CN103097838B - Freezing method - Google Patents
Freezing method Download PDFInfo
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- CN103097838B CN103097838B CN201180043849.1A CN201180043849A CN103097838B CN 103097838 B CN103097838 B CN 103097838B CN 201180043849 A CN201180043849 A CN 201180043849A CN 103097838 B CN103097838 B CN 103097838B
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D31/00—Other cooling or freezing apparatus
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/066—Cooling mixtures; De-icing compositions
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- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Freezing, Cooling And Drying Of Foods (AREA)
- Devices That Are Associated With Refrigeration Equipment (AREA)
Abstract
The invention provides a kind of freezing method.Under the state configuring frozen thing in the mode leaving airtight container wall, in the free convection below-16 DEG C, cool this frozen thing, and after supercooling, this frozen thing is freezed.At this moment, preferably from room temperature, frozen thing and gas around thereof are cooled.In addition, preferably use that to form molecule be by more than three former molecular polyatomic molecule gases or contain the gas of described polyatomic molecule gas to be full of closed container, the ratio of heat capacities containing described polyatomic molecule gas is large with the thermal capacity of the dry air of molecular number.
Description
Technical field
The present invention relates to the freezing method of food, internal organs, tissue, zooblast, microorganism etc.
Background technology
When freezing the frozen thing of the low-water-content materials such as zooblast, the ice crystal nucleus (iceseeds) that frozen thing inside occurs can become to grow up to larger-size ice crystal, therefore the cell membrane of frozen thing sustains damage, thus causes going out moisture when thawing from the stream of cells of damage.Containing intracellular fluid in the moisture (drip) of this outflow, the fluid loss produced when thawing can have a huge impact the quality of freezing of frozen thing.
The freezing speed of frozen thing is faster, more can suppress the increase of Ice crystal size.Therefore, generally at the low-temperature space of larger less than-50 DEG C of the temperature difference with environment temperature, frozen thing is cooled rapidly.But, need to consume a large amount of electric power owing to carrying out cooling at low-temperature space, unsatisfactory from the viewpoint of economize energy.
Therefore, Patent Document 1 discloses following technology: by save room by food precooling and after making it to be in supercooling state, send into cold air and cool rapidly in this save room at the temperature of-7 DEG C, this food is changed into from supercooling and freezes.
And in patent document 2, disclosing following a kind of technology: steam ejection liquefaction carbon dioxide in the storehouses such as freezer, utilizes this gasification latent heat cool rapidly and storehouse temperature need not be made to change, thus freezes the food etc. be kept in storehouse.
Prior art document
Patent document
Patent document 1: Japanese Patent Publication No. 4253775 publication
Patent document 2: Japanese publications is real opens clear 51-50444 publication
Summary of the invention
The technical problem that invention solves
But, in freezing method disclosed in patent document 1, formed and only the part that the top layer of food is freezed freezed, be difficult to preserve on the basis of long-period freshness preserving.
The present invention in view of the above problems, its object is to provide on a kind of basis reliably carrying out freezing, can realizing the freezing method reducing the fluid loss that frozen thing occurs when thawing.
The technological means of technical solution problem
The feature of freezing method of the present invention is, under the state configuring frozen thing in the mode leaving airtight container wall, cools described frozen thing in the free convection below-16 DEG C, freezes after supercooling to this frozen thing.
According to freezing method of the present invention, because frozen thing is configured to leave wall, therefore surround by gas around frozen thing, thermal insulation increases, and degree of supercooling increases.And, owing to being freeze frozen thing under the state of the free convection of low temperature, the latent heat of solidification short time heat absorption after can removing supercooling, thus can realizing frozen thing, produce the high-quality of less fluid loss when thawing freezing.
In addition, in freezing method of the present invention, preferably from room temperature, frozen thing and gas around thereof are cooled.
In this case, by cooling environmental gas from room temperature, compared with the situation in advance environmental gas cooled, the initial stage cooling velocity of frozen thing can be made slack-off, and increase degree of supercooling.
In addition, in freezing method of the present invention, be preferably be full of form molecule by more than three former molecular polyatomic molecule gas or comprise polyatomic molecule gas following gas airtight container in frozen thing is freezed, described gas refers to: contain described polyatomic molecule gas to make the ratio of heat capacities of the gas in container with the mode that the thermal capacity of the dry air of molecular number is large.
In this case, the gas covered around frozen thing forms molecule by more than three former molecular polyatomic molecule gases or a kind of gas containing described polyatomic molecule gas with the ratio of heat capacities of the gas in container with the mode that the thermal capacity of the dry air of molecular number is large, the ratio of heat capacities of this gas as air principal component will large one mole (mol ratio thermal capacitance) by the thermal capacity of the nitrogen molecular of two atomic buildings or oxygen molecule.
If temperature difference or initial stage pressure identical, then pyroconductivity is determined by the specific heat capacity of the fluid contacted with frozen thing in free convection.The thermal conductivity ratio air of described polyatomic molecule gas large.Therefore, after supercooling status releasing, with using air compared with the situation of environmental gas, can pyroconductivity be improved, and accelerate the freezing speed of frozen thing.
In addition, because freezing speed is accelerated, the time of latent heat treatment shortens, and is in the time shorten of solidification point near zero degree because latent heat of solidification causes.So, the ice crystal nucleus produced in the inside of frozen thing can be alleviated and grow into larger-size ice crystal and the degree of the damage that causes the cell membrane of frozen thing to be subject to.Therefore, it is possible to reduce the fluid loss that frozen thing produces when thawing.
In addition, the closed container that needs use compared with frozen thing, volume is enough large.So frozen thing is preferably the research such as tissue, zooblast, the microorganism test portion etc. of small volume.But, when employing fully can guarantee the cold storage warehouse etc. of refrigerating chamber volume, also can freeze by the frozen thing large to food equal-volume.
In addition, degree till frozen thing central part can be reached in order to realize supercooling state, expecting that initial stage cooling velocity is comparatively slow, and cooling with speed fast as far as possible after supercooling is removed, therefore, it is possible to absorb heat to latent heat of solidification at short notice, thus realize good freezing.
So, in freezing method of the present invention, after supercooling being carried out to frozen thing under the state of free convection, under the state of forced convertion, described frozen thing is freezed, thus improve cooling velocity when freezing.
Accompanying drawing explanation
Fig. 1 be represent test portion freeze after thaw time the figure of percentage of water loss.
Fig. 2 be represent test portion freeze after thaw time percentage of water loss and the constant voltage mol ratio thermal capacitance of environmental gas between the figure of relation.
Fig. 3 be represent test portion freeze after thaw time the figure of percentage of water loss.
Fig. 4 be represent test portion freeze after thaw time the figure of percentage of water loss.
Fig. 5 be represent test portion freeze after thaw time the figure of percentage of water loss.
Fig. 6 represents according to the schematic diagram freezing utensil of the present invention.
Fig. 7 represents to freeze the schematic diagram of utensil according to of the present invention another.
Detailed description of the invention
(freezing principle)
The damage of frozen thing when freezing comprises: the damage that the cracking of degree of injury and the growth in direct ratio of heat absorption speed causes and being inversely proportional to the increase of the Ice crystal size diminished and the damage caused with heat absorption speed.When not considering the preservation of frozen thing and thawing and only study the freezing of frozen thing, can think that damage when freezing is above-mentioned two kinds of degree of injury sums.
The cracking of frozen thing when freezing refers to that the outer section of frozen thing is chapped or produces the damage of distortion.Cracking is that the outer section freezed the earliest owing to absorbing heat from top layer causes because of expansion when inside is freezed.On frozen thing, Ice crystal size increases the damage caused is that the ice crystal nucleus occurred due to frozen thing inside is grown up and the increase of the size of the ice crystal occurred in frozen thing is caused.
When frozen thing be moisture content lower (65% ~ 85%), thinner thickness zooblast etc., the degree of injury that causes of ftractureing is comparatively light, and it is the main cause that frozen thing damages when freezing that the Ice crystal size on frozen thing increases the damage caused.On the other hand, when frozen thing is the unicellular microorganism etc. of moisture content higher (more than 90%), the damage that cracking causes becomes the main cause of frozen thing damage.
The increase of Ice crystal size can suppress in the following manner: cool rapidly frozen thing, makes frozen thing be in the time shorten of the solidification point near 0 DEG C because of latent heat of solidification.Therefore, improve freezing speed to carry out freezing being very important.But, when low-temperature space cools, owing to needing to consume a large amount of electric power, therefore unsatisfactory from the viewpoint of economize energy.
In addition, when freezing through cooling procedure, by increasing degree of supercooling, supercooling being carried out to the inside of cooled animal, supercooling can be shortened and remove the after coagulation latent heat treatment time, thus can carry out high-quality freezing.Due to the release time in order to shorten latent heat of solidification, the larger pyroconductivity of thermal capacity of contact cold-producing medium is higher, so the cold-producing medium that preferably thermal capacity is large.
Particularly when freezing a small amount of frozen thing through cooling procedure, by controlling larger by the thermal capacity of environmental gas, the heat absorption speed of latent heat of solidification can be accelerated.Its reason is as follows: if temperature difference is identical with initial stage pressure, then pyroconductivity is determined by the specific heat capacity of the fluid contacted with frozen thing in free convection, so, by controlling larger by the thermal capacity of contact cold-producing medium, the freezing speed of frozen thing just can be accelerated.
Specifically, such as, by the frozen thing of hanging, place it on netted frame, thus make to be formed the frozen thing almost overall frozen environment being in the state of being surrounded by this gas.
In addition, when adopting formation molecule to be the polyatomic molecule gas of more than 3 atoms, its molar specific heat is larger than air.As this gas, such as, can enumerate the gases such as carbon dioxide, steam, CFC (chlorofluorocarbon/CFC), methane (methane), ethane (ethane), propane (propane), butane (butane).
Like this, the gas mixing molar specific heat larger than air around frozen thing surrounds this frozen thing, carries out freezing while generation free convection in supercooling temperature province to frozen thing.In addition ,-10 DEG C ~-40 DEG C can be approximately through the solidification point district of cooling procedure.Therefore, hang frozen thing in the mode do not come in contact with the wall in airtight container, the gas that the specific heat capacities such as mixing carbon dioxide gas body are larger also seals, and this frozen thing is put into the refrigerating chamber being in described humidity province and cools.In addition, the thermal capacity due to the environmental gas in airtight container is temperature difference between frozen thing and environmental gas and the molar specific heat of environmental gas and the product of molal quantity, if so gas is identical, the larger then thermal capacity of temperature difference is larger.But if temperature difference is excessive, then the cooling velocity at initial stage rises, and degree of supercooling declines.So, there is suitable temperature range.When freezing storehouse temperature is more than-10 DEG C, then temperature difference is less, and thermal capacity is not enough and cause dehydration more.In addition, when freezing storehouse temperature is below-30 DEG C, initial stage cooling velocity is too fast, and degree of supercooling declines, and dehydration increases.So the suitable temperature district of storehouse temperature is approximately in the scope of-15 DEG C ~-25 DEG C.
Therefore, under the cryogenic conditions of-15 DEG C ~-25 DEG C, dissolve by itself supercooling under the state of free convection, and frozen thing would not ftracture, and can shorten the release time of latent heat of solidification.So storehouse temperature is preferably set in the scope of-15 DEG C ~-25 DEG C.
(appraisal procedure)
In the prior art, by the quality of frozen thing freezed or thaw by measure freeze fluid loss when removing, the elasticity number after removing that thaws, freeze time the method for Ice crystal size or organoleptic examination assess.But, when using these assay methods or the method for inspection, assessed value can be differed greatly because the position of frozen thing is different, have problems in Evaluation accuracy and repeatability.Therefore, the quality of frozen frozen thing does not exist too big-difference time, be then difficult to difference and freeze quality, hamper the exploitation of new freezing method.
Therefore, first present inventor uses koya-tofu (freeze-driedkoyabeancurd) as the sample of the low-water-content materials such as zooblast, develops and assesses by the fluid loss measured when thawing a kind of method freezing quality.
As the sample of the frozen thing of low-water-content, use the powder of koya-tofu is mixed into shaping in the aqueous agar solution of percentage by weight 1.5% after test portion.Koya-tofu is also referred to as frozen bean curd, is bean curd to be freezed dried a kind of fresh-keeping foodstuff.The moisture content of this test portion is about 80%, is that the moisture content of the meat such as fish and shellfish and beast meat of 65% ~ 85% is comparatively close with moisture content.
Specifically, koya-tofu is milled to Powdered with grater.Then, the koya-tofu powder being 7% by the percentage by weight of the water weight of the aqueous agar solution relative to the percentage by weight 1.5% after boiling is mixed in this aqueous agar solution, stirs and puts into container after 5 minutes, and use frozen water cooled containers, content is solidified.Then, after the water droplet of condensation in removing container, use the cylindrical mold of internal diameter 12mm to carry out stripping forming, the cylindrical shape test portion of obtained diameter 12mm, height 10mm.And the test portion after this is shaping is put in the polybag of band slide fastener, refrigerates one day under the environment of temperature 4 DEG C.
Then, use this test portion, obtain percentage of water loss in the following manner.
First, measure the test portion weight Wep before freezing, then test portion is not loaded in container or sack, implement under various conditions to freeze.Then, be in the state freezed at test portion under, put into the centrifuge tube (centrifugetube) being provided with filter and dispensing container, utilize horizontal (swingrotor) centrifuge under the gravity of 220G centrifugal 40 minutes, make it naturally thaw.Then, from centrifuge tube, take out test portion, and measure its weight Wer, then according to freezing the test portion weight difference of front and back, being obtained by formula (1) and freezing percentage of water loss Rer.
Rer=100×(Wep－Wer)／Wep···(1)
On the other hand, after measuring the test portion weight Wep before freezing, horizontal type centrifuger is utilized to implement centrifugal 40 minutes the test portion do not freezed under 220G gravity.Then, measure centrifugal after test portion weight Wc.Further, according to test portion before centrifugation after weight difference, obtain centrifugal percentage of water loss Rc by formula (2).
Rc=100×(Wc－Wep)／Wep···(2)
Finally, according to formula (3), and utilize the difference freezed between percentage of water loss Rer and centrifugal percentage of water loss Rc to obtain percentage of water loss Re, compare the difference of the percentage of water loss Re caused by different freezing condition.
Re=Rer－Rc···(3)
But, dispersed owing to existing when manufacturing test portion, therefore use the comparison carrying out percentage of water loss Re with batch test portion manufactured.
Carry out stored refrigerated by sealing bag to test portion due in after shaping day, the water droplet on test portion surface is attached on sack, has a certain amount of moisture to evaporate in bag simultaneously.So, can by control errors in more among a small circle.And owing to thawing when implementing centrifugal, the dehydration of middle generation of thawing can be separated, and can not be absorbed by agar or koya-tofu again.In addition, owing to using horizontal type centrifuger, can squeeze test portion in vertical direction, thus by control errors in more among a small circle.
(assessment result)
Test portion is hung in airtight container in the mode do not come in contact with wall, by volume be the large volume of test portion volume 500 times airtight container in environmental gas be set to following gas respectively, and after airtight container being put into the freezer of-16 DEG C, under the state of free convection, test portion is freezed.Described each gas as environmental gas refers to: the air (Air+CO being mixed with carbon dioxide with 20% volume ratio
2); Be saturated the air (Air+H of steam
2o); Put into drier and carry out dry air (Air); The air (Air+Ar) of argon gas has been mixed into 20% volume ratio.In addition, by shown in Figure 1 for each percentage of water loss Re.
Fig. 2 shows the relation between the constant voltage molar specific heat (constant voltage mol ratio thermal capacitance) of above-mentioned environmental gas and percentage of water loss.As can be known from Fig. 2, Air+CO
2, Air+H
2the percentage of water loss Re of O, Air, Air+Ar increases successively, and namely constant voltage mol ratio thermal capacitance is larger, and percentage of water loss Re is larger.This phenomenon can be thought because following reason causes: namely, the thermal capacity of environmental gas is larger, and the freezing speed of frozen thing is faster, and the growth of ice crystal is inhibited, and Ice crystal size increases and alleviated the damage that frozen thing causes.
In addition, Fig. 3 represents the chart with the percentage of water loss when putting into four test portions when to put into two test portions in isometric airtight container.As can be seen from Figure 3, it is fewer that number put into by test portion, and fluid loss is fewer.This illustrates that the thermal capacity of the environmental gas of each frozen thing is larger, and fluid loss is fewer.
In addition, the reason that the difference of the percentage of water loss of each environmental gas of Fig. 1 and Fig. 2 is less is because the gas and vapor permeation ratio in airtight container is lower.But dispersiveness is lower in the mensuration of percentage of water loss, thus imply above-mentioned tendency fully.
So can learn: in the airtight container of large volume through cooling procedure is freezed a small amount of frozen thing, as long as the gas larger than the thermal capacity of air is used as environmental gas, compared with air being used as the situation of environmental gas, the fluid loss that frozen thing produces when thawing can be reduced, thus can realize good freezing quality.
Then, hang test portion in the mode do not come in contact with the wall of airtight container, respectively using air as the environmental gas in container, airtight container is put into the freezer of-20 DEG C, under the state of free convection, test portion is freezed.At this moment, the air of airtight container and inside thereof is set to the general normal temperature air under the precooled air and normal temperature being reduced to-20 DEG C in advance respectively.By shown in Figure 4 for both percentage of water loss Re.
As can be known from Fig. 4, be chilled to the air of-20 DEG C in advance compared with the situation begun to cool down from room temperature (+20 DEG C), percentage of water loss Re is larger.So known, when a small amount of frozen thing being freezed in the airtight container of large volume, environmental gas is set as the situation of room temperature is ideal.This result shows that then fluid loss is less if the difference between test portion temperature and environment temperature is less.Room temperature is preferably set to more than+10 DEG C.
Fig. 5 represents that the chart of percentage of water loss when freezing is carried out in the bottom surface of hanging percentage of water loss test portion freezes in the mode of the wall leaving airtight container and allowing test portion touch airtight container in airtight container.As can be known from Fig. 5, the fluid loss when wall leaving airtight container cools test portion is less.This result shows: when surrounding by environmental gas around test portion, fluid loss is lower, and gas and solid-phase are than having very high thermal insulation, and initial stage cooling velocity slowly situation more can obtain good refrigerating effect.
From Fig. 4 and Fig. 5, the cooling velocity at preferred initial stage slowly and after supercooling process is removed, adopt cooling fast.
(freezing utensil)
As shown in Figure 6, the utensil 1 that freezes in the present invention has following formation: arrange in airtight container 2 and hang rod 4, and hanging suspension body 3, this suspension body 3 inside accommodates frozen thing.Here, suspension body 3 adopts resinous mesh bag or the string bag.Airtight container 2 is placed into the interior cooling of freezer (not shown) of-10 DEG C ~-20 DEG C.
In addition, the inner space of airtight container 2 is divided into upper and lower two parts by barrier film 5, and these two spaces are isolated from each other.Suspension body 3 is configured in upper space.
Upper space is connected with top air inlet pipe 6, and lower space is connected with bottom air inlet pipe 7.Further, top air inlet pipe 6 and bottom air inlet pipe 7 are connected with the gas tank 8 being filled with liquefied carbon dioxide gas respectively by adjuster 9,10.In addition, intake valve 11,12 is respectively arranged with in the midway of top air inlet pipe 6 and bottom air inlet pipe 7.
In addition, upper space is connected with top blast pipe 13, and lower space is connected with lower exhaust pipe 14.The midway of top blast pipe 13 and lower exhaust pipe 14 is respectively arranged with air bleeding valve 15,16.
The freezing method using and freeze utensil 1 is below described.
First, inside is enclosed the suspension body 3 of the frozen thing of such as cell or microorganism by lid (not shown) hanging hanging on rod 4 in airtight container 2.Then, close described lid airtight container 2 is sealed.In this stage, all valves 11,12,15,16 cut out.
Then, open top air bleeding valve 15, discharged the air in upper space by top blast pipe 13, open bottom intake valve 12 simultaneously, by supplying carbon dioxide in bottom air inlet pipe 7 lower portion space.At upper space through being fully vented and after being full of carbon dioxide in lower space, closing top air bleeding valve 15 and bottom intake valve 12.
Then, open lower exhaust valve 16, discharged the carbon dioxide in upper space by lower exhaust pipe 14, open top air inlet valve 11 simultaneously, in upper space, supply carbon dioxide by top air inlet pipe 6.Be filled with carbon dioxide in lower space through fully exhaust, upper space and after barrier film 5 and container lower surface close contact, close lower exhaust valve 16 and top air inlet valve 11.Then, in this condition, freezer inside sealing container 2 being placed into-10 DEG C ~-20 DEG C cools.
Thisly freezing utensil 1 by using, can the concentration of the carbon dioxide of inner space be controlled very high.Therefore, it is possible to increase the thermal capacity of the environmental gas in airtight container 2, can freeze with high thermoconductivity, and the fluid loss produced when thawing can be reduced.In addition, the air at room temperature being saturated steam also can be used to replace carbon dioxide.
In addition, as shown in Figure 7, airtight bag 21 also can be used to freeze utensil as of the present invention.Airtight bag 21 is provided with airtight slide fastener 22.By closed airtight slide fastener 22, make to keep airtight conditions in airtight bag 21.
In addition, the suspension body 23 loading frozen thing is provided with in airtight bag 21 inside.Suspension body 23 adopts resinous mesh bag or the string bag.In addition, band valve port 24 is set in airtight bag 21, for discharging inner gas and making inside be full of carbon dioxide.
Use such airtight bag 21, because the air capacity of originally internal residual is less, by making its inside be full of carbon dioxide, the concentration of carbon dioxide can be improved and kept.So, the thermal capacity of the environmental gas in airtight bag 21 can be increased, allow frozen thing freeze through cooling, thus the fluid loss of frozen thing when thawing can be reduced.
Claims (4)
1. a freezing method, it is characterized in that, under the state configuring frozen thing in the mode leaving airtight container wall, be full of form molecule be in the airtight container of former molecular polyatomic molecule gas or following gas by more than three, to the free convection of less than-15 DEG C, described frozen thing is cooled more than-25 DEG C, and freeze described frozen thing after supercooling, described gas contains described polyatomic molecule gas to make the ratio of heat capacities of the gas in described airtight container large with the thermal capacity of the dry air of molecular number.
2. freezing method according to claim 1, is characterized in that, cools from room temperature to the gas around described frozen thing and described frozen thing.
3. freezing method according to claim 1, is characterized in that, after carrying out supercooling, is freezed described frozen thing by forced convertion by free convection to described frozen thing.
4. freezing method according to claim 2, is characterized in that, after carrying out supercooling, is freezed described frozen thing by forced convertion by free convection to described frozen thing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-205724 | 2010-09-14 | ||
| JP2010205724 | 2010-09-14 | ||
| PCT/JP2011/070889 WO2012036167A1 (en) | 2010-09-14 | 2011-09-13 | Freezing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103097838A CN103097838A (en) | 2013-05-08 |
| CN103097838B true CN103097838B (en) | 2016-01-20 |
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| CN201180043849.1A Expired - Fee Related CN103097838B (en) | 2010-09-14 | 2011-09-13 | Freezing method |
| CN2011800438504A Pending CN103189692A (en) | 2010-09-14 | 2011-09-13 | Freezing method and freezing device |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2011800438504A Pending CN103189692A (en) | 2010-09-14 | 2011-09-13 | Freezing method and freezing device |
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| JP (2) | JPWO2012036166A1 (en) |
| CN (2) | CN103097838B (en) |
| WO (2) | WO2012036166A1 (en) |
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| US9310140B2 (en) | 2012-02-07 | 2016-04-12 | Rebound Technologies, Inc. | Methods, systems, and devices for thermal enhancement |
| JP2014066451A (en) * | 2012-09-26 | 2014-04-17 | Honda Munetaka | Ocean deep water sherbet ice |
| US10995993B2 (en) | 2014-09-27 | 2021-05-04 | Rebound Technologies, Inc. | Thermal recuperation methods, systems, and devices |
| BR112018010037A2 (en) * | 2015-11-19 | 2018-11-21 | Blanctec Co., Ltd. | ice, soda, method of producing ice, a chilled article and fresh frozen plants / animals or portions thereof, chilling material, defrosted article, and, freezing material |
| JP2019516053A (en) * | 2016-03-21 | 2019-06-13 | リバウンド テクノロジーズ, インク.Rebound Technologies, Inc. | Method, system and apparatus for heat recovery |
| US10584904B2 (en) | 2017-03-27 | 2020-03-10 | Rebound Technologies, Inc. | Cycle enhancement methods, systems, and devices |
| WO2019165328A1 (en) | 2018-02-23 | 2019-08-29 | Rebound Technologies, Inc. | Freeze point suppression cycle control systems, methods, and devices |
| WO2020132467A1 (en) | 2018-12-20 | 2020-06-25 | Rebound Technologies, Inc. | Thermo-chemical recuperation systems, devices, and methods |
| CN114088487A (en) * | 2021-11-12 | 2022-02-25 | 中国地质调查局油气资源调查中心 | Preparation method and modulus analysis method of sediment sample containing block hydrate |
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- 2011-09-13 WO PCT/JP2011/070888 patent/WO2012036166A1/en active Application Filing
- 2011-09-13 JP JP2012534015A patent/JPWO2012036166A1/en active Pending
- 2011-09-13 CN CN201180043849.1A patent/CN103097838B/en not_active Expired - Fee Related
- 2011-09-13 CN CN2011800438504A patent/CN103189692A/en active Pending
- 2011-09-13 JP JP2012534016A patent/JP5867893B2/en not_active Expired - Fee Related
- 2011-09-13 WO PCT/JP2011/070889 patent/WO2012036167A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2012036167A1 (en) | 2012-03-22 |
| CN103097838A (en) | 2013-05-08 |
| JP5867893B2 (en) | 2016-02-24 |
| JPWO2012036166A1 (en) | 2014-02-03 |
| WO2012036166A1 (en) | 2012-03-22 |
| JPWO2012036167A1 (en) | 2014-02-03 |
| CN103189692A (en) | 2013-07-03 |
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