JPH06340890A - Preparation of tall oil - Google Patents

Abstract

PURPOSE: To obtain tall oil at a low cost under good environmental conditions by acidifying the tall oil soap with the use of hydrochloric acid instead of sulfuric acid in the conventional method.

CONSTITUTION: In preparing tall oil from tall oil soft soap by acidifying tall oil soft soap and separating the tall oil thus obtained, the acidification is carried out with the use of hydrochloric acid. This acidification is carried out at 60°C-220°C, preferably 85°C-100°C. At a temperature of higher than 100°C, the acidification is carried out under pressure. The reaction time of the acidification is most preferably 10-30 minutes.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing tall oil from tall oil soft soap produced as a by-product in the cellulose industry by separating mother liquor from water and lignin.

[0002]

BACKGROUND OF THE INVENTION As a by-product of the cellulose industry, useful tall oil soft soaps are produced, which during concentration of the mother liquor during pulp production (ie, with water evaporation),
Accumulates on the solution surface. The soft soap is scraped from the surface of the container and acidified to produce tall oil. The tall oil is further distilled, which yields useful rosin acids and fatty acids as a distillate fraction.

The reaction is chemically simple and the sodium salt of the rosin acid and fatty acid is reacted with sulfuric acid, which produces the respective carboxylic acid and sodium sulfate. Sulfuric acid has been used for acidification of tall oil soft soaps, which is well suited for the above purposes as it allows the addition of neutralized sulfuric acid in the pulp mill chemical cycle. The sulfuric acid produced in this manner is a useful additive for suppressing the amount of sulfur loss in the pulp forming process. However, there are restrictions in terms of environmental protection, and pulp mills to the extent that the sulfuric acid used in the acidification process of tall oil soft soaps cannot be used in pulp mills to prevent a significant reduction in sulfur loss. It has reduced the amount of sulfur released. Therefore, efforts have been made to develop acidification substitutes in producing tall oil.

[0004]

DISCLOSURE OF THE INVENTION In connection with the present invention,
It has been surprisingly found that monovalent hydrochloric acid can be used instead of divalent sulfuric acid for the acidification of tall oil soft soaps. The amount of hydrochloric acid required for an equivalent amount of tall oil soft soap is equal to the amount of divalent sulfuric acid required. Hydrochloric acid is inexpensive, readily available, and the effluent produced when acidifying hydrochloric acid has many environmental advantages over the effluent produced when acidifying sulfuric acid. Regarding corrosivity, sulfuric acid and hydrochloric acid are very similar. However, under certain conditions and under certain concentrations, sulfuric acid is more corrosive than hydrochloric acid. This is another reason why the use of sulfuric acid is recommended.

[0005]

The essential features of the invention are set forth in the appended claims. With respect to hydrochloric acid, dilute, concentrated or gaseous hydrochloric acid can be used, provided the amount is sufficient to neutralize the fatty acids and rosin acids present in tall oil soft soaps.

Acidification of tall oil soft soaps is carried out in the temperature range 60.
To 220 ° C, preferably 85 to 100 ° C. At temperatures above 100 ° C, pressure reactions must be considered. The reaction time was not very important, but the best time was found to be 10 to 30 minutes. Prolonging the reaction time has no advantage.

The difference in quality of tall oil soft soaps depends on the quality of the wood used in making the pulp. When only pine is pulped, high quality tall oil soft soap is produced. The tall oil obtained therefrom has an acid number of 140 to 160 mg KOH / g and a rosin acid content of 30 to 50%. However, when pulping birch, the acid value of each tall oil is 100 to 120 mg KOH / g, and may be lower, because the quality of the soft soap changes. The rosin acid content is 20 to 30%. Regardless of this quality, hydrochloric acid can be used in place of sulfuric acid in the tall oil acidification process as appropriate.

After this acidification step, the tall oil layer can be separated from the mother liquor water and the lignin layer can be separated either by allowing this layer to separate naturally or by centrifuging with a centrifuge.

The present invention will be described in detail by the following examples.

[0010]

【Example】

Example 1 42 ml of 37% hydrochloric acid was used, to which 42 ml of water was added.
The mixture was heated to 80 ° C. 50% in this mixture
190 g tall oil soft soap was gradually added. 80 this
Mix at 10 ° C for 10 minutes and 90 ° C for 15 minutes, then
This mixture was poured into a graduated cylinder. 3 at 80 ° C
The layers were allowed to separate for 0 minutes and the tall oil could be decanted. The analysis results of tall oil thus obtained are as follows. Yield *% 57.5 Acid value mg KOH / g 150 Rosin acid% 34 Unsaponifiable matter% 12 Fatty acid% 54 * Calculation: Separated tall oil / tall oil soft soap x1
00%

Example 2 50 ml of water was used, to which 50 ml of 40% sulfuric acid was added.
The mixture was heated to 90 ° C and to it was added 200g tall oil soft soap at 45 ° C. This was mixed at 80 ° C. for 10 minutes and 90 ° C. for 15 minutes, after which the mixture was poured into a graduated cylinder. The layers were allowed to separate at 80 ° C. for 30 minutes and the tall oil could be decanted. The analysis results of tall oil thus obtained are as follows. Yield *% 55% Acid value mg KOH / g 150 Rosin acid% 35 Unsaponifiable matter% 12 Fatty acid% 53 * Calculation: Separated tall oil / tall oil soft soap x10
0%

The materials obtained in Examples 1 and 2 were subjected to gas chromatographic analysis. The column was a 25 meter quartz capillary column and used butanediol succinate liquid phase (BDS). Development was carried out isothermally at 197 ° C. The main components are as follows. Example 1 Example 2 9-C18: 1 (oleic acid) 14.6% 14.4% 9.12-C18: 2 (linoleic acid) 20.5% 19.9% abietic acid 13.1% 11. 7% Dehydroabietic acid 7% 7%

From the above results, it can be seen that when hydrochloric acid is used, tall oil is completely comparable in quality and yield to tall oil produced using sulfuric acid.

Example 3 34 ml of 37% hydrochloric acid was used, to which 34 ml of water was added. The mixture was heated to 90 ° C. 5 in this mixture
280 g of 0 ° C. tall oil soft soap was added. 90 this
After mixing for 30 minutes at 0 ° C., the mixture was poured into a graduated cylinder. The layers were allowed to separate at 90 ° C. for 60 minutes and the tall oil could be decanted. The analysis results of tall oil thus obtained are as follows. Yield *% 21 Acid value mg KOH / g 108 Water% 4.5 Rhosinic acid% 34 Unsaponifiables% 12 * Calculation: Separated tall oil / tall oil soft soap x10
0%

Example 4 34 ml of 37% hydrochloric acid was used, to which 34 ml of water was added.
The mixture was heated to 90 ° C. To this mixture was added 150 g tall oil soft soap at 50 ° C. This at 90 ℃ 3
After mixing for 0 minutes, the mixture was poured into a graduated cylinder. The layers were allowed to separate at 90 ° C. for 60 minutes and the tall oil could be decanted. The analysis results of tall oil thus obtained are as follows. Yield *% 37 Acid value mg KOH / g 149 Water% 1.5 Rosin acid% 32.7 Fatty acid% 51.4 Unsaponifiables% 15.9 * Calculation: Tall oil / Tall oil soft soap x10 separated
0%

The materials obtained in Examples 3 and 4 were subjected to gas chromatographic analysis. The column was a 25 meter quartz capillary column and used butanediol succinate liquid phase (BDS). Development was carried out isothermally at 197 ° C. The main components are as follows. Example 3 Example 4 9-C18: 1 (oleic acid) 14.3% 17.7% 9.12-C18: 2 (linoleic acid) 19.3% 24.7% abietic acid 11.6% 16. 0% Dehydroabietic acid 7.8% 5.9%

From the above results, varying the tall oil soft soap / hydrochloric acid ratio does not have a significant effect on the quality of the separated tall oil, but only on the layer separation rate. Recognize.

Example 5 34 ml of 37% hydrochloric acid was used, to which 34 ml of water was added. The acid mixture was heated to 60 ° C and to this was added 190 g of 50 ° C tall oil soft soap. This mixture at 60 ° C
After mixing for 30 minutes, it was poured into a graduated cylinder. The layers were allowed to separate for 75 minutes and the tall oil could be decanted. The analysis results of tall oil thus obtained are as follows. Yield *% 26 Acid value mg KOH / g 151 Rosin acid% 35 Unsaponifiable matter% 13 Fatty acid% 52 * Calculation: Tall oil / Tall oil soft soap x10 separated
0%

From this result, it can be seen that at the above-mentioned low temperature, the yield is lowered and the layer separation becomes more difficult.

Example 6 63 g of tall oil soft soap, 11.3 ml of 37% concentrated hydrochloric acid and 11.3 ml of water were used. The ingredients were placed in an autoclave and the temperature was raised to 170 ° C. The mixture was mixed at 170 ° C. for 30 minutes, then cooled and the separated tall oil was decanted. The analysis results of tall oil thus obtained are as follows. Yield *% 50 Acid value mg KOH / g 134 Rosinic acid% 32.9 Unsaponifiable matter% 14.7 Fatty acid% 52.4 * Calculation: Separated tall oil / tall oil soft soap x10
0%

The tall oil obtained by the method described in Examples 5 and 6 was subjected to gas chromatography analysis (BDS column, 197 ° C., isothermal development). The main components of tall oil are as follows. Example 5 Example 6 9-C18: 1 14.7% 13.9% 9.12-C18: 2 20.4% 18.2% Abietic acid 19.7% 18.8% Dehydroabietic acid 6.8 % 10.2%

Example 7 34 ml of 37% concentrated hydrochloric acid was used, to which 34 ml of water was added. The mixture was heated to 97 ° C. and 190 g of 50 ° C. tall oil soft soap was added. 30 at 97 ℃
After mixing for minutes, the mixture was poured into a graduated cylinder. After some time, the separated lignin and tall oil were decanted from the mother liquor water. The mixture was poured into a centrifuge tube and centrifuged at 5300 × g for 20 minutes.
The analysis results of tall oil thus obtained are as follows. Yield *% 47 Acid value mg KOH / g 152.5 Unsaponifiable matter% 13.2 * Calculation: Separated tall oil / tall oil soft soap *
100%

Based on gas chromatographic analysis (BDS column, 197 ° C., isothermal development), the main components of tall oil are as follows. 9-C18: 1 (oleic acid) 15.3
% 9.12-C18: 2 (linoleic acid) 14% abietic acid 25% dehydroabietic acid 7.8
%

Based on the results of the analysis, the properties of tall oil separated by centrifugation are excellent.

Example 8 63 g of soap, 11.3 ml of 37% concentrated hydrochloric acid and water 11.
3 ml was used. The ingredients were placed in an autoclave and the temperature was raised to 220 ° C. The pressure was 14 bar. The mixture was mixed at 220 ° C. for 30 minutes, then cooled and the separated tall oil was decanted. The analysis results of tall oil thus obtained are as follows. Yield *% 49 Acid value mg KOH / g 124 Rosin acid% 29 Unsaponifiable matter% 19 Fatty acid% 48 * Calculated value: Separated tall oil / tall oil soft soap x1
00%

The low acid number of the separated tall oil is apparently due to esterification or decarboxylation.

The tall oil obtained by the method of Example 8 was subjected to gas chromatographic analysis (BDS column, 1
97 ℃, isothermal development). The main components of tall oil are as follows. 9-C18: 1 (oleic acid) 15.5% 9.12-C18: 2 (linoleic acid) 15.5% abietic acid 11.3% dehydroabietic acid 15.9%

Based on the results of the gas chromatographic analysis, a difference comparable to the difference found in the early stage was found in the above-mentioned acid distribution at high temperature, resulting in isomerization of linoleic acid and abietic acid. Is expected.

Continuation of the front page (72) Inventor Rabaska, Matti Elias Finland S-F 90100 Ourse Pankatsu 9 Be 10

Claims (4)

[Claims] 1. A method for producing tall oil from tall oil soft soap by acidifying tall oil soft soap and separating the obtained tall oil, wherein the acidification is carried out using hydrochloric acid. A method for producing tall oil. 2. The acidification above comprises 60 ° C. to 220 ° C.,
The method according to claim 1, wherein the temperature is preferably 85 ° C to 100 ° C. 3. The acidification reaction is carried out at 100 ° C. under pressure.
The manufacturing method according to claim 1 or 2, wherein the manufacturing method is performed at a temperature higher than the above. 4. The process according to claim 1, wherein the tall oil obtained has an acid value of 100 to 160 mg KOH / g.