Crystallization system with frame elements
10143971 ยท 2018-12-04
Assignee
Inventors
Cpc classification
B01D9/0018
PERFORMING OPERATIONS; TRANSPORTING
B01D2311/2642
PERFORMING OPERATIONS; TRANSPORTING
B01D9/0072
PERFORMING OPERATIONS; TRANSPORTING
B01D61/005
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01D61/36
PERFORMING OPERATIONS; TRANSPORTING
B01D61/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A system for crystallizing a material that is dissolved in a solvent includes: a crystallization device through which a solution that is to be concentrated flows, the solution including the solvent containing the material to be crystallized and dissolved in the solvent, and a liquid having a lower temperature than the solution to be concentrated. The system includes at least one flow channel guiding the solution to be concentrated and at least one flow channel guiding the liquid, where the inner space of each respective flow channel guiding the liquid is delimited at least in part by a membrane wall that is permeable for the vaporous solvent, where a vapor pressure difference enables the solvent to pass from the solution to be concentrated across the membrane wall.
Claims
1. A system for the crystallization of a material dissolved and to be crystallized in a solvent, having a crystallization apparatus flowed through by a solution to be concentrated, the solution having the solvent with the material dissolved and to be crystallized therein, and by a liquid that has a lower temperature than the solution to be concentrated, wherein the crystallization apparatus has at least one flow passage conducting the solution to be concentrated and has at least one flow passage conducting the liquid, wherein the internal space of the at least one flow passage conducting the solution to be concentrated is bound at least partly by a membrane wall permeable for a vapor-like solvent but not for the liquid solvent, and the at least one flow passage conducting the liquid is adjacent to the at least one flow passage conducting the solution to be concentrated, whereby a vapor pressure difference is set via the membrane wall in such a way that the vapor-like solvent passes from the solution to be concentrated through the membrane wall, wherein: the crystallization apparatus has a plurality of frame elements that can be combined with one another for the formation of different functional units, to form stacks comprising at least two frame elements, wherein each of the plurality of frame elements has an outer frame, a central internal region bound by the outer frame and a sediment collection region arranged beneath the central internal region, the crystallization apparatus has at least two different types of frame elements that are alternatingly combined to form a stack, wherein the central internal region of the one type of frame element forms a part of the at least one flow passage conducting the solution to be concentrated and the central internal region of the other type of frame element forms a part of the at least one flow passage conducting the liquid, the membrane wall is arranged on each side of the central internal region of the one type of frame element, the membrane wall being permeable for the vapor-like solvent but not for the liquid solvent, a vapor-tight and liquid-tight film arranged on each side of the central internal region of the other type of frame element, and an intermediate space between the membrane wall and the film forms a part of the at least one flow passage provided for the conducting away of the solvent which has passed through the membrane wall, wherein the at least one flow passage conducting the solution to be concentrated and the at least one flow passage conducting the liquid are arranged in alternating directions so as direct the solution and the liquid in a cross-flow pattern.
2. The system in accordance with claim 1, wherein the stacks comprise at least ten frame elements.
3. The system in accordance with claim 1, wherein the membrane wall is welded to each side of the central internal region of the one type of frame element.
4. The system in accordance with claim 1, wherein the vapor-tight and liquid-tight film is respectively welded to each side of the central internal region of the other type of frame element.
5. The system in accordance with claim 1 wherein the liquid flows through the crystallization apparatus in counter-flow with respect to the solution to be concentrated.
6. The system in accordance with claim 1 wherein the crystallization apparatus has a plurality of stages connected in series, wherein each stage comprises a plurality of flow passages conducting the solution to be concentrated and arranged in parallel with one another and wherein at least two of the stages have a different number of flow passages conducting the solution to be concentrated.
7. The system in accordance with claim 1, wherein the system has a heat exchanger that cools a liquid flowing out of the crystallization apparatus.
8. The system in accordance with claim 1 wherein the system has a cooling element and has a heating element and both the at least one flow passage conducting the solution to be concentrated and the at least one flow passage conducting the liquid are flowed through by the solution to be concentrated, wherein the cooling element and an input of the at least one flow passage conducting the liquid are connected downstream of an output of the at least one flow passage conducting the solution to be concentrated and wherein the heating element and an input of the at least one flow passage conducting the solution to be concentrated are connected downstream of an output of the at least one flow passage conducting the liquid.
Description
(1) The invention will be described in detail in the following by means of embodiments with reference to the drawings. In these there is shown:
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(16) In a schematic illustration
(17) Whereas
(18) The system illustrated in
(19) The flow passage 18 conducting the liquid 14 is adjacent to the flow passage 16 conducting the solution 12 to be concentrated. In the embodiment shown in the
(20) The liquid 14 has a lower vapor pressure than the solution 12 to be concentrated due to its lower temperature. Consequently, the vapor pressure in the internal space of the flow passage 16 conducting the solution 12 to be concentrated is larger than at the side of the membrane wall 20 adjacent thereto, this means in the internal space of the flow passage 18 conducting the liquid 14. This vapor pressure difference over the membrane wall 20 has the effect that the solvent passes from the solution 12 to be concentrated through the membrane wall 20 in vapor form. For this reason, the solvent is removed from the solution 12 to be concentrated on its path through the flow passage 16, with the solvent being supplied to the liquid 14. Nucleation and crystallization start through the increasing concentration of the material dissolved and to be crystallized in the solution 12 to be concentrated along the flow passage 16.
(21) The flow passage 16 for the solution 12 to be concentrated at least partly has an opening at its lower side at which a sediment collection container 22 adjoins. The crystals arising during the crystallization can sediment into the sediment collection container 22. The flow passage 18 for the liquid 14 generating the potential difference is terminated towards the bottom. The sediment collection container 22 filled with the solution 12 to be concentrated is, however, not flowed through by the solution 12 to be concentrated.
(22) The membrane wall 20 can, for example, be produced from microporous, hydrophobic materials, for example from polytetrafluoroethylene, polypropylene, polyethylene or polyvinylidene fluoride.
(23) The flow of the solution 12 to be concentrated and of the liquid 14 through the respective flow passage 16 or 18 can, for example, be generated by pumps not illustrated in the
(24) The solution 12 to be concentrated can have a concentration of the material to be crystallized close to the saturation already on entry into the flow passage 16. Through the reduction of the solvent in the solution 12 to be concentrated the concentration of the material to be crystallized increases along the flow passage 16, whereby finally saturation and oversaturation are achieved and nucleation and crystal growth are brought about. The degree of oversaturation can be set via the flow velocity and the driving inclination caused by the vapor pressure difference over and via the membrane wall 20 and in this way the shape and particle size of the generated crystals can be influenced.
(25) Having regard to thermal methods a small thermal requirement of energy is to be striven for. This is achieved in the crystallization apparatus 10 shown in the
(26) In a schematic representation
(27) The flow passages 16 and 18 are alternatingly arranged next to one another in the stage 30. Between adjacent flow passages 16 and 18 a membrane wall 20 is respectively arranged permeable for the vapor-like solvent but not for the liquid solvent. The membrane wall 20 separates the respective flow passages 16 and 18 from one another. The flow passages 16 and 18 respectively separated by a membrane wall 20 are directly adjacent to one another at respective opposite sides of the membrane wall 20. As is shown in
(28) The solution 12 to be concentrated is introduced into the stage 30 at the point A; subsequently the solution 12 to be concentrated flows through the three flow passages 16, wherein the solvent passes through the membrane walls 20 into the adjacent flow passages 18 due to the lower vapor pressure of the liquid 14 and condenses there in the liquid 14. The concentration of the material to be crystallized in the solution 12 to be concentrated is thereby increased along the flow passages 16. Moreover, the solution 12 to be concentrated cools during this process. Finally, the solution 12 is conducted away from the stage 30 at the point B.
(29) At the point B the liquid 14 is furthermore supplied to the stage 30 having the lower vapor pressure and is subsequently distributed to the three parallel flow passages 18. During the process taking place in the stage 30 the liquid is heated by means of the condensation of the solvent. The heated liquid 14 exits the stage 30 at the point A. The liquid 14 flows through the stage 30 in counter-flow with respect to the solution 12 to be concentrated.
(30) The flow passages 16 for the solution 12 to be concentrated are respectively at least partly downwardly open into a sediment collection container 22. The crystals arising in the process sediment into the sediment collection spaces 22. The flow passages 18 for the liquid 14 generating the potential difference are thus terminated towards the bottom.
(31) In a schematic illustration
(32) Furthermore, the two stages 32 and 34 are assembled similar to the stage 30 shown in
(33) The solution 12 to be concentrated is introduced into the stage 32 at the point A, transitions into the stage 34 switched thereafter at the point B and exits the stage 34 at the point C. The liquid 14 having the lower vapor pressure is introduced into the stage 34 at the point C, exits into the stage 32 at the point B and leaves the stage 32 at the point A.
(34) Through the switching after one another of the stages 32 and 34 the flow passages 16 add in the length and the flow lengths required for the sedimentation can be achieved in a simple manner.
(35) In a schematic illustration
(36) The stages 36 and 40 are assembled similar to the stage 34 in accordance with
(37) The stage 38 is assembled similar to the stage 32 in accordance with
(38) As soon as the volume of the solution 12 to be concentrated flowing through the stages 36, 38 and 40 per unit in time is approximately equal for each of the stages 36, 38 and 40, the flow velocity of the solution 12 to be concentrated is increased in the stage 38 having a reduced number of flow passages 16 and the kinetics of the crystallization is influenced.
(39) In a schematic illustration
(40) In the embodiment in accordance with
(41) As the vapor-tight and liquid-tight wall 46 is thermally conductive, the liquid 12 cools the material present in the flow passage 44 via the wall 46 and generates a vapor pressure there that is lower than in the flow passage 16 conducting the solution 12 to be concentrated, from which a vapor pressure difference results via the respective membrane wall 20.
(42) Driven by this vapor pressure difference, the solvent exits as vapor from the solution 12 to be concentrated through the membrane wall 20 and condenses at the wall 46 that is both vapor-tight and liquid-tight for the solvent and that separates the flow passage 44 from the flow passage 18 conducting the liquid 14. The flow passage 44 permits a simple conducting away of the solvent passed through the membrane wall 20 and the condensed solvent.
(43) At the start of the process the flow passage 44 provided for the conducting away of the solvent passed through the membrane wall 20 can be filled with environmental air; after the start of the process it is, however, rapidly filled with the solvent. Through the flow passage 44 arranged between a respective flow passage 16 conducting the solution 12 to be concentrated and a respective flow passage 18 conducting the liquid 14 it is prevented that the solvent passing through the membrane wall 20 dilutes the liquid 14 present in the adjacent flow passage 18.
(44) In the embodiment shown in
(45) The liquid 14 flows through the crystallization apparatus 10 in counter-flow with respect to the solution 12 to be concentrated. Furthermore, the flow passages 16 for the solution 12 to be concentrated are respectively at least partly downwardly open into a sediment collection space 22. The crystals arising in the process sediment into the sediment collection spaces 22. The flow passages 18 for the liquid 14 generating the potential difference are thus terminated towards the bottom.
(46) If the membrane wall 20 is microporous and a crystallization is brought about in the membrane wall 20, then this can lead to a growth of the crystals through the membrane wall 20. As a consequence, the solution 12 to be concentrated can arise through a membrane wall 20 via the crystals grown through from the flow passage 16 into the flow passage 18. In this case the relative pressure between the flow passages 16 and 18 can be set in such a way that the pressures in the flow passages 16 and 18 are equal or the pressure in the flow passage 18 is higher than in the flow passage 16. For example, a back-flushing of the pores can be brought about through which the crystal growth has taken place. The pressure difference between the flow passages 16 and 18 can also be periodically built up.
(47) In a schematic illustration
(48) The solution 12 to be concentrated is introduced into the stage 50 at the point A, transitions into the stage 52 switched thereafter at the point B and exits the stage 52 at the point C. The cold liquid 14 is introduced into the stage 52 at the point C, goes over into the stage 50 at the point B and exits the stage 50 at the point A. Furthermore, outlets for the solvent conducted away by the flow passages 44 are provided at the points A and C.
(49) In a schematic illustration
(50) In
(51) The heated liquid 14 exiting from the crystallization apparatus 10 is cooled in the heat exchanger 56 and the solution 12 to be concentrated exiting from the crystallization apparatus 10 is heated. In the heat exchanger 58 the solution 12 to be concentrated coming from the heat exchanger 56 is further heated until it is warmer than the liquid 14 exiting the crystallization apparatus 10 at the point A. In the heat exchanger 60 the liquid 14 coming from the heat exchanger 56 is cooled so far until it is colder than the solution 12 to be concentrated is at the point B, this means until a sufficient potential difference for the material transfer from the solution 12 to be concentrated into the liquid 14 is achieved. The heat exchangers 58 and 60 can generally be configured as heating and/or cooling elements.
(52) The volume flow of the liquid 14 is increased by means of material transfer from the solution 12 to be concentrated. This additional volume flow 62 of the liquid 14 can be removed from the liquid 14 at the point C. Likewise the volume flow reduced by means of material transfer of the solution 12 to be concentrated can be filled up by a volume flow 64 at the point C. Moreover, it is possible to exclude a part 66 of the solution 12 to be concentrated from the system at the point C.
(53) In a schematic illustration
(54) In the embodiment illustrated in
(55) Besides the crystallization apparatus 10, the system illustrated in
(56) The depleted solution 12 to be concentrated exits from the flow passages 16 of the crystallization apparatus 10 at the point B. The solution 12 to be concentrated can then be completely or partly conducted away from the system with a flow 82. If the solution 12 to be concentrated exiting from the crystallization apparatus 10 at the point B is again supplied completely or partly to the crystallization apparatus 10, then the solution 12 to be concentrated is cooled so far with the heat exchanger 76 that it has such a temperature on entrance into the flow passages 18 at the point B that a driving potential is always present via the flow passages 44 in the flow passages 16 for the solution 12 to be concentrated. The solution 12 to be concentrated can be resupplied via a flow 84. The solution 12 to be concentrated that is cooled by means of the heat exchanger 76 is then supplied to the flow passages 18 of the stage 72.
(57) The heat exchanger 74 is heated via a heating flow 86 and the heat exchanger 76 is cooled by a cooling flow 88. Alternatively, heating elements or cooling elements of different design can be used.
(58) The system described herein for the crystallization of a material dissolved and to be crystallized in a solvent and in particular the crystallization apparatus can be assembled from a plurality of frame elements that can be combined for the formation of different functional units. In this connection the crystallization apparatus 10 can, for example, be assembled from two different types of frame element that are alternatingly combined to form a stack. In the
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(60) The distribution and collection passages 102 and 104 are respectively connected to the central internal region 106 via an opening 110 or 112 in the frame element 100. Furthermore, the central internal region 106 is connected to the sediment collection region 108 via an opening 114 in the frame element 100.
(61) The distribution passage 102 leads the solution 12 to be concentrated into the central internal region 106 via the opening 110. From there the solution 12 to be concentrated arrives in the collection passage 104 via the opening 112. Via the opening 114 the crystals can sediment into the sediment collection region 108. Beneath the sediment collection region 108 an opening 116 can be provided in the frame element 100 via which the crystal sediment into the sediment collection region 108 can be removed. The central internal region 106 of the frame element 100 can have a grid structure for mixing the solution 12 to be concentrated.
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(63) The potential difference for the concentration and crystallization is generated in the frame element 120. The frame element 120 is provided at both sides with a membrane wall 20 permeable for the vapor-like solvent but not for the liquid solvent. The membrane wall 20 covers the complete central internal region 106, wherein the distribution passage 102, the collection passage 104 and the sediment collection region 108 are not covered by the membrane wall 20. Preferably, the membrane wall 20 is welded to the frame element 120.
(64) The liquid 14 having a lower vapor pressure in comparison to the solution 12 to be concentrated is conducted into the central internal region 106 and/or conducted away from there via inlets 122 and outlets 124 arranged at the edges of the central internal region 106. The central internal region 106 of the frame element 120 can have a grid structure for mixing the liquid 14 and for supporting the membrane wall 20. The inlets and outlets 122 and 124 are not directly covered by the membrane wall 20.
(65) The passages of the inlets 122 and 124 furthermore pass through the frame element 100 shown in
(66) The types of frame element 100 and 120 shown in the
(67) Crystallization apparatuses 10 can be created by means of the frame elements 100 and 120 in which a respective flow passage 18 conducting the liquid 14 is directly adjacent to the membrane wall 20 of a respective flow passage 16 conducting the solution 12 to be concentrated. Examples of such crystallization apparatuses 10 are shown in the
(68) Crystallization apparatuses 10 such as are shown, for example, in the
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(70) Furthermore, the frame element 130 is provided at both sides with a membrane wall 20 permeable for the vapor-like solvent but not for the liquid solvent. The membrane wall 20 covers the complete central internal region 106, wherein the distribution passage 102, the collection passage 104, the sediment collection region 108, the inlets 122 and the outlets 124 are not covered by the membrane wall 20. Preferably, the membrane wall 20 is welded to the frame element 130.
(71) Furthermore, the frame element 130 has openings 132 through which the solvent passed through the membrane wall 20 can be conducted away. The openings 132 are not covered by the membrane wall 20.
(72) During the crystallization process the solution 12 to be concentrated is guided into the central internal region 106 of the frame element 130 via the distribution passage 102 and the opening 110. From there the solution 12 to be concentrated passes into the collection passage 104 via the opening 112. Via the opening 114 the generated crystals can sediment into the sediment collection region 108. The central internal region 106 of the frame element 130 can have a grid structure for mixing the solution 12 to be concentrated and for supporting the membrane wall 20.
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(74) The frame element 140 is provided at both sides with a vapor-tight and liquid-tight film 142. The film 142 covers the complete central internal region 106, wherein the distribution passage 102, the collection passage 104, the sediment collection region 108, the inlets 122, the outlets 124 and the openings 132 are not covered by the film 142. Preferably, the film 142 is welded to the frame element 140.
(75) The liquid 14 having a lower vapor pressure in comparison to the solution 12 to be concentrated is conducted into the central internal region 106 of the frame element 140 and/or conducted away from there via the inlets 122 and the outlets 124. The central internal region 106 of the frame element 140 can have a grid structure for mixing the liquid 14 and for supporting the film 142.
(76) The frame elements 130 and 140 are alternatingly arranged next to one another for the assembly of a crystallization apparatus 10 and are preferably welded to one another. In this connection the frame elements 130 and 140 are expediently configured in such a way that the distribution passages 102, the collection passages 104, the sediment collection regions 108, the inlets 122, the outlets 124 and the openings 132 of the frame elements 130 and 140 arranged next to one another respectively align with one another.
(77) During the operation of the crystallization apparatus 10 the solvent passed through the membrane wall 20 collects in the intermediate space that is formed by the alternating arrangement of the frame elements 130 and 140 next to one another between a respective membrane wall 20 and the adjacent film 142. The solvent collected there can be conducted away by the openings 132.
(78) Suitable materials for the previously described frame elements 100, 120, 130 and 140 are, for example, polypropylene, polyethylene, polyamide and polyvinylidene fluoride.
(79) In a schematic illustration
(80) The heat exchanger 154 is assembled from frame elements 130 and 140, wherein the frame elements 130 and 140 are alternatingly assembled to form stacks and the membrane wall 20 has been omitted in the frame element 130. The solution 12 to be concentrated flows through the central internal regions 106 of the frame elements 130, whereas the central internal regions 106 of the frame elements 140 are flowed through by a heating flow 160 supplied from the outside to the heat exchanger 154. Alternatively, it could also be plausible to let the solution 12 to be concentrated flow through the central internal regions 106 of the frame elements 140 and the heating flow 160 flow through the central internal regions 106 of the frame elements 130.
(81) The solution 12 to be concentrated enters at the flow passages 18 of the crystallization apparatus 10 into the heat exchanger 154 at the point A. Through the heat transfer from the heating flow 160 through the films 142 of the frame elements 140 the solution to be concentrated is heated on passing through the heat exchanger 154. The thereby heated solution 12 to be concentrated is supplied to the flow passages 16 of the crystallization apparatus 10 at the point A.
(82) In a corresponding manner the heat exchanger 158 is assembled from frame elements 130 and 140, wherein the frame elements 130 and 140 are alternatingly assembled to form stacks and the membrane wall 20 has been omitted in the frame element 130. The solution 12 to be concentrated flows through the central internal regions 106 of the frame elements 130, whereas the central internal regions 106 of the frame elements 140 are flowed through by a coolant flow 162 supplied from the outside to the heat exchanger 158.
(83) The solution 12 to be concentrated enters at the flow passages 16 of the crystallization apparatus 10 into the heat exchanger 158 at the point B. With the aid of the cooling flow 162 the solution 12 to be concentrated is cooled on the passage through the heat exchanger 158. Subsequently, the cooled solution 12 to be concentrated is supplied to the flow passages 18 of the crystallization apparatus 10 at the point B.
(84) The continuous cooling of the solution 12 to be concentrated taking place in the heat exchanger 158 reduces the solubility of most of the dissolved materials and a further crystallization takes place. The thus generated crystals sediment into the sediment collection containers 22 formed from the sediment collection regions 108 of the frame elements 130 and 140.
(85) The solvent collected in the flow passages 44 of the crystallization apparatus 10 can be conducted away via the openings 132 in the frame elements 130 and 140 and exits the system at the points 164 and 166.
(86) As an alternative to the vapor-permeable but liquid-tight membrane wall 20, an ion-selective membrane wall can be used in the above-described crystallization apparatuses 10 at whose one side a draw solution having a high concentration and in this way a high osmotic pressure is present instead of the liquid 14 and at whose other side the solution 12 to be concentrated is present having a reduced concentration and a reduced osmotic pressure. Due to the concentration differences and the in this way associated osmotic pressure difference the solvent passes through the ion-selective membrane wall into the draw solution. The ions of the material to be crystallized are retained by the membrane wall and the desired concentration of the solution arises.
(87) It should be noted that, during the forwards osmosis, the flow passage 18 conducting the draw solution is always directly adjacent to the ion-selective membrane wall of the flow passage 16 conducting the solution 12 to be concentrated. Consequently, the forwards osmosis can only be realized using the crystallization apparatuses 10 shown in the
LIST OF REFERENCE NUMERALS
(88) 10 crystallization apparatus 12 solution to be concentrated 14 liquid 16 flow passage 18 flow passage 20 membrane wall 22 sediment collection container 30 stage 32 stage 34 stage 36 stage 38 stage 40 stage 42 stage 44 flow passage 46 wall 50 stage 52 stage 54 stage 56 heat exchanger 58 heat exchanger 60 heat exchanger 62 flow 64 flow 66 flow 70 stage 72 stage 74 heat exchanger 76 heat exchanger 78 position 80 position 82 flow 84 flow 86 heating flow 88 cooling flow 100 frame element 102 distribution passage 104 collection passage 106 central internal region 108 sediment collection region 109 welded web structure 110 opening 112 opening 114 opening 116 opening 120 frame element 122 inlet 124 outlet 130 frame element 132 opening 140 frame element 142 film 150 stage 152 stage 154 heat exchanger 158 heat exchanger 160 heating flow 162 cooling flow 164 point 166 point