JPS60184597A - Purification of crude glyceride oil composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for purifying crude glyceride oil compositions using semipermeable membranes.

Vegetable oils commonly used as edible oils include soybean oil, rapeseed oil, sunflower oil, and safflower oil. To produce these vegetable oils, first, depending on the oil content in the raw materials, the raw materials are either compressed or extracted with an organic solvent such as hexano to form miscella, and the solvent is evaporated from the miscella. removal to obtain a crude glyceride oil composition. This crude glyceride oil composition usually contains about 1.5 to 3% of impurities mainly composed of phospholipids such as lecithin, so-called gum, and this gum breaks down when the oil is heated. It is necessary to remove as much gummy matter as possible from the crude glyceride oil composition, since it may color the oil, give off an off-flavor, or impair its taste.

Conventionally, water is added to a crude glyceride oil composition to hydrate, swell, and solidify the gum, and then degum is performed by centrifugation. It contains about 1% by weight, and usually after repeated degumming using chemicals, the product is obtained by deoxidizing, decolorizing, deodorizing, and reducing the gum quality to loOppm or less. However, such conventional refining methods require repeated and complicated degumming operations, and the degumming operations inevitably result in the loss of a considerable amount of oil.

In order to eliminate such disadvantages, a new method for purifying crude glyceride oil compositions has been proposed in JP-A-50-153010. In this method, a crude glyceride oil composition diluted with an organic solvent such as hexane is brought into contact with a semipermeable membrane made of a synthetic organic polymer under pressure, and hexane and glyceride oil are extracted from the concentrated membrane retentate through the membrane. The membrane permeate is separated as a permeate, and the organic solvent is removed from the membrane permeate to obtain a purified oil, while phospholipids such as lecithin are recovered from the concentrated membrane non-permeate as necessary.

However, there are various problems in actually obtaining purified glyceride oil by membrane processing a crude glyceride oil composition on an industrial scale. The biggest problem among these is that in order to obtain purified glyceride oil as a membrane permeate with a high recovery rate, it is usually necessary to
The micella must be concentrated approximately 20 to 60 times, but as the micella is concentrated and the phospholipid concentration in the micella increases, its viscosity increases and the amount of liquid permeating through the membrane decreases significantly. Therefore, in order to continuously concentrate micella to a vf2 reduction factor of 10 times or more in a single membrane treatment operation, not only a very large equipment is required, but also energy efficiency deteriorates. , the advantages of membrane treatment are lost, which is industrially unfavorable.

As a result of intensive research to solve the above-mentioned problems in refining crude glyceride oil compositions using semipermeable membranes, the present inventors have found that the micella of crude glyceride oil compositions are sequentially treated in multiple stages using semipermeable membranes. , and by performing membrane treatment while maintaining the concentration ratio in each stage within a predetermined range, the concentration ratio of micella can be increased. It was discovered that purified glyceride oil can be obtained continuously at a high recovery rate by minimizing the time required for 7f4 contraction, and the present invention was developed based on this finding.

A method for purifying a crude glyceride oil composition according to the present invention involves diluting a crude glyceride oil composition containing glyceride oil and phospholipids with an organic solvent to form miscella, and bringing the miscella into contact with a semipermeable membrane under pressure. The semipermeable membrane permeate liquid and the semipermeable membrane non-permeate liquid are separated, and the organic solvent is removed from at least one of the semipermeable membrane permeate liquid and the semipermeable membrane non-permeate liquid to produce crude glycerin oil and/or purified phosphorus. In the method of obtaining lipids, the semipermeability %
are installed in n stages (where n indicates an integer of 2 or more),
Semipermeable membrane The unpermeated liquid is sequentially treated with each stage of semipermeable membrane,
When concentrating to the final concentration factor
('v/Y) (where K represents a number from 0.7 to 1.3).

That is, in the method of the present invention, n stages (n is an integer of 2 or more) of membrane modules are connected in series and installed in the flow direction of the membrane non-permeate liquid of Micella. is sequentially concentrated in the semipermeable membrane module of each stage, and in this way, when concentrated to a predetermined concentration factor X in the semipermeable membrane module of the final stage, the i-th stage (where i By setting the concentration ratio Xi at The amount of permeated liquid from the semipermeable membrane module in the stage can be maximized, in other words, the time required to concentrate to a predetermined concentration ratio can be minimized. However, the concentration factor Xi in the i-th stage is (the first
The total quantum of the membrane permeable liquid from stage to i-th stage is defined as (the amount of membrane non-permeable liquid in the i-th stage)/(the amount of membrane non-permeable liquid in the i-th stage).

In the above formula, when the value of K is smaller than 0.7,
Although the membrane permeation rate of micella in the i-th stage is high, since the concentration ratio is small, a large amount of micella remains to be treated in the membrane modules from the 1st stage to the nth stage, and therefore Concentration up to the nth stage will take a long time. On the other hand, when the value of K is larger than 1.3, the membrane permeation rate decreases significantly because the concentration ratio in the i-th stage is too large.
The i-th stage concentration takes a long time. In this way, whether the value of K is too small or too large, it will take a long time to concentrate the micella as a whole.

In the method of the present invention, when concentrating miscella continuously by 3 to 80 times, preferably 5 to 70 times, particularly preferably 20 to 60 times the original amount using n-stage membrane modules, the concentration rate in each stage is adjusted. As mentioned above, by setting the final concentration ratio to a predetermined value defined by the value of The overall process is minimized and micella can be processed in the shortest possible time.

FIG. 1 shows an example of an apparatus configuration for carrying out the method of the present invention, in which semipermeable membranes are connected in two stages. In this device, micella is circulated and supplied from a storage tank 1 to a semipermeable membrane 2 in the first stage, where it is separated into a membrane permeate 3 and a concentrated submembrane permeate 4, and a portion of the submembrane permeate 4 is recycled again. It is returned to storage tank 1.

Part or all of the IFJ non-permeate liquid 4 is circulated and supplied to the second-stage semipermeable membrane 6 via another storage tank 5, and is again separated into a membrane permeate liquid 3' and a submembrane permeate liquid 4'. A portion of the lower permeate 4' is returned to the storage tank 5 again. In this way, the miscella is concentrated to the final concentration factor in a steady state, and part or all of it is continuously removed from the apparatus as the concentrate 7.

The semipermeable membrane used in the present invention can be a module in any form such as a tubular shape, a capillary shape, a flat plate shape, or a spiral shape. The pressure at which micella is supplied to these 111 modules is not particularly limited.

Usually, it is about 1 to 50 kg/cJ, although it varies depending on the membrane shape.

In the present invention, these semipermeable membranes usually have a molecular weight of 1,000 to 10
A semipermeable membrane having a molecular weight fractionation of 0,000, preferably 10,000 to 50,000 and is usually called an ultrafiltration membrane is preferred. This is because if the molecular weight fractionation value is too small, the amount of permeate tends to be small, while if it is too large, the ability to separate gummy substances tends to be poor.

Here, molecular weight fractionation can be determined by measuring the exclusion rate of a semipermeable membrane for a solute of known molecular weight. In practice, for example, it is preferable to measure the rejection rate of a membrane using a toluene solution containing polyethylene glycol as a solute (concentration 5000 ppm), whose average molecular weight is known and whose molecular weight distribution is monodisperse. Therefore, here too,
The rejection rate was measured using toluene solutions of polyethylene glycol with different average molecular weights under a pressure of 3 kg/cJ at a temperature of 25 °C, and the lowest molecular weight of polyethylene glycol with an rejection rate of at least 95% was determined as the molecular weight of the membrane. It is fractionated.

Lecithin, a typical component of phospholipids, has a molecular weight almost the same as triglyceride, but under the membrane treatment conditions of the present invention, tens of molecules to hundreds of molecules associate with each other to form micelles. Therefore, by bringing it into contact with a semipermeable membrane having a molecular weight fractionation in the above range, the phospholipids are almost completely removed by the membrane, and thus purified glyceride oil can be obtained.

In the present invention, the crude glyceride oil composition is diluted,
The organic solvent for preparing micellar must not dissolve the semipermeable membrane described above, and its molecular weight should be smaller than that of glyceride oil, usually 50 to 200, preferably 60 to 1.
It is 50. Specifically, aliphatic hydrocarbons such as pentane, hexane, heptane, and octane, aliphatic hydrocarbons such as cyclopropane, cyclopenkune, cyclohexane, and cyclohebutane, aromatic hydrocarbons such as benzene, toluene, and cylene, acetone, and methyl ethyl ketone. One type or a mixture of two or more types of aliphatic ketones such as ethyl acetate, lower fatty acid esters such as butyl acetate, etc. are used, but aliphatic hydrocarbons such as hexano are preferably used.

Micella obtained by diluting a crude glyceride oil composition with these organic solvents usually contains 10 to 80% by weight of glyceride oil, preferably 20 to 50% by weight, but,
It is not limited to this.

As mentioned above, depending on the raw material, the crude glyceride oil composition is extracted directly from the raw material with an organic solvent, but in the present invention, such an extract may be subjected to membrane treatment as it is, and this "extraction" can also be performed using an organic solvent. It is interpreted as synonymous with dilution. In addition, so-called degummed oil obtained by distilling off the solvent after solvent extraction in conventional refining methods can also be used as the crude glyceride oil composition in the present invention, and of course, a composition squeezed from raw materials can also be used as the crude glyceride oil. be able to. Furthermore, if desired, gummy glyceride oils obtained at any stage of conventional refining processes can also be used as crude glyceride oils. In the present invention, micellar refers to a solution of a crude glyceride oil composition in an organic solvent in the above sense.

Next, in the present invention, the miscella of the glyceride oil composition manufactured by 1.
The semipermeable membrane is contacted under pressure at a temperature of 0° C. or lower, at which the solvent used does not significantly evaporate, preferably in the range of 10° C. to 60° C. Generally, the higher the treatment temperature, the greater the amount of permeate that can be obtained.

Although the method of the present invention is suitable for purifying vegetable crude glyceride oil compositions containing a large amount of phospholipids such as lecithin, it can also be applied to purifying animal crude glyceride oil compositions. etc. are useful valuable ingredients,
If necessary, it can also be appropriately recovered from the submembrane permeate. Usually, highly purified phospholipids can be obtained by diluting the submembrane permeate again with an organic solvent such as hexanoate, treating it with a membrane, and then removing the organic solvent from the submembrane permeate.

According to the method of the present invention, as described above, when performing membrane treatment on micella, continuous concentration is carried out using an apparatus formed by connecting multiple stages of semipermeable membranes in series for the submembrane permeate, and the concentration at each stage is By setting the magnification to a predetermined value, it is possible to maximize the rate of membrane permeation through the entire device, minimizing the device and thus treating the micelles in the shortest possible time.

The present invention will be explained below with reference to Examples.

Example 1 Internal pressure type tubular ultrafiltration membrane with an inner diameter of 12 mm (molecular weight fractionation 2
0000) 18 tubes were connected in series and housed in a metal tube with an outer diameter of 107 mm, and the membrane length was 770 mm and the effective membrane area was 0.
．． A 48% tubular membrane module was fabricated.

These two membrane modules were connected by piping as shown in FIG. 1 to constitute a two-stage apparatus consisting of a first-stage and a second-stage membrane module.

In this device, both the first and second stage membrane modules have an average processing pressure of 3.2 kg/cA and a temperature of 40°.
2°28 at a miscella flow rate of 171/min in each stage of C1.
Soybean oil micella consisting of 22 parts by weight of a crude soybean oil composition containing % by weight of phospholipids and 78 parts by weight of hexane (21.5% by weight of soybean oil, 0.5% by weight of phospholipids in micella)
100# was continuously concentrated so that the final concentration ratio was 40 times.

However, in order to measure the processing time in each stage, we first tested each membrane module in the first and second stages.

After filling the storage tank and piping system containing micella at the predetermined concentration ratio shown in Table 1, the membrane permeate and sub-membrane permeate are continuously supplied while continuously supplying micella to the first stage membrane module. The time required for the treatment of Micella 100j2 was measured while the submembrane permeate was stored in a separately prepared storage tank. Next, this submembrane permeate is continuously supplied from this storage tank to the second stage membrane module, the time required for the second stage is measured, and the total time required for each stage determined in this way is calculated. The required time was taken as the time required.

Table 1 shows the processing time and total time required in each stage when the concentration ratio and value in each stage were varied. According to the method of the present invention, a predetermined amount of micella can be concentrated to a predetermined final Na reduction factor while minimizing the total time required. According to the comparative examples in which K(iiiI in the above formula is smaller than 0°7 or larger than 1.3), the total time required is significantly long.

In addition, in the above concentration treatment, the phospholipid fluxes in the permeate were all 4 oppm or less.

Example 2 1400 internal pressure capillary type ultrafiltration membranes (molecular weight fractionation 10000) with an inner diameter of 1.5 mm and a tube wall thickness of 0.4 fins were connected in parallel in a metal tube with an outer diameter of 107 mm. A membrane module with a membrane length of 770mm and an effective membrane area of 3rd was fabricated. Four of these membrane modules were connected in series via piping to construct an apparatus consisting of four stages of membrane modules.

In this equipment, the average processing pressure for each stage is 1.5 kg.
/Creating temperature 30°C Micellar flow rate at each stage 150
! / minute condition, rapeseed oil micella (rapeseed oil in micella) consisting of 30 parts by weight of a crude rapeseed oil composition containing 2.28% by weight of phospholipids and 0 parts by weight of Hexa2F was prepared.
3% by weight, phospholipid (0.7% by weight)) 100n was kept at maximum P, and continuous concentration was performed so that the concentration ratio was 40 times.

In the same manner as in Example 1, the concentration ratio of each stage, the value of in the above formula at that time, the time required for the concentration process at each stage,
and the required time for the Research Institute. The results are shown in Table 2.

Obviously, when the concentration factor in each stage is within the range defined by the present invention, the time required for research can be minimized. On the other hand, according to a comparative example in which the value of the above formula is outside the range specified by the present invention, the time required for the research institute is long.

In addition, in the above concentration treatment, the phospholipid concentration in the permeate was all below 1100 pp.

[Brief explanation of drawings]

The drawing shows a device configuration for carrying out the method of the invention. 1... Storage tank, 2... First stage membrane module, 5...
- Storage tank, 6... second stage membrane module. Patent Applicant Linol Oil Co., Ltd. Continuation of page 1 ■ Inventor Buita Fujihiko @ Inventor Yasuo Sumiyoshi @ Inventor Disc Kentabe @ Inventor Akio Iwama @ Inventor Nishi 1) Yuji @ Inventor Imamura Yuko 0 shots Akira Toyoshi Isooka 37-15 Shiomi-cho, Minato-ku, Nagoya-shi Nagoya Factory 1 Nagoya Factory I Ibaraki City, Ibaraki City, Ibaraki City, Ibaraki City

Claims (3)

[Claims] (1) A crude glyceride oil composition containing glyceride oil and phospholipids is diluted with a solvent to form micella, and the micella is brought into contact with a semipermeable membrane under pressure to form a semipermeable membrane permeate and a semipermeable membrane. A method for obtaining crude glyceride oil and/or purified phospholipid by separating the liquid into a non-permeable liquid and removing the organic solvent from at least one of the semipermeable membrane permeable liquid and the semipermeable membrane non-permeable liquid,
Semipermeable membranes are installed in n stages (where n is an integer of 2 or more), and the semipermeable membrane non-permeable liquid is sequentially processed through each stage of semipermeable membranes to concentrate to a final concentration factor of X. In this case, the concentration factor Xi (where i is an integer such as 1≦i≦n) by the first stage semipermeable membrane is defined as X1=K(qX)' (however, K is 0.7 to 1.3 A method for producing a crude glyceride oil composition, characterized in that: (2) A method for refining a crude glyceride oil composition according to claim 1, characterized in that the glyceride oil content in the miscella is 10 to 80% by weight. (3) The molecular weight fractionation of the semipermeable membrane is 1000 to 100000
A method for refining a crude glyceride oil composition according to claim 1, characterized in that: