PT2016058068B - Method for producing hydrogenated resin gum and products produced thereby - Google Patents
Method for producing hydrogenated resin gum and products produced thereby Download PDFInfo
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- PT2016058068B PT2016058068B PT0015915A PT0015915A PT2016058068B PT 2016058068 B PT2016058068 B PT 2016058068B PT 0015915 A PT0015915 A PT 0015915A PT 0015915 A PT0015915 A PT 0015915A PT 2016058068 B PT2016058068 B PT 2016058068B
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- hydrogenated
- reactor
- gum
- turpentine
- bar
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- 239000011347 resin Substances 0.000 title claims description 19
- 229920005989 resin Polymers 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title description 5
- 238000000034 method Methods 0.000 claims description 22
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 18
- 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 claims description 18
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane Chemical compound CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 claims description 18
- 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 claims description 18
- 241000779819 Syncarpia glomulifera Species 0.000 claims description 16
- 239000001739 pinus spp. Substances 0.000 claims description 16
- 229940036248 turpentine Drugs 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 229930006728 pinane Natural products 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims 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 claims 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 claims description 4
- 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 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 235000011334 Pinus elliottii Nutrition 0.000 claims description 4
- 241000142776 Pinus elliottii Species 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 239000000498 cooling water Substances 0.000 claims description 4
- 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 claims description 4
- 229940118781 dehydroabietic acid Drugs 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 19
- 238000005984 hydrogenation reaction Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 4
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 4
- 235000005205 Pinus Nutrition 0.000 description 4
- 241000218602 Pinus <genus> Species 0.000 description 4
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 4
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 4
- 229930006722 beta-pinene Natural products 0.000 description 4
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 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 description 2
- 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
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 239000003205 fragrance Substances 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- MLBYBBUZURKHAW-MISYRCLQSA-N Palustric acid Chemical compound C([C@@]12C)CC[C@@](C)(C(O)=O)[C@@H]1CCC1=C2CCC(C(C)C)=C1 MLBYBBUZURKHAW-MISYRCLQSA-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
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 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
- 231100001261 hazardous Toxicity 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
- 238000002156 mixing Methods 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
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 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
- 239000000126 substance 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
- 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
- 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
- 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
DESCRIÇÃODESCRIPTION
PROCESSO DE OBTENÇÃO DE GOMA RESINA HIDROGENADA EPROCESS FOR OBTAINING HYDROGENED RESIN GUM AND
PRODUTOS OBTIDOS ATRAVÉS DO MESMOPRODUCTS OBTAINED THEREOF
A presente patente de invenção refere-se a um processo de obtenção de goma resina hidrogenada e produtos obtidos através do mesmo, pertencentes à área quimica, particularmente a um processo de hidrogenação parcial catalítica da goma resina do breu (colofónia), derivada de Pinus Elliotti e Pinus Tropicallis e/ou outras, na obtenção de um breu menos suscetível à oxigenação e de uma terebintina rica em pinano, utilizando-se catalisadores de paládio e de niquel.The present invention relates to a process for obtaining hydrogenated resin gum and chemical products thereof, particularly to a catalytic partial hydrogenation process of rosin resin rosin (rosin) derived from Pinus Elliotti. and Pinus Tropicallis and / or others, to obtain a less susceptible pitch to oxygenation and a pinane rich turpentine, using palladium and nickel catalysts.
A invenção é dirigida ao mercado de resinas e derivados de breu, o qual possui uma procura atual de produtos de coloração mais clara, os quais são mais atrativos para o consumidor final dos seus produtos, sendo mais resistentes às oxidações por degradação térmica e intempéries naturais e, é também dirigida 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.The invention is directed to the rosin and resin derivatives market, which has a current demand for lighter colored products, which are more attractive to the end consumer of their products, being more resistant to oxidation by thermal degradation and natural weathering. It is also aimed at the fragrance market, since pinane production offers new synthetic alternatives different from those found with the use of alpha and beta pinene.
ANTECEDENTES DA TÉCNICA breu e a terebintina são produtos obtidos através da extração de goma de árvores de pinho (Pinus) . São feitas estrias nestas árvores e, tal como sucede como o látex nas seringueiras, a goma proveniente destas estrias é recolhida.BACKGROUND ART pitch and turpentine are products obtained by extracting gum from pine trees (Pinus). Stretch marks are made on these trees and, like latex in rubber trees, the gum from these streaks is collected.
A goma obtida dos pinheiros (Pinus) é depois destilada, onde se separam 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 utilização em produtos de limpeza. São também utilizados no segmento de fragrâncias, entre outras finalidades. A fração pesada é conhecida como breu (colofónia), que à temperatura ambiente se apresenta como um sólido com uma cor de amarelada a âmbar. 0 breu é composto principalmente de ácidos resinicos, nos quais se destacam os ácidos abiético, pimárico, levopimárico, palústrico, isopimárico, deidroabiético e neoabiético, os quais possuem, na sua estrutura, ligações duplas passíveis de sofrer oxidação do ar e que levam ao escurecimento da cor breu e dos seus derivados nas suas aplicações industriais.The gum obtained from pine (Pinus) is then distilled, where the light (most 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 pitch (rosin), which at room temperature is a yellow to amber solid. The rosin is mainly composed of resinic acids, in which the abietic, pimamaric, levopimamaric, palustric, isopimaric, dehydroabietic and neoabietic acids, which have in their structure, double bonds capable of oxidation of the air and leading to darkening. rosin and its derivatives in their industrial applications.
Normalmente, num processo de hidrogenação, o breu é dissolvido em solventes orgânicos, tais como tolueno e etanol, por exemplo, e hidrogenado em pressões elevadas (40— 130 bar H2) , a fim de reduzir estas ligações duplas tomandoas inertes à ação do oxigénio do ar. Após o processo de hidrogenação a mistura de breu mais solvente é destilada para separar o solvente orgânico e o breu hidrogenado recolhido.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) to reduce these double bonds by inerting them with oxygen. donate. After the hydrogenation process the pitch plus solvent mixture is distilled to separate the organic solvent and the hydrogenated pitch collected.
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).The hydrogenation process makes the pitch of rosin (now rich in fully hydrogenated tetrahydroabietic acid) less yellowish, making it very attractive to the resin and derivatives industry (lighter products are more desired by corporate marketing) .
Devido à sua complexa mistura de isómeros 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 de hidrogenação. A descarboxilação conduz a uma perda de acidez e a isomerização leva a isómeros (mudanças na estrutura da molécula) resistentes à hidrogenação.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 darkening and poison the catalyst. During hydrogenation pitch may 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 molecule structure) resistant to hydrogenation.
Como parte do estado da técnica, existem algumas patentes, tais como as patentes: CN 102453435, CN 102070988, JP 2145668 e US 0150778, as quais se referem a processos de hidrogenação do breu envolvendo, no entanto, pressões elevadas (40-130 bar de pressão de hidrogénio), o que acarreta processos dispendiosos e perigosos. São dispendiosos porque necessitam de reatores muito espessos para suportar as pressões elevadas, e perigosos devido à alta pressão de hidrogénio, que é um gás inflamável. Assim, os processos que utilizam pressões reduzidas são altamente desejados pelas indústrias.As part of the prior art, there are some patents, such as patents: CN 102453435, CN 102070988, JP 2145668 and US 0150778, which refer to pitch hydrogenation processes involving, however, high pressures (40-130 bar pressure), which entails costly and dangerous processes. They are expensive because they require very thick reactors to withstand the high pressures, and dangerous due to the high pressure of hydrogen, which is a flammable gas. Thus, processes utilizing reduced pressures are highly desired by industries.
Além disso, tal como relatado anteriormente, na maioria dos processos, utilizam-se 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, dado que se teria de a manter aquecida durante todo o tempo, provocando um grande gasto energético e, consequentemente, um encarecimento no processo, para que se tornasse fluida e fácil de operar.In addition, as previously reported, in most processes petroleum-derived organic solvents are used 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 be keep it warm all the time, causing a great deal of energy expenditure and hence a process increase so that it becomes fluid and easy to operate.
uso de solventes orgânicos derivados de petróleo em processos industriais é algo que tem de ser evitado, pois toma o processo perigoso, tanto para o processo em si, como para os funcionários envolvidos diretamente no mesmo. 0 tolueno, que é bastante utilizado, é um bom solvente para o breu que pode, no entanto, provocar dependência quando inalado frequentemente (o tolueno é utilizado na cola de sapateiro, por exemplo). Além disso, o tolueno é obtido do petróleo, uma matéria-prima não renovável.The use of petroleum-based organic solvents in industrial processes must be avoided as it makes the process hazardous to both the process itself and the employees directly involved in it. Toluene, which is widely used, is a good rosin solvent which can, however, cause dependence when inhaled frequently (toluene is used in cobbler glue, for example). In addition, toluene is obtained from petroleum, a non-renewable raw material.
Em relação ao catalisador utilizado no processo, existem algumas patentes, tais como: US 0150778 e US 6755963, mas nenhuma delas é financeiramente atrativa para ser utilizada em processos industriais. Atualmente os catalisadores mais utilizados são os de paládio (Pd), por fornecerem bons resultados, mas, por serem dispendiosos, também se emprega o uso de catalisadores de niquel (Ni) , devendo verificar-se a relação custo/beneficio do processo envolvido.Regarding the catalyst used in the process, there are some patents, such as: US 0150778 and US 6755963, but none of them are financially attractive for use in industrial processes. Currently the most used catalysts are palladium (Pd), as they provide good results, but because they are expensive, the use of nickel (Ni) catalysts is also employed, and the cost / benefit ratio of the process involved should be verified.
Assim, a presente patente de invenção tem como objetivo a utilização direta da goma, que se mostra uma excelente alternativa, uma vez que 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 em todo o mundo.Thus, the present invention is directed to the direct use of gum, which is an excellent alternative, as turpentine acts as a natural solvent for the process and there is no need for the addition of non-renewable solvents. In addition, the use of renewable products is a growing trend worldwide.
DESCRIÇÃO RESUMIDA DA INVENÇÃOBRIEF DESCRIPTION OF THE INVENTION
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 Tropicallis e/ou outras.The present invention provides a process for obtaining hydrogenated resin gum and products obtained therefrom, whereby hydrogenated pitch is obtained by hydrogenating to 20 - 30 bar H2 resin gum derived from Pinus Elliotti and Pinus Tropicallis and / or others. .
DESCRIÇÃO DETALHADA DA INVENÇÃODETAILED DESCRIPTION OF THE INVENTION
O processo de obtenção de goma resina hidrogenada compreende as seguintes etapas:The process of obtaining hydrogenated resin gum comprises the following steps:
1.- adicionam-se de 98 - 99,9 % de goma resina, derivada de Pinus Elliotti ou Tropicallis e/ou outras, a um reator, juntamente com 0,1 - 2 % m/m de catalisador Pd/C 5 % ou Ni/C 21 %;1.- 98 - 99.9% gum resin, derived from Pinus Elliotti or Tropicallis and / or others, is added to a reactor together with 0.1 - 2% w / w 5% Pd / C catalyst or Ni / C 21%;
2.- fecha-se o reator e inicia-se a agitação mecânica;2.- close the reactor and start mechanical agitation;
3.- purga-se hidrogénio por três vezes a fim de esgotar o oxigénio do interior do reator e mantém-se a pressão a 20 3 0 bar H2;3. hydrogen is purged three times to exhaust oxygen from the interior of the reactor and the pressure is maintained at 2030 bar H2;
4.- aquece-se o reator (através de eletricidade, óleo térmico, etc.) elevando-se a temperatura até 60° C e mantémse a pressão a 20 - 30 bar H2;4.- the reactor is heated (by electricity, thermal oil, etc.) by raising the temperature to 60 ° C and maintaining the pressure at 20 - 30 bar H2;
5.- após atingir as condições acima, a reação é mantida durante uma hora;5.- After reaching the above conditions, the reaction is maintained for one hour;
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 seja necessário;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. - após atingir as condições acima, a reação é mantida durante mais 3 horas;7. After reaching the above conditions, the reaction is maintained for a further 3 hours;
8. - após as 3 horas de reação, o reator é arrefecido (por meio de água de arrefecimento, etc.) até atingir a temperatura ambiente, entre 15 - 25 °C;8. After 3 hours of reaction, the reactor is cooled (by cooling water, etc.) to room temperature, between 15 - 25 ° C;
9. - após atingir a temperatura ambiente, o reator é despressurizado e a agitação desligada;9. After reaching room temperature, the reactor is depressurized and the stirring is turned off.
10. - o conteúdo do reator (goma hidrogenada) é recolhido;10. the contents of the reactor (hydrogenated gum) are collected;
11. - a goma hidrogenada obtida é filtrada, para separar o catalisador, utilizando-se placas metálicas filtrantes;11. the hydrogenated gum obtained is filtered to separate the catalyst using filtering metal plates;
12. - a goma hidrogenada e filtrada é destilada numa coluna de destilação, separando-se a terebintina hidrogenada (na sua maioria pinano) e o breu hidrogenado.12. The filtered hydrogenated gum is distilled off on a distillation column, separating the hydrogenated turpentine (mostly pinane) and the hydrogenated pitch.
Através do processo acima descrito, obtêm-se os seguintes produtos:Through the process described above, the following products are obtained:
- terebintina hidrogenada contendo de 70,0 - 80,0 % de pinano.- hydrogenated turpentine containing from 70.0 - 80.0% pinane.
- breu hidrogenado contendo ácido tetraidroabiético entre 30,0 - 55,0 % e ácido deidroabiético entre 10,0- hydrogenated pitch containing tetrahydroabetic acid between 30.0 - 55.0% and dehydroabietic acid between 10.0
30,0 %, entre outros.30.0%, among others.
EXEMPLO DE OBTENÇÃOOBTAINING EXAMPLE
A seguir serão apresentados dois exemplos de obtenção da invenção, com o intuito de ilustrar a viabilidade prática, sem limitar a abrangência da invenção.The following are two examples of obtaining the invention in order to illustrate practical feasibility without limiting the scope of the invention.
EXEMPLO 1EXAMPLE 1
Processo de obtenção de obtenção de goma resina hidrogenada com utilização de goma resina Tropicallis:Process for obtaining hydrogenated resin gum using Tropicallis resin gum:
1. - adicionaram-se 69,3 g de goma resina a um reator, juntamente com 0,7 g de catalisador Pd/C 5 %;1. 69.3 g of resin gum was added to a reactor together with 0.7 g of 5% Pd / C catalyst;
2. - fechou-se o reator e iniciou-se a agitação mecânica;2. The reactor was closed and mechanical agitation started.
3. - purgou-se hidrogénio por três vezes, a fim de esgotar o oxigénio de dentro do reator e manteve-se a pressão a 20 3 0 bar H2;3. hydrogen was purged three times to exhaust oxygen from the reactor and the pressure was maintained at 2030 bar H2;
4. - aqueceu-se o reator, através de eletricidade, elevandose a temperatura até 60°C e manteve-se a pressão a 20 - 30 bar H2;4. the reactor was heated by electricity by raising the temperature to 60 ° C and maintaining the pressure at 20 - 30 bar H2;
5. - após atingir as condições acima, a reação foi mantida durante uma hora;5. After reaching the above conditions, the reaction was maintained for one hour;
6. - em seguida o reator foi aguecido, elevando-se a temperatura para 200 °C e manteve-se a pressão a 20 - 30 bar η2;6. The reactor was then heated and the temperature raised to 200 ° C and the pressure maintained at 20 - 30 bar η 2 .
7. - após atingir as condições acima, a reação foi mantida durante mais 3 horas;7. After reaching the above conditions, the reaction was held for a further 3 hours;
8. - após as 3 horas de reação, o reator foi arrefecido com água de arrefecimento até atingir a temperatura ambiente, entre 15 - 25 °C;8. After 3 hours of reaction, the reactor was cooled with cooling water to room temperature between 15 - 25 ° C;
9. - após atingir a temperatura ambiente, o reator foi despressurizado e a agitação desligada;9. After reaching room temperature, the reactor was depressurized and the stirring turned off;
10. - o conteúdo do reator (goma Tropicallis hidrogenada) foi recolhida;10. the contents of the reactor (hydrogenated Tropicallis gum) were collected;
11. - a goma hidrogenada obtida foi filtrada, para separar o catalisador, utilizando-se placas metálicas filtrantes;11. the hydrogenated gum obtained was filtered to separate the catalyst using filtering metal plates;
12. - a goma Tropicallis hidrogenada e filtrada foi destilada numa coluna de destilação, separando-se a terebintina hidrogenada, do breu hidrogenado.12. The filtered hydrogenated Tropicallis gum was distilled on a distillation column separating the hydrogenated turpentine from the hydrogenated rosin.
[11] Através do exemplo acima descrito, foram obtidos os seguintes produtos:[11] Through the example described above, the following products were obtained:
- terebintina hidrogenada contendo 80 % de pinano- hydrogenated turpentine containing 80% pinane
- breu hidrogenado contendo 40, 0 - 55, 0 % de ácido tetraidroabiético (totalmente hidrogenado) e 10,0 15,0 % de ácido deidroabiético (parcialmente hidrogenado)- hydrogenated pitch containing 40,0 - 55,0% tetrahydroabietic acid (fully hydrogenated) and 10,0 15,0% dehydroabietic acid (partially hydrogenated)
ANÁLISE COMPARATIVA DO RESULTADOCOMPARATIVE ANALYSIS OF RESULTS
Foram obtidos os seguintes resultados:The following results were obtained:
índice de iodo (medida indireta da % de 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 % de hidrogenação da ordem de 54 %, condizente com um breu parcialmente hidrogenado (30 - 75 %).The iodine index (indirect measure of% hydrogenation) for hydrogenated pitch was 75.8, a much lower number than that found in the starting pitch, which is 163.4, giving a% hydrogenation of 54 %, consistent with partially hydrogenated rosin (30 - 75%).
O breu obtido possui cor Gardner 2 a 4, em 50 % toluol, e acidez de 145 mg/KOH.The pitch obtained has Gardner color 2 to 4 in 50% toluol and acidity of 145 mg / KOH.
EXEMPLO 2EXAMPLE 2
Processo de obtenção de goma resina hidrogenada com utilização de goma resina Elliotti:Process for obtaining hydrogenated resin gum using Elliotti resin gum:
1. - adicionaram-se 68,6 g de goma resina a um reator, juntamente com 1,4 g de catalisador Ni/C 21 %;1. 68.6 g of resin gum was added to a reactor together with 1.4 g of 21% Ni / C catalyst;
2. - fechou-se o reator e iniciou-se a agitação mecânica;2. The reactor was closed and mechanical agitation started.
3. - purgou-se hidrogénio por três vezes, a fim de esgotar o oxigénio do interior do reator e manteve-se a pressão a 20 - 3 0 bar H2;3. hydrogen was purged three times to exhaust oxygen from the interior of the reactor and the pressure was maintained at 20-30 bar H2;
4. - aqueceu-se o reator, através de eletricidade, elevandose a temperatura até 60 °C e manteve-se a pressão a 20 - 30 bar H2;4. the reactor was heated by electricity by raising the temperature to 60 ° C and maintaining the pressure at 20 - 30 bar H2;
5. - após atingir as condições acima, a reação foi mantida durante uma hora;5. After reaching the above conditions, the reaction was maintained for one hour;
6. - em seguida o reator foi aquecido, elevando-se a temperatura para 200 °C e manteve-se a pressão a 20 - 30 bar H2;6. then the reactor was heated, raising the temperature to 200 ° C and maintaining the pressure at 20 - 30 bar H 2 ;
7. - após atingir as condições acima, a reação foi mantida durante mais 3 horas;7. After reaching the above conditions, the reaction was held for a further 3 hours;
8. - após as 3 horas de reação, o reator foi arrefecido com água de arrefecimento até atingir a temperatura ambiente, entre 15 - 25 °C;8. After 3 hours of reaction, the reactor was cooled with cooling water to room temperature between 15 - 25 ° C;
9. - após atingir a temperatura ambiente, entre 15 - 25 °C, o reator foi despressurizado e a agitação desligada;9. - After reaching room temperature, between 15 - 25 ° C, the reactor was depressurised and the stirring turned off;
10. - o conteúdo do reator (goma Elliotti hidrogenada) foi recolhido;10. the contents of the reactor (hydrogenated Elliotti gum) were collected;
11. - a goma hidrogenada obtida foi filtrada, para separar o catalisador utilizando-se placas metálicas filtrantes;11. the hydrogenated gum obtained was filtered to separate the catalyst using filtering metal plates;
12. - a goma Elliotti hidrogenada e filtrada foi destilada em uma coluna de destilação, separando-se a terebintina hidrogenada, do breu hidrogenado.12. The filtered hydrogenated Elliotti gum was distilled on a distillation column, separating the hydrogenated turpentine from the hydrogenated rosin.
Através do exemplo acima descrito, foram obtidos os seguintes produtos:Through the example described above, the following products were obtained:
- terebintina hidrogenada contendo 70 - 80 % de pinano- hydrogenated turpentine containing 70 - 80% pinane
- breu hidrogenado contendo 32, 0 - 40, 0 % de ácido tetraidroabiético (totalmente hidrogenado) e 20,0 26,0 % de ácido deidroabiético (parcialmente hidrogenado)- hydrogenated rosin containing 32.0 - 40.0% tetrahydroabietic acid (fully hydrogenated) and 20.0 26.0% dehydroabietic acid (partially hydrogenated)
ANÁLISE COMPARATIVA DO RESULTADOCOMPARATIVE ANALYSIS OF RESULTS
Foram obtidos os seguintes resultados:The following results were obtained:
O indice de iodo (medida indireta da % de 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 % de hidrogenação da ordem de 73 %, condizente com um breu parcialmente hidrogenado (30 - 75 %).The iodine index (indirect measure of% hydrogenation) for 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 rosin (30 - 75%).
O breu obtido possui cor Gardner 2 a 4, em 50 % toluol, e acidez de 145 mg/KOH.The pitch obtained has Gardner color 2 to 4 in 50% toluol and acidity of 145 mg / KOH.
VANTAGENS OBTIDAS COM A INVENÇÃOADVANTAGES OBTAINED FROM THE INVENTION
Com o processo assim obtido, obtiveram-se as seguintes e extraordinárias vantagens:By the process thus obtained, the following extraordinary advantages were obtained:
Uso de menor pressão de hidrogenação, acarretando em maior segurança no processo de obtenção de breu hidrogenado e custos envolvidos;Use of lower hydrogenation pressure, resulting in greater safety in the process of obtaining hydrogenated pitch and costs involved;
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);Direct use of gum, without the need for mixing with another solvent, rather than the use of pitch dissolved in non-renewable solvents (toluene, for example);
Obtenção de pinano diretamente da terebintina, o qual pode ser utilizado com precursor para a indústria de perfumaria.Obtaining pinane directly from turpentine, which can be used as a precursor for the perfumery industry.
A abrangência da presente patente de invenção, não deve ser limitada aos exemplos, mas sim, aos termos definidos nas reivindicações e seus equivalentes.The scope of the present invention should not be limited to the examples but to the terms defined in the claims and their equivalents.
Claims (12)
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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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