UA44558C2 - Method for producing fat substrate - Google Patents

Abstract

The proposed method for producing fat substrate involves fermentative splitting of fats in the presence of water and activator at the temperature required for the ferment activity. As the ferment, lipolaktyne is used, and as the activator, - "Amirol-M" adsorptive active additive. The process is carried out at the initial temperature of 15-17 DEGREE C with the subsequent exothermic elevation of the temperature to 34-37 DEGREE C and maintaining thetemperature at this level and with pH value of 5.8-6.3.

Description

The invention relates to a biotechnological method of obtaining a fatty substrate, which can be used in various processes of petrochemical synthesis, in particular, in the production of lubricants, lubricating and cooling fluids, lubricating preparations, etc.

There is a known reactive method of fat hydrolysis, which is carried out in the presence of a mixture of sulfuric and sulfonic acids at a temperature of about 100 "С, as well as a non-reactive method, which is implemented at a temperature of 200-22570 and a pressure of 2.0-2.5 MPa ("Chemistry of fats", ed. Kolos", M. 1992, pp. 225-229). These methods ensure a fairly high quality of fatty acids and glycerol. However, their use instead of technical fats in a number of petrochemical synthesis productions is not economically justified and not rational, since the initial stage of the above processes involves mandatory refining of fat, during which part of it is lost, as well as technically valuable products accompanying fats.

There is a well-known method of extracting fatty acids by alkaline processing of fat followed by decomposition of soap with sulfuric or hydrochloric acid (B.N. Tyutyunnikov, P.V. Naumenko, "Technology of fat processing", "Pishchevaya promshlennost", Moscow, 1970). Despite the cumbersome design of the equipment, the energy- and labor-intensiveness of the process, the loss of unused glycerin, the presence of a large amount of contaminated wastewater, and, therefore, the environmental problem, this method is still used in factory practice, including at JSC "AZMOL" (city of Berdyansk), where the extracted acids, as a technical product, are used in multi-volume production, for example, lubricants, lubricating and cooling fluids, lubricating preparations and in other petrochemical syntheses.

Microbial technical fat (TU 59.03.045.86-85), which is a by-product of feed yeast biosynthesis from hydrocarbons, was used as a new type of industrial raw material in the mining industry, as well as for processing to obtain lubricants, phosphatides and biologically active substances. In industry, microbial fat is obtained by extracting previously prepared biomass of microorganisms with gasoline. Depending on the defects of the strain of microorganisms, the source of hydrocarbon nutrition, the cultivation conditions, the composition of microbial fats varies within certain limits and is characterized by the following physicochemical parameters: acid number, mg KOH/g, no more than 50 sediments by mass, 95, no more than 8 saponification number, mg KOH/g, not less than 130 solidification temperature, "С, not higher than 5 content of unsaponifiable matter, 956, not more than 45

A restraining factor for the wider use of microbial fat is the significant content of unsaponifiable substances and substances of different chemical nature under the general name "scum by mass".

The technical literature notes the prospects of enzymatic splitting of a number of products, including fats (K. D. Nenitsescu "Organic chemistry", ed. of foreign literature, M. 1963; P.

Karrer "Course of organic chemistry", "Goshimizdat", L. 1960; B.N. Tyutyunnikov, F.F. Hladkyi, "Chemistry of Zhirov", ed. "Colossus", Moscow, 1992).

The closest technical solution to the intended invention is the method of enzymatic splitting of fats, which is carried out in the presence of 30-359omas. of water, at a temperature of 25-35", using 5-1095 lipase enzyme isolated from castor. The activator of the enzymatic cleavage process is acetic acid (0.06-0.190) and/or manganese sulfate (0.15-0.295). Duration of cleavage of fat to 80905 is 24 hours or more.

The disadvantages of this method include its duration, insufficient depth of cleavage, difficulties associated with processing the intermediate layer, which holds a significant amount of difficult-to-extract fatty acids and glycerol, (N.I. Kozin "Khimiya i tovarovedenie pischevkh zhirov", "Hostopizdat", Moscow, 1958, p. 102).

The basis of the work was the task of improving the method of enzymatic splitting of fats by using lipolactin (4-69 mass) as an enzyme and the adsorption-active additive "Amirol-M" (5-995 mass) as an activator, when the process is carried out in the initial temperature range of 15- 17" with subsequent exothermic rise and further maintenance at the level of 34-377"С at a medium pH of 5.8-6.3, which makes it possible to obtain a new, cheaper saponified raw material - a fat substrate intended for use in petrochemical synthesis, economically a profitable, technologically simple and environmentally safe way of processing natural fats.

Depending on the purpose of the fat substrate, both low-melting fats and their mixtures with high-melting fats can be subjected to enzymatic cleavage, provided that the melting temperature of the fat mixture does not exceed the temperature optimum for the activity of the enzyme.

Lipolactin - TU op 42-5800665-3-92 - an enzyme preparation obtained during the in-depth cultivation of the mushroom culture of Oozrog Iasiykh pcs. uzLM-2. Lipolactin is widely used for degreasing leather raw materials and carrying out a number of biotechnological processes.

Amirol-M - adsorption-active additive - pat. of Ukraine Me20862, TU 38.301-48-49-97. It is used as an additive to soap (application Me95111792/13/020306 dated 07.07.95), the decision on issuing a patent of the Russian Federation dated 02.04.97, independently used as a concentrate of water-miscible lubricating and cooling fluids in metalworking processes, as an additive to lubricants and oils, as a component of a method for cleaning a metal surface (application Me2000063496 dated 15.06.00), decision on the issuance of a patent of Ukraine dated 22.01.01.

By setting up special experiments, the optimal amount of water, stoichiometrically necessary to perform the function of hydrogen ion donor, was determined. An auxiliary donor of hydrogen ions is the Amirol-M additive, which contains a number of compounds, the dissociation of which under conditions of possible enzyme influence can predict the presence of a significant amount of hydrogen ions.

The method of obtaining a fatty substrate includes the stage of splitting the fat, settling the reaction products, their subsequent separation and use for the intended purpose. One of the determining factors of the efficiency of the process of enzymatic destruction of fat, along with the composition of the reaction mixture and the ratio of components, is the temperature regime, which is reflected in the examples below.

The proposed method of obtaining a fatty substrate is as follows.

Example 1.

37Okg of water (condensate), 500kg of fat, 80kg of adsorption-active additive "Amirol-M" are fed to the reactor, equipped with a stirring device and a jacket for heating or cooling the reaction mass, and are mixed at at a temperature of 15-177"C for 20-30 minutes. Then add 50 kg of lipolactin and strengthen the mixing, turning on the circulation system.

A temperature of 15-17"С is sufficient for the start of the process of enzymatic splitting of fat, which in the next process proceeds in an exothermic mode. In the next 1.5-2 hours, the temperature of the mixture reaches 34-37"С and is maintained for 5-7 hours of the active phase of destruction fat, the depth of which is 65-70905.

In the future, the activity of the fat splitting process weakens a bit, and to ensure its depth 82-8595, the optimal temperature is maintained by heating for another 2-3 hours. According to the proposed method, the fat splitting process is considered complete at this stage, but, depending on the purpose of the fat substrate, the depth of fat splitting can vary from 45 to 9095. After the end of enzymatic fat splitting, the temperature in the reactor is raised to 80-857"C. Under the influence at this temperature, the proteins are precipitated, the enzyme is destroyed. Then the stirring is stopped and the product is allowed to stand for 1.5-2 hours, after which the lower water-glycerol layer, intermediate and fat substrate are drained separately. At this point, the process of enzymatic splitting of fat is considered complete. The total duration of the production process fat substrate is 10-14 hours, and the actual destruction of fat is carried out in 8.5-12 hours.

This method allows, under several changed conditions, to achieve complete destruction of fat, but one of the tasks of the proposed invention is to obtain, with favorable technical and economic indicators, such a product that can be more rationally used on a large industrial scale with a great effect.

Example 2.

Similarly to example 1, the same raw components are loaded into the reactor, in the same ratio, intensive mixing of the mass is carried out at the initial process temperature of 10-1176.

The breakdown of fats in this mode proceeds sluggishly. Exothermicly, the temperature increases by 5-7"C for 1.5-2 hours, and then the intensity of the reaction practically does not increase. Maintaining the temperature in the range of 34-377"C by heating the mixture somewhat activates the fat splitting process. But in 14 hours the destruction of the latter is 30-3505.

Example 3.

Without changing the composition and ratio of the components taken for enzymatic fat splitting according to example 1, with the same intensity of stirring, the reaction mixture is heated to 25"C, lipolactin is introduced and the heating is stopped. The temperature activation of the process is accompanied by a rapid flow of the fat splitting reaction, sharp, an uncontrollable rise in temperature above 40"C, which is maintained at this level for 1-1.5 hours, and its sharp drop for the same amount of time. The next artificial maintenance of the temperature regime at the level of 34-37"С practically does not give positive results. In 14 hours of the process, the fat is split into 37-4295.

Thus, when implementing the proposed method of obtaining a fatty substrate by splitting fat using the enzyme lipolactin, the optimal temperature for the beginning of the process is 15-177C with subsequent exothermic rise and subsequent maintenance at 34-3770C.

The proposed method makes it possible to halve the time of fat destruction compared to the prototype and to obtain final products, the further processing of which does not cause difficulties.

The efficiency of the fat splitting method, the composition and properties of the final product, in addition to technological factors, largely depend on the selected enzyme and activator (the so-called coenzyme), taking into account their optimal concentration.

The decisive factor in the use of lipolactin as an enzyme for breaking down fats was its specificity, which was manifested in the selective effect on fats during skin degreasing.

The complex of specific properties of the adsorption-active additive "Amirol-M" served as the basis for its use in combination with lipolactin as an activator of the process of splitting fats.

By conducting a series of experiments (table 1), in which the technological parameters of the process described in example 1 remained unchanged, the limit concentrations of the enzyme and activator were determined, which provided optimal conditions for the fat splitting process, as well as the composition and properties of the final products.

Table 1

Examples of samples of the reaction mixture of the reco UT oil oil

Enzyme "Lipapactin" | 8 | 8 | 4 | 4 | 5 | 5 | 6 | 6 | 2 | 2 (Additive "Amirol-M" | 5 | - | is | - | 8 | - | 7 | - | " |-

As a result of the experimental verification, it was established that the duration of fat splitting in the first four samples does not differ much and is an average of 12-14 hours, and in the fifth sample the process dies out without reaching the optimal temperature for the course of the reaction. At an enzyme concentration of 4-5-69omas. (samples 2-3-4) in the presence of 9-8-79omas, respectively. "Amirol-M" additives, fat splitting occurs in an exothermic mode and the need to heat the product occurs after its destruction at 65-7090.

In the fifth sample, even with constant maintenance of the temperature in the reactor at 34-377"C by means of heating, it is not possible to achieve fat destruction, which is of practical interest.

In the first sample, fat splitting proceeds quite actively in the initial stage and is accompanied, in a number of cases, by a rise in temperature above the optimal limit, in connection with which, in order to prevent a critical mark, there is a need to cool the reaction mixture. However, with a decrease in temperature to the optimal value after stopping cooling, the exothermic reaction is practically not restored and fat splitting occurs only during heating. Thus, the technological process is complicated.

Although the depth of fat splitting is somewhat higher compared to other samples, the use of the enzyme in a higher concentration is technologically and economically irrational.

In the absence of the "Amirol-M" additive in the reaction mixture (samples Ta, 2a, Za, 4a, 5a), the duration of the fat splitting reaction increases and is 16-18 hours.

After the fat splitting process is over, the products in the reactor are distributed layer by layer. One of the factors affecting the controllability of the aggregate state of these products in the total volume is the presence of the additive "Amirol-M" in the optimal amount.

In samples 1, 2, 3, 4, there is a clear distribution of the post-reaction mixture into three layers: the upper one is a fatty substrate; medium - thickened, containing impurities accompanying fats adsorbed by the additive "Amirol-M", deactivated enzyme, some amount of fat; the bottom - a solution of glycerin in water.

In the fifth sample, the products of partial splitting of fat, adsorbed by the additive "Amirol-M", are agglomeratively distributed throughout the volumetric mixture.

In samples Ta, 2a, Za, 4a, 5a, which do not contain "Amirol-M" additives, there is no clear layer-by-layer distribution of substances formed in the process of fat destruction. The function of the additive "Amirol-M" as an accelerator of the process of enzymatic splitting of fat is determined, to a large extent, by the ability of the compounds included in its composition, including acid soap, when dissociating in water, to maintain the acidity of the environment within the pH range of 5.8- 6.3, which is the most favorable for regulating enzyme activity.

As a result of the implementation of the proposed method of enzymatic splitting of fat, a fatty substrate is obtained, characterized by the quality indicators listed in Table 2.

Table 2

Qualitative characteristics of the fat substrate burned Tuesday

The data given in Table 2 show that the fatty substrate obtained according to the proposed method is characterized by high acidity due to the content of about 70-8295 fatty acids. Glycerides are found to be a saponifying component in the substrate. The hydroxyl number indicates the presence of hydroxyl-containing compounds, which can be represented by mono- and diglycerides, which are products of incomplete fat breakdown.

The MeZ sample with a sufficient depth of fat splitting and the best aggregate state of the reaction products was taken as the optimal one, which contributes to their clearer separation and subsequent effective disposal. Deviation of the quantitative ratio of components from the stated limits (samples 2, 3, 4) in sample 5 does not ensure the energetic development of the process of enzymatic splitting of fat, and the composition of sample 1 is technologically and economically unjustified.

In samples 1а, 2а, За, 4а, 5а, in the absence of the activator - additive "Amirol-M", the amount of split fat decreases.

The set of properties of the fatty substrate determined the possibility of its use as a new source of fatty raw materials in both traditional and new directions of petrochemical synthesis. The information provided in the patent sources made it possible to identify new trends in the development of industrial production, for example, lubricants, lubricating and cooling fluids, fat-enriching preparations, which are based on the use of biodegradable products (5 5595965 A, 6C 10М 117/00, 21.01.97 05 5641734 А, 6С 10М 161/00, 24.06.97), including synthetic fats (ММО 9617909 А1, 6С 10М 105/38, 13.06.96; 005 5658863 А, 6С 10М 129/70, 19.01. 1997), hydroxyl-containing compounds (V. A. Vainshtok, N. Abdul-Bary Kasem "The influence of hydroxyl-containing compounds on the properties of foundry lubricants based on vegetable saponified sulfur", "Neftepererabotka i neftekhimiya", M. Mo7 1999), mono -, di- and triglycerides of various organic acids. And if each of these components is intended to improve individual characteristics of the final product, then the use of a fatty substrate, which includes a complex of types of similar compounds in various combinations, moreover, taking into account the synergistic effect, allows you to expand the possibilities of petrochemical synthesis and obtain a product with several improved quality indicators.

In industrial conditions at JSC "AZMOL" by the proposed method of enzymatic destruction of sunflower oil, three samples (one ton each) of fat substrate with different depth of cleavage were obtained for use in three different directions. The by-products of this process are disposed of in the same factories. The obtained practical results confirmed the expediency of using a fat substrate as a new type of raw material, the possibility of simplifying and shortening the technological process of its production, improving the quality of the target products, and served as material for the registration of three independent applications for alleged inventions.

Claims (1)

The method of obtaining a fatty substrate by enzymatic splitting of fats in the presence of water and an activator, at a temperature that ensures the viability of the enzyme, which is characterized by the fact that lipolactin is used as an enzyme, and the adsorption-active additive "Amirol-M" is used as an activator, taken respectively 4-695 mass and 5-995 wt., and the process is carried out at an initial temperature of 15-17"7C with subsequent exothermic increase and further maintenance at the level of 34-37"C at a medium pH of 5.8-6.3.