WO2024131217A1 - Procédé écologique de congélation par immersion à ultra-basse température à température constante basé sur un couplage entre un milieu de réfrigération de solution sans congélation et de la glace sèche - Google Patents

Procédé écologique de congélation par immersion à ultra-basse température à température constante basé sur un couplage entre un milieu de réfrigération de solution sans congélation et de la glace sèche Download PDF

Info

Publication number
WO2024131217A1
WO2024131217A1 PCT/CN2023/123957 CN2023123957W WO2024131217A1 WO 2024131217 A1 WO2024131217 A1 WO 2024131217A1 CN 2023123957 W CN2023123957 W CN 2023123957W WO 2024131217 A1 WO2024131217 A1 WO 2024131217A1
Authority
WO
WIPO (PCT)
Prior art keywords
temperature
freezing
dry ice
unit
antifreeze
Prior art date
Application number
PCT/CN2023/123957
Other languages
English (en)
Chinese (zh)
Inventor
丁玉庭
杨月
贾世亮
周绪霞
丁祎程
Original Assignee
浙江工业大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 浙江工业大学 filed Critical 浙江工业大学
Publication of WO2024131217A1 publication Critical patent/WO2024131217A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B4/00—General methods for preserving meat, sausages, fish or fish products
    • A23B4/06—Freezing; Subsequent thawing; Cooling
    • A23B4/08—Freezing; Subsequent thawing; Cooling with addition of chemicals or treatment with chemicals before or during cooling, e.g. in the form of an ice coating or frozen block
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • the invention belongs to the technical field of food freezing and fresh-keeping processing, and particularly relates to a constant temperature immersion green ultra-low temperature freezing method of an antifreeze refrigerant coupled with dry ice.
  • the antifreeze immersion freezing method is considered to be a new and efficient low-temperature preservation processing technology because of its high cold storage density, large heat transfer coefficient (more than 20 times higher than air medium) and fast freezing speed. Moreover, the antifreeze has the advantages of low freezing point, large heat transfer coefficient, safety and non-toxicity, and can effectively maintain food quality and extend the shelf life of food.
  • liquid nitrogen immersion freezing can achieve rapid low-temperature freezing of food, the intense heat exchange with the food material can easily cause excessive mechanical stress on the surface of the frozen material and cause low-temperature freezing cracking.
  • there are certain restrictions on the size of food materials When the size of the food material is large, freezing will also cause problems such as freezing cracks and freeze burn on the food surface.
  • CO 2 is a colorless, odorless gas at room temperature and pressure. When the temperature is -56.6°C and the pressure is 0.52MPa, it exists in a solid state, namely "dry ice". The sublimation temperature of solid CO 2 is very low, at -78.5°C, which can achieve the purpose of rapid cooling and refrigeration. In addition, CO 2 is stable in nature. When it comes into direct contact with food materials, it is not easy to react with the ingredients in the food materials. It can well maintain the original flavor and quality of the materials and can be widely used in food preservation.
  • the present invention mainly utilizes the large latent heat of vaporization and low vaporization temperature of dry ice, which can promote the rapid cooling of antifreeze, clarify the heat exchange and the amount of dry ice added during the freezing process of dry ice coupled with antifreeze; dry ice has the advantages of low price and environmental protection, and quickly sublimates into gas without causing pollution to the environment; this method has a fast freezing speed, and the time in the maximum ice crystal generation zone is short, which truly realizes low-temperature rapid freezing processing.
  • the real-time balance of the refrigerant maintains an ultra-low temperature constant freezing temperature, and the freezing of fish bodies at different times can achieve the same muscle ice crystal formation, ensuring the quality of food after freezing-thawing.
  • the present invention provides a green ultra-low temperature freezing method of constant temperature immersion by coupling an antifreeze coolant with dry ice.
  • a constant temperature immersion green ultra-low temperature freezing method using an antifreeze coolant coupled with dry ice comprises the following steps:
  • the food material is fresh food
  • the slurry ice is a commonly used food pre-cooling method, and its main components are water and salt;
  • the antifreeze liquid is a food-grade antifreeze liquid, which is usually used for immersion freezing of food materials to achieve the effects of rapid freezing and preservation, and is commercially available;
  • step 4 Dry ice coupled antifreeze immersion freezing: the food material pre-cooled in step 2) is placed in the antifreeze cooled in step 3) for immersion freezing, and dry ice is added at the same time;
  • a dry ice automatic discharging device based on a cold matching mode can be used to quantitatively add cold source dry ice (vaporization latent heat 573 kJ/kg, vaporization temperature -78.5°C) to the ultra-low temperature food antifreeze (temperature ⁇ -45°C), and stir at the same time, vaporize in the antifreeze to release cold, and balance the coolant in real time to maintain an ultra-low temperature constant freezing temperature;
  • the dry ice may be in the form of granules, blocks, flakes, or columns, and more preferably columnar dry ice;
  • step 5 Using a temperature recorder, record the change of the center temperature of the food material in step 4), and terminate the freezing when the center temperature of the food material reaches the target temperature.
  • the heat transfer during the freezing process of the food material and the amount of dry ice added can be determined by the following steps:
  • Q3 is the cooling capacity released by dry ice, unit: J; 573 is the heat absorbed by sublimation of unit mass of dry ice, unit: kJ/kg; m is the mass of dry ice added, unit: kg;
  • Q11 is the heat released by the food material during the freezing process before adding dry ice, unit: J;
  • Q21 is the heat absorbed by the antifreeze during the cooling process, unit: J;
  • Q4 is the cooling capacity of the antifreeze equipment, unit: W;
  • Q12 is the heat released by the food material during the freezing process after adding dry ice, unit: J;
  • Q22 is the total heat absorbed by the antifreeze during the cooling process, unit: J;
  • Q3 is the cold released by dry ice, unit: J;
  • Q4 is the refrigeration capacity of the antifreeze equipment, unit: W;
  • Q13 is the cold absorbed by the food material during the freezing process, unit: J;
  • Q23 is the total heat released during the heating process of the antifreeze, unit: J;
  • Q4 is the cooling capacity of the antifreeze equipment, unit: W;
  • the amount of dry ice to be added can be determined
  • Q1 is the total heat released by the food material during the freezing process, unit: J;
  • Q3 is the cold released by dry ice, unit: J;
  • Q4 is the refrigeration capacity of the antifreeze equipment, unit: J.
  • the present invention provides a green ultra-low temperature freezing technology that uses dry ice as a cold source and combines it with an antifreeze solution.
  • the dry ice automatic discharging device based on the cold quantity matching mode is used to quantitatively add the cold source dry ice into the ultra-low temperature food-grade antifreeze solution (temperature ⁇ -45°C). Ice (vaporization latent heat 573kJ/kg, vaporization temperature -78.5°C) vaporizes in the antifreeze to release cold, and the coolant is balanced in real time to maintain an ultra-low temperature constant freezing temperature.
  • the freezing of fish bodies at different times can achieve the same formation of muscle ice crystals.
  • the CO2 gas formed after the sublimation of dry ice exists in the antifreeze in the form of bubbles. With the continuous generation of bubbles, it stirs the antifreeze and stabilizes the temperature of the antifreeze. It better solves the problem of temperature fluctuations during the process of freezing food in antifreeze.
  • the present invention also clarifies the cooling capacity released by dry ice in the process of freezing food by coupling dry ice with antifreeze, as well as mathematical problems such as heat exchange during the freezing of food.
  • This invention uses antifreeze coupled with dry ice to achieve rapid low-temperature freezing of food, which can not only reduce the size of ice crystals in frozen products and reduce the damage of ice crystals to tissue structure, but also increase the freezing rate, balance the refrigerant in real time to maintain an ultra-low temperature constant freezing temperature, and freeze the fish body at different times to achieve the same muscle ice crystal formation, thereby maintaining the quality of the food.
  • This freezing technology is novel and environmentally friendly, filling the gap in the field of food freezing.
  • FIG. 1 is a schematic diagram of an experimental device of the present invention.
  • Figure 2 is a schematic diagram of the temperature change curve of the fish body and the antifreeze during the freezing process of the present invention: wherein the X-axis represents time, unit: min; the Y-axis represents temperature, unit: ° C; T0 represents the initial temperature of the large yellow croaker before freezing, unit: ° C; T1 represents the center temperature of the large yellow croaker at the end of precooling, unit: ° C; T2 represents the center temperature of the large yellow croaker at the end of freezing, unit: ° C; ta represents the time point of adding dry ice, unit: min; tb represents the time when the antifreeze reaches the lowest temperature, unit: min; tc represents the time when the large yellow croaker ends freezing, unit: min; Ta represents the set temperature reached by the antifreeze, unit: ° C; Tb represents the temperature when the antifreeze temperature rises to the required temperature of adding dry ice, unit: ° C; Tc represents the lowest temperature reached by the antifree
  • Figure 3 is a schematic diagram of the intrinsic fluorescence of myofibrillar protein of large yellow croaker under three different freezing methods of the embodiments of the present invention and the comparative examples:
  • A is a -40°C refrigerator freezing the yellow croaker to a center temperature of -18°C;
  • B1 and B2 are respectively freezing the yellow croaker to -18°C and -30°C at the center using -45°C antifreeze without dry ice;
  • C1 and C2 are respectively freezing the yellow croaker to -18°C and -30°C at the center using -45°C antifreeze with dry ice added.
  • FIG. 4 is a freezing curve of large yellow croaker under three different freezing methods according to the embodiments of the present invention and the comparative example.
  • the antifreeze used in the following examples was provided by Hangzhou Qiandao Lake Development Group Co., Ltd., and the freezing point was -48.6°C.
  • Example 1 Freezing large yellow croaker by soaking in antifreeze solution without dry ice
  • Freezing treatment by immersion in antifreeze The pre-cooled fish is immersed in antifreeze to freeze quickly.
  • the temperature measuring probe is inserted into the geometric center of the fish fillet to record the temperature.
  • the freezing is terminated when the center temperature of the fish fillet freezes to -18°C and -30°C respectively. Under this freezing method, it only takes 12.4 minutes to pass through the maximum ice crystal formation zone, while traditional refrigerator freezing takes about 257 minutes.
  • Example 2 Freezing large yellow croaker fillets by dipping in antifreeze solution with dry ice
  • Antifreeze immersion freezing treatment Wrap the pre-cooled fish with plastic wrap and immerse it in -45°C food-grade antifreeze for quick freezing.
  • Stir the antifreeze with a stirrer at the same time. Insert the temperature measuring probe into the geometric center of the yellow croaker to record the temperature. The freezing is terminated when the center temperature of the fish body freezes to -18°C and -30°C respectively.
  • the freezing technology of this embodiment only takes 6.4 minutes to freeze the fish fillet through the maximum ice crystal formation zone, while the traditional refrigerator freezing takes about 257 minutes. This technology is short in time to pass through the maximum ice crystal formation zone, and truly realizes low-temperature rapid freezing processing.
  • Q1 is the total heat released by the large yellow croaker during the freezing process, unit: J; c is the specific heat capacity of the large yellow croaker (3.18J/(kg ⁇ °C)); M1 is the mass of the large yellow croaker (8.80kg); T2 is the center temperature of the large yellow croaker at the end of freezing (-18°C); T1 is the center temperature of the large yellow croaker before freezing (2°C). That is, the total heat released by the large yellow croaker during the freezing process is 559.68J.
  • Q11 is the heat released in the process of antifreeze freezing large yellow croaker before adding dry ice, unit: J;
  • Q21 is the heat absorbed in the process of antifreeze cooling, unit: J;
  • Q4 is the cooling capacity of antifreeze equipment, unit: W.
  • Q12 is the heat released by the food material during the freezing process after adding dry ice, unit: J;
  • Q22 is the total heat absorbed by the antifreeze during the cooling process, unit: J;
  • Q3 is the cold released by dry ice, unit: J;
  • Q4 is the refrigeration capacity of the antifreeze equipment, unit: W.
  • the amount of dry ice to be added can be determined
  • Q1 is the total heat released by large yellow croaker during the freezing process, which is 559.68 J; P is the output power of the antifreeze equipment, which is 200 J/s; 573 is the heat absorbed by the sublimation of unit mass of dry ice, unit: kJ/kg; t1 is the freezing time of large yellow croaker, which is 20 min, so the amount of dry ice added is calculated to be 0.86 kg.
  • adding 0.86kg of dry ice can better maintain the stability of the antifreeze temperature, reduce the temperature fluctuation of the antifreeze during the freezing process, and increase the freezing rate.
  • Refrigerator freezing treatment put the pre-cooled fish into a ziplock bag and freeze it in a -40°C refrigerator. Insert the temperature measuring probe into the geometric center of the fish fillet to record the temperature. The freezing is terminated when the center temperature of the fish fillet freezes to -18°C.
  • the concentration of the extracted myofibrillar protein was adjusted to 0.5 mg/mL, and the spectrum was scanned using an endogenous fluorescence spectrometer.
  • the scanning range was 300 nm to 500 nm
  • the emission spectrum range was 300 nm to 400 nm
  • the excitation wavelength was 293 nm
  • the excitation slit was 10 nm
  • the emission slit was 10 nm.
  • the scan was repeated 3 times.
  • the endogenous fluorescence graph of myofibrillar protein was plotted with the wave number as the horizontal axis and the fluorescence intensity as the vertical axis. As can be seen from Figure 3, the fluorescence intensity of myofibrillar protein from large yellow croaker frozen with the antifreeze solution after adding dry ice was the highest, and the tertiary structure of the protein was relatively stable.
  • Determination of the freezing curve of large yellow croaker insert the temperature probe into the geometric center of the fish body, and connect the computer to the temperature recorder to collect the temperature data in Example 1, Example 2 and Comparative Experiment 1 in real time. With time as the abscissa and temperature as the ordinate, a time-temperature curve is drawn, which is the freezing curve of large yellow croaker. As can be seen from Figure 4, freezing of the antifreeze solution after adding dry ice can significantly increase the freezing rate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Freezing, Cooling And Drying Of Foods (AREA)

Abstract

L'invention concerne un procédé de congélation par immersion à température constante basé sur le couplage entre un milieu de réfrigération de solution sans congélation et de la glace sèche, comprenant les étapes suivantes : 1) le nettoyage d'une matière alimentaire et l'enveloppement de celle-ci à l'aide d'une enveloppe en plastique ; 2) le pré-refroidissement de la matière alimentaire jusqu'à une température interne de 2 ± 0,5 °C à l'aide d'un coulis de glace et l'enregistrement de changements de température de la matière alimentaire à l'aide d'un enregistreur de température ; 3) le refroidissement de la solution sans congélation à l'aide d'un dispositif de bain réactif à température constante basse température, refroidissant jusqu'à une température définie de -45 °C et l'enregistrement de changements de température à l'aide de l'enregistreur de température ; 4) la réalisation d'une congélation par immersion par couplage d'une solution sans congélation et de glace sèche : le placement de la matière alimentaire pré-refroidie à l'étape 2) dans la solution sans congélation refroidie à l'étape 3) pour une congélation par immersion et l'ajout de glace sèche en même temps ; et 5) l'enregistrement de changements de la température interne de la matière alimentaire à l'étape 4) à l'aide de l'enregistreur de température et la cessation de la congélation lorsque la température interne de la matière alimentaire atteint une température cible. Le procédé comprend en outre la détermination du transfert de chaleur de la matière alimentaire et d'une quantité d'ajout de la glace sèche pendant la congélation.
PCT/CN2023/123957 2022-12-22 2023-10-11 Procédé écologique de congélation par immersion à ultra-basse température à température constante basé sur un couplage entre un milieu de réfrigération de solution sans congélation et de la glace sèche WO2024131217A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211656758.1 2022-12-22
CN202211656758.1A CN116076557A (zh) 2022-12-22 2022-12-22 一种不冻液载冷剂耦合干冰的恒温浸渍绿色超低温冻结方法

Publications (1)

Publication Number Publication Date
WO2024131217A1 true WO2024131217A1 (fr) 2024-06-27

Family

ID=86207420

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/123957 WO2024131217A1 (fr) 2022-12-22 2023-10-11 Procédé écologique de congélation par immersion à ultra-basse température à température constante basé sur un couplage entre un milieu de réfrigération de solution sans congélation et de la glace sèche

Country Status (2)

Country Link
CN (1) CN116076557A (fr)
WO (1) WO2024131217A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116076557A (zh) * 2022-12-22 2023-05-09 浙江工业大学 一种不冻液载冷剂耦合干冰的恒温浸渍绿色超低温冻结方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06153888A (ja) * 1992-07-07 1994-06-03 Nippon Kayaku Co Ltd 食品の冷凍方法
JPH10309162A (ja) * 1997-05-12 1998-11-24 Toru Sueyoshi 生鮮食品の貯蔵方法
JP2014212784A (ja) * 2013-04-25 2014-11-17 株式会社ミツヤコーポレーション 冷凍解凍法とその冷凍解凍液
JP2019069401A (ja) * 2017-10-06 2019-05-09 大陽日酸株式会社 極低温凍結粗粉砕方法及び装置、種実類の薄皮剥き方法、極低温凍結粗粉砕装置の清掃方法
CN114152014A (zh) * 2021-11-23 2022-03-08 江南大学 一种基于冰晶体调控的低频超声辅助液化co2速冻装置及方法
CN114557381A (zh) * 2022-03-11 2022-05-31 浙江工业大学 一种大黄鱼的速冻保鲜方法
CN116076557A (zh) * 2022-12-22 2023-05-09 浙江工业大学 一种不冻液载冷剂耦合干冰的恒温浸渍绿色超低温冻结方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104799394B (zh) * 2015-05-20 2018-07-10 河南农业大学 一种食品的快速冷冻工艺
CN106857785A (zh) * 2017-02-08 2017-06-20 刘富来 一种用干冰加工冰鲜鸡的方法
CN110100874B (zh) * 2019-06-12 2022-07-22 中国科学院理化技术研究所 一种鱼类的冷冻工艺

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06153888A (ja) * 1992-07-07 1994-06-03 Nippon Kayaku Co Ltd 食品の冷凍方法
JPH10309162A (ja) * 1997-05-12 1998-11-24 Toru Sueyoshi 生鮮食品の貯蔵方法
JP2014212784A (ja) * 2013-04-25 2014-11-17 株式会社ミツヤコーポレーション 冷凍解凍法とその冷凍解凍液
JP2019069401A (ja) * 2017-10-06 2019-05-09 大陽日酸株式会社 極低温凍結粗粉砕方法及び装置、種実類の薄皮剥き方法、極低温凍結粗粉砕装置の清掃方法
CN114152014A (zh) * 2021-11-23 2022-03-08 江南大学 一种基于冰晶体调控的低频超声辅助液化co2速冻装置及方法
CN114557381A (zh) * 2022-03-11 2022-05-31 浙江工业大学 一种大黄鱼的速冻保鲜方法
CN116076557A (zh) * 2022-12-22 2023-05-09 浙江工业大学 一种不冻液载冷剂耦合干冰的恒温浸渍绿色超低温冻结方法

Also Published As

Publication number Publication date
CN116076557A (zh) 2023-05-09

Similar Documents

Publication Publication Date Title
Kauffeld et al. Handbook on ice slurries
WO2024131217A1 (fr) Procédé écologique de congélation par immersion à ultra-basse température à température constante basé sur un couplage entre un milieu de réfrigération de solution sans congélation et de la glace sèche
CN103865495B (zh) 一种用于浸渍法冷冻食品的冷冻液
CN103168828B (zh) 变频超声波强化提高荔枝冷冻速度与品质的方法
Chevalier et al. Freezing and ice crystals formed in a cylindrical food model: part II. Comparison between freezing at atmospheric pressure and pressure-shift freezing
Diao et al. Effects of immersion freezing methods on water holding capacity, ice crystals and water migration in grass carp during frozen storage
CN101138362A (zh) 一种低频超声波改善速冻果蔬解冻品质的方法
Xu et al. Experimental and application study of Na 2 SO 4· 10H 2 O with additives for cold storage
Haiying et al. Experimental study on the freezing characteristics of four kinds of vegetables
US20210259288A1 (en) Ultrasonic freezing equipment and freezing method using same
CN113455537B (zh) 一种金鲳鱼的节能速冻方法
CN101664222B (zh) 一种具有抗氧化护色作用的水产品低温速冻液
Li et al. Experimental study on a wet precooling system for fruit and vegetables with ice slurry
Fikiin Emerging and novel freezing processes
CN205280624U (zh) 一种研究电磁场对冻结过程影响的实验平台
Long Some thermodynamic properties of fish and their effect on the rate of freezing
CN110100874A (zh) 一种鱼类的冷冻工艺
Kuang et al. Comparison of air freezing, liquid immersion freezing and pressure shift freezing on freezing time and quality of snakehead (Channa Argus) fillets
Liu et al. Preparation and stability analysis of glycine water-based phase change materials modified with potassium sorbate for cold chain logistics
CN101455217B (zh) 一种超声强化冷冻面团的设备及方法
CN108378125A (zh) 一种小龙虾急速玻璃化冷冻冷却介质及利用其冷冻小龙虾的方法
CN107758059A (zh) 一种使用磁场与微冻液的食品冷冻保鲜装置
Hakim et al. Phase change material‐assisted freezing of tuna: Impact on freezing process and thawing loss
CN204811885U (zh) 一种食品快速冻结的装置
CN102455098A (zh) 一种速冻果蔬加工冷却设备及方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23905390

Country of ref document: EP

Kind code of ref document: A1