FI93868C - Manufacture of tall oil - Google Patents

Description

93868 Manufacture of tall oil - Framstälining av talloije

The invention relates to a process for the production of tall oil from pine feldspar formed as a by-product of the cellulose industry by acidifying pine soap and separating the tall oil thus obtained from its mother liquor and lignin.

As a by-product of the cellulose industry, valuable pine-10 soap is formed, which accumulates on the surface of the solution during the production of cellulose by concentrating the mother liquor, i.e. in connection with the evaporation of water. This soap is scraped off the surface of the tank and acidified to form tall oil. Tall oil is further distilled to give valuable resin and fatty acids as distillation fractions.

Chemically, the reaction is simple and, as sodium salts, the resin and fatty acids in the pine salt are reacted with sulfuric acid to form the corresponding carboxylic acids and sodium sulfate.

Sulfuric acid has hitherto been used for the acidification of pine soup, which is quite well suited for this purpose, since neutralized sulfuric acid may have been added to the chemical cycle of the cellulose mill. The resulting sodium sulfate was a useful supplement to compensate for sulfur losses in the cellulose process. Now, however, due to environmental restrictions, the pulp mills have reduced sulfur emissions so that the sulfuric acid used in the acidification of the pine cane can no longer be used to compensate for the significantly reduced sulfur losses of the pulp mill. For this reason, efforts have been made to develop alternative acidification options in the production of tall oil.

In the context of the present invention, it has surprisingly been found that monovalent hydrochloric acid can be used instead of divalent sulfuric acid for the acidification of pine clay. Hydrochloric acid is required for the same amount of pine soap as 2,93868 divalent sulfuric acids. Hydrochloric acid is inexpensive, readily available, and wastewater generated in hydrochloric acid acidification is more water-friendly than that generated in sulfuric acid acidification.

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Sulfuric acid and hydrochloric acid have almost similar corrosion properties. However, under certain conditions and at certain concentrations, sulfuric acid is more corrosive than hydrochloric acid, so the use of hydrochloric acid is therefore also recommended.

The essential features of the invention are set out in the appended claims.

As the hydrochloric acid, dilute, concentrated or gaseous hydrochloric acid can be used, as long as it is sufficient to neutralize the sodium salts of the fatty and resin acids in the pine feldspar. There are, of course, additional costs associated with overuse.

: Acidification of the pine felt is carried out in the temperature range 60 ° -220 ° C, preferably in the range 85 ° -100 ° C. At temperatures above 100 ° C, a pressure reaction is possible. The reaction time is not very important, but a suitable time was observed to be 10-30 minutes. No benefit was achieved in the longer term.

Variations in the quality of pine felt depend on the quality of wood used in the production of cellulose. When boiling pine alone, a benign pine soap is formed, from which the acid oil has an acid number of 140-160 mg KOH / g and a rosin acid content of • 30-50%. However, when birch is boiled, the quality of the sap changes so that the corresponding tall oil has an acid number of 100-120 mg KOH / g, even lower, and a rosin acid content of 20-30%.

35 Irrespective of the quality, hydrochloric acid can be used quite well in place of sulfuric acid in the acidification of pine soils.

3,93868

After acidification, the tall oil layer can be separated from the mother liquor and lignin layers either by allowing the layers to separate or by centrifuging them apart.

In the following, the invention will be illustrated by means of examples.

Example 1

42 ml of 37% hydrochloric acid were taken and 42 ml of water were added. The mixture was heated to 80 ° C. To this mixture, 190 g of pine soap at 50 ° C was gradually added. Stirred for 10 minutes at 80 ° C and 15 minutes at 90 ° C / after which the mixture was poured into a beaker. The layers were allowed to separate at 80 ° C for 30 minutes, after which the tall oil could be decanted apart. The analyzes of the tall oil thus obtained were 15% yield *% 57.5 acid number mg KOH / g 150 resin acids% 34. * 20 unsaponifiable% 12 fatty acids% 54 «Calculated: separated roe / pine soap * 100% 25

Example 2

50 ml of water were taken and 50 ml of 40% sulfuric acid was added. The mixture was heated to 90 ° C and 200 g of 45 ° C pine soap was added. After stirring for 10 minutes at 80 ° C and 15 minutes at 90 ° C, the mixture was poured into a beaker. The layers were allowed to separate at 80 ° C for 30 minutes, after which the tall oil could be decanted apart. The analyzes of the tall oil thus obtained were as follows: 4,93868 yield *% 55 acid number mg KOH / g 150 rosin acids% 35 saponified ton% 12 5 fatty acids% 53 ♦ Calculated: separated roe / pine soap * 100%

Examples 1 and 2 were subjected to gas chromatographic analysis; As a 10 column, a 25 m quartz capillary column butanediol succinate as liquid phase (BDS) was used. The run was performed isothermally at 197 ° C. The main components were:

Example 1 Example 2 9-C18: 1 14.6% 14.4% (oleic acid) 9.12-C18: 2 20.5% 19.9% (linoleic acid) * 20 abietic acid 13.1% 11.7% dehydroabietic acid 7% 7%

From the above results, it can be seen that when hydrochloric acid is used, both the quality and yield of tall oil are completely comparable to tall oil made with sulfuric acid.

Example 3

34 ml of 37% hydrochloric acid were taken and 34 ml of water were added. The mixture was heated to 90 ° C. To this mixture was gradually added 280 g of pine soap at 50 ° C. After stirring for 30 minutes at 90 ° C, the mixture was poured into a beaker. The layers were allowed to separate at 90 ° C for 60 minutes, after which the tall oil could be decanted apart. The analyzes of the tall oil thus obtained were as follows: 5,93868 yield *% 21 acid number mg KOH / g 108 water% 4/5 resin acids% 34 5 unsaponifiable% 12 ♦ Calculated: separated roe / pine soap * 100% 10 Example 4

34 ml of 37% hydrochloric acid were taken and 34 ml of water were added. The mixture was heated to 90 ° C and 150 g of 50 ° C pine soap was added. Stirred for 30 minutes at 90 ° C / after which the mixture was poured into a beaker. The layers were allowed to separate at 90 ° C for 60 minutes, after which the tall oil could be decanted off. The analyzes of the tall oil thus obtained were as follows: yield *% 37 20 acid number mg KOH / g 149 water% 1.5 resin acids% 32.7 fatty acids% 51.4 unsaponifiable% 15.9 25 ♦ Calculated: separated roe / pine soap * 100%

Examples 3 and 4 were subjected to gas chromatographic analysis; a 25 m quartz capillary column as butane diol succinate liquid phase (BDS) was used as the column. The run was performed isothermally at 197 ° C. The main components were: 6,93868

Example 3 Example 4 9-C18: 1 14.3% 17.7% (oleic acid) δ 9.12-C18: 2 19.3% 24.7% (linoleic acid) abietic acid 11.6% 16.0% dehydroabietic acid 7 .8% 5.9% 10 From the above results, it can be seen that the change in the soap / hydrochloric acid ratio does not greatly affect the quality of the tall oil separated, only the rate of separation of the layers.

15 Example 5

34 ml of 37% hydrochloric acid were taken and 34 ml of water were added. The acid mixture was heated to 60 ° C and 190 g of 50 ° C pine soap was added to the mixture. After stirring for 30 minutes at 60 ° C, the mixture was poured into a beaker. Layers were allowed to separate for 75 minutes, after which the tall oil could be decanted off. The analyzes of the tall oil thus obtained were as follows: yield *% 26 25 acid number mg KOH / g 151 resin acids% 35 unsaponifiable% 13 fatty acids% 52 30 * Calculation separated mö / pine soap * 100% ·. It can be seen from the results that at such a low temperature the yield decreases and the separation of the layers becomes more difficult.

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Example 6

63 g of soap and 11.3 ml of conc. 37% hydrochloric acid and 11.3 ml of water. The ingredients were placed in an autoclave and the heat was raised to 170 ° C. After stirring for 30 minutes at 5,170 ° C, the mixture was allowed to cool and the separated tall oil was decanted off. The analyzes of the pine oil thus obtained were as follows: yield *% 50 10 acid number mg KOH / g 134 resin acids% 32.9 unsaponifiable% 14.7 fatty acids% 52.4 15 * Calculated: separated mö / pine soap * 100%

The tall oil obtained according to Examples 5 and 6 was subjected to gas chromatographic analysis (BDS column, 197 ° C, isothermal run). The main components of tall oil were:

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 conc. 37% hydrochloric acid and 34 ml of water were added thereto. The mixture was heated to 97 ° C and> 190 g of 50 ° C pine soap was added. After stirring for 30 minutes at 97 ° C, the mixture was poured into a beaker and after a while the separated lignin and pine-35 oil layer were separated from the mother liquor. The mixture was poured into a centrifuge tube and centrifuged at 5300 x g for 20 minutes. The analyzes of the tall oil thus obtained were as follows: 93868 8 yield *% 47 acid number mg KOH / g 152.5 unsaponifiable% 13.2 5 * Calculated: separated roe / pine soap * 100%

Based on gas chromatographic analysis (BDS column, 197 ° C, isothermal run), the main components of tall oil were: 10 9-C18: 1 15.3% (oleic acid) 9.12-018: 2 14% (linoleic acid) 15 abietic acid 25% dehydroabietic acid 7 .8%

Based on the analyzes, the tall oil separated by centrifugation is also of good quality.

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Example 8

63 g of soap and 11.3 ml of conc. 37% hydrochloric acid and 11.3 ml of water. The ingredients were placed in an autoclave and the heat was raised to 220 ° C; then the pressure was 14 bar. After stirring for 30 minutes at 220 ° C, the mixture was allowed to cool and the separated tall oil was decanted off. The analyzes of the tall oil thus obtained were as follows: 30 yield *% 49 acid number mg KOH / g 124 resin acids% 29 unsaponifiable% 19 fatty acids% 48 ♦ Calculated: separated mö / pine soap * 100% 35 9 93868

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

The tall oil obtained according to Example 8 was subjected to gas-5 chromatographic analysis (BDS column, 197 ° C, isothermal run). The main components of tall oil were: 9-C18: 1 15.5% (oleic acid) 10 9.12-C18: 2 15.5% (linoleic acid) abietic acid 11.3% dehydroabietic acid 15.9% 15

On the basis of gas chromatographic analysis, it appears that differences in acid distributions are beginning to appear at this high temperature; isomerization of linoleic and abietic acid occurs.

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Claims (4)

93868 1. A process for the production of tall oil from soft tallow oil by acidification of soft tallow oil and by separation of the thus obtained tail oil, characterized in that the acidification is carried out with hydrochloric acid. 1. Menetelmä mentölyn valmistamiseksi mäntysuovasta ha-potamalla mäntysuopa ja erottamalla näin saatu mentöly, tunnettu siitä, etä hapotus suoritetaan suolahapolla. 5 Process according to claim 1, characterized in that the acidification is carried out at 60 to 220 ° C, preferably at 85 to 100 ° C. 2. Patenttivaatimuksen 1 mukainen menetelmä, tunnettu siitä, etä hapotus suoritetaan appropriate pulp tillillä 60 ° ja 220 ° C, edullisesti velillä 85 ° ja 100 ° C. Process according to Claim 1 or 2, characterized in that the acidification reaction is carried out under conditions of elevated pressure at a temperature above 100 ° C. 30 3. Patenttivaatimuksen 1 tai 2 mukainen menetelmä, thinet tu siitä, etä hapotus reactio suoritetaan yli 100 ° C: n suitable pettilassa paineen alaisena. 4. Patenttivaatimuksen 1 mukainen menetelmä, tunnettu sii-tä, one such men's oil gel happoluku on 100-160 mg KOH / g. 4. A process according to claim 1, characterized in that the acid number of the thus obtained tallow iron is 100 to 160 mg KOH / g.