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    • 专利摘要:
    A process for recovering fatty acids and/or rosin acid with a high purity which comprises first introducing a tall oil skimming soap or a tall oil soap into a thin film evaporator equipped with a rake in which the clearance between the blade tips and the surrounding evaporator wall is zero or not more than 1 mm, heating the same at a temperature higher than the melting point of the soap contained therein to evaporate and remove water and unsaponifiables, and then adding an alkali to the thus obtained crude soap to saponify the same, thereby decomposing the esters of rosin acid and fatty acids with sterols and other alcohols; or first saponifying a tall oil skimming soap or a tall oil soap with an alkali to decompose esters of rosin acid and fatty acids with sterols and other alcohols, and then introducing the thus obtained saponification product to the above-said thin film evaporator equipped with a rake, heating the same at a temperature higher than the melting point of the soap contained therein to evaporate and remove water and unsaponifiables; followed by subjecting the resultant saponification product to acid decomposition and distillation, thereby obtaining the desired fatty acids and/or rosin acid. In the above process, it is possible to recover not only the high purity fatty acids and/or rosin acid but also sterols by introducing, prior to the acid decomposition, the saponification product into the above-mentioned thin film evaporator equipped with a rake and then heating the same at a temperature higher than the melting point of the soap contained therein to evaporate and separate sterols and heavy unsaponifiable matters.
    公开号:SU873891A3
    申请号:SU762403405
    申请日:1976-09-22
    公开日:1981-10-15
    发明作者:Харада Тецуя；Юмото Тунемаса
    申请人:Джапан Синтетик Рабеер Ко.Лтд.(Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR ISOLATING FATTY AND RESINS The invention relates to an improved method for separating fatty acids and resinous acids from soap, which is formed in the manufacture of kraft pulp. Various methods are known for the isolation of fatty and resin acids from stripping soaps, which are sodium soaps mixed with layered ethers of higher alcohols and steroids. Depending on the type and sequence of processing of the soap, different results are achieved in terms of the yield and purity of the resulting fatty and resin acids. Thus, in some cases, resinous and fatty soaps separated from black liquor (removed tall soap) are washed with a solution of sodium sulphate to free them from lignin and other impurities, and then decomposed (washed with water, filtered and injected in 20-50%). sulfuric acid) at a pH of not higher than 6. Next, after settling (4-5 hours), the oil is washed until neutral and receive up to 50% tall oil oil (from the soap used). To separate the latter with the release of various products of fatty and resin acids, as well as other substances. ACID is subjected to distillation, distillation, rectification. In some cases, crude tallow oil is purified by treatment with various solvents, for example, gasoline, hydroxy acids are separated, and treatment of the gasoline solution with hydrogen chloride or chlorine removes the contamination 1. The closest technical solution to the proposed method is to isolate fatty acids. acid and resin acids from stripped tall soap by decomposing it in a solution of 5% sulfuric acid, followed by a stepwise evaporation of the resulting crude tall oil, after the first of the vaporizer light fraction i.vody. The resulting residue is transferred to a second evaporator, in which the pitch is separated, and the vapor phase, containing fatty and resin acids, is then separated by distillate. Tie 2. However, in this scheme for the isolation of fatty and resin acids, by directly converting the removed tall soap into acids, it is possible to form from them both higher alcohols and sterol esters, which leads to a reduction in the yield of fatty and resin acids. These esters, which are at the interface, as well as sodium sulfate, which is formed after acidification, create difficulties in separating the aqueous and oil phases. In addition, crude tall oil contains a large amount of heavy hydrocarbons, which, having a boiling point close to fatty acid and baking, necessitate large quantities of evaporation stages under reduced pressure, which entails high energy costs. The aim of the invention is to increase the yield and purity of the fatty and resin acids recovered from the removed tall soap. The goal is achieved by the proposed method, in which the removed tall soap is subjected to simultaneous saponification and isomerization with alkali, taken in an amount 1.2–3.5 times the theoretical, at a temperature of 120-210 ° С and a pressure of 1-5 atm in the presence of 2,2-thiobis (4-methyl-b-tert-butylphenol) followed by a three-stage thin-film evaporation of the saponification and isomerization, with a first stage separation at the melting point of soap or higher not more than and pressure of 10-50 mmHg. water and light unwashed products; at the second — at a temperature from the melting point of soap to 320 ° C and a pressure of 3-5 mm Hg. heavy unwashed products containing higher alcohols, and a third at 320-350 ° C and a pressure of 0.1-1 mm Hg. the residual soap thus obtained is subjected to sulfuric acid decomposition with the separation of an oily product (tall oil), which is further directed to a two-stage separation with a high boiling fraction and water at the first stage and a second product resin acids, and in the form of head products fatty acids. This provides greater output; and better quality, target fatty acids, and resin acids, better separation of sitosterol and other unwashed substances that affect the quality of the target acids. In addition, the soap supplied for sulfuric acid decomposition does not contain impurities of ester of higher alcohols, sterols, and, consequently, there are no difficulties with the separation of water and oil phase formed during the treatment with 5% sulfuric acid, and also soap does not contain impurity )}, having a point to neither close to liberated fatty resinous acids. In the examples, the removed tall fuel containing 45% by weight of water is used as the starting material. FIG. 1 and 2 show schemes for implementing the method, variants. Example 1. The implementation is carried out according to scheme 1. The calculation of the amount of alkali required for saponification and isomerization of that tall soap containing wt.% Of water. The acid number of the total soap is 125.0 mg KOH / g, a saponification layer of tall oil embedded in the removed tall soap 4, 6 mg KOH / H. The number of saponification of complex high-yarns of tall oil 144.65-19, 6 mg KOH / H. For example, the original stripped tall soap contains 5.64 kg of tall tall by 10 kg. Supply of a stripped tam12733, 5 g / h of molten soap Fatty acid content in the form of ester 3.7 wt.% With alcohol or 475.8 g / h sterol. Content of resin acid in the form of ester with alcohol or 0.4 weight. % Sterol 52.6 g / h Approximate molecular weight of fatty acid 280 Approximate molecular weight of resin acid 310.5 NaOH requirement for saponification of fatty acid acid and hydroxylic acid 5.8x esters | § 52.6 X 68.0+ 6.8 4.8 g NaOH / h 25.1 wt.% Soap content 3206.3 g / h of resin acid 14.5 wt.% Soap content 1858.5 g / h fatty acid 2.8 wt.% Content Soap 357.3 g / hydroxy acid 40 in Soaps 3206.3 g / h to -,;: + -H 1858.5 x + 357.3 x § 383.4 + 244.0 +47.0674, 4 g NaOH / h during saponification esters and -milk 74.8 + 674.4 749.2 g NaOH / h 749.2 X 1.2 899.0 g NaOH / h 899.0 - 674.4 224.6 g / h Consequently, there must be 499.1 g of 45% NaOH, in which is kept 224.6 g of NaOH. This is 1.2 times higher than the required equivalent amount for the saponification of the fatty, resin, and hydroxy-acid esters present in the tall tamper vstsaie, Na-soap of the indicated acids and NaOH in the soaps. The process is as follows. 12733.5 g / h of removed tall soap are concentrated (remove 5282.7 g / h of water) in apparatus 2. Then 499.1 g / h of a 45% aqueous solution of sodium hydroxide, 65.2, are added to the concentrate. The g / h of disproportionation catalyst is 2,2-thiobis- (4-methyl-6-tert-butylphenol), and the mixture is held at 2 hours in reactor 2 for saponification and isomerization. After that, the mixture is introduced into a thin-film evaporator 1tel, in which there is no gap between the blade and the wall and the surface area is 0.3 m and evaporation is carried out at a reduced pressure of 25 rm. Art. and 240-260 ° C with release of low-boiling unwashed and water through line 4 directed to separator 5. The number of low-boiling neumalized products is 297.6 g / h and water is 812.1 g / h after evaporation. Next, the molten soap enters the evaporator 6, where there is no gap between the blade and the wall and the surface area is 0.1 m. The evaporation process is performed under a reduced pressure of 2 mm Hg. and 270-300 ° C, as a result of which the 363.4 g / h fraction of the heavy unwashed fractions containing higher alcohol 7 is distilled off. The residue is then sent along line 8 to the evaporator 9, in which there is no gap between the blade and the wall and the area the surface is 0.1 m-. Evaporation is carried out under reduced pressure of 0.1 mm Hg. when separating the sterol 10. Soaps drawn from the bottom of the evaporator 9 are subjected to sulfuric acid decomposition in apparatus 11 (1460.9 g / h with 98% H, and 1460.9 g / h H.) with an aqueous solution. and then, in apparatus 12, the aqueous and oil layers are separated. The latter is a mixture of acidic products 13 (tall oil) of non-washed products. From the resulting acidic product at a pressure of 10 mm Hg. in column 14, 528.5 g / h of heavy fractions 15 containing relatively high boiling point hydroxy acids (which accelerate the polymerization of resin acid and fatty acids) are distilled off. The mixture of acid vapors 16, from which the heavy fraction was removed, is sent to the distillation column 17, the process is carried out at a pressure of 30 mm from the bottom of the column and at a pressure of 5. mm Hg. 2843.2 g / h of resin acids 18 with a high degree of purity are taken from the bottom of the column 17, and 110.7 g / h of palmitic acid (a, acids-19) with a high degree of purity are recovered from the top of the column, boiling it at a pressure of 5 mm Hg, an intermediate fraction 20, (1837.0 g / h) consisting mainly of fatty acid, which is purified in a separate distillation column, is obtained as the shoulder strap collected from the top plate of the column. The processors are first carried out at a pressure of 60 mm Hg. the top of the column and then at a pressure of 5 mm Hg. top of the column. From the top of the distillation column 21, 1695.5 g / h of fatty acid 22 with a high degree of purity is obtained, 137 g / h of the mixture of acids 23 is taken from the bottom of the column 21. The content of abietic acid in fatty acid is 1% or less, i.e. the reaction was almost complete disproportionation. In addition, the amount of acid with conjugated ddo bonds in the fatty acid is.49%, which indicates the past isomerization reaction. The content of palmitic acid 80% or more. Losses 479.2 g / h. Example 2 (comparative). The implementation is carried out according to Scheme 2. 12773.5 g / h of removed tall soap 1 is acidified with. (98%. 1095.9 g / h + 1095.9 g / h) in a sulfuric acid decomposition reactor 2, then settled, after which the water and oil layers are separated in separator 3. 6320.0 g / crude tall oil 4. Crude tall oil 4 is heated (and 10 mm Hg) in a stripping column 5, where 6 resin and fatty acids (their amounts cannot be determined) are taken from the top of the column, and from the bottom of the column Puff 7, containing esters. Next, in distillation column 8, 2780.0 g / h of resin acid 9 are removed from the bottom of the column, and low-boiling overhead product 10 is distilled off from the top of the column in the amount of 114 g / h (456, 25 uncleanable) and from the middle part of the column. The fraction (1201 g / h) with a boiling point of 223 ° C / 8 mm Hg containing fatty acids is isolated 11. Then this fraction is heated at 240 ° C and a pressure of 15 mm Hg. bottom and pressure of 7 mm Hg. the top of the column in the stripping column 12 for distilling off the remaining light boilers of product 13 and then subjected to rectification at a pressure of 30 mm Hg. bottom of the column in a distillation column 12 fatty acids; C get from the top of the column 1043 g / h of fatty acid 14. Containing
    权利要求:
    Claims (1)
    [1]
    Claim
    The method of separation of fatty and resin acids from tall soap, obtained in the production of kraft cellulose using sulfuric acid decomposition, separation of tall oil, stepwise evaporation and distillation with the release of fatty and resin acids, characterized in that, in order to increase the yield and purity of the target products, the original removed tall soap is subjected to saponification and isomerization in the presence of a catalyst of 2,2-thiobis- (4-methyl-6-tert-butylphenol) using alkali, taken in an amount exceeding 1.2-3.5 times the theoretical, At 120–210 ° С and a pressure of 1–5 atm, followed by a three-stage thin-film evaporation of the saponification and isomerization product with isolation at the first stage at a soap melting point or higher of no more than 50 ° С and a pressure of 10–50 mm Hg. Art. water and light unsaponifiable products, in the second stage at a temperature from the melting point of soap to 320 ° C and a pressure of 3-5 mm Hg heavy unsaponifiable products, including heavy alcohols, and the third at 320-350 ° C and a pressure of 0.1-1 mm Hg sterols and the direction of the remaining soap to the stage of sulfuric acid decomposition.
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    同族专利:
    公开号 | 公开日
    DE2642414B2|1981-04-23|
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    SE429445B|1983-09-05|
    JPS5544120B2|1980-11-10|
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    引用文献:
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    US2475361A|1946-03-06|1949-07-05|Benjamin Clayton|Process of treating waste pulp liquors|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP11449275A|JPS5544120B2|1975-09-22|1975-09-22|
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