DE2040087C - Process for improving the color and smell of tallol resin acids - Google Patents

Description

and saturated fat, which have higher volatility than tall oil resin (which consists mainly of abietic and pimaric acids), as head products to be collected. The Taüölharz distillate fraction is removed as an intermediate cut. The pitch fraction consists essentially of non-distillable Compounds with a significantly lower volatility than tall oil resin and remains as a residue back.

It is important that the tall oil resin distillate fraction contains essentially no more than about 10 weight percent tall oil fatty acids. When the stake of the fatty acids increases above about 10%, then the heat treatment converts a considerable part of this Fettsäuisn in non-distillable compounds, soft a significantly lower volatility than that Have tall oil resin, resulting in product loss. When the pitch fraction is present during the heat treatment as it is during the heat treatment is the case of crude tall oil, then the removal of the color and odor in the End product lower than if a tall oil resin desullate fraction, from which the pitch fraction has been removed, is heat-treated.

The purpose of the heating step is to remove the colored and odorous substances in the resin distillate to bring into a form that can be easily separated from the tall oil resin distillate fraction. The odorous bodies are unknown, but have a pronounced odor of mercaptans and other sulfur compounds. The color bodies are not yet in terms of their composition have been examined, but they contribute in a defined manner to the dark, blackish appearance of the crude tall oil and the resin fraction.

When heated, the coloring and odorous substances are transformed into heavy ends, which have a considerably lower volatility than the tall oil resin distillate fraction. The term "considerably lower volatility" should be understood to mean that the vapor pressure of the heavy ends at the same temperature is considerably lower than that of the tall oil resin. So come z. B. the heavy ends are not present as a significant part of the overhead fraction if the temperature is increased to about 350 ° C. during the separation stage, ie during the distillation at a pressure of 10 mm Hg. In contrast, the tall oil rosin will appear as top fraction at a pressure of 1 to 10 mm Hg at a temperature from 200 to 280 ⁰ C.

The heating of the resin distillate is carried out for a sufficient time and at a sufficiently high temperature that a considerable part of the colored and odorous bodies is converted into heavy ends. The time and temperature parameters are essentially inversely proportional to one another during heating. For example, when the resin acids fraction is heated to a temperature of 200 ⁰ C, then a period of 20 hours may be required, while is required upon heating at a temperature of about 300 ° C, a period of from 1 to 3 hours. The essence of the heating cycle is to transfer a sufficient amount of the color and odorous bodies into heavy ends, so that only a small amount of these bodies is carried over into the resin acid fraction. Therefore, after the separation, the resin has a very little color and a very little odor. The preferred conditions for the heating cycle are about 240 to 280 ⁰ C and about 2 to

ίο 8 hours.

When heating the tall oil resin distillate, as described in the second stage, it is preferred keeping the batch in a substantially inert environment. Under a »essentially

is inert environment "should be understood that the surrounding atmosphere is essentially free of oxygen and other reactive gases. As is well known Oxygen has a tendency to react with "tall oil resin distillate, resulting in products which give the resin a darker color. Other compounds or impurities as well can react with the tall oil resin, resulting in poorer products. To avoid these problems it is

»5 therefore much better, the system with nitrogen gas to purge or hold a nitrogen blanket over the tall oil resin distillate fraction.

After the heat treatment step, the tall oil resin is separated from the converted coloring and odorous substances, ie the heavy ends. This is preferably done by distillation at a temperature of about 200 to 280 ⁰ C and at a pressure of 1 to 10 mm Hg. The distillate is a tall oil rosin having reduced staining and reduced with! Smell won. The heavy ends encompass the converted coloring and odorous matter and are separated as bottoms or residue. Essentially, the bottoms contain about 15 to 12 percent by weight of the charge (resin distillate).

The tall oil resin acids treated according to the invention are suitable, for example, as sizing or finishing agents for paper manufacture.
The invention is illustrated in the examples.

In the absence of any information to the contrary, all parts are

Parts by weight. ... ,,
example 1

Crude tall oil was dried and vacuum distilled using resin, tajl oil fatty acids and pitch

Fractions were separated. The tall oil barz distillate fraction contained about 6% fatty acids and essentially no bad luck. It was rated for its smell, color, and acid number examined. The tall oil resin distillate fraction was heated to 215 ° C. for 18 hours with slow stirring heated. A nitrogen gas blanket was maintained over the reaction vessel. After the After heat treatment, the resin distillate was vacuum distilled. The distillate containing the resin was rated. The following results were obtained:

G-H staining odor Acid number Residue Tall oil resin distillate (TÖHD)
Increase Tall oil rosin (18 hours at 215 ⁰ C) 8 to 9
5 very strong
small amount 174.7
181.0 5.4%

The following abbreviations are used in this and the following examples:

1. TÖHD means a heated tall oil resin distillate fraction, obtained from the distillation of crude tall oil.

2nd increase Tall oil resin means the heat-treated tall oil resin distillate fraction which is subsequently distilled and from which the heavy ends were removed.

3. The G-H color refers to the Gardner Hellige 1933 Standard Color Scale.

4. The residue means the residue after the tall oil resin has been separated off from the heavy ends and is given as percent by weight of the TÖHD added.
S.

Example 2

The procedure of Example 1 was repeated except that slightly different ίο Conditions of the heat treatment have been worked.

G-H staining odor Sour ahl Residue TÖHD 8 to 9
3 very strong
none 174.7
170.8 Increase Tall oil rosin (20 hours at 250 ⁰ C) 12.2%

example

The procedure of Example 1 was repeated except that under slightly different conditions the heat treatment has been carried out.

280 ° Q G-H staining odor Acid: iahl Residue TÖHD 8 to 9
4th very strong
very low 174.7
177.5 ₆ - _{0 / a} Increase Tall oil resin (1 hour at

example

The procedure of Example 1 was repeated except that under slightly different conditions the heat treatment has been carried out.

G-H coloring odor Acidicahl Residue TÖHD 8 to 9
3 to 4 very strong
none 174.3
174.5 8.5 *% Increase Tall oil rosin (3 hours at 280 ⁰ C)

Example 5

Crude tall oil was ^{heat treated for 2 hours at 280 °} C. and distilled to remove the rosin and tall oil fatty acids fraction from the pitch and heavy ends. The tall oil resin was then obtained by distilling the tall oil resin-tall oil fatty acids fraction. A similar portion of the crude tall oil was first distilled, removing the tall oil resin acid fraction. This TaIlölharz distillate fraction containing 7% tall oil fatty acids containing, for 2 hours at 280 ⁰ C was heated and distilled

Looking into it, Erh. crude tall oil a heat-treated crude tall oil means which has been distilled and from which the tall oil resin fraction away.

G-H staining odor

Sttureitahl

Residue

Raw tall oil used as a batch

Increase crude tall oil (2 hours at 280 ⁰ C)

Increase Tall oil distillate (2 hours at 280 ⁰ C)

17 to 7 very strong

strict / moderate

none

166.2
177.4
177.4

20.4%
6.58%

The above table therefore shows the importance of odor and a color of 4 obtained. In addition Separation of the tall oil resin from the pitch and the 65 in comparison is a resin product which has a Tall oil fatty acids from the crude tall oil. With a strong to moderate odor and a coloration of 7 Separation and treatment, as appropriate, obtained by heating crude tall oil Invention ensued, a product was made with none.

Example 6

Crude tall oil was separated according to Example 1. The distilled tall oil resin fraction was based on in the presence of 0.03 weight percent iodine the batch, heated.

G-H-
coloring odor Back
was standing TÖHD ... 8 to 9
4th very
strong
lower /
none Increase Tall oil resin with
0.03 ⁰ Z ₀ JOd ₈
(2 hours at 235 ° C) .... 4.2%

Example 7

Similar samples 1, 2 and 3 were taken of crude tall oil. The sample 1 was placed in a flask in this way and heated ^{to a temperature of 260 ° C. under nitrogen for 6 hours.} At the end of the 6 hour period, the heat treated crude tall oil was transferred to a stripping unit operated at 10 mm Hg and a temperature of 300 ° C to separate the tall oil resin-tall oil fatty acid product from the residual pitch. A residue of 22.5% by weight of the crude tall oil originally used as a batch was obtained. The distillate fraction was then transferred to a fractionation column for separation into a tall oil fatty acid top cut and a tall oil resin distillate cut with less than 10% fatty acids. The tall oil resin distillate had a Gardner coloration of 3 and had a moderate odor which was readily noticeable.

Samples 2 and 3 were mixed and transferred to a stripping unit which was operated under the same conditions as the above. It became a completely distilled. Tall oil (ie a tall oil resin and a tall oil fatty acid fraction) and a pitch residue are obtained. The pitch residue constituted 15% by weight of the crude tall oil added. All of the distilled tall oil was then divided into two equal parts, Samples 4 and 5. The sample 4 was transferred to a vessel and heat treated 6 hours under nitrogen at a temperature of 26O ⁰ C. The heat treated product was then transferred to a fractionation column to separate the heavy ends formed during the heat treatment from the tall oil fatty acids and tall oil resin. The heavy ends produced as residue accounted for 8.4 percent by weight of the crude tall oil fed. The distillate was then fractionally distilled in a distillation column. This was operated at the same temperatures as the column that was used in the above procedure to contain the Taflölharz distillate product. The tall oil resin product obtained had a moderate odor which was readily perceptible and had a G ard η er coloration of 3. There were losses of 23.4 percent by weight of the crude tall oil used as the starting product.

The sample S was placed in a fractionation column transferred, which was operated under the same conditions as the fractional distillation column in the above process measures. After the distillation, a tall oil resin distillate fraction was obtained. The resin distillate contained 4 Ge weight percent tall oil fatty acids. The pitch fraction was removed from it by previous distillation been. The resin distillate fraction was transferred to a vessel and under nitrogen for 6 hours heat-treated at a temperature of 260 ° C, as happened in the other heat treatments was. The heat-treated product was then put into one under the same conditions as above operated stripper unit to the heavier formed during the heat treatment process Remove ends from the tall oil resin. It became a slightly colored tall oil resin with a color after G a r d η e r of 3, which was essentially odorless, was obtained. The residue was 2 percent by weight of the crude tall oil originally used. There were losses of 17 percent by weight of the crude tall oil used as the starting material in the form of residues.

Comparative example

It was made of three samples of the same size, which are designated as Sample 1, Sample 2 and Sample 3) were assumed.

Sample 1 was initially under nitrogen! Heated to a temperature of 260 ^° C. for 6 hours. This heat treated crude tall oil was then passed into a pitch removal unit to separate the volatile materials from the pitch residue. The pitch residue accounted for 22.5% of the original crude tall oil. The distillate obtained was then transferred to a distillation column in order to carry out a separation into a top cut from fatty acids, a cut from distilled tall oil and a cut from resin acids. The tall oil resin product had a Gardner color of 3 and exhibited a moderate odor which was readily noticeable.

Samples 2 and 3 were mixed and placed in a pitch remover used in the same Temperature and at the same pressure as above. In this way it became a distillate obtained from all of the distilled tall oil and a pitch fraction. The pitch residue was 15 percent by weight of the crude tall oil used. The all of the distilled tall oil was then split into two equal parts, namely sample 4 and sample 5, divided.

The Sample 4 was 6 hours under nitrogen aui a temperature of 260 ⁰ C is heated, then in a stripper is introduced, whereby a fraction of fatty acids, resin and distilled tall oil (DTO fraction) were obtained as distillate and a pitch residue as the distillation residue. The pitch residue accounted for 8.4% of the crude tall oil introduced. The distillate was then transferred to a fractional distillation column, which was operated at the same temperature as the fractional distillation column with sample 1. This Taflole resin product had a moderate odor which was readily perceptible. The Gardner stain was 3.

Sample S was placed in the same fractional distillation column and distilled at the same temperature as Sample 4. In this way, a fatty acid, a distilled tall oil and a resin cut were obtained. This resin cut contained 4 ⁴ V ₁

309629/33

9 10

Fatty acids and was found under nitrogen on a resinous product which shows a moderate odor.

Temperature of 260 ⁰ C 6 hours as the samples 1 2. A completely distilled tall oil, which has a substantial

and 4 heated. The heat-treated resin was borrowed from tall oil fatty acids, yields when

placed in a pitch remover, which with the same 6-hour heat treatment under nitrogen

Chen temperature was operated as above. At 5 260 ⁰ C a loss as a residue of 23.4 weight

In this way, a light-colored resin was made with a percentage of the original starting material.

Gardner number of 3 obtained, the essentially set crude tall oil and yields a resin product,

was odorless. This residue made 2 weight- which shows a moderate odor. 3. A tall oil resin

percent of the initial crude tall oil. Distillate fraction obtained by fractional distillation

The above values show: io of a completely distilled tall oil with 4% fatty acids

was obtained, results in a 6 hour

1. Crude tall oil yields when there is a nitrogen at a temperature of 26O ⁰ C heated for 6 hours under heat treatment under nitrogen at 26O ⁰ C loss as a residue of 17 percent by weight of is, a product loss of 22.5 wt supplied as the starting material crude tall oil and percent of the crude tall oil and a resin product, 15 provides a tall oil resin product having essentially that of a moderate odor. no smell.

2. A total of distilled tall oil results if the above explanations can be seen heated under nitrogen for 6 hours at 260 ° C lent that the long heat treatment stage is preceded, a product loss of 23.4%, preferably between 2 to 8 hours, as in accordance with originally introduced crude tall oil and 20 of the invention takes place, basically the heating of a a resin product that exhibits a moderate odor to at least significant tall oil resin distillate fraction, borrowed removal of a faction that was a tall oil pitch

3. A resin acid fraction, which results from a total (an undistillable residue) and to Distilled tall oil with 4% fatty acids has been used to remove significant amounts of the tall oil fat which has been fractionally distilled as acid fraction (essentially not more than 10 Ge in the 6-hour heat treatment, weight percent of the distillate fraction). It is also verunter Nitrogen a product loss of 17 Understandably that the presence of small amounts weight percentage of the originally crude tall oil from conventional rubber resins and from and a resin product containing essentially crude tall oil agents such as iodine, boron Odor has 3 ° oxides, phosphorus compounds in the heat treatment of the tall oil resin distillate fraction (under the

The above examples show the following: 1. Raw assumption that they are achieving good

Tall oil essentially does not produce any color or odor results when subjected to heat treatment in the east

disturb under nitrogen at a temperature of 260 ° C) are permitted, although they are used to obtain a

a loss in the form of residues of 22.5 g of tall oil resin with very good color and one very

weight percent of the crude tall oil and provides a tall oil-low odor are not necessary.

Claims (1)

1 2 Claim · Product to be treated in order to make it suitable for papermaking. Processes for improving the color and the color, but these documents only describe Odors of tall oil resin acids, which no longer allow the treatment of mixtures containing tall oil resin than 10 percent by weight of fatty acids, based on 5, but which do not contain the resin component which contain ... resin acids, are thereby identified. Treatment of tall oil resin zetchnet that the resin acids 1 to acids which do not contain more than 10% fatty acids Hold for 20 hours at a temperature of 200 to, but is not described there or near- about 300 ° C placed in an inert atmosphere heat-treated. and then the resin acids from the selected io Further processes are used in the Swedish rend of warming, formed severe end. Patent 92 743 and in the Chemisches Zentralblatt products separated by distillation 1961, p. 1.053, described. These procedures speak, however, regarding their conduct of the proceedings the above procedures. The invention relates to a method for improving the color and smell of tall oil resin 82 372 is first separated by centrifugation, a resin acid, which no more than 10 percent by weight residue, whereupon, the residue with fatty acids , based on the resin acids. extracted with a solvent. According to the German patent I OU 550, tall oil resin is the main component of the known tall oil resin, which is a by-product of certain acids that are added to a part of the sulphate process in papermaking. to cause the crude oil to precipitate. Other constituents of the crude tall oil are pitch. However, with regard to the ver tall oil fatty acids, stearins and the like. which is largely due to the presence of heavy 25 The invention is therefore based on the object Gel compounds, such as mercaptans, are attributed to a tall oil resin with significantly reduced color and is. The coloring is mainly due to the present with considerably reduced odor from a tall oil attributed to bad luck. In the case of the known resin distillate with odor and color bodies drive to purification of crude tall oil to tall oil - minimal product losses in the form of no Resins were used to obtain the residues that could be distilled through the coloring and odorous bodies 30, conditional odor and color in the finished tall oil- This object is achieved according to the invention resin product transferred. solved that the distillate fraction is long enough One of the basic methods of cleaning is being heated to a high enough temperature of crude tall oil to form a purified tall oil- at least a significant part of the coloring and resin with diminished coloring and diminished odorous body in heavy ends with a lower Odor consisted in heating the crude tall oil as the distillate fraction and that volatility about 1 to 15 hours at a temperature between getting the distillate fraction from the heavy ends has heated about 225 to 300 ⁰ C, whereupon the separated off, whereby a tall oil resin with reduced heat-treated product is distilled and the tall oil color and with reduced odor is obtained, resin has separated. Another procedure consisted of 40 A preferred embodiment of the appointment therein, a tall oil distillate, the resin and fatty acid according to the process is characterized contained and obtained from crude tall oil that the separation of the distillate fraction from the was to subject a heat treatment by making heavy ends by distillation, only the volatile components, d. H. the tall oil- Another advantageous embodiment of the resin and the tall oil fatty acids from the pitch fraction 45. were distilled off. After the heat treatment draws that one is heating the distillate fraction of the distillate and after the distillation, an essentially inert environment was Tall oil resin with a decreased coloration and one leads. get reduced odor. In this procedure, finally, a further embodiment of the However, significant losses occur in the form of return 50 method according to the invention characterized thereby- stand on what to the polymerization and the net, that you get the distillate fraction for about 2 to 8 hours Final carboxylation of the heat-sensitive tall oil to a temperature between about 42 and 82 ° C Fatty acids. Because of this product- heated. Losses increase the cost of manufacturing. B. the following advantages purified tall oil resin. 55 a: It provides a simple and inexpensive method U.S. Patent 3,377,333 teaches the manufacture of tall oil resin with reduced coloration Treatment of a distilled tall oil described, and reduced odor, whereby the by the distillation in the presence of phenol- the formation of non-distillable compounds sulfide is carried out. Subject of the USA .-- (heavy ends) contingent losses during the Patent specification 3,396,182 describes a process for the heat treatment of the distillate fraction Reduction of the odor and color of tall oil products. Fatty acids. In US Pat. No. 2,143,344, a tall oil resin distillate fraction is described in a general manner under the designation “tall oil resin distillate fraction, a process for the distillation of liquids in tion”. The distillation of stand are made by distillation of crude Resin fatty acids is only marginally obtained in it. This stage is preferred mentioned. In U5A.-Patent 2143 345 it is carried out in such a way that crude tall oil fraction describes a process for the purification of tall oil, is niert-distilled, whereby the tall oil fatty acids, in which the raw resin soaps and the fatty acid z. B. linoleic, oleic, palmitic acid, the hydroxy acids