KR101334397B1 - Preparation method of dimer acid with high purity - Google Patents

Abstract

The present invention provides a preparation method of dimer acid with high purity which comprises the following steps: (a) inserting a catalyst into animal and vegetable fat to synthesize the dimer acid; (b) filtering the reaction result of (a) to remove the catalyst, and dehydrating the reaction result in the vacuum condition to remove water; and (c) separating the dimer acid from the dehydrated reaction result by thin film distillation. [Reference numerals] (AA) Inserting a catalyst into fatty acid material (activated clay +lithium hydroxide)��gt; polymerize dimer acid;(BB) First filtration of reactant (remove sludge);(CC) Bleaching process of reactant (inject diatomite +hypophosphoric acid);(DD) Second filtration of reactant (remove catalyst);(EE) Vacuum dehydration process of reactant;(FF) Thin-film distillation of reactant ��gt; separate dimer acid

Description

Preparation method of high purity dimer acid {Preparation Method of Dimer Acid with High Purity}

The present invention relates to a method for producing dimer acid, and more particularly, it is possible to produce raw materials of animal and vegetable waste, which are waste resources, and to mass produce high-purity dimer acid in high yield by using the same. The present invention relates to a production method of dimer acid which can provide dimer acid, thereby generating huge profits in the related industries as well as import substitution effect.

Dimer acids are prepared through radical polymerization of unsaturated fatty acids and are used in a variety of applications, including as raw materials for paints, inks, and polyamides.

Currently, domestic production of dimer acid is gradually increasing to an average of 1200 tons per month. Nevertheless, due to the lack of technology that can be produced in large quantities in Korea, it is currently required to import dimer acid from all over the world, and thus measures are required to supply dimer acid at a more stable and lower price.

The method for producing dimer acid is specifically disclosed in Korean Patent Nos. 10-0356436 to 2000-00060896, but these methods are necessary to artificially add water to increase the pressure of the reactor. On the contrary, it was confirmed that there is a problem of lowering the yield of dimer acid by preventing water from interfering with the reaction between the reaction raw material and the catalyst.

The present invention has been made to solve the problems of the prior art as described above, the purpose of which can be a raw material of animal and vegetable fats and wastes as a raw material and to use it to mass-produce high purity dimer acid in high yield As a result, it is possible to provide dimer acid at a more stable and lower price, thereby providing import substitution effects and generating huge profits for related industries by waste resource recycling.

The technical problem of the present invention as described above is achieved by the following means.

(1) (a) adding a catalyst to animal and vegetable fats and oils to synthesize dimer acid; (b) filtering the reactants of step (a) to remove the catalyst and then vacuum dehydrating to remove water from the reactants; (c) thin film distillation of the dehydrated reactant to separate the dimer acid.

(2) The method according to claim 1,

The catalyst introduced in step (a) is a production method of high purity dimer acid, characterized in that the activated clay and lithium hydroxide.

(3) The method according to claim 1,

Process for producing high purity dimer acid, characterized in that the diatomaceous earth and hypophosphorous acid is added to the reaction in the filtration step of the reaction in step (b).

(4) The method according to claim 1,

Process for producing a high-purity dimer acid, characterized in that further comprising the step of vacuum dewatering the reactant prior to the catalyst in step (a).

(5) The method according to claim 1,

The method of producing a high purity dimer acid, characterized in that further comprising the step of filtering the reactant after the vacuum dehydration in step (b).

According to the present invention as described above, the animal and vegetable fats and wastes as waste resources can be used as a raw material, and by using this, it is possible to mass-produce high purity dimer acid in high yield, so that the dimer acid can be more stably provided at a low price. Therefore, it provides not only the effect of import substitution but also the generation of enormous profits from related industries by recycling waste resources.

1 is an overall configuration diagram of an apparatus for producing dimer acid according to the present invention.
2 is a production process diagram of the dimer acid according to the present invention.

The present invention comprises the steps of (a) adding a catalyst to the animal and vegetable fats and oils to synthesize a dimer acid; (b) filtering the reactants of step (a) to remove the catalyst and then vacuum dehydrating to remove water from the reactants; (C) a method for producing a high-purity dimer acid comprising the step of separating the dimer acid by thin film distillation of the dehydrated reactant.

1 is an overall configuration diagram of an apparatus for producing dimer acid according to the present invention. However, the various pumps (including the vacuum pump) installed in the connection piping among the following configurations are omitted for the sake of understanding.

Dimer acid production apparatus according to the present invention is a raw material supply unit (1), bar response tube (2), the first cooling means (3), the first filtration means (4), the bleaching tube (5), the second filtration means (6) , Storage tank (7), dehydration pipe (8), second cooling means (9), third filtration means (10), thin film distillation pipe (11), boiler (12), third cooling means (13), cooling tower 14, the first collecting means 15, the second collecting means 16, the fourth filtering means 17, and the fourth cooling means 18.

The fatty acid raw material used in the present invention is introduced into the raw material supply unit 1 as animal or vegetable fatty acid.

In the reaction tube (2), a dimer acid polymerization process is performed by adding a fatty acid raw material, activated clay, and lithium hydroxide as catalysts.

In the present invention, it is preferable that the reaction tube 2 is provided with a means capable of vacuum dehydration in order to remove water contained in the reactants in the step before the catalyst is added. First, the water contained in the reactant is evaporated in the reaction tube (2) in a vacuum state and discharged to the outside by using a vacuum pump, etc., while liquefying through the first cooling means (3).

The first filtration means 4 is connected to the rear end of the reaction tube 2 to primaryly filter the sludge mixed with activated clay contained in the reactant produced as a result of the dimer synthesis reaction and fats and oils as impurities. Preferably, the primary filtration means 4 may include a decanter.

The bleaching tube 5 is a place to decolorize the reactants, for which diatomaceous earth and phosphoric acid are introduced. The decolorizing tube 5 is connected to the rear end of the first filtration means 4 to decolorize the reactant while stirring, and oxidation of the dimer acid is prevented by the action of the phosphoric acid in this process.

In order to remove the catalyst contained in the reactant, a second filtration means 6 is connected to the rear end of the bleaching tube 5. Preferably, the second filtration means 6 receives the decolorized reactant with a filter made of a hydraulic filter plate and performs secondary filtration at 80 to 90 ° C. The clean reactant, which has undergone secondary filtration, is stored in the storage tank (7).

The storage tank 7 is connected to the dehydration tube 8 at the rear end, and the dehydration tube 8 completely removes the remaining water in the reactant by vacuum evaporation. To this end, preferably, the dehydration pipe 6 is connected to at least two or more in series so as to sequentially perform vacuum dehydration. To this end, the operating conditions of the dehydration pipe is preferably maintained at a vacuum degree of 750 ~ 760mmhg, temperature 150 ~ 160 ℃. At this time, the water exiting the dehydration pipe 8 is condensed through the second cooling means 9 to be liquefied and removed.

The rear end of the dehydrating pipe 8 is connected with a third filtration means 10 for removing foreign matter such as soot (carbide) contained in the reactants. Preferably, the third filtration means 10 is a filter net made of a synthetic nonwoven fabric or a stainless net, and receives the dehydrated reactant to perform filtration. After the third filtration process, the reactant is introduced into the thin film distillation tube (11).

The thin film distillation tube 11 is distilled off from dimer acid while vaporizing and removing a monomer or trimer which is a reaction micropolymer contained in the reactant. The thin film distillation tube (11) can be vaporized at a lower temperature as the vacuum degree is higher and the color stability is higher, preferably maintained at a vacuum degree of 750 ~ 760mmhg, the distillation point of the dimer of 240 ℃.

Inside the thin film distillation pipe 11, a cooling pipe 11b through which cooling water flows from the cooling tower 14 is installed, and a heating part to which the heat medium oil supplied from the boiler 12 is supplied as a heat supply source for distillation of the dimer. 11a is mounted.

The micropolymer as an impurity is vaporized in the thin film distillation tube 11 and sent to the third cooling means 13. The third cooling means 13 is preferably arranged in series in a plurality of stages (13a, 13b, 13c), and liquefied micropolymers and other impurities in each stage are sequentially separated and removed. In order to process the remaining gas, a vacuum booster (not shown) or the like is mounted at the end of the cooler 13, collected, cooled, and discharged.

As described above, the micropolymer is collected in the second collectors 16a, 16b, and 16c while passing through the third cooling means 13a, 13b, and 13c, respectively. At this time, each second collector may be equipped with a warm jacket for warming to prevent aggregation of unreacted monomers and the like.

On the other hand, the dimer acid is distilled at a temperature higher than the distillation point in the thin film distillation pipe 11 and discharged in contact with the internally-cooled cooling pipe 11a to be collected in the first collector 15.

The dimer acid collected in the first collector 15 is separated by filtration of impurities again through the fourth filtration means 17 and cooling to a temperature suitable for product inspection in the fourth cooling means 18.

Hereinafter, with reference to the production process diagram of the dimer acid according to the present invention of Figure 2 step by step the content of the present invention in detail.

Preparation of Raw Fatty Acids

First, crude fatty acid is extracted by distilling glycerin as a double conjugate from animal and vegetable oils. The crude fatty acid thus obtained is subjected to vacuum dehydration treatment at a temperature of 150 to 160 캜 and a vacuum of 750 to 760 mmhg.

The dehydrated crude fatty acid is again indirectly preheated to 240-260 ° C. in a vacuum of 755-760 mmhg for distillation. At this time, crude fatty acid having an unseparated acid value of 185 (AV) or less is re-processed by sinking to the bottom without vaporization. The crude fatty acid having an acid value of 185 (AV) or more is vaporized in a distillation tube and indirectly cooled with 33 ° C. water in a cooling condenser to be liquefied.

Fatty acid obtained by such a procedure is acid value (AV) 200-205, saponification value (SV) 203-207, and temperature specific gravity is 0.88 kg / L at 25 degreeC.

Preparation of Dimer Acid

0.2 to 3 parts by weight of activated clay and lithium are respectively added to 100 parts by weight of the raw fatty acid in the reaction tube (2), and the polymerization reaction is carried out at a reaction temperature of 220 to 230 ° C. and a reaction pressure of 3 to 4 k for 2 to 4 hours.

In the present invention, the moisture contained in the raw fatty acid is removed by vacuum dehydration in a step before the catalyst is added to the raw fatty acid. Water must be removed at the pre-reaction stage because water can interfere with the contact between the catalyst and fatty acids, which can significantly reduce the yield of the polymerization reaction.

The reaction product obtained by the above process is subjected to primary filtration using a decantor or a centrifugal filter at 80 ° C to 90 ° C. By this process, sludge consisting of activated clay and oil is precipitated and removed.

The primary filtered reaction product is provided with a predetermined color through the decolorization tube 5 in which 0.2 to 3 parts by weight of diatomaceous earth and hypophosphoric acid are added to 100 parts by weight of fatty acid, and prevents oxidation of the dimer acid.

The reactant, which has passed through the bleaching tube 5, is subjected to secondary filtration at a filter (for example, a hydraulic filter plate) 6 at 80 to 90 ° C to remove the catalyst and the like contained in the reactant.

Thereafter, the second filtered product is introduced into the dehydration tube 8 under a vacuum degree of 750 to 760 mmhg and a temperature of 150 to 160 ° C., and subjected to vacuum dehydration. This process removes the water contained in the reactants, which reduces the yield of dimer acid, the final product. In order to remove water more completely, the vacuum dehydration process may be performed twice. In this case, the reactant is firstly dehydrated via the first dehydration pipe, and then the second dehydration is performed via the second dehydration pipe. Water evaporated by the above process is removed through a predetermined cooling treatment.

The dehydrated reactant removes carbides (or soots) that may be contained in the reactants using a filter net (eg, synthetic nonwoven or 20 mesh stainless steel) at 170-180 ° C. (tertiary filtration).

The reactant after filtration is put into a thin film distillation tube (11) maintained at a vacuum degree of 750 to 760 mmhg and a distillation point of dimer acid at 240 ° C., and is subjected to thin film distillation. The trimer acid is immediately vaporized and then separated by condensation through a cooler, and the dimer acid is distilled at a distillation point, cooled, discharged into a liquefied state, and collected separately.

In order to recover the dimer acid, cooling water of about 28 ° C. is supplied from the cooling tower and circulated in the thin film distillation tube. The dimer acid thus distilled is cooled to 180-190 ° C. through heat exchange, and is liquefied and discharged. It cools down to about 70 degreeC. On the other hand, in the case of monomer acid to trimer acid which is cooled after being vaporized and discharged, the temperature is increased to about 44 ° C. in order to prevent solidification at a low temperature.

According to the above process, it is possible to produce fatty acids from animal or vegetable fats and oils, and to supply a large amount of inexpensive and high-purity dimer acid using the obtained fatty acids as raw materials.

Hereinafter, the present invention will be described in more detail with reference to examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Example 1

An animal fatty acid having an acid value (AV) 201 and an iodine value (IV) 74 was added to the reaction tube (1), followed by vacuum dehydration treatment at 740 mmhg, followed by heating the fatty acid at 220 ° C. for 2 hours, followed by 100 weights of animal fatty acid. 0.2 parts by weight of activated clay and 0.2 parts by weight of lithium hydroxide were added to the reaction tube 1, and the mixture was heated and reacted at a reaction temperature of 230 ° C. and a reaction pressure of 4k for 2 hours, and then cooled to 80 ° C. for 1 hour.

The reaction was sent to a decanter (2) to remove the sludge mixed with clay and oil at 90 ° C by primary filtration. The sludge-reacted reactant was decolorized with stirring by sending it to a decolorization tube (3) containing 0.2 parts by weight of diatomaceous earth and 0.2 parts by weight of phosphoric acid based on 100 parts by weight of animal fatty acid.

In order to remove the catalyst contained in the reactant, the decolorized reactant was sent to a filter (4) made of a hydraulic filter plate and subjected to secondary filtration at 80 ° C.

The clean reactant, which had undergone secondary filtration, was stored in a storage tank (5) and then sent to a vacuum dewatering tube (6). Two vacuum dehydration tubes (6) were connected in series. Each vacuum dehydration tube was maintained at a vacuum degree of 750 mmhg and a temperature of 160 ° C. and completely removed moisture remaining in the reactants.

The vacuum dehydrated reactant was preheated in a preheater 70 maintained at a temperature of 140 ° C. and subjected to tertiary filtration in a filter 80 maintained at 170 ° C. to remove residual soot (carbide).

The tertiary filtered product was sent to the thin film distillation tube 9 to remove the monomer or trimer, which is a micropolymer contained in the reactant, by vaporization. The thin film distillation tube 9 is maintained at a vacuum degree of 759.5 mmhg and a distillation vaporization point temperature of 240 ° C., and the dimer acid is cooled and discharged to about 180 ° C. through heat exchange with the cooling water supplied from the cooling tower 10. Thereafter, the dimer acid was once again filtered in the filter 11 and then cooled to 70 ° C. in the cooler 12 to perform product inspection.

On the other hand, the micro-polymer is vaporized in the distillation tube and hit the internal cooling tube is discharged into a low-temperature liquid phase, in order to prevent solidification was heated to about 44 ℃ with a thermal jacket (13) was also performed a product inspection.

The gases discharged from the thin film distillation tube (9) were sequentially cooled through a series of coolers (14) arranged in series, liquefied, heated in a similar manner to prevent solidification, and then separately collected and separated.

[Example 2]

Dimer acid was prepared under the same conditions as in Example 1 except that 1 part by weight of activated clay, 1 part by weight of lithium hydroxide, 3 parts by weight of diatomaceous earth, and 3 parts by weight of phosphoric acid were added to 100 parts by weight of soybean oil fatty acid.

[Experimental Example 1]

Comparative Example was carried out in the same manner as in Example 1, except that the fatty acid raw material was not subjected to the dehydration treatment before the reaction, and the components separated from the Examples 1, 2 and Comparative Examples as a result of the component analysis As shown in Table 1, it was confirmed that the dimer acid was produced significantly more than the comparative example in the embodiment according to the present invention.

Analysis Analysis item Example 1 Example 2 Comparative Example Acid value (AV) 200 202 185 Neutralization value (SV) 204 206 196 Dimer Mountain 65% (viscosity: 8100, temperature: 27 degrees Celsius) 73% (viscosity: 8300, temperature: 27 degrees Celsius) 46% (viscosity: 6800, temperature: 26 degrees Celsius) Monomeric acid 20% 16% 38% Trimmer acid 10% 8% 11%

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It can be understood that

1: Raw material supply department
2: Reaction tube
3: first cooling means
4: first filtration means
5: bleaching tube
6: second filtration means
7: storage tank
8: dewatering pipe
9: second cooling means
10: third filtration means
11: Thin film distillation tube
13: third cooling means
14: cooling tower
15: first collector
17: fourth filtration means
18: fourth cooling means

Claims (5)

(a) synthesizing dimer acid by adding activated clay and lithium hydroxide as catalysts to maintain the flora and fauna; (b) filtering the reactants of step (a) to remove the catalyst and then vacuum dehydrating to remove water from the reactants; (c) thin film distillation of the dehydrated reactant to separate the dimer acid. delete The method of claim 1,
Process for producing high purity dimer acid, characterized in that the diatomaceous earth and hypophosphorous acid is added to the reaction in the filtration step of the reaction in step (b). The method of claim 1,
Process for producing a high-purity dimer acid, characterized in that further comprising the step of vacuum dewatering the reactant prior to the catalyst in step (a). The method of claim 1,
The method of producing a high purity dimer acid, characterized in that further comprising the step of filtering the reactant after the vacuum dehydration in step (b).

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