Patent Grant
10512883
The present application claims priority under 35 USC § 119 to German application, DE 10 2016 210 478.0, filed on Jun. 14, 2016, the contents of which is incorporated herein by reference in its entirety.
The invention relates to a process for dehumidifying a moist gas mixture. The invention further relates to an apparatus for dehumidifying a moist gas mixture and to the use of said apparatus in the process according to the invention.
Dehumidification of moist gas mixtures is necessary in a multitude of technical fields. For instance ventilation and air conditioning of buildings or vehicles generally necessitates not only cooling but also dehumidification of the air since the air to be cooled is often so humid that during cooling to the desired temperature the temperature falls below the dew point temperature. Hence in conventional air conditioning systems dehumidification of the air accounts for a large part of the electricity consumption.
The electricity consumption of air conditioning systems for buildings is reduced by dehumidifying the air by adsorption or absorption of water with a drying medium and subsequently regenerating the water-laden drying medium by heating to a temperature at which the water is desorbed again. Compared to adsorption on a solid absorbent, the advantage of absorption in a liquid absorption medium is that drying of air can be performed with reduced equipment complexity and with less drying medium and that regeneration of the water-laden drying medium using solar heat is easier to carry out.
A further technical field where dehumidifying of moist gas mixtures is employed is the field of absorption chillers (principle described in WO 2014/079675 A1; according to the invention “absorption chiller” is used synonymously with “absorption heat pump”) Here, the damp gas mixture is formed during evaporation of water under low pressure. The water vapour thus formed needs to be removed from the moist gas mixture so that said mixture may then be returned to the water evaporation to pass through a new cycle. Here too, absorption in a liquid absorption medium is favoured over adsorption on a solid adsorption medium.
Finally, dehumidification of moist gas mixtures is also important in the field of natural gas extraction, as described in DE 10 2010 004 779 A1 for example.
Examples of materials incorporated in air or natural gas dehumidifying plants and in chillers include titanium, copper and noble metals. Components based on aluminium too are installed in air dehumidifying plants. Compared to alternative materials such as titanium, copper or stainless steel, aluminium has the advantage that it has a higher thermal conductivity. It is additionally easier to process, lighter and cheaper. Hence in automobile manufacture in particular air conditioning systems made of aluminium are preferred over other materials.
The aqueous solutions of lithium bromide, lithium chloride or calcium chloride hitherto employed as liquid absorption media in commercial air conditioning systems have the disadvantage that they are corrosive towards the materials of construction typically employed in air conditioning systems and that they thus necessitate the use of expensive specific materials of construction. This problem is encountered particularly for aluminium. These solutions can additionally cause problems due to salt crystallizing out of the absorption medium.
Y. Luo et al., Appl. Thermal Eng. 31 (2011) 2772-2777 proposes using the ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate in place of an aqueous solution of lithium bromide for drying of air. However, this ionic liquid has the disadvantage of only poor absorption capability. Y. Luo et al., Solar Energy 86 (2012) 2718-2724 proposes using the ionic liquids 1,3-dimethyimidazolium acetate as an alternative to 1-ethyl-3-methylimidazolium tetrafluoroborate for drying of air. However, 1,3-dimethyimidazolium acetate is not stable and decomposes to a not inconsiderable extent during desorption.
This problem is also encountered for the ionic liquids proposed in US 2011/0247494 A1, paragraph [0145]. This document proposes using trimethylammonium acetate or 1-ethyl-3-methylimidazolium acetate as liquid drying agent in place of aqueous lithium chloride solution. Example 3 compares water uptake from moist air for a series of further ionic liquids. CN 102335545 A describes aqueous solutions of ionic liquids that do not suffer from the abovementioned problems as absorption media for air dehumidification. The absorption media are reported to be noncorossive toward steel. Ionic liquids described are, inter alia, 1,3-dimethyimidazolium dimethylphosphate, 1-ethyl-3-methylimidazolium dimethylphosphate and 1-butyl-3-methylimidazolium dimethylphosphate. However, CN 102335545 A is chiefly concerned with steel-based air dehumidifiers. Yet this material is disadvantageous compared to aluminium for the abovementioned reasons. Additionally the heat transfer achieved with the ionic liquids cited in CN 102335545 A, which is important for efficient air dehumidification, was relatively low.
Yet, heat transfer is an important parameter which must be accounted for when choosing absorption media. Thus, in the field of air dehumidification absorption media which ensure a particularly good heat transfer between themselves and further constituents of an air dehumidifier are particularly readily employable. In air dehumidifiers in which metallic components (for example aluminium) are employed this heat transfer takes place at least partially between the absorption media and metallic surfaces.
The present invention accordingly has for its object to provide absorption media that ensure improved heat transfer compared with prior art absorption media when used in aluminium-based air conditioning systems, air dehumidifiers, absorption chillers etc.
Absorption media have now been found which, surprisingly, fulfil this object.
The present invention accordingly relates in a first aspect to a process for dehumidifying a moist gas mixture G, in particular moist air, in an apparatus V1, comprising the steps of:
wherein the apparatus V1 at least partially comprises a surface made of an aluminium material of construction OA1 and in the apparatus V1 at least one of the liquid absorption media selected from the group consisting of AVE, AVE1, AVE2 contacts the surface made of an aluminium material of construction OA1 via at least one contact surface,
characterized in that
Q+ is a dialkylimidazolium cation in which, in particular, the alkyl groups each independently of one another have 1 to 10 carbon atoms,
wherein A− is an anion selected from the group consisting of R*COO−, R′SO3−, HSO4−, R″SO4−, wherein R*, R′, R″, RA, RB, RC, are each independently of one another an alkyl group, in particular having 1 to 10 carbon atoms,
wherein R1, R2, R3 are each independently of one another an alkyl group, in particular having 1 to 10 carbon atoms,
and wherein M+ is an alkali metal ion, preferably Li+, K+ or Na+ more preferably K+ or Na+.
The gas mixture G is not particularly restricted.
“Moist” is to be understood as meaning in the context of the invention “comprising water, in particular water vapour”.
“Dehumidifying” is to be understood as meaning at least partially removing water.
“At least partially” is to be understood as meaning in the context of the invention “partially or completely”.
“Moist gas mixture G” is accordingly to be understood as meaning in the context of the invention that the gas mixture G comprises water, preferably water vapour (“water vapour” is to be understood as meaning water in the gaseous physical state), and that its composition is otherwise not particularly restricted. The water content of this moist gas mixture is not particularly restricted and is in particular from 0.01 vol % to 99.99 vol % (“vol %” indicates the volume of water vapour based on the overall volume of moist gas mixture G). The composition of the moist gas G may otherwise vary depending on the application of the process according to the invention. The moist gas mixture G is in particular selected from moist natural gas, moist air (this may be moist indoor air or the moist air resulting from evaporation of water in absorption chillers), preferably moist air. For moist natural gas the water content is in particular from 0.01 vol % to 15.00 vol %, for moist air said content is in particular from 0.01 vol % to 15.00 vol % in the case of moist indoor air or in particular from 95.00 vol % to 99.99 vol % which is the preferred range when moist air resulting from evaporation of water in absorption chillers is concerned.
The process according to the invention is carried out in an apparatus V1 which at least partially comprises a surface made of an aluminium material of construction OA1 (in the context of the invention OA1 is short for “surface made of an aluminium material of construction”) and in which at least one of the liquid absorption media selected from the group consisting of AVE, AVE1, AVE2 contacts the surface made of an aluminium material of construction OA1 via at least one contact surface.
It is in particular possible to employ an apparatus V1 having the following components:
The water absorption unit Wabs1 is the component in which step a) of the process according to the a invention in particular is carried out. Employable as water absorption unit Wabs1 are in particular the water absorbers known to those skilled in the art. Said absorbers are based on the principle of increasing the surface area of the liquid absorption medium AVE and simultaneously achieving the longest possible residence time of the liquid absorption medium AVE in the water absorber during absorption of water. It is in particular possible here to employ water absorbers selected from the group of: packed beds, spray columns, falling-films, bubble columns, tray columns, wet scrubbers (for example Venturi scrubbers), stirred tanks and combinations of these absorbers. It is particularly preferable to employ as water absorbers falling-films, in particular shell and tube falling-films. The water absorption unit Wabs1 may in particular also comprise an additional heat exchanger Wz1 set up such that the liquid absorption medium AVE is coolable.
The water desorption unit Wdes1 which comprises a heat exchanger Wx1 is the unit in which step b) of the process according to the invention in particular is carried out. The water desorption unit Wdes1 is based on the principle of supplying heat to the water-laden liquid absorption medium AVE (in particular AVE1), increasing the surface area of the water-laden liquid absorption medium AVE (in particular AVE1) and simultaneously achieving the longest possible residence time of the water-laden liquid absorption medium AVE (in particular AVE1) in the water desorption unit.
Employable as water desorption unit Wdes1 comprising a heat exchanger Wx1 are in particular the combinations of heat exchanger and water desorber known to those skilled in the art, in particular horizontal tube evaporators having an upstream heat exchanger, in particular shell and tube heat exchangers, plate and frame heat exchangers. In addition the water desorption unit Wdes1 comprising a heat exchanger Wx1 may also be a water desorber having an integrated heat exchanger. Such water desorbers having an integrated heat exchanger are in particular climbing film evaporators, long tube vertical evaporators, short tube vertical evaporators, forced circulation evaporators, agitated thin film evaporators. It is particularly preferable to employ as water desorption unit Wdes1 falling-films, in particular shell and tube falling-films.
Circuit U1 in particular passes AVE1 from step a) of the process according to the invention from the water absorption unit Wabs1 to the water desorption unit Wdes1 and more preferably—in particular when the process according to the invention is carried out in continuous fashion—additionally passes AVE2 from step b) of the process according to the invention from the water absorption unit Wdes1 to the water desorption unit Wabs1
The circuit U1 is in particular a conduit, in particular selected from the group consisting of tube, hose.
In a further preferred embodiment the circuit U1 also comprises a pump.
A first step of the process according to the invention comprises contacting the moist gas mixture G with a liquid absorption medium AVE comprising a mixture of at least one trialkyl phosphate of the structure (I)
and at least one salt S selected from the group consisting of Q+A−, Q+(R1O)2PO2−, (Q+)2R2OPO32−, Q+M+R3OPO32−. The contacting may be effected in any way known to those skilled in the art, in particular in a water absorption unit Wabs1. The contacting causes the absorption medium AVE to at least partially absorb moisture, i.e. water, from the moist gas stream G to afford a liquid absorption medium AVE1 having an elevated water content compared to the liquid absorption medium AVE and a gas mixture G1 having a relatively low water content compared to the moist gas mixture G.
It is preferable to cool the absorption medium AVE during contacting of the moist gas mixture G in order that as much moisture as possible is absorbed from the moist gas mixture G. This may be achieved, for example, via an additional heat exchanger Wz1 in the water absorption unit Wabs1. The temperature of the absorption medium AVE during contacting of the moist gas mixture G is thus preferably in the range of from 2° C. to 100° C., preferably from 3° C. to 80° C., more preferably from 4° C. to 50° C., most preferably from 5° C. to 30° C.
The absorption medium AVE comprises a mixture of at least one trialkyl phosphate of the structure (I)
and at least one salt S selected from the group consisting of Q+A−, Q+(R1O)2PO2−, (Q+)2R2OPO32−, Q+M+R3OPO32−,
wherein Q+ is a 1,3-dialkylimidazolium cation in which in particular the alkyl groups each independently of one another have 1 to 10 carbon atoms,
wherein A− is an anion selected from the group consisting of R*COO−, R′SO3−, HSO4−, R″SO4−, wherein R*, R′, R″, RA, RB, RC, are each independently of one another an alkyl group, in particular having 1 to 10 carbon atoms,
wherein R1, R2, R3 are each independently of one another an alkyl group, in particular having 1 to 10 carbon atoms,
and wherein M+ is an alkali metal ion, preferably Li+, K+ or Na+, yet more preferably K+ or Na+.
In a preferred embodiment of the process according to the invention the salt S is selected from the group consisting of Q+A−, Q+(R1O)2PO2−, and Q+ is a dialkylimidazolium cation in which the alkyl groups each independently of one another have 1 to 6, preferably 1 or 4, more preferably 1 or 2 carbon atoms, and A− is an anion selected from the group consisting of R*COO−, R′SO3−, R″SO4−, wherein R*, R1, R′, R″, RA, RB, RC are each independently of one another an alkyl group having 1 to 6, preferably 1 to 4, more preferably 1 or 2, carbon atoms.
In a more preferred embodiment of the process according to the invention, the salt S has the general formula Q+(R1O)2PO2−, and Q+ is a dialkylimidazolium cation in which the alkyl groups are each independently of one another methyl or ethyl, and R1, RA, RB, RC are each independently of one another methyl or ethyl.
In a yet more preferred embodiment of the process according to the invention, the salt S has the general formula Q+(R1O)2PO2−, and Q+ is selected from the group consisting of 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium; RA, RB, RC, R1 is methyl or ethyl.
It is moreover particularly preferable in all of the aforementioned embodiments of the process according to the invention when RA, RB, RC are independently of one another selected from methyl, ethyl; yet more preferably RA=RB=RC=methyl or RA=RB=RC=ethyl; particularly preferably RA=RB=RC=ethyl.
This is because it has now been found that, surprisingly, imidazolium salts with at least one ethyl group have a particularly small contact angle and thus ensure particularly good surface wetting. This results in a relatively large contact area, thus also in fewer nonwetted spaces and thus in improved heat transfer inside the apparatus V1 and thus also in a particularly efficient process.
The liquid absorption medium AVE may, in the process according to the invention, be employed in the form of the pure mixture of the trialkyl phosphates of the structure (I) and the salts S.
Alternatively and more preferably in the process according to the invention, the liquid absorption medium AVE is an aqueous solution in which, in particular, the total weight of all trialkyl phosphates of structure (I) and all salts S is in the range from 65 wt % to 95 wt % based on the total weight of the aqueous solution. It is yet more preferable when the total weight of all trialkyl phosphates of structure (I) and all salts S in AVE is in the range from 70 wt % to 90 wt % based on the total weight of the aqueous solution, yet more preferably in the range from 75 wt % to 87 wt %.
In the process according to the invention the ratio of all trialkyl phosphates of structure (I) to the salts S in the absorption medium AVE is not further restricted. However, it is preferable to employ in the process according to the invention an absorption medium AVE in which the ratio of the total weight of all trialkyl phosphates of structure (I) to the total weight of all salts S is in the range 1:9999 to 1:9, more preferably 1:9999 to 1:99, yet more preferably 1:9999 to 1:999.
The gas mixture G1 obtained in the first step of the process according to the invention and having a relatively low water content compared to the moist gas mixture G then represents the dehumidified gas stream which, depending on the application, can be returned to living or working spaces in the form of dehumidified air or in the case of natural gas can be supplied to power generation.
The absorption medium AVE1 obtained in the first step of the process according to the invention has an elevated water content compared to the liquid absorption medium AVE. It will be appreciated that AVE1, in terms of the trialkyl phosphates of structure (I) comprised in it and of the salts S comprised in it, is identical to AVE and is preferably distinguished therefrom only by the water content.
A second step of the process according to the invention comprises at least partially removing water from the liquid absorption medium AVE1 to obtain a liquid absorption medium AVE2 having a relatively low water content compared to the liquid absorption medium AVE1. This additionally comprises supplying heat in particular to the liquid absorption medium AVE1. The supply of heat and the at least partial removal may be effected in any way known to those skilled in the art, in particular in a water desorption unit Wdes1 comprising a heat exchanger Wx1. The at least partial removal of water from the liquid absorption medium AVE1 affords a liquid absorption medium AVE2 having a relatively low water content compared to the liquid absorption medium AVE1.
It will be appreciated that the liquid absorption medium AVE2, in terms of the trialkyl phosphates of structure (I) comprised in it and of the salts S comprised in it, is identical to AVE1 and is preferably distinguished therefrom only by the water content.
An essential feature of the process according to the invention is that the apparatus V1 at least partially comprises a surface made of an aluminium material of construction OA1 (in the context of the invention OA1 is an abbreviation for “surface made of an aluminium material of construction”).
An aluminium material of construction in the context of the present invention is to be understood as meaning both unalloyed aluminium and aluminium alloys where in particular the mass fraction of aluminium is greater than the mass fraction of every other element. The aluminium material of construction is preferably unalloyed aluminium.
Unalloyed aluminium is in particular aluminium having a purity of >80 wt %, more preferably >85 wt %, yet more preferably >90 wt %, yet still more preferably >95 wt %, yet still more preferably >98 wt %. It is in particular highest purity aluminium having a purity of >99.0 wt %, more preferably >99.5 wt %, more preferably >99.9 wt %.
Aluminium alloys comprise in addition to the aluminium in particular at least one alloying metal selected from the group consisting of magnesium, manganese, silicon, zinc, lead, copper, titanium, iron, more preferably selected from the group consisting of magnesium, manganese, silicon, zinc, lead, copper, titanium. The aluminium material of construction may then in particular be in the form of a wrought alloy or of a cast alloy.
A further essential feature of the process according to the invention is that in the apparatus V1 at least one of the liquid absorption media selected from the group consisting of AVE, AVE1, AVE2 contacts the surface made of an aluminium material of construction OA1 via at least one contact surface. This is to be understood as meaning that at this contact surface the liquid absorption medium AVE in question, AVE1 or AVE2, is in direct contact with the surface made of an aluminium material of construction OA1. In the context of the present invention “in direct contact” is to be understood as meaning “wetting”. It will be appreciated that the liquid absorption medium selected from the group consisting of AVE, AVE1, AVE2 and the aluminium comprised in the contact surface are thus in direct contact. The aluminium comprised in the contact surface is not particularly restricted and is in particular selected from the group consisting of elemental aluminium or aluminium compounds such as in particular passivated aluminium (where passivated aluminium is to be understood as meaning in particular aluminium oxide).
In the embodiment according to the invention in which an apparatus V1 is employed and comprises the following components:
the contact surface at which the liquid absorption medium selected from the group consisting of AVE, AVE1, AVE2 contacts the surface made of an aluminium material of construction OA1, is disposed in particular in at least one of the components selected from the group water absorption unit Wabs1, water desorption unit Wdes1, circuit U1, preferably in at least one of the components selected from the group water absorption unit Wabs1, water desorption unit Wdes1.
This is because it has now been found that, surprisingly, the mixtures of at least one trialkyl phosphate of structure (I) and at least one salt S according to the invention show particularly good wetting of aluminium materials of construction, thus ensure particularly good heat transfer and are thus particularly suitable as liquid absorption media in the apparatus V1 having a surface made of an aluminium material of construction OA1, in which one of the absorption media selected from the group consisting of AVE, AVE1, AVE2 is in direct contact with the surface made of an aluminium material of construction OA1.
In a further preferred embodiment the process according to the invention is carried out in continuous fashion. This is to be understood as meaning in particular that following step b) the steps a) and b) are performed at least one more time and that the liquid absorption medium AVE employed in the steps a) additionally performed in each case is at least partially the liquid absorption medium AVE2 obtained from the step b) performed immediately beforehand, i.e. in particular the water content of the liquid absorption medium AVE employed in the step a) additionally performed in each case and of the liquid absorption medium AVE2 from the immediately preceding step b) is identical.
It is more preferable when this embodiment comprises heating liquid absorption medium AVE1 with heat from liquid absorption medium AVE2. This may be carried out in an additional heat exchanger Wy1, in particular selected from the group consisting of shell and tube heat exchangers and plate and frame heat exchangers. This makes it possible to carry out the process according to the invention in a particularly energy efficient fashion.
The invention also relates in a further aspect to an apparatus V2 for dehumidifying a moist gas mixture, in particular moist air, comprising the components:
The apparatus according to the invention V2 is suitable for dehumidifying a moist gas mixture, in particular moist air. Said apparatus comprises the following components:
As a first component the apparatus V2 according to the invention comprises a liquid absorption medium AVO which comprises a mixture of at least one trialkyl phosphate of structure (I)
and at least one salt S selected from the group consisting of Q+A−, Q+(R1O)2PO2−, (Q+)2R2OPO32−, Q+M+R3OPO32−, Q+ is a dialkylimidazolium cation in which in particular the alkyl groups each independently of one another have 1 to 10 carbon atoms,
wherein A− is an anion selected from the group consisting of R*COO−, R′SO3−, HSO4−, R″SO4−, wherein R*, R′, R″, RA, RB, RC, are each independently of one another an alkyl group, in particular having 1 to 10 carbon atoms,
wherein R1, R2, R3 are each independently of one another an alkyl group, in particular having 1 to 10 carbon atoms,
and wherein M+ is an alkali metal ion, preferably Li+, K+ or Na+, yet more preferably K+ or Nat
In a preferred embodiment of the apparatus V2 according to the invention in the absorption medium AVO, the salt S is selected from the group consisting of Q+A−, Q+(R1O)2PO2−, and Q+ is a dialkylimidazolium cation in which the alkyl groups each independently of one another have 1 to 6, preferably 1 or 4, more preferably 1 or 2 carbon atoms, and A− is an anion selected from the group consisting of R*COO−, R′SO3−, R″SO4−, wherein R*, R1, R′, R″, RA, RB, RC are each independently of one another an alkyl group having 1 to 6, preferably 1 to 4, more preferably 1 or 2, carbon atoms.
In a more preferred embodiment of the apparatus V2 according to the invention in the absorption medium AVO the salt S has the general formula Q+(R1O)2PO2−, and Q+ is a dialkylimidazolium cation in which the alkyl groups are each independently of one another methyl or ethyl, and R1, RA, RB, RC are each independently of one another methyl or ethyl.
In a yet more preferred embodiment of the apparatus V2 according to the invention in the absorption medium AVO the salt S has the general formula Q+(R1O)2PO2−, and Q+ is selected from the group consisting of 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium; RA, RB, RC, R1 is methyl or ethyl.
It is moreover particularly preferable in all of the aforementioned embodiments of the apparatus V2 according to the invention when in the absorption medium AVO RA, RB, RC are independently of one another selected from methyl, ethyl; yet more preferably RA=RB=RC=methyl or RA=RB=RC=ethyl; particularly preferably RA=RB=RC=ethyl.
This is because it has now been found that, surprisingly, imidazolium salts where R=ethyl group have a particularly small contact angle and thus ensure particularly good surface wetting. This results in a relatively large contact area, thus also in fewer nonwetted spaces and thus in improved heat transfer inside the apparatus V2.
The liquid absorption medium AVE may be employed in the apparatus V2 according to the invention in the form of the pure mixture of the trialkyl phosphates of the structure (I) and the salts S.
Alternatively, and more preferably, in the apparatus V2 according to the invention the liquid absorption medium AVO is an aqueous solution in which, in particular, the total weight of all trialkyl phosphates of structure (I) and all salts S is in the range from 65 wt % to 95 wt % based on the total weight of the aqueous solution.
It is yet more preferable when the total weight of all trialkyl phosphates of structure (I) and all salts S in AVO is in the range 70 wt % to 90 wt % based on the total weight of the aqueous solution, yet more preferably in the range 75 wt % to 87 wt %.
In the apparatus V2 according to the invention the ratio of all trialkyl phosphates of structure (I) to the salts S in the absorption medium AVO is not further restricted. However, it is preferable to employ in the apparatus V2 according to the invention an absorption medium AVO in which the ratio of the total weight of all trialkyl phosphates of structure (I) to the total weight of all salts S is in the range 1:9999 to 1:9, more preferably 1:9999 to 1:99, yet more preferably 1:9999 to 1:999.
As a second component the apparatus V2 according to the invention comprises a water absorption unit Wabs2 set up for contacting the moist gas mixture with the liquid absorption medium AVO. The water absorption unit Wabs2 may in particular comprise an additional heat exchanger Wz2 set up such that the liquid absorption medium AVO is coolable. Employable as such a water absorption unit Wabs2 are in particular the water absorbers known to those skilled in the art. Said absorbers are based on the principle of increasing the surface area of the liquid absorption medium AVO and simultaneously achieving the longest possible residence time of the liquid absorption medium AVO in the water absorber during absorption of water. It is in particular possible here to employ water absorbers selected from the group of: packed beds, spray columns, falling-films, bubble columns, tray columns, wet scrubbers (for example Venturi scrubbers), stirred tanks and combinations of these absorbers. It is particularly preferable to employ as water absorbers falling-films, in particular shell and tube falling-films.
As a third component the apparatus V2 according to the invention comprises a water desorption unit Wdes2 which comprises a heat exchanger Wx2 and is set up for at least partially removing water from the liquid absorption medium AVO. Employable therefor are in particular the combinations of heat exchanger and water desorber known to those skilled in the art. The water desorption unit Wdes2 is based on the principle of supplying heat to the liquid absorption medium AVO, increasing the surface area of the liquid absorption medium AVO and simultaneously achieving the longest possible residence time of the liquid absorption medium AVO in the water desorption unit.
Employable as water desorption unit Wdes2 comprising a heat exchanger Wx1 are in particular the combinations of heat exchanger and water desorber known to those skilled in the art, in particular horizontal tube evaporators having an upstream heat exchanger, in particular shell and tube heat exchangers, plate and frame heat exchangers. In addition the water desorption unit Wdes2 comprising a heat exchanger Wx2 may also be a water desorber having an integrated heat exchanger. Such water desorbers having an integrated heat exchanger are in particular climbing film evaporators, long tube vertical evaporators, short tube vertical evaporators, forced circulation evaporators, agitated thin film evaporators. It is particularly preferable to employ as water desorption unit Wdes2 falling-films, in particular shell and tube falling-films.
As a fourth component the apparatus V2 according to the invention comprises a circuit U2 which connects the water absorption unit Wabs2 with the water desorption unit Wdes2 and by means of which the liquid absorption medium AVO may be circulated. The circuit U2 is preferably a conduit, more preferably selected from the group consisting of tube, hose. In a further preferred embodiment the circuit U2 also comprises a pump.
An essential feature of the apparatus V2 according to the invention is that said apparatus at least partially comprises a surface made of an aluminium material of construction OA1 (in the context of the invention OA1 is an abbreviation for “surface made of an aluminium material of construction”).
An aluminium material of construction in the context of the present invention is to be understood as meaning both unalloyed aluminium and aluminium alloys where in particular the mass fraction of aluminium is greater than the mass fraction of every other element. The aluminium material of construction is preferably unalloyed aluminium.
Unalloyed aluminium is in particular highest purity aluminium having a purity of >99.0 wt %, more preferably >99.9 wt %.
Aluminium alloys comprise in addition to the aluminium in particular at least one alloying metal selected from the group consisting of magnesium, manganese, silicon, zinc, lead, copper, titanium, iron, more preferably selected from the group consisting of magnesium, manganese, silicon, zinc, lead, copper, titanium. The aluminium material of construction may then in particular be in the form of a wrought alloy or of a cast alloy.
A further essential feature of the apparatus V2 according to the invention is that disposed in said apparatus is a contact surface at which the liquid absorption medium AVO contacts the surface made of an aluminium material of construction OA1. This is to be understood as meaning that at this contact surface the liquid absorption medium AVO is in direct contact with the surface made of an aluminium material of construction OA1. In the context of the present invention “in direct contact” is to be understood as meaning “wetting”. It will be appreciated that the liquid absorption medium AVO and the aluminium comprised in the contact surface are thus in direct contact. The aluminium comprised in the contact surface is not particularly restricted and is in particular selected from the group consisting of elemental aluminium or aluminium compounds such as in particular passivated aluminium (where passivated aluminium is to be understood as meaning in particular aluminium oxide).
In a preferred embodiment the apparatus V2 comprises a further heat exchanger Wy2 (additional to the heat exchanger Wx2 comprised in the water desorption unit Wdes2). The heat exchanger Wy2 is set up such that liquid absorption medium AVO sent from the water absorption unit Wabs2 to the water desorption unit Wdes2 is suppliable with heat from liquid absorption medium AVO, said medium being conducted away from the water desorption unit Wdes2. This can be ensured by employing as heat exchanger Wy2 in particular a heat exchanger selected from shell and tube heat exchangers, plate and frame heat exchangers.
In a further preferred embodiment the apparatus V2 is part of an absorption heat pump. This absorption heat pump then comprises as further components a condenser, an evaporator and a coolant, wherein the coolant is water.
The condenser is in particular connected to the water desorption unit Wdes2 via a conduit and is set up for condensing water at least partially removed from the liquid absorption medium AVO in the water desorption unit Wdes2. The condenser preferably also comprises a cooling water circuit.
The evaporator is in particular connected to the condenser via a conduit (which may comprise a throttling means) and connected to the water absorption unit Wabs2 via a further conduit and is set up for evaporating condensed water from the condenser. The evaporator preferably also comprises a pressure of <1 bar, more preferably <0.1 bar, to permit evaporation of the condensed water at the lowest possible temperatures. The evaporator may further preferably additionally comprise an apparatus from which heat may be drawn and so that the condensed water may be evaporated (for example a coolant conduit in which coolant is passed into the space in which water is evaporated).
The
The apparatus V2 shown in
Apparatus V1 corresponds to apparatus V2 without absorption medium AVO, wherein in the figure description for
The process according to the invention will now be illustratively described with reference to apparatus V1 using
A stream of moist gas mixture G (said stream may be moist air, moist natural gas or moist gas mixture originating from the evaporator of an absorption chiller—see also
The absorption chiller shown in
In an embodiment of the process according to the invention (described hereinbelow with reference to apparatus V1 using
The examples which follow are intended to elucidate the present invention without limiting said invention in any way.
Inventive examples I1 to 16 and the comparative examples C1 and C2 were carried out. In tests C1, I1-I3 anhydrous solutions were employed. In tests C2, I4-I6 aqueous solutions were employed.
1. Chemicals Employed
EMIM DEP (=ethylmethylimidazolium diethylphosphate) was obtained from Iolitec.
TEP (=triethyl phosphate) was obtained from Sigma Aldrich.
2. Test Procedure
3 drops of the respective solution were dropped onto an aluminium plate (highest purity aluminium, purity >99.0%) having dimensions of 3 cm×7 cm and a maximum thickness of 3 mm. The contact angle determination was carried out according to SOP 1827. The results are shown in the table which follows.
C1 is the comparative test with pure EMIM DEP while in the tests I1, I2 and I3 mixtures of EMIM DEP and 10 wt %, 1 wt % and 0.1 wt % of TEP respectively (the wt % values are based on the total weight of the mixture) were analyzed.
C2 is the comparative test with a mixture of EMIM DEP and 10 wt % of water while in the tests I4, I5 and I6 mixtures of EMIM DEP and 10 wt % of water and 10 wt %, 1 wt % and 0.1 wt % of TEP respectively (the wt % values are based on the total weight of the mixture) were analyzed.
3. Results
The results show that the absorption media according to the invention (I1-I3, I4-I6) exhibit a small contact angle to the aluminium-containing surface compared to those of the prior art (C1, C2) and thus ensure good heat conduction in the process according to the invention/for the apparatus according to the invention. The use of imidazolium salts in combination with trialkyl phosphate (in this case triethylphosphate) accordingly surprisingly achieves better wetting of the aluminium-containing surface and thus greater and more efficient heat exchange.
All references cited herein are fully incorporated by reference. Having now fully described the invention, it will be understood by those of skill in the art that the invention may be practiced within a wide and equivalent range of conditions, parameters and the like, without affecting the spirit or scope of the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2016 210 478 | Jun 2016 | DE | national |
| Number | Name | Date | Kind |
|---|---|---|---|
| 1882258 | Randel | Oct 1932 | A |
| 2516625 | Haury | Jul 1950 | A |
| 2601673 | McMillan et al. | Jun 1952 | A |
| 2802344 | Witherell | Aug 1957 | A |
| 3276217 | Bourne et al. | Oct 1966 | A |
| 3317654 | Yonkers | May 1967 | A |
| 3580759 | Albertson et al. | May 1971 | A |
| 3609087 | Chi et al. | Sep 1971 | A |
| 3927151 | Ishmail | Dec 1975 | A |
| 4046719 | Stanaback | Sep 1977 | A |
| 4079263 | Inoue | Mar 1978 | A |
| 4094957 | Sartori et al. | Jun 1978 | A |
| 4106904 | Oude Alink et al. | Aug 1978 | A |
| 4112051 | Sartori et al. | Sep 1978 | A |
| 4152900 | Chopra et al. | May 1979 | A |
| 4152901 | Munters | May 1979 | A |
| 4201721 | Hallgren | May 1980 | A |
| 4217238 | Sartori et al. | Aug 1980 | A |
| 4251494 | Say | Feb 1981 | A |
| 4360363 | Ferrin et al. | Nov 1982 | A |
| 4405579 | Sartori et al. | Sep 1983 | A |
| 4405586 | Sartori et al. | Sep 1983 | A |
| 4466915 | Lai | Aug 1984 | A |
| 4489563 | Kalina | Dec 1984 | A |
| 4524587 | Kantor | Jun 1985 | A |
| 4525294 | Sartori et al. | Jun 1985 | A |
| 4605743 | Malz et al. | Aug 1986 | A |
| 4643000 | Rheinfelder | Feb 1987 | A |
| 4701530 | Swearingen et al. | Oct 1987 | A |
| 4714597 | Trevino | Dec 1987 | A |
| 4889938 | Kristen et al. | Dec 1989 | A |
| 4941324 | Peterson et al. | Jul 1990 | A |
| 5016445 | Wehr | May 1991 | A |
| 5126189 | Tanny et al. | Jun 1992 | A |
| 5186009 | Rockenfeller | Feb 1993 | A |
| 5186010 | Wehr | Feb 1993 | A |
| 5245070 | Nishikawa | Sep 1993 | A |
| 5255534 | Ryan | Oct 1993 | A |
| 5303565 | Pravada | Apr 1994 | A |
| 5390509 | Rockenfeller et al. | Feb 1995 | A |
| 5583270 | Nishiguchi | Dec 1996 | A |
| 5873260 | Linhardt et al. | Feb 1999 | A |
| 6117963 | Boinowitz et al. | Sep 2000 | A |
| 6128917 | Riesch et al. | Oct 2000 | A |
| 6130347 | Julius et al. | Oct 2000 | A |
| 6155057 | Angell et al. | Dec 2000 | A |
| 6165433 | Chakravarti et al. | Dec 2000 | A |
| 6184433 | Harada et al. | Feb 2001 | B1 |
| 6395948 | Hope et al. | May 2002 | B1 |
| 6423282 | Araki et al. | Jul 2002 | B1 |
| 6475370 | Lehmann et al. | Nov 2002 | B2 |
| 6672099 | Yoshimi et al. | Jan 2004 | B1 |
| 6680047 | Klaveness et al. | Jan 2004 | B2 |
| 6727015 | Putter et al. | Apr 2004 | B1 |
| 7419646 | Cadours et al. | Sep 2008 | B2 |
| 7435318 | Arlt et al. | Oct 2008 | B2 |
| 7638636 | Zhou et al. | Dec 2009 | B2 |
| 7666813 | Hoefer et al. | Feb 2010 | B2 |
| 7754053 | Maase | Jul 2010 | B2 |
| 7827820 | Weimer et al. | Nov 2010 | B2 |
| 7998714 | Gellett et al. | Aug 2011 | B2 |
| 8069687 | Jork et al. | Dec 2011 | B2 |
| 8167983 | Seiler et al. | May 2012 | B2 |
| 8277615 | Ruffert et al. | Oct 2012 | B2 |
| 8318117 | Lichtfers et al. | Nov 2012 | B2 |
| 8357344 | Bouillon et al. | Jan 2013 | B2 |
| 8362095 | Schwab et al. | Jan 2013 | B2 |
| 8382962 | Massonne et al. | Feb 2013 | B2 |
| 8470079 | Agar et al. | Jun 2013 | B2 |
| 8500867 | Seiler et al. | Aug 2013 | B2 |
| 8500892 | Seiler et al. | Aug 2013 | B2 |
| 8506839 | Shiflett et al. | Aug 2013 | B2 |
| 8523978 | Rojey et al. | Sep 2013 | B2 |
| 8603226 | Garcia Andarcia et al. | Dec 2013 | B2 |
| 8609572 | Earl et al. | Dec 2013 | B2 |
| 8623123 | Seiler et al. | Jan 2014 | B2 |
| 8664460 | Earle et al. | Mar 2014 | B2 |
| 8696928 | Seiler et al. | Apr 2014 | B2 |
| 8703451 | Haas et al. | Apr 2014 | B2 |
| 8715521 | Shiflett et al. | May 2014 | B2 |
| 8784537 | Seiler et al. | Jul 2014 | B2 |
| 8809576 | Schraven et al. | Aug 2014 | B2 |
| 8932478 | Seiler et al. | Jan 2015 | B2 |
| 9221007 | Rolker et al. | Dec 2015 | B2 |
| 9409122 | Qi et al. | Aug 2016 | B2 |
| 9630140 | Willy et al. | Apr 2017 | B2 |
| 9840473 | Wang et al. | Dec 2017 | B1 |
| 9878285 | Schraven et al. | Jan 2018 | B2 |
| 10105644 | Zehnacker et al. | Oct 2018 | B2 |
| 10138209 | Bahlmann et al. | Nov 2018 | B2 |
| 20020169071 | Sauvage et al. | Nov 2002 | A1 |
| 20020198100 | Mehnert et al. | Dec 2002 | A1 |
| 20030085156 | Schoonover | May 2003 | A1 |
| 20030106680 | Serpico | Jun 2003 | A1 |
| 20030118887 | Serpico | Jun 2003 | A1 |
| 20040016631 | Madkour | Jan 2004 | A1 |
| 20040133058 | Arlt et al. | Jul 2004 | A1 |
| 20050010076 | Wassercheid et al. | Jan 2005 | A1 |
| 20050070717 | Wasserscheid et al. | Mar 2005 | A1 |
| 20050129598 | Chinn | Jun 2005 | A1 |
| 20050164082 | Kishi et al. | Jul 2005 | A1 |
| 20050202967 | Hoefer et al. | Sep 2005 | A1 |
| 20050245769 | Kohler et al. | Nov 2005 | A1 |
| 20060070919 | Vallee et al. | Apr 2006 | A1 |
| 20060104877 | Cadours et al. | May 2006 | A1 |
| 20060128996 | Vaultier et al. | Jun 2006 | A1 |
| 20060150665 | Weimer et al. | Jul 2006 | A1 |
| 20060197053 | Shiflett et al. | Sep 2006 | A1 |
| 20060251961 | Olbert et al. | Nov 2006 | A1 |
| 20060264645 | Zhou et al. | Nov 2006 | A1 |
| 20070004903 | Hoff et al. | Jan 2007 | A1 |
| 20070095645 | Masse | May 2007 | A1 |
| 20070142685 | Elomari et al. | Jun 2007 | A1 |
| 20070144186 | Shiflett | Jun 2007 | A1 |
| 20070164462 | Liu et al. | Jul 2007 | A1 |
| 20070264180 | Carrette et al. | Nov 2007 | A1 |
| 20070286783 | Carrette et al. | Dec 2007 | A1 |
| 20080028777 | Boesmann et al. | Feb 2008 | A1 |
| 20080114105 | Hell et al. | May 2008 | A1 |
| 20080283383 | Ruffert et al. | Nov 2008 | A1 |
| 20080306319 | Earle et al. | Dec 2008 | A1 |
| 20090029121 | Hammermann et al. | Jan 2009 | A1 |
| 20090029887 | Schwab et al. | Jan 2009 | A1 |
| 20090036334 | Schwab et al. | Feb 2009 | A1 |
| 20090139232 | Collis | Jun 2009 | A1 |
| 20090170734 | Schwab et al. | Jul 2009 | A1 |
| 20090199709 | Rojey et al. | Aug 2009 | A1 |
| 20090211447 | Lichtfers et al. | Aug 2009 | A1 |
| 20090326228 | Vaultier et al. | Dec 2009 | A1 |
| 20100011958 | Cadours et al. | Jan 2010 | A1 |
| 20100016205 | Schwab | Jan 2010 | A1 |
| 20100029519 | Schwab et al. | Feb 2010 | A1 |
| 20100071557 | Seiler et al. | Mar 2010 | A1 |
| 20100084597 | Schwab et al. | Apr 2010 | A1 |
| 20100086983 | Gellett et al. | Apr 2010 | A1 |
| 20100095703 | Jork et al. | Apr 2010 | A1 |
| 20100104490 | Bouillon et al. | Apr 2010 | A1 |
| 20100132551 | Bouillon et al. | Jun 2010 | A1 |
| 20100186590 | Vorberg et al. | Jul 2010 | A1 |
| 20100192770 | Andarcia | Aug 2010 | A1 |
| 20100269528 | Gerhard et al. | Oct 2010 | A1 |
| 20100288126 | Agar et al. | Nov 2010 | A1 |
| 20100300870 | Massonne et al. | Dec 2010 | A1 |
| 20100324318 | Prakash et al. | Dec 2010 | A1 |
| 20100326126 | Seiler et al. | Dec 2010 | A1 |
| 20110000236 | Seiler et al. | Jan 2011 | A1 |
| 20110081287 | Bouillon et al. | Apr 2011 | A1 |
| 20110094381 | Lichtfers et al. | Apr 2011 | A1 |
| 20110118504 | Haas et al. | May 2011 | A1 |
| 20110135549 | Lichtfers et al. | Jun 2011 | A1 |
| 20110185901 | Jacquin et al. | Aug 2011 | A1 |
| 20110247494 | Dinnage | Oct 2011 | A1 |
| 20110256043 | Blair et al. | Oct 2011 | A1 |
| 20110309295 | Joh et al. | Dec 2011 | A1 |
| 20120011886 | Shiflett et al. | Jan 2012 | A1 |
| 20120017762 | Seiler et al. | Jan 2012 | A1 |
| 20120024756 | Verma et al. | Feb 2012 | A1 |
| 20120080644 | Seiler et al. | Apr 2012 | A1 |
| 20120117991 | Rached | May 2012 | A1 |
| 20120186993 | Huang et al. | Jul 2012 | A1 |
| 20120247144 | Seiler et al. | Oct 2012 | A1 |
| 20120308458 | Seiler et al. | Dec 2012 | A1 |
| 20120315366 | Zehnacher et al. | Dec 2012 | A1 |
| 20130011314 | Porcheron et al. | Jan 2013 | A1 |
| 20130023712 | Porcheron et al. | Jan 2013 | A1 |
| 20130026073 | Martinez Palou | Jan 2013 | A1 |
| 20130031930 | Seiler et al. | Feb 2013 | A1 |
| 20130031931 | Seiler et al. | Feb 2013 | A1 |
| 20130118350 | Rolker et al. | May 2013 | A1 |
| 20130133327 | Milam et al. | May 2013 | A1 |
| 20130219949 | Seiler et al. | Aug 2013 | A1 |
| 20130247758 | Seiler et al. | Sep 2013 | A1 |
| 20130255287 | Forkosh | Oct 2013 | A1 |
| 20130255496 | Zhang et al. | Oct 2013 | A1 |
| 20130263743 | Seiler et al. | Oct 2013 | A1 |
| 20130319022 | Becze et al. | Dec 2013 | A1 |
| 20130327084 | Shiflett et al. | Dec 2013 | A1 |
| 20140005344 | Rinker et al. | Jan 2014 | A1 |
| 20140079613 | Andarcia et al. | Mar 2014 | A1 |
| 20140090558 | Rolker | Apr 2014 | A1 |
| 20140091008 | Hardarce et al. | Apr 2014 | A1 |
| 20140105801 | Rolker et al. | Apr 2014 | A1 |
| 20140120016 | Rolker et al. | May 2014 | A1 |
| 20140127103 | Qi et al. | May 2014 | A1 |
| 20140356268 | Schraven | Dec 2014 | A1 |
| 20140360369 | Schraven et al. | Dec 2014 | A1 |
| 20150024106 | Huller et al. | Jan 2015 | A1 |
| 20150024247 | Lockett et al. | Jan 2015 | A1 |
| 20150125373 | Willy et al. | May 2015 | A1 |
| 20150141315 | Jin | May 2015 | A1 |
| 20150175738 | Willy et al. | Jun 2015 | A1 |
| 20150175740 | Willy et al. | Jun 2015 | A1 |
| 20150308720 | Zehnacker et al. | Oct 2015 | A1 |
| 20150321139 | Schraven et al. | Nov 2015 | A1 |
| 20160045857 | Rolker et al. | Feb 2016 | A1 |
| 20160115827 | Rached | Apr 2016 | A1 |
| 20160153318 | Busse et al. | Jun 2016 | A1 |
| 20160175766 | Zehnacker | Jun 2016 | A1 |
| 20170022447 | Atkins et al. | Jan 2017 | A1 |
| 20170107449 | Hruschka et al. | Apr 2017 | A1 |
| 20170354921 | Zehnacker et al. | Dec 2017 | A1 |
| 20170354922 | Zehnacker et al. | Dec 2017 | A1 |
| 20170354924 | Irfan et al. | Dec 2017 | A1 |
| 20170355680 | Wang et al. | Dec 2017 | A1 |
| 20170355681 | Bahlmann et al. | Dec 2017 | A1 |
| 20170355682 | Willy et al. | Dec 2017 | A1 |
| 20180134987 | Fedor et al. | May 2018 | A1 |
| 20180134988 | Fedor et al. | May 2018 | A1 |
| 20180148665 | Goodrich et al. | May 2018 | A1 |
| 20180169572 | Zehnacker | Jun 2018 | A1 |
| Number | Date | Country |
|---|---|---|
| 2 817 704 | May 2012 | CA |
| 1076380 | Sep 1993 | CN |
| 102335545 | Feb 2012 | CN |
| 102031202 | May 2012 | CN |
| 105061496 | Nov 2015 | CN |
| 400 488 | Aug 1924 | DE |
| 633 146 | Jul 1936 | DE |
| 737031 | Jul 1943 | DE |
| 36 23 680 | Jan 1988 | DE |
| 266 799 | Apr 1989 | DE |
| 195 11 709 | Oct 1996 | DE |
| 103 33 546 | Feb 2005 | DE |
| 10 2004 053 167 | May 2006 | DE |
| 10 2010 001 070 | Jul 2011 | DE |
| 10 2010 004 779 | Jul 2011 | DE |
| 10 2011 055 859 | Jun 2013 | DE |
| 10 2013 010 035 | Dec 2014 | DE |
| 10 2014 214 670 | Jan 2016 | DE |
| 10 2014 214 674 | Jan 2016 | DE |
| 10 2014 214 682 | Jan 2016 | DE |
| 10 2014 110190 | Jan 2016 | DE |
| 10 2015 212 749 | Jan 2017 | DE |
| 10 2016 210 481 | Jun 2017 | DE |
| 10 2016 204 928 | Sep 2017 | DE |
| 10 2016 204 929 | Sep 2017 | DE |
| 10 2016 204 930 | Sep 2017 | DE |
| 10 2016 204 931 | Sep 2017 | DE |
| 10 2016 204 932 | Sep 2017 | DE |
| 10 2016 204 937 | Sep 2017 | DE |
| 0 033 529 | Jan 1981 | EP |
| 0 047 967 | Sep 1981 | EP |
| 0 079 767 | May 1983 | EP |
| 0 187 130 | Jul 1986 | EP |
| 0 193 327 | Sep 1986 | EP |
| 0 302 020 | Feb 1989 | EP |
| 0 558 019 | Feb 1993 | EP |
| 0 791 643 | Aug 1997 | EP |
| 2 636 715 | Sep 2013 | EP |
| 2 940 394 | Nov 2015 | EP |
| 670 497 | Nov 1929 | FR |
| 2 861 084 | Apr 2005 | FR |
| 2 900 841 | Nov 2007 | FR |
| 1 306 853 | Feb 1973 | GB |
| 1 501 195 | Feb 1978 | GB |
| 2 047 681 | Dec 1980 | GB |
| 2 528 494 | Jan 2016 | GB |
| 33-009879 | Nov 1958 | JP |
| 57-191407 | Nov 1982 | JP |
| 61-129019 | Jun 1986 | JP |
| 62-73055 | Apr 1987 | JP |
| 1-134180 | May 1989 | JP |
| H01-198679 | Aug 1989 | JP |
| 2-298767 | Dec 1990 | JP |
| 4-268176 | Sep 1992 | JP |
| 6-307730 | Nov 1994 | JP |
| 7-167521 | Jul 1995 | JP |
| 09 313864 | Dec 1997 | JP |
| 2000-202299 | Jul 2000 | JP |
| 2001-219164 | Aug 2001 | JP |
| 2002-047258 | Feb 2002 | JP |
| 2004-44945 | Feb 2004 | JP |
| 2006-160969 | Jun 2006 | JP |
| 2006-239516 | Sep 2006 | JP |
| 2006-282525 | Oct 2006 | JP |
| 2010-034301 | Feb 2010 | JP |
| 2010-54136 | Mar 2010 | JP |
| 2013-051238 | Mar 2013 | JP |
| 2013-139425 | Jul 2013 | JP |
| 2013-250186 | Dec 2013 | JP |
| 2 101 625 | Jan 1998 | RU |
| 2 122 642 | Nov 1998 | RU |
| 2 183 003 | May 2002 | RU |
| WO 9313367 | Jul 1993 | WO |
| WO 0061698 | Oct 2000 | WO |
| WO 2002016671 | Feb 2002 | WO |
| WO 2004016631 | Feb 2004 | WO |
| WO 2004082809 | Sep 2004 | WO |
| WO 2006012097 | Feb 2006 | WO |
| WO 2006048182 | May 2006 | WO |
| WO 2007099041 | Sep 2007 | WO |
| WO 2007101397 | Sep 2007 | WO |
| WO 2007138307 | Dec 2007 | WO |
| WO 2009032959 | Mar 2009 | WO |
| WO 2009074535 | Jun 2009 | WO |
| WO 2009133059 | Nov 2009 | WO |
| WO 2010037109 | Apr 2010 | WO |
| WO 2010136783 | Dec 2010 | WO |
| WO 2011131552 | Oct 2011 | WO |
| WO 2012082093 | Jun 2012 | WO |
| WO 2012110987 | Aug 2012 | WO |
| WO 2012150051 | Nov 2012 | WO |
| WO 2013041300 | Mar 2013 | WO |
| WO 2013050230 | Apr 2013 | WO |
| WO 2013050242 | Apr 2013 | WO |
| WO 2013072147 | May 2013 | WO |
| WO 2015000637 | Jan 2015 | WO |
| WO 2015079262 | Jun 2015 | WO |
| WO 2016005769 | Jan 2016 | WO |
| WO 2016189330 | Dec 2016 | WO |
| WO 2016189333 | Dec 2016 | WO |
| WO 2017005538 | Jan 2017 | WO |
| Entry |
|---|
| “Mutual Solubility of Water and Pyridine Derivatives” by Richard M. Stephenson, J. Chem. Eng. Data 38, p. 428-431, (Jul. 1993). |
| “Review of Organic Functional Groups: Introduction to Medicinal Organic Chemistry” by Thomas L. Lemke, Lippincott Williams & Wilkins, p. 40 (2003). |
| “Review of Organic Functional Groups: Introduction to Medicinal Organic Chemistry” by Thomas L. Lemke, Lippincott Williams & Wilkins, p. 39 (2003). |
| Brennecke, et al., “Ionic Liquids: Innovative Fluids for Chemical Processing,” AIChE Journal 47(11):2384-2389 (Nov. 2001). |
| Chua, et al., “Improved Thermodynamic Property Fields of LiBr—H2O Solution,” International Journal of Refrigeration 23:412-429 (Sep. 2000). |
| De Lucas, et al., “Vapor Pressures, Densities, and Viscosities of the (Water + Lithium Bromide + Lithium Formate) System and (Water + Lithium Bromide + Potassium Formate) System,” Journal of Chemical and Engineering Data, American Chemical Society, US 48(1):18-22 (Jan. 2003). |
| De Lucas, et al., “Absorption of Water Vapor into Working Fluids for Absorption Refrigeration Systems,” Industrial & Engineering Chemistry Research, American Chemical Society, US 46(1):345-350 (2007); (published online Dec. 2006). |
| Domanska, et al., Solubility of 1-Alkyl-3-ethylimidazolium-Based Ionic Liquids in Water and 1-Octanol, J. Chem. Eng. Data 53:1126-1132 (Apr. 2008). |
| Galán, et al., “Solvent Properties of Functionalized Ionic Liquids for CO2 Absorption,” IChemE 85(A1):31-39 (Jan. 2007). |
| Glebov, et al., “Experimental Study of Heat Transfer Additive Influence on the Absorption Chiller Performance,” International Journal of Refrigeration 25:538-545 (Aug. 2002). |
| Kim, et al., “Surface tension and viscosity of 1-butyl-3-methylimidazolium iodide and 1-butyl-3-methylimidazolium tetrafluoroborate, and solubility of lithium bromide+1-butyl-3-methylimidazolium bromide in water,” Korean J. Chem. Eng. 23(1):113-116 (Jan. 2006). |
| Kim, et al., “Performance Evaluation of Absorption Chiller Using LiBr + H2N(CH2)2OH + H2O, LiBr + HO(CH2)3OH + H2O, and LiBr + (HOCH2CH2NH + H2O as Working Fluids,” Applied Thermal Engineering 19:217-225 (Feb. 1999). |
| Kim, et al., “Refractive Index and Heat Capacity of 1-Butyl-3-Methylimidazolium Bromide and 1-Butyl-3-Methylimidazolium Tetrafluoroborate, and Vapor Pressure of Binary Systems for 1-Butyl-3-Methylimidazolium Tetrafluoroborate—Trifluoroethanol,” Fluid Phase Equilibria 218:215-220 (Apr. 2004). |
| Li, et al., “Correlation and Prediction of the Solubility of CO2 and H2S in an Aqueous Solution of 2-Piperidineethanol and Sulfolane,” Ind. Eng. Chem. Res. 37:3098-3104 (May 1998). |
| Liu, et al., The physical properties of aqueous solution of room-temperature ionic liquids based on imidazolium:Database and Evaluation, J. Mol. Liquids 140:68-72 (Jan. 2008). |
| Mitsubishi Heavy Industries, Ltd., “Flue Gas CO2 Recovery Technology and Its Application to EOR: an Effective Strategy for Addressing the Issues of Global Warming and Peaking Oil Supply,” vol. 44, p. 20-23 (2007). |
| Perez-Blanco, “A Model of an Ammonia-Water Falling Film Absorber,” ASHRAE Transactions vol. 94, pp. 467-483, 1988; Presented at the winter meeting in Dallas Texas of the American Society of Heating, Refrigerating and Air-Conditioning Engineers, Inc. (1988). |
| Wasserscheid, et al., “Ionic Liquids—New “Solutions” for Transition Metal Catalysis,” Angew. Chem. Int. Ed. 39:3772-3789 (Nov. 2000). |
| Wu, et al., “Novel Ionic Liquid Thermal Storage for Solar Thermal Electric Power Systems,” Proceeding of Solar Forum. Solar Energy: The Power to Choose (Apr. 21-25, 2001). |
| Yoon, et al., “Cycle Analysis of Air-Cooled Absorption Chiller Using a New Working Solution,” Energy 24:795-809 (Sep. 1999). |
| Zhang, et al., “Screening of ionic Liquids to Capture CO2 by COSMO-RS and Experiments,” AIChE Journal 54(10):2171-2728 (Oct. 2008). |
| Zhou, The Vapor Surfactant Theory of Absorption and Condensation Enhancement, Proc. Int. Sorption Heat Pump Conference, (Sep. 24-27, 2002). |
| Ziegler, et al., “Heat-Transfer Enhancement by Additives,” International Journal of Refrigeration 19:301-309 (Jun. 1996). |
| Ziegler, et al., “Multi-effect absorption chillers,” Rev. Int. Froid 16(5):301-311 (1993). |
| Ziegler, et al., “Recent developments and future prospects of sorption heat pump systems,” Int. J. Therm. Sci. 38:191-208 (Mar. 1999). |
| U.S. Appl. No. 15/742,436, filed Jan. 5, 2018, Zehnacker. |
| English language translation of the German Search Report for corresponding German application DE 10 2016 210 478.0, filed Jun. 14, 2016. |
| English language translation of Singaporian Written Opinion for corresponding Singapore application 10201704817P, filed Jun. 12, 2017. |
| Kuhlmann, et al., “Imidazolium dialkylphosphates—a class of versatile, halogen-free and hydrolytically stable ionic liquids,” Green Chem. 9:233-242 (2007). |
| Li, et al., “Efficient absorption of ammonia with hydroxyl-functionalized ionic liquids,” RCS Adv. 5:81362-81370 (2015). |
| Abelló, et al., “Supported choline hydroxide (ionic liquid) as heterogeneous catalyst for aldol condensation reactions,” Chem. Comm. 1096-1097 (2004). |
| Alcade, et al., “A Simple Halide-to-Anion Exchange Method for Heteroaromatic Salts and Ionic Liquids,” Molecules 17:4007-4027 (2012). |
| Cole, et al., “Novel Brønsted Acidic Ionic Liquids and Their Use as Dual Solvent—Catalysts,” J. Am. Chem. Soc. 124:5962-5963 (2002). |
| Ishiguro, et al., “Structure, solvation, and acid-base property in ionic liquids,” Pure Appl. Chem. 82(10):1927-1941 (Aug. 2010). |
| Manic, et al., “Extraction of Free Fatty Acids from Soybean Oil Using Ionic Liquids or Poly(ethyleneglycol)s,” AIChE 57(5):1344-1355 (May 2011). |
| Nockemann, et al., “Task-Specific Ionic Liquid for Solubilizing Metal Oxides,” J. Phys. Chem. 110(42): 20978-20992 (Oct. 2006). |
| Smiglak, et al., “New hydrogen carbonate precursors for efficient and byproduct-free synthesis of ionic liquids based on 1,2,3,-tirmethylimidazolium and N,N-dimethylpyrrolidinium cores,” Green Chem. 12:491-501 (2010). |
| Zhao, et al., “Review: Use of ionic liquids as ‘green’ solvents for extractions,” J. Chem. Technol. Biotechnol. 80: 1089-1096 (published online May 2005). |
| Kanakubo, et al., “CO2 solubility in and physical properties for ionic liquid mixtures of 1-butyl-3-methylimidazolium acetate and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide,” Journal of Molecular Liquids 217:112-119 (2016); available online Feb. 12, 2016. |
| Krannich, et al., “Characterization of Six Hygroscopic Ionic Liquids with Regard to Their Suitability for Gas Dehydration: Density, Viscosity, Thermal and Oxidative Stability, Vapor Pressure, Diffusion Coefficient, and Activity Coefficient of Water,” Journal of Chemical Engineering & Data 61:1162-1176 (Feb. 2016). |
| Kriebel, et al., “Absorption, 2. Design of Systems and Equipment,” Ulmann's Encyclopedia of Industrial Chemistry, vol. 1, pp. 75-90 (2008). |
| Lall-Ramnarine, et al., “Probing the Physical Properties, Synthesis and Cellulose Dissolution Ability of Dialkyl Phosphate Ionic Liquids,” Phosphorous, Sulfur, and Silicon 190:891-895 (2015). |
| Lungwitz, Ralf, “Ionische Flüssigkeiten—Polarität und Wechselwirkungen mit silikatischen Oberflächen,” Dissertation Technische Universität Chemnitz (Nov. 2011); with English language translation of relevant parts. |
| English language translation of Mao, et al., “Development and Application of New Technique for Recovery of Low Partial Pressure Carbon Dioxide,” Journal of Chemical Industry & Engineering 25(3):12-15 (Jun. 2004). |
| English language translation of Rolker, et al., “Separation of carbon dioxide from flue gases by means of absorption,” Chemie Ingenieur Tecknik 78(4):416-424 (Jul. 2006). |
| OECD Guidelines for the Testing of Chemicals, Test No. 104, items 14-19, (adopted May 1981). |
| Projekt der Deutschen Bundesstiftung: Gasreinigung mit ionischen Flüssigkeiten Umwelt; Endbericht (Sep. 2009); with English language translation of relavant parts. |
| English language translation of Xiao, “Study on Technique for Recovery of Carbon Dioxide from Flue Gas,” Modern Chemical Industry 24(5):47-49 (May 2004). |
| German Search Report dated Feb. 21, 2017 for counterpart German application DE 10 2016 210 478 with partial machine translation. |
| U.S. Appl. No. 15/486,300, filed Apr. 13, 2017, Bahlmann. |
| U.S. Appl. No. 15/619,561, filed Jun. 12, 2017, Irfan. |
| U.S. Appl. No. 15/619,566, filed Jun. 12, 2017, Willy. |
| U.S. Appl. No. 15/619,567, filed Jun. 12, 2017, Wang. |
| U.S. Appl. No. 15/619,577, filed Jun. 12, 2017, Zehnacker. |
| U.S. Appl. No. 15/619,584, filed Jun. 12, 2017, Zehnacker. |
| Blachly, et al., “Stabilization of Monoethanolmine Solutions in Carbon Dioxide Scrubbers,” J. Chem. Eng. Data 11(3):401-403 (Jul. 1966). |
| Call,“Aminoxyle—eine Klasse stabiler,” Pharmazie in unserer Zeit 3:83-95 (Jan. 1977); with English language translation attached. |
| Kirchhoff, et al., “Triacetoneamine Derivatives Industrial Applications and Recent Developments,” pp. 1-9, Addcon World '99 (Two-Day Conference, Oct. 1999). |
| Lewin, et al., “Molecular Features Associated with Polyamine Modulation of NMDA Receptors,” J. Med. Chem. 41:988-995 (published online Feb. 1998). |
| Luo, et al., “Dehumidification performance of [EMIM]BF4,” Applied Thermal Engineering 31(14-15):2772-2777 (Oct. 2011). |
| Luo, et al., “Investigation of feasibility of ionic liquids used in solar liquid desiccant air conditioning system,” Solar Energy 86(9):2781-2724 (Sep. 2012). |
| Satori, et al., “Sterically Hindered Amines for CO2 Removal from Gases,” Ind. Eng. Chem. Fundam. 22(2):239-249 (accepted Jan. 1983). |
| Gerald Scott, Develpoments in polymer stabilization-5, Chapter 3: Antioxidant action of sterically hindered amines and related compounds, Shlyapintokh and Ivanor; pp. 41-70, Applied Science Publishers (1982). |
| Shao & Stangeland, “Amines Used in CO2 Capture—Health and Environmental Impacts,” Bellona Report (Sep. 2009). |
| Ulmann's Encyclopedia of Industrial Chemistry, 5th Edition, vol. 83, “Antioxidants” pp. 91-104 (1985). |
| Wellner, et al., “Entwässerung ionischer Flüssigkeiten in einem Fallfilmverdampfer,” Chemie Ingenieur Technik 83(9):1493-1501(Jul. 2011); with complete English language translation. |
| Yunus, “Gaslöslichkeit in ionischen Flüssigkeiten,” IsoSORP Application Note Nr. 4:1-2 (Feb. 2014); with complete English language translation. |
| Encylopedia of Chemical Process and Design, Ed. John J. McKetta, vol. 32. Marcel Deckker, Inc. (1990) pp. 123-126. |
| Office Action for U.S. Appl. No. 15/619,577, sent Feb. 14, 2019. |
| Response to Office Action dated Feb. 14, 2019 for U.S. Appl. No. 15/619,577, filed May 13, 2019. |
| Office Action for U.S. Appl. No. 14/973,084, sent Nov. 1, 2017. Application is now abandoned. Application was published as US 2016/0175766. |
| Office Action for U.S. Appl. No. 15/619,566, sent May 29, 2018. Application is now abandoned. Application was published as US 2017/0355682. |
| Office Action for U.S. Appl. No. 15/619,561, sent Feb. 22, 2019. |
| Response to Office Action dated Feb. 22, 2019 for U.S. Appl. No. 15/619,561, filed May 14, 2019. |
| Chung, et al., “Dehumidification of Moist Air With Simultaneous Removal of Selected Indoor Pollutants by Triethylene Glycol Solutions in a Packed-Bed Absorber,” Separation Science and Technology 30(7-9):1807-1832 (1995). |
| U.S. Appl. No. 16/300,466, filed Nov. 9, 2018, Wang. |
| Notice of Allowance dated Jul. 30, 2019 for copending U.S. Appl. No. 15/619,561. |
| Notice of Allowance dated Aug. 8, 2019 for copending U.S. Appl. No. 15/619,577. |
| Notice of Allowance dated Aug. 12, 2019 for copending U.S. Appl. No. 15/742,436. |
| Number | Date | Country | |
|---|---|---|---|
| 20170354923 A1 | Dec 2017 | US |
