WO2010131184A1

WO2010131184A1 - Recovery of tetracosanol from a mixture derived from tall oil pitch

Info

Publication number: WO2010131184A1
Application number: PCT/IB2010/052054
Authority: WO
Inventors: Miguel Angel Fuenzalida Diaz; Alejandro Markovits Rojas; Miriam Berrios Cornejo; Mabel Keller Mena; Jose Rodrigo Vergara Salinas; Glenda Cea Barcia; Andres Illanes Frontaura; Rolando Arturo Chamy Maggi; Andres Markovits Schersl; Araceli Olivares Miralles
Original assignee: Pontificia Universidad Catolica De Valparaiso; Härting S.A.
Priority date: 2009-05-13
Filing date: 2010-05-10
Publication date: 2010-11-18
Also published as: CL2009001166A1

Abstract

The invention relates to a method for obtaining tetracosanol from a complex mixture derived from tall oil pitch, containing terpenoids, rosin alcohols, rosin aldehydes, aliphatic alcohols, hydrocarbons and stilbene derivatives. The method includes a step comprising the crystallisation of the mixture from hexane and the fractional distillation of the crystallised solids, thereby producing tetracosanol that is more than 90% pure.

Description

Recovery of tetracosanol from a mixture derived from the pitch of tall oil.

The present invention relates to a process for the recovery of tetracosanol from the light neutral matter from the distillation of the "tall oil" pitch.

Background

The tall oil pitch is a byproduct or residue of the distillation of tall oil to obtain fatty acids and resin acids. Tall oil is obtained in turn from black liquor soaps. These soaps are a byproduct of the Kraft process of pulping coniferous trees. Coniferous woods, especially pine, contain free form resin acids, fatty acids mostly in the form of triglycerides, a series of non-saponifiable or neutral compounds, and volatile terpenes. During the pulping process, said compounds are separated from the wood. The glycerides of fatty acids and resin acids are saponified by the alkaline cooking liquor, and the resulting soaps dissolve in the pulping liquor. When the used pulping liquor, also called black liquor, is concentrated after digestion, the sodium soaps of these mixed acids are concentrated on the surface, together with the neutral compounds. The complex mixture called black liquor soaps or "tall oil" soaps can be separated from the surface. This material, which contains between 50 to 70% solids, can be used as fuel or acidified which leads to what is known as crude tall oil (CTO or crude tall oil). In turn, the CTO can be used as fuel, or as a source of a series of chemicals.

Black liquor soaps constitute a complex mixture, formed by the sodium salts of fatty acids, resin acids, which constitute the saponifiable fraction of the mixture, and a series of other compounds, such as sterols, fatty alcohols or policosanols, mono and diterpenes which together constitute the non-saponifiable fraction or neutral fraction of the black liquor soaps. A treatment of these soaps with dilute sulfuric acid transforms the sodium salts into fatty acids and free rosinic acids. As a consequence, an aqueous phase containing sodium sulfate and an oil phase are formed with the rest of the components. The oil phase separated from the aqueous phase is known as "tall-oil".

Tall oil is used to obtain industrial fatty acids that are known in the technical literature as TOFA ("tall oil fatty acids") and rosinic acids known as TORA ("tall oil rosin acids"), which have a wide range of commercial application TORA and TOFA are obtained from the vacuum fractional distillation of tall oil. The bottom of the distillation or "piten", which contains the majority of the components of the unsaponifiable, has been used as fuel or in the preparation of asphalt emulsions.

However, lately the pitch has been revalued developing a novel process for the recovery of sterols of the pitch that is taken on a commercial scale (Arboris LLC). The process is disclosed in US Patent No. ^Q 6,297,353. One of the by-products of the process that has been termed as light neutral matter contains significant amounts of tetracosanol. Tetracosanol is itself a useful product in the formulation of detergents but more importantly it can be a convenient raw material for the production of tetracosanoic acid or lignoceric acid that is an excellent wetting agent for shampoo, creams and cosmetic lotions. Thus, the objective of the present invention is to develop a process for the recovery of tetracosanol from the light neutral matter.

Composition of the light neutral matter.

Light neutral matter is a complex mixture of chemical substances of different nature in which about forty substances have been identified among diterpenoids, monoterpenic alcohols, diterpenic aldehydes, aliphatic long chain alcohols, steroidal alcohols, hydrocarbons and stilbene derivatives. Table 1 shows the components of the light neutral matter, a typical average composition and the fluctuation range of its components. Said variability is a consequence of the variability of the matter for the production of cellulose and variations in the process conditions, but it has been observed that tetracosanol is always among the main constituents.

Table 1 Components, typical average composition and composition range of the components of the light raw material.

n _nmnnnantB . Composition Typical Component Range% composition%

13-Epimanool 0.19 0.01 -15

8 (17), E-13-epimanoil-15-ol 0.54 0.01 -15

Granddaughter has 0.78 0.01 -15

Abietal 3.28 0.1 -15

Abietol 0.98 0.1 -15

Agatadiol 6.29 0.1 -55

Beta sitostanol 0.33 0-20

Beta sitosterol 2.14 0-20

Campestanol 0.01 0-20

Campesterol 0.06 0-20

Dehydroabietta has 0.39 0.01 -15

Dehydroabietal 1.78 0.1 -15

Dehydroabietol 0.57 0.01 -15

Docosanol 2.58 0.1 -50

Eicosanol 0.25 0.1 -30

Stigmasterol 0.01 0-20

Geranilgeraniol 1.80 0.1 -15

Heneicosanol 1.06 0.01 -30

Hexacosanol 4.32 0.1 -51

Isoagatadiol 8.65 0.1 -55

Isopimaradiene 1.90 0.1 -15

Isopimaral 7.14 0.1 -50

Isopimarol 7.03 0.1 -50

Manool 0.38 0.01 -15

Neo granddaughter has 0.20 0.01 -15

Neoabietal 0.60 0.01 -15

Neoabietol 0.20 0.01 -15

Octacosanol 1.26 0.1 -40

Palustral 0.20 0.01 -15

Pentacosanol 1.08 0.01 -30

Pimaradiene 1.40 0.1 -15

Pimaral 6.08 0.1 -50

Pimarol 6.32 0.1 -30

Sadaracopimaral 0.39 0.01 -15

Sandaracopimaradiene 0.20 0.01 -15

Sandaracopimarol 0.60 0.01 -15

Scualenum 0.41 0.01 -15

Terpineol 0.60 0.01 -15

Tetracosanol 10.58 0.1 -60

Trans-Communal 0.60 0.01 -15

Trans-Comunol 6.96 0.1 -45

Trans-Pinosylvin dimetilester 9.21 0.1 -50

Tricosanol 0.65 0.1 -20 However, the complexity of the light neutral matter has found a surprisingly simple process for the recovery of tetracosanol from the light neutral matter by means of a process comprising:

a) forming a mixture by contacting the light neutral matter with hexane and heating the mixture to form a solution of the composition of matter in hexane;

b) cooling the solution to a temperature of at least 10 ^Q C to form a solid phase and a liquid phase;

c) separating the solid phase from the liquid phase, and

d) fractionating the solid phase by distillation to obtain a fraction comprising tetracosanol.

Detailed description of the process.

The light neutral matter is mixed with hexane and the mixture is heated to form a solution. The heating can be carried out by heating the mixture at reflux at the normal boiling temperature of hexane in a container provided with a reflux refrigerant or it can also be carried out at a higher temperature in a pressurized container.

When the solution is carried out at reflux in a transparent container, the formation of solution is detected visually through the transition from a turbid mixture to a crystalline solution. In cases where it is not possible to visually detect the formation of solution either because the reflux heating is carried out in a non-transparent container or in a pressurized container, the heating of the mixture, for a certain reason between the mass of hexane and the mass of light neutral matter, is maintained for a period of time at least equal to the time necessary for the formation of a solution for the same reason between the mass of hexane and the mass of light neutral matter determined under reflux conditions in a transparent container

When the heating is at reflux and with a ratio between the mass of hexane and the mass of light neutral matter from 3 to 1, the solution is obtained in at least 10 minutes of heating from the beginning of the boiling.

After the solution has been formed, said solution is cooled to at least 10 ⁵ C and maintained at said temperature for at least 8 minutes until the formation of a solid phase and a liquid phase that are preferably separated by filtration, and the solid phase Separately wash with hexane and dry.

It has been found that, surprisingly, the solid phase obtained according to the described procedure is composed exclusively (99.6%) of long chain aliphatic alcohols present in the light neutral matter and that in addition the recovery of tetracosanol has a yield on 90% while the recovery of docosanol or hexacosanol has 77 and 48% respectively, as seen in Example 1.

To recover tetracosanol from the purity of the solid phase obtained in accordance with the described procedure, said solid phase is fractionated in a distillation column and the purest fraction that can contain 90% or more by weight of tetracosanol Although the person versed in the technique has no difficulty in experimentally determining the conditions for obtaining the richest fraction of tetracosanol, either in a continuous distillation or batch distillation, Example 2 illustrates the case of a fractional distillation in batches. a laboratory column

Example 1. Crystallization of light neutral matter.

600 g of light neutral matter were mixed with 1800 g of hexane in a 4 L Erlenmeyer flask provided with a reflux coolant and heated on a reflux heating plate for 35 minutes until a solution was obtained. The composition of long chain aliphatic alcohols was in% by weight of the light neutral matter: docosanol 8.2; tetracosanol 10.63; hexacosanol 1, 56 and octacosanol 1, 37 that is a total of 21.8 of long chain aliphatic alcohols. Given that previous experiences showed that the crystallized fraction obtained by the process of the invention consists practically entirely of aliphatic alcohols independently of the relative amount of the other constituents in the light neutral matter, those constituents were not analyzed separately.

The solution was then placed on ice until the temperature dropped to 10 ^Q C , observing the formation of crystals. The liquid solid suspension was filtered on Büchner filter through Watmann filter paper 1 applying vacuum and washed with hexane. The resulting solids were dried in a vacuum oven at 40 ⁵ C and 350 mbar. 104 g of dry solids were obtained, representing a 79.51% yield with respect to the total content of aliphatic alcohols of the light neutral matter.

The relative composition of alcohols in% of the crystallized mixture was: docosanol 36.3; tetracosanol 55.6; hexacosanol 4.9 and octacosanol 3.3. This composition represents the following recovery yields of individual animals in

%: docosanol 77; tetracosanol 90.6; hexacosanol 53 and octacosanol 41.

The analyzes of the alcohols in the samples were performed as described below.

Analysis of crystallized solids.

The long chain aliphatic alcohols of the solvent-free crystals were determined by an HP 6890 gas chromatograph with self-sample provided with an HP-5 column (3Om ^* 0.25 mm diameter ^* 025 μm) and FID flame ionization detector) and operated in split mode (30: 1) The injector temperature was 300 ^Q C and the detector 320 ^Q C The initial temperature of the column is 160 ^Q C and is increased at a rate of 5 ^Q C / min and maintaining the isothermal For 10 minutes. Helium was used as a carrier (1 mL / min) at constant flow.

Derivatization of samples for analysis.

Between 400 to 500 mg of sample are weighed in a scintillation vial with 20 to 30 mg of cholesterol as an internal standard. Then 15 mL of chloroform are added and the mixture is dissolved in a vortex shaker or if necessary it is also sonified. 500 µl_ are transferred to a chromatography vial and evaporated under nitrogen. Then 300 µL of silanizing reagent (Bis (trimethyl) silyltrifluoroacetamide) and 400 µL of pyridine are added. The vial is closed and heated for 15 minutes, stirred again and a volume of 1.0μL is injected into the chromatograph.

From the chromatographic report, the areas of the different alcohols are identified by the retention times obtained from the corresponding standards; with purities of 99% or more and the percentage by weight of each species is calculated.

Example 2. Fractional distillation of the crystallized sample.

A batch distillation system of the following characteristics was used:

• 120 cm double glazed glass distillation column 24/40, Ace Glass, USA

• Packing of striated sheet steel frames of 1 cm square area per frame.

• Column heating blanket with three independent sections of 225 W each with potentiometric regulator, Glass-Col, USA • Condensing head with variable reflux, 24/40 frosted glass connections, Kontes, USA.

• Rotary condensate receiver with five 24/40 frosted glass connections with four outlets, Kontes, USA

• Two flexible heating tapes for the condenser of 938 W each, Thermolyne.

• Electromagnetic controller, Kontes.

• Distillation balloon (reboiler) of 500 ml_, with 2 female mouths 24/40, Schott Duran, Germany.

• Heating blanket for the 190 W reboiler mouth with potentiometric regulator, Quimis Aparelhos Científicos, Brazil.

• Heating blanket for 200 W reboiler ball, with potentiometric regulator, Glass-Col, USA

• Rotary vacuum pump 370 W, 8.6 / 9.9 cubic meters per hour, Trivac model RZ 8.

• Cold trap GFK 100Oi, Vacuubrand.

Process.

100 g of the solids obtained according to Example 1 were loaded into the distillation balloon and the system was evacuated with the vacuum pump to the pressure of 0.4 mbar and the heating of the solids that once melted began to boil was started The temperature of 240 ^Q C. The temperature of the condensation head was 70 ^Q C. It was left at full reflux for one hour and then passed at a reflux ratio of 3/1 (reflux / distillate). And distillate fractions began to accumulate over time. At 4.5 hours after the start of the operation with the indicated reflux ratio, Ia boiling temperature in the reboiler was 220 ^Q C and under these conditions the distillate had a purity of 34.7% in tetracosanol. An additional 1.5 hours were continued operating until the boiling temperature reached 300 ^Q C, terminating the operation. Between 4.5 hours and the end of the distillation, 43.4 g of distillate were obtained with a content of 90.2% in tetracosanol, which is equivalent to a recovery yield of 78.1%.

For distillation operation systems other than those described in Example 2, the person skilled in the art may determine by routine tests the conditions for obtaining fractions with high tetracosanol content of mixtures of long chain aliphatic alcohols containing it.

Claims

1. A process for obtaining tetracosanol from a composition of matter comprising tetracosanol CHARACTERIZED because the composition of matter has the following composition:

13-Epimanool 0.01 -15%

8 (17), E-13-epimanoyl-15-ol 0.01 -15%

Granddaughter has 0.01 -15%

Abietal 0.1 -15%

Abietol 0.1 -15%

Agatadiol 0.1 - 55%

Beta sitostanol 0-20%

Beta sitosterol 0-20%

Campestanol 0-20%

Campesterol 0-20%

Dehydroabietta has 0.01 -15%

Dehydroabietal 0.1 - 15%

Dehydroabietol 0.01 -15%

Docosanol 0.1 - 50%

Eicosanol 0.1 -30%

Stigmasterol 0-20%

Geranilgeraniol 0.1 -15%

Heneicosanol 0.01 - 30%

Hexacosanol 0.1 - 51%

Isoagatadiol 0.1 - 55%

Isopimaradiene 0.1 - 15%

Isopimaral 0.1 - 50%

Isopimarol 0.1 - 50%

Manool 0.01 -15%

Neoabieta has 0.01 -15%

Neoabietal 0.01 -15%

Neoabietol 0.01 -15%

Octacosanol 0.1 -40%

Palustral 0.01 -15%

Pentacosanol 0.01 - 30%

Pimaradiene 0.1 - 15%

Pimaral 0.1 - 50%

Pimarol 0.1 -30%

Sadaracopimaral 0.01 -15%

Sandaracopimaradiene 0.01 -15%

Sandaracopimarol 0.01 -15%

Scualene 0.01 - 15%

Terpineol 0.01 -15%

Tetracosanol 0.1 - 60%

Trans-Communal 0.01 -15% Trans-Comunol 0.1 - 45%

Trans-Pinosylvin d i metí este r 0.1 - 50%

Tricosanol 0.1 - 20%

and because tetracosanol is obtained from said composition of matter by means of the process comprising: e) forming a mixture by contacting the composition of matter with hexane and heating the mixture to form a solution of the composition of matter in hexane;

f) cooling the solution to a temperature of at least 10 ^Q C to form a solid phase and a liquid phase;

g) separating the solid phase from the liquid phase, and

h) fractionating the solid phase by distillation to obtain a fraction comprising tetracosanol.

2. A process according to claim 1 CHARACTERIZED in that the ratio between hexane masses and the composition of matter is 1: 3.

3. A process according to claim 1 CHARACTERIZED in that the hexane mixture and composition of matter are heated to reflux.

4. A process according to claim 1 CHARACTERIZED in that the hexane mixture and composition of matter are heated to a temperature greater than the normal boiling point of hexane.

5. A process according to claim 1 CHARACTERIZED in that the solid phase is distilled in a packed column and at the pressure of at most 1 mbar.

6. A process according to any of the preceding claims CHARACTERIZED because the distilled fraction comprises at least 90% by weight of tetracosanol.