JPH01296948A - Purification of honey and purified honey - Google Patents

Abstract

PURPOSE:To obtain purified honey of high-degree keeping coloring matter and fragrance component characteristic for natural honey by filtration-treating of raw honey with cross-flow filtration method using specific permselective membrane. CONSTITUTION:Raw honey is filtration-treated using a permselective membrane having <=0.1mum maximum pore diameter on the surface, >=75% obstructing ratio to dextran T-500 and <=70% obstructing ratio to dextran T-10, preferably at 0-70 deg.C. Next, said filtered material is subjected to ion exchange treatment. By said process, waste cake or unpleasant odor is lost and effective working is able to be performed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a new method for purifying honey using a selective NJ membrane.

[Prior art]

There are many types of honey, and their components can be roughly divided into water-insoluble and water-soluble components. In addition to proteins and beeswax, water-insoluble components include pollen, wood chips, leaf chips, fine particulate contaminants, and various fungi. On the other hand, water-soluble components include low-molecular substances such as water-soluble high-molecular proteins, sugars, minerals, organic acids, amino acids, and pigments.

In this way, raw honey, which is a raw material, contains many components, so when raw honey is used as a processing raw material, acid resistance,
It has disadvantages such as poor fruit juice resistance.

For example, when diluting with water like soft drinks,
Water-insoluble proteins in crude honey precipitate, producing a scum-like substance. Further, when mixed with fruit juice or the like containing pectin or other polymeric substances, similar sludge-like substances are generated. Therefore,
Crude honey cannot be used as a raw material for processing, and today honey that has been purified in various ways is currently used.

Honey purification mainly consists of two processes: decolorization and filtration, and deionization. The decolorization and filtration processes involve activated carbon treatment and press filtration using diatomaceous earth as a filter medium, and the deionization process involves treatment with ion exchange resin. It is being done. There are various combinations of refining process sequences, but basically, crude honey, which often has whitened crystals, is first heated and dissolved, and then activated carbon is added to this aqueous solution, which becomes muddy with water. After charging and adsorbing impurities, filtration is performed using a press filter using diatomaceous earth, the resulting filtrate is subjected to ion exchange treatment, and finally concentrated to an appropriate concentration.

Only 1. Therefore, there are still some unresolved problems with the above-mentioned purification methods.

The first is that the water-insoluble proteins, beeswax, and bacteria contained in the raw materials are not completely removed. Water-insoluble proteins cause the formation of sludge when honey is used for drinking water, so currently they are removed by press filtration using activated carbon and diatomaceous earth, but it is possible to remove them in just one treatment. Therefore, depending on the type of crude honey, it cannot be removed unless this process is repeated or a phosphate-based protein coagulant is added. Beeswax has a relatively low melting point, so it dissolves at high temperatures but precipitates at room temperature. Even if it is treated in the same way as water-insoluble proteins, it often cannot be removed because it has a low molecular weight. is the current situation. In addition, raw honey contains aerobic bacteria, aerobic heat-resistant bacteria, anaerobic bacteria, and anaerobic heat-resistant bacteria, which have recently become a problem as a cause of potulinosis in infants. Clostridium botulinum belongs to the anaerobic fungi. Since these bacteria are usually present in crude honey with sizes ranging from submicrons to several tens of microns, they cannot be completely removed by press filtration using activated carbon or diatomaceous earth. Therefore, microscopic bacteria remain in honey after purification.

The second problem is the waste cake produced from the refining process. In the current refining process, activated carbon and diatomaceous earth are used as filter media.1.・Due to the filtration process, for example, 20.5 to 1.0 tons of a mixture of activated carbon and diatomaceous earth is produced as industrial waste when refining the raw material raw honey10).
These processes have become a problem.

The third problem is the smell that comes from the refining process. In the conventional process, the tank is opened during the process, which causes the strong smell of raw honey to spread not only in the work room but throughout the factory, causing discomfort.

Fourth, since refined honey is treated with activated carbon and ion exchange, even the pigments and aromatic components unique to honey are removed.

One possible way to solve these problems is to use selective separation membranes, which have been put into practical use in various fields in recent years, although no attempt has been made to purify honey yet. In other words, if it becomes possible to remove water-insoluble proteins, beeswax, and bacteria using selective membranes such as reverse osmosis membranes, loose RO membranes, ultrafiltration membranes, and microfiltration membranes, it will be possible to remove water-insoluble proteins, beeswax, and bacteria. It was possible to omit the tongue charcoal treatment and press filtration treatment, eliminate the problem of waste cake and odor in the refining process, and expect to obtain purified honey that is close to natural.

It is obvious that even sugar, which is an essential ingredient, is removed. In addition, in contrast to reverse osmosis membranes and loose RO membranes, microfiltration membranes have too large pores, so although sugars can pass through them, water-insoluble proteins, beeswax, and even bacteria that need to be removed can also pass through. There is a risk that it will happen. On the other hand, ultrafiltration membranes are considered to be the most likely option as the membrane pore size is located between the separation membranes listed above, but in any case, honey purification using stiff selective separation membranes is possible. The current situation is that there have been no examples of this in the past, and even if an ultrafiltration membrane is used, in addition to selecting the optimal pore size of the membrane to be used, treatment methods,
Processing conditions, how to combine with other processes, etc. must be appropriately set.

[Purpose of the invention]

The present invention was developed as a result of research aimed at solving the above-mentioned problems in honey purification methods, and it has been found that water-insoluble impurities in crude honey can be removed by using a selective separation membrane with an appropriate membrane pore size. The aim is to reliably remove the foreign proteins, beeswax and bacteria in crude honey, while obtaining high-quality purified honey that retains the pigments and aroma components characteristic of natural honey. To provide a method for refining honey that can eliminate the production of industrial waste (waste cake) and the leakage of unpleasant odors during the refining process.

[Structure of the invention]

That is, in the present invention, coarse honey has a maximum surface pore diameter of O0ltI1.
m or the inhibition rate of dextran T-10 is 70
% or less, and the inhibition rate of dextran T-50O is 75
% or more selective separation membrane by a cross-flow filtration method, and if necessary depending on the purpose, further performs an ion exchange treatment after the filtration treatment. and purified honey characterized by having bacteria, proteins, etc. removed by this method.

Crude honey in the present invention is obtained by collecting sweet liquid such as honey from plants, adding substances produced by the honey itself such as secreted enzymes, and storing it in a honeycomb to ripen it. It's called natural honey.

The material for the selective separation membrane used in the present invention is preferably one with excellent heat resistance, chemical resistance, etc., but is not particularly limited. Regarding the shape, it may be a flat membrane, a hollow fiber membrane, or a tubular membrane, but a hollow fiber membrane is suitable because it has a large membrane area per module and can perform cross-flow filtration.

The properties of a selective separation membrane depend on the maximum pore size of its surface. The surface referred to in the present invention refers to the surface of a thin, dense layer on the surface of the membrane that prevents the permeation of solutes or suspended particles.Actually, it refers to the surface that comes into contact with the raw honey solution to be filtered. be. The pores on the surface are generally not circular or oval, but often have a complex shape, but the maximum pore diameter in this invention is the length of the longest part of the complex shape observed by electron microscopy. It is. However, if the pore size becomes smaller, it cannot be measured by electron microscopy, and the upper limit of the maximum pore size is 0 for the selective separation membrane used in the present invention.
．． Less than 1 μm, or the rejection rate of Dextran T-10 (average molecule N 140,000) is 7θ% or less, and the lower limit is the rejection rate of Dextran T-500 (average molecule N 500,000) 75%
Those within the above range are suitable. Dextran T-10
A rejection rate of 70% corresponds to a maximum pore size of 0.1μ as measured by electron microscopy, and if the pore size is larger than this, beeswax and bacteria, which are impurities in honey, cannot be sufficiently removed. Can not. Additionally, depending on the membrane, solutes may begin to clog the inside of the membrane, resulting in a rapid decrease in filtration rate and, in addition, poor cleaning recovery performance.
becomes impractical.

On the other hand, the pore size of the membrane was 7 in the rejection rate of dextran T-500.
5% is a range in which the pore size cannot be measured by electron microscopy, and if the pore size is smaller than this, it will also block sugars, which are the main components of honey, and the purpose of the present invention cannot be achieved. .

The filtration step using the selective separation membrane in the present invention can be introduced at any point in the various honey purification steps, but it is preferable to carry out the filtration step immediately after dissolving and diluting the raw honey. The filtrate contains the impurities in honey, such as water-insoluble proteins, beeswax, and bacteria, in their natural state, making it easy to filter. After filtration, you can simply follow the conventional process.
If you want to increase the degree of purification, such as by reducing coloring, you can use ion exchange treatment, which is included in the conventional process.If you want to retain the pigments and aroma components unique to natural honey, you can use ion exchange treatment. Instead, the vacuum concentration step should be started immediately.

The raw material, raw honey, usually has a concentration of -80 Brix, which is difficult to process due to its high viscosity, so in the conventional refining process, it is diluted twice by adding the same amount of water to achieve a concentration of 40 Brix. In the method of the invention, the concentration of the filtration stock solution varies depending on the filtration temperature, but the filtration temperature needs to be kept below 70°C in relation to the melting point of beeswax;
In this temperature range, the concentration is preferably 30 to 65 brix, and the filtration temperature is below O'C, or the concentration is 65
If the concentration exceeds 3, the viscosity increases, the filtration speed becomes slow, workability deteriorates, and it is not practical.
If the brix is lower than 0, the filtration rate is high and the work is easy, but after the purification process, more water must be removed in the vacuum concentration process, resulting in an increase in cost. When the filtration temperature exceeds 70°C, the beeswax that has aggregated in the crude honey melts and can no longer be removed by the selective separation membrane having the specific membrane pore size range of the present invention. Selective separation membranes that can be removed even when melted have smaller pore diameters, but they may also remove sugar components that are essential for honey, making them undesirable for honey refining. .

Although the method of filtration is not necessarily limited, since the purpose of the present invention is to remove particulate components from honey, if the removed particulate components are deposited on the membrane surface, The filtration speed decreases and the filtration process cannot be continued for a long time.

Therefore, it is desirable to use the so-called cross-flow filtration method, in which the filtration solution is flowed in a direction perpendicular to the permeation direction of the membrane, that is, in a direction parallel to the membrane surface, whereby the particulate components remaining on the membrane surface are carried away together with the filtration solution. Since the membrane surface can always be kept fresh, long-term filtration processing is possible.

〔Effect of the invention〕

According to the present invention, problems in conventional honey purification methods,
In other words, l) life ≠ concubine protein contained in raw honey;
It can solve the problems of removing beeswax and bacteria, 2) the problem of waste cake produced as industrial waste, 3) the problem of odor, and 4) the problem of retaining the pigments and aroma components unique to natural honey.
For unprecedented processing! It becomes possible to supply lIban, and its use can be expanded not only as a soft drink but also as a highly hygienic food and a nutritional food, which is extremely useful industrially.

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

Example-1 An aqueous honey solution was prepared by adding the same amount of water to Chinese buckwheat honey and diluting it by 1/2 to prepare a filtration stock solution. The selective separation membrane is manufactured by Pharmacia Fine Chem.
Dextran T-500 and T-1 manufactured by icals
Hollow fiber selective separation membrane (effective membrane area 785 cd, effective length 50 cm) with a rejection rate of 95% and 10% for
), the stock solution was subjected to internal pressure filtration under the conditions of IO1, filtration temperature 60°C, circulation volume 60ffi/h, inlet pressure 2.5 kg/cd, and outlet pressure 1.0 kg/cd to obtain purified honey. Ta.

Comparative Example-1 Using the same filtration stock solution as in Example-1, activated carbon treatment and diatomaceous earth press filtration treatment were repeated twice according to the conventional method.
After performing ion exchange treatment, it was concentrated under reduced pressure.

For the purified honey and crude honey obtained, the number of bacteria and 4
The absorbance at a wavelength of 00 to 750 cm was examined, and fruit juice resistance and general resistance tests were also conducted.

The results are shown in Table 1, Table 2, and Figure 1. According to the method of the present invention, bacteria contained in crude honey were completely removed (Table 1). In the conventional method, most of the pigment is removed, but in the method of the present invention, the absorbance at around 400 nm, which indicates brown color, is high (Figure 1), indicating that the pigment unique to natural honey remains. From Table 2, it was found that the honey has excellent fruit juice resistance and general tolerance, and as a result, the honey can be used for various food processing purposes. It has become clear that it can also be used for fruit juice drinks and carbonated drinks.

Table 1 Table 2 Juice resistance test × O Acid resistance test × O Alcohol resistance test × O
Salt resistance test × ○ The number of bacteria was determined by the method of Matsumoto et al. [Tokyo Institute of Health Annual Report, Vol.

35, 192 (1984)), an anaerobic culture jar manufactured by BBL was used for culturing anaerobic live bacteria and anaerobic heat-resistant live bacteria. The test methods for fruit juice resistance and maximum resistance were as follows.

1) Fruit juice resistance test Fruit juice concentration 10%, honey 13.5%, and citric acid 0.1% are heated to 90''C, and after cooling, the condition is observed when left for 24 hours.

2) Acid resistance test Make 50 cc of 7% honey solution to 250 cc with water.

Add 7 cc of 12N hydrochloric acid, boil for 5 minutes, and observe the condition 24 hours later.

3) Alcohol resistance test Dissolve 1 g of honey in 1°Od of 50% or 60% alcohol and observe the condition 24 hours later.

4) Salt resistance test Mix equal amounts of 7% honey solution and 20% salt solution, and observe the state.

The evaluation was based on the following three levels: O: No precipitation occurs and the sample is clear.

Δ: Causes slight turbidity and turbidity.

×: Precipitation occurs.

Example 2 In the same manner as in Example 1, a filtration stock solution of honey was prepared and subjected to filtration treatment using minute MM. The obtained filtrate was then subjected to ion exchange treatment and vacuum concentration in the same manner as conventional methods to obtain purified honey.

Comparative Example-2 In Comparative Example-1, the activated carbon treatment and the press filtration treatment using diatomaceous earth were carried out once. Refined honey was prepared using conventional methods.

The remaining amount of protein was examined for each lO lot of purified honey of Example-2, Comparative Example-1, and Comparative Example-2. The remaining protein amount for each loft is shown in Table 3, the protein remaining amount after each treatment is shown in Table 4, and the remaining protein amount after purification is (-) and (±). The amount of protein remaining after treatment is shown in Table 5. As is clear from these results, there is clearly a residual amount of protein in the conventional purification method, and Tables 4 and 5 show that the final amount of protein remaining as a result of activated carbon treatment and press filtration treatment is You can see what it shows.

Therefore, in order to obtain honey from which water-insoluble proteins have been removed using the conventional method, only honey with activated carbon treatment and press filtration with a (-) remaining amount of protein is allowed to proceed to the next process, and other There is no other way than to return the protein to the activated carbon treatment.On the other hand, it can be seen that 100% protein is removed by the purification method according to the present invention.

Table 3 Table 4 Table 5 The method for testing the remaining amount of protein was as follows.

Add grape juice and citric acid solution to honey and dispense into two test tubes. One at room temperature and the other at 90°C
After heating in a hot water bath for 15 minutes, leave it to stand and observe the state after 1 hour and 24 hours.

The evaluation was performed as follows.

(++): After 1 hour, a precipitate was observed both at room temperature and when heated (+11 hours later, a precipitate was observed only from the heated sample (±) = After 24 hours, a precipitate was observed Ta (-):
No precipitate was observed under any conditions.

Comparative Example 3 Similar filtration treatments were carried out on Example 1 in which the filtration temperature was 70°C and on a selective separation membrane with a membrane surface pore diameter of 0.2 μm. The obtained permeate, crude honey and the essence of Example-1? ! Ether extraction was performed on honey to determine the remaining amount of beeswax.

The results are shown in Table 6, and it can be seen that if the filtration temperature and membrane pore size are inappropriate, beeswax will be mixed into the permeate, that is, the purified honey liquid.

Table 6 Comparative Example-4 Selective separation membrane has a maximum pore diameter of O, I tt ts
and Dextran T-10 and Dextran T-5
The filtration treatment was carried out in the same manner and under the same conditions as in Example-1, except that both the rejection rates of 00 and 00 were 0. The change in permeation rate over time at that time is shown in Table 7 together with the case of Example-1.

From this result, as the pore size of the membrane increases, the i3 overrate decreases rapidly, and eventually becomes lower than that of a membrane with a small pore size.
It turns out it's not practical.

Table 7 Comparative Example-5 A flat membrane with a surface pore size of 0.04 μm was used as the separation membrane, and the same filtration stock solution as in Example-1 was filtered at a filtration temperature of 50°C and a pressure of 2.0 kg/cd. When the total filtration method was used, the permeation flow rate began to decrease rapidly 5 minutes after the start of filtration, and the permeation flow rate decreased to about 1/3 after 30 minutes. A large amount of mud was deposited on the membrane surface, and it was assumed that this was hindering the permeation of the liquid.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the absorbance of crude honey and purified honey. Patent applicant: Sumitomo Bake → Ito Co., Ltd.

Claims (5)

[Claims] (1) Crude honey is processed using a selective separation membrane with a surface maximum pore diameter of less than 0.1 μm or a dextran T-10 rejection rate of 70% or less and a dextran T-500 rejection rate of 75% or more. A method for purifying honey, which comprises filtering it by a cross-flow filtration method. (2) The method for refining honey according to claim (1), further comprising performing an ion exchange treatment after the filtration treatment. (3) The method for refining honey according to claim (1) or claim (2), wherein the temperature during the filtration treatment is in the range of 0 to 70°C. (4) Sterilized honey characterized by having been purified by removing bacteria by the method according to claim (1). (5) Deproteinized honey, characterized in that it has been purified by removing proteins by the method according to claim (1).