climáticas que afeta diretamente o nosso dia a dia. Emissões de gases diversos tem alterado o clima de nosso planeta de uma forma bastante negativa. [0034] A abrangência da presente patente de invenção, portanto, não deve ser limitada aos exemplos de obtenção, mas sim, apenas aos termos definidos nas reivindicações e seus equivalentes. “PROCESS FOR PRODUCING RENEWABLE ADDITIVE FOR USE IN MARINE DIESEL CONTAINING PARTIAL GLYCERIDES AND PRODUCT THEREFORE OBTAINED” FIELD OF APPLICATION [0001] This invention concerns a process for producing renewable additive for use in marine diesel containing partial glycerides and product thus obtained, belonging to the technical chemistry sector, more particularly the invention is based on the development of additives containing high energy power with renewable materials to be used and/or mixed in marine diesel and in other applications replacing traditional materials of petrochemical origin. Such additives have the main benefits of being sulfur-free, high calorific value, multiple performances, providing energy and acting as lubricity agents at a competitive cost and can be mixed with petrochemical materials in numerous proportions. FUNDAMENTALS OF THE TECHNIQUE [0002] The current market is regulated by the National Petroleum Agency (ANP) and there is a specific standard that regulates its use through the ANP Resolution nº 51/2010. One of the biggest impacts on marine diesel is the sulfur content, which in the past had a limit of 3% and was reduced to 0.5% from 2020 onwards. Even with this reduction in the limit, this still means 10 times more compared to road diesel which is 0.05%. The use of non-petrochemical materials, such as biodiesel, is still not permitted due to its impact on cost, but it exists in the ordinance itself, which is periodically reviewed and permission must be given when its cost is feasible. [0003] Globally there is very strong pressure to reduce environmental impacts due to the emission of toxic gases such as SO3, CO2 and others harmful to human health. [0004] Several studies are being conducted to enable the use of new materials. The company Quadrise Fuels developed a mixture of heavy fuel with glycerin called bioMSAR, the heavy fuel is the residue from oil refining. [0005] Patent US810105399B2 describes the production of a renewable diesel composed of fatty acids, fatty acid glycerides, low sulfur glycerin and free glycerin. [0006] The company Maine Maritime Academy (MMA) developed a formulation containing a high glycerin content called Eco-Hybride and submitted a patent that must be pending. [0007] Publications, citations, research projects, bibliographic reviews have been intensifying exponentially on public domain websites, demonstrating the pressure and public and private interest on the subject. Most likely, new materials made from renewable sources will be available in the very near future. OBJECTIVE OF THE INVENTION [0008] Based on the above, the present invention exactly fills this gap in the market and provides a process for producing a renewable additive for use in marine diesel containing partial glycerides and the product thus obtained, which aims to: - Use fatty materials from renewable sources, and waste materials that do not compete with the food chain; - Use a simple esterification and transesterification process; - Use alkaline catalyst, more specifically potassium hydroxide; - Use SAFREE glycerin of high purity and competitive cost; - Use SAFREE glycerin concentration; - Obtain with this product with high calorific value; - Obtain concentration-free sulfur content, guaranteeing very low emissions compared to conventional diesel; - Obtain products with a flash point that guarantees greater safety in handling and storing products; - Obtain additives that can be mixed with petrochemical marine diesel. BRIEF DESCRIPTION OF THE INVENTION [0009] The process of producing a renewable additive for use in marine diesel containing partial glycerides comprises the steps of: charging a reactor with residual palm fatty acid with an oleic acidity index of 45%; SAFREE glycerin 97% purity; and potassium hydroxide 85%; stirring and heating the product by applying a vacuum; resting the product at a controlled temperature and cooling the product at a controlled temperature. DETAILED DESCRIPTION OF THE INVENTION [0010] The process of producing a renewable additive for use in marine diesel containing partial glycerides comprises the following steps: 1 - It is loaded into a reactor with the following materials by weight: 80 – 90% acid residual palm fat with an oleic acid value of 45%; 10 – 15% SAFREE glycerin 97% purity; and 0.2 – 1.0% potassium hydroxide 85%; where the partial fatty acid glycerides are: palm, palm kernel, tallow, soy, sunflower, canola, peanut, produced from oils and/or residual fatty acids, with a composition of 5% to 20% combined glycerin and free glycerin below 3% to guarantee a homogeneous product, without separation; 2 - Stirring is switched on at 50 to 70 rpm and heating begins to a temperature between 200 and 220ºC (Degrees Celsius) by applying a vacuum between 90 and 110 mmHg; 3 – Keep the product at rest for between 1 and 2 hours at a temperature between 200 and 220ºC; 3 – Cool the product to a temperature between 70 and 90ºC. [0011] The product obtained through the production process of a renewable additive for use in marine diesel containing partial glycerides comprises the following characteristics: Calorific value and sulfur content of the products: 6800 kcal/kg, sulfur free; 7200 to 7800 kcal/kg, sulfur with 4 to 12ppm; Flash point of products: 190 to 197ºC Degrees Celsius; Acidity value of 0.8%; and Combined glycerin content of 12.8%. EXAMPLES OF OBTAINMENTS Example 1: [0012] In a 2000ml reactor, 1000g of residual palm fatty acid with an oleic acid value of 45%, 150g of SAFREE glycerin 97% purity and 3g of potassium hydroxide 85%; [0013] Stirring was switched on at 60 rpm and heating began to 215ºC Degrees Celsius by applying a vacuum of 100 mmhg; [0014] After 1 hour at 215ºC Celsius, the acidity index was measured and the value was 0.8%; [0015] Product was cooled to 80ºC Celsius and the combined glycerin content obtained was 12.8%; [0016] A product with the following characteristics was obtained: Calorific value and sulfur content of the products: 7400 kcal/kg, sulfur 4ppm; Flash point of products: 190ºC Celsius. Example 2: [0017] In a 2000ml reactor, 1000g of palm oil with an oleic acid value of 3%, 50g of SAFREE glycerin 97% purity and 3g of potassium hydroxide 85% were loaded; [0018] Stirring was switched on at 60 rpm and heating began to 215ºC Degrees Celsius by applying a vacuum of 100 mmhg; [0019] After 2 hours at 215ºC Celsius, the acidity value was measured and the value was 0.8% and free glycerin 2.1%; [0020] Product was cooled to 80ºC Celsius and the combined glycerin content obtained was 30%; [0021] A product with the following characteristics was obtained: Calorific value and sulfur content of products: 7800 kcal/kg, sulfur 8ppm; Flash point of products: 182ºC Celsius. Example 3: [0022] In a 2000ml reactor, 1000g of hydrolyzed soy sludge fatty acid with an oleic acid value of 65%, 140g of SAFREE glycerin 97% purity and 3g of potassium hydroxide 85% were loaded; [0023] Stirring was switched on at 60 rpm and heating began to 215ºC Degrees Celsius by applying a vacuum of 100 mmhg; [0024] After 2 hours at 215ºC Celsius, the acid value was measured and the value was 1.2% and free glycerin was 3.2%; [0025] Product was cooled to 80ºC Celsius and the combined glycerin content obtained was 14.1%; [0026] A product with the following characteristics was obtained: Calorific value and sulfur content of the products: 7200 kcal/kg, sulfur 12ppm; Flash point of products: 192ºC Celsius. Example 4: [0027] In a 2000ml reactor, 1000g of crude soybean oil with an oleic acid value of 4%, 70g of SAFREE glycerin 97% purity and 3g of potassium hydroxide 85% were loaded; [0028] Stirring was switched on at 60 rpm and heating began to 215ºC Degrees Celsius by applying a vacuum of 90 mmHg; [0029] After 2 hours at 215ºC Celsius, the acidity value was measured and the value was 1.6% and free glycerin 2.0%; [0030] Product was cooled to 80ºC Celsius and the combined glycerin content obtained was 15.2%; [0031] A product with the following characteristics was obtained: Calorific value and sulfur content of the products: 6800 kcal/kg, sulfur free; Flash point of products: 197ºC Celsius. ADVANTAGES OF THE INVENTION [0032] The process of producing a renewable additive for use in marine diesel containing partial glycerides and the product thus obtained, offers the following advantages: - Provides an additive to be mixed in petrochemical diesel, reducing its environmental impacts; - Uses partial fatty acid glycerides such as: palm, palm kernel, tallow, soy, sunflower, canola, peanut, produced from oils and/or residual fatty acids, with a composition of 5% to 20% combined glycerin and free glycerin below 3% to guarantee a homogeneous product, without separation; - These chemical characteristics provide multiple performances to the product, the most relevant of which are high calorific value, lubricity, sulfur-free and extremely competitive cost; - Additionally, the glycerin used in these compositions is free of salts, but without the need for distillation, an expensive process that generates environmental waste; It is - This is glycerin produced by SAFREE (salt free) technology, which uses the liquid/liquid extraction process. [0033] The present invention deals with one of the most sensitive topics today because it is directly linked to climate change that directly affects our daily lives. Emissions of various gases have changed our planet's climate in a very negative way. [0034] The scope of the present invention patent, therefore, should not be limited to the examples of obtaining, but rather, only to the terms defined in the claims and their equivalents.

Claims

REIVINDICAÇÕES 1. Processo de produção de aditivo renovável para uso em diesel marítimo contendo glicerídeos parciais de ácido graxo caracterizado por compreender as seguintes etapas: a) carregar um reator com glicerídeos parciais de ácido graxo; b) ligar a agitação com 50 a 70 rpm e iniciar o aquecimento para uma temperatura entre 200 e 220ºC, aplicando um vácuo entre 90 e 110 mmhg; c) manter o produto em repouso entre 1 e 2 horas a uma temperatura entre 200 e 220ºC; e d) resfriar o produto a uma temperatura entre 70 e 90ºC. 2. Processo, de acordo com a reivindicação 1, caracterizado pelo fato de que os glicerídeos parciais de ácido graxo são selecionados do grupo que compreende: glicerídeos parciais de ácido graxo de palma, palmiste, sebo, soja, girassol, canola, amendoim, com índice de acidez oleica de 20% a 90%, produzidos a partir de óleos e/ou ácidos graxos residuais, com composição de 5% a 20% de glicerina combinada e glicerina livre abaixo de 3%. 3. Processo, de acordo com as reivindicações 1 e 2, caracterizado pelo fato de que, na etapa a), os glicerídeos parciais de ácido graxo e suas respectivas quantidades em % em peso carregados no reator são: 80 – 90% de ácido graxo de palma residual com índice de acidez oleica de 45%; 10 – 15% de glicerina SAFREE 97% de pureza; e 0,2 – 1,0% de hidróxido de potássio 85%. 4. Aditivo renovável para uso em diesel marítimo contendo glicerídeos parciais de ácido graxo obtido através do processo conforme definido em qualquer uma das reivindicações 1 a 3 caracterizado por apresentar um poder calorífico na faixa de 6800 kcal/kg a 7800 kcal/kg, um teor de enxofre na faixa de 0 ppm a 12 ppm; um ponto de flash na faixa de 190 a 197ºC; um índice de acidez na faixa de 0,8% a 1,6%; e um teor de glicerina combinado na faixa de 12,8% a 30%. CLAIMS 1. Process for producing a renewable additive for use in marine diesel containing partial fatty acid glycerides characterized by comprising the following steps: a) charging a reactor with partial fatty acid glycerides; b) turn on the agitation at 50 to 70 rpm and start heating to a temperature between 200 and 220ºC, applying a vacuum between 90 and 110 mmHg; c) keep the product at rest for between 1 and 2 hours at a temperature between 200 and 220ºC; and d) cool the product to a temperature between 70 and 90ºC. 2. Process according to claim 1, characterized by the fact that the partial fatty acid glycerides are selected from the group comprising: partial fatty acid glycerides of palm, palm kernel, tallow, soybean, sunflower, canola, peanut, with oleic acidity index of 20% to 90%, produced from oils and/or residual fatty acids, with a composition of 5% to 20% combined glycerin and free glycerin below 3%. 3. Process according to claims 1 and 2, characterized by the fact that, in step a), the partial fatty acid glycerides and their respective quantities in % by weight loaded into the reactor are: 80 – 90% fatty acid residual palm with an oleic acid value of 45%; 10 – 15% SAFREE glycerin 97% purity; and 0.2 – 1.0% potassium hydroxide 85%. 4. Renewable additive for use in marine diesel containing partial fatty acid glycerides obtained through of the process as defined in any one of claims 1 to 3 characterized by having a calorific value in the range of 6800 kcal/kg to 7800 kcal/kg, a sulfur content in the range of 0 ppm to 12 ppm; a flash point in the range of 190 to 197ºC; an acid number in the range of 0.8% to 1.6%; and a combined glycerin content in the range of 12.8% to 30%.
PCT/BR2023/050266 2022-08-18 2023-08-18 Process for producing a renewable additive for use in marine diesel containing partial glycerides and product thus obtained WO2024036390A1 (en)

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US20030163949A1 (en) * 2001-12-19 2003-09-04 Institut Francais Du Petrole Diesel fuel compounds containing glycerol acetals
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