CA1106686A - Process and apparatus for the production of frozen granulates - Google Patents
Process and apparatus for the production of frozen granulatesInfo
- Publication number
- CA1106686A CA1106686A CA293,821A CA293821A CA1106686A CA 1106686 A CA1106686 A CA 1106686A CA 293821 A CA293821 A CA 293821A CA 1106686 A CA1106686 A CA 1106686A
- Authority
- CA
- Canada
- Prior art keywords
- liquid
- cooling agent
- product liquid
- granulate
- product
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B5/00—Drying solid materials or objects by processes not involving the application of heat
- F26B5/04—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum
- F26B5/06—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum the process involving freezing
- F26B5/065—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum the process involving freezing the product to be freeze-dried being sprayed, dispersed or pulverised
-
- 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
- A23B4/03—Drying; Subsequent reconstitution
- A23B4/037—Freeze-drying, i.e. cryodessication, lyophilisation; Apparatus therefor
-
- 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
- A23B4/062—Freezing; Subsequent thawing; Cooling the materials being transported through or in the apparatus with or without shaping, e.g. in the form of powder, granules or flakes
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/36—Freezing; Subsequent thawing; Cooling
- A23L3/37—Freezing; Subsequent thawing; Cooling with addition of or treatment with chemicals
- A23L3/375—Freezing; Subsequent thawing; Cooling with addition of or treatment with chemicals with direct contact between the food and the chemical, e.g. liquid nitrogen, at cryogenic temperature
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/40—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by drying or kilning; Subsequent reconstitution
- A23L3/44—Freeze-drying
-
- 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
- F25C—PRODUCING, WORKING OR HANDLING ICE
- F25C1/00—Producing ice
-
- 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
- F25D3/00—Devices using other cold materials; Devices using cold-storage bodies
- F25D3/10—Devices using other cold materials; Devices using cold-storage bodies using liquefied gases, e.g. liquid air
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Food Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- Nutrition Science (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Molecular Biology (AREA)
- Drying Of Solid Materials (AREA)
- Freezing, Cooling And Drying Of Foods (AREA)
- Medical Preparation Storing Or Oral Administration Devices (AREA)
- Confectionery (AREA)
- Non-Alcoholic Beverages (AREA)
- Glanulating (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A uniform, spheroidal frozen granulate is provided by contacting a stream of a product liquid to be frozen with a stream of readily evaporatable liquid, for example, liquid nitrogen; the invention is especially suitable for use in the food and pharmaceutical industries.
A uniform, spheroidal frozen granulate is provided by contacting a stream of a product liquid to be frozen with a stream of readily evaporatable liquid, for example, liquid nitrogen; the invention is especially suitable for use in the food and pharmaceutical industries.
Description
The present invention is concerned with a process and apparatus for the production of ~rozen granulates It is known to preserve foodstuffs, for example, fish, meat and vegetables, by freezing. Drinks, for example, fruit juices, coffee, tea and soups, can be converted, by freezing and drying in a frozen state, into readily soluble granulates, i.e. into so called instant powders. Pharmaceutical pre-parations, too, which are administered in the form of a solution but which are not stable in the solvent to be used, have, for many years, been stored in the form of lyophilisates In order to avoid the destruction of the structure of the solid foodstuffs or the demixing of the solutions, it i~ necessary to freeze these products as suddenly as possible.
In the past, a large number of techniques have been developed, particularly for freezing solutions.
Thus, it is known to freeze out the solvents in cooled containers in block form and to comminute the blocks by cold grinding. According to another process, the liquid ~ is sprayed on to a cooled, rotating cylinder or on to a 20 cooled conveyor belt from which, after solidification, it is again removed by means of appropxiate scrapers or scratchers.
In the case of one variant of these apparatus, heat is removed not by cooling the ~ubstrate but by spraying on readily evapo-rating cooling agents, for example, carbon dioxide, nitrous o~ide and, especially, liquid nitrogen~ A disadvantage common to all of the3e processes is that, due to the comminution or removal of ~he frozen product, particles are obtained of greatly varying size and shape, together with a considerable amount of fine~, which makes difficult the further working up by the freeze drying ~see Schormuller, Handbuch der Lebensmittelchemie, pp. 262-266, pubo Springer-Verlag, 1974). Furthermore, frozen granulates which are readily flowable, i.e~ are substantially spheroidal, are also desired for the production of porous tablets according to the process described in German Offenlegungsschriften No. 2,246,013 Heinemann et al, filed 20~9,72, published 28.3.74 and ~o. 2,S56,561, Knitsch et al filed 16.12.75, published 30.6.77 It is known from German Offenlegungsschrift No.
In the past, a large number of techniques have been developed, particularly for freezing solutions.
Thus, it is known to freeze out the solvents in cooled containers in block form and to comminute the blocks by cold grinding. According to another process, the liquid ~ is sprayed on to a cooled, rotating cylinder or on to a 20 cooled conveyor belt from which, after solidification, it is again removed by means of appropxiate scrapers or scratchers.
In the case of one variant of these apparatus, heat is removed not by cooling the ~ubstrate but by spraying on readily evapo-rating cooling agents, for example, carbon dioxide, nitrous o~ide and, especially, liquid nitrogen~ A disadvantage common to all of the3e processes is that, due to the comminution or removal of ~he frozen product, particles are obtained of greatly varying size and shape, together with a considerable amount of fine~, which makes difficult the further working up by the freeze drying ~see Schormuller, Handbuch der Lebensmittelchemie, pp. 262-266, pubo Springer-Verlag, 1974). Furthermore, frozen granulates which are readily flowable, i.e~ are substantially spheroidal, are also desired for the production of porous tablets according to the process described in German Offenlegungsschriften No. 2,246,013 Heinemann et al, filed 20~9,72, published 28.3.74 and ~o. 2,S56,561, Knitsch et al filed 16.12.75, published 30.6.77 It is known from German Offenlegungsschrift No.
2,140,747 Briggs et al, filed 13.8.71, published 17.2.72, that granulates of substantially uniform shape and size can be obtained when the solution to be frozen is sprayed through appropriate nozzles into a moving bath of a boiling fluorinated hydrocarbon, such as Freon (trademark), as cooling agent. The resultant granulate is normally removed discontinuously since a continuous removal requires the use of expensive apparatus.
Products frozen on to parts of the apparatus, especially on to the stirrer, make it difficult to change quickly from one product to another, this only being possible after complete emptying, warming and thorough cleaning of the plant Therefore, the problem exists of providing a con-tinuous proces~ for the production of uniform, frozen granulates for freeze drying which, with the lowest possible expense for apparatus, permits a rapid change from one product to another.
The present invention overcom~3s this problem in that, in suEficiently cooled surroundings, a stream of a readily evaporatable liquid cooling agent is brought into contact with a stream of liquid product, for exa~ple, a solution, the liquid cooling agent evaporates and the heat energy for the evaporation i~ taken from the product liquid which is thereby suddenly frozen. The frozen granulate being found to be in the form of small, spheroida~ particles, These sph~roids can then easily b~ separated from the gaseous cooling agent, freeze dried in a conventional manner and further worked up.
, The freeze-dried granulates produced in this manner are, surprisingl~, very uniform, dissolve readily and can be readily worked up due to their spheroidal shape, whereas, non-uniformly-formed granules or snowflake-like products of greatly varying size distribution were to have been expected.
According to the invention there is provided a process for the production of a frozen granulate from a product liquid comprising, contacting the product liquid with a moving stream of readily evaporatable liquid cooling agent, allo~ing the liquid cooling agent to evaporate and frozen granulate to form from said product liquid, and recovering said frozen granulate; said cooling agent being inert to said product liquid.
Especially good results are achieved when the product liquid and the cooling agent streams run in the direction of gravitational force since an especially long-lasting heat exchange is thex~by achieved. On the other hand, by an oblique guiding of the streams from below upwardly the result is achieved that the granules formed, on the basis of their size, drop down from the stream of cooling agent at diffexent speeds and thus a classification or grading is achieved insofar as there are again formed granules of greatly differing size.
As cooling agent, there can be used all liquid materials which evaporate at atmospheric pressure ~elow the freezing point of the product liquid and which do not react with the productn By way of example, there can be mentioned nitrous oxide, alkylene oxides, ammonia, carbon dioxide, low boiling point hydrocarbons, for example, butane and propane, and fluorinated hydrocarbons, for example, Freon (trademark).
Liquid nitrogen ~as proved to be especially advantageous since it is inexpansive to obtain, does not react with any of the product liquids, does not cause contamination of the environment 2~i due to escaping gases and, because of its low bsiling point, - cools the product very quickly to a low temperature. In the case of prcducts which are not sensitive to oxygen, liquid air can also be used in the same manner.
In a further aspect of the invention there is pro-vided a frozen granulate pr ~luced by the process of the invention and characterized by a spheroidal shape and sub-stantially uniform dimensions.
The present i~vention also provides an apparatus for the continuous productivn of granulates, comprising a cooling column, supply means for streams of cooling agent and streams of product liquid in an upper part of the column, a removal opening for the granulate at the lower end of the cooling column and removal means for the gaseous cooling agent.
' The supply means for the streams suitably comprise injection nozzles disposed so as to introduce said streams into the centre of the upper part of the column.
It will be understood that the column is appropriately dimensioned to permit granulate formation. In particular the height of the column, or more particularly of the contact zone for product liquid and cooling agent, should be sufficient to permit evaporation of the liquid cooling agent in contact ~ith the product liquid to form a frozen granulate of said product liquid.
The invention can be employed with any product liquid which can be frozen, the invention is especially suitable for producing a frozen granulate from a solution. In particular the invention is suitable for forming a frozen granulate from agueous product liguids~ It will be understood, however, that other liquid media might be employed although water will be the most common medium. Of course, the liquid m~dium should be one which will provide a product liquid having a freezing point such that it can be readily frozen by the cooling effect of the evaporation of the liquid cooling agent. The suitability of potential liquld media in conjunction with particular liquid cooling agents can be readily determined by simple experiment and/or a determination of the freezing point of a particular product liquid employing a particular liquid medium~
The invention is illustrated in a particularly preferred embodlment by reference to the accompanying drawings in which:
FIGURE 1 shows a,~ apparatus according to the invention, and FIGURE 2 shows a detail of the injection noæzles in the apparatus of Figure 1.
With further reference to Figure 1 an apparatus A for the continuous production of granulates comprises a cooling column 1, a storage container 12 of cooling agent, a storage container 13 of product solution, a freeze drying plant 18 and a confectioning or storage station 19.
The column 1 is vertically up-standing, having an upper cylindrical portion and a lower conically-shaped portion which narrows in the downward direction; the upper part of the colurnn 1 has a centrally positioned inlet nozzle 2 for a cooling agent, as well as one or more nozzles 3 for a product liquid an outlet 4 is located in a lower end of the column 1 for the remov~l of frozen granulate and for the e.scape of evapo-rating cooling agent.
The column 1 is suitably provided with an insulating outer mantel 5 and an inner lining 6, between which the evaporating cooling agent can flow off, as cooling and insulating material, via a va~ve 7.
For the upply of cooling agent and of product solution, , there are provided regulatable valves 8 and 9 in pipe lines 11 ;3$
and 15 respectively.
The amount of gaseous cooling agent flowing off via valve 7, which serves for the cooling o~ the outer mantel 5, can ~e regulated by an additional overpressure valve 10 in pipe line 14. The inlet nozzle 2 communicates via pipe line 11 with the storage container 12, the pressure in container 12 ~ringing about the conveyencing o~ the cooling agent. The nozzle(s) 3 communicate via pipe line 15 with the storage container 13, which is preferably also constructed with double walls and can be cooled by cooling agent removed vla valves 7 and 10 through the pipe line 14. A pump 16 is disposed in pipe line 15 and forces product solution into the product nozzle 3 vla valve 9. The product nozzle 3 is preferably heatable in order to prevent freezing up~
The frozen granulate falls out through the outlet 4 due to the gravitational force and can be collected in a collection container and passed discontinuously to a freeze drying plant.
Preferably, however, the granulate falling out is passed continuously on a conveyor belt 17 through the continuous freeze drying plant 18 and thereafter passes into the confection-ing or ~torage station 19.
For protection against ambient temperature and moisture, the conveyor belt 17 is, up to the point of entry into the freeze drying plant 18, also surrounded by a mantel 20, the inner space of which can also be cooled by the evaporating cooling agent. If liquid nitrogen or liquid air i5 not u~ed a~ the cooling agent, then it is also necessary to provide a device for the collection or reliquifaction of the evaporated cooling agent.
With furthex reference to Figure 2 there i~ shown 6 product nozzles 3 communicating with supply pipe 15 and the cool-ing agent nozzle 2 o~ the apparatus A of Figure 1.
It has proved to be advantageous to supply the pro-duct liquid to the nozzles 3 with a temperature just a little above the freezing point of the product liquid since, in this way, the cooling agent is best utilised. By variation of the size of the nozzles 2 and 3 and of the pressure with which the cooling agent and the product liquid is fed in, the size of the granules can be varied within wide limits. For economic reasons, the amount of liquid cooling agent ~ed in is adjusted in such a manner that it just su~fices to freeze the product liquid and to cover the heat losses to the surroundings.
Depending upon the concentration of the product liquid, in the case of the preferred use of liquid nitrogen, the con-sumption of cooling agent is 2 - 3 kg. per kg. of product liquid.
In operation product solution is pumped from - container 13 by pump 16, via pipe line 15 and valve 9 and is injected through nozzles 3 into a stream of cooling agent injected into column 1 through inlet nozzle 2, The cooling agent evaporates thereby cooling the product solution and freezing it to form small, spheroidal particles which fall through outlet 4 onto conveyor belt 17. The spheroidal particles are conveyed through freeze drying plant 18, where ~; they are freeze dried, on conveyor belt 17 and are collected ; in the confectioning or storage station 19.
Of course, numerous variations of the above-described apparatus are conceivable with which the process according to the present invention can also be carried out. Thus, for example, the column 1 can, of course, also be cylindrical 30 or double-conical, instead of a simple cooling agent and product feed in, several such nozzles can also be provided and the products can, instead of being continuously passed to a reeze drying plant, also be collected in a storage tank and then used at some later time.
~ or the construction of the apparatus, it is possible to use practically all materials which still have, at the temperature of the liquid cooling agent, a sufficient stability and strength, stainless steel, copper, polyethylene and the like being mentioned by way of example.
By a simultaneous spraying in, vla two different nozzles, it is possible to spray components which are incompatible with one another and thus to obtain a statistically mixed granulate. By means of a different nozzle size or of a different spray pressure, if desired there can also be obtained a differing particle size for a particular granulate.
The following Example is given for the purpose of illustrating the present invention:-1. Formation of the frozen granulate.
Use was made of a cocliny column 1 according to ~ Figure 1 of the accompanying drawings which had a height of200 cm., a diameter of 80 cm. and an ou~let 4 with a width of 20 cm. The upper cylindrical part of the column had a length of 60 cm. and the conically-shaped part had an angle of 30 from the vertical. Pipes, valves and storage vessels were according ~o Figure 1 but instead of the illustrated continuously operating freeze drying plant, th re was employed a c~oled storage vessel below the outlet 4.
1 kg. Saccharose was dissolved in 10 litres distilled water to give a l~/o solution which was placed in a thermo-statically contr~olled storage vessel 13 and kept there at atemperature of about ~1C., the freezing point of this solution being about -0.5C
, . - , . , ~ : , . . . . .
æ~
From a second storage container 12, liquid nitrogen (LN2) was supplied via an insulated copper pipe 11 and a regulating valve 8 to the LN2 nozzle, this nozzle having an inner diameter of 8 mm. The column 1 was pre-cooled until, at the outlet 4, a temperature of about -50C. was achieved in the outflowing stream of nitrogen.
Then, by means of pump 16, at a spraying in pres-sure of 1.5 bar., the saccharose solution was sprayed, via a polyethylene pipe 15, a regulating valve 9 and six product nozzles 3, into the stream of liquid nitrogen. The six nozzles 3, which were arranged in the form of a circle at a conical angle of 60 around the LN2 stream, each had an inner diameter of about 0.15 mm. The distance between the exit point of the LN2 from the LN2 nozzle 2 and the point of mixing with the solution was 125 mm. and the distance from the product nozzle 3 to the mixing point was 30 mm. Upon contact with the LN stream, the saccharose solution froze suddenly to give small spheroids, whereas the greater part of the L~2 evaporated~ This gaseous, cold nitrogen was further used for cooling the column 1 and the storage container 13~ - -The frozen spheroids fell down~ardly in the reaction chamber 1 and were removed through the outlet 4 and collected in a deep-cooled Dewar vessel. The diameter size of these pheroids was between 0.16 and 1.0 mm,, the Gaussian dis-;~ tribution having it~ maximum at 0.63 mm. with 85% by weight of the particles. Over 9~! of the granulate had a spheroidal 3hape. The granulate flowed readily and did not stick together.
In a cooled container, the granulate can be stored practically without time limit, The consumption of LN2 was 2,5 kg~/kg. of solution (including pxe-cooling of the reaction chamber and losses).
2. Freeze dryinq of the frozen granulate.
The f~ozen spheroids collected in the De~ar vessel were shaken on to a pre-cooled metal sheet (-50C.) of a lyophilisation plant and discontinuously freeze-dried under the following conditions:
a) 13 hours at 0.2 mbar and 25C.
b) 5 hours at 1.333 10 3 mbar and 25C.
After lyophilisation, the particle size distribution and the spheroidal form of the granulate had not changed from that of the frozen state. Its density was calculated to be about 116 kgO/m3. The residual water content was 1.6~
by weight. The product had a homogeneous, white colour Upon shaking up and sieving, the granulate retained its shape.
It could easily be rubbed between the fingers. The electro-static charginy was low. The spheroids scarcely stuck together and did not stick at all to the walls of bottles in which it was ~tored. The flowability was very good, the flow behaviour of the granulate resembling that of a liqu-d. In order again to produce the initlal concentration of the 1~/9 saccharose solution, 100 g. of granulate were added to 1 litre of distilled water. Without mechanical movement of the liquid, the dis301ving time was 32 seconds.
It will be understood~that the dimensions of the drop-lets of product liquid in the stream of product liquid, and ~-hence the dimension of the granulate will depend on a number of factors. In particular the dimensions will depend on the diameter of the orifices of the nozzles 3, the pressure under which the product liquid is delivered into column 1, and the vi3cosity of the product liquid. It will be apparent that these three parameters can be varied within wide boundarie~ and that appropriate parameters for any desired granulate can be ' readily determined by experiment. Similarly the diam~ter of the orifice of inlet nozzle 2 is subject to wide variation.
In a general manner, however, and having regard to economic realities it is convenient to employ nozzles 3 having orifices with a diameter of 0.005 to 2 mm, with the product liquid being delivered under a pressure of 1.1 - 10 bar. The orifice(s) of the inlet nozzle 2 for liquid cooling agent may conveniently have a diameter of 1 - 20 mm. There is, o~ course, no limit to the number of nozzles 3 which might be employed, nevertheless it i9 found convenient to employ from 3 to 8 nozzles bearing in mind the limitations of plant size and spatial disposition.
I~ will be understood that the inlet nozzle 2 and the nozzle or nozzles 3 may be single orifice or multi-orifice nozzle~ for injection of liquid into column 1.
Generally speaking the pressure of delivery of the product liquid through product nozzle 3 is sufficient t~ pre-vent product liquid from freeziny and solidifying on the orifice~. Furthermore, as described previously, product nozzle 3 may suitably include means for heating it to prevent build-up of frozen product liquid in the nozzle line.
The invention h s been described in general by reference to an embodiment in which the product liquid is a solution. As indicated previously the inventlon can be employed with liquids other than solutions, for example, dispersions, suspensions and emulsions.
- ~ The invention finds special application in the manu-facture of particular diagnostic materials, however, it has wide application and can be employed in the particular industries described in the ~ ove description of the prior artJ
Products frozen on to parts of the apparatus, especially on to the stirrer, make it difficult to change quickly from one product to another, this only being possible after complete emptying, warming and thorough cleaning of the plant Therefore, the problem exists of providing a con-tinuous proces~ for the production of uniform, frozen granulates for freeze drying which, with the lowest possible expense for apparatus, permits a rapid change from one product to another.
The present invention overcom~3s this problem in that, in suEficiently cooled surroundings, a stream of a readily evaporatable liquid cooling agent is brought into contact with a stream of liquid product, for exa~ple, a solution, the liquid cooling agent evaporates and the heat energy for the evaporation i~ taken from the product liquid which is thereby suddenly frozen. The frozen granulate being found to be in the form of small, spheroida~ particles, These sph~roids can then easily b~ separated from the gaseous cooling agent, freeze dried in a conventional manner and further worked up.
, The freeze-dried granulates produced in this manner are, surprisingl~, very uniform, dissolve readily and can be readily worked up due to their spheroidal shape, whereas, non-uniformly-formed granules or snowflake-like products of greatly varying size distribution were to have been expected.
According to the invention there is provided a process for the production of a frozen granulate from a product liquid comprising, contacting the product liquid with a moving stream of readily evaporatable liquid cooling agent, allo~ing the liquid cooling agent to evaporate and frozen granulate to form from said product liquid, and recovering said frozen granulate; said cooling agent being inert to said product liquid.
Especially good results are achieved when the product liquid and the cooling agent streams run in the direction of gravitational force since an especially long-lasting heat exchange is thex~by achieved. On the other hand, by an oblique guiding of the streams from below upwardly the result is achieved that the granules formed, on the basis of their size, drop down from the stream of cooling agent at diffexent speeds and thus a classification or grading is achieved insofar as there are again formed granules of greatly differing size.
As cooling agent, there can be used all liquid materials which evaporate at atmospheric pressure ~elow the freezing point of the product liquid and which do not react with the productn By way of example, there can be mentioned nitrous oxide, alkylene oxides, ammonia, carbon dioxide, low boiling point hydrocarbons, for example, butane and propane, and fluorinated hydrocarbons, for example, Freon (trademark).
Liquid nitrogen ~as proved to be especially advantageous since it is inexpansive to obtain, does not react with any of the product liquids, does not cause contamination of the environment 2~i due to escaping gases and, because of its low bsiling point, - cools the product very quickly to a low temperature. In the case of prcducts which are not sensitive to oxygen, liquid air can also be used in the same manner.
In a further aspect of the invention there is pro-vided a frozen granulate pr ~luced by the process of the invention and characterized by a spheroidal shape and sub-stantially uniform dimensions.
The present i~vention also provides an apparatus for the continuous productivn of granulates, comprising a cooling column, supply means for streams of cooling agent and streams of product liquid in an upper part of the column, a removal opening for the granulate at the lower end of the cooling column and removal means for the gaseous cooling agent.
' The supply means for the streams suitably comprise injection nozzles disposed so as to introduce said streams into the centre of the upper part of the column.
It will be understood that the column is appropriately dimensioned to permit granulate formation. In particular the height of the column, or more particularly of the contact zone for product liquid and cooling agent, should be sufficient to permit evaporation of the liquid cooling agent in contact ~ith the product liquid to form a frozen granulate of said product liquid.
The invention can be employed with any product liquid which can be frozen, the invention is especially suitable for producing a frozen granulate from a solution. In particular the invention is suitable for forming a frozen granulate from agueous product liguids~ It will be understood, however, that other liquid media might be employed although water will be the most common medium. Of course, the liquid m~dium should be one which will provide a product liquid having a freezing point such that it can be readily frozen by the cooling effect of the evaporation of the liquid cooling agent. The suitability of potential liquld media in conjunction with particular liquid cooling agents can be readily determined by simple experiment and/or a determination of the freezing point of a particular product liquid employing a particular liquid medium~
The invention is illustrated in a particularly preferred embodlment by reference to the accompanying drawings in which:
FIGURE 1 shows a,~ apparatus according to the invention, and FIGURE 2 shows a detail of the injection noæzles in the apparatus of Figure 1.
With further reference to Figure 1 an apparatus A for the continuous production of granulates comprises a cooling column 1, a storage container 12 of cooling agent, a storage container 13 of product solution, a freeze drying plant 18 and a confectioning or storage station 19.
The column 1 is vertically up-standing, having an upper cylindrical portion and a lower conically-shaped portion which narrows in the downward direction; the upper part of the colurnn 1 has a centrally positioned inlet nozzle 2 for a cooling agent, as well as one or more nozzles 3 for a product liquid an outlet 4 is located in a lower end of the column 1 for the remov~l of frozen granulate and for the e.scape of evapo-rating cooling agent.
The column 1 is suitably provided with an insulating outer mantel 5 and an inner lining 6, between which the evaporating cooling agent can flow off, as cooling and insulating material, via a va~ve 7.
For the upply of cooling agent and of product solution, , there are provided regulatable valves 8 and 9 in pipe lines 11 ;3$
and 15 respectively.
The amount of gaseous cooling agent flowing off via valve 7, which serves for the cooling o~ the outer mantel 5, can ~e regulated by an additional overpressure valve 10 in pipe line 14. The inlet nozzle 2 communicates via pipe line 11 with the storage container 12, the pressure in container 12 ~ringing about the conveyencing o~ the cooling agent. The nozzle(s) 3 communicate via pipe line 15 with the storage container 13, which is preferably also constructed with double walls and can be cooled by cooling agent removed vla valves 7 and 10 through the pipe line 14. A pump 16 is disposed in pipe line 15 and forces product solution into the product nozzle 3 vla valve 9. The product nozzle 3 is preferably heatable in order to prevent freezing up~
The frozen granulate falls out through the outlet 4 due to the gravitational force and can be collected in a collection container and passed discontinuously to a freeze drying plant.
Preferably, however, the granulate falling out is passed continuously on a conveyor belt 17 through the continuous freeze drying plant 18 and thereafter passes into the confection-ing or ~torage station 19.
For protection against ambient temperature and moisture, the conveyor belt 17 is, up to the point of entry into the freeze drying plant 18, also surrounded by a mantel 20, the inner space of which can also be cooled by the evaporating cooling agent. If liquid nitrogen or liquid air i5 not u~ed a~ the cooling agent, then it is also necessary to provide a device for the collection or reliquifaction of the evaporated cooling agent.
With furthex reference to Figure 2 there i~ shown 6 product nozzles 3 communicating with supply pipe 15 and the cool-ing agent nozzle 2 o~ the apparatus A of Figure 1.
It has proved to be advantageous to supply the pro-duct liquid to the nozzles 3 with a temperature just a little above the freezing point of the product liquid since, in this way, the cooling agent is best utilised. By variation of the size of the nozzles 2 and 3 and of the pressure with which the cooling agent and the product liquid is fed in, the size of the granules can be varied within wide limits. For economic reasons, the amount of liquid cooling agent ~ed in is adjusted in such a manner that it just su~fices to freeze the product liquid and to cover the heat losses to the surroundings.
Depending upon the concentration of the product liquid, in the case of the preferred use of liquid nitrogen, the con-sumption of cooling agent is 2 - 3 kg. per kg. of product liquid.
In operation product solution is pumped from - container 13 by pump 16, via pipe line 15 and valve 9 and is injected through nozzles 3 into a stream of cooling agent injected into column 1 through inlet nozzle 2, The cooling agent evaporates thereby cooling the product solution and freezing it to form small, spheroidal particles which fall through outlet 4 onto conveyor belt 17. The spheroidal particles are conveyed through freeze drying plant 18, where ~; they are freeze dried, on conveyor belt 17 and are collected ; in the confectioning or storage station 19.
Of course, numerous variations of the above-described apparatus are conceivable with which the process according to the present invention can also be carried out. Thus, for example, the column 1 can, of course, also be cylindrical 30 or double-conical, instead of a simple cooling agent and product feed in, several such nozzles can also be provided and the products can, instead of being continuously passed to a reeze drying plant, also be collected in a storage tank and then used at some later time.
~ or the construction of the apparatus, it is possible to use practically all materials which still have, at the temperature of the liquid cooling agent, a sufficient stability and strength, stainless steel, copper, polyethylene and the like being mentioned by way of example.
By a simultaneous spraying in, vla two different nozzles, it is possible to spray components which are incompatible with one another and thus to obtain a statistically mixed granulate. By means of a different nozzle size or of a different spray pressure, if desired there can also be obtained a differing particle size for a particular granulate.
The following Example is given for the purpose of illustrating the present invention:-1. Formation of the frozen granulate.
Use was made of a cocliny column 1 according to ~ Figure 1 of the accompanying drawings which had a height of200 cm., a diameter of 80 cm. and an ou~let 4 with a width of 20 cm. The upper cylindrical part of the column had a length of 60 cm. and the conically-shaped part had an angle of 30 from the vertical. Pipes, valves and storage vessels were according ~o Figure 1 but instead of the illustrated continuously operating freeze drying plant, th re was employed a c~oled storage vessel below the outlet 4.
1 kg. Saccharose was dissolved in 10 litres distilled water to give a l~/o solution which was placed in a thermo-statically contr~olled storage vessel 13 and kept there at atemperature of about ~1C., the freezing point of this solution being about -0.5C
, . - , . , ~ : , . . . . .
æ~
From a second storage container 12, liquid nitrogen (LN2) was supplied via an insulated copper pipe 11 and a regulating valve 8 to the LN2 nozzle, this nozzle having an inner diameter of 8 mm. The column 1 was pre-cooled until, at the outlet 4, a temperature of about -50C. was achieved in the outflowing stream of nitrogen.
Then, by means of pump 16, at a spraying in pres-sure of 1.5 bar., the saccharose solution was sprayed, via a polyethylene pipe 15, a regulating valve 9 and six product nozzles 3, into the stream of liquid nitrogen. The six nozzles 3, which were arranged in the form of a circle at a conical angle of 60 around the LN2 stream, each had an inner diameter of about 0.15 mm. The distance between the exit point of the LN2 from the LN2 nozzle 2 and the point of mixing with the solution was 125 mm. and the distance from the product nozzle 3 to the mixing point was 30 mm. Upon contact with the LN stream, the saccharose solution froze suddenly to give small spheroids, whereas the greater part of the L~2 evaporated~ This gaseous, cold nitrogen was further used for cooling the column 1 and the storage container 13~ - -The frozen spheroids fell down~ardly in the reaction chamber 1 and were removed through the outlet 4 and collected in a deep-cooled Dewar vessel. The diameter size of these pheroids was between 0.16 and 1.0 mm,, the Gaussian dis-;~ tribution having it~ maximum at 0.63 mm. with 85% by weight of the particles. Over 9~! of the granulate had a spheroidal 3hape. The granulate flowed readily and did not stick together.
In a cooled container, the granulate can be stored practically without time limit, The consumption of LN2 was 2,5 kg~/kg. of solution (including pxe-cooling of the reaction chamber and losses).
2. Freeze dryinq of the frozen granulate.
The f~ozen spheroids collected in the De~ar vessel were shaken on to a pre-cooled metal sheet (-50C.) of a lyophilisation plant and discontinuously freeze-dried under the following conditions:
a) 13 hours at 0.2 mbar and 25C.
b) 5 hours at 1.333 10 3 mbar and 25C.
After lyophilisation, the particle size distribution and the spheroidal form of the granulate had not changed from that of the frozen state. Its density was calculated to be about 116 kgO/m3. The residual water content was 1.6~
by weight. The product had a homogeneous, white colour Upon shaking up and sieving, the granulate retained its shape.
It could easily be rubbed between the fingers. The electro-static charginy was low. The spheroids scarcely stuck together and did not stick at all to the walls of bottles in which it was ~tored. The flowability was very good, the flow behaviour of the granulate resembling that of a liqu-d. In order again to produce the initlal concentration of the 1~/9 saccharose solution, 100 g. of granulate were added to 1 litre of distilled water. Without mechanical movement of the liquid, the dis301ving time was 32 seconds.
It will be understood~that the dimensions of the drop-lets of product liquid in the stream of product liquid, and ~-hence the dimension of the granulate will depend on a number of factors. In particular the dimensions will depend on the diameter of the orifices of the nozzles 3, the pressure under which the product liquid is delivered into column 1, and the vi3cosity of the product liquid. It will be apparent that these three parameters can be varied within wide boundarie~ and that appropriate parameters for any desired granulate can be ' readily determined by experiment. Similarly the diam~ter of the orifice of inlet nozzle 2 is subject to wide variation.
In a general manner, however, and having regard to economic realities it is convenient to employ nozzles 3 having orifices with a diameter of 0.005 to 2 mm, with the product liquid being delivered under a pressure of 1.1 - 10 bar. The orifice(s) of the inlet nozzle 2 for liquid cooling agent may conveniently have a diameter of 1 - 20 mm. There is, o~ course, no limit to the number of nozzles 3 which might be employed, nevertheless it i9 found convenient to employ from 3 to 8 nozzles bearing in mind the limitations of plant size and spatial disposition.
I~ will be understood that the inlet nozzle 2 and the nozzle or nozzles 3 may be single orifice or multi-orifice nozzle~ for injection of liquid into column 1.
Generally speaking the pressure of delivery of the product liquid through product nozzle 3 is sufficient t~ pre-vent product liquid from freeziny and solidifying on the orifice~. Furthermore, as described previously, product nozzle 3 may suitably include means for heating it to prevent build-up of frozen product liquid in the nozzle line.
The invention h s been described in general by reference to an embodiment in which the product liquid is a solution. As indicated previously the inventlon can be employed with liquids other than solutions, for example, dispersions, suspensions and emulsions.
- ~ The invention finds special application in the manu-facture of particular diagnostic materials, however, it has wide application and can be employed in the particular industries described in the ~ ove description of the prior artJ
Claims (18)
1. An apparatus for the continuous production of granulates, comprising:
a cooling column, a supply means in an upper part of the column for a stream of liquid cooling agent comprising an injection nozzle disposed centrally of said column to direct the stream of cooling agent vertically downwardly, supply means in an upper part of the column for a stream of product liquid comprising a plurality of injection nozzles communicating with a common supply means of product liquid, said plurality of nozzles being disposed so as to direct streams of said product liquid towards said stream of cooling agent;
a removal opening for the granulate at a lower end of the cooling column and removal means for gaseous cooling agent.
a cooling column, a supply means in an upper part of the column for a stream of liquid cooling agent comprising an injection nozzle disposed centrally of said column to direct the stream of cooling agent vertically downwardly, supply means in an upper part of the column for a stream of product liquid comprising a plurality of injection nozzles communicating with a common supply means of product liquid, said plurality of nozzles being disposed so as to direct streams of said product liquid towards said stream of cooling agent;
a removal opening for the granulate at a lower end of the cooling column and removal means for gaseous cooling agent.
2. An apparatus according to claim 1, wherein the product removal opening communicates via a conveyor belt with a continuously operating freeze drying plant.
3. An apparatus according to claim 1, wherein said column is defined by an inner wall and an outer wall spaced from said inner wall to define a passage for flow of gaseous cooling agent from said lower end of the column around an outer surface of said inner wall so as to cool and insulate the column, said passage communicating with a gas outlet line from said column.
4. An apparatus according to claim 1, 2 or 3, wherein said plurality of nozzle circumscribe the centrally disposed injection nozzle to direct product liquid inwardly, down-wardly towards the stream of liquid cooling agent.
5. An apparatus according to claim 3, wherein the centrally disposed injection nozzle communicates via a first pipe line with a first storage container for liquid cooling agent, and said plurality of nozzles communicate via a second pipe line with said common supply means, said common supply means comprising a second storage container for product liquid, said first and second storage containers being constructed with double walls so that each is surrounded by a cooling space, each cooling space communicating with said gas outlet line.
6. An apparatus for the continuous production of granulates comprising a cooling chamber, first injection means disposed in an upper part of the chamber effective to direct a stream of liquid cooling agent centrally, downwardly in said chamber;
at least a second injection means disposed in said upper part effective to direct a stream of product liquid into said stream of cooling agent;
an outlet in a lower part of said chamber for granulate; and outlet means for vapourized cooling agent;
said chamber having a height effective to provide sufficient time for evaporation of said liquid cooling agent in contact with said product liquid to form a frozen granulate of said product liquid.
at least a second injection means disposed in said upper part effective to direct a stream of product liquid into said stream of cooling agent;
an outlet in a lower part of said chamber for granulate; and outlet means for vapourized cooling agent;
said chamber having a height effective to provide sufficient time for evaporation of said liquid cooling agent in contact with said product liquid to form a frozen granulate of said product liquid.
7. An apparatus according to claim 6, wherein said first injection means communicates via a first conduit means with a first storage vessel for said liquid cooling agent; and said at least one second injection means communicates via a second conduit means with a second storage vessel for said product liquid.
8. An apparatus according to claim 7, wherein said chamber is defined by an inner wall and an outer wall spaced from said inner wall to define a space for flow of vapourized cooling agent from said lower part of said chamber around an outer surface of said inner wall so as to cool and insulate said chamber.
9. An apparatus according to claim 7, wherein said outlet for granulate communicates via means for conveying fallen granulate from said chamber, with a freeze drying plant.
10. An apparatus according to claim 7, 8 or 9, including a plurality of said second injection means circumscribing said first injection means.
11. A process for the production of a frozen granulate from a product liquid comprising;
contacting the product liquid with a moving stream of readily evaporatable liquid cooling agent, allowing the liquid cooling agent to evaporate and frozen granulate to form from said product liquid, and recovering said frozen granulate; said cooling agent being inert to said product liquid.
contacting the product liquid with a moving stream of readily evaporatable liquid cooling agent, allowing the liquid cooling agent to evaporate and frozen granulate to form from said product liquid, and recovering said frozen granulate; said cooling agent being inert to said product liquid.
12. A process according to claim 11, wherein the moving stream moves downwardly in the direction of the gravitational force.
13. A process according to claim 11 or 12, wherein said product liquid is contacted with said liquid cooling agent in a plurality of streams.
14. A process according to claim 11 or 12, wherein size and solids content of the granulate is predetermined by appropriately adjusting concentration, viscosity and pressure of introduction of the product liquid, as well as by predeter-mining the dimensions of nozzles for contacting said liquid and said agent.
15. A process according to claim 11 or 12, wherein the liquid cooling agent is liquid nitrogen.
16. A process according to claim 11 or 12, including a step of freeze drying the recovered frozen granulate.
17. A process according to claim 11, wherein said liquid cooling agent is evaporatable at atmospheric pressure at a temperature below the freezing point of the product liquid.
18. A process according to claim 17, wherein said product liquid is at a temperature just above the freezing point of the liquid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762659546 DE2659546A1 (en) | 1976-12-30 | 1976-12-30 | METHOD FOR PRODUCING FROZEN GRANULES |
| DEP2659546.0 | 1976-12-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1106686A true CA1106686A (en) | 1981-08-11 |
Family
ID=5997030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA293,821A Expired CA1106686A (en) | 1976-12-30 | 1977-12-23 | Process and apparatus for the production of frozen granulates |
Country Status (18)
| Country | Link |
|---|---|
| JP (1) | JPS53114783A (en) |
| AR (1) | AR214108A1 (en) |
| AT (1) | AT356498B (en) |
| AU (1) | AU506746B2 (en) |
| BE (1) | BE862370A (en) |
| CA (1) | CA1106686A (en) |
| CH (1) | CH625332A5 (en) |
| DD (1) | DD133295A5 (en) |
| DE (1) | DE2659546A1 (en) |
| FI (1) | FI773941A (en) |
| FR (1) | FR2375901A1 (en) |
| GB (1) | GB1559920A (en) |
| IE (1) | IE46022B1 (en) |
| IL (1) | IL53695A0 (en) |
| IT (1) | IT1089419B (en) |
| NL (1) | NL7714401A (en) |
| SE (1) | SE7714822L (en) |
| ZA (1) | ZA777184B (en) |
Families Citing this family (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3042955A1 (en) * | 1980-11-14 | 1982-10-21 | Helmut 7702 Gottmadingen Ruh | METHOD AND DEVICE FOR PREPARING FRESH HERBS OR HERBAL MIXTURES AND MOLDED BODIES THEREOF |
| FR2566515B1 (en) * | 1984-06-22 | 1987-03-27 | Air Liquide | METHOD AND INSTALLATION FOR COOLING, USING A REFRIGERANT FLUID OF A POWDER |
| US4704873A (en) * | 1985-11-14 | 1987-11-10 | Taiyo Sanso Co., Ltd. | Method and apparatus for producing microfine frozen particles |
| EP1065456B1 (en) * | 1989-03-01 | 2006-06-28 | Polar Technologies Holdings B.V. | Portable snow-making apparatus |
| DE69005800T2 (en) * | 1989-05-01 | 1994-05-19 | Alkermes Inc | METHOD FOR PRODUCING SMALL PARTICLES OF BIOLOGICALLY ACTIVE MOLECULES. |
| JPH0753704Y2 (en) * | 1989-06-05 | 1995-12-13 | 大陽酸素株式会社 | Frozen grain production equipment |
| JPH089582Y2 (en) * | 1990-08-31 | 1996-03-21 | 大陽酸素株式会社 | Frozen grain production equipment |
| US5318636A (en) * | 1991-04-19 | 1994-06-07 | Eva Abony Szucs | Method for cleaning surfaces, in particular sensitive surfaces |
| DE4112890A1 (en) * | 1991-04-19 | 1992-10-22 | Abony Szuecs Eva | METHOD AND DEVICE FOR CLEANING SURFACES, ESPECIALLY SENSITIVE SURFACES |
| JPH06323712A (en) * | 1993-04-20 | 1994-11-25 | E I Du Pont De Nemours & Co | Method and equipment for manufacturing frozen particle by using confinement band of atomized cryogenic droplet |
| DE4344393C2 (en) * | 1993-12-24 | 1998-10-01 | Ftd Foam Tech Dev Gmbh | Device for producing ice cream, frozen dessert and fruit masses, pie masses, dough masses, from several difficult-to-mix fluid matrices, which consist of at least one material component |
| US5737928A (en) * | 1995-03-09 | 1998-04-14 | The Boc Group, Inc. | Process fluid cooling means and apparatus |
| DE19813101A1 (en) * | 1998-03-25 | 1999-09-30 | Herbert Dressler | Device for spraying chemical-technical products and process therefor |
| NO311164B1 (en) * | 1998-06-02 | 2001-10-22 | Leiv Eiriksson Nyfotek As | Process for freeze-drying of solutions |
| JP2003510550A (en) * | 1999-09-30 | 2003-03-18 | サイテック ソチエタ ア レスポンサビリタ リミタタ | Method and apparatus for cooling a liquid mixture and changing the state of the liquid mixture |
| DE10243483A1 (en) * | 2002-09-19 | 2004-04-08 | Messer Griesheim Gmbh | System for micropelletizing solutions or melts |
| ITMI20032367A1 (en) * | 2003-12-03 | 2005-06-04 | Air Liquide Italia S P A | METHOD AND PLANT FOR FLUID COOLING |
| WO2005061088A1 (en) | 2003-12-22 | 2005-07-07 | Finlay Warren H | Powder formation by atmospheric spray-freeze drying |
| ATE542095T1 (en) | 2004-07-23 | 2012-02-15 | Bayer Technology Services Gmbh | METHOD FOR STERILE FREEZING, DRYING, STORAGE, ANALYZING AND FILLING (SFD-SAF METHOD) (METHOD FOR FREEZE DRYING GRANULES FOR PARENTERAL BIOPHARMACEUTICS) |
| NZ550563A (en) * | 2006-10-16 | 2009-01-31 | Agres Ltd | Improvements in spray freeze drying |
| US7861551B2 (en) * | 2007-11-30 | 2011-01-04 | Whirlpool Corporation | Method and device for producing ice droplets on demand |
| WO2009109550A1 (en) | 2008-03-05 | 2009-09-11 | Sanofi Pasteur | Process for stabilizing an adjuvant containing vaccine composition |
| EP2143440A1 (en) | 2008-07-09 | 2010-01-13 | Sanofi Pasteur | Stabilising agent and vaccine composition comprising one or several attenuated living flavivirus |
| US9945611B2 (en) | 2010-08-04 | 2018-04-17 | Ima Life North America Inc. | Bulk freeze drying using spray freezing and agitated drying |
| ITBS20110076A1 (en) * | 2011-05-25 | 2012-11-26 | K190 S R L | APPARATUS AND PROCEDURE FOR THE PREPARATION OF ICE CREAM OR SIMILAR FOOD PRODUCTS |
| FR2983286B1 (en) * | 2011-11-24 | 2018-04-13 | L'air Liquide,Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | DEVICE FOR COOLING BULK PRODUCTS |
| CN103123196B (en) * | 2013-02-06 | 2015-08-26 | 邹杰 | A kind of cold-storage apparatus |
| JP5837670B2 (en) * | 2014-10-24 | 2015-12-24 | アイエムエー ライフ ノース アメリカ インコーポレーテッド | Bulk freeze drying using spray freezing and stirring drying |
| CN105597622B (en) * | 2016-03-09 | 2017-11-21 | 苏州大学 | The controllable spray chilling tower for being used to prepare micron order ice hockey particle of freezing temperature |
| CN106113314B (en) * | 2016-08-15 | 2019-06-21 | 浙江心源科技有限公司 | A kind of spray crystallization prilling granulator and its prilling process |
| DE202016106243U1 (en) | 2016-09-21 | 2016-11-17 | Dressler Group GmbH & Co. KG | Device for the production of powdery plastics with the most spherical structure possible |
| DE102018002750B8 (en) * | 2018-04-06 | 2020-09-24 | Messer France S.A.S. | Device for cooling products |
| CN108709369A (en) * | 2018-04-20 | 2018-10-26 | 大连工业大学 | A kind of ultrasonic atomization freeze drying plant |
| CN109820130B (en) * | 2019-04-03 | 2022-09-16 | 河南工业大学 | Soluble dietary fiber extraction element |
| WO2022047366A1 (en) * | 2020-08-31 | 2022-03-03 | Cornell University | Systems and methods for rapidly freezing a liquid |
| CN112774571A (en) * | 2020-12-26 | 2021-05-11 | 深圳万和制药有限公司 | Dispersing and condensing production process of high-uniformity large-particle-size pellets |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2751687A (en) * | 1952-05-21 | 1956-06-26 | Proctor Drying And Freezing Co | Process and apparatus for producing stabilized products |
-
1976
- 1976-12-30 DE DE19762659546 patent/DE2659546A1/en not_active Withdrawn
-
1977
- 1977-12-02 ZA ZA00777184A patent/ZA777184B/en unknown
- 1977-12-22 AU AU31922/77A patent/AU506746B2/en not_active Expired
- 1977-12-23 CA CA293,821A patent/CA1106686A/en not_active Expired
- 1977-12-26 IL IL53695A patent/IL53695A0/en unknown
- 1977-12-27 NL NL7714401A patent/NL7714401A/en not_active Application Discontinuation
- 1977-12-27 CH CH1609077A patent/CH625332A5/en not_active IP Right Cessation
- 1977-12-27 BE BE183889A patent/BE862370A/en unknown
- 1977-12-27 AR AR270534A patent/AR214108A1/en active
- 1977-12-28 JP JP15864477A patent/JPS53114783A/en active Pending
- 1977-12-28 FI FI773941A patent/FI773941A/en not_active Application Discontinuation
- 1977-12-28 GB GB53984/77A patent/GB1559920A/en not_active Expired
- 1977-12-28 IT IT31361/77A patent/IT1089419B/en active
- 1977-12-28 SE SE7714822A patent/SE7714822L/en not_active Application Discontinuation
- 1977-12-29 DD DD7700203008A patent/DD133295A5/en unknown
- 1977-12-29 IE IE2638/77A patent/IE46022B1/en unknown
- 1977-12-29 FR FR7739583A patent/FR2375901A1/en active Pending
- 1977-12-29 AT AT940677A patent/AT356498B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| NL7714401A (en) | 1978-07-04 |
| DD133295A5 (en) | 1978-12-27 |
| DE2659546A1 (en) | 1978-07-13 |
| IL53695A0 (en) | 1978-03-10 |
| AU3192277A (en) | 1979-06-28 |
| AU506746B2 (en) | 1980-01-24 |
| ATA940677A (en) | 1979-09-15 |
| AR214108A1 (en) | 1979-04-30 |
| FR2375901A1 (en) | 1978-07-28 |
| BE862370A (en) | 1978-06-27 |
| ZA777184B (en) | 1978-10-25 |
| GB1559920A (en) | 1980-01-30 |
| JPS53114783A (en) | 1978-10-06 |
| CH625332A5 (en) | 1981-09-15 |
| IE46022B1 (en) | 1983-01-26 |
| AT356498B (en) | 1980-04-25 |
| SE7714822L (en) | 1978-07-01 |
| IE46022L (en) | 1978-06-30 |
| FI773941A (en) | 1978-07-01 |
| IT1089419B (en) | 1985-06-18 |
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