BR102014025671B1 - PROCESS FOR OBTAINING HYDROGENATED RESIN GUM - Google Patents
PROCESS FOR OBTAINING HYDROGENATED RESIN GUM Download PDFInfo
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- gum
- hydrogenated
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- resin
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane Chemical compound CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 241000779819 Syncarpia glomulifera Species 0.000 claims abstract description 13
- 239000001739 pinus spp. Substances 0.000 claims abstract description 13
- 229940036248 turpentine Drugs 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229930006728 pinane Natural products 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 235000011334 Pinus elliottii Nutrition 0.000 claims abstract description 5
- 241000142776 Pinus elliottii Species 0.000 claims abstract description 5
- 235000005101 Pinus tropicalis Nutrition 0.000 claims abstract description 5
- 241001236197 Pinus tropicalis Species 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000000498 cooling water Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 17
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract description 13
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 abstract description 13
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 abstract description 13
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 235000008331 Pinus X rigitaeda Nutrition 0.000 abstract description 4
- 235000011613 Pinus brutia Nutrition 0.000 abstract description 4
- 241000018646 Pinus brutia Species 0.000 abstract description 4
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 abstract description 3
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 abstract description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 abstract description 3
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 abstract description 3
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 abstract description 3
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 abstract description 3
- 229930006722 beta-pinene Natural products 0.000 abstract description 3
- 239000003205 fragrance Substances 0.000 abstract description 3
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000006213 oxygenation reaction Methods 0.000 abstract description 2
- 230000036961 partial effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 19
- 239000002904 solvent Substances 0.000 description 5
- YPGLTKHJEQHKSS-ASZLNGMRSA-N (1r,4ar,4bs,7r,8as,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,7,8,8a,9,10,10a-dodecahydrophenanthrene-1-carboxylic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@H](C(C)C)C[C@@H]2CC1 YPGLTKHJEQHKSS-ASZLNGMRSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 3
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 description 3
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 description 3
- 229940118781 dehydroabietic acid Drugs 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000005205 Pinus Nutrition 0.000 description 2
- 241000218602 Pinus <genus> Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010040925 Skin striae Diseases 0.000 description 1
- 208000031439 Striae Distensae Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
- C09D193/04—Rosin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F3/00—Obtaining spirits of turpentine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
PROCESSO DE OBTENÇÃO DE GOMA RESINA HIDROGENADA E PRODUTOS OBTIDOS ATRAVÉS DO MESMO. Trata-se a presente patente de invenção, de um processo de obtenção de goma resina hidrogenada e produtos obtidos através do mesmo, pertencente a área química, particularmente um processo de hidrogenação parcial catalftica da goma resina do breu (colofônia), derivado de Pinus Elliotti e Pinus Tropicalis, na obtenção de um breu menos suscetível à oxigenação e de uma terebintina rica em pinano, utilizando-se catalisadores de Paládio e de Níquel. O invento atende ao mercado de resinas e derivados de breu, o qual possui uma demanda atual por produtos de coloração mais clara, os quais são mais atrativos para o consumidor final de seus produtos, sendo mais resistentes às oxidações por degradação térmica e intempéries naturais e, atendendo também ao mercado de fragrâncias, já que a produção de pinano oferece novas alternativas sintéticas diferentes das encontradas com a utilização do alfa e beta pineno. A presente invenção apresenta um processo de obtenção de goma resina hidrogenada e produtos obtidos através do mesmo, através do qual o breu hidrogenado é obtido através da hidrogenação a 20 - 30 bar H2 de goma resina derivada de pinus Elliotti e pinus Tropicalis.PROCESS FOR OBTAINING HYDROGENATED RESIN GUM AND PRODUCTS OBTAINED THROUGH IT. The present invention patent is a process for obtaining hydrogenated resin gum and products obtained through it, belonging to the chemical area, particularly a catalytic partial hydrogenation process of resin gum (rosin), derived from Pinus Elliotti and Pinus Tropicalis, in obtaining a pitch less susceptible to oxygenation and a turpentine rich in pinane, using Palladium and Nickel catalysts. The invention serves the resins and rosin derivatives market, which has a current demand for lighter colored products, which are more attractive to the final consumer of their products, being more resistant to oxidation by thermal degradation and natural weathering and , also serving the fragrance market, since the production of pinane offers new synthetic alternatives different from those found with the use of alpha and beta pinene. The present invention presents a process for obtaining hydrogenated resin gum and products obtained therefrom, through which the hydrogenated pitch is obtained through the hydrogenation at 20 - 30 bar H2 of gum resin derived from Elliotti pine and Tropicalis pine.
Description
[1] Trata-se a presente patente de invenção, de um processo de obtenção de goma resina hidrogenada e produtos obtidos através do mesmo, pertencente a área química, particularmente um processo de hidrogenação parcial catalítica da goma resina do breu (colofônia), derivado de Pinus elliottii e pinus tropicais, na obtenção de um breu menos suscetível à oxigenação e de uma terebintina rica em pinano, utilizando-se catalisadores de Paládio e de Níquel.[1] The present invention patent is a process for obtaining hydrogenated resin gum and products obtained through it, belonging to the chemical area, particularly a catalytic partial hydrogenation process of the resin gum (rosin), derived of Pinus elliottii and tropical pine, in obtaining a pitch less susceptible to oxygenation and a turpentine rich in pinane, using Palladium and Nickel catalysts.
[2] O invento atende ao mercado de resinas e derivados de breu, o qual possui uma demanda atual por produtos de coloração mais clara, os quais são mais atrativos para o consumidor final de seus produtos, sendo mais resistentes às oxidações por degradação térmica e intempéries naturais e, atendendo também ao mercado de fragrâncias, já que a produção de pinano oferece novas alternativas sintéticas diferentes das encontradas com a utilização do alfa e beta pineno.[2] The invention serves the resins and pitch derivatives market, which has a current demand for lighter colored products, which are more attractive to the final consumer of their products, being more resistant to oxidation by thermal degradation and weather conditions and, also serving the fragrance market, since the production of pinane offers new synthetic alternatives different from those found with the use of alpha and beta pinene.
[3] Breu e terebintina são produtos obtidos através da extração de goma de árvores de pinho (Pinus). Nestas árvores são feitas estrias e, assim como o látex nas seringueiras, a goma proveniente destas estrias é recolhida.[3] Pitch and turpentine are products obtained by extracting gum from pine trees (Pinus). Stretch marks are made on these trees and, like the latex in rubber trees, the gum from these streaks is collected.
[4] A goma obtida dos pinheiros (Pinus) é então destilada, onde separam-se as frações leves (mais voláteis) e pesadas (menos voláteis) da goma. A fração leve é conhecida como terebintina e esta é rica em alfa-pineno e beta-pineno, que são produtos utilizados, por exemplo, na produção de óleo de pinho, para o uso em produtos de limpeza. São também utilizados no segmento de fragrâncias, dentre outras finalidades. A fração pesada é conhecida como breu (colofônia), que à temperatura ambiente se apresenta como um sólido de cor amarelada a âmbar. O breu é composto principalmente de ácidos resínicos, nos quais se destacam os ácidos Abiético, Pimárico, Levopimárico, Palústrico, Isopimárico, Deidroabiético e Neoabiético, os quais possuem, em sua estrutura, ligações duplas passíveis de sofrer oxidação do ar e levando ao escurecimento da cor breu e seus derivados em suas aplicações industriais.[4] The gum obtained from pine trees (Pinus) is then distilled, where the light (more volatile) and heavy (less volatile) fractions of the gum are separated. The light fraction is known as turpentine and it is rich in alpha-pinene and beta-pinene, which are products used, for example, in the production of pine oil, for use in cleaning products. They are also used in the fragrance segment, among other purposes. The heavy fraction is known as rosin (rosin), which at room temperature appears as a yellowish to amber solid. The rosin is composed mainly of resin acids, in which the Abietic, Pimaric, Levopimaric, Palústric, Isopimaric, Dehydroabietic and Neoabietic acids stand out, which have, in their structure, double bonds that can undergo oxidation in the air and lead to the darkening of the surface. rosin color and its derivatives in their industrial applications.
[5] Normalmente num processo de hidrogenação, o breu é dissolvido em solventes orgânicos, como o tolueno e etanol, por exemplo, e hidrogenado em pressões elevadas (40-130 bar H2), a fim de reduzir estas ligações duplas tornando-as inertes à ação do oxigênio do ar. Após o processo de hidrogenação, a mistura breu mais solvente é destilada para separar o solvente orgânico e o breu hidrogenado recolhido.[5] Normally in a hydrogenation process, rosin is dissolved in organic solvents, such as toluene and ethanol, for example, and hydrogenated at high pressures (40-130 bar H2) in order to reduce these double bonds making them inert. to the action of oxygen in the air. After the hydrogenation process, the pitch plus solvent mixture is distilled to separate the organic solvent and the collected hydrogenated pitch.
[6] O processo de hidrogenação faz com que a coloração do breu (agora rico em ácido tetraidroabiético, totalmente hidrogenado) se torne menos amarelada, deixando o mesmo bastante atrativo para a indústria de resinas e derivados (produtos mais claros são mais desejados pelo marketing das empresas).[6] The hydrogenation process causes the color of the pitch (now rich in tetrahydroabietic acid, fully hydrogenated) to become less yellowish, making it very attractive to the resin and derivatives industry (lighter products are more desired by marketing of companies).
[7] Devido à sua complexa mistura de isômeros e algumas impurezas, a hidrogenação do breu é particularmente complicada. As impurezas (enxofre proveniente da extração da goma, por exemplo) contribuem para o escurecimento e envenenam o catalisador. Durante a hidrogenação, o breu pode sofrer descarboxilação (perda de CO2) e isomerização, e estas reações são competitivas com as hidrogenação. A descarboxilação conduz a uma perda de acidez e a isomerização leva a isômeros (mudanças na estrutura da molécula) resistentes à hidrogenação.[7] Due to its complex mixture of isomers and some impurities, the hydrogenation of rosin is particularly complicated. Impurities (sulfur from gum extraction, for example) contribute to browning and poison the catalyst. During hydrogenation, pitch can undergo decarboxylation (loss of CO2) and isomerization, and these reactions are competitive with hydrogenation. Decarboxylation leads to a loss of acidity and isomerization leads to isomers (changes in the structure of the molecule) resistant to hydrogenation.
[8] Como parte do estado da técnica, existem algumas patentes tais como as patentes: CN 102453435, CN 102070988, JP 2145668 e US 0150778, as quais referem-se a processos de hidrogenação do breu, porém envolvem pressões elevadas (40-130 bar de pressão de hidrogênio), o que acarreta em processos caros e perigosos. Caros porque necessitam de reatores muito espessos para suportar as pressões elevadas e perigosos devido à alta pressão de hidrogênio, que é um gás inflamável. Assim, processos utilizando pressões reduzidas são altamente desejados pelas indústrias.[8] As part of the state of the art, there are some patents such as patents: CN 102453435, CN 102070988, JP 2145668 and US 0150778, which refer to processes of hydrogenation of rosin, but involve high pressures (40-130 bar of hydrogen pressure), which leads to expensive and dangerous processes. Expensive because they need very thick reactors to withstand the high pressures and dangerous due to the high pressure of hydrogen, which is a flammable gas. Thus, processes using reduced pressures are highly desired by industries.
[9] Além disso, como relatado anteriormente, usa-se, na maioria dos processos, solventes orgânicos derivados de petróleo para dissolver o breu, que é uma resina sólida à temperatura ambiente, tornando o seu uso direto no processo, muito complicado, pois, teria de manter ela aquecida o tempo todo, causando um grande gasto energético e, consequentemente, um encarecimento no processo, para que ser tornasse fluida e fácil de operar.[9] In addition, as previously reported, organic solvents derived from petroleum are used in most processes to dissolve rosin, which is a solid resin at room temperature, making its direct use in the process very complicated, as , it would have to keep it heated all the time, causing a great energy expenditure and, consequently, an increase in the process, so that it becomes fluid and easy to operate.
[10] O uso de solventes orgânicos derivados de petróleo em processos industriais é algo que tem de ser evitado, pois, torna o processo perigoso, tanto para o processo em si, quanto para os funcionários envolvidos diretamente nele. O tolueno, que é bastante empregado, é um bom solvente para o breu, porém, ele pode causar dependência quando inalado frequentemente (tolueno é utilizado na cola de sapateiro, por exemplo). Além disso, o tolueno é obtido do petróleo, uma matéria-prima não renovável.[10] The use of petroleum-derived organic solvents in industrial processes is something that must be avoided, as it makes the process dangerous, both for the process itself and for the employees directly involved in it. Toluene, which is widely used, is a good solvent for pitch, but it can be addictive when inhaled frequently (toluene is used in shoe glue, for example). In addition, toluene is obtained from petroleum, a non-renewable raw material.
[11] Com relação ao catalisador empregado no processo, existem algumas patentes, tais como: US 0150778 e US 6755963, porém nenhuma delas é financeiramente atrativa para ser empregada em processos industriais. Atualmente os catalisadores mais empregados são os de Paládio (Pd), por fornecerem bons resultados, porém, por serem caros, também se emprega o uso de catalisadores de Níquel (Ni), devendo se verificar a relação custo/benefício do processo envolvido.[11] Regarding the catalyst used in the process, there are some patents, such as: US 0150778 and US 6755963, but none of them is financially attractive to be used in industrial processes. Currently, the most used catalysts are Palladium (Pd), as they provide good results, however, because they are expensive, Nickel (Ni) catalysts are also used.
[12] Assim, a presente patente de invenção tem como objetivo a utilização direta da goma, que se mostra uma excelente alternativa, pois, a terebintina atua como um solvente natural para o processo, não havendo a necessidade da adição de solventes não-renováveis. Além disso, a utilização de produtos renováveis é uma tendência crescente no mundo todo.[12] Thus, the present invention patent aims at the direct use of the gum, which proves to be an excellent alternative, since turpentine acts as a natural solvent for the process, without the need for the addition of non-renewable solvents. . In addition, the use of renewable products is a growing trend worldwide.
[13] A presente invenção apresenta um processo de obtenção de goma resina hidrogenada e produtos obtidos através do mesmo, através do qual o breu hidrogenado é obtido através da hidrogenação a 20 – 30 bar H2 de goma resina derivada de Pinus elliottii ou pinus tropicais.[13] The present invention presents a process for obtaining hydrogenated resin gum and products obtained therefrom, whereby hydrogenated rosin is obtained through hydrogenation at 20 - 30 bar H2 of gum resin derived from Pinus elliottii or tropical pine.
[14] O processo de obtenção de goma resina hidrogenada compreende as seguintes etapas: 1 .- adiciona-se de 98 - 99,9% de goma resina, derivada de Pinus elliottii ou pinus tropicais, a um reator, junto de 0,1 - 2% m/m de catalisador Pd/C 5% ou Ni/C 21%; 2 .- fecha-se o reator e inicia-se a agitação mecânica; 3 .- purga-se hidrogênio por três vezes, a fim de esgotar o oxigênio de dentro do reator e mantém-se a pressão a 20 - 30 bar H2; 4 .- aquece-se o reator (através de eletricidade, óleo térmico, etc.) elevando-se a temperatura até 60°C e mantém-se a pressão a 20 - 30 bar H2; 5 .- após atingir as condições acima, a reação é mantida por uma hora; 6 .- em seguida o reator é aquecido, elevando-se a temperatura para 200°C e mantém-se a pressão a 20 - 30 bar H2, corrigindo-a, caso necessário; 7 .- após atingir as condições acima, a reação é mantida por mais 3 horas; 8 .- após as 3 horas de reação, o reator é resfriado (por meio de água de resfriamento, etc) até atingir a temperatura ambiente; 9 .- após atingir a temperatura ambiente, o reator é despressurizado e a agitação desligada; 10 .- o conteúdo do reator (goma hidrogenada) é recolhido; 11 .- a goma hidrogenada obtida é filtrada, para separar o catalisador, utilizando-se placas metálicas filtrantes; 12 .- a goma hidrogenada e filtrada é destilada em uma coluna de destilação, separando-se a terebintina hidrogenada (em sua maioria pinano) e o breu hidrogenado.[14] The process for obtaining hydrogenated resin gum comprises the following steps: 1 .- 98 - 99.9% of resin gum, derived from Pinus elliottii or tropical pine, is added to a reactor, together with 0.1 - 2% m/m of 5% Pd/C or 21% Ni/C catalyst; 2 .- close the reactor and start the mechanical agitation; 3 .- hydrogen is purged three times in order to exhaust the oxygen inside the reactor and the pressure is maintained at 20 - 30 bar H2; 4 .- the reactor is heated (through electricity, thermal oil, etc.) raising the temperature to 60°C and maintaining the pressure at 20 - 30 bar H2; 5 .- after reaching the above conditions, the reaction is maintained for one hour; 6 .- then the reactor is heated, raising the temperature to 200°C and maintaining the pressure at 20 - 30 bar H2, correcting it if necessary; 7 .- after reaching the above conditions, the reaction is maintained for another 3 hours; 8 .- after 3 hours of reaction, the reactor is cooled (by means of cooling water, etc.) until reaching room temperature; 9 .- after reaching room temperature, the reactor is depressurized and the agitation is turned off; 10 .- the contents of the reactor (hydrogenated gum) are collected; 11 .- the hydrogenated gum obtained is filtered, to separate the catalyst, using metal filter plates; 12 .- the hydrogenated and filtered gum is distilled in a distillation column, separating the hydrogenated turpentine (mostly pinane) and the hydrogenated pitch.
[15] Através do processo acima descrito, obtém-se os seguintes produtos: - terebintina hidrogenada contendo de 70,0 - 80,0 % de Pinano. - breu hidrogenado contendo Ácido Tetraidroabiético entre 30,0 - 55,0 % e Ácido Deidroabiético entre 10,0 - 30,0 %, dentre outros.[15] Through the process described above, the following products are obtained: - hydrogenated turpentine containing 70.0 - 80.0% Pinane. - hydrogenated pitch containing Tetrahydroabietic Acid between 30.0 - 55.0% and Dehydroabietic Acid between 10.0 - 30.0%, among others.
[16] A seguir serão apresentados dois exemplos de obtenção do invento, com o intuito de ilustrar a viabilidade prática, sem limitar a abrangência do invento.[16] Next, two examples of obtaining the invention will be presented, in order to illustrate the practical feasibility, without limiting the scope of the invention.
[17] Processo de obtenção de obtenção de goma resina hidrogenada com utilização de goma resina Tropicalis: 1 .- adicionou-se 69,3g de goma resina a um reator, junto com 0,7 g de catalisador Pd/C 5%; 2 .- fechou-se o reator e iniciou-se a agitação mecânica; 3 .- purgou-se hidrogênio por três vezes, a fim de esgotar o oxigênio de dentro do reator e manteve-se a pressão a 20 - 30 bar H2; 4 .- aqueceu-se o reator, através de eletricidade, elevando-se a temperatura até 60°C e manteve-se a pressão a 20 - 30 bar H2; 5 .- após atingir as condições acima, a reação foi mantida por uma hora; 6 .- em seguida o reator foi aquecido, elevando-se a temperatura para 200°C e manteve-se a pressão a 20 - 30 bar H2; 7 .- após atingir as condições acima, a reação foi mantida por mais 3 horas; 8 .- após as 3 horas de reação, o reator foi resfriado com água de resfriamento até atingir a temperatura ambiente; 9 .- após atingir a temperatura ambiente, o reator foi despressurizado e a agitação desligada; 10 .- o conteúdo do reator (goma Tropicalis hidrogenada) foi recolhida; 11 .- a goma hidrogenada obtida foi filtrada, para separar o catalisador utilizando-se placas metálicas filtrantes; 12 .- a goma Tropicalis hidrogenada e filtrada foi destilada em uma coluna de destilação, separando-se a terebintina hidrogenada, do breu hidrogenado.[17] Process for obtaining hydrogenated resin gum using Tropicalis gum resin: 1.- 69.3 g of resin gum were added to a reactor, together with 0.7 g of 5% Pd/C catalyst; 2 .- the reactor was closed and the mechanical agitation started; 3 .- hydrogen was purged three times in order to exhaust the oxygen inside the reactor and the pressure was maintained at 20 - 30 bar H2; 4 .- the reactor was heated by electricity, raising the temperature to 60°C and the pressure maintained at 20 - 30 bar H2; 5 .- after reaching the above conditions, the reaction was maintained for one hour; 6 .- then the reactor was heated, raising the temperature to 200°C and maintaining the pressure at 20 - 30 bar H2; 7 .- after reaching the above conditions, the reaction was maintained for another 3 hours; 8 .- after 3 hours of reaction, the reactor was cooled with cooling water until reaching room temperature; 9 .- after reaching room temperature, the reactor was depressurized and the agitation turned off; 10 .- the contents of the reactor (hydrogenated Tropicalis gum) was collected; 11 .- the hydrogenated gum obtained was filtered to separate the catalyst using metal filter plates; 12 .- the hydrogenated and filtered Tropicalis gum was distilled in a distillation column, separating the hydrogenated turpentine from the hydrogenated pitch.
[18] Através do exemplo acima descrito, obteve-se os seguintes produtos: - terebintina hidrogenada contendo 80% de Pinano - breu hidrogenado contendo 40,0 - 55,0 % de Ácido Tetraidroabiético (totalmente hidrogenado) e 10,0 - 15,0 % de Ácido Deidroabiético (parcialmente hidrogenado)[18] Using the example described above, the following products were obtained: - hydrogenated turpentine containing 80% Pinan - hydrogenated pitch containing 40.0 - 55.0% of Tetrahydroabietic Acid (fully hydrogenated) and 10.0 - 15, 0% Dehydroabietic Acid (partially hydrogenated)
[19] Foram obtidos os seguintes resultados:
[20] O índice de iodo (medida indireta da % hidrogenação) para o breu hidrogenado foi de 75,8, um número muito menor do que o encontrado no breu de partida, que é de 163, 4, dando uma % hidrogenação da ordem de 54 %, condinzente com um breu parcialmente hidrogenado (30 - 75%)[20] The iodine number (indirect measure of % hydrogenation) for the hydrogenated pitch was 75.8, a much lower number than that found in the starting pitch, which is 163.4, giving a % hydrogenation of the order 54%, consistent with a partially hydrogenated pitch (30 - 75%)
[21] O breu obtido possui cor Gardner 2 a 4, em 50% toluol, e acidez de 145 mg/KOH.[21] The pitch obtained has Gardner color 2 to 4, in 50% toluol, and acidity of 145 mg/KOH.
[22] Processo de obtenção de goma resina hidrogenada com utilização de goma resina Elliotti: 1 .- adicionou-se 68,6 g de goma resina a um reator, junto com 1,4 g de catalisador Ni/C 21%; 2 .- fechou-se o reator e iniciou-se a agitação mecânica; 3 .- purgou-se hidrogênio por três vezes, a fim de esgotar o oxigênio de dentro do reator e manteve-se a pressão a 20 - 30 bar H2; 4 .- aqueceu-se o reator, através de eletricidade, elevando-se a temperatura até 60°C e manteve-se a pressão a 20 - 30 bar H2; 5 .- após atingir as condições acima, a reação foi mantida por uma hora; 6 .- em seguida o reator foi aquecido, elevando-se a temperatura para 200°C e manteve-se a pressão a 20 - 30 bar H2; 7 .- após atingir as condições acima, a reação foi mantida por mais 3 horas; 8 .- após as 3 horas de reação, o reator foi resfriado com água de resfriamento até atingir a temperatura ambiente; 9 .- após atingir a temperatura ambiente, o reator foi despressurizado e a agitação desligada; 10 .- o conteúdo do reator (goma Elliotti hidrogenada) foi recolhida; 11 .- a goma hidrogenada obtida foi filtrada, para separar o catalisador utilizando-se placas metálicas filtrantes; 12 .- a goma Elliotti hidrogenada e filtrada foi destilada em uma coluna de destilação, separando-se a terebintina hidrogenada, do breu hidrogenado.[22] Process for obtaining hydrogenated resin gum using Elliotti gum resin: 1.- 68.6 g of resin gum were added to a reactor, together with 1.4 g of 21% Ni/C catalyst; 2 .- the reactor was closed and the mechanical agitation started; 3 .- hydrogen was purged three times in order to exhaust the oxygen inside the reactor and the pressure was maintained at 20 - 30 bar H2; 4 .- the reactor was heated by electricity, raising the temperature to 60°C and the pressure maintained at 20 - 30 bar H2; 5 .- after reaching the above conditions, the reaction was maintained for one hour; 6 .- then the reactor was heated, raising the temperature to 200°C and maintaining the pressure at 20 - 30 bar H2; 7 .- after reaching the above conditions, the reaction was maintained for another 3 hours; 8 .- after 3 hours of reaction, the reactor was cooled with cooling water until reaching room temperature; 9 .- after reaching room temperature, the reactor was depressurized and the agitation turned off; 10 .- the contents of the reactor (hydrogenated Elliotti gum) was collected; 11 .- the hydrogenated gum obtained was filtered to separate the catalyst using metal filter plates; 12 .- the hydrogenated and filtered Elliotti gum was distilled in a distillation column, separating the hydrogenated turpentine from the hydrogenated pitch.
[23] Através do exemplo acima descrito, obteve-se os seguintes produtos: - terebintina hidrogenada contendo 70 - 80% de pinano - breu hidrogenado contendo 32,0 - 40,0 % de Ácido Tetraidroabiético (totalmente hidrogenado) e 20,0 - 26,0 % de Ácido Deidroabiético (parcialmente hidrogenado)[23] Using the example described above, the following products were obtained: - hydrogenated turpentine containing 70 - 80% of pinane - hydrogenated pitch containing 32.0 - 40.0% of Tetrahydroabietic Acid (totally hydrogenated) and 20.0 - 26.0% Dehydroabietic Acid (partially hydrogenated)
[24] Foram obtidos os seguintes resultados:
[25] O índice de iodo (medida indireta da % hidrogenação) para o breu hidrogenado foi de 66,2, um número muito menor do que o encontrado no breu de partida, que é de 251,9, dando uma %hidrogenação da ordem de 73%, condinzente com um breu parcialmente hidrogenado (30 - 75%).[25] The iodine value (indirect measure of % hydrogenation) for the hydrogenated pitch was 66.2, a much lower number than that found in the starting pitch, which is 251.9, giving a %hydrogenation of the order of 73%, consistent with a partially hydrogenated pitch (30 - 75%).
[26] O breu obtido possui cor Gardner 2 a 4, em 50% toluol, e acidez de 145 mg/KOH.[26] The pitch obtained has Gardner color 2 to 4, in 50% toluol, and acidity of 145 mg/KOH.
[27] Com o processo assim obtido, obteve-se as seguintes e extraordinárias vantagens: - Uso de menor pressão de hidrogenação, acarretando em maior segurança no processo de obtenção de breu hidrogenado e custos envolvidos; - Uso direto da goma, sem necessidade de mistura com outro solvente, em detrimento da utilização do breu dissolvido em solventes não renováveis (tolueno, por exemplo); - Obtenção de pinano diretamente da terebintina, o qual pode ser utilizado com precursor para a indústria de perfumaria.[27] With the process thus obtained, the following extraordinary advantages were obtained: - Use of lower hydrogenation pressure, resulting in greater safety in the process of obtaining hydrogenated pitch and costs involved; - Direct use of the gum, without the need to mix it with another solvent, to the detriment of the use of rosin dissolved in non-renewable solvents (toluene, for example); - Obtaining pinane directly from turpentine, which can be used as a precursor for the perfumery industry.
[28] A abrangência da presente patente de invenção, não deve ser limitada aos exemplos, mas sim, aos termos definidos nas reivindicações e seus equivalentes.[28] The scope of the present invention patent should not be limited to the examples, but rather to the terms defined in the claims and their equivalents.
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| BR102014025671-7A BR102014025671B1 (en) | 2014-10-15 | 2014-10-15 | PROCESS FOR OBTAINING HYDROGENATED RESIN GUM |
| ES201790018A ES2647235B2 (en) | 2014-10-15 | 2015-10-15 | Process for obtaining hydrogenated resin rubber and products obtained through it |
| PT0015915A PT2016058068B (en) | 2014-10-15 | 2015-10-15 | Method for producing hydrogenated resin gum and products produced thereby |
| PCT/BR2015/000159 WO2016058068A1 (en) | 2014-10-15 | 2015-10-15 | Method for producing hydrogenated resin gum and products produced thereby |
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| BR102014025671-7A BR102014025671B1 (en) | 2014-10-15 | 2014-10-15 | PROCESS FOR OBTAINING HYDROGENATED RESIN GUM |
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| GB340338A (en) * | 1929-10-04 | 1931-01-01 | Edward Davis Feldman | Process for the recovery of utilisable products from the residues obtained from the distillation of oil of turpentine, gum resins and like resinous substances |
| JP2790404B2 (en) * | 1993-03-26 | 1998-08-27 | 隆太郎 木下 | Method for producing hydrogenated rosin |
| US5820749A (en) * | 1996-11-22 | 1998-10-13 | Exxon Chemical Patents, Inc. | Hydrogenation process for unsaturated hydrocarbons |
| US6755963B2 (en) * | 1997-07-15 | 2004-06-29 | Exxonmobil Chemical Patents Inc. | Hydrogenation process for hydrocarbon resins |
| CN1185317C (en) * | 2001-09-03 | 2005-01-19 | 广西大学 | Production process and equipment for hydrogenated rosin and pinane with high cis-to-trans ratio |
| CN1317348C (en) * | 2004-09-27 | 2007-05-23 | 广西大学 | Method for producing pale disproportionated rosin with high content dehydroabietic acid and P-camphogen simultinuously |
| CN1317347C (en) * | 2004-09-27 | 2007-05-23 | 广西大学 | Water-white hydrogenating rosin production |
| CN102453435A (en) * | 2010-10-19 | 2012-05-16 | 张勇 | Hydrogenated rosin synthesis technology |
| CN102070988B (en) * | 2011-01-20 | 2014-04-02 | 广西梧州日成林产化工股份有限公司 | Method for producing water-white hydrogenated rosin |
| CN102872863B (en) * | 2012-10-12 | 2014-12-31 | 康纳新型材料(杭州)有限公司 | Carrier type catalyst and application of carrier type catalyst in low-pressure rosin hydrogenation |
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| WO2016058068A1 (en) | 2016-04-21 |
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