Patent Grant
10493400
The present application claims priority under 35 USC § 119 to European application, EP 16174299.4, 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 and to the absorption medium used in the process. 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 air dehumidification can be carried out 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 (synonymous with “absorption heat pump”, principle described in WO 2014/079675 A1). 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.
To absorb moisture from ionic liquids the prior art suggests a series of ionic liquids. Thus, DE 10 2010 004 779 A1 mentions 1-ethyl-3-methylimidazolium ethylsulfate, 1-ethyl-3-methylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium diethylphosphate, 1-ethyl-3-methylimidazolium methylsulfonate, 1-butyl-3-methylimidazolium bistrifluoromethanesulfonimide, 1-butyl-3-ethylimidazolium chloride for example.
CN 102335545 A describes a series of ionic liquids based on alkyl phosphates, namely inter alia 1,3-dimethyimidazolium dimethylphosphate, 1-ethyl-3-methylimidazolium dimethylphosphate and 1-butyl-3-methylimidazolium dimethylphosphate.
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 air dehumidification. However, this ionic liquid has the disadvantage of only poor absorption capability.
These and further ionic liquids are also discussed by Krannich et al., J. Chem. Eng. Data 61 (2016), 1162-1176.
Y. Luo et al., Solar Energy 86 (2012) 2718-2724 proposes the ionic liquid 1,3-dimethyimidazolium acetate as an alternative to 1-ethyl-3-methylimidazolium tetrafluoroborate for air dehumidification. The acetates are also discussed by M. Kanakubo et al., J. Mol. Liq. 217 (2016) 112-119.
US 2011/0247494 A1 proposes a further ionic liquid for this purpose, namely 1-ethyl-3-methylimidazolium acetate.
The application of these ionic liquids in absorption chillers is also discussed in WO 2013/050242 A1.
One important criterion for choosing an ionic liquid as absorption medium is the viscosity thereof. It is thus desirable to employ an absorption medium having the lowest possible viscosity since easier flowability of the absorption medium markedly simplifies the use thereof in air dehumidification. In an absorption chiller, in which the absorption medium needs to pumped, a more flowable absorption medium can be transported with reduced energy consumption which markedly enhances the economy of such a chiller. In addition, a lower viscosity also results in fewer outages caused for instance by cavity blockages.
Such blockages also have a further cause: It was observed that many ionic liquids described in the literature show a propensity to precipitate on contact with CO2, thus forming solid deposits. However, the presence of CO2 in the gas streams for dehumidification is in many cases unavoidable and in specific applications, for example dehumidification of natural gas, the proportion of CO2 in the gas stream for dehumidification is very high.
It is accordingly an object of the present inventions to provide an absorption medium which does not exhibit the abovementioned problems, i.e. has the lowest possible viscosity and a low propensity to precipitate on contact with CO2.
An absorption medium which achieves this object has now surprisingly been found.
The present invention accordingly relates to a process for dehumidifing a moist gas mixture G1, wherein the moist gas mixture G1 is contacted with a liquid absorption medium A1 which comprises a mixture of triethylene glycol and at least one salt S selected from the group consisting of Q+A−, Q+(R1O)2PO2−, (Q+)2R2OPO32−, Q+M+R3OPO32− to obtain a gas mixture G2 which has a lower water content compared to moist gas mixture G1 and a liquid absorption medium A2 which has an elevated water content compared to the liquid absorption medium A1, wherein Q+ is a dialkylimidazolium cation in which the alkyl groups each independently of one another have 1 to 6 carbon atoms, wherein A− is an anion selected from the group consisting of acetate, propionate, R′SO3−, HSO4−, R″SO4−, wherein R′, R″ are each independently of one another an alkyl group having 1 to 6 carbon atoms, wherein R1, R2, R3 are each independently of one another an alkyl group having 1 to 6 carbon atoms and M+ is an alkali metal ion, with the proviso that the salt S is not dimethylimidazolium methylsulfonate. Triethylene glycol has CAS number 112-27-6.
“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 in accordance with the invention “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 G1” is accordingly to be understood as meaning in the context of the invention that the gas mixture G1 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 the 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 G1). The composition of the moist gas G1 may otherwise vary depending on the application of the process according to the invention. The moist gas mixture G1 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 5.00 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 gas mixture G1 in particular comprises CO2. The gas mixture G1 preferably comprises CO2 in a proportion of 1 to 140000 ppm, more preferably 100 ppm to 20000 ppm, yet more preferably 350 ppm to 10000 ppm.
The proportion of CO2 in the gas mixture G1 may be determined by those skilled in the art with commercially available devices (CO2 sensors) or IR spectroscopy for example as a matter of routine.
The process according to the invention is in particular carried out in an apparatus V1. The apparatus V1 is restricted only to the extent that it shall be suitable for carrying out the process according to the invention. In particular, an apparatus V1 having the following components may be employed:
The water absorption unit Wabs1 in particular carries out the process according to the invention. Employable water absorption units Wabs1 include 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, in particular A1, and simultaneously achieving the longest possible residence time of the liquid absorption medium A1 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 falling-films, in particular shell and tube falling-films, as water absorbers. The water absorption unit Wabs1 may in particular also comprise an additional heat exchanger Wz1 set up such that the liquid absorption medium, in particular A1 is coolable.
The water desorption unit Wdes1, which comprises a heat exchanger Wx1 in particular carries out an optional step of the process according to the invention [“step b)”, wherein in this context the process would be step a)]. The water desorption unit Wdes1 is based on the principle of supplying heat to the water-laden liquid absorption medium A1, increasing the surface area of the water-laden liquid absorption medium A1 and simultaneously achieving the longest possible residence time of the water-laden liquid absorption medium A2 in the water desorption unit Wdes1.
Employable water desorption units Wdes1 comprising a heat exchanger Wx1 include 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 falling-films, in particular shell and tube falling-films, as water desorption unit Wdes1.
Circuit U1 in particular passes A2 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 A3 from step b) of the process according to the invention from the water desorption unit Wdes1 to the water absorption 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.
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 A1 to at least partially absorb moisture, i.e. water, from the moist gas stream G1.
It is preferable to cool the absorption medium A1 during contacting of the moist gas mixture G1 in order that as much moisture as possible is absorbed from the moist gas mixture G1. This may be achieved, for example, via an additional heat exchanger Wz1 in the water absorption unit Wabs1. The temperature of the absorption medium A1 during contacting of the moist gas mixture G is thus preferably in the range from 15° C. to 90° C., more preferably from 20° C. to 80° C., most preferably from 20° C. to 40° C.
In the process according to the invention the moist gas mixture G1 is contacted with a liquid absorption medium A1 which comprises a mixture of triethylene glycol and at least one salt S selected from the group consisting of Q+A−, Q+(R1O)2PO2−, (Q+)2R2OPO32−, Q+M+R3OPO32−. Here, Q+ is a dialkylimidazolium cation in which the alkyl groups each independently of one another have 1 to 6 carbon atoms and A− is an anion selected from the group consisting of acetate, propionate, R′SO3−, HSO4−, R″SO4−, wherein R′, R″ are independently of one another an alkyl group having 1 to 6 carbon atoms, wherein R1, R2, R3 are each independently of one another an alkyl group having 1 to 6 carbon atoms and M+ is an alkali metal ion, preferably Li+, K+ or Na+, yet more preferably K+ or Na+. However, according to the invention the salt S is not dimethylimidazolium methylsulfonate (which is of course also the case in the preferred embodiments of the invention).
In a preferred embodiment of the process according to the invention Q+ is a dialkylimidazolium cation in which the alkyl groups each independently of one another have 1 to 4 carbon atoms and R1, R2, R3 are each independently of one another methyl or ethyl and A− is selected from the group consisting of acetate, propionate R′SO3−, HSO4−, R″SO4−, wherein R′, R″ are independently of one another methyl or ethyl.
In a more 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 are each independently of one another methyl, ethyl, n-propyl, iso-propyl or n-butyl and A− is an anion selected from the group consisting of acetate, propionate, R′SO3−, R″SO4−, wherein R′, R″ are independently of one another an alkyl group having 1 to 4 carbon atoms, wherein R1 is methyl or ethyl.
In a more 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 are each independently of one another methyl, ethyl, n-propyl, iso-propyl or n-butyl and A− is an anion selected from the group consisting of acetate, propionate, R′SO3−, R″SO4−, wherein R′, R″ are independently of one another an alkyl group having 1 to 2 carbon atoms, wherein R1 is methyl or ethyl.
In a yet more 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 selected from the group consisting of 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation and A− is an anion selected from the group consisting of acetate, propionate, MeSO3−, EtSO3−, MeSO4−, EtSO4− and R1 is methyl or ethyl.
In a yet still more 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 selected from the group consisting of 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation and A− is an anion selected from the group consisting of acetate, propionate, MeSO3−, EtSO4− and R1 is methyl or ethyl, yet more preferably R1=ethyl.
In a particularly preferred embodiment of the process according to the invention Q+ is selected from the group consisting of 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation and A− is an anion selected from the group consisting of acetate, propionate. It is yet still more preferable if Q+ is then a 1,3-dimethylimidazolium cation.
This is because in addition to the previously discussed effect yet another positive effect of the process according to the invention is observed in the case of the acetates and propionates: When CO2 is present in the moist gas stream acetates and propionates precipitate which results in undesired deposits in the apparatus. It has now been found that this propensity is negated for these salts S when they are present in a mixture with triethylene glycol. This observation was likewise entirely surprising.
The liquid absorption medium A1 may be employed in the process according to the invention in the form of the pure mixture of triethylene glycol and the salts S. Alternatively and more preferably the liquid absorption medium A1 is an aqueous solution. It is preferable when in said aqueous solution the total weight of triethylene glycol and all salts S is at least 70 wt % based on the total weight of the aqueous solution. In said aqueous solution the total weight of triethylene glycol and all salts S is yet more preferably at least 80 wt % based on the total weight of the aqueous solution, yet more preferably 85 wt %, yet more preferably 90 wt %, yet still more preferably 99 wt %.
In the process according to the invention the ratio of triethylene glycol to the salts S in the absorption medium A1 is not further restricted. However, it is preferable to employ in the process according to the invention an absorption medium A1 in which the ratio of the total weight of the triethylene glycol to the total weight of all salts S is in the range 1:9 to 9:1, more preferably 2:8 to 8:2, yet more preferably 3:7 to 7:3, yet still more preferably 3:7 to 6:4, yet still more preferably 3:7 to 1:1, most preferably 3:7 to 4:6, with very greatest preference 3:7.
The gas mixture G2 obtained in the process according to the invention and having a relatively low water content compared to the moist gas mixture G1 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 liquid absorption medium A2 obtained in the process according to the invention has an elevated water content compared to the liquid absorption medium A1* it will be appreciated that in terms of the salts S comprised by it and in terms of the triethylene glycol comprised by it A2 is identical to A1 and is preferably distinguished therefrom only by its water content.
An optional additional step of the process according to the invention [“optional step b)”, wherein the process according to the invention is to be understood as “step a)”] then effects the at least partial removal of water from the liquid absorption medium A2 to obtain a liquid absorption medium A3 having a relatively low water content compared to the liquid absorption medium A2. Heat is additionally supplied to the liquid absorption medium A2 here. 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 A2 affords a liquid absorption medium A3 having a relatively low water content compared to the liquid absorption medium A2.
It will be appreciated that in terms of the salts S comprised by it and in terms of the triethylene glycol comprised by it A3 is identical to the A2 and is preferably distinguished therefrom only by its water content.
In a further preferred embodiment the process according to the invention is carried out in continuous fashion. This means in particular that following step b) steps a) and b) are performed at least one further time and the liquid absorption medium A1 employed in the step a) additionally performed in each case is at least partially the liquid absorption medium A3 obtained from the step b) performed immediately beforehand. This means that in particular the water content of the liquid absorption medium A1 employed in the step a) additionally performed in each case and of the liquid absorption medium A3 from the step b) performed immediately beforehand is identical.
It is yet more preferable when in this embodiment liquid absorption medium A2 is supplied with heat from liquid absorption medium A3. 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 which in particular comprises CO2, comprising the components
The apparatus according to the invention V2 is suitable for dehumidification of a moist gas mixture, in particular comprising CO2, preferably comprising CO2 in a proportion of 1 to 140000 ppm, more preferably 100 ppm to 20000 ppm, yet more preferably 350 ppm to 10000 ppm.
The apparatus V2 according to the invention comprises the following components:
As a first component the apparatus according to the invention V2 comprises a liquid absorption medium A1* which comprises a mixture of triethylene glycol 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 dialkylimidazolium cation in which the alkyl groups each independently of one another have 1 to 6 carbon atoms,
In a preferred embodiment of the apparatus V2 according to the invention in A1*, Q+ is a dialkylimidazolium cation in which the alkyl groups each independently of one another have 1 to 4 carbon atoms and R1, R2, R3 are each independently of one another methyl or ethyl and A− is selected from the group consisting of acetate, propionate R′SO3−, HSO4−, R″SO4−, wherein R′, R″ are each independently of one another methyl or ethyl.
In a more preferred embodiment of the apparatus V2 according to the invention the salt S in A1* is selected from the group consisting of Q+A−, Q+(R1O)2PO2−, and Q+ is a dialkylimidazolium cation in which the alkyl groups are each independently of one another methyl, ethyl, n-propyl, iso-propyl or n-butyl and A− is an anion selected from the group consisting of acetate, propionate, R′SO3−, R″SO4−, wherein R′, R″ are independently of one another an alkyl group having 1 to 4 carbon atoms, wherein R1 is methyl or ethyl.
In a more preferred embodiment of the apparatus V2 according to the invention the salt S in A1* is selected from the group consisting of Q+A−, Q+(R1O)2PO2−, and Q+ is a dialkylimidazolium cation in which the alkyl groups are each independently of one another methyl, ethyl, n-propyl, iso-propyl or n-butyl and A− is an anion selected from the group consisting of acetate, propionate, R′SO3−, R″SO4−, wherein R′, R″ are independently of one another an alkyl group having 1 to 2 carbon atoms, wherein R1 is methyl or ethyl.
In a yet more preferred embodiment of the apparatus V2 according to the invention the salt S in A1* is selected from the group consisting of Q+A−, Q+(R1O)2PO2−, and Q+ is selected from the group consisting of 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation and A− is an anion selected from the group consisting of acetate, propionate, MeSO3−, EtSO3−, MeSO4−, EtSO4− and R1 is methyl or ethyl.
In a yet still more preferred embodiment of the apparatus V2 according to the invention the salt S in A1* is selected from the group consisting of Q+A−, Q+(R1O)2PO2−, and Q+ is selected from the group consisting of 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation and A− is an anion selected from the group consisting of acetate, propionate, MeSO3−, EtSO4−, and R1 is methyl or ethyl, yet more preferably R1=ethyl.
In a particularly preferred embodiment of the apparatus V2 according to the invention Q+ is selected from the group consisting of 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, and A− is an anion selected from the group consisting of acetate, propionate. It is yet still more preferable if Q+ is then a 1,3-dimethylimidazolium cation.
The liquid absorption medium A1* may be employed in the form of the pure mixture of triethylene glycol and all salts S. Alternatively and more preferably the liquid absorption medium A1* is an aqueous solution in which the total weight of triethylene glycol and all salts S is preferably at least 70 wt % based on the total weight of the aqueous solution. It is yet more preferable when the total weight of triethylene glycol and all salts S in A1* is at least 80 wt % based on the total weight of the aqueous solution, yet more preferably 85 wt %, yet more preferably 90 wt %, yet still more preferably 99 wt %.
In the liquid absorption medium A1* the ratio of triethylene glycol to the salts S in the absorption medium is not further restricted. However, it is preferable to employ in the apparatus V2 according to the invention an absorption medium A1* in which the ratio of the total weight of the triethylene glycol to the total weight of all salts S is in the range 1:9 to 9:1, more preferably 2:8 to 8:2, yet more preferably 3:7 to 7:3, yet still more preferably 3:7 to 6:4, yet still more preferably 3:7 to 1:1, most preferably 3:7 to 4:6, with very greatest preference 3:7.
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 A1*. The water absorption unit Wabs2 may in particular comprise an additional heat exchanger Wz2 set up such that the liquid absorption medium A1* is coolable. Employable water absorption units Wabs2 of this kind include 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 A1* and simultaneously achieving the longest possible residence time of the liquid absorption medium A1* in the water absorber during absorption of the 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 falling-films, in particular shell and tube falling-films, as water absorbers.
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 A1*. Particularly the combinations of heat exchanger and water desorber known to those skilled in the art may be employed therefor. The water desorption unit Wdes2 is based on the principle of supplying heat to the liquid absorption medium A1*, increasing the surface area of the liquid absorption medium A1* and simultaneously achieving the longest possible residence time of the liquid absorption medium A1* in the water desorption unit.
Employable water desorption units Wdes2 comprising a heat exchanger Wx2 include 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 A1* may be circulated. The circuit U2 is preferably a conduit, yet more preferably selected from the group consisting of tube, hose. In a further preferred embodiment the circuit U2 also comprises a pump.
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 A1* sent from the water absorption unit Wabs2 to the water desorption unit Wdes2 may be supplied with heat from liquid absorption medium A1*, said medium being conducted away from the water desorption unit Wdes2. This can be ensured in particular 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 chiller (synonymous with “absorption heat pump” according to the invention). This absorption chiller 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 A1* 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).
Finally, the present invention also relates to the absorption medium A1* itself, wherein the absorption medium A1* comprises a mixture of triethylene glycol 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 dialkylimidazolium cation in which the alkyl groups each independently of one another have 1 to 6 carbon atoms,
In a preferred embodiment of the absorption medium A1* according to the invention Q+ therein is a dialkylimidazolium cation in which the alkyl groups each independently of one another have 1 to 4 carbon atoms and R1, R2, R3 are each independently of one another methyl or ethyl and A− is selected from the group consisting of acetate, propionate R′SO3−, HSO4−, R″SO4−, wherein R′, R″ are each independently of one another methyl or ethyl.
In a more preferred embodiment of the absorption medium A1* 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 are each independently of one another methyl, ethyl, n-propyl, iso-propyl or n-butyl and A− is an anion selected from the group consisting of acetate, propionate, R′SO3−, R″SO4−, wherein R′, R″ are independently of one another an alkyl group having 1 to 4 carbon atoms, wherein R1 is methyl or ethyl.
In a more preferred embodiment of the absorption medium A1* according to the invention the salt S therein is selected from the group consisting of Q+A−, Q+(R1O)2PO2−, and Q+ is a dialkylimidazolium cation in which the alkyl groups are each independently of one another methyl, ethyl, n-propyl, iso-propyl or n-butyl and A− is an anion selected from the group consisting of acetate, propionate, R′SO3−, R″SO4−, wherein R′, R″ are independently of one another an alkyl group having 1 to 2 carbon atoms, wherein R′ is methyl or ethyl.
In a yet more preferred embodiment of the absorption medium A1* according to the invention the salt S therein is selected from the group consisting of Q+A−, Q+(R1O)2PO2− and Q+ is selected from the group consisting of 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, and A− is an anion selected from the group consisting of acetate, propionate, MeSO3−, EtSO3−, MeSO4−, EtSO4−, and R1 is methyl or ethyl.
In a yet still more preferred embodiment of the absorption medium A1* according to the invention the salt S therein is selected from the group consisting of Q+A−, Q+(R1O)2PO2− and Q+ is selected from the group consisting of 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation and A− is an anion selected from the group consisting of acetate, propionate, MeSO3−, EtSO4−, and R1 is methyl or ethyl, yet more preferably R1=ethyl.
In a particularly preferred embodiment of the absorption medium A1* according to the invention S therein is a salt having the structure Q+A−, wherein A− is an anion selected from the group consisting of acetate, propionate.
The liquid absorption medium A1* may be employed in the form of the pure mixture of triethylene glycol and all salts S. Alternatively and more preferably the liquid absorption medium A1* is an aqueous solution in which the total weight of triethylene glycol and all salts S is preferably at least 70 wt % based on the total weight of the aqueous solution. It is yet more preferable when in A1* the total weight of triethylene glycol and all salts S is at least 80 wt % based on the total weight of the aqueous solution, yet more preferably 85 wt %, yet more preferably 90 wt %, yet still more preferably 99 wt %.
In the absorption medium A1* according to the invention the ratio of triethylene glycol to the salts S in the absorption medium is not further restricted. However, in the absorption medium A1* the ratio of the total weight of the triethylene glycol to the total weight of all salts S is preferably in the range 1:9 to 9:1, more preferably 2:8 to 8:2, yet more preferably 3:7 to 7:3, yet still more preferably 3:7 to 6:4, yet still more preferably 3:7 to 1:1, most preferably 3:7 to 4:6, with very greatest preference 3:7.
The
The apparatus V1 shown in
The process according to the invention will now be illustratively described with reference to apparatus V1 using
A stream of a moist gas mixture G1 having a temperature of 30° C. to 100° C. (said stream may for example be moist air, moist natural gas or moist gas mixture—see also
The absorption chiller shown in
The examples which follow are intended to elucidate the present invention without limiting said invention in any way.
1. Materials
The ionic liquids used were obtained from Sigma-Aldrich or by procedures described in the prior art (e.g. summarized in DE 10 2014 214 670 A1). The CO2 content of the gas stream was determined by infrared spectroscopy.
2. Viscosity Measurements
The viscosity of the following ionic liquids (comparative experiments: pure; inventive examples in admixture with 30 wt % of triethylene glycol) was measured according to DIN 54453. The results are shown in Table 1 which follows.
It is apparent from the table that for the mixtures comprising 30 wt % of TEG according to the inventive examples a lower viscosity compared to the pure ionic liquid was achieved for all ionic liquids. The mixtures according to the inventive examples are therefore much more suitable for use for instance in dehumidification of gas streams than the pure substances.
3. Experiments Concerning Gas Streams Comprising CO2
100 mL of the ionic liquids listed in Table 2, in pure form and in admixture with 30 wt % of triethylene glycol respectively, were contacted with a gas stream comprising 140000 ppm of CO2 in a bubble cell reaction vessel comprising a frit at 40° C. for 1 h. The results observed are summarized in Table 2.
It is apparent from the results according to table 2, that precipitation of the ionic liquids upon contact with CO2 was prevented by addition of triethylene glycol only in the case of MMIM Ac and MMIM Prop.
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 |
|---|---|---|---|
| 16174299 | Jun 2016 | EP | regional |
| 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 |
| 3317654 | Johnson et al. | Jun 1964 | A |
| 3276217 | Bourne et al. | Oct 1966 | 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 et al. | May 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 et al. | 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 et al. | 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 et al. | 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 et al. | 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 | 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 et al. | 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 |
| 20170354923 | Zehnacker 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 et al. | Jun 2018 | A1 |
| 20180202048 | Kirste | Jul 2018 | A1 |
| 20180216233 | Kirste | Aug 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 |
|---|
| 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, 1995, vol. 30, pp. 1807-1832 (Year: 1995). |
| 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 Universitat 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). |
| European Search Report completed Nov. 21, 2016 for counterpart European application EP 16 17 4299 with a partial english language machine translation attached. |
| U.S. Appl. No. 14/124,472, filed Dec. 6, 2013, 2014-0090558 A1, Apr. 3, 2014, Rolker. |
| U.S. Appl. No. 14/373,350, filed Jul. 19, 2014, 2014-0356268 A1, Dec. 4, 2014, Schraven. |
| U.S. Appl. No. 14/973,084, filed Dec. 17, 2015, 2016-0175766 A1, Jun. 23, 2016, Zehnacker. |
| U.S. Appl. No. 15/486,300, filed Apr. 13, 2017, Bahlmann. |
| 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. 15/619,573, filed Jun. 12, 2017, Zehnacker. |
| U.S. Appl. No. 15/619,577, filed Jun. 12, 2017, Zehnacker. |
| U.S. Appl. No. 15/619,584, filed Jun. 12, 2017, Zehnacker. |
| Philippine Search Report and Written Opinion for corresponding Philippine application No. 1/2017/000172 filed Jun. 2017. |
| “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). |
| English language translation of the European Search Report for corresponding application EP 16 17 4299, filed Jun. 14, 2016. |
| 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). |
| U.S. Appl. No. 15/742,436, filed Jan. 5, 2018, 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. |
| 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 Bronsted 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). |
| Office Action for U.S. Appl. No. 15/619,577, dated 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, dated Nov. 1, 2017. Application is now abandoned. Application was published as US 2016/0175766. |
| Office Action for U.S. Appl. No. 15/619,566, dated May 29, 2018. Application is now abandoned. Application was published as US 2017/0355682. |
| Office Action for U.S. Appl. No. 15/619,573, dated Feb. 14, 2019. |
| Response to Office Action dated Feb. 14, 2019 for U.S. Appl. No. 15/619,573, filed May 13, 2019. |
| U.S. Appl. No. 16/300,466, filed Nov. 9, 2018, Wang. |
| U.S. Appl. No. 15/742,436, filed Jan. 15, 2018, US 2018/0169572 A1, Jun. 21, 2018, Zehnacker. |
| Notice of Allowance dated Aug. 7, 2019 for co-pending U.S. Appl. No. 15/619,573. |
| Notice of Allowance dated Aug. 8, 2019 for co-pending U.S. Appl. No. 15/619,577. |
| Notice of Allowance dated Aug. 12, 2019 for co-pending U.S. Appl. No. 15/742,436. |
| Number | Date | Country | |
|---|---|---|---|
| 20170354924 A1 | Dec 2017 | US |
