阅读说明：本技术 一种含水磷脂弹性体的制备方法 (Preparation method of aqueous phospholipid elastomer ) 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领域,具体涉及一种含水磷脂弹性体的制备方法：取含水磷脂进行搅拌,得到含水磷脂弹性体。本发明制备得到的含水磷脂弹性体用以改变含水磷脂的物体色,由棕色转变为黄色,解决行业长期依赖化学漂白脱色的缺陷；同时,用以改变含水磷脂的状态,由流体转变半固体,由此改变了含水磷脂的干燥性能,使含水磷脂中的水分在干燥时能够快速蒸发同时给物料降温,因此可以承受高达160℃的干燥温度,解决了目前从含水磷脂制备固体磷脂的干燥效率低、无法实现工业化生产的技术难题,使制备固体磷脂的干燥脱水时间缩短到6-20min。(The invention belongs to the field of phospholipid processing, and particularly relates to a preparation method of a water-containing phospholipid elastomer, which comprises the following steps: and (3) taking the water-containing phospholipid and stirring to obtain the water-containing phospholipid elastomer. The aqueous phospholipid elastomer prepared by the invention is used for changing the body color of the aqueous phospholipid from brown to yellow, and solves the defect that the industry depends on chemical bleaching for a long time for decolorization; meanwhile, the method is used for changing the state of the water-containing phospholipid and converting the liquid into the semisolid, so that the drying performance of the water-containing phospholipid is changed, the water in the water-containing phospholipid can be quickly evaporated and the material can be cooled during drying, the drying temperature of 160 ℃ can be borne, the technical problems that the existing method for preparing the solid phospholipid from the water-containing phospholipid is low in drying efficiency and cannot realize industrial production are solved, and the drying and dehydrating time for preparing the solid phospholipid is shortened to 6-20 min.)

1. A method for preparing an aqueous phospholipid elastomer, comprising the steps of: and (3) taking the water-containing phospholipid and stirring to obtain the water-containing phospholipid elastomer.

2. The method of claim 1, wherein the aqueous phospholipid elastomer has a storage modulus G' 5 to 10 times greater than a loss modulus G "and an organoleptic index of yellow opaque semi-solid.

3. The method as claimed in claim 1, wherein the rotation speed of the stirring is 800-1200 rpm.

4. The method of claim 3, wherein the agitation is continuous, the aqueous phospholipid is continuously pushed into the agitator at a speed of 10-100cm/min for 5-30s to obtain a continuous output of aqueous phospholipid elastomer.

5. The method of claim 1, wherein the aqueous phospholipid is obtained by a hydration process of soybean oil foot.

6. The method according to claim 5, wherein the aqueous phospholipid comprises phospholipids, fats and oils and water as main components, has a water content of 25 to 65g/100g and a dry acetone insoluble content of 85g/100g or more.

7. The method of claim 5, wherein the aqueous phospholipid is prepared by a process comprising the steps of: self-aggregating or low-iron aqueous phospholipids prepared from soybean oil residue, and concentrating to obtain aqueous phospholipids.

8. The method of claim 7, wherein the self-aggregating aqueous phospholipid is prepared by: soaking soybean oil residue in water to obtain saturated water-absorbing oil residue, and naturally settling to obtain self-aggregating water-containing phospholipid.

9. The method of claim 7, wherein the low-iron aqueous phospholipid is prepared by: soaking soybean oil residue in water to obtain saturated water-absorbing oil residue, centrifuging, settling, removing phospholipid metal salt to obtain fluid, standing, and layering to obtain low-iron water-containing phospholipid.

10. Use of an aqueous phospholipid elastomer prepared by the method according to any one of claims 1 to 9 for preparing a solid phospholipid or a powdered phospholipid.

Technical Field

The invention belongs to the field of phospholipid processing, and particularly relates to a preparation method of a water-containing phospholipid elastomer.

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.

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) aqueous phospholipids are not completely 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 obtains solid phospholipid and powdered 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.

The literature "rheological Properties of surfactant aggregates" (M.M.H.rheological Properties of surfactant aggregates [ J. daily chemical industry, 2002,32(2):38-40) describes the basic theory of colloidal elastomers. Although the elastomer of colloid chemistry is a mature concept, from the industrial technology point of view, the unique components of the soybean aqueous phospholipid and the method for preparing the elastomer thereof, the excellent drying property of the elastomer for the aqueous phospholipid, the improvement of the body color of the elastomer and the application of the elastomer in preparing solid phospholipid and powder phospholipid are not reported.

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 still not high enough, the color improvement is still not separated from the chemical bleaching method, the dehydration efficiency of the hydration method still does not reach the industrial level, and the process technology has defects in the aspects of integrity, continuity and automation.

Therefore, it is necessary to develop a method for preparing an aqueous phospholipid elastomer which can solve the above-mentioned problems.

Disclosure of Invention

The invention aims to provide a preparation method of a water-containing phospholipid elastomer, wherein the water-containing phospholipid elastomer prepared by the preparation method is used for changing the object color of water-containing phospholipid from brown to yellow, so that the defect that the industry depends on chemical bleaching for decolorization for a long time is overcome; the method is used for changing the state of the water-containing phospholipid and converting the liquid into the semisolid, thereby changing the drying performance of the water-containing phospholipid, enabling the water in the water-containing phospholipid to be quickly evaporated during drying, solving the technical problems that the existing method for preparing the solid phospholipid from the water-containing phospholipid is low in drying efficiency and cannot realize industrial production, and shortening the drying and dehydrating time of the prepared solid phospholipid to 6-20 min. The preparation method of the aqueous phospholipid elastomer is not reported in the phospholipid processing field and related researches.

The second purpose of the invention is to provide the application of the aqueous phospholipid elastomer prepared by the preparation method in preparing solid phospholipid or powder phospholipid.

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

a method for preparing an aqueous phospholipid elastomer, comprising the steps of: and (3) taking the water-containing phospholipid and stirring to obtain the water-containing phospholipid elastomer.

The aqueous phospholipid elastomer is an elastomer form of an aqueous phospholipid, which is rheologically characterized by a storage modulus G '5-10 times greater than a loss modulus G' and exhibits a stronger solid character (elasticity) while a liquid character (viscosity) becomes weaker, and is therefore called an elastomer.

Preferably, the sensory index of the aqueous phospholipid elastomer is a yellow opaque semi-solid; the sensory index of the aqueous phospholipid is a brown translucent fluid. The aqueous phospholipid elastomer changes the physical color of the aqueous phospholipid from brown to yellow; the aqueous phospholipid elastomer changes the state of the aqueous phospholipid and changes from a fluid to a semi-solid.

Preferably, the rotation speed of the stirring is 800-.

Preferably, the stirring is a continuous mode, the water-containing phospholipid is continuously pushed into the stirrer, the pushing speed is 10-100cm/min, and the stirring time is 5-30s, so that the water-containing phospholipid elastomer which is continuously output is obtained.

Preferably, the aqueous phospholipid is prepared from soybean oil foot by a hydration method.

More preferably, the main components of the water-containing phospholipid are phospholipid, grease and water, the water content is 25-65g/100g, and the content of insoluble acetone on a dry basis is more than or equal to 85g/100 g.

More preferably, the source of the aqueous phospholipid comprises liquid crystal state aqueous phospholipid (water content is less than or equal to 65% and dry acetone insoluble content is 86.05%) prepared from soybean oil foot in the literature, "research on liquid crystal state separation and purification of soybean phospholipid"), or hydrated phospholipid (water content is less than or equal to 65% and dry acetone insoluble content is 90-92%) prepared from soybean oil foot in patent CN107325125A, or aqueous phospholipid prepared from soybean oil foot by other hydration methods.

More preferably, the aqueous phospholipid is prepared by the following two preparation methods:

method (1): preparing self-aggregating aqueous phospholipid from soybean oil residue, and concentrating to obtain aqueous phospholipid, comprising the following steps:

preparing self-aggregating aqueous phospholipids: soaking soybean oil residue in water to obtain saturated water-absorbing oil residue, and naturally settling to obtain self-aggregating water-containing phospholipid.

The obtained self-aggregation water-containing phospholipid comprises main components of phospholipid, grease and water, and the water content is 70-80g/100 g; the content of acetone insoluble substances is 92.5-95.5g/100g on a dry basis; the sensory index was a brown translucent fluid.

② preparing the aqueous phospholipid: concentrating the water content of the self-aggregating aqueous phospholipid to 25-65g/100g to obtain the aqueous phospholipid.

Method (2): preparing low-iron aqueous phospholipid from soybean oil residue, and concentrating to obtain aqueous phospholipid, comprising the following steps:

preparing low-iron water-containing phospholipid: soaking soybean oil residue in water to obtain saturated water-absorbing oil residue, centrifuging, settling, removing phospholipid metal salt to obtain fluid, standing, and layering to obtain low-iron water-containing phospholipid.

The obtained low-iron water-containing phospholipid comprises phospholipid, oil and water as main components, and has water content of 70-80g/100 g; the content of acetone insoluble substances is 92.5-95.5g/100g on a dry basis; the iron content is less than or equal to 18mg/kg based on the acetone insoluble substance.

② preparing the aqueous phospholipid: concentrating the water content of the low-iron aqueous phospholipid to 25-65g/100g to obtain the aqueous phospholipid.

The soaking in the method (1) and the method (2) means that the soybean oil residue is in a dispersed phase in water, and the water is in a continuous phase, so that a soaking system is formed.

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, in the method (1), the natural settling time 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.

More preferably, in the method (2), the centrifugal sedimentation is batch centrifugal sedimentation.

The intermittent centrifugal sedimentation means that the loading and unloading are necessarily carried out at the shutdown. Continuous centrifuges cannot be used here because they cause severe emulsification of the material during the feeding and discharge and do not achieve the desired separation effect. Because the saturated water absorption oil foot and the fluid obtained by centrifugal sedimentation are all fluids with excellent fluidity and can be automatically loaded and unloaded, the operation of the batch centrifuge can be automated through program design so as to meet the requirement of large-scale industrial production.

In the centrifugal sedimentation process, the saturated water absorption oil foot is divided into two components of slag and fluid in a batch centrifuge, wherein the slag is mainly phospholipid metal salt and is tightly attached to the rotary drum wall of the centrifuge in the form of slag, and the slag is taken out from the upper part of the centrifuge in a slag discharging mode. The fluid is primarily grease, water and low iron aqueous phospholipids, and is referred to as a fluid because it can flow. After the shutdown, the fluid can automatically flow into the standing layering tank from the bottom of the centrifuge, and grease, water and low-iron water-containing phospholipid in the fluid are divided into three layers due to different specific gravities.

More preferably, the temperature of the centrifugal sedimentation is 60 to 95 ℃.

More preferably, the rotational speed of the centrifugal sedimentation is 500-2000 rpm.

More preferably, the time of the centrifugal sedimentation is 5-15 min.

More preferably, in the method (2), the temperature of the standing delamination is 60 to 95 ℃.

The invention also relates to the application of the prepared aqueous phospholipid elastomer in preparing solid phospholipid and powder phospholipid.

Preferably, the application of the aqueous phospholipid elastomer in preparing the solid phospholipid comprises the following specific processes: continuously drying the water-containing phospholipid elastomer at the temperature of 120-160 ℃ under normal pressure or vacuum for 6-20min to reduce the water content to 3-10g/100g, thereby obtaining strip-shaped yellow solid phospholipid which is continuously output; the continuous drying feed inlet is a round, square or special-shaped hole, and the aperture or the maximum side length is 2-6 mm.

Preferably, the application of the aqueous phospholipid elastomer in preparing the powdered phospholipid is as follows: crushing solid phospholipid, sieving with 18 mesh sieve, vacuum drying at 60 deg.C for 30-60min to obtain powder phospholipid with water content of 2g/100g or less, insoluble acetone content of 85g/100g or more, and yellow sensory index, and the product meets national standard GB28401 food additive phospholipid.

The moisture content of the powder phospholipid is equal to the drying decrement of the national standard GB28401 food additive phospholipid.

The invention has the beneficial effects that:

(1) the method changes the object color of the aqueous phospholipid from brown to yellow: the water-containing phospholipid is brown, and the solid phospholipid obtained after drying and dehydration is also brown, so that the brown phospholipid does not meet the large trend of light-colored phospholipid demanded by the market and is a great defect; the aqueous phospholipid elastomer prepared by the invention changes the color of the aqueous phospholipid from brown to yellow, and the solid phospholipid obtained after drying and dehydration is also yellow, so that the requirements of the market on light-colored phospholipid can be met, and the aqueous phospholipid elastomer has industrial development value.

(2) The method of the present invention changes the state of the aqueous phospholipid from a fluid to a semi-solid, thereby changing the drying properties of the aqueous phospholipid: the aqueous phospholipid is fluid, a dry hard film is formed on the surface of the phospholipid during drying and dehydration, the evaporation of water in the phospholipid is prevented, the drying time of the aqueous phospholipid reaches 240min, and the technical bottleneck for preparing the solid phospholipid by the aqueous phospholipid is prevented; the aqueous phospholipid elastomer prepared by the invention enables the aqueous phospholipid to be converted from fluid to semisolid, and a porous structure is formed on the surface of the phospholipid during drying and dehydration, so that continuous and rapid evaporation of water in the phospholipid is facilitated, and the temperature of the material is reduced, so that the aqueous phospholipid elastomer can bear a drying temperature of up to 160 ℃, the drying time of the aqueous phospholipid is shortened to 6-20min, and the problem of drying the aqueous phospholipid is thoroughly solved.

(3) The aqueous phospholipid elastomer prepared by the invention is natural yellow: the existing phospholipids can be used for producing yellow products only by chemical bleaching, and the bleached phospholipids have oxidation byproducts, so that potential food safety hazards exist, and the quality guarantee period is greatly shortened; the aqueous phospholipid elastomer prepared by the invention can obtain natural yellow solid phospholipid and powder phospholipid without chemical bleaching.

Drawings

FIG. 1 is a flow chart of a process for preparing an aqueous phospholipid elastomer by stirring an aqueous phospholipid;

FIG. 2 is a schematic diagram of a process for preparing solid phospholipid by drying after converting aqueous phospholipid into aqueous phospholipid elastomer by stirring;

wherein: (1) is an aqueous phospholipid; (2) is an aqueous phospholipid elastomer; (3) is a solid phospholipid; a is a speed-regulating gear pump; b is a pipeline stirrer; c is a continuous dryer;

FIG. 3 is a flow diagram of a process for preparing self-aggregating aqueous phospholipids from soybean oil foot;

FIG. 4 is a flow diagram of a process for preparing low iron aqueous phospholipids from soybean oil residues;

FIG. 5 is a graph of the rheological profile of storage modulus G 'versus loss modulus G' for the aqueous phospholipid elastomer of example 2;

FIG. 6 is a graph of the rheological characteristics of storage modulus G 'versus loss modulus G' for the aqueous phospholipid elastomer of example 4.

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.