阅读说明：本技术 一种自聚集含水磷脂 (Self-aggregating aqueous phospholipid ) 是由 徐子谦 于 2020-05-26 设计创作，主要内容包括：本发明属于磷脂加工技术领域,具体涉及一种自聚集含水磷脂。所述自聚集含水磷脂,其主要成分是磷脂、油脂和水,含水量为70-80g/100g,以干基计丙酮不溶物含量为92.5-95.5g/100g,感官指标为棕色半透明流体。本发明解决了现有的含水磷脂的丙酮不溶物含量不高、以及行业长期依赖溶剂法制备粉末磷脂的缺陷,还解决了水化法粉末磷脂无法实现工业化生产的技术难题。本发明自聚集含水磷脂的用途是制备水化法粉末磷脂,丙酮不溶物含量高达92.5-95.5g/100g,色泽为自然黄色,不漂白、无溶剂,可以取代溶剂法粉末磷脂,避免溶剂法粉末磷脂带来的环境污染和食品安全隐患,并且水化法粉末磷脂的生产成本远低于溶剂法。(The invention belongs to the technical field of phospholipid processing, and particularly relates to self-aggregating aqueous phospholipid. The self-aggregation water-containing phospholipid comprises main components of phospholipid, grease and water, wherein the water content is 70-80g/100g, the content of acetone insoluble substances is 92.5-95.5g/100g on a dry basis, and the sensory index is brown semitransparent fluid. The invention solves the defects that the content of acetone insoluble substances of the existing water-containing phospholipid is not high and the industry depends on a solvent method for preparing the powdered phospholipid for a long time, and also solves the technical problem that the powdered phospholipid prepared by a hydration method can not realize industrial production. The self-aggregation aqueous phospholipid is used for preparing hydration-method powdered phospholipid, the content of acetone insoluble substances reaches 92.5-95.5g/100g, the color is natural yellow, bleaching is avoided, no solvent exists, the solvent-method powdered phospholipid can be replaced, environmental pollution and food safety hidden trouble caused by solvent-method powdered phospholipid are avoided, and the production cost of the hydration-method powdered phospholipid is far lower than that of a solvent method.)

1. A self-aggregating aqueous phospholipid, characterized in that the main components of the self-aggregating aqueous phospholipid are phospholipid, oil and fat and water, the water content is 70-80g/100g, and the acetone insoluble content is 92.5-95.5g/100g on a dry basis.

2. The self-aggregating aqueous phospholipid as set forth in claim 1, wherein the self-aggregating aqueous phospholipid is a brown translucent fluid.

3. The self-aggregating aqueous phospholipid as set forth in claim 1, wherein the preparation method of the self-aggregating aqueous phospholipid comprises the steps of: soaking soybean oil residue in water to obtain saturated water-absorbing oil residue, and naturally settling.

4. The self-aggregating aqueous phospholipid as claimed in claim 3, wherein the mass ratio of the soybean oil foot to the water is 1:1 to 3.5.

5. The self-aggregating aqueous phospholipid as set forth in claim 3, wherein the soaking temperature is 60 to 95 ℃, the soaking time is 1 to 3 hours, and the natural settling time is 3 to 8 hours.

6. The self-aggregating aqueous phospholipid as claimed in claim 3, wherein the soybean oil foot is broken up in water into granules with a particle size of 5mm or less, preferably 0.3 to 3mm, by stirring before the soaking.

7. The self-aggregating aqueous phospholipid as set forth in claim 3, wherein the preparation method further comprises adding an electrolyte to the soaking system.

8. The self-aggregating aqueous phospholipid as claimed in claim 7, wherein the electrolyte has a mass fraction in water of 0.01 to 0.3%.

9. The self-aggregating aqueous phospholipid of claim 7, wherein the electrolyte comprises at least one of an acid, a base and a salt, preferably the electrolyte is at least one of DL-sodium malate, L-malic acid, DL-malic acid, glacial acetic acid, citric acid, potassium citrate, sodium citrate, monosodium citrate, sodium gluconate, lactic acid, potassium lactate, sodium lactate, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium sulfate, potassium chloride, potassium hydroxide, sodium hydroxide, hydrochloric acid, phosphoric acid and sodium chloride.

10. Use of a self-aggregating aqueous phospholipid as defined in any one of claims 1 to 9 in the preparation of a powdered phospholipid.

Technical Field

The invention belongs to the technical field of phospholipid processing, and particularly relates to self-aggregating aqueous phospholipid.

Background

The raw material for processing the phospholipid is soybean oil residue, which is called hydrated oil residue for short, is a byproduct of a hydration degumming process in the soybean oil refining process in the field of oil processing, and is also called hydrated oil residue, wherein the main components comprise 30-45g/100g of phospholipid, 20-30g/100g of soybean oil and 30-50g/100g of water, and the trace components comprise metal ions, such as calcium, magnesium, iron and the like, and exist in the form of phospholipid metal salts, such as iron ion content, usually 50-100mg/kg calculated by acetone insoluble substances, and the content is up to more than 150mg/kg in individual cases.

The method for processing the industrial phospholipid mainly comprises two methods, one is that the concentrated phospholipid is prepared by a hydration method, namely the concentrated phospholipid is obtained by directly drying and dehydrating after soybean oil residue is extracted from crude soybean oil in a hydration manner, and the concentrated phospholipid is also called as fluid phospholipid due to the fluidity, and the content of dry acetone insoluble substances is 60-65g/100 g; and secondly, preparing the powdered phospholipid by a solvent method, namely taking soybean oil residue or concentrated phospholipid as a raw material, and extracting the raw material by using acetone to remove grease to obtain the powdered phospholipid, wherein the content of dry acetone insoluble substances is 95-98g/100 g. The mainstream product in the market is concentrated phospholipid, and the ratio of the powdered phospholipid in the market is less than 5%.

Although the soybean oil residue is mostly processed into concentrated phospholipids, the concentrated phospholipids have a great disadvantage. For example, documents "a process for producing concentrated phospholipids from soybean (Huxing. a process for producing concentrated phospholipids from soybean [ J ]. China fat, 2007,32(9):20-21) and" a process for preparing concentrated phospholipids (Houqing et al. a process for preparing concentrated phospholipids [ J ]. China fat, 2002,27(1):39-40) describe a method for producing concentrated phospholipids by dehydrating and oxidizing and bleaching hydrated oil residues as raw materials. The process has the disadvantages that the content of acetone insoluble substances in the concentrated phospholipid is too low (60-65g/100g), chemical bleaching is needed, the market price is only 0.4 ten thousand yuan/ton, and the price has a large difference with the price of 4 ten thousand yuan/ton of powder phospholipid.

Chinese patent CN103665029A discloses a method for preparing soybean powder phospholipid, which adopts acetone as solvent to extract hydrated oil residue, separates out acetone insoluble substances, and then carries out low-temperature vacuum drying on the acetone insoluble substances to remove the solvent, thus obtaining the powder phospholipid. The method has the defects that an acetone solvent is used, the production cost is high, the potential safety hazard of environmental pollution and solvent residue exists, and the method is difficult to popularize generally, so that the structure upgrade of a product converted from concentrated phospholipid to powdered phospholipid in the field of oil processing cannot be promoted, and the current situation of high oil refining loss cannot be improved.

For example, chinese patent CN107325125A discloses a method for preparing a phospholipid hydrate from soybean oil residue and a phospholipid hydrate (hereinafter referred to as phospholipid hydrate) prepared by the method, and the method includes the following steps: adding softened water into soybean oil residue, mixing, standing, and performing chromatography; after the chromatography is finished, controlling the temperature to be 85-95 ℃, and carrying out centrifugal separation to obtain the hydrated phospholipid, wherein the acetone insoluble matter can reach 90-92%. This patent has the following drawbacks:

(1) the dry acetone insoluble content of the hydrated phospholipids is low: the patent is a homogeneous hydration method, namely oil residue and water are mixed uniformly, emulsification inevitably occurs when the mixing is uniform, and phospholipid and oil are difficult to re-separate if the emulsification is serious. In order to avoid serious emulsification, the patent adopts two measures, namely strictly controlling the water adding amount which is 0.25-0.74 times of the weight of oil residue; second, sodium hydroxide or sulfuric acid is added, acting as a demulsifier. The problem brought by the measures is that the main components of phospholipid, grease and phospholipid metal salt in the soybean oil residue are not effectively separated, the content of dry acetone insoluble substances of the hydrated phospholipid reaches only 92 percent at most, and has a certain difference compared with 95-98 percent of acetone insoluble substances in a solvent method;

(2) hydrated phospholipids are not thoroughly dried and lack industrial utility: the hydrated phospholipid is subjected to concentration dehydration, preservative addition, pasteurization and packaging to obtain an aqueous phospholipid product with the water content of 22.5-41.2 percent, but the aqueous phospholipid product does not meet the regulation of national standard GB28401 food additive phospholipid on that the water content cannot exceed 2 percent and cannot be sold; if the drying is performed according to the existing method for preparing powdered phospholipids, the time is too long, the productivity is too low, and the industrial production is not feasible, and the powdered phospholipids can not be sold or further processed, so that the powdered phospholipids are not industrially used.

Another prior art for extracting phospholipid by hydration method is disclosed in the document "research on liquid crystal separation and purification of soybean phospholipid" (Leziming et al. research on liquid crystal separation and purification of soybean phospholipid [ J ]. Chinese food and oil institute, 2007,22(1):31-32), hereinafter referred to as liquid crystal phospholipid. The method of the document has the following technical defects: (1) the content of insoluble acetone on dry basis of the liquid crystal state phospholipid is low: the homogeneous hydration method is adopted, the water adding amount is 0.67 times of oil residue, and the content of the obtained liquid crystal state phospholipid in dry acetone insoluble matters is only 86.05 percent, which is the same as the defect of the hydrated phospholipid; (2) lack of industrial use: the drying problem of the liquid crystal phospholipid is the same as that of the hydrated phospholipid, although the liquid crystal phospholipid is obtained into powder phospholipid by a batch vacuum drying mode, the drying time is too long, and the color of the phospholipid product is dark (brown), so that the liquid crystal phospholipid cannot be applied to industrial production.

Chinese patent CN102517148A discloses a two-step decolorization method of phospholipid, which adopts two-step decolorization methods of hydrogen peroxide bleaching and silica gel adsorption, and has the following defects: (1) chemical bleaching and decoloring, so that phospholipid generates oxidation byproducts, the naturalness of the phospholipid is damaged, and meanwhile, food safety risks exist and the method does not conform to the large trend of green development; (2) the adsorption and decoloration effects of silica gel are poor, and the invalid silica gel becomes waste residue, which is not beneficial to environmental protection; (3) bleaching destroys the beneficial antioxidant components in the phospholipid, reduces the antioxidant and nutritive values of the phospholipid, and shortens the shelf life of the phospholipid.

In the phospholipid processing field, the substitution of the powdered phospholipid for the concentrated phospholipid is the future direction from the product perspective, the substitution of the hydration method for the solvent method is the future direction from the method perspective, and although some researches on the hydration method exist at present, the purity of the phospholipid prepared by the hydration method is not high enough, the color improvement is not separated from the chemical bleaching method, the dehydration efficiency of the hydration method does not reach the industrial level, and the process technology is not enough in the aspects of integrity and continuity.

Therefore, it is necessary to develop a self-aggregating aqueous phospholipid which can solve the above-mentioned technical problems.

Disclosure of Invention

The first object of the present invention is to provide a self-aggregating aqueous phospholipid which has the following advantages: the water content is saturated, the dry acetone insoluble content is the highest in all known hydration methods, and the dry acetone insoluble content is close to or even reaches the level of solvent method powder phospholipid. The self-aggregation aqueous phospholipid is an intermediate product necessary for preparing hydration-method powdered phospholipid, and from the industrial development perspective, the hydration-method powdered phospholipid finally replaces solvent-method powdered phospholipid to become a mainstream product so as to eliminate environmental pollution caused by organic solvent and hidden food safety hazards caused by solvent residue and reduce production cost. The invention solves the technical problem that the prior art can not prepare high-purity water-containing phospholipid and powder phospholipid from soybean oil residue by a hydration method. The self-aggregating aqueous phospholipids have not been reported in the field of phospholipid processing and related studies.

The second object of the present invention is to provide the use of said self-aggregating aqueous phospholipids for the preparation of powdered phospholipids.

In order to achieve the above purpose, the technical scheme provided by the invention is as follows:

a self-aggregating aqueous phospholipid whose main components are phospholipid, oil and fat and water, has a water content of 70-80g/100g and an acetone-insoluble content of 92.5-95.5g/100g on a dry basis.

Preferably, the self-aggregating aqueous phospholipid is a brown translucent fluid.

The self-aggregation water-containing phospholipid refers to an aggregate formed by the spontaneous combination and the spontaneous aggregation of phospholipid in the soybean oil residue and water.

Preferably, the method for preparing the self-aggregating aqueous phospholipid comprises the following steps: soaking soybean oil residue in water to obtain saturated water-absorbing oil residue, and naturally settling.

The soaking means that the soybean oil residue is a dispersed phase in water, and the water is a continuous phase, so that a soaking system is formed.

As a result of the soaking, a saturated water-absorbing oil foot was obtained. And after soaking, the water absorption capacity of the phospholipid in the saturated water absorption oil residue reaches saturation, namely the water content of the phospholipid reaches 70-80g/100 g.

More preferably, the mass ratio of the soybean oil foot to the water is 1: 1-3.5.

When the weight of the water is less than 1.0 time of that of the oil residue, the soybean oil residue can not be effectively soaked in the water, and the combination of the phospholipid and the water is further influenced. When the water is more than 3.5 times of the mass of the oil residue, although the soaking of the soybean oil residue is facilitated, the cost of water, the energy consumption and the volume of the equipment are increased.

More preferably, the temperature of the soaking is 60-95 ℃.

In water at 0 ℃ to 100 ℃, the combination of phospholipid and water can occur, and the combination efficiency is higher at higher temperature. Therefore, the water temperature is increased, and the soaking time can be shortened. However, in boiling water, stabilization of self-aggregating aqueous phospholipids is not favored, and boiling evaporation of water wastes energy. The temperature of the soaking is therefore preferably 60-95 ℃. When the temperature is above 60 deg.C, the sterilization temperature can prevent oil residue from deteriorating during soaking, and when the temperature is below 95 deg.C, water can be prevented from boiling.

More preferably, the soaking time is 1-3 h.

The soaking time refers to the time required for obtaining the saturated water-absorbing oil foot, and the soaking time is from the time when the soybean oil foot is in a granular shape and stands still in water for soaking until brown self-aggregation water-containing phospholipid begins to appear in the soybean oil foot. The soybean oil residue in the soaking was yellow and the self-aggregating aqueous phospholipid appeared brown, so that it was possible to visually judge whether the end time of the soaking was reached.

More preferably, the soaking is still soaking.

During the soaking period, stirring operation is not suitable to prevent emulsification.

More preferably, the soybean oil foot is broken up into particles in water with stirring before soaking.

More preferably, the particle size of the soybean oil foot particles is less than or equal to 5 mm.

More preferably, the particle size of the soybean oil foot particles is 0.3 to 3 mm.

The smaller the particle size of the soybean oil residue is, the larger the contact area of the oil residue and water is, and the mass transfer and heat transfer efficiency of phospholipid and water in the soybean oil residue is improved. However, the soybean oil residue has a too small particle size, and there is a risk that the soybean oil residue and water are uniformly mixed and homogenized, and the soaking system is damaged.

More preferably, the preparation method further comprises adding an electrolyte to the soaking system.

More preferably, the electrolyte has a mass fraction in water of 0.01 to 0.3%.

The proper amount of electrolyte is beneficial to the combination of the phospholipid and water in the soybean oil residue, the combination of the phospholipid and the water can be inhibited when the electrolyte is too much, and the water content of the self-aggregation water-containing phospholipid is higher when the electrolyte is too little or not added, so that the energy waste during dehydration is caused.

More preferably, the electrolyte includes at least one of an acid, a base, and a salt.

More preferably, the electrolyte is at least one of DL-sodium malate, L-malic acid, DL-malic acid, glacial acetic acid, citric acid, potassium citrate, sodium citrate, monosodium citrate, sodium gluconate, lactic acid, potassium lactate, sodium carbonate, potassium bicarbonate, sodium sulfate, potassium chloride, potassium hydroxide, sodium hydroxide, hydrochloric acid, phosphoric acid, and sodium chloride.

More preferably, the time of natural settling is 3-8 h.

As a result of said natural sedimentation, self-aggregating aqueous phospholipids are obtained. At the end of natural sedimentation, two components, namely the self-aggregating aqueous phospholipid and the residue of the oil residue, are obtained from the saturated water-absorbing oil residue. During the natural settling period, stirring operation is not suitable to prevent emulsification.

The invention also relates to the use of said self-aggregating aqueous phospholipids for preparing powdered phospholipids.

Preferably, the self-aggregating aqueous phospholipid is used for preparing a powdered phospholipid, comprising the steps of:

(1) preparation of concentrated aqueous phospholipids: concentrating the self-aggregating aqueous phospholipid under vacuum at 90-110 deg.C to a water content of 25-65g/100g to obtain a concentrated aqueous phospholipid having a dry acetone insoluble content of 92.5-95.5g/100g and a sensory index of brown translucent fluid.

(2) Preparation of aqueous phospholipid elastomer: and pushing the concentrated aqueous phospholipid into a stirrer at the speed of 10-100cm/min, wherein the stirring rotation number is 800-1200rpm, and the stirring time is 5-30s, so as to obtain the continuously output aqueous phospholipid elastomer, wherein the water content and the acetone insoluble content of the aqueous phospholipid elastomer are the same as those of the concentrated aqueous phospholipid, but the sensory index is changed into yellow opaque semisolid.

The aqueous phospholipid elastomer is an elastomer in the colloid chemistry category, the rheological property of the aqueous phospholipid elastomer is that the storage modulus G 'is 5-10 times larger than the loss modulus G' and the aqueous phospholipid elastomer shows stronger solid characteristics (elasticity) and weaker liquid characteristics (viscosity) and belongs to the elastomer.

(3) Preparing solid phospholipid: and (2) feeding the continuously output water-containing phospholipid elastomer into a normal-pressure or vacuum continuous dryer through a feed inlet with the aperture of 2-6mm, and drying at the temperature of 120-160 ℃ for 6-20min to obtain continuously output strip-shaped solid phospholipid, wherein the water content of the strip-shaped solid phospholipid is 3-10g/100g, the content of the dry acetone insoluble substances is 92.5-95.5g/100g, and the sensory index of the strip-shaped solid is yellow strip-shaped solid.

(4) Preparing powder phospholipid: and (2) crushing and sieving the strip-shaped solid phospholipid, and performing vacuum drying at 60 ℃ for 30-60min to obtain powder phospholipid, wherein the water content of the powder phospholipid is less than or equal to 2g/100g, the content of dry acetone insoluble substances is 92.5-95.5g/100g, the sensory index of the powder phospholipid is yellow powder, and the product meets the national standard GB28401 food additive phospholipid.

The water content of the powder phospholipid in the step (4) is equal to the drying decrement described in the national standard GB28401 food additive phospholipid.

The vacuum is 0.01-0.004 MPa.

The invention has the beneficial effects that:

firstly, the water content of the self-aggregation water-containing phospholipid reaches 70-80g/100g, the water absorption capacity of the phospholipid reaches saturation: when the water absorption capacity of the phospholipid reaches saturation, the lipophilicity of the phospholipid is reduced to the minimum, namely the oil content of the self-aggregation water-containing phospholipid is the minimum, the purity of the phospholipid is the highest, and the content of dry acetone insoluble matters reaches 92.5-95.5g/100 g.

Second, the dry acetone insoluble content of the self-aggregating aqueous phospholipids of the present invention is highest in all current hydration processes: the dry acetone insoluble content of the self-aggregation water-containing phospholipid is 92.5-95.5g/100g, the content of the patent-disclosed hydrated phospholipid is 90-92g/100g, and the content of the liquid crystal state phospholipid reported in the literature is 86.05g/100 g.

Third, the dry acetone insoluble content of the self-aggregating aqueous phospholipids of the present invention is most similar to the solvent method: the dry acetone insoluble content of the self-aggregating aqueous phospholipid of the invention is 92.5-95.5g/100g, which is close to or even reaches the level of 95-98g/100g of solvent method powder phospholipid. From the perspective of industrial development, a hydration method is a mainstream product to replace a solvent method finally so as to eliminate environmental pollution caused by organic solvent and food safety hidden trouble caused by solvent residue and reduce production cost.

Fourthly, the self-aggregation aqueous phospholipid and the powder phospholipid prepared by the self-aggregation aqueous phospholipid have complete process technology from soybean oil residue to powder phospholipid, have great advantages in the aspects of quality, quality guarantee period, production cost, environmental protection and food safety, and are suitable for industrial production.

Drawings

FIG. 1 is a process flow diagram of a process for obtaining self-aggregating aqueous phospholipids by soaking soybean oil foot and naturally settling.

FIG. 2 is a schematic diagram of a process for obtaining self-aggregating aqueous phospholipids by soaking soybean oil bottoms and naturally settling. Wherein:

(a) is a schematic diagram of soybean oil foot in water;

(b) the soaking system is a schematic diagram of a soaking system with soybean oil residue particles as a dispersed phase and water as a continuous phase;

(c) a schematic diagram of self-aggregating aqueous phospholipids with natural sedimentation beginning with saturated water-absorbing oil bottoms;

(d) is a schematic diagram of the saturated water-absorbing oil residue which is naturally settled to obtain the self-aggregating aqueous phospholipid and the oil residue.

FIG. 3 is a process flow diagram for preparing solid phospholipids from aggregated aqueous phospholipids.

FIG. 4 is a schematic diagram of a process for concentrating aqueous phospholipids to prepare solid phospholipids.

FIG. 5 is a graph of the rheological characteristics of storage modulus G 'and loss modulus G' for aqueous phospholipid elastomers prepared using the self-aggregating aqueous phospholipid of example 1.

FIG. 6 is a graph showing the rheological characteristics of storage modulus G 'and loss modulus G' of an aqueous phospholipid elastomer prepared by self-aggregating an aqueous phospholipid in application example 2.

Wherein: (1) is a continuous phase of water; (2) is soybean oil residue; (3) is dispersed phase soybean oil foot particles; (4) is saturated water absorption oil residue; (5) is a self-aggregating aqueous phospholipid; (6) is residue of oil residue; (7) is a concentrated aqueous phospholipid; (8) is an aqueous phospholipid elastomer; (9) is a solid phospholipid. A is a soaking tank; b is a speed-regulating gear pump; c is a pipeline stirrer; d is a continuous dryer.

Detailed Description

The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are commercially available; the vacuum is 0.01-0.004 MPa.

Definition of dry acetone insoluble yield from aggregated aqueous phospholipids:

the yield of dry acetone insoluble matter of self-aggregated aqueous phospholipid is the weight of dry acetone insoluble matter of self-aggregated aqueous phospholipid/the weight of dry acetone insoluble matter of soybean oil residue.