CN104498195A - High value utilization method of plant oil hydrated oil foots - Google Patents

Abstract

The invention discloses a method for high-value utilization of vegetable oil hydration oil bottoms, which comprises the following steps: (1) adjusting the temperature of hydration oil bottoms to 40-65°C, adding lipase or phospholipase to it, stirring and reacting to The acetone insoluble matter in the system loses weight by 20-45%; (2) centrifuging or static separation to obtain a light phase mainly composed of oil and a heavy phase containing modified phospholipids. The method uses lipase or phospholipase to moderately hydrolyze the hydrated oil bottoms, and then separates to obtain a light phase mainly composed of oil and a heavy phase containing modified phospholipids, both of which have higher value. By using the method of the invention, the high-value utilization of vegetable oil hydration oil bottoms is realized.

Description

A high-value utilization method of vegetable oil hydration oil residue

technical field

The invention relates to a high-value utilization method of vegetable oil hydration bottoms, which can be used for deep processing of vegetable oil processing by-product hydration bottoms and to increase added value.

Background technique

Many crude vegetable oils, such as soybean oil, rapeseed oil, sunflower oil, corn oil, peanut oil, etc., contain a lot of phospholipids. Degumming in vegetable oil processing is mainly to remove phospholipids. Hydration degumming is a method of partially removing vegetable oil colloids by simply adding water. One of the products of this degumming process is hydration oil foot, which is a common by-product of oil processing plants. Hydrated oily feet generally contain about 50% water, nearly 40% neutral oil in the dry matter of oily feet, and nearly 60% phospholipids. In addition, they also contain a small amount of protein, glycolipids, sterols, amino acids, and various trace elements and vitamins. .

Phospholipids in vegetable oils can be divided into hydratable phospholipids and non-hydratable phospholipids according to hydration. Phospholipids in oil bottoms are mainly hydrated phospholipids, which are composed of complex phosphorus-containing organic compounds and inorganic compounds, mainly including Phosphatidylcholine (lecithin), phosphatidylethanolamine (cephalin), and phosphatidylinositol (inositol phospholipids), etc. Vegetable oil factories often use the method of salting out hydration oil residues. After recovering part of the neutral oil, it is often treated as waste, because it also contains 30% neutral oil and phospholipids and other nutritious substances that are wasted. The oily bottoms have a high water content and are easily fermented and rancid. The oil factory also cannot deal with the oily bottoms in time, which affects production and affects the environment at the same time.

Patents such as CN01102724, CN001281313, and CN971253021 disclose methods for separating vegetable oil from oily bottoms, but they basically simply use electrolytes to change the aggregation state of phospholipids to separate vegetable oils. Exploitation has become more difficult, and currently, these methods are rarely used.

At present, the utilization of hydrated oil bottoms by oil processing plants mainly includes: using oil bottoms to extract concentrated phospholipids and then produce refined phospholipids, which is the most commonly used method at present; using oil bottoms to hydrolyze to produce fatty acids; solvent leaching and recovery of oil bottoms The oil in it; put the oil foot into the wet meal, steam off-line and mix it with the meal as feed, etc. When oil bottoms are leached by solvent to recover the oil, the phospholipids are easily re-dissolved in the solvent and enter the recovered oil, resulting in a vicious cycle of phospholipids in the production system. Putting the oil foot into the steamer can easily lead to agglomeration of desolventized meal, decreased desolventization effect, deepened meal color and other undesirable phenomena. The utilization method of the above hydration oil foot avoids the waste of the hydration oil foot and improves the utilization value of the oil foot. However, the existing methods for utilizing hydration oil feet generally have the problem of low added value.

Contents of the invention

The purpose of the present invention is to develop a high-value utilization method for vegetable oil residues in view of the shortcomings of the prior art, which is of great significance for improving the comprehensive benefits of oil processing plants.

Our research group found that when lipase or phospholipase is used to hydrolyze vegetable oil hydration oil bottoms, when a reasonable degree of hydrolysis is controlled, the oil bottoms will be clearly stratified. The stratification of oil feet under the action of enzymes provides convenience for the separation of oil from oil feet; moreover, the hydrolysis reaction generates a large amount of lysophospholipids, and lysophospholipids have higher added value. On the basis of the above studies and discoveries, the present invention has been formed.

A method for high-value utilization of vegetable oil hydration oil residue, comprising the following steps:

(1) Adjust the temperature of the hydration oil foot to 40-65°C, add lipase or phospholipase to it, and stir the reaction until the acetone-insoluble matter in the system loses 20-45% in weight;

(2) centrifugation or static separation to obtain a light phase mainly composed of oil and a heavy phase containing modified phospholipids.

After separation, the obtained light phase oils and heavy phase modified phospholipids usually have higher added value, realizing the high value utilization of hydration oil bottoms.

The vegetable oil of the present invention includes soybean oil, rapeseed oil, sunflower oil, corn oil, peanut oil, etc., preferably soybean oil and rapeseed oil.

The present invention adopts lipase or phospholipase to catalyze the reaction under the water environment, and the generated reaction is hydrolysis reaction. Generally speaking, the boundary between lipase and phospholipase is often not clear enough. In most cases, lipase also has phospholipase activity, and phospholipase also has certain lipase activity. An interesting phenomenon is that through the analysis of the hydrolyzate, it is found that even with lipase, there is still a large amount of lysophospholipids, and the amount of partial glycerides is not large. Therefore, it is speculated that in the composition of vegetable oil hydration oil In the reaction system, both lipase and phospholipase act preferentially on phospholipids. The research of our research group also shows that no matter whether phospholipase or lipase is used, the oil foot can be effectively stratified. From the above results, it can be seen that both lipase and phospholipase can be used for the purpose of the present invention. The lipase and phospholipase used are one or more mixtures derived from the genus Rhizome, Aspergillus, Maozyme, bacteria, yeast and animal pancreas.

As for the enzyme reaction temperature, for most enzyme preparations, the optimum reaction temperature can be 40-65°C, and some lipases can tolerate higher temperatures. Generally, the temperature of hydration degumming is about 80°C, and the hydration oil feet transported from the production line need to be cooled to meet the temperature requirements of the enzyme reaction. For the amount of enzyme added, generally 1~50IU/g oil base is desirable. The amount of enzyme used is related to the reaction time. Adding more enzymes will shorten the time required for the reaction, but too much enzyme amount will be affected by the high cost of enzymes. economy. The mechanism of oil foot stratification has not yet been reported, and it is speculated that it is related to the formation of lysophospholipids. We know that the HLB value of phospholipids is about 3 to 4, and the lipophilicity is relatively strong. Before the enzyme reaction, the neutral oil is wrapped by phospholipids. When phospholipids are hydrolyzed into lysophospholipids, the HLB value of lysophospholipids is close to 7, and the lipophilicity is weakened, thereby releasing the oil. According to this theory, the key to the stratification of oil feet is related to the hydrolysis of phospholipids. Due to the different sources and different processes of oil bottoms, its internal composition can change greatly. Therefore, it is difficult to use acid value as a monitoring index to guide production. Our research group found that there is a good correlation between the reduction of acetone insolubles and the quality of stratification. Therefore, the reduction of acetone insolubles is used as a monitoring index. In the present invention, it is advisable to react until the reduction of acetone insolubles is 20-45%, and more preferably, it is desirable to react until the reduction of acetone insolubles is 25-35%.

When studying the stratification conditions of oil foot hydrolyzate, it was found that adding a certain amount of NaCl to the reaction product was helpful for stratification. However, in the present invention, the effect of adding NaCl is not only to facilitate delamination, but to produce a special delamination phenomenon. NaCl can break the emulsion and is often used in the processing of oil feet. In the operation of extracting grease from the oil foot, generally, 10% salt of the oil foot weight is slowly added in the oil foot, and the process is constantly stirred and heated. Let it stand for half an hour to extract the oil layer by layer. In the present invention, the layering phenomenon caused by adding NaCl is significantly different from the direct addition of NaCl in oil bottoms. Centrifuge the reaction product of oil foot enzyme added with NaCl, it is found that the stratification is more rapid, and at this time, the water phase can obviously appear. Usually, the reaction system is divided into the following density from light to heavy: (a) light phase mainly composed of oil; (b) intermediate phase mainly composed of modified phospholipids; (c) heavy phase mainly composed of waste water and impurities. Mutually. The appearance of the water phase is important information, because the water phase can be separated conveniently, which reduces the energy consumption of product drying, and can greatly reduce the cost of deep processing of oil feet. On the other hand, the water phase can remove some impurities. The amount of NaCl added is related to the water content in the reaction system. According to 5-15% (w/w) of the water in the reaction system, a higher proportion of NaCl is good for improving the separation, but it will increase the production cost. . For the three-phase system, industrially, three-phase centrifuges can be used for separation; two centrifuges can also be used for two centrifuges.

For the product containing lysophospholipids separated from the reaction system of the hydrated oil foot enzymatic method, it still contains a large amount of water and needs to be dried. The drying method can be carried out by means of thin film evaporator, spray drying, etc., or it can be dried by adsorption on solid materials. These drying methods are common industry technologies.

For the oil separated from oil bottoms, it contains a large amount of free fatty acids, which are usually called high acid value oils, and can be added to crude oil for refining, but adding directly to crude oil for refining is not the most economical method. One way to utilize the oil is to separate free fatty acids and glycerides by molecular distillation. Molecular distillation is a general separation method, which is a technology that uses the difference in the free path of molecular motion of different substances to separate materials containing different substances in a liquid-liquid state. It can separate the different substances contained in the liquid at a temperature far below its boiling point. Since it operates under high vacuum, and because of its special structure, it has low distillation pressure, short heating time, The characteristics of high degree of separation can greatly reduce the separation temperature of high boiling point materials, and excellently protect the quality of heat sensitive substances, thus solving a large number of problems that cannot be solved by conventional distillation techniques. Molecular distillation is one of the effective methods for the removal of fatty acids in the high acid value oils obtained in the present invention. The main conditions involved in the molecular distillation work include distillation temperature, distillation pressure, etc. For the separation involved in the present invention, the distillation temperature is usually selected to be 180-210° C., and the distillation pressure is 0.1-3 Pa. The free fatty acids obtained by molecular distillation can be used in the field of oleochemicals, while the glyceride part can be added to crude oil for further refining or other uses.

Concentrated phospholipids are directly dried from hydrated oils, but if the dried concentrated phospholipids are rehydrated to the state of hydrated oil, and then the same enzyme reaction is carried out, the reaction effect is found to be unsatisfactory. It is possible that the state of phospholipids and water complexes formed naturally by phospholipids is destroyed during the process of drying the hydrated oil into concentrated phospholipids. Therefore, the present invention emphasizes that the substrate of the enzyme reaction is the hydrated oil, not only because of the use of hydrated oil The feet can save energy, and because the hydration oil feet have a higher enzyme reaction efficiency. Therefore, the present invention specifically limits the substrate of the reaction to be hydrated oil bottoms. The hydration oil foot refers to the product removed during the hydration and degumming of crude vegetable oil.

Compared with traditional technology, the present invention has the following characteristics and advantages:

(1) The present invention provides a new deep processing method of vegetable oil hydration oil bottoms, which is a high-value utilization method of vegetable oil hydration oil bottoms with application value.

(2) Modified phospholipids and oils are obtained through deep processing of vegetable oil hydration oil residue, which increases the added value.

(3) Enzyme engineering technology is adopted, which is natural and environmentally friendly.

Detailed ways

According to the method of the invention, vegetable oil hydration bottoms can be separated into several useful products, and the process is simple, which is a technical method for high-value utilization of vegetable oil hydration bottoms. The present invention will be further described below through embodiment.

In the embodiment, the analysis of the enzyme activity adopts the potentiometric titration method, referring to the national standard GB/T23535-2009. The lipase activity uses emulsified olive oil as the substrate, and the assay method of phospholipase activity is the same as the lipase activity analysis method, but the substrate uses egg yolk phospholipid instead of olive oil to make the emulsion.

Example 1

The water content of soybean oil hydrated oil bottom analysis is 51.8%, the acetone insoluble matter in dry matter is 63.1%, and the rest is acetone soluble oil. Take 100 g of the oil residue, place it in a Erlenmeyer flask, and put it in a water bath at 50° C. for 30 min, and add phospholipase Lecitase Ultra (Novozymes, Denmark) at 1 IU/g of the oil residue. Leciatase Ultra is strictly a lipase, but it also has high catalytic activity for phospholipid substrates. Therefore, the enzyme preparation can also be considered as a phospholipase. The reaction was stirred in a water bath at 50° C. until the acetone insoluble matter was reduced by about 20%, and the reaction was carried out for 38 hours. Take 10g of the reactant and centrifuge, the upper layer is a clear layered oil phase, and the lower layer is a heterogeneous turbidity. The weight of the upper layer oil phase is 1.43g, and the acid value is 40.2.

Example 2

The water content of soybean oil hydrated oil bottom analysis is 51.8%, the acetone insoluble matter in dry matter is 63.1%, and the rest is acetone soluble oil. Take 100 g of the oil bottom, place it in a conical flask, add phospholipase Lecitase Ultra (from Novozymes, Denmark) according to 10 IU/g oil bottom after a 40°C water bath for 30min, and stir the reaction in a water bath at 40°C until the acetone insolubles are reduced by about 45%. The reaction was carried out for 22 hr. Take 10g of the reactant and centrifuge, the upper layer is a clearly layered oil phase, and the lower layer is a heterogeneous turbidity. The weight of the upper oil phase is 2.28g, and the acid value is 78.7.

Example 3

The water content of soybean oil hydrated oil bottom analysis is 51.8%, the acetone insoluble matter in dry matter is 63.1%, and the rest is acetone soluble oil. Take 100 g of the oily bottom, place it in a conical flask, and add porcine pancreas phospholipase A2 (Sigma Company) at 10 IU/g of the oily bottom after a 65°C water bath for 30 minutes, and stir the reaction in a 65°C water bath until the acetone insolubles are reduced by about 28%. , the reaction was carried out for 6hr. Take 10g of the reactant and centrifuge, the upper layer is a clearly layered oil phase, and the lower layer is a heterogeneous turbidity. The weight of the upper oil phase is 2.16g, and the acid value is 62.6.

Example 4

The water content of soybean oil hydrated oil bottom analysis is 51.8%, the acetone insoluble matter in dry matter is 63.1%, and the rest is acetone soluble oil. Take 100 g of the oil base, place it in an Erlenmeyer flask, add phospholipase Lecitase Ultra (from Novozymes, Denmark) at 5 IU/g after bathing in a water bath at 50° C. for 30 min, and stir the reaction in a water bath at 50° C. until the acetone insolubles are reduced by about 30%. The reaction was carried out for 12 hr. Take 10g of the reactant and centrifuge, the upper layer is a clear layered oil phase, and the lower layer is a heterogeneous turbidity. The weight of the upper layer oil phase is 2.05g, and the acid value is 60.5.

Example 5

The operation of the enzyme reaction was the same as that in Example 4. After the reaction was completed, NaCl was added to the reaction system according to the water content of 5% (2.59g). 10 g of the reactant was taken for centrifugation, and the upper layer was a clearly stratified oil phase, the middle layer was turbid, and the lower layer was an aqueous phase. The weight of the upper oil phase was 2.08g, and the acid value was 61.5.

Example 6

The operation of the enzyme reaction was the same as that in Example 4. After the reaction was completed, NaCl was added to the reaction system according to 10% (5.18 g) of the water content. 10 g of the reactant was taken for centrifugation, and the upper layer was a clearly stratified oil phase, the middle layer was turbid, and the lower layer was an aqueous phase. The weight of the upper oil phase was 2.10g, and the acid value was 61.8.

Example 7

The operation of the enzyme reaction was the same as that in Example 4. After the reaction was completed, NaCl was added to the reaction system according to the moisture content of 7% (3.63g). 10 g of the reactant was taken for centrifugation, and the upper layer was a clearly stratified oil phase, the middle layer was turbid, and the lower layer was an aqueous phase. The weight of the upper oil phase was 2.11g, and the acid value was 60.9.

Example 8

The water content of soybean oil hydrated oil bottom analysis is 51.8%, the acetone insoluble matter in dry matter is 63.1%, and the rest is acetone soluble oil. Get 100g of the oily bottom, place it in a conical flask, add lipase Lipozyme RM (Danish Novozymes company) according to 20IU/g oily bottom after 45 DEG C water bath for 30min, stir and react in a 45 DEG C water bath until the acetone insoluble matter reduces by about 30%, The reaction was carried out for 12 hr. Take 10g of the reactant and centrifuge, the upper layer is a clear layered oil phase, and the lower layer is a heterogeneous turbidity. The weight of the upper layer oil phase is 1.91g, and the acid value is 80.6.

Example 9

The water content of the rapeseed oil hydration oil foot analysis is 50.6%, the acetone insoluble matter in the dry matter is 62.8%, and the rest is acetone soluble oil. Get 1000kg of this oil foot, in the stirring reaction kettle, adjust the oil foot temperature to be 50 ℃, add phospholipase Lecitase Ultra (Danish Novozymes company) according to 5IU/g oil foot, stir reaction 10hr, now acetone insoluble matter reduces 28.6%. The reactant is separated by a tubular centrifuge to obtain oil, and the residue of the separated oil is dried under reduced pressure to obtain a dry product mainly composed of lysophospholipid, which can be used in animal nutrition or chemical industry. The separated oil is separated by molecular distillation, and the temperature of the molecular distillation column is 180-210°C to obtain a light phase mainly composed of fatty acids, with an acid value of 183.5; at the same time, a heavy phase mainly composed of glycerides, with an acid value of 1.3, can be added Refined in crude oil or used for other purposes.

Claims (7)

1. a higher value application method for vegetable oil hydration oil foot, is characterized in that, comprise following steps:

(1) adjusting hydrated oil foot temperature is 40 ~ 65 DEG C, and adds lipase or Phospholipid hydrolase wherein, acetone insoluble matter loss of weight 20 ~ 45% in stirring reaction to system;

(2) centrifugal or standing separation, obtains taking grease as the light phase of main component and the heavy phase comprising modified phospholipid.

2. method according to claim 1, is characterized in that, the product removed out when described hydrated oil foot refers to vegetables oil crude oil hydration degum.

3. method according to claim 2, is characterized in that, after step (1) has been reacted, by the weight percent meter of moisture in reaction system, adds the NaCl of 5 ~ 10%, then carries out step (2) operation.

4. method according to claim 3, is characterized in that, the dosage of described enzyme is 1 ~ 50IU/g oil foot.

5. the method according to claim 1 or 2 or 3 or 4, is characterized in that, also comprise and the light of resulting separation is separated into free fatty acids and glyceride component further across molecular distillation.

6. method according to claim 5, is characterized in that, described vegetables oil is one or more the mixture in soybean oil, rapeseed oil, sunflower seed oil, Semen Maydis oil, peanut oil.

7. the method according to claim 1 or 2 or 3 or 4, is characterized in that, described lipase and Phospholipid hydrolase are derive from one or more the mixture in root enzyme genus, Aspergillus, hair enzyme genus, bacterium, yeast, animal pancreas.