CN104762065A - Organic rankine cycle mixed working medium and preparation method thereof - Google Patents
Organic rankine cycle mixed working medium and preparation method thereof Download PDFInfo
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Abstract
The invention provides an organic Rankine cycle mixed working medium and a preparation method thereof. The organic Rankine cycle mixed working medium is composed of following components: trifluorodichloroethane, pentafluoropropane, 1,1,1-trifluoropropane, 1,1-difluoroethane and 1,1,1,2-tetrafluoroethane, in a binary manner or a ternary manner, according to a certain mass ratio. The organic Rankine cycle mixed working medium is free of destroying ozone layer, is less in greenhouse effect influence, can satisfy environment protection, is proper in thermotechnical parameters and is excellent in cycle performances.
Description
Technical field
The present invention relates to low temperature exhaust heat energy use technology field, particularly a kind of organic Rankine bottoming cycle (Organic Rankine Cycle, ORC) mixing medium and preparation method thereof.
Background technology
According to the difference of temperature levels, residual heat resources can be divided into three kinds: high-temperature residual heat (more than 500 DEG C), middle temperature waste heat (between 200-500 DEG C) and low temperature exhaust heat (less than 200 DEG C).For the high-grade energies such as coal, oil, Sweet natural gas, the utilisable energy that the low grade residual heat of less than 200 DEG C comprises in same units is lower, utilizes difficulty large.But because low temperature exhaust heat amount is very large, and be not substantially used effectively, therefore low-grade industrial exhaust heat utilizes and will play an important role to energy-saving and emission-reduction.
Garbage incinerating power plant funnel temperature is usually between 150-200 DEG C, and single line exhaust smoke level is usually at 60000 ~ 100000Nm
3/ h, the heat that this part flue gas is taken away, accounts for about 20% of whole power generation system energy expenditure, belongs to low-temperature flue gas waste heat.Low-temperature flue gas waste heat resource gas-to electricity is economical poor, is because the energy grade of flue gas is low on the one hand, is lack the cycle fluid be applicable on the other hand.
Summary of the invention
The invention provides a kind of mixed working fluid for organic rankine cycle, described mixed working fluid for organic rankine cycle is by trifluorobichloroethane, pentafluoropropane, 1,1,1-Halothane, 1,1-C2H4F2 C2H4F2 and 1, the mixing medium that binary in these five kinds of organic working medium of 1,1,2-Tetrafluoroethane or ternary form according to certain mass ratio.
In one embodiment of the invention, the component of described mixed working fluid for organic rankine cycle and content are: the trifluorobichloroethane of 10% ~ 60% and the pentafluoropropane of 10% ~ 80%.
In one embodiment of the invention, the component of described mixed working fluid for organic rankine cycle and content are: the trifluorobichloroethane of 3% ~ 97% and 1,1, the 1-Halothane of 3% ~ 97%.
In one embodiment of the invention, the component of described mixed working fluid for organic rankine cycle and content are: the trifluorobichloroethane of 40% ~ 90% and the HFA 134a of 10% ~ 55%.
In one embodiment of the invention, the component of described mixed working fluid for organic rankine cycle and content are: the pentafluoropropane of 50% ~ 85% and 1,1, the 1-Halothane of 15% ~ 50%.
In one embodiment of the invention, the component of described mixed working fluid for organic rankine cycle and content are: the pentafluoropropane of 45% ~ 90% and 1, the 1-C2H4F2 C2H4F2 of 10% ~ 55%.
In one embodiment of the invention, the component of described mixed working fluid for organic rankine cycle and content are: the pentafluoropropane of 50% ~ 70% and the HFA 134a of 30% ~ 50%.
In one embodiment of the invention, the component of described mixed working fluid for organic rankine cycle and content are: the trifluorobichloroethane of 20% ~ 80%, the pentafluoropropane of 15% ~ 50% and 5% ~ 50% HFA 134a.
In one embodiment of the invention, the component of described mixed working fluid for organic rankine cycle and content are: the trifluorobichloroethane of 25% ~ 65%, the pentafluoropropane of 10% ~ 50% and 25% ~ 55% 1,1-C2H4F2 C2H4F2.
In one embodiment of the invention, the component of described mixed working fluid for organic rankine cycle and content are: the trifluorobichloroethane of 20% ~ 60%, 1,1, the 1-Halothane of 5% ~ 20% and 30% ~ 50% HFA 134a.
The present invention also provides a kind of method preparing above-mentioned mixed working fluid for organic rankine cycle, and described method comprises carries out physical mixed by each constituent element material at normal temperatures by set quality proportioning.
Above-mentioned mixed working fluid for organic rankine cycle does not damage the ozone layer, and Greenhouse effect impact is lower, meets environmental requirement, and thermal parameter is suitable for, and cycle performance is excellent.
Accompanying drawing explanation
Following accompanying drawing of the present invention in this as a part of the present invention for understanding the present invention.Shown in the drawings of embodiments of the invention and description thereof, be used for explaining principle of the present invention.
In accompanying drawing:
Fig. 1 shows the example of the waste heat flue gas generation driving force circulation device based on organic Rankine bottoming cycle.
Embodiment
In the following description, a large amount of concrete details is given to provide more thorough understanding of the invention.But, it is obvious to the skilled person that the present invention can be implemented without the need to these details one or more.In other example, in order to avoid obscuring with the present invention, technical characteristics more well known in the art are not described.
In order to thoroughly understand the present invention, by following description, detailed structure is proposed.Obviously, execution of the present invention is not limited to specific details appreciated by those skilled in the art.Preferred embodiment of the present invention is described in detail as follows, but except these are described in detail, the present invention can also have other embodiments.
Should be understood that, " comprise " when using term in this manual and/or " comprising " time, it indicates exists described feature, entirety, step, operation, element and/or assembly, but does not get rid of existence or additional other features one or more, entirety, step, operation, element, assembly and/or their combination.
Organic Rankine bottoming cycle is the Rankine cycle adopting lower boiling organic working medium.The heat source temperature that organic Rankine bottoming cycle requires is lower, and the thermal source of about 100 DEG C just can maintain it and normally run.The working medium that current low temperature ranking cycle system uses all concentrates in pure matter, and the alkanes being representative mainly with butane pentane etc. is greatly working medium, and it is fewer that it is applied to actual organic working medium, only have 1, a few working medium such as 1,1,2-Tetrafluoroethane (R134a), ammonia.Although alkanes material circulation heating power better performances, it is extremely inflammable and explosive, has higher risk, thus limits its further genralrlization and uses.Therefore, develop the novel working medium that a kind of environmental friendliness, thermal performance are excellent, most important to the development of low temperature organic Rankine bottoming cycle technology.
The invention provides a kind of mixed working fluid for organic rankine cycle, this mixed working fluid for organic rankine cycle is by trifluorobichloroethane (R123), pentafluoropropane (R245fa), 1,1,1-Halothane (R236fa), 1,1-C2H4F2 C2H4F2 (R152a) and 1, the mixing medium that binary in these five kinds of organic working medium of 1,1,2-Tetrafluoroethane (R134a) or ternary form according to certain mass ratio.Wherein, each constituent element material mass percentage ratio sum of often kind of mixing medium is 100%.Table 1 shows the basic parameter table of each constituent element material of the mixed working fluid for organic rankine cycle according to the embodiment of the present invention.
Table 1
In Table 1, T
brepresent working medium normal boiling point, T
crepresent working medium critical temperature, P
crepresent working medium emergent pressure.
The present invention also provides a kind of method preparing above-mentioned mixed working fluid for organic rankine cycle, and the method comprises carries out physical mixed by each constituent element material at normal temperatures by set quality proportioning.
According to embodiments of the invention 1, the component of mixed working fluid for organic rankine cycle and content can be: the R123 of 10% ~ the 60% and R245fa of 10% ~ 80%.Such as, 20 are got
mass%R123 and 80
mass%R245fa, carries out after physical mixed at normal temperatures as refrigeration agent.
According to embodiments of the invention 2, the component of mixed working fluid for organic rankine cycle and content can be: the R123 of 3% ~ the 97% and R236fa of 3% ~ 97%.Such as, 11 are got
mass%R123 and 89
mass%R236fa, carries out after physical mixed at normal temperatures as refrigeration agent.
According to embodiments of the invention 3, the component of mixed working fluid for organic rankine cycle and content can be: the R123 of 40% ~ the 90% and R134a of 10% ~ 55%.Such as, 50 are got
mass%R123 and 50
mass%R134a, carries out after physical mixed at normal temperatures as refrigeration agent.
According to embodiments of the invention 4, the component of mixed working fluid for organic rankine cycle and content can be: the R245fa of 50% ~ the 85% and R236fa of 15% ~ 50%.Such as, 45 are got
mass%R245fa and 55
mass%R236fa, carries out after physical mixed at normal temperatures as refrigeration agent.
According to embodiments of the invention 5, the component of mixed working fluid for organic rankine cycle and content can be: the R245fa of 45% ~ the 90% and R152a of 10% ~ 55%.Such as, 60.5 are got
mass%R245fa and 39.5
mass%R152a, carries out after physical mixed at normal temperatures as refrigeration agent.
According to embodiments of the invention 6, the component of mixed working fluid for organic rankine cycle and content can be: the R245fa of 50% ~ the 70% and R134a of 30% ~ 50%.Such as, 67.5 are got
mass%R245fa and 32.5
mass%R134a, carries out after physical mixed at normal temperatures as refrigeration agent.
According to embodiments of the invention 7, the component of mixed working fluid for organic rankine cycle and content can be: the R134a of the R123 of 20% ~ 80%, the R245fa of 15% ~ 50% and 5% ~ 50%.Such as, 22.5 are got
mass%R123,43.5
mass%R245fa and 34
mass%R134a, carries out after physical mixed at normal temperatures as refrigeration agent.
According to embodiments of the invention 8, the component of mixed working fluid for organic rankine cycle and content can be: the R152a of the R123 of 25% ~ 65%, the R245fa of 10% ~ 50% and 25% ~ 55%.Such as, 22.5 are got
mass%R123,25
mass%R245fa and 52.5
mass%R152a, carries out after physical mixed at normal temperatures as refrigeration agent.
According to embodiments of the invention 9, the component of mixed working fluid for organic rankine cycle and content can be: the R134a of the R123 of 20% ~ 60%, the R236fa of 5% ~ 20% and 30% ~ 50%.Such as, 32.5%R123,11 is got
ass%R236fa and 56.5
mass%R134a carries out after physical mixed at normal temperatures as refrigeration agent.
In existing garbage incinerating power plant, low-temperature flue gas directly enters air after being all through fly-ash separator, and mass energy is not fully utilized.Can be electric energy by the thermal energy of the low-temperature flue gas of incinerator afterbody after fly-ash separator process by the power generation system with residual heat of fume based on organic Rankine bottoming cycle, improve the utilization ratio of the energy.
Fig. 1 shows the example of the waste heat flue gas generation driving force circulation device based on organic Rankine bottoming cycle.As shown in Figure 1, organic working medium of the present invention is heated into the saturated of expander inlet state point 1 or superheated vapour middle by the waste heat flue gas of discharging from incinerator afterbody fly-ash separator, steam enter expander acting, after the generating of decompressor drive electrical generators, exhaust steam enters in condenser, cooled water condensation is the liquid 5 under condensing pressure, the liquid state point 6 under evaporating pressure is pressurized to again by working medium force (forcing) pump, enter vaporizer by flue gas heating to state point 1, enter decompressor acting, complete a circulation, thus realize utilizing the power recovery of waste heat.Low temperature exhaust heat organic Rankine bottoming cycle can be made up of vaporizer, decompressor, condenser, working medium force (forcing) pump, water coolant and the part such as waste heat medium transport subsystem and generator.Vaporizer can be divided into three heating zones: 1. preheating section; 2. evaporator section; 3. superheat section.Condenser can be divided into three phases: 1. superheat section; 2. condensation segment; 3. super cooled sect.
Usually, ORC (organic Rankine cycle) low-temperature afterheat generating system often adopts single organic working medium to do work, very limited to the adaptability of thermal source load.Incinerator tail flue gas quantity discharged is large, and restricts by process upstream engineering, and the temperature of flue gas, flow are in the state of constantly fluctuation.Above-mentioned mixed working fluid for organic rankine cycle provided by the invention adopts binary or ternary mix working medium as refrigeration agent, and stronger to the adaptability of load, evaporating pressure scope is more extensive, is suitable as very much the working medium of above-mentioned fume afterheat generating.
The mixed working fluid for organic rankine cycle that table 2 shows above-mentioned 9 embodiments is applied to parameter based on the power generation system with residual heat of fume of organic Rankine bottoming cycle and performance table.
Table 2
As shown in Table 2, the mixed working fluid for organic rankine cycle thermal parameter according to the embodiment of the present invention is suitable for, and cycle performance is excellent, and does not damage the ozone layer, and Greenhouse effect impact is lower, meets environmental requirement.In addition, can need to adjust each component ratio according to the change of vaporization temperature according to the mixed working fluid for organic rankine cycle of the embodiment of the present invention, make system have higher heat utilization efficiency.
Particularly, the power generation system with residual heat of fume be applied to based on organic Rankine bottoming cycle according to the mixed working fluid for organic rankine cycle of the embodiment of the present invention has the following advantages:
(1) environmental performance: ODP equals 0, environmental characteristics is excellent;
(2) thermal parameter: for flue gas of garbage furnace cogeneration power circulation system design conditions (such as, flue gas flow is 34.17kg/s, gas approach temperature is 150 DEG C, expander inlet temperature is 110 DEG C, condensing temperature is 38 DEG C, cooling water inlet temperature is 25 DEG C, the terminal temperature difference of vaporizer is 15 DEG C, the terminal temperature difference of condenser is 5 DEG C) under evaporating pressure at 1-3MPa, condensing pressure is at 0.2-0.7MPa, and ratio of expansion is about 5;
(3) cycle performance: the Rankine cycle efficiency under above-mentioned design conditions is about 7%, system net power output substantially in about 150kw (Isentropic Efficiency of Expansion Machine be the condition of 0.65 under), cycle performance is excellent;
(4) cycling hot utilization ratio is high: be zeotrope, there is obvious temperature glide, match with heat transfer temperature difference during phase transformation, effectively can improve heat, thus improves system thermal efficiency.
The present invention is illustrated by above-described embodiment, but should be understood that, above-described embodiment just for the object of illustrating and illustrate, and is not intended to the present invention to be limited in described scope of embodiments.In addition it will be appreciated by persons skilled in the art that the present invention is not limited to above-described embodiment, more kinds of variants and modifications can also be made according to instruction of the present invention, within these variants and modifications all drop on the present invention's scope required for protection.Protection scope of the present invention defined by the appended claims and equivalent scope thereof.
Claims (11)
1. a mixed working fluid for organic rankine cycle, it is characterized in that, described mixed working fluid for organic rankine cycle is by trifluorobichloroethane, pentafluoropropane, 1,1,1-Halothane, 1,1-C2H4F2 C2H4F2 and 1,1, the mixing medium that binary in these five kinds of organic working medium of 1,2-Tetrafluoroethane or ternary form according to certain mass ratio.
2. mixed working fluid for organic rankine cycle according to claim 1, is characterized in that, the component of described mixed working fluid for organic rankine cycle and content are: the trifluorobichloroethane of 10% ~ 60% and the pentafluoropropane of 10% ~ 80%.
3. mixed working fluid for organic rankine cycle according to claim 1, is characterized in that, the component of described mixed working fluid for organic rankine cycle and content are: the trifluorobichloroethane of 3% ~ 97% and 1,1, the 1-Halothane of 3% ~ 97%.
4. mixed working fluid for organic rankine cycle according to claim 1, is characterized in that, the component of described mixed working fluid for organic rankine cycle and content are: the trifluorobichloroethane of 40% ~ 90% and the HFA 134a of 10% ~ 55%.
5. mixed working fluid for organic rankine cycle according to claim 1, is characterized in that, the component of described mixed working fluid for organic rankine cycle and content are: the pentafluoropropane of 50% ~ 85% and 1,1, the 1-Halothane of 15% ~ 50%.
6. mixed working fluid for organic rankine cycle according to claim 1, is characterized in that, the component of described mixed working fluid for organic rankine cycle and content are: the pentafluoropropane of 45% ~ 90% and 1, the 1-C2H4F2 C2H4F2 of 10% ~ 55%.
7. mixed working fluid for organic rankine cycle according to claim 1, is characterized in that, the component of described mixed working fluid for organic rankine cycle and content are: the pentafluoropropane of 50% ~ 70% and the HFA 134a of 30% ~ 50%.
8. mixed working fluid for organic rankine cycle according to claim 1, it is characterized in that, the component of described mixed working fluid for organic rankine cycle and content are: the trifluorobichloroethane of 20% ~ 80%, the pentafluoropropane of 15% ~ 50% and 5% ~ 50% 1,1,1,2-Tetrafluoroethane.
9. mixed working fluid for organic rankine cycle according to claim 1, it is characterized in that, the component of described mixed working fluid for organic rankine cycle and content are: the trifluorobichloroethane of 25% ~ 65%, the pentafluoropropane of 10% ~ 50% and 25% ~ 55% 1,1-C2H4F2 C2H4F2.
10. mixed working fluid for organic rankine cycle according to claim 1, is characterized in that, the component of described mixed working fluid for organic rankine cycle and content are: the trifluorobichloroethane of 20% ~ 60%, 5% ~ 20% 1,1,1-Halothane and 30% ~ 50% 1,1,1,2-Tetrafluoroethane.
11. 1 kinds of methods preparing the mixed working fluid for organic rankine cycle described in any one in claim 1-10, it is characterized in that, described method comprises carries out physical mixed by each constituent element material at normal temperatures by set quality proportioning.
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| CN105694818A (en) * | 2016-02-29 | 2016-06-22 | 哈尔滨工程大学 | Diesel engine waste heat recovery Rankine cycle mixed work medium hexafluoropropane and pentafluoroethane and method for recycling waste heat |
| CN109679583A (en) * | 2018-12-17 | 2019-04-26 | 江苏大学 | The mixed working fluid of middle low temperature Organic Rankine Cycle |
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