JP3081680B2 - Manufacturing method of natural seasonings - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a natural seasoning comprising a protein hydrolyzate, and more particularly, to a method for filtering a protein material extracted from the bones of birds and animals by filtering it through a microporous membrane. And the filtrate is hydrolyzed with hydrochloric acid to reduce the content of dichloropropanol (DCP) and monochloropropanediol (MCP), or a natural seasoning composed of a protein hydrolyzate not containing these Related to the method of manufacturing the ingredients.

[0002] Since ancient times, the pursuit of the taste and health of food has not changed, but in particular, recently, the improvement of eating habits,
With the diversification of tastes and the sophistication, more delicious things, genuine nature-oriented, and health-oriented are the mainstream demanded by modern people.
Under such a supply-demand trend, natural seasonings that maintain the flavors of agriculture, water, and livestock products in a more natural manner have attracted attention. However, in hydrochloric acid-degraded natural seasonings,
Dichloropropanol (DCP) which is a carcinogen,
It has become clear that undesirable chlorinated compounds such as monochloropropanediol (MCP), which is a sperm growth inhibitor, are by-produced during the hydrolysis reaction, and have recently become a problem from the viewpoint of food safety. The present invention relates to a method suitable for producing a natural seasoning comprising the hydrolyzate of animal protein hydrochloride, wherein the seasoning produced by the method of the present invention comprises dichloropropanol (DCP), monochloropropanediol Since the content of (MCP) s is low or does not contain them, it shows an effect that matches well in the age when health-oriented products are required.

[0003]

2. Description of the Related Art As a method for producing a protein degradation product from a protein raw material extracted from the bones of birds and animals, first, the bones of the birds and animals are heated (pressurized if necessary) to extract the extract, and then separated by standing. Then, bone bone and oil layer are removed to make protein raw material. Concentrated hydrochloric acid is added to the mixture,
The reaction is carried out for 0 to 20 hours. After completion of the reaction, the mixture is cooled, neutralized with sodium carbonate or sodium hydroxide, and the remaining unhydrolyzed substance is filtered off. However, protein hydrolysates produced using hydrochloric acid can cause unwanted chlorinated compounds such as dichloropropanols (DCP) such as 1,3 dichloropropanediol and monochloropropanediol (MCP) in a side reaction. Therefore, there has been a problem of preventing such formation. In order to solve this problem, a method in which insoluble matter is first removed from a protein hydrolyzed with hydrochloric acid, and then dichloropropanol (DCP) and monochloropropanediol (MCP) are further hydrolyzed and removed (Japanese Patent Laid-Open No. 2-135056). No., JP-A-2-15
No. 0241), a method of removing generated chlorinated compounds by gel permeation chromatography (Japanese Patent Application Laid-Open No. 2-135057). First, as an operation of performing a hydrolysis reaction with hydrochloric acid, the reaction is carried out at a low temperature. Thereafter, a method of suppressing the generation of dichloropropanol and monochloropropanediol by using a heating program (Japanese Patent Laid-Open No. 2-1)
No. 35058) and the like.

[0004] However, the method of removing dichloropropanol and monochloropropanediol by the above method has a problem that the operation is complicated and the cost is high even if it is carried out on an industrial level.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a natural seasoning comprising a protein hydrolyzate which can easily suppress undesirable by-products of chlorinated compounds. .

[0006]

Means for Solving the Problems In light of such an object, the present inventors have made intensive studies and as a result, have found that dichloropropanol (DCP), monochloropropanediol (MC
Focusing on fat, which is one of the precursors forming P), remove as much as possible fat and oil mixed in the raw protein extracted from the bones of birds and animals, and then hydrolyze with hydrochloric acid to obtain dichloropropanol, The inventors have found that the by-product of monochloropropanediol can be significantly reduced, and have completed the present invention.

Conventionally, a method has been used in which an extracted protein solution is allowed to stand for several hours in an extraction tank or the like to remove an oil layer, or a method of separating oil and liquid using a lantern glass or the like. However, even if the oil layer is completely removed, it is impossible to completely remove the oil that is slightly suspended or dissolved in the liquid, and when such a raw material is used to perform hydrochloric acid hydrolysis, The slightly remaining oil reacts with hydrochloric acid to produce harmful substances such as dichloropropanol and monochloropropanediol. As a method for reliably removing oil, for example, a method using an ultracentrifuge has conventionally been used. However, when processing a protein raw material as used in the present invention, the operation is periodically stopped because solids (extracted cake) adheres to the bowl, and the bowl needs to be cleaned. Installation is required,
Due to the high equipment costs, it has not yet been put to practical use.

[0008] From these viewpoints, the present inventors effectively remove oil from protein raw materials extracted from bird and animal bones, do not generate DCP and MCP, and have the same taste and flavor as conventional products. Various studies have been conducted for the purpose of developing natural seasonings. As a result, it was found that by combining the liquid separated by the conventional method with the filtration step using a microporous membrane, the oil in the liquid could be completely separated by a simple process and a simple method. Hydrolysis of hydrochloric acid as a raw material, dichloropropanol, monochloropropanediol significantly reduced content,
Alternatively, the present invention has been completed by confirming that a natural seasoning not containing them can be obtained.

As the protein material used in the present invention, bones of livestock such as cows, pigs and chickens (whether or not they have meat meat) are generally used. As a method for obtaining an extract from the raw material bone, a method conventionally used in the art can be used.
A method of heating and pressurizing for about 0 minutes to 3 hours is exemplified. After the extraction, the mixture is allowed to stand and separated to remove the bone rattle and the oil layer, thereby obtaining a protein extract.

[0010] The concentration of the starting protein in the case of performing the treatment with the microporous membrane is not particularly limited, but is usually preferably in the range of 5 to 15% by weight. Protein concentration of 15% by weight
When it exceeds, the viscosity of the liquid increases and the permeation flux of the microporous membrane is slowed. On the other hand, when it is less than 5% by weight, a large amount of energy and time are required for concentrating the protein because the concentration of the protein used for hydrolyzing hydrochloric acid becomes low.

As the microporous membrane used in the present invention, any microporous membrane may be used as long as it allows protein to permeate and cannot pass through an emulsion of fats and oils. To achieve the above object, the pore diameter of the membrane is preferably in the range of 0.01 to 1.0 μm. In addition, inorganic materials such as ceramic filters can be used as long as they have a pore size substantially within the above range. The membrane is preferably in the shape of a hollow fiber capable of cross-flow filtration, and has an inner diameter of 0.1
It is preferable in terms of efficiency and operability to use a membrane module made of a hollow fiber membrane having a shape of 10 to 10 mm and a thickness of 0.05 to 5 mm.

The protein solution is permeated through the microporous membrane,
Separate the protein and fat emulsion. In this case, the membrane material is preferably hydrophilic in order to prevent proteins and oils and fats from adhering to the membrane surface and reducing the permeability during the operation. Here, the hydrophilic membrane means that a so-called water permeation pressure of 0.8 kg / cm ^{2, in which} water pressure is applied from one side of the membrane in a dry state and water permeation is observed on the other side of the membrane.
25 ° C., 1 kg / cm
² is a membrane having a water permeability of 15% or more as compared with a membrane obtained by previously treating a membrane with ethanol. As a film having such properties, a microporous film made of a cellulose-based hydrophilic polymer is famous, but it has poor chemical resistance such as acid resistance and alkali resistance, and has low mechanical strength. It is most preferable to use a composite membrane made hydrophilic by bonding a graft chain having a neutral hydroxyl group to at least the surface of a hydrophobic substrate film having excellent chemical properties and strength. In order to meet such a purpose, a hollow fiber microporous membrane module comprising a synthetic polymer composite membrane is already commercially available.

Next, a method for removing oil using a hollow fiber microporous membrane will be described in detail. A protein raw material containing oil suspended in an emulsion is supplied to a membrane module provided with a microporous membrane, and the protein raw material is selectively removed as a membrane permeate, while a membrane retentate containing oil is circulated. The so-called cross flow method is the most efficient. The average pressure of the filtration is preferably 0.1 to 2.0 kg / cm ² . When the membrane is clogged and the permeation flux decreases, the permeation flux can be recovered to some extent by backwashing the microporous membrane with water.

[0014] The membrane permeate obtained from the membrane module can be concentrated by an appropriate concentration means as required.
The protein concentrate obtained as described above is hydrolyzed with hydrochloric acid. The hydrochloric acid hydrolysis method is no different from the method usually performed in the art, for example, at a temperature of 110 to 110.
120 ° C., time 10-20 hours. After hydrolysis, neutralize to a pH of 5.0 to 5.5 with a suitable alkali such as sodium carbonate or sodium hydroxide and filter off residual unhydrolyzed material. The filtrate after filtration is a conventional method,
For example, decolorization can be performed using activated carbon or an ion exchange resin. The hydrolysis filtrate is then concentrated, for example, by vacuum to precipitate some of the formed salts, and then re-filtered to remove the precipitated salts and obtain a liquid hydrolyzed protein product. It is further concentrated to avoid spoilage and denaturation by microorganisms, or
It is preferable that the product is dried to obtain a paste or powder product. The product obtained in this way has the same taste and flavor as the product obtained by the conventional method, and the contents of dichloropropanol and monochloropropanediol are significantly reduced.

[0015]

Next, the present invention will be described in more detail by way of examples.

[0016]

Example 1 In a 5-liter high-pressure autoclave,
3600 g of pig bone and 720 g of water are sealed and heated.
When the internal pressure of the autoclave reaches 0.5 kg / cm ² , the air inside the autoclave is evacuated, sealed again and heated to raise the internal pressure of the autoclave to 5 kg / cm ² ,
Cooked for 1 hour. After cooling, the entire amount of the liquid in the autoclave was transferred to a 5-liter separating funnel to remove the oil in the upper layer to obtain 2400 ml of the lower-layer pork bone extract, which was used as a protein raw material.

[0017] The protein material was used as E-manufactured by Asahi Kasei Corporation.
Using an MP-113 module (hydrophilic synthetic polymer composite microporous membrane, pore diameter 0.25 μm, hollow fiber membrane inner diameter 2.0 mm), inlet pressure 0.6 kg / cm ² , outlet pressure 0.4 kg /
The mixture was filtered by a cross-flow method of cm ² , and when the amount of the raw material liquid became small, water was added to perform a further filtration operation to collect the protein in the module. After concentrating the membrane permeate with an evaporator so that the protein concentration becomes 35% by weight, the concentrate is placed in a 200-ml heat-resistant bottle.
5 g and 60 g of an aqueous hydrochloric acid solution (specific gravity 1.18) were added, and the reaction was carried out at 110 ° C. for 20 hours in a steam autoclave. After completion of the reaction, the mixture is cooled and adjusted to pH 5.5 with sodium carbonate.
To Toyo No. 2 Filter through filter paper, taste,
Natural flavors consisting of good protein hydrolyzate were obtained for both flavors.

As a result of analyzing this product, MC
P, 10 ppm or less; DCP, 0.05 ppm or less. As is apparent from the results, MCP and DCP in the permeated solution of the hydrophilic microporous membrane were all below the detection limit.
In addition, the analysis of MCP and DCP was performed by gas chromatography: mass fragment method according to "Test method of 3-chloro-1,2-propanediol and 1,3-dichloro-2-propanol" (Japan Food Research Laboratories). .
Here, the detection limits of MCP and DCP by this method were 10 ppm and 0.05 ppm, respectively.

[0019]

Comparative Example 1 In the same manner as in Example 1, the oil was separated by a separating funnel, and the lower layer extract was concentrated and hydrolyzed with hydrochloric acid in the same manner as in Example 1 without performing the treatment with a microporous membrane. After decomposing and neutralizing, MCP and DCP were analyzed. As a result, MCP was 48 ppm; DCP was 0.36 ppm.

[0020]

Example 2 A protein raw material was obtained in the same manner as in Example 1, and 2,000 g of the obtained protein extract was used as it was in Example 1 without performing oil separation using a separating funnel. By filtration through the membrane permeate 153
0 g was obtained. In the same manner as in Example 1, concentration, hydrolysis with hydrochloric acid, and neutralization were performed, and analysis of DCP and MCP was performed. As a result, MCP, 10 ppm or less;
Even when a raw material containing an excessive amount of oil was used, the DCP and MCP of the product could both be reduced to below the detection limit by performing the hydrophilic microporous membrane treatment.

[0021]

As described above, according to the method of the present invention, the oil content in the protein raw material is removed by using a microporous membrane, so that the taste and the flavor are excellent, and dichloropropanol (DCP), A product with significantly reduced chloropropanediol (MCP) can be obtained.

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Claims (1)

(57) [Claims] 1. An oil component is removed from a protein raw material extracted from bird and animal bone by filtering it through a microporous membrane having an average pore size of 0.01 to 1.0 μm, and the filtrate is hydrolyzed with hydrochloric acid. A method for producing a natural seasoning comprising a protein hydrolyzate.