WO2016058068A1

WO2016058068A1 - Method for producing hydrogenated resin gum and products produced thereby

Info

Publication number: WO2016058068A1
Application number: PCT/BR2015/000159
Authority: WO
Inventors: Jose Pinto da Rocha Jorge FERREIRA
Original assignee: Resinas Brasil Industria E Comercio Ltda
Priority date: 2014-10-15
Filing date: 2015-10-15
Publication date: 2016-04-21
Also published as: ES2647235B2; BR102014025671B1; BR102014025671A2; ES2647235R1; ES2647235A2; PT2016058068B

Abstract

The present invention patent relates to a method for producing hydrogenated resin gum and to products produced thereby, pertaining to the chemical sector, and relates particularly to a method of partial catalytic hydrogenation of rosin (colophony) resin gum, from Pinus elliotti and Pinus tropicalis, for producing rosin that is less susceptible to oxygenation and pinane-rich turpentine, using palladium and nickel catalysts. The invention serves the market of rosin derivatives and resins, which currently has a demand for lighter coloured products which are more attractive to the end consumer of products thereof and are more resistant to oxidation from heat degradation and natural weathering, and also serves the market of fragrances, since the production of pinane offers novel synthetic alternatives different to those found using alpha- and beta-pinene. The present invention provides a method for producing hydrogenated resin gum and products produced thereby, wherein the hydrogenated rosin is produced by hydrogenation at 20-3.0 bar H₂ of resin gum from Pinus elliotti and Pinus tropicalis.

Description

PROCESS FOR OBTAINING HYDROGENED RESIN GUM AND PRODUCTS OBTAINED THEREOF

[1] The present invention is a process for obtaining hydrogenated resin gum and chemical products thereof, particularly a catalytic partial hydrogenation process for rosin (rosin) gum derived from Pinus Elliotti and Pinus Tropicalis, in order to obtain a rosin less susceptible to oxygenation and a pinane rich turpentine, using palladium and nickel catalysts.

[2] The invention serves the rosin resin and 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 weathering and also taking into account the fragrance market, since pinane production offers new synthetic alternatives different from those found with the use of alpha and beta pinene.

TECHNICAL BACKGROUNDS

[3] Pitch and turpentine are products obtained by extracting pine tree gum (Pinus). Stretch marks are made on these trees and, like latex on rubber trees, the gum from these streaks is collected.

[4] The pine gum (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 rosin (rosin), which at room temperature is as a yellow to amber solid. The rosin is mainly composed of resin acids, in which the Abietic, Pammaric, Levopimamaric, Palustric, Isopimaric, Dehydroabietic and Neoabietic acids stand out, which have, in their structure, double bonds that may undergo air oxidation and leading to the darkening of the air. pitch black and its derivatives in its industrial applications.

[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 H ₂ ) to reduce these double bonds by 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 hydrogenated pitch collected.

[6] The hydrogenation process makes the pitch of rosin (now rich in fully hydrogenated tetrahydroabetic acid) less yellowish, making it very attractive to the resin and derivatives industry (lighter products are more desired by marketing companies).

[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 darkening and poison the catalyst. During hydrogenation, rosin may undergo decarboxylation (loss of CO ₂ ) 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.

[8] 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, but involve high pressures (40-130 bar hydrogen pressure), which entails expensive and hazardous processes. Expensive because they need very thick reactors to withstand the high and dangerous pressures due to the high pressure of hydrogen, which is a flammable gas. Thus, processes using reduced pressures are highly desired by industries.

[9] In addition, as previously reported, petroleum-derived organic solvents 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 because , would have to keep it warm all the time, causing a great deal of energy expenditure and hence an increase in the process so that it would be fluid and easy to operate.

[10] 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 solvent for pitch, but it can 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.

[11] Regarding the catalyst employed in the process, there are some patents, such as: US 0150778 and US 6755963, but none of them are financially attractive to be employed in industrial processes. Currently the most used catalysts are Palladium (Pd), because 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.

[12] Accordingly, the present invention patent aims at Direct use of the gum, which is an excellent alternative, as turpentine acts as a natural solvent for the process, and there is no need to add non-renewable solvents. In addition, the use of renewable products is a growing trend worldwide.

BRIEF DESCRIPTION OF THE INVENTION

[13] 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 H ₂ resin gum derived from Elliotti pinus and Pinus Tropicalis. .

DETAILED DESCRIPTION OF THE INVENTION

[14] The process for obtaining hydrogenated resin gum comprises the following steps:

1. - 98 - 99.9% gum resin, derived from Elliotti or Tropicalis pine, is added to a reactor, together with 0.1 - 2% w / w 5% Pd / C or Ni / C catalyst. 21%;

2. The reactor is closed and mechanical agitation is started.

3. hydrogen is purged three times to exhaust oxygen from the reactor and the pressure is maintained at 20 - 30 bar H ₂ ;

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 H ₂ ;

5. After reaching the above conditions, the reaction is maintained for one hour;

6. - the reactor is then heated, raising the temperature to 200 ° C and maintaining the pressure at 20 - 30 bar H ₂ , correcting it if necessary;

7. After reaching the above conditions, the reaction is held for 3 more hours;

8. After 3 hours of reaction, the reactor is cooled (by cooling water, etc.) to room temperature;

9. - after reaching room temperature, the reactor is depressurized and the agitation off;

10. the contents of the reactor (hydrogenated gum) are collected;

1. the obtained hydrogenated gum is filtered to separate the catalyst using filtering metal plates;

12. The filtered hydrogenated gum is distilled off a distillation column, separating the hydrogenated turpentine (mostly pinane) and the hydrogenated pitch.

[15] By the process described above, the following products are obtained:

- hydrogenated turpentine containing from 70.0 - 80.0% Pinano.

- hydrogenated pitch containing Tetrahydroabietic Acid between 30.0 - 55.0% and Dehydroabietic Acid between 10.0 - 30.0, among others.

OBTAINING EXAMPLE

[16] The following are two examples of obtaining the invention in order to illustrate practical feasibility without limiting the scope of the invention.

EXAMPLE 1

[17] Procedure for obtaining hydrogenated resin gum using Tropicalis resin gum:

1. 69.3 g of resin gum was added to a reactor, together with 0.7 g of 5% Pd / C catalyst;

2. The reactor was closed and mechanical agitation started.

3. hydrogen was purged three times to exhaust oxygen from the reactor and the pressure was maintained at 20 - 30 bar H ₂ ;

4. the reactor was heated by electricity by raising the temperature to 60 ° C and maintaining the pressure at 20 - 30 bar H ₂ ;

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 H ₂ ;

7. After reaching the above conditions, the reaction was maintained for a further 3 hours;

8. After 3 hours of reaction, the reactor was cooled with cooling water to room temperature;

9. After reaching room temperature, the reactor was depressurized and the stirring turned off;

10. the contents of the reactor (hydrogenated Tropicalis gum) were collected;

1. the obtained hydrogenated gum was filtered to separate the catalyst using filtering metal plates;

12. The filtered hydrogenated Tropicalis gum was distilled off on a distillation column separating the hydrogenated turpentine from the hydrogenated pitch.

[18] Through the example described above, the following products were obtained:

- hydrogenated turpentine containing 80% Pinano

- hydrogenated rosin containing 40.0 - 55.0% Tetrahydroabietic Acid (fully hydrogenated) and 10.0 - 15.0% Dehydroabietic Acid (partially hydrogenated)

COMPARATIVE ANALYSIS OF RESULTS

[19] The following results were obtained:

Acid Before Hydrogenating After Hydrogenating

Dehydroabietic 4.0 - 7.0% 10.0 - 15.0%

Tetrahydroabietic - 40.0 - 55.0%

Turpentine Before Hydrogenating After Hydrogenating

Alpha, beta pinene 70.0 - 80.0% -

Pinano - 70.0 - 80.0% [20] 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 the order 54%, similar to a partially hydrogenated rosin (30 - 75%)

[21] The pitch obtained has Gardner color 2 to 4 in 50% toluol and acidity of 145 mg / KOH.

EXAMPLE 2

[22] Process for obtaining hydrogenated resin gum using Elliotti resin gum:

1. 68.6 g of resin gum was added to a reactor, along with 1.4 g of 21% Ni / C catalyst;

2. The reactor was closed and mechanical agitation started.

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 H ₂ ;

10. the contents of the reactor (hydrogenated Elliotti gum) were collected;

1. The obtained hydrogenated gum was filtered to separate the catalyst. using filtering metal plates;

12. The filtered hydrogenated Elliotti gum was distilled on a distillation column, separating the hydrogenated turpentine from the hydrogenated pitch.

[23] Through the example described above, the following products were obtained:

- hydrogenated turpentine containing 70 - 80% pinane

- hydrogenated rosin containing 32.0 - 40.0% Tetrahydroabietic Acid (fully hydrogenated) and 20.0 - 26.0% Dehydroabietic Acid (partially hydrogenated)

COMPARATIVE ANALYSIS OF RESULTS

[24] The following results were obtained:

[25] 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 73%, similar to a partially hydrogenated pitch (30 - 75%).

[26] The pitch obtained has Gardner color 2 to 4 in 50% toluol and acidity of 145 mg / KOH.

ADVANTAGES OBTAINED FROM THE INVENTION

[27] The procedure thus obtained resulted in the following and Extraordinary advantages:

- Use of lower hydrogenation pressure, resulting in greater safety in the process of obtaining hydrogenated pitch and costs involved;

- Direct use of gum, without mixing with another solvent, to the detriment of the use of pitch 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] The scope of this invention should not be limited to the examples but to the terms defined in the claims and their equivalents.

Claims

1. PROCESS FOR OBTAINING HYDROGENED RESIN GUM, comprising the following steps:

1. 98 - 99.9% gum resin is added to a reactor, together with 0.1 - 2% w / w catalyst;

2. The reactor is closed and mechanical agitation is started.

3. hydrogen is purged three times to exhaust oxygen from the reactor and the pressure is maintained at 20 - 30 bar ¾;

4. heat the reactor by raising the temperature to 60 ° C and maintaining the pressure at 20 - 30 bar H ₂ ;

7. After reaching the above conditions, the reaction is held for 3 more hours;

8. After 3 hours of reaction, the reactor is cooled to room temperature;

9. After reaching room temperature, the reactor is depressurized and the stirring 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 filtering metal plates;

Hydrogenated resin gum production process according to claim 1, characterized in that the resin gum is derived from Pinus Elliotti or Tropicalis. HYDROGENED RESIN GUM PROCESS according to claim 1, characterized in that the catalyst is Palladium Pd / C 5% or Nickel Ni / C 21%.

4. The hydrogenated resin gum process according to claim 1, characterized in that the reactor is heated by electricity, thermal oil.

Hydrogenated resin resin gumming process according to Claim 1, characterized in that the reactor is cooled by cooling water.

6.- PRODUCTS, characterized in that they are obtained through the process claimed in 1, where we obtained:

- hydrogenated turpentine containing from 70.0 - 80.0% Pinano

- hydrogenated pitch containing Tetrahydroabetic Acid between 30.0 - 55.0% and Dehydroabietic Acid between 10.0 - 30.0%, among others.