Recycle processes with supercritical siloxanes

Abstract

The invention provides circular processes using siloxanes as high-temperature heat transfer fluid (HTF), wherein the siloxanes go over from the state of the supercooled liquid into the state of the high-density supercritical fluid by means of heat uptake without a phase transition and energy is then transferred as energy without a phase transition.

Claims

1. A circular process of heat transfer employing siloxanes as a high-temperature heat transfer fluid (HTF), comprising: transitioning the siloxanes from a state of a supercooled liquid into a state of a high-density supercritical fluid due to heat uptake, and transferring energy to an energy consumer without a phase transition of the siloxanes.

2. The circular process of claim 1, wherein the siloxanes are cooled in the state of the supercritical liquid and in the cooling process transfer heat to an energy consumer.

3. The circular process of claim 1, wherein the siloxanes in the state of the supercritical liquid are firstly depressurized to below their critical pressure in order to generate mechanical work directly and only then are cooled and condensed in order to transfer heat to an energy consumer.

4. The circular process of claim 1, wherein the siloxanes used as the HTF comprise methylpolysiloxanes.

5. The circular process of claim 4, wherein the siloxanes used as the HTF are mixtures of linear methylpolysiloxanes of the formula I
Me.sub.3SiO—(Me.sub.2SiO).sub.x—SiMe.sub.3  (I), and cyclic compounds of the formula II
(Me.sub.2SiO).sub.y  (II), Where Me is a methyl radical, x has values of greater than or equal to zero and the arithmetic mean of x weighted according to the molar proportions over all linear methylpolysiloxanes is in the range of from 3 to 20 and y has values greater than or equal to 3 and the arithmetic mean of y weighted according to the molar proportions over all cyclic methylpolysiloxanes is in the range of from 3 to 6.

6. The circular process of claim 1, wherein the siloxanes used as the HTF are branched compounds of the formula III
(Me.sub.3SiO.sub.1/2).sub.w(SiO.sub.4/2).sub.z  (III) Where w is an integer from 4 to 20, z is an integer from 1 to 15 and Me is a methyl radical.

Description

OVERVIEW OF THE DRAWINGS

(1) FIG. 1: Generalized heat transfer medium circular process according to the prior art.

(2) FIG. 1a: A primary heat transfer medium circular process is coupled to a secondary circular process for obtaining mechanical work (A).

(3) FIG. 1b: A CSP power station is operating using heat transfer fluid (HTF), where a primary heat transfer medium circular process is coupled to a second circular process for obtaining mechanical work (A).

(4) FIG. 2: A heat transfer fluid is heated to above its critical temperature and depressurized as supercritical fluid to a pressure below its critical pressure in order to provide mechanical work before it transfers heat to a heat consumer.

(5) FIG. 2a: A CSP power station is operating using a heat transfer fluid, where heat transfer fluid is heated to above its critical temperature and then depressurized as supercritical fluid to a pressure below its critical pressure to provide mechanical work before it transfers heat to a heat consumer.

(6) FIG. 3.1: Heating of HELISOL® 5A only to below the critical point, transfer of heat without work being provided, according to the prior art.

(7) FIG. 3.2: Heating of HELISOL® 5A to above the critical point, transfer of heat without work being provided.

(8) FIG. 3.3: Heating of HELISOL® 5A to above the critical point, depressurization with work being provided before transfer of heat.

(9) FIG. 3.4: Heating of QM4 to above the critical point, transfer of heat without work being provided.

(10) FIG. 3.5: Heating of QM4 to above the critical point, depressurization with provision of work before transfer of heat.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

(11) In the following examples, all amounts and percentages are by weight, all pressures are 0.10 MPa (abs.) and all temperatures are 20° C. unless indicated otherwise in the particular case.

EXAMPLES

Example 1

(12) Demonstrates the prior art: The heat transfer fluid is heated above its vapor pressure only to below its critical temperature, i.e. is always present as liquid.

(13) In a generalized heat transfer medium circular process according to the prior art (FIG. 1), a quantity of heat (Qin) is transferred from a heat source (WQ) to a high-temperature heat transfer fluid (HTF) in a heat exchanger (WA1) and transferred again (Qk) to a heat consumer (WV) in the heat exchanger (WA2). The heat transfer fluid according to the prior art is a liquid at a pressure above its vapor pressure and transfers a heat stream from a heat source having a relatively high temperature to a heat consumer at a lower temperature without providing mechanical work. The heat transfer medium pump (P1) is necessary to overcome the pressure drop in the heat transfer medium circular process.

(14) A primary heat transfer medium circular process is frequently coupled to a secondary circular process for obtaining mechanical work (A) (FIG. 1a). The heat consumer (WV) is in this case the secondary circular process which is operated using a working medium (AM).

(15) The working medium is vaporized on the secondary side of the heat exchanger (WA2) by uptake of heat from the primary heat transfer medium circular process at high pressure in order to generate mechanical work (A) on depressurization to a low pressure in the turbine (AMT). The working medium is then condensed in the condenser (AMK) and recompressed by means of a feed water pump (AMP) to the high pressure for the vaporization step. The pressure to which the working medium can be depressurized in the turbine (AMT) corresponds to the vapor pressure of the working medium (AM) at the condensation temperature in the condenser (AMK), which has to be greater than the temperature of the heat sink (WS) available at the location in order to be able to take up the heat of condensation (Qk).

(16) In the specific case of a solar-thermal power station (CSP), the heat source (WQ) is the Sun (FIG. 1b). The radiative heat (Qin) is transferred to the heat transfer fluid (HTF) in the solar field (S). The solar field (S) is a particular embodiment of a heat exchanger (WA1) and generally consists of a plurality of subfields (SF) which each consist of a plurality of parallel loops with receivers (R) connected in series. The distribution/collection conduits for the loops are referred to as headers (HD), and the connecting conduits between the subfields and main conduits are referred to as runners (RJ).

(17) In the specific example 1, a CSP power station (FIG. 1b) is operated using the heat transfer fluid (HTF) HELISOL® 5A, with the heat transfer fluid being heated from 295° C. to 395° C., only to below its critical temperature, and thus being, according to the prior art, present as liquid in the entire primary heat transfer medium circular process.

(18) HELISOL® 5A is a mixture of linear methylpolysiloxanes of the general formula I and cyclic compounds of the general formula II.

(19) At a maximum operating temperature up to 400° C., the critical temperature of HELISOL® 5A is in the range pcrit=13 to 14 bar and the critical temperature is in the range Tcrit=415 to 430° C.

(20) In the secondary circular process, water (AM) is vaporized at 120 bar and superheated to 385° C. (10° C. temperature difference from the primary heat transfer medium temperature).

(21) The condensation temperature is 50° C. (heat sink (WS) is ambient air; no cooling water is available at the location). For an ideal Carnot cycle process, a theoretical thermal efficiency η.sub.th<1−T.sub.condensation [K]/T.sub.steam [K]<50.9% is the limiting case, but this is unattainable in practice.

(22) In the case of a steam turbine having an isentropic efficiency of 92%, a real thermal efficiency of the secondary circular process (turbine power-pump power)/introduced thermal energy) of 34.8% is obtained.

(23) In practice, a complicated multistage, at least two-stage, arrangement with intermediate superheating is necessary for the steam turbine, since in the case of a single-stage depressurization the steam would become too wet (this also applies to the following examples).

(24) 4.7% of the heat (Qin) taken up in the solar field is consumed to provide the driving power for the pump (P1) in the primary heat transfer medium circular process; here, the real thermal efficiency of the secondary circular process for generating mechanical work is taken into account.

(25) In the case of a CSP power station having an effective work power of 50 MW, a thermal power of 150.8 MW consequently has to be provided in the heat exchanger (WA2), plus heat losses.

(26) The primary heat transfer medium circular process is shown in the TP diagram in FIG. 3.1:

(27) Heat uptake in the solar receiver loops (1), pressure drop in the collection tube conduits (headers and runners) (2), heat transfer in the heat exchanger (WA2) to the secondary steam turbine circular process (3), increase of pressure in the heat transfer medium pump (P1) (4) and pressure drop in the distributor tube conduits (runners and headers) (5).

(28) The transfer of 1 MW of thermal power requires 17.2 t/h of HELISOL® 5A, and the enthalpy difference is 209 KJ/kg.

Example 2

(29) The heat transfer fluid is, according to the invention, heated to above its critical temperature and is then present as supercritical fluid, mechanical work is not provided.

(30) A CSP power station (FIG. 1b) is operating using the high-temperature heat transfer fluid (HTF) HELISOL® 5A, with the heat transfer fluid being heated from 300° C. to 425° C., to above its critical temperature. At a maximum operating temperature of 425° C., the critical pressure of HELISOL® 5A is pcrit=15 to 16 bar and the critical temperature is Tcrit=400 to 410° C. The change in the critical point is caused by the temperature-dependent establishment of chemical equilibrium.

(31) The entire heat transfer medium circular process takes place above the critical pressure. When heat is taken up in the solar field, a continual change in state from the supercooled liquid to the high-density supercritical fluid occurs without a noticeable phase transition.

(32) The supercritical fluid nevertheless behaves like a real gas, i.e. it occupies all the volume available, it is compressible and the density is a function of pressure and temperature, and a “vapor pressure” is nonexistent.

(33) When it is transferred to a heat consumer (WV) in the heat exchanger (WA2), a change in state of the supercritical fluid back to supercooled liquid takes place. Mechanical work is not provided here, and the pressure drop has to be applied by means of the heat transfer medium pump (P1).

(34) The heat consumer (WV) is a thermal steam power station as in Example 1.

(35) At the maximum temperature of 425° C. in the primary HTF circuit, a steam temperature of 415° C. can be realized in the secondary circular process.

(36) The condensation temperature is 50° C. (heat sink=ambient air, no cooling water available at the location). For an ideal Carnot cycle process, a theoretical thermal efficiency η.sub.th<1−T.sub.condensation [K]/T.sub.steam [K]<53.0% is obtained as a limiting value, but this is not attainable in practice.

(37) In the case of a steam turbine having an isentropic efficiency of 92%, a real thermal efficiency of the secondary circular process (turbine power-pump power)/introduced thermal energy) of 35.2% is obtained (+0.4% compared to Example 1).

(38) Only about 2.6% of the heat taken up in the solar field is consumed for providing the driving power for the pump P1 in the primary heat transfer medium circular process.

(39) In the case of a CSP power station having an effective work power of 50 MW, a thermal power of only 145.8 MW consequently has to be provided now (−3.3% compared to Example 1), plus heat losses.

(40) The primary heat transfer medium circular process is shown for a specific case in the TP diagram in FIG. 3.2.

(41) Only 12.9 t/h of HELISOL® 5A are now required for transferring 1 MW of thermal power; the enthalpy difference is 280 KJ/kg.

Example 3

(42) The heat transfer fluid is heated to above its critical temperature according to the invention and then depressurized as supercritical fluid to a pressure below its critical pressure to provide mechanical work, before it transfers heat to a heat consumer (FIG. 2)

(43) A CSP power station (FIG. 2a, solar field shown in simplified form as heat exchanger WA1) is operated using the heat transfer fluid (HTF) HELISOL® 5A, with the heat transfer fluid being, as in Example 2, heated in the solar receiver loops firstly to 425° C., namely above its critical temperature (1). The pressure is reduced in the collection tube conduits (headers and runners) due to the pressure drop (2). The heat transfer fluid is then firstly depressurized, without a phase transition, in an ORC turbine (T) to a pressure below its critical pressure, see FIG. 3.3 (3), providing the mechanical work (A1). Internal heat exchange takes place in the recuperator (4,7) in order to set the entry temperature into the solar field.

(44) The depressurization from the supercritical region to the region of the superheated saturated gas occurs without a phase transition since the two-phase region is only touched tangentially. This is an in-principle advantage over a steam turbine, which can advantageously be utilized for automatic load regulation. In the case of a steam turbine, superheating always has to be adhered to exactly so that the steam does not become too wet on depressurization.

(45) Heat is then transferred to a secondary steam turbine circular process (5), resulting in the heat transfer fluid condensing. The pressure of the condensed heat transfer liquid is increased by means of the ORC pump (6) and HTF pump (8) in the example.

(46) The increasing of the pressure can also be carried out in a single stage.

(47) After the pressure drop in the conduits (runners and headers) (9), the heat transfer fluid is again present as supercooled liquid in order to take up heat again (1) in the receiver loops.

(48) In contrast to Example 2, the HTF entry temperature into the ORC turbine (T) is 10° C. higher than the entry temperature of the working medium (AM) into the turbine (AMT) in the secondary circular process.

(49) For an ideal Carnot cycle process, a theoretical thermal efficiency η.sub.th<1−T.sub.condensation [K]/T.sub.steam [K]<53.7%, which is 0.7% higher than in Example 2, is therefore obtained as limiting value for Example 3, but this is not attainable in practice.

(50) The primary heat transfer medium circular process is shown in the TP diagram in FIG. 3.3.

(51) The amount of HELISOL® 5A for transferring the thermal power in the solar field and the enthalpy difference is identical to that in Example 2.

(52) Only 2.6% of the heat taken up in the solar field is consumed for providing the driving power for the pump P1 in the primary heat transfer medium circular process, which is identical to Example 2.

(53) However, HELISOL® 5A provides as much as 6.63 kJ/kg of useful mechanical work (A1) on depressurization from 17.7 to 7 bar in an ORC turbine (isentropic efficiency 92%).

(54) In summary, an overall thermal efficiency (turbine powers (A1+A2)−pump powers (AMP+P2))/introduced thermal power of 35.8% (+0.6% compared to Example 2) is obtained in Example 3.

(55) The same amount of HELISOL® 5A has to be pumped through the solar field in order to take up 1 MW of thermal power.

(56) However, owing to the better overall efficiency, a thermal power of only 143.3 MW (−5.0% compared to Example 1), plus heat losses, has to be provided for a CSP power station having the effective work power of 50 MW.

Example 4

(57) In Example 4, WACKER QM4 is used as HTF instead of WACKER HELISOL® 5A.

(58) QM4 is a siloxane-based one-component system which has its critical point at about 350° C. and 8 bar.

(59) QM4 is the compound of the general formula III in which z=1 and w=4.

(60) According to the prior art, this heat transfer fluid would not be usable in the high-temperature range of >350° C.

(61) However, according to the invention QM4 is, like HELISOL® 5A, usable as HTF fluid in the temperature range up to 425° C.

(62) The primary heat transfer medium circular process using QM4 without work being provided is shown in the TP diagram in FIG. 3.4 for the same application in a CSP power station corresponding to Example 2 using HELISOL® 5A (for comparison, see FIG. 3.3).

(63) Compared to HELISOL® 5A, QM4 as one-component system has a vapor pressure curve in the TP diagram which ends at the critical point, while HELISOL® 5A as multicomponent system has a two-phase region with boiling curve and condensation curve, the two of which join and end at the critical point of the mixture, in the TP diagram.

(64) In the case of QM4, the supercritical region is significantly more pronounced than in the case of HELISOL® 5A.

(65) 13.12 t/h of QM4 are required for the transfer of 1 MW of thermal power; the enthalpy difference is 274 kJ/kg.

(66) The thermal efficiency of the secondary circular process is 35.2% and is identical to that in Example 2.

(67) 3.2% (rather than 2.6% in Example 2) of the heat taken up in the solar field is consumed for providing the driving power for the pump P1 in the primary heat transfer medium circular process.

(68) In the case of a CSP power station having an effective work power of 50 MW, a thermal power of 146.7 MW has to be provided (+0.6% compared to Example 2), plus heat losses.

Example 5

(69) The primary heat transfer medium circular process using QM4 with provision of work is shown in the TP diagram in FIG. 3.5 for the same application in a CSP power station corresponding to that of Example 3 using HELISOL® 5A (see FIG. 3.3).

(70) The overall primary heat transfer medium circular process now takes place around the critical point which is effectively in the center.

(71) In Example 5, the ORC turbine assumes 6.5% of the effective total work power, while in Example 3 it contributes only 4.3% to the effective total work power.

(72) The overall thermal efficiency in Example 5 is 36.3% and is thus 0.5% higher than in Example 3 using HELISOL® 5A.

(73) A thermal power of only 142.2 MW therefore has to be provided from the solar field (−5.8% compared to reference example 1 according to the prior art) for a CSP power station having an effective work power of 50 MW.