PROCESS FOR DEHUMIDIFYING MOIST GAS MIXTURES
20170354921 · 2017-12-14
Assignee
Inventors
- Olivier Zehnacker (Dortmund, DE)
- Benjamin Willy (Dusseldorf, DE)
- Xinming Wang (Kanagawa-ken, JP)
- Rolf Schneider (Grundau-Rothenbergen, DE)
Cpc classification
C07D233/56
CHEMISTRY; METALLURGY
C01D5/00
CHEMISTRY; METALLURGY
C07F9/091
CHEMISTRY; METALLURGY
C07F9/11
CHEMISTRY; METALLURGY
International classification
Abstract
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
Claims
1. A process for dehumidifying a moist gas mixture G, in an apparatus V.sub.1, comprising: (a) contacting the moist gas mixture G with an aqueous liquid absorption medium A.sub.VE comprising a mixture of at least one trialkyl phosphate of structure (I): ##STR00006## and at least one salt S selected from the group consisting of Q.sup.+A.sup.−, Q.sup.+(R.sup.1O).sub.2PO.sub.2.sup.−, (Q.sup.+).sub.2R.sup.2OPO.sub.3.sup.2−, and Q.sup.+M.sup.+R.sup.3OPO.sub.3.sup.2−, wherein A.sub.VE at least partially absorbs water from the moist gas mixture G, to afford an aqueous liquid absorption medium A.sub.VE1 having an elevated water content compared to A.sub.VE and a gas mixture G.sub.1 having a relatively low water content compared to the moist gas mixture G; (b) partially removing water from A.sub.VE1 to obtain an aqueous liquid absorption medium A.sub.VE2 having a relatively low water content compared to A.sub.VE1; wherein the apparatus V.sub.1 at least partially comprises a surface made of a steel material of construction O.sub.st and, in the apparatus V.sub.1, at least one of A.sub.VE, A.sub.VE1 and A.sub.VE2 contacts the surface made of a steel material of construction O.sub.st via at least one contact surface; wherein: Q.sup.+ is a dialkylimidazolium cation, A.sup.− is an anion selected from the group consisting of R*COO.sup.−, R′SO.sub.3−, HSO.sub.4.sup.−, R″SO.sub.4.sup.−, R*, R′, R″, R.sup.A, R.sup.B, R.sup.C, R.sup.1, R.sup.2, R.sup.3 are each independently of one another an alkyl group, and wherein M.sup.+ is an alkali metal ion.
2. The process of claim 1, wherein G is moist air.
3. The process of claim 1, wherein: a) Q.sup.+ is a dialkylimidazolium cation in which the alkyl groups each independently of one another have 1 to 10 carbon atoms; b) R*, R′, R″, R.sup.A, R.sup.B, R.sup.C, R.sup.1, R.sup.2, R.sup.3 are each independently of one another an alkyl group having 1 to 10 carbon atoms; and c) M.sup.+=Li.sup.+, K.sup.+ or Na.sup.+.
4. The process of claim 1, wherein: a) salt S is selected from the group consisting of: Q.sup.+A.sup.− and Q.sup.+(R.sup.1O).sub.2PO.sub.2.sup.−; b) Q.sup.+ is a dialkylimidazolium cation in which the alkyl groups each independently of one another have 1 to 6 carbon atoms; and c) A.sup.− is an anion selected from the group consisting of R*COO.sup.−, R′SO.sub.3.sup.−, and R″SO.sub.4.sup.−, and d) R*, R.sup.1, R′, R″, R.sup.A, R.sup.B, R.sup.C are each independently of one another an alkyl group having 1 to 6 carbon atoms.
5. The process of claim 1, wherein R.sup.A, R.sup.B, R.sup.C are independently of one another selected from the group consisting of: methyl and ethyl.
6. The process of claim 1, wherein, in the aqueous liquid absorption medium A.sub.VE, the total weight of all trialkyl phosphates of structure (I) and all salts S is in the range 65 wt % to 95 wt % based on the total weight of the aqueous solution.
7. The process of claim 1, wherein, in the aqueous liquid absorption medium A.sub.VE, 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.
8. The process of claim 3, wherein R.sup.A, R.sup.B, and R.sup.C are independently of one another selected from the group consisting of: methyl and ethyl.
9. The process of claim 8, wherein, in the aqueous liquid absorption medium A.sub.VE, the total weight of all trialkyl phosphates of structure (I) and all salts S is in the range 65 wt % to 95 wt % based on the total weight of the aqueous solution.
10. The process of claim 9, wherein, in the aqueous liquid absorption medium A.sub.VE, 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.
11. An apparatus, V.sub.2, for dehumidifying a moist gas mixture, comprising the components: (i) an aqueous liquid absorption medium, A.sub.VO, which comprises a mixture of at least one trialkyl phosphate of structure (I): ##STR00007## and at least one salt, S, selected from the group consisting of: Q.sup.+A.sup.−, Q.sup.+(R.sup.1O).sub.2PO.sub.2.sup.−, (Q.sup.+).sub.2R.sup.2OPO.sub.3.sup.2−, and Q.sup.+M.sup.+R.sup.3OPO.sub.3.sup.2−; (ii) at least one water absorption unit, W.sub.abs2, set up for contacting the moist gas mixture with the aqueous liquid absorption medium A.sub.VO; (iii) at least one water desorption unit, W.sub.des2, which comprises a heat exchanger, W.sub.x2, and is set up for at least partially removing water from an aqueous liquid absorption medium A.sub.VO; and (iv) a circuit, U.sub.2, which connects the water absorption unit W.sub.abs2 with the water desorption unit W.sub.des2 and by means of which the aqueous liquid absorption medium A.sub.VO may be circulated, wherein at least one of the components selected from the group consisting of: the water absorption unit W.sub.abs2; the water desorption unit W.sub.des2; and the circuit U.sub.2, at least partially comprises a surface made of a steel material of construction O.sub.ST; wherein, disposed in the apparatus V.sub.2, is at least one contact surface at which the aqueous liquid absorption medium A.sub.VO contacts the surface made of a steel material of construction O.sub.st; and wherein: Q.sup.+ is a dialkylimidazolium cation; A.sup.− is an anion selected from the group consisting of R*COO.sup.−, R′SO.sub.3−, HSO.sub.4.sup.−, R″SO.sub.4.sup.−; R*, R′, R″, R.sup.A, R.sup.B, R.sup.C, R.sup.1, R.sup.2, R.sup.3 are each independently of one another an alkyl group; and M.sup.+ is an alkali metal ion.
12. The apparatus V.sub.2 of claim 11, wherein: a) Q.sup.+ is a dialkylimidazolium cation in which the alkyl groups each independently of one another have 1 to 10 carbon atoms; b) R*, R′, R″, R.sup.A, R.sup.B, R.sup.C, R.sup.1, R.sup.2, R.sup.3 are each independently of one another an alkyl group having 1 to 10 carbon atoms; and c) M.sup.+=Li.sup.+, K.sup.+ or Na.sup.+.
13. The apparatus V.sub.2 of claim 11, wherein: a) salt S is selected from the group consisting of: Q.sup.+A.sup.−, and Q.sup.+(R.sup.1O).sub.2PO.sub.2.sup.−; b) Q.sup.+ is a dialkylimidazolium cation in which the alkyl groups each independently of one another have 1 to 6 carbon atoms; c) A.sup.− is an anion selected from the group consisting of R*COO.sup.−, RSO.sub.3.sup.−, and R″SO.sub.4.sup.−, and d) R*, R.sup.1, R′, R″, R.sup.A, R.sup.B, R.sup.C are each independently of one another an alkyl group having 1 to 6 carbon atoms.
14. The apparatus V.sub.2 of claim 11, wherein R.sup.A, R.sup.B and R.sup.C are independently of one another selected from the group consisting of: methyl and ethyl.
15. The apparatus V.sub.2 of claim 11, wherein, in the aqueous liquid absorption medium A.sup.VO, the total weight of all trialkyl phosphates of structure (I) and all salts S is in the range 65 wt % to 95 wt % based on the total weight of the aqueous solution.
16. The apparatus V.sub.2 of 11, wherein, in the aqueous liquid absorption medium A.sub.VO, 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.
17. The apparatus of claim 12, wherein R.sup.A, R.sup.B, R.sup.C are independently of one another selected from the group consisting of: methyl and ethyl.
18. The apparatus of claim 17, wherein, in the aqueous liquid absorption medium A.sub.VE, the total weight of all trialkyl phosphates of structure (I) and all salts S is in the range 65 wt % to 95 wt % based on the total weight of the aqueous solution.
19. The apparatus of claim 18, wherein, in the aqueous liquid absorption medium A.sub.VE, 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.
20. An absorption heat pump, comprising the apparatus V.sub.2 of claim 11 and further comprising a condenser, an evaporator and a coolant, wherein the coolant is water.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0016]
[0017]
DETAILED DESCRIPTION OF THE INVENTION
[0018] 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 V.sub.1, comprising the steps of: [0019] (a) contacting the moist gas mixture G with an aqueous liquid absorption medium A.sub.VE comprising a mixture of at least one trialkyl phosphate of structure (I):
##STR00001## [0020] and at least one salt S selected from the group consisting of Q.sup.+A.sup.−, Q.sup.+(R.sup.1O).sub.2PO.sub.2.sup.−, (Q.sup.+).sub.2R.sup.2OPO.sub.3.sup.2−, Q.sup.+M.sup.+R.sup.3OPO.sub.3.sup.2−, [0021] wherein A.sub.VE at least partially absorbs water from the moist gas mixture G, to afford an aqueous liquid absorption medium A.sub.VE1 having an elevated water content compared to A.sub.VE and a gas mixture G.sub.1 having a relatively low water content compared to the moist gas mixture G, [0022] (b) partially removing water from A.sub.VE1 to obtain an aqueous liquid absorption medium A.sub.VE2 having a relatively low water content compared to A.sub.VE1, [0023] wherein the apparatus V.sub.1 at least partially comprises a surface made of a steel material of construction O.sub.st and in the apparatus V.sub.1 at least one of A.sub.VE, A.sub.VE1, A.sub.VE2 contacts the surface made of a steel material of construction O.sub.st via at least one contact surface, [0024] characterized in that [0025] Q.sup.+ is a dialkylimidazolium cation in which in particular the alkyl groups each independently of one another have 1 to 10 carbon atoms, [0026] wherein A.sup.− is an anion selected from the group consisting of R*COO.sup.−, R′SO.sub.3−, HSO.sub.4.sup.−, R″SO.sub.4.sup.−, [0027] wherein R*, R′, R″, R.sup.A, R.sup.B, R.sup.C, R.sup.1, R.sup.2, R.sup.3 are each independently of one another an alkyl group, in particular having 1 to 10, preferably 1 to 8, more preferably 1 to 6, yet more preferably 1 to 4, still more preferably 1 to 2, carbon atoms [0028] and wherein M′ is an alkali metal ion, preferably Li.sup.+, K.sup.+ or Na.sup.+, yet more preferably K.sup.+ or Na.sup.+.
[0029] The moist gas mixture G employed in the process is not particularly restricted.
[0030] “Moist” is to be understood as meaning in the context of the invention “comprising water, in particular water vapour”.
[0031] “Aqueous” is to be understood as meaning that the particular solution (i.e. in the case of the aqueous liquid absorption media said absorption media) comprises water.
[0032] “Dehumidifying” is to be understood as meaning at least partially removing water.
[0033] “At least partially” is to be understood as meaning in the context of the invention “partially or completely”.
[0034] “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 %-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.
[0035] The process according to the invention is carried out in an apparatus V.sub.1 which at least partially comprises a surface made of a steel material of construction O.sub.st (in the context of the invention O.sub.st is short for “surface made of a steel material of construction”) and in which at least one of the aqueous liquid absorption media selected from the group consisting of A.sub.VE, A.sub.VE1, A.sub.VE2 contacts the surface made of a steel material of construction O.sub.st via at least one contact surface.
[0036] In particular, an apparatus V.sub.1 having the following components may be employed: [0037] (i) at least one water absorption unit W.sub.abs1 set up for contacting the moist gas mixture with the aqueous liquid absorption medium A.sub.VE, [0038] (ii) at least one water desorption unit W.sub.des1 which comprises a heat exchanger W.sub.x1 and is set up for at least partially removing water from an aqueous liquid absorption medium A.sub.VE, [0039] (iii) and a circuit U.sub.1 which connects the water absorption unit W.sub.abs1 with the water desorption unit W.sub.des1 and by means of which the aqueous liquid absorption medium A.sub.VE may be circulated.
[0040] The water absorption unit W.sub.abs1 is the component in which step a) of the process according to the invention in particular is carried out. Employable water absorption units W.sub.abs1 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 aqueous liquid absorption medium A.sub.VE and simultaneously achieving the longest possible residence time of the aqueous liquid absorption medium A.sub.VE 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 W.sub.abs1 may in particular also comprise an additional heat exchanger W.sub.z1 set up such that the aqueous liquid absorption medium A.sub.VE is coolable.
[0041] The water desorption unit W.sub.des1 which comprises a heat exchanger W.sub.x1 is the unit in which step b) of the process according to the invention in particular is carried out. The water desorption unit W.sub.des1 is based on the principle of supplying heat to the water-laden liquid absorption medium A.sub.VE(in particular A.sub.VE1), increasing the surface area of the water-laden liquid absorption medium A.sub.VE (in particular A.sub.VE1) and simultaneously achieving the longest possible residence time of the water-laden liquid absorption medium A.sub.VE (in particular A.sub.VE1) in the water desorption unit.
[0042] Employable water desorption units W.sub.des1 comprising a heat exchanger W.sub.x1 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 W.sub.des1 comprising a heat exchanger W.sub.x1 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 W.sub.des1.
[0043] Circuit U.sub.1 in particular passes A.sub.VE1 from step a) of the process according to the invention from the water absorption unit W.sub.abs1 to the water desorption unit W.sub.des1 and more preferably—in particular when the process according to the invention is carried out in continuous fashion—additionally passes A.sub.VE2 from step b) of the process according to the invention from the water absorption unit W.sub.des1 to the water desorption unit W.sub.abs1.
[0044] The circuit U.sub.1 is in particular a conduit, in particular selected from the group consisting of tube, hose.
[0045] In a further preferred embodiment the circuit U.sub.1 also comprises a pump.
[0046] A first step of the process according to the invention comprises contacting the moist gas mixture G with an aqueous liquid absorption medium A.sub.VE comprising a mixture of at least one trialkyl phosphate of structure (I):
##STR00002##
and at least one salt S selected from the group consisting of Q.sup.+A.sup.−, Q.sup.+(R.sup.1O).sub.2PO.sub.2.sup.−, (Q.sup.+).sub.2R.sup.2OPO.sub.3.sup.2−, Q.sup.+M.sup.+R.sup.3OPO.sub.3.sup.2−. The contacting may be effected in any way known to those skilled in the art, in particular in a water absorption unit W.sub.abs1. The contacting causes the absorption medium A.sub.VE to at least partially absorb moisture, i.e. water, from the moist gas stream G to afford an aqueous liquid absorption medium A.sub.VE1 having an elevated water content compared to the aqueous liquid absorption medium A.sub.VE and a gas mixture G.sub.1 having a relatively low water content compared to the moist gas mixture G.
[0047] It is preferable to cool the absorption medium A.sub.VE 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 W.sub.zj in the water absorption unit W.sub.abs1. The temperature of the absorption medium A.sub.VE during contacting of the moist gas mixture G is thus preferably in the range from 2° C. to 100° C., preferably 3° C. to 80° C., more preferably 4° C. to 50° C., yet more preferably 5° C. to 30° C.
[0048] The absorption medium A.sub.VE comprises water and a mixture of at least one trialkyl phosphate of structure (I):
##STR00003##
and at least one salt S selected from the group consisting of Q.sup.+A.sup.−, Q.sup.+(R.sup.1O).sub.2PO.sub.2.sup.−, (Q.sup.+).sub.2R.sup.2OPO.sub.3.sup.2−, Q.sup.+M+R.sup.3OPO.sub.3.sup.2−,
wherein Q.sup.+ 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.sup.− is an anion selected from the group consisting of R*COO.sup.−, R′SO.sub.3−, HSO.sub.4.sup.−, R″SO.sub.4.sup.−,
wherein R*, R′, R″, R.sup.A, R.sup.B, R.sup.C, R.sup.1, R.sup.2, R.sup.3 are each independently of one another an alkyl group, in particular having 1 to 10 carbon atoms,
and wherein M.sup.+ is an alkali metal ion, preferably Li.sup.+, K.sup.+ or Na.sup.+, yet more preferably K.sup.+ or Na.sup.+.
[0049] In a preferred embodiment of the process according to the invention the salt S is selected from the group consisting of Q.sup.+A.sup.−, Q.sup.+(R.sup.1O).sub.2PO.sub.2.sup.−, and Q.sup.+ 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.sup.− is an anion selected from the group consisting of R*COO.sup.−, R′SO.sub.3.sup.−, R″SO.sub.4.sup.−, wherein R*, R.sup.1, R′, R″, R.sup.A, R.sup.B, R.sup.C are each independently of one another an alkyl group having 1 to 6, preferably 1 to 4, more preferably 1 or 2, carbon atoms.
[0050] In a more preferred embodiment of the process according to the invention, the salt S has the general formula Q.sup.+(R.sup.1O).sub.2PO.sub.2.sup.−, and Q.sup.+ is a dialkylimidazolium cation in which the alkyl groups are each independently of one another methyl or ethyl, and R.sup.1, R.sup.A, R.sup.B, R.sup.C are each independently of one another methyl or ethyl.
[0051] In a yet more preferred embodiment of the process according to the invention, the salt S has the general formula Q.sup.+(R.sup.1O).sub.2PO.sub.2.sup.−, and Q.sup.+ is selected from the group consisting of 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium; R.sup.A, R.sup.B, R.sup.C, R.sup.1 is methyl or ethyl.
[0052] It is moreover particularly preferable in all of the aforementioned embodiments of the process according to the invention when R.sup.A, R.sup.B, R.sup.C are independently of one another selected from methyl, ethyl; yet more preferably R.sup.A=R.sup.B=R.sup.C=methyl or R.sup.A=R.sup.B=R.sup.C=ethyl; particularly preferably R.sup.A=R.sup.B=R.sup.C=ethyl.
[0053] This is because it has been found that, surprisingly, imidazolium salts having 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 V.sub.1 and thus also in a particularly efficient process.
[0054] The liquid absorption medium A.sub.VE is aqueous, i.e. it comprises water and is thus an aqueous solution.
[0055] In particular, in the aqueous liquid absorption medium A.sub.VE 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. Yet more preferably the total weight of all trialkyl phosphates of structure (I) and all salts S in A.sub.VE 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 %.
[0056] In the process according to the invention the ratio of all trialkyl phosphates of structure (I) to the salts S in the absorption medium A.sub.VE is not further restricted. However, it is preferable to employ in the process according to the invention an absorption medium A.sub.VE 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.
[0057] The gas mixture G.sub.1 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.
[0058] The aqueous liquid absorption medium A.sub.VE1 obtained in the first step of the process according to the invention has an elevated water content compared to the aqueous liquid absorption medium A.sub.VE. It will be appreciated that in terms of the trialkyl phosphates of structure (I) comprised by it and the salts S comprised by it, A.sub.VE1 is identical to A.sub.VE and is preferably distinguished therefrom only by its water content.
[0059] The second step of the process according to the invention then comprises partially removing water from the aqueous liquid absorption medium A.sub.VE1 to obtain an aqueous liquid absorption medium A.sub.VE2 having a relatively low water content compared to the aqueous liquid absorption medium A.sub.VE1.
[0060] This in particular comprises additionally supplying heat to the aqueous liquid absorption medium A.sub.VE1. 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 W.sub.des1 comprising a heat exchanger W.sub.x1. The partial removal of water from the aqueous liquid absorption medium A.sub.VE1 affords an aqueous liquid absorption medium A.sub.VE2 having a relatively low water content compared to the aqueous liquid absorption medium A.sub.VE1.
[0061] It will be appreciated that in terms of the trialkyl phosphates of structure (I) comprised by it and the salts S comprised by it the aqueous liquid absorption medium A.sub.VE2 is identical to A.sub.VE1 and is preferably distinguished therefrom only by its water content.
[0062] It is an essential feature of the process according to the invention that the apparatus V.sub.1 at least partially comprises a surface made of a steel material of construction O.sub.st (in the context of the invention O.sub.st is short for “surface made of a steel material of construction”).
[0063] A “steel material of construction” in the context of the present invention is to be understood as meaning in particular any iron alloy where the mass fraction of iron is greater than the mass fraction of every other element present. The proportion of iron in the steel material of construction is preferably >50 wt %, more preferably ≧60 wt %, yet more preferably ≧70 wt %, yet more preferably ≧80 wt %, yet more preferably ≧99 wt %.
[0064] In accordance with the invention in addition to iron the steel material of construction comprises in particular at least one alloying metal selected from the group consisting of nickel, chromium, vanadium, molybdenum, niobium, tungsten, cobalt, magnesium, manganese, silicon, zinc, lead, copper, titanium, more preferably selected from the group consisting of nickel, chromium, vanadium, molybdenum, niobium, tungsten, cobalt, magnesium, manganese, titanium, particularly chromium, wherein this yet more preferably has a mass fraction in the steel material of construction greater than 10.5 wt % but smaller than 50 wt %.
[0065] It is yet more preferable when at the same time the carbon content in the steel material of construction is then always <2.06 wt %, yet more preferably ≦1.2 wt %.
[0066] It will be appreciated that the sum of the contents of iron, alloying metal (for example chromium) and carbon in the steel material of construction must not exceed 100 wt %.
[0067] The steel material of construction may in particular be in the form of a wrought alloy or of a cast alloy.
[0068] It is a further essential feature of the process according to the invention that in the apparatus V.sub.1 at least one of the aqueous liquid absorption media selected from the group consisting of A.sub.VE, A.sub.VE1, A.sub.VE2 contacts the surface made of a steel material of construction O.sub.st via at least one contact surface. This means that the particular aqueous liquid absorption medium A.sub.VE, A.sub.VE1 or A.sub.VE2 is in direct contact with the surface made of a steel material of construction O.sub.st at this contact surface. In the context of the present invention “in direct contact” is to be understood as meaning in particular “wetting”. It will be appreciated that the aqueous liquid absorption medium selected from the group consisting of A.sub.VE, A.sub.VE1, A.sub.VE2 and the steel material of construction comprised in the contact surface are thus in direct contact. This is because it has been found that, surprisingly, the contact angle of the absorption media according to the invention are particularly small and thus ensure particularly good heat transfer in the case where said media are aqueous.
[0069] In the embodiment according to the invention in which an apparatus V.sub.1 is employed and comprises the following components: [0070] (i) at least one water absorption unit W.sub.abs1 set up for contacting the moist gas mixture with the aqueous liquid absorption medium A.sub.VE, [0071] (ii) at least one water desorption unit W.sub.des1 which comprises a heat exchanger W.sub.x1 and is set up for at least partially removing water from an aqueous liquid absorption medium A.sub.VE, [0072] (iii) and a circuit U.sub.1 which connects the water absorption unit W.sub.abs1 with the water desorption unit W.sub.des1 and by means of which the aqueous liquid absorption medium A.sub.VE may be circulated,
the contact surface at which the aqueous liquid absorption medium selected from the group consisting of A.sub.VE, A.sub.VE1, A.sub.VE2 contacts the surface made of a steel material of construction O.sub.st is disposed in particular in at least one of the components selected from the group water absorption unit W.sub.abs1, water desorption unit W.sub.des1, circuit U.sub.1, preferably in at least one of the components selected from the group water absorption unit W.sub.abs1, water desorption unit W.sub.des1.
[0073] This is because it has 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 steel materials of construction, thus ensure particularly good heat transfer and are thus particularly suitable as absorption media in the apparatus V.sub.1 having a surface made of a steel material of construction O.sub.st in which one of the aqueous liquid absorption media selected from the group consisting of A.sub.VE, A.sub.VE1, A.sub.VE2 is in direct contact with the surface made of a steel material of construction O.sub.st.
[0074] 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 aqueous liquid absorption medium A.sub.VE employed in the steps a) additionally performed in each case is at least partially the aqueous liquid absorption medium A.sub.VE2 obtained from the step b) performed immediately beforehand, i.e. in particular the water content of the aqueous liquid absorption medium A.sub.VE employed in the step a) additionally performed in each case and of the aqueous liquid absorption medium A.sub.VE2 from the immediately preceding step b) is identical.
[0075] It is yet more preferable when this embodiment comprises heating aqueous liquid absorption medium A.sub.VE1 with heat from aqueous liquid absorption medium A.sub.VE2. This may be carried out in an additional heat exchanger W.sub.y1, 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.
[0076] The invention also relates in a further aspect to an apparatus V.sub.2 for dehumidifying a moist gas mixture, in particular moist air, comprising the components [0077] (i) an aqueous liquid absorption medium A.sub.VO which comprises a mixture of at least one trialkyl phosphate of structure (I):
##STR00004## [0078] and at least one salt S selected from the group consisting of Q.sup.+A.sup.−, Q.sup.+(R.sup.1O).sub.2PO.sub.2.sup.−, (Q.sup.+).sub.2R.sup.2OPO.sub.3.sup.2−, Q.sup.+M.sup.+R.sup.3OPO.sub.3.sup.2−, [0079] (ii) at least one water absorption unit W.sub.abs2 set up for contacting the moist gas mixture with the aqueous liquid absorption medium A.sub.VO, [0080] (iii) at least one water desorption unit W.sub.des2 which comprises a heat exchanger W.sub.x2 and is set up for at least partially removing water from an aqueous liquid absorption medium A.sub.VO, [0081] (iv) and a circuit U.sub.2 which connects the water absorption unit W.sub.abs2 with the water desorption unit W.sub.des2 and by means of which the aqueous liquid absorption medium A.sub.VO may be circulated,
wherein at least one of the components water absorption unit W.sub.abs2, water desorption unit W.sub.des2, circuit U.sub.2 at least partially comprises a surface made of a steel material of construction O.sub.st, and
wherein disposed in the apparatus V.sub.2 is at least one contact surface at which the aqueous liquid absorption medium A.sub.VO contacts the surface made of a steel material of construction O.sub.st, characterized in that
Q.sup.+ is a dialkylimidazolium cation in which in particular the alkyl groups each independently of one another have 1 to 10 carbon atoms,
wherein A.sup.− is an anion selected from the group consisting of R*COO.sup.−, R′SO.sub.3−, HSO.sub.4.sup.−, R″SO.sub.4.sup.−,
wherein R*, R′, R″, R.sup.A, R.sup.B, R.sup.C, R.sup.1, R.sup.2, R.sup.3 are each independently of one another an alkyl group, in particular having 1 to 10, preferably 1 to 8, more preferably 1 to 6, yet more preferably 1 to 4, still more preferably 1 to 2, carbon atoms
and wherein M.sup.+ is an alkali metal ion, preferably Li.sup.+, K.sup.+ or Na.sup.+, yet more preferably K.sup.+ or Na.sup.+.
[0082] The apparatus V.sub.2 according to the invention is suitable for dehumidifying a moist gas mixture, in particular moist air. Said apparatus comprises the following components:
[0083] As the first component, the apparatus V.sub.2 according to the invention comprises an aqueous liquid absorption medium A.sub.VO, which comprises a mixture of at least one trialkyl phosphate of structure (I):
##STR00005##
and at least one salt S selected from the group consisting of Q.sup.+A.sup.−, Q.sup.+(R.sup.1O).sub.2PO.sub.2.sup.−, (Q.sup.+).sub.2R.sup.2OPO.sub.3.sup.2−, Q.sup.+M.sup.+R.sup.3OPO.sub.3.sup.2−, wherein Q.sup.+ is a dialkylimidazolium cation in which in particular the alkyl groups each independently of one another have 1 to 10 carbon atoms,
wherein A.sup.− is an anion selected from the group consisting of R*COO.sup.−, R′SO.sub.3−, HSO.sub.4.sup.−, R″SO.sub.4.sup.−,
wherein R*, R′, R″, R.sup.A, R.sup.B, R.sup.C, R.sup.1, R.sup.2, R.sup.3 are each independently of one another an alkyl group, in particular having 1 to 10 carbon atoms,
and wherein M.sup.+ is an alkali metal ion, preferably Li.sup.+, K.sup.+ or Na.sup.+, yet more preferably K.sup.+ or Na.sup.+.
[0084] In a preferred embodiment of the apparatus V.sub.2 according to the invention in the absorption medium A.sub.VO the salt S is selected from the group consisting of Q.sup.+A.sup.−, Q.sup.+(R.sup.1O).sub.2PO.sub.2.sup.−, and Q.sup.+ 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.sup.− is an anion selected from the group consisting of R*COO.sup.−, R′SO.sub.3−, R″SO.sub.4.sup.−, wherein R*, R.sup.1, R′, R″, R.sup.A, R.sup.B, R.sup.C are each independently of one another an alkyl group having 1 to 6, preferably 1 to 4, more preferably 1 or 2, carbon atoms.
[0085] In a more preferred embodiment of the apparatus V.sub.2 according to the invention in the absorption medium A.sub.VO the salt S has the general formula Q.sup.+(R.sup.1O).sub.2PO.sub.2.sup.−, and Q.sup.+ is a dialkylimidazolium cation in which the alkyl groups are each independently of one another methyl or ethyl, and R.sup.1, R.sup.A, R.sup.B, R.sup.C are each independently of one another methyl or ethyl.
[0086] In a yet more preferred embodiment of the apparatus V.sub.2 according to the invention in the absorption medium A.sub.VO the salt S has the general formula Q.sup.+(R.sup.1O).sub.2PO.sub.2.sup.−, and Q.sup.+ is selected from the group consisting of 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium; R.sup.A, R.sup.B, R.sup.C, R.sup.1 is methyl or ethyl.
[0087] It is moreover particularly preferable in all of the aforementioned embodiments of the apparatus V.sub.2 according to the invention when in the absorption medium A.sub.VO R.sup.A, R.sup.B, R.sup.C are independently of one another selected from methyl, ethyl; yet more preferably R.sup.A=R.sup.B=R.sup.C=methyl or R.sup.A=R.sup.B=R.sup.C=ethyl; particularly preferably R.sup.A=R.sup.B=R.sup.C=ethyl.
[0088] This is because it has 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 V.sub.2.
[0089] The liquid absorption medium A.sub.VO is aqueous, i.e. it comprises water and is thus an aqueous solution.
[0090] In particular, in the apparatus V.sub.2 according to the invention in the aqueous liquid absorption medium A.sub.VO 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. Yet more preferably the total weight of all trialkyl phosphates of structure (I) and all salts S in A.sub.VO 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 %.
[0091] In the apparatus V.sub.2 according to the invention the ratio of all trialkyl phosphates of structure (I) to the salts S in the absorption medium A.sub.VO is not further restricted. However, it is preferable to employ in the apparatus V.sub.2 according to the invention an absorption medium A.sub.VO 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.
[0092] As a second component the apparatus V.sub.2 according to the invention comprises a water absorption unit W.sub.abs2 set up for contacting the moist gas mixture with the aqueous liquid absorption medium A.sub.VO. The water absorption unit W.sub.abs2 may in particular comprise an additional heat exchanger W.sub.z2 set up such that the aqueous liquid absorption medium A.sub.VO is coolable. Employable water absorption units W.sub.abs2 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 aqueous liquid absorption medium A.sub.VO and simultaneously achieving the longest possible residence time of the aqueous liquid absorption medium A.sub.VO 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.
[0093] As a third component the apparatus V.sub.2 according to the invention comprises a water desorption unit W.sub.des2 which comprises a heat exchanger W.sub.x2 and is set up for at least partially removing water from the aqueous liquid absorption medium A.sub.VO. Particularly the combinations of heat exchanger and water desorber known to those skilled in the art may be employed therefor. The water desorption unit W.sub.des2 is based on the principle of supplying heat to the aqueous liquid absorption medium A.sub.VO, increasing the surface area of the aqueous liquid absorption medium A.sub.VO and simultaneously achieving the longest possible residence time of the aqueous liquid absorption medium A.sub.VO in the water desorption unit.
[0094] Employable water desorption units W.sub.des2 comprising a heat exchanger W.sub.x2 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 W.sub.des2 comprising a heat exchanger W.sub.x2 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 W.sub.des2 falling-films, in particular shell and tube falling-films.
[0095] As a fourth component the apparatus V.sub.2 according to the invention comprises a circuit U.sub.2 which connects the water absorption unit W.sub.abs2 with the water desorption unit W.sub.des2 and by means of which the aqueous liquid absorption medium A.sub.VO may be circulated. The circuit U.sub.2 is preferably a conduit, yet more preferably selected from the group consisting of tube, hose. In a further preferred embodiment the circuit U.sub.2 also comprises a pump.
[0096] It is an essential feature of the apparatus V.sub.2 according to the invention that said apparatus at least partially comprises a surface made of a steel material of construction O.sub.st (in the context of the invention O.sub.st is short for “surface made of a steel material of construction”).
[0097] It is a further essential feature of the apparatus V.sub.2 according to the invention that disposed in said apparatus is a contact surface at which the aqueous liquid absorption medium A.sub.VO contacts the surface made of a steel material of construction O.sub.st. This is to be understood as meaning that at this contact surface the aqueous liquid absorption medium A.sub.VO is in direct contact with the surface made of a steel material of construction O.sub.st. In the context of the present invention “in direct contact” is to be understood as meaning in particular “wetting”. It will be appreciated that the aqueous liquid absorption medium A.sub.VO and the steel material of construction comprised in the contact surface are thus in direct contact.
[0098] In a preferred embodiment the apparatus V.sub.2 comprises a further heat exchanger W.sub.y2 (additional to the heat exchanger W.sub.x2 comprised in the water desorption unit W.sub.des2). The heat exchanger W.sub.y2 is set up such that aqueous liquid absorption medium A.sub.VO sent from the water absorption unit W.sub.abs2 to the water desorption unit W.sub.des2 is suppliable with heat from aqueous liquid absorption medium A.sub.VO, said medium being conducted away from the water desorption unit W.sub.des2. This can be ensured in particular by employing as heat exchanger W.sub.y2 in particular a heat exchanger selected from shell and tube heat exchangers, plate and frame heat exchangers.
[0099] In a further preferred embodiment the apparatus V.sub.2 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.
[0100] The condenser is in particular connected to the water desorption unit W.sub.des2 via a conduit and is set up for condensing water at least partially removed from the aqueous liquid absorption medium A.sub.VO in the water desorption unit W.sub.des2. The condenser preferably also comprises a cooling water circuit.
[0101] 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 W.sub.abs2 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).
[0102] The
[0103]
[0104] The apparatus V.sub.2 shown in
[0105] Apparatus V.sub.1 corresponds to apparatus V.sub.2 without absorption medium A.sub.VO, wherein in the figure description for
[0106] The process according to the invention will now be illustratively described with reference to apparatus V.sub.1 using
[0107] A stream of moist gas mixture G (said stream may for example be moist air, moist natural gas or moist gas mixture originating from the evaporator of an absorption chiller—see also
[0108]
[0109] The absorption chiller shown in
[0110] In an embodiment of the process according to the invention (described hereinbelow with reference to apparatus V.sub.1 using
[0111] The examples which follow are intended to elucidate the present invention without limiting said invention in any way.
EXAMPLES
[0112] Inventive examples 11 to 13 and comparative example C1 were carried out.
[0113] 1. Chemicals Used
[0114] EMIM DEP (=ethylmethylimidazolium diethyl phosphate) was obtained from lolitec.
[0115] TEP (=triethyl phosphate) was obtained from Sigma Aldrich.
[0116] 2. Experimental Procedure
[0117] 3 drops of the respective solution were dropped onto a steel plate (steel, 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.
[0118] C1 is the comparative test with a mixture of EMIM DEP and 10 wt % of water, while in the examples I1, I2 and I3 mixtures of EMIM DEP, 10 wt % of water and 10 wt %, 1 wt % and 0.1 wt % of TEP respectively (the wt % values are always based on the total weight of the mixture) were analyzed.
[0119] 3. Results
TABLE-US-00001 Contact Experi- angle ment solution employed (°) C1 90 wt % of EMIM DEP + 10 wt % of water 52.9 I1 80 wt % of EMIM DEP + 10 wt % of water + 10 wt % 36 of TEP I2 89 wt % of EMIM DEP + 10 wt % of water + 1 wt % 37.2 of TEP I3 89.9 wt % of EMIM DEP + 10 wt % of water + 0.1 47.5 wt % of TEP
[0120] The results show that the inventive absorption media (I1-I3), which comprise a trialkyl phosphate (in this case triethyl phosphate), exhibit a small contact angle to the steel-containing surface compared to those of the prior art (C1). This results in improved surface wetting and thus in greater and more efficient heat exchange in the process according to the invention and the apparatus according to the invention.
[0121] 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.