JPH03142351A - Method and apparatus for measuring electrolyte concentration in oily material - Google Patents

Abstract

PURPOSE:To easily and automatically make accurate measurement by determining the electrolyte concn. in a water phase in accordance with the measurement of an electrical conductivity by using the previously determined correlative relation between the electrolyte concn. and the electrical conductivity. CONSTITUTION:The oil material transferred in a piping 21 is first introduced into an introducing pipe 123 and a flow passage 12 by operating a suction pump 22 and is discharged from a stationary introducing pipe 121 side to substitute the inside of the flow passage 12 with the oily material. The while volume of the oily material in the stationary introducing pipe 120 is held in an axial rotating body 13 and is rotated in this state when the rotating body is half rotated. This oily material is brought into a flow passage 11. A transfer pump is then operated and the oily material in the flow passage 11 is extruded into a measuring container 17 by extracting water. The mixing ratio with the extracting water is known by measuring the whole liquid volume in the introducing pipe 120, i.e. in the container 17 when the volume of the oily material is known at this time. The oil phase and the water phase are separated to the two layers, upper and lower, when the liquid is rested after sufficient dissolving by the rotation of a stirrer 26. The electrical conductivity is measured by a sensor 18 disposed in the water layer.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a simple and rapid method for measuring the content of salts and other electrolytes contained in oily substances, such as salts in oily foods such as butter or margarine. Regarding the device.

[Technical Background and Prior Art] Butter that is generally consumed at home is called salted butter, which is produced by adding a predetermined amount of a supersaturated salt suspension during the working process of butter production. This salt is kneaded into butter in a fine crystalline state or in a state dissolved in an aqueous phase, and its concentration is an extremely important factor that affects the texture and flavor of butter. It is involved in preventing proliferation. Therefore, the salt concentration inspection process in the salted butter manufacturing process is considered to be an extremely important and essential process for quality control.

Conventionally, the salt content of salted butter has been measured by mixing a predetermined amount of the sample with boiling water, and titrating the salt extracted into the aqueous phase with a silver chloride solution using potassium chromate as an indicator. This method does not automate the sampling, weighing, and extraction titration operations, requires human labor, and is manual, resulting in large errors by the measurer. Since it requires a high degree of accuracy, real-time manufacturing process control is difficult, and measurement cannot be carried out frequently enough.

Currently commercialized butter salinity automatic analyzers equipped with in-line sensors require irradiation of the sample with gamma rays, which may generate radioactive substances in the target material. It is undesirable to target foods because of the nature of the irradiation, and the irradiation equipment is expensive, so there are problems in practical application.

On the other hand, attempts have been made to measure the salinity of butter using a coulometric titration salinity measuring device equipped with an autoinjector, but this method has the feature of automatically and highly accurate measurement; However, manual procedures such as weighing and dissolution are required, which is time-consuming, and at present, no automatic sampler for production lines has been developed, making it difficult to perform in-line measurements.

In view of the above-mentioned current situation, the present inventors have conducted intensive studies on a method for measuring the salt concentration in salted butter in-line and in real time during the manufacturing process with more satisfactory accuracy. When predetermined amounts of salt and extraction water are mixed and dissolved, and the salt is extracted into the aqueous phase,
b) There is a high correlation between the electrical conductivity of the aqueous phase and the salt concentration in butter, and the electrical conductivity value of the aqueous phase can be sufficiently used as a constant index of the salt concentration in butter; The correlation is that by adding an emulsifier to the extracted water, the measurement accuracy can be increased and the time required for measurement can be shortened. The present invention was completed based on the findings of the following: discovery of a mechanism that can automate sampling, mixing with extracted water, and measurement.

It has also been found that the present invention can be applied to electrolytes in general, including oily substances other than butter and salts other than salt.

[Objective and Summary of the Invention] An object of the present invention is to easily, quickly, and automatically measure the concentration of electrolytes, including salts contained in oily substances, such as salt in oily foods such as butter or margarine. The object of the present invention is to provide a method and apparatus for measuring the same, and furthermore, to provide the above-mentioned method and apparatus capable of automatic sub-ringing even when the oily substance flows continuously in a pipe.

That is, one aspect of the present invention is to stir and dissolve predetermined amounts of an oily substance containing an electrolyte and its extracted water, extract the electrolyte into an aqueous phase, and then measure the electrolyte concentration in the aqueous phase. In the method for measuring the electrolyte concentration in the oily substance, an emulsifier is added to the extracted water, and the electrolyte concentration in the aqueous phase is determined by using a predetermined correlation between the electrolyte concentration and the electrical conductivity. to determine based on measurements;
Another aspect of the present invention is a method for measuring an electrolyte concentration in an oily substance, which is characterized by having the following configuration (0 to (+1)). This is a device that performs the measurement method.

(I) In the outer body +33 that surrounds the shaft rotating body 13 and its surrounding wall and slides in liquid-tight contact in the rotational direction, it communicates with the rotational conduction pipes 11G and 120 that pass through the shaft rotating body 13, and both ends of each of these. Fixed conduction pipe 111 penetrating the mantle body +33
and 112 and 121 and 122.
and 12 are formed, and by a predetermined rotation of the shaft rotating body 13, both ends of one rotary conduit tube +20 are replaced at the same position as both ends of the other rotary conduit tube 110. Sampling loop 30, (b) fixed conduit 1
12, a holding container 14 communicates with the channel 11 and holds the extracted water to which an emulsifier has been added; (d) an oily substance introduction pipe 123 communicating with the flow path 12 via a fixed conduction pipe 122; Detailed Description of the Invention] In the present invention, a test sample to be measured , in food,
In addition to salted butter, margarine, miso, spreads, and foods, cosmetics, ointments, and toothpastes are products that are mainly composed of fats and oils, or products that exhibit high viscosity and that generally contain various salts and electrolytes. It contains. For example, salted butter contains a lot of milk fat and contains salt in the form of microcrystals and hydrated butter, so the salt content cannot be measured as is using an ion electrode or the like. Therefore, extraction water is used to extract the salts in the oily substance into the aqueous phase.

It is preferable to use deionized water as the extraction water so that the influence of its own electrical conductivity is negligible.For example, in the case of salted butter, the measurement order of the extraction liquid is about several ms/m, so it is preferable to use deionized water. As long as it is less than 102 to 10-' of this value, there will be no problem.

The mixing ratio of the oily substance and extracted water is appropriately selected depending on the concentration of salts and electrolytes contained in the oily substance, but in general, the electrical conductivity of the extracted liquid is 1 to 10m5/α.
Decide so that

The emulsifier used is not particularly limited as long as it dissolves easily in water and has an excellent emulsifying effect, but for example, IC
Tveen 20, Tveen 40, Tveen 6 manufactured by one company
0 (-Tveen 6G), ) Vienna 80
(Tveen 80), etc., Tween 20 is preferable in terms of solubility. The amount added is about 0.5% based on the extracted water.

First, the apparatus of the present invention will be explained based on the drawings. Figure 1
1 is an explanatory diagram (layout diagram) showing one embodiment of the device of the present invention. In the figure, reference numeral 21 denotes a pipe through which the oily substance is continuously transferred, and the oily substance is transferred from the sampling port 19 to the flow path 12 of the sampling loop 30 via the suction pump 22 provided in the introduction pipe +23. will be introduced to This flow path 12 includes a rotary conduit tube 120 that is bent into a substantially arc shape and passes through the shaft rotating body 13, and two fixed conduit tubes +21 and 21 that communicate with both ends of this rotary conduit tube 120 and pass through the mantle body 133. 122, and the outer body 133 surrounds the shaft rotating body 13 and slides into fluid-tight contact with each other when the shaft rotating body 13 rotates. Both are made of, for example, laminated glass. On the other hand, the flow path 1 having the same structure as the flow path 12
Extraction water to which an emulsifier has been added is introduced from the holding container 14 into the flow path 11 from the fixed introduction pipe 112 side via the transfer pump 24 and the opening/closing valve 15. and one fixed introduction tube 11+
A discharge pipe +13 with a stop pulp 25 communicates with it. A measuring container is provided at a position to receive the liquid flowing out from the discharge pipe IN, and this measuring container is provided with a sensor 18 for measuring electrical conductivity and a stirring bar 26 of a magnetic stirrer for stirring the stored liquid. There is.

The measurement method using this device is carried out as follows.

First, the suction pump 22 is activated, and the oily substance transferred through the pipe 21 is introduced into the introduction pipe 123 and the flow path 12, and is discharged from the fixed introduction pipe 12+ side, replacing the inside of the flow path 12 with the oily substance. . If the oily substance is highly viscous during this introduction, a heater 27 is provided to heat the introduction tube +23 to reduce the viscosity and facilitate introduction. When the rotating shaft 13 is rotated half a turn, the oily substance in the fixed introduction tube 120 slides liquid-tightly on the inner and outer surfaces of the rotating shaft 13 and the outer mantle +33, so that the entire amount is retained inside. It is rotated as it is and held in the flow path 11. That is, fixed inlet tubes 120 and +10 completely replace each other.

Next, the transfer pump is operated and the on-off valves 15 and 2 are opened.
5 is opened, and the extracted water pushes out the oily substance in the channel 11 into the measurement container 17. At this time, if the volume of the oily substance in the fixed introduction pipe +20 is known, the mixing ratio with the extraction water can be determined by measuring the total amount of liquid in the measurement container 17. When the mixture is sufficiently dissolved by rotation of the stirrer 26 and allowed to stand still, an oil phase and an aqueous phase are separated into two layers, upper and lower, and the electrical conductivity is measured by a sensor 18 placed in the aqueous layer. In order to prevent the electrical conductivity from being affected by temperature, it is preferable to use means for keeping the holding container 14 and the measuring container I7 at a constant temperature.

Next, the present invention will be explained in detail by showing test examples.

(Test Example 1) Effect of emulsifier Using the above-mentioned device, butter that had been prepared to have a constant salt concentration after the wakifugu process during the production of salted butter was sampled from inside the pipe, and after mixing and dissolving it with a predetermined amount of dissolved water, When measuring the electrical conductivity of the aqueous phase, we investigated the effect of adding an emulsifier to the extracted water.

First, Tween 20 was used as an emulsifier and added to extraction water at a concentration of 0.5%, and kept at about 50°C.

Further, the capacity of the rotating conduction tube 120 in one of the sampling loops was 2 ml.

Next, the suction pump 22 is used to flow through the heated introduction tube + 23 and the flow path 12, and when the air inside is completely replaced with butter, the rotating shaft 13 of the sampling loop is rotated by half a turn, and the fixed conduit tube is replaced with butter. Interchange 120 and +10. Open stop valve 15 and pump 2
4, the sample was extruded with extraction water kept at about 50°C and discharged into the measurement container I7 kept at the same temperature, and when the extraction water volume reached 40 ml from the scale of the measurement container 17, The on-off valve 25 was closed, and the mixture was stirred for about 2 minutes using a stirrer 26 using a rotating blade of a magnetic cooler. After standing still, the electrical conductivity of the aqueous phase of the separated oil phase and aqueous phase is measured with a sensor 18 provided at the bottom of the measurement container, and then the electrolyte is discharged from the drain valve 28, and the extracted water is then retained. It flows from the container 14 to the measurement container 17, and each conduction pipe sensor and the measurement container 17 are cleaned in place.

The above operations and measurements were repeated with and without the addition of an emulsifier.

In addition, as to what kind of influence the above-mentioned cleaning had on the measured values of this test, that is, whether the cleaning effect was sufficient or not, the following test determined that the effect was sufficient. That is, at the time when 32 ml of extraction water to which an emulsifier was added to extrude the butter in the sampled pipe was poured, the open end 1
The electrical conductivity of the extracted water collected from No. 6 was approximately 0. Of m
S/m (average value), indicating that the butter and salt in the pipes were cleaned without any problems. Also,
When no emulsifier was added, the measured values tended to be high, indicating that cleaning was insufficient.

FIG. 2 shows the electrical conductivity values for each measurement order.

In the same figure, the case where an emulsifier is added is shown by the symbol ◯, and the case where the emulsifier is not added is shown by the symbol x. The following can be learned from the results shown in the figure.

If no emulsifier is added, the measurement values will vary widely,
There was a lack of stability, and there was a tendency for the measured values to gradually decrease as the number of measurements increased, but it was found that this was due to the influence of dirt on the electrodes due to fat, etc. On the other hand, in the case of adding an emulsifier, the variation is small and shows a constant value over time. Furthermore, when comparing the two, the absolute value of the measured value is lower with the addition of an emulsifier, but this is due to the non-electrolyte in the emulsifier interfering with conductivity.

(Test Example 2) Correlation between electrical conductivity of aqueous phase and salinity A sample of butter with a known salinity (salt 0 to 1.6 wt%) and water extracted with 0.5% emulsifier Tween 20 were prepared, and Test Example 1
Test example 1, such as the mixing ratio of both, using the measurement container 17 of
The electrical conductivity of the aqueous phase was measured in the same manner as above.

The results are shown in FIG. Also, from the same figure, the salt content in butter, X (%), and the electrical conductivity, y, (mS/s) will be added.

Therefore, it has been found that the salinity of butter can be measured by mixing butter with extraction water (emulsifier added) in a fixed ratio and measuring the electrical conductivity of the aqueous phase.

(Test Example 3) Temperature characteristics of electrical conductivity The electrical conductivity The degree of

The results are shown in FIG. A nearly proportional relationship was observed, and its coefficient (slope) was 0.031 m5/a/'C.

In order to keep the butter salt measurement error within ±2%, it is necessary to measure the electrical conductivity with an accuracy of ±0.02 m5. Therefore, in order to perform measurements with this accuracy, it is known that it is desirable to control the temperature to within ±0.5° C. or to perform accurate temperature compensation.

Next, the present invention will be explained in detail with reference to Examples.

(Example 1) In the production of butter with a salt concentration of 1.6%, sampling was performed from the butter transfer pipe after the working process using the apparatus shown in Figure 1, and the electrical conductivity was measured over time. We conducted an inspection of the salt content in butter from a quality control perspective.

It should be noted that the capacity of the rotating conduit tube 120 in one of the sampling loops, that is, the capacity of the sampling butter, was set to 2 ml, and the sampling butter was pushed out with extraction water to which the emulsifier Tween 20 was added to a concentration of 0.5%. 40 ml of extraction water was used at one time, at approximately 50°C.
The temperature of the measurement container was maintained at approximately 50°C, the stirring time of the measurement container was 2 minutes and 30 seconds, and the above formula (1) was used as the correlation between salinity and electrical conductivity. In addition, the cleaning time between measurement intervals was approximately 3 minutes, and the electrical conductivity was measured in the same manner as in Experimental Example 2. At the same time, the equation (
The salinity was calculated from 1).

Data for 2 hours during production are shown below.

As described above, the amount of salt in butter was easily and automatically measured at short intervals. In addition, when measuring for 60 minutes and 90 minutes, the salt content (%) was actually measured using the conventional method described above using potassium chromate (indicator) and silver nitrate solution.
were 1.62 and 1.58, respectively, which were equivalent values.

(Example 2) Determination of fat content freshness of butter oil General butter flavor is obtained by hydrolyzing milk fat (butter oil) into fatty acids using lipase. In flavor production, it is necessary to accurately and conveniently monitor the freshness of fat hydrolysis, as it greatly affects flavor.

Since some of the decomposed fatty acids become water-soluble, by knowing in advance the correlation between the electrical conductivity of the aqueous phase and the degree of decomposition, it is possible to easily measure the appropriate fatty acid freshness using the means of the present invention. .

(Preliminary experiment) 2 wt% of lipase (pancreatic lipase, manufactured by Sigma) was added to a stirred and dissolved mixture of milk fat (butter oil) and water in a ratio of 7=3, and the mixture was stirred at 37°C while continuing to stir. It was enzymatically degraded and sampled as appropriate. The degree of milk fat decomposition was determined as the volume of N/10 sodium hydroxide solution required to neutralize 1 g of the oil phase of the decomposition product. Meanwhile, 2 g of the decomposition product was mixed with 40 g of water and stirred,
The electrical conductivity of the aqueous phase was measured and its correlation with the degree of milk fat decomposition was investigated. As a result, the relationship between milk fat decomposition degree (Xml) and electrical conductivity (yXIOμs/1) is a linear relationship as shown in FIG. 5, and X and y are expressed by formula (2): It turns out that it can be expressed as Furthermore, it was found that the butter flavor obtained at a milk fat decomposition degree of 6.7 ml had a good flavor.

(Production of butter flavor) The above experiment was scaled up and the decomposition degree was 6.7 m under the same conditions.
A butter flavor of 1 was produced.

Ifloo 300kg of water and 700kg of butter oil
The mixture was stirred and dissolved in a 1-liter jacketed tank, and 2 kg of the same lipase as in the above experiment was added and kept at 37° C. with stirring to perform enzymatic decomposition.

After the start of decomposition, using the apparatus of the present invention shown in FIG. 1, the sampling port 19 at the tip of the introduction pipe 123 is attached to the circulation pipe 40 having the pump 41 of the tank as shown in FIG. Sampling was carried out and the electrical conductivity was measured.

The volume of the sampled decomposition liquid was 2 ml, and the extraction water to which the emulsifier Tween 20 was added to about 0.5% was used, and the relationship between decomposition degree and electrical conductivity (2)
Electric conductivity was measured over time in the same manner as in Example 1, except that . Figure 7 shows the changes in measured values over time.

And the electrical conductivity is 7.8, which corresponds to the target resolution.
Measured value close to XIOμs? , 4XI (1 μs), the enzyme was inactivated by passing steam through the tank jacket and heating at 80° C. for approximately 10 minutes.

Then, the three-way pump 42 was switched, the pump 41 was started, and the centrifugal separator 43 separated the aqueous phase portion and the oil cake portion. The aqueous phase was discarded through outlet 44. Outlet 4 of oil phase
By cooling after discharging from No. 5, 6SQ kg of butter flavor with good flavor was obtained.

In addition, the samples to be measured in the present invention are not limited to the above-mentioned butter oil, but also salts in general, such as margarine, miso, and spreads in food products, and cosmetics, ointments, toothpaste, etc. It is also applicable to oily substances and high viscosity substances containing electrolytes when measuring their concentration.

[Effects of the Invention] (1) Salt in oily foods such as butter or margarine, as well as electrolytes such as salts in oily substances, can be measured easily and in a short time.

(2) Continuously flowing oily substances can be automatically sampled from piping and the content of electrolytes such as salts can be easily measured.

(3) Since the measurement interval can be shortened, it is possible to substantially continuously and automatically measure the content of electrolytes such as salts.

[Brief explanation of the drawing]

FIG. 1 is a layout diagram of the device of the present invention, FIG. 2 is a graph showing the measured values of electrical conductivity for each measurement order, and FIG. 3 is a graph showing the relationship between electrical conductivity and salinity. 4 is a graph showing the relationship between electrical conductivity and temperature. Figure 5 is a graph showing the relationship between fat freshness and electrical conductivity, and Figure 6
1 is a layout diagram showing the installation of an apparatus for carrying out the method of the present invention; FIG. FIG. 7 is a graph showing changes in electrical conductivity over time. (Explanation of symbols) +1.12; flow path 111, 120.121.122, fixed conduction pipe 121
1, +10, rotating conduction tube 13; shaft rotating body 30, sampling loop 14; holding container 17, measuring container 18, electric conductivity measurement sensor
A 5 meeting 6

Claims (2)

[Claims] (1) Stir and dissolve predetermined amounts of each of an oily substance containing an electrolyte and extracted water, extract the electrolyte into an aqueous phase, and then measure the electrolyte concentration in the aqueous phase to determine the electrolyte concentration in the oily substance. In the method for measuring, adding an emulsifier to the extracted water, and determining the electrolyte concentration in the aqueous phase based on the measurement of electrical conductivity using a predetermined correlation between electrolyte concentration and electrical conductivity. ,
A method for measuring electrolyte concentration in an oily substance, characterized by: (2) An apparatus for carrying out the measuring method according to claim 1, characterized in that it has the following configurations (a) to (d). (a) In the outer body 133 that surrounds the shaft rotating body 13 and its surrounding wall and slides in liquid-tight contact in the rotational direction, it communicates with the rotational conduction pipes 110 and 120 that pass through the shaft rotating body 13 and both ends of each of these. Fixed conduction pipe 111 passing through the mantle 133
and 112 and 121 and 122.
and 12 are formed, and are arranged in such a relationship that, by a predetermined rotation of the shaft rotating body 13, both ends of one rotary conduit tube 120 are replaced at the same positions as both ends of the other rotary conduit tube 110. a sampling loop 30, (b) communicating with the flow path 11 via a fixed conduit 112;
a holding container 14 that holds extraction water to which an emulsifier has been added; (c) a measuring container 17 that receives the liquid flowing out from the flow path 11 via the fixed conduction pipe 111 and is equipped with a sensor 18 for measuring electrical conductivity; (d) ) an oily substance introduction pipe 123 communicating with the flow path 12 via a fixed conduit pipe 122;