WO1988006728A1 - Method and device for determining the temperature-time-relation during phase transformation - Google Patents

Method and device for determining the temperature-time-relation during phase transformation Download PDF

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Publication number
WO1988006728A1
WO1988006728A1 PCT/SE1988/000086 SE8800086W WO8806728A1 WO 1988006728 A1 WO1988006728 A1 WO 1988006728A1 SE 8800086 W SE8800086 W SE 8800086W WO 8806728 A1 WO8806728 A1 WO 8806728A1
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WIPO (PCT)
Prior art keywords
mixture
temperature
time
phase transformation
amount
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Application number
PCT/SE1988/000086
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French (fr)
Inventor
Hans Riese
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Alfa-Laval Licens Ab
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Filing date
Publication date
Application filed by Alfa-Laval Licens Ab filed Critical Alfa-Laval Licens Ab
Publication of WO1988006728A1 publication Critical patent/WO1988006728A1/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/14—Investigating or analyzing materials by the use of thermal means by using distillation, extraction, sublimation, condensation, freezing, or crystallisation
    • G01N25/147—Investigating or analyzing materials by the use of thermal means by using distillation, extraction, sublimation, condensation, freezing, or crystallisation by cristallisation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/02—Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering

Definitions

  • the present invention relates to a method and a device for determining the temperature-time-relationship during phase transformation, as melting, dissolving and crystallization of one or several components in a mixture, at which the mixture is brought to flow in a pipeline with a predetermined rate and a known temperature.
  • SE 445 677 there is described a method and a device for measuring the content of crystals in a mixture of liquid and crystals, where the difference in temperature in a flow which flows at a constant rate is measured both before and after heating of the flow. A heat effect is added to the flow which is sufficient for melting all the crystals in the flow. With knowledge about the flow rate, the heat effect added to the flow, the temperature differences in the same and known values about the specific heat of the liquid and the melting heat of the crystals the content of crystals in the mixture may be determined.
  • This method has functioned well in practice and has been used to determine the amount of ice when freeze stabilizing sparkling wine.
  • a method is therefore proposed according to which r4 ⁇ e amount of information about the tempera ture-time-relationship during phase transformation is increased strongly and a device for carrying through this method.
  • crystal size as size distribution may be determined in a mixture containing crystals.
  • the method according to the invention is characterized mainly in that a predetermined amount of heat is added to or taken away from the mixture and that the temperature in a partial amount of the mixture is sensed at several measuring points. These measuring points are arranged such that the partial amount during the flow through the pipeline is brought to pass these measuring points at time intervals which are determined with knowledge of the flow rate of the mixture.
  • the temperature measurement of the flowing mixture gives the change in the temperature as a function of the time. From this information figures will be obtained which may be used to determine some or several values regarding amount, crystal size or size distribution for the component/s in the mixture which have passed phase transformation.
  • the method according to the invention for determining the phase transformation in a mixture which flows through a pipeline may be carried through both continuously and at predetermined time intervals. In a continuous industrial process the determination takes place continuously with advantage, while when analyzing a raw material which is to be used for industrial production it may be sufficient to determine for example the crystal size in a smaller test quantity.
  • the determination may relate to crystallized components, where these values are determined with the use of the temperature change as a function of the time after heating. This type of determination is probably the most usual, but it is also possible that in the case where the mixture consists of an emulsion to determine the content or the contents of components which may crystallize after a cooling of the emulsion with the use of the temperature change as a function of the time.
  • a device for carrying through the method for determining the temperature-time-relationship during phase transformation comprises a unit to transmit a predetermined amount of heat to or from the mixture and several temperature sensing means arranged at a distance from each other along the pipeline. These means are connected to a device which in relation to the values about the flow rate of the mixture registers the temperature of the partial amount as a function of the time and with knowledge of the specific heat and melting or solution heat counts the desired values for the component/s which have passed phase transformation.
  • the invention relies on the knowledge that the temperature change as a function of the time during phase transformation of a component in a mixture is obtained in the form of a graph, which is typical for the crystal size and the mixture of crystal sizes found in the actual product.
  • thermal energy is added to a mixture containing crystals, it takes a certain time for the crystals to melt. This time is dependent on the size of the crystals, since the melting can take place only at the surface of the crystal. Small crystals have a proportionally larger surface than large crystals on the assumption that the crystals have the same form. The temperature of the surrounding liquid will be higher than that of the crystal as long as the melting continues. As the melting crystal must take its energy from the surroundings its temperature falls slower if the crystals are larger.
  • the temperature change in the mixture is shown as a function of the time.
  • the temperature change AO is a measure of the total amount of crystals which melt during the measuring.
  • the time OB is a measure of the size of the crystals.
  • the graph shows the relation if the crystals are small. In a real case the graph would probably be somewhat bent exponentially depending on the fact that the total exposed surface diminishes during the melting and on the fact that the temperature difference between the crystal surface and the liquid diminishes.
  • fig 3 there is shown a further relation of the melting of crystals.
  • the lowering of the temperature is the same as in fig 1 and 2 and at that also the total amount of crystals.
  • the time is also the same as in fig 2.
  • the graph still does not follow the same pattern as in fig 2.
  • the graph shows the relation for a mixture which contains as many small as large crystals.
  • the part BC shows the melting of small crystals, the part BE large crystals and the graph ADE is the sum of both the parts.
  • fig 4 there is shown a further mixture.
  • the fall of the temperature AO indicates the amount of crystals which have melted.
  • OD shows the time it takes to melt small crystals and OE the time to melt large crystals. If the amount of the two crystal types should be equal, the small should melt according to CD and the large according to CE and together they should form the graph BFE. In this case, however, the amount of small crystals is double the amount of large and the small melt according to the line BD. The mixture then melts and the melting line AFE is obtained.
  • the graphs and the measuring results may be used to control the processes which give the crystals or control and adapt the following processes handling a product containing crystals.
  • butter production from cream or ice-cream production may be mentioned.
  • a device for carrying through the method according to the claims is provided with means to bring the mixture to flow through pipelines with a predetermined flow rate.
  • a pump which works with a positive deplacement, as for example an eccentric screw pump may suitably be used. With such a pump a controlled flow rate may be obtained, which is necessary in order to obtain a sufficient accuracy in the measuring.
  • the determination of the relation during the phase transformation may take place with all the mixture passing through the pipeline.
  • the pipeline consists of a by-pass to the pipeline for the main flow.
  • an amount of heat is added to or removed from the flow. In the simpliest case this addition takes place by use of an electrical resistance thread. It is also possible to heat the mixture from the outside of the pipeline or by addition of micro wave energy. Removal of a certain amount of heat may take place by inserting a cooling coil or by cooling the outside of the pipeline.
  • the added amount of heat should be so large that all crystals are dissolved. In the opposite case a sufficient amount of cold must be added in order to crystallize the whole amount of crystallizable components.
  • the measuring of the temperature takes place by using sensing bodies, the accuracy of which is 0,01°C.
  • the measuring result is transmitted from the measuring point to a unit, which stores the measuring values and compares them to each other in such a way that the temperature of the same partial amount in the mixture is controlled as it flows forward in the pipeline.
  • the determination of the phase transformation takes place in a space controlled by a thermostat.
  • the result of the distribution of crystal sizes obtained at the determination of the temperature-time-relationship during the phase transformation may be shown in the form of a staple diagram or as a graph of the distribution.
  • the time up to the start of the crystallization may give a measure of the purity of the mixture.
  • composition and mixture conditions in a mixture consisting of a component which after heating or cooling is phase transformed.

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
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Abstract

Determination of the temperature-time-relationship during phase transformation, as melting, dissolving and crystallization of one or several components in a mixture takes place by making the mixture flow in a pipeline with a predetermined flow rate and a known temperature. A predetermined amount of heat is added to or removed from the mixture, after which the temperature in a partial amount of the mixture is sensed at a number of measuring points. These are arranged such that the partial amount during the flow through the pipeline is brought to pass these measuring points at time intervals which are determined with use of the flow rate of the mixture. The temperature change in the partial amount is obtained as a function of the time and gives values which are used to determine some or several measuring values for amount, crystal size or size distribution for the component/s in the mixture which have passed phase transformation.

Description

Method and device for determining the temperature-time- relation. during phase transformation.
The present invention relates to a method and a device for determining the temperature-time-relationship during phase transformation, as melting, dissolving and crystallization of one or several components in a mixture, at which the mixture is brought to flow in a pipeline with a predetermined rate and a known temperature.
In SE 445 677 there is described a method and a device for measuring the content of crystals in a mixture of liquid and crystals, where the difference in temperature in a flow which flows at a constant rate is measured both before and after heating of the flow. A heat effect is added to the flow which is sufficient for melting all the crystals in the flow. With knowledge about the flow rate, the heat effect added to the flow, the temperature differences in the same and known values about the specific heat of the liquid and the melting heat of the crystals the content of crystals in the mixture may be determined.
This method has functioned well in practice and has been used to determine the amount of ice when freeze stabilizing sparkling wine.
It has been found that in many instances the sole measuring of the content of crystals in the mixture is not sufficient. Within the chocolate industry there is a strong demand to be able to determine as well crystal size as size distribution in chocolate masses. The same demand is also present within the sugar industry.
According to the invention a method is therefore proposed according to which r4ιe amount of information about the tempera ture-time-relationship during phase transformation is increased strongly and a device for carrying through this method.
According to the invention as well crystal size as size distribution may be determined in a mixture containing crystals.
The method according to the invention is characterized mainly in that a predetermined amount of heat is added to or taken away from the mixture and that the temperature in a partial amount of the mixture is sensed at several measuring points. These measuring points are arranged such that the partial amount during the flow through the pipeline is brought to pass these measuring points at time intervals which are determined with knowledge of the flow rate of the mixture. The temperature measurement of the flowing mixture gives the change in the temperature as a function of the time. From this information figures will be obtained which may be used to determine some or several values regarding amount, crystal size or size distribution for the component/s in the mixture which have passed phase transformation.
The method according to the invention for determining the phase transformation in a mixture which flows through a pipeline may be carried through both continuously and at predetermined time intervals. In a continuous industrial process the determination takes place continuously with advantage, while when analyzing a raw material which is to be used for industrial production it may be sufficient to determine for example the crystal size in a smaller test quantity.
The determination may relate to crystallized components, where these values are determined with the use of the temperature change as a function of the time after heating. This type of determination is probably the most usual, but it is also possible that in the case where the mixture consists of an emulsion to determine the content or the contents of components which may crystallize after a cooling of the emulsion with the use of the temperature change as a function of the time.
A device for carrying through the method for determining the temperature-time-relationship during phase transformation according to the invention comprises a unit to transmit a predetermined amount of heat to or from the mixture and several temperature sensing means arranged at a distance from each other along the pipeline. These means are connected to a device which in relation to the values about the flow rate of the mixture registers the temperature of the partial amount as a function of the time and with knowledge of the specific heat and melting or solution heat counts the desired values for the component/s which have passed phase transformation.
The invention relies on the knowledge that the temperature change as a function of the time during phase transformation of a component in a mixture is obtained in the form of a graph, which is typical for the crystal size and the mixture of crystal sizes found in the actual product.
If thermal energy is added to a mixture containing crystals, it takes a certain time for the crystals to melt. This time is dependent on the size of the crystals, since the melting can take place only at the surface of the crystal. Small crystals have a proportionally larger surface than large crystals on the assumption that the crystals have the same form. The temperature of the surrounding liquid will be higher than that of the crystal as long as the melting continues. As the melting crystal must take its energy from the surroundings its temperature falls slower if the crystals are larger.
The temperature-time-relationship for several different mixtures containing a component which has passed phase transformation, in this case crystals which are brought to melt, is shown schematically in four figures in the attached drawing.
In fig 1 the temperature change in the mixture is shown as a function of the time. The temperature change AO is a measure of the total amount of crystals which melt during the measuring. The time OB is a measure of the size of the crystals. The graph shows the relation if the crystals are small. In a real case the graph would probably be somewhat bent exponentially depending on the fact that the total exposed surface diminishes during the melting and on the fact that the temperature difference between the crystal surface and the liquid diminishes.
In fig 2 there is shown the relation if the mixture contains large crystals. The lowering of the temperature Is the same as in fig 1, i.e. the total content of crystals is the same. The time for the melting Is longer anyhow.
In fig 3 there is shown a further relation of the melting of crystals. The lowering of the temperature is the same as in fig 1 and 2 and at that also the total amount of crystals. The time is also the same as in fig 2. The graph still does not follow the same pattern as in fig 2. The graph shows the relation for a mixture which contains as many small as large crystals. The part BC shows the melting of small crystals, the part BE large crystals and the graph ADE is the sum of both the parts.
In fig 4 there is shown a further mixture. The fall of the temperature AO indicates the amount of crystals which have melted. OD shows the time it takes to melt small crystals and OE the time to melt large crystals. If the amount of the two crystal types should be equal, the small should melt according to CD and the large according to CE and together they should form the graph BFE. In this case, however, the amount of small crystals is double the amount of large and the small melt according to the line BD. The mixture then melts and the melting line AFE is obtained.
In this way graphs are obtained which are typical for the distribution and the size of the crystals which melt during the measuring. In the drawing the graphs have been drawn schematically in order to show how information may be obtained from the form of the graph.
By increasing the number of measuring points a better control of the distribution of the size of the crystals may be obtained. The graphs and the measuring results may be used to control the processes which give the crystals or control and adapt the following processes handling a product containing crystals. As example of such uses butter production from cream or ice-cream production may be mentioned.
A device for carrying through the method according to the claims is provided with means to bring the mixture to flow through pipelines with a predetermined flow rate. A pump which works with a positive deplacement, as for example an eccentric screw pump may suitably be used. With such a pump a controlled flow rate may be obtained, which is necessary in order to obtain a sufficient accuracy in the measuring. At low flow the determination of the relation during the phase transformation may take place with all the mixture passing through the pipeline. In other cases the pipeline consists of a by-pass to the pipeline for the main flow.
In order to change the phase condition of the component which is to be determined an amount of heat is added to or removed from the flow. In the simpliest case this addition takes place by use of an electrical resistance thread. It is also possible to heat the mixture from the outside of the pipeline or by addition of micro wave energy. Removal of a certain amount of heat may take place by inserting a cooling coil or by cooling the outside of the pipeline.
The added amount of heat should be so large that all crystals are dissolved. In the opposite case a sufficient amount of cold must be added in order to crystallize the whole amount of crystallizable components.
The measuring of the temperature takes place by using sensing bodies, the accuracy of which is 0,01°C. The measuring result is transmitted from the measuring point to a unit, which stores the measuring values and compares them to each other in such a way that the temperature of the same partial amount in the mixture is controlled as it flows forward in the pipeline.
In the case where the mixture which flows through the pipeline has a temperature which strongly differs from the room temperature or the surrounding temperature, the determination of the phase transformation takes place in a space controlled by a thermostat.
The result of the distribution of crystal sizes obtained at the determination of the temperature-time-relationship during the phase transformation, may be shown in the form of a staple diagram or as a graph of the distribution.
When determining the relation during phase transformation, which results in the formation of crystals, the time up to the start of the crystallization may give a measure of the purity of the mixture.
Depending on the desired purpose a large amount of information may be obtained according to the invention as stated in the claims about the composition and mixture conditions in a mixture consisting of a component which after heating or cooling is phase transformed. According to the invention it is also possible to follow the temperature-time-relationship for a mixture which comprises crystals of different components, for example a fat mixture.

Claims

Claims
1. Method for determination of temperature-time-relationship during phase transformation, as melting, dissolving and crystal lization of one or several components in a mixture, where the mixture Is brought to flow in a pipeline at a predetermined flow rate and a known temperature, c ha r a c t e r i z e d i n that a predetermined amount of heat is added to or removed from the mixture at first, that the temperature in a partial amount of the mixture is sensed at a number of measuring points, which measuring points are arranged such that the partial amount during the flow through the pipeline is brought to pass these measuring points at time intervals which are decided with knowledge of the flow rate of the mixture, at which the temperature change in the partial amount is obtained as a function of the time, giving informations which may be used to determine some or several values regarding amount, crystal size or size distribution for the component/s in the mixture which have passed phase transformation.
2. Method according to claim 1, c h a r a c t e r i z e d i n that the determination of the temperature-time-relationship is carried through continuously.
3. Method according to claim 1, c ha r a c t e r i z e d i n that the mixture comprises crystals and in that the crystal size or size distribution is determined using the temperature change as a function of the time after heating.
4. Method according to claim 1, c h a r a c t e r i z e d i n that the mixture consists of an emulsion comprising a component which is crystallized when cooled, at which the content of component is determined making use of the temperature change as a function of the time after the cooling.
5. Arrangement for carrying through the method for determining the temperature-time-relationship during phase transformation according to claim 1, comprising a pipeline, through which a mixture is brought to flow with a predetermined flow rate and a known temperature, c h a r a c t e r i z e d i n that there is a unit for transmission of a predetermined amount of heat to or from the mixture and in that a number of temperature sensing means are arranged at a distance from each other along the pipeline, which means are connected to a unit which with knowledge of the flow rate of the mixture registers the temperature of the partial amount as a function of the time and with knowledge of specific heat and melting or solution heat calculates the desired values for the components which have passed phase transformation.
PCT/SE1988/000086 1987-03-02 1988-02-26 Method and device for determining the temperature-time-relation during phase transformation WO1988006728A1 (en)

Applications Claiming Priority (2)

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SE8700870A SE460155B (en) 1987-03-02 1987-03-02 SET FOR DETERMINATION OF TEMPERATURE-TIME PROGRESS DURING PHASE CONVERSION
SE8700870-2 1987-03-02

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110203511A1 (en) * 2010-02-25 2011-08-25 Japan Aviation Electronics Industry Limited Precision Apparatus Using Low Thermal Expansion Component

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3150515A (en) * 1961-07-20 1964-09-29 Velsicol Chemical Corp Method and apparatus for the continuous measurement of freezing points
US3229499A (en) * 1963-12-23 1966-01-18 Gen Electric Method and apparatus for measuring fluid thermal characteristics
US3577765A (en) * 1967-12-26 1971-05-04 Monsanto Co Apparatus for determining crystalization temperature
WO1982001248A1 (en) * 1980-09-26 1982-04-15 Corp Hetra Method of and apparatus for nondestructively determining the composition of an unknown material sample
US4448545A (en) * 1982-03-02 1984-05-15 Southern California Gas Company Non-intrusive thermal power monitor and method
SE445677B (en) * 1984-11-19 1986-07-07 Alfa Laval Food & Dairy Eng PROCEDURE FOR SATURING THE CONTENT OF CRYSTALS IN A MIXTURE OF LIQUID AND CRYSTALS AND A DEVICE FOR IMPLEMENTATION OF THE PROCEDURE

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3150515A (en) * 1961-07-20 1964-09-29 Velsicol Chemical Corp Method and apparatus for the continuous measurement of freezing points
US3229499A (en) * 1963-12-23 1966-01-18 Gen Electric Method and apparatus for measuring fluid thermal characteristics
US3577765A (en) * 1967-12-26 1971-05-04 Monsanto Co Apparatus for determining crystalization temperature
WO1982001248A1 (en) * 1980-09-26 1982-04-15 Corp Hetra Method of and apparatus for nondestructively determining the composition of an unknown material sample
US4448545A (en) * 1982-03-02 1984-05-15 Southern California Gas Company Non-intrusive thermal power monitor and method
SE445677B (en) * 1984-11-19 1986-07-07 Alfa Laval Food & Dairy Eng PROCEDURE FOR SATURING THE CONTENT OF CRYSTALS IN A MIXTURE OF LIQUID AND CRYSTALS AND A DEVICE FOR IMPLEMENTATION OF THE PROCEDURE

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110203511A1 (en) * 2010-02-25 2011-08-25 Japan Aviation Electronics Industry Limited Precision Apparatus Using Low Thermal Expansion Component
US8490570B2 (en) * 2010-02-25 2013-07-23 Japan Aviation Electronics Industry, Limited Precision apparatus using low thermal expansion component

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Publication number Publication date
SE8700870L (en) 1988-09-03
SE8700870D0 (en) 1987-03-02
SE460155B (en) 1989-09-11

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