阅读说明：本技术 一种果汁中棒曲霉素的消减方法和果汁的安全生产方法 (Method for reducing patulin in fruit juice and safe production method of fruit juice ) 是由 刁恩杰 许桓源 赵芋汀 王月 胡云 黄澄 吴桂花 谢鹏 毛瑞峰 钱时权 宋虎卫 于 2019-11-26 设计创作，主要内容包括：本发明提供了一种果汁中棒曲霉素的消减方法和一种果汁的安全生产方法,属于果汁加工安全控制技术领域。本发明以L-半胱氨酸为脱毒剂,将果汁半成品与L-半胱氨酸混合后,经巴氏杀菌,完成消减果汁中污染的棒曲霉素,具体机理为L-半胱氨酸是含有一个巯基(-SH)的氨基酸,具有还原性,棒曲霉素具有亲电特性,能与含巯基的半胱氨酸亲核试剂在巴氏杀菌条件下发生Michael加成反应,生成多种更加稳定的加合物,且产物的毒性远小于棒曲霉素本身的毒性、甚至无毒。(The invention provides a method for reducing patulin in fruit juice and a method for safely producing the fruit juice, belonging to the technical field of fruit juice processing safety control. The invention takes L-cysteine as a detoxifying agent, mixes the semi-finished fruit juice with the L-cysteine, and pasteurizes the mixture to finish the patulin for reducing the pollution in the fruit juice, and the specific mechanism is that the L-cysteine is amino acid containing one sulfydryl (-SH), has reducibility, and has electrophilic property, and can generate Michael addition reaction with cysteine nucleophilic reagent containing sulfydryl under the pasteurization condition to generate a plurality of more stable adducts, and the toxicity of the product is far less than the toxicity of the patulin, even is nontoxic.)

1. A method for reducing patulin in fruit juice is characterized by comprising the following steps:

and mixing the semi-finished fruit juice with L-cysteine, and carrying out pasteurization to complete the reduction of the patulin in the fruit juice.

2. The trim method according to claim 1, wherein the pasteurization is carried out under closed conditions at a temperature of 70 to 100 ℃ for 10 to 20 min.

3. The subtractive process according to claim 1 or 2, wherein the L-cysteine is added in the form of a solution of clear juice of L-cysteine.

4. The subtractive method according to claim 3, wherein the clear juice solution of L-cysteine has a L-cysteine mass concentration of 20 to 25%.

5. The subtractive method according to claim 4, wherein the volume ratio of the juice intermediate to the clear juice solution of L-cysteine is 1000:0.50 to 0.80.

6. The subtractive process according to claim 4 or 5, wherein the juice semifinished product is an apple juice semifinished product and the clear juice solution of L-cysteine is a clear apple juice solution of L-cysteine; the semi-finished apple juice is a product obtained by sequentially carrying out pretreatment, crushing, juicing and filtering on an apple raw material, or a product obtained by sequentially carrying out pretreatment, crushing, pulping, enzymolysis, juicing and clarification on the apple raw material.

7. The reduction method according to claim 6, wherein when the semi-finished apple juice is used for producing clear apple juice, the semi-finished apple juice is a product obtained by sequentially carrying out pretreatment, crushing, pulping, enzymolysis, juicing and clarification on an apple raw material, and the volume ratio of the semi-finished apple juice to a clear apple juice solution of L-cysteine is 1000: 0.50-0.60; the method also comprises ultrafiltration before pasteurization.

8. The reduction method according to claim 6, wherein when the semi-finished apple juice is used for producing concentrated apple juice, the semi-finished apple juice is a product obtained by sequentially carrying out pretreatment, crushing, pulping, enzymolysis, juicing and clarification on an apple raw material, and the volume ratio of the semi-finished apple juice to a clarified apple juice solution of L-cysteine is 1000: 0.55-0.65; the method further comprises ultrafiltration and concentration before pasteurization.

9. The reduction method according to claim 6, wherein when the semi-finished apple juice is used for producing turbid apple juice, the semi-finished apple juice is obtained by sequentially carrying out pretreatment, crushing, juicing and filtering on an apple raw material, and the volume ratio of the semi-finished apple juice to a clear apple juice solution of L-cysteine is 1000: 0.60-0.80; before pasteurization, degassing is also included.

10. A safe production method of fruit juice is characterized by comprising the following steps:

producing a semi-finished fruit juice product, and then reducing the semi-finished fruit juice product according to the reducing method of any one of claims 1 to 9, and then carrying out aseptic filling to obtain the fruit juice.

Technical Field

The invention relates to the field of fruit juice processing safety control, in particular to a method for reducing patulin in fruit juice and a method for safely producing the fruit juice.

Background

Patulin (Patulin, PAT), also called Patulin, is a secondary metabolite produced mainly by penicillium expansum, has carcinogenic, teratogenic, neurotoxic, genotoxic and cytotoxic properties, and is organized by IARC as a class III carcinogen. Apple juice (including clear apple juice, cloudy apple juice and concentrated apple juice) is very popular among consumers due to its advantages of being rich in nutrients, good in taste and easy to store. China is a big country for producing and consuming apple juice, however, the apple juice produced at home and abroad is often detected to be patulin, which seriously threatens the health of consumers and causes huge economic loss to production operators. Therefore, countries such as Europe, America and China stipulate that the maximum residual limit of patulin in apple juice is 50 mug/L.

At present, the main method for removing patulin in fruit juice enterprises is to use a macroporous resin adsorption method, and although the method can effectively remove patulin, the problems of complex pretreatment, high use cost, easy carrying of peculiar smell, large product loss, easy secondary cross pollution, environmental pollution and the like exist, so that an efficient, safe, environment-friendly and economic method for reducing patulin in fruit juice is urgently needed to be developed.

Disclosure of Invention

The invention aims to provide a method for reducing patulin in fruit juice and a method for safely producing the fruit juice.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a method for reducing patulin in fruit juice, which comprises the following steps:

and mixing the semi-finished fruit juice with L-cysteine, and carrying out pasteurization to complete the reduction of the patulin in the fruit juice.

Preferably, the pasteurization is carried out under a closed condition, the temperature is 70-100 ℃, and the time is 10-20 min.

Preferably, the L-cysteine is added in the form of a solution, which is a clear juice solution of L-cysteine.

Preferably, the mass concentration of the L-cysteine in the clear juice solution of the L-cysteine is 20-25%;

preferably, the volume ratio of the semi-finished fruit juice to the clear fruit juice solution of L-cysteine is 1000: 0.50-0.80.

Preferably, the semi-finished fruit juice product is an apple juice semi-finished product, and the clear fruit juice solution of the L-cysteine is a clear apple juice solution of the L-cysteine; the semi-finished apple juice is a product obtained by sequentially carrying out pretreatment, crushing, juicing and filtering on an apple raw material, or a product obtained by sequentially carrying out pretreatment, crushing, pulping, enzymolysis, juicing and clarification on the apple raw material.

Preferably, when the semi-finished apple juice is used for producing clear apple juice, the semi-finished apple juice is a product obtained by sequentially carrying out pretreatment, crushing, pulping, enzymolysis, juicing and clarification on an apple raw material, and the volume ratio of the semi-finished apple juice to a clear apple juice solution of L-cysteine is 1000: 0.50-0.60; the method also comprises ultrafiltration before pasteurization.

Preferably, when the semi-finished apple juice is used for producing concentrated apple juice, the semi-finished apple juice is a product obtained by sequentially carrying out pretreatment, crushing, pulping, enzymolysis, juicing and clarification on an apple raw material, and the volume ratio of the semi-finished apple juice to a clarified apple juice solution of L-cysteine is 1000: 0.55-0.65; the method further comprises ultrafiltration and concentration before pasteurization.

Preferably, when the semi-finished apple juice is used for producing turbid apple juice, the semi-finished apple juice is a product obtained by sequentially carrying out pretreatment, crushing, juicing and filtering on an apple raw material, and the volume ratio of the semi-finished apple juice to a clear apple juice solution of L-cysteine is 1000: 0.60-0.80; before pasteurization, degassing is also included.

The invention also provides a safe production method of the fruit juice, which comprises the following steps:

and (3) producing a semi-finished fruit juice product, reducing the semi-finished fruit juice product according to the reduction method of the technical scheme, and performing aseptic filling to obtain the fruit juice.

The method takes L-cysteine as a detoxifying agent, mixes the semi-finished fruit juice with the L-cysteine, and pasteurizes the mixture to reduce the contaminated patulin in the fruit juice, and the specific mechanism is that the L-cysteine is an amino acid containing one sulfydryl (-SH) and has reducibility, the patulin has electrophilic property, and can generate Michael addition reaction with a cysteine nucleophilic reagent containing sulfydryl under the pasteurization condition to generate a plurality of more stable adducts, and the toxicity of the product is far less than that of the patulin, even is non-toxic. The reduction method provided by the invention can be completed under the pasteurization condition, when the reduction method is applied to fruit juice production, the overall preparation process of the fruit juice is not changed, and the fruit juice with low patulin content and even without patulin can be obtained by adding L-cysteine before pasteurization, so that the reduction method is suitable for industrial application.

Drawings

FIG. 1 is a flow diagram of the production of apple juice in an embodiment of the present invention;

FIG. 2 is a graph showing the results of testing the effect of the extract from patulin extraction of juice obtained by the subtractive process of the present invention on the viability of HepG2 cells;

FIG. 3 is a graph of the morphological changes of HepG2 cells in a cytotoxicology test.

Detailed Description

The invention provides a method for reducing patulin in fruit juice, which comprises the following steps:

and mixing the semi-finished fruit juice with L-cysteine, and carrying out pasteurization to complete the reduction of the patulin.

In the invention, L-cysteine is an amino acid containing one sulfydryl (-SH), has reducibility, patulin has electrophilic property, and can generate Michael addition reaction with a sulfydryl-containing cysteine nucleophilic reagent under pasteurization conditions to generate a plurality of more stable products, and the toxicity of the products is far less than that of the patulin, even is non-toxic, and the reaction formula of the Michael addition reaction is shown as the following formula:

in the invention, the pasteurization is preferably carried out under a closed condition, the temperature is preferably 70-100 ℃, and the time is preferably 10-20 min.

In the present invention, the L-cysteine (detoxified for short) is preferably added in the form of a solution, preferably a clear juice solution of L-cysteine (detoxified for short); the clear juice for the formulation of the clear juice solution of L-cysteine is preferably a clear juice without patulin. In the invention, L-cysteine is in a solid powder state at normal temperature, and in order to ensure that the cysteine is fully dissolved and uniformly dispersed in the fruit juice, the L-cysteine is firstly dissolved in a small amount of fruit juice and then added into the fruit juice in production.

In the invention, the mass concentration of the L-cysteine in the clear juice solution of the L-cysteine is preferably 20-25%; the volume ratio of the semi-finished fruit juice to the clear fruit juice solution of L-cysteine is preferably 1000: 0.50-0.80.

The invention is not particularly limited to which step the semi-finished fruit juice product is, and those skilled in the art can regard the semi-finished product obtained in any step before pasteurization as the semi-finished fruit juice product in the invention according to the process for producing fruit juice; furthermore, the person skilled in the art may add further process steps between the step of adding L-cysteine and the step of pasteurising, depending on the process requirements for producing the juice.

In the embodiment of the invention, the fruit juice semi-finished product is preferably an apple juice semi-finished product, and the clear fruit juice solution of L-cysteine is preferably a clear apple juice solution of L-cysteine; the semi-finished apple juice is preferably a product obtained by sequentially carrying out pretreatment, crushing, juicing and filtering on an apple raw material, or is preferably a product obtained by sequentially carrying out pretreatment, crushing, pulping, enzymolysis, juicing and clarification on an apple raw material; the clarified juice is preferably a clarified juice free of patulin. The source of the clear apple juice is not particularly limited, and the clear apple juice can be clear apple juice without patulin sold in the market or clear apple juice produced by the safe production method of the clear apple juice.

The operation of the pretreatment, the crushing, the juicing and the filtering is not specially limited, and the method can be carried out according to the conventional operation mode used in apple juice production; the operation of pretreatment, crushing, pulping, enzymolysis, juicing and clarification is not specially limited, and the method can be carried out according to the conventional operation mode used for producing apple juice; in the present invention, the pretreatment is the steps of washing, selecting and heat-treating the apple raw material in the conventional production of apple juice.

The content of patulin in the semi-finished fruit juice product is not specially limited, and the semi-finished fruit juice product meets the regulation of GB2761-2017 'mycotoxin limit in national food safety standard', namely, the content is less than 50 mu g/L.

In the embodiment of the invention, when the semi-finished apple juice is used for producing clear apple juice, the semi-finished apple juice is preferably a product obtained by sequentially carrying out pretreatment, crushing, pulping, enzymolysis, juicing and clarification on an apple raw material, and the volume ratio of the semi-finished apple juice to a clear apple juice solution of L-cysteine is preferably 1000: 0.50-0.60, and more preferably 1000: 0.55; the method also comprises ultrafiltration before pasteurization.

In the embodiment of the invention, when the semi-finished apple juice is used for producing concentrated apple juice, the semi-finished apple juice is preferably a product obtained by sequentially carrying out pretreatment, crushing, pulping, enzymolysis, juicing and clarification on an apple raw material, and the volume ratio of the semi-finished apple juice to a clarified apple juice solution of L-cysteine is 1000: 0.55-0.65, and more preferably 1000: 0.60; the method further comprises ultrafiltration and concentration before pasteurization.

In the embodiment of the invention, when the semi-finished apple juice is used for producing turbid apple juice, the semi-finished apple juice is preferably a product obtained by sequentially pretreating, crushing, juicing and filtering an apple raw material, and the volume ratio of the semi-finished apple juice to a clear apple juice solution of L-cysteine is 1000: 0.60-0.80, and more preferably 1000: 0.60; before pasteurization, degassing is also included.

In the invention, after the patulin is reduced, aseptic filling is carried out, and the fruit juice can be obtained. In addition, one skilled in the art can post-treat (e.g., blend with other types of juices to prepare other flavors of juices) after trimming, if desired, and then fill aseptically.

The invention also provides a safe production method of the fruit juice, which comprises the following steps:

and (3) producing a semi-finished fruit juice product, reducing the semi-finished fruit juice product according to the reduction method of the technical scheme, and performing aseptic filling to obtain the fruit juice.

In embodiments of the invention, the fruit juice is preferably cloudy apple juice, clear apple juice or concentrated apple juice;

when the fruit juice is turbid apple juice, the method specifically comprises the following steps:

pretreating, crushing, juicing and filtering an apple raw material in sequence to obtain an apple juice semi-finished product;

mixing the semi-finished apple juice with L-cysteine, and then sequentially performing degassing, pasteurization and aseptic filling to obtain turbid apple juice;

when the fruit juice is clear apple juice, the method specifically comprises the following steps:

sequentially carrying out pretreatment, crushing, pulping, enzymolysis, juicing and clarification on an apple raw material to obtain an apple juice semi-finished product;

mixing the semi-finished apple juice with L-cysteine, and sequentially carrying out ultrafiltration, pasteurization and aseptic filling to obtain clear apple juice;

when the fruit juice is concentrated apple juice, the method specifically comprises the following steps:

sequentially carrying out pretreatment, crushing, pulping, enzymolysis, juicing and clarification on an apple raw material to obtain an apple juice semi-finished product;

and mixing the semi-finished apple juice with L-cysteine, and sequentially carrying out ultrafiltration, concentration, pasteurization and aseptic filling to obtain clear apple juice.

In the embodiment of the invention, when the fruit juice is cloudy apple juice, the operation of pretreatment, crushing, juicing and filtering is not particularly limited, and the fruit juice can be produced according to the conventional production method of a semi-finished fruit juice product. In embodiments of the present invention, the pre-treatment preferably comprises washing, sorting and heat treatment; the cleaning preferably comprises primary cleaning and secondary cleaning, wherein the primary cleaning is preferably soaking cleaning which can remove silt, stones, metals and the like on the surface of the apples, and the secondary cleaning is preferably spraying cleaning which further cleans the apples; the selection refers to selecting rotten and deteriorated fruits, impurities and the like, wherein the rotten and deteriorated fruit rate of the obtained apples is preferably less than or equal to 2 percent after the selection; the heat treatment is preferably carried out in water at 42-47 ℃, the time is preferably 40-50 min, and the heat treatment can improve the juice yield and stability of the turbid juice; the granularity of the fruit blocks in the crushed fruit pulp is preferably 4-6 mm, and Vc accounting for 0.05 percent of the mass of the apples to be crushed and NaCl accounting for 0.02 percent of the mass of the apples to be crushed are added during crushing to perform color protection treatment; the juicing is preferably carried out by squeezing the crushed fruit pulp by using a double-screw squeezer, the juice after squeezing enters a primary filtering process, the juice yield of the fruit juice reaches more than 80%, and the residual fruit residues are added with water and extracted in the squeezer and subjected to secondary squeezing; the L-cysteine is preferably added in the form of a solution, the solution is preferably a clear apple juice solution of the L-cysteine, and the mass concentration of the L-cysteine in the clear apple juice solution of the L-cysteine is preferably 20-25%; the volume ratio of the semi-finished fruit juice to the clear apple juice solution of L-cysteine is preferably 1000: 0.60-0.80; the pasteurization conditions are the same as the pasteurization conditions in the abatement method described above and are not described in detail herein; the operation of degassing and aseptic filling in the present invention is not particularly limited, and may be performed by the conventional degassing and aseptic filling operation for producing fruit juice, for example, aseptic filling may be performed by filling fruit juice into aseptic bags under the sterilization condition of >95 ℃.

In the invention, when the fruit juice is clear apple juice, the operation of pretreatment, crushing, pulping, enzymolysis, juicing, clarification, ultrafiltration, sterilization and sterile filling is not specially limited, and the fruit juice can be produced by adopting a conventional production method of a semi-finished fruit juice product. In the embodiment of the invention, the pretreatment and crushing operations are the same as those in the production of turbid apple juice, and are not described again; the enzyme used for enzymolysis is preferably pectinase and amylase, the enzymolysis temperature is preferably 50-53 ℃, the enzymolysis time is preferably 90min, and the dosage of the pectinase and the amylase can be selected by a person skilled in the art according to needs; conveying the juice subjected to enzymolysis to a squeezing device for juicing, and then clarifying; the ultrafiltration can remove insoluble substances and substances (including microorganisms) with molecules larger than 0.02 μm in the juice and impurities such as metal debris which may exist; the L-cysteine is preferably added in the form of a solution, the solution is preferably a clear apple juice solution of the L-cysteine, and the mass concentration of the L-cysteine in the clear apple juice solution of the L-cysteine is preferably 20-25%; the volume ratio of the semi-finished fruit juice to the clear apple juice solution of L-cysteine is preferably 1000: 0.50-0.60; the pasteurization and aseptic filling operations are the same as those in the production of cloudy apple juice and are not described in detail herein.

In the invention, when the fruit juice is concentrated apple juice, the operation of pretreatment, crushing, pulping, enzymolysis, juicing, clarification, ultrafiltration, concentration, pasteurization and sterile filling is not specially limited, and the conventional operation for producing the concentrated apple juice is adopted; the L-cysteine is preferably added in the form of a solution, the solution is preferably a clear apple juice solution of the L-cysteine, and the mass concentration of the L-cysteine in the clear apple juice solution of the L-cysteine is preferably 20-25%; the volume ratio of the semi-finished fruit juice to the clear apple juice solution of L-cysteine is preferably 1000: 0.55-0.65; in the embodiment of the invention, the operations except the concentration are the same as those in the production of clear apple juice, and the details are not repeated; concentration can be carried out as desired by those skilled in the art.

The method for reducing patulin in fruit juice and the method for safely producing apple juice provided by the invention are described in detail with reference to the following examples, but they should not be construed as limiting the scope of the invention.