CN112409993B - Safe and efficient mixed working medium suitable for LNG cold energy utilization - Google Patents
Safe and efficient mixed working medium suitable for LNG cold energy utilization Download PDFInfo
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Abstract
The invention discloses a safe and efficient mixed working medium suitable for LNG cold energy utilization, which comprises a first component and a second component, wherein the first component is one of R290, R125 and R161, and the second component is at least one of R23, R116, R32, R1270 or R116. The mixed working medium is formed by mixing a first component and a second component in a normal pressure liquid phase state. The preparation method of the mixed working medium is simple and easy to realize. The mixed working medium has good environmental performance, ODP is 0, and GWP is lower; and the flammability of the flammable working medium is greatly reduced by mixing with the non-flammable gas, and the safety is very high. In addition, the mixed working medium has the power generation efficiency superior to alkane working media such as propane and the like.
Description
Technical Field
The invention belongs to the technical field of LNG cold energy utilization, and particularly relates to a safe and efficient mixed working medium suitable for LNG cold energy utilization.
Background introduction
At present, the LNG cold energy utilization field is wide, and comprises cold energy power generation, sea water desalination, air separation, light hydrocarbon separation, a freezing warehouse, dry ice manufacture, an air conditioner, low-temperature crushing, low-temperature medical treatment and the like. The method for establishing the Organic Rankine Cycle (ORC) power generation system by utilizing the LNG cold energy is considered to be a promising LNG cold energy power generation utilization technology, and has the advantages of simple structure, high efficiency, environmental protection and the like. Therefore, it is critical to improve the performance of the power generation system and increase the net output power.
The most conventional LNG cold energy Rankine cycle power generation system comprises an evaporator, a condenser, a working medium pump and a turbine, the LNG cold energy Rankine cycle power generation process is shown in figure 1, any other LNG cold energy Rankine cycle power generation system is improved or optimized on the basis, a power generation working medium is pumped into the evaporator in a pressurizing mode through the working medium pump, the gas exchanges heat with a heat source in the evaporator to become gas with certain pressure, then the gas enters the turbine to do work through expansion and drive a generator to generate power, a low-pressure power generation working medium after the work through expansion enters the condenser, is condensed by the LNG to become power generation working medium liquid, and then enters the working medium pump to perform the next cycle.
At present, the most commonly used power generation working medium of the LNG cold energy organic Rankine cycle power generation system is monopropellant propane, LNG cold energy at minus 162 ℃ to minus 35 ℃ can be recovered, although certain advantages are provided in environmental protection, the ODP value is 0, and the GWP value is 20, but the condensation process of the monopropellant power generation working medium is constant temperature phase change, and is not matched with a heat exchange curve during LNG heat exchange, so that a large amount of LNG can be lost
And energy, the LNG cold energy utilization rate is low. And the propane has extremely flammable and explosive characteristics, has high requirements on equipment (such as working medium pumps and turbines) and site safety, and increases the initial investment and production danger of the system.
Chinese patent CN 106939802A discloses a system and a method for cascade power generation and residual cold output by using mixed working media of LNG cold energy, wherein the adopted power generation working media are mixed working media of methane, ethylene and propane; the Chinese patent application CN 110847987A provides a system and a method for generating electricity and comprehensively utilizing LNG cold energy of a mixed working medium, wherein the mixed working medium used by the system is a mixture of methane, ethane and propane; chinese patent CN 106194302a discloses a comprehensive utilization system of LNG cold energy, wherein the mixed working medium adopted in the power generation system is a mixture of methane, ethylene and propane. The technical scheme optimizes the power generation working medium from the angle of a mixed working medium, but the selected working medium is an alkane organic working medium, has extremely flammable and explosive characteristics, belongs to a working medium with a very high risk coefficient, and can be limited in use. In addition, methane is a gas with high greenhouse effect, and GWP analysis shows that the greenhouse effect of methane is 25 times larger than that of carbon dioxide in unit molecule number, and the environment-friendly performance of the methane is poor.
Disclosure of Invention
In order to solve the technical problems, the primary object of the present invention is to provide a high-efficiency and safe mixed working medium suitable for LNG cold energy utilization, which has good environmental friendliness, high safety, and good thermodynamic properties, and can improve the LNG cold energy utilization rate.
In order to achieve the above object, the present invention provides the following technical solutions:
a safe and efficient mixed working medium suitable for LNG cold energy utilization comprises a first component and a second component, wherein the first component is one of R290, R125 and R161, and the second component is at least one of R23, R116, R32, R1270 or R116.
The mixed working medium is formed by mixing a first component and a second component in a normal pressure liquid phase state.
As a preferable technical scheme of the mixed working medium, the first component is R290, and the second component is one of R23, R116 and R32.
Further, by mass percent, the proportion of R290 in the mixed working medium is 65-99%, and the proportion of R23 is 1-35%.
Further, in percentage by mass, the proportion of R290 in the mixed working medium is 35-99%, and the proportion of R116 is 1-65%.
Further, in percentage by mass, the proportion of R290 in the mixed working medium is 68-99%, and the proportion of R32 is 1-32%.
The first component R290 is a safety class a3, extremely flammable gas.
A second component: the R23 has the safety grade of A1, does not combust gas, can be used as a gas fire extinguishing agent, and has the characteristics of cleanness, low toxicity, good fire extinguishing effect and the like. R116 has a safety rating of A1 and is non-combustible. The safety rating of R32 is A2, the ignition temperature is 648 ℃, the fire-resistant cable can not be ignited except open fire, and the fire-resistant cable can automatically extinguish once the fire leaves the open fire.
After R290 is respectively mixed with R23, R116 or R32, the flammability of R290 is greatly reduced by non-combustible gas or flame-retardant gas, and the safety of the mixed working medium is improved.
As another preferred technical scheme of the mixed working medium, the first component is R125, and the second component is R1270 or R32.
Further, the proportion of R125 in the mixed working medium is 40-99% and the proportion of R1270 is 1-60% in percentage by mass.
Further, the proportion of R125 in the mixed working medium is 90-99% and the proportion of R32 is 1-10% in percentage by mass.
The first component R125 has a safety rating of A1 and is non-combustible.
A second component: the safety rating of R1270 is a3, extremely flammable gas. After R1270 and R125 are mixed, because R125 is non-combustible gas, the flammability of R1270 is greatly reduced, and the safety of the mixed working medium is improved.
As another preferable technical scheme of the mixed working medium, the first component is R161, and the second component is R116.
Further, by mass percentage, the proportion of R161 in the mixed working medium is 30-65%, and the proportion of R116 is 35-70%.
The first component R161 was a safety rating of a2, a lightly flammable gas. The second component R116 is a safety rating of a1, non-combustible gas. After R161 and R116 are mixed, R116 is non-combustible gas, so that the flammability of R161 is greatly reduced, and the safety of the mixed working medium is improved.
The invention also provides a preparation method of the mixed working medium suitable for LNG cold energy utilization, wherein the first component and the second component are physically mixed according to the mass ratio under the normal-pressure liquid phase state to obtain a binary mixed working medium.
The invention has the beneficial effects that:
the preparation method of the mixed working medium is simple and easy to realize. The mixed working medium has good environmental performance, ODP is 0, and GWP is lower; and the flammability of the flammable working medium is greatly reduced by mixing with the non-flammable gas, and the safety is very high. In addition, the mixed working medium has the power generation efficiency superior to alkane working media such as propane and the like.
Drawings
Fig. 1 is a flow chart of LNG cold energy rankine cycle power generation.
FIG. 2 is a heat exchange curve of the mixed working medium with propane and LNG.
Detailed Description
The invention provides a safe mixed working medium suitable for an LNG cold energy Rankine cycle power generation system, and in order to enable technical schemes of the invention to be better understood by persons skilled in the art, the technical schemes are clearly and completely described below by combining with embodiments, and the described embodiments are only partial embodiments of the invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present application.
In the embodiment, the proportions of the components are mass percent, and the sum of the mass percent of all the components in the mixed working medium is 100%.
Example 1
Taking 65% of R290 and 35% of R23, and physically mixing in a normal pressure liquid phase state to obtain the mixed working medium.
Example 2
Taking 35% of R290 and 65% of R116, and physically mixing in a normal pressure liquid phase state to obtain a mixed working medium.
Example 3
Taking 68% of R290 and 32% of R32, and physically mixing in a normal pressure liquid phase state to obtain the mixed working medium.
Example 4
And taking 40% of R125 and 60% of R1270, and physically mixing under a normal pressure liquid phase state to obtain a mixed working medium.
Example 5
And taking 90% of R125 and 10% of R32, and physically mixing in a normal pressure liquid phase state to obtain the mixed working medium.
Example 6
And taking 30% of R161 and 70% of R116, and physically mixing in a normal-pressure liquid phase state to obtain a mixed working medium.
The mixed working medium of the embodiment is used for LNG Rankine cycle power generation, the process is shown in figure 1, and the specific parameters are as follows: the LNG mass flow is 200t/h, the pressure is 9MPag, the LNG cold energy recovery temperature section is-162 ℃ to-35 ℃, the evaporation temperature of the power generation working medium is 20 ℃, and the condensation pressure is 30 kPag. The mixed working medium is pressurized and pumped into an evaporator by a working medium pump, the mixed working medium is subjected to heat exchange with a heat source in the evaporator to be changed into gas with the pressure of 30kPag, then the gas enters a turbine to be expanded and acted and drives a generator to generate power, the low-pressure mixed working medium subjected to expansion and action enters a condenser to be condensed by LNG to be changed into mixed working medium liquid, and then the mixed working medium liquid enters the working medium pump to perform the next cycle. The heat source can be natural seawater, low-grade industrial waste heat and the like.
The output power of the single working medium adopted by the mixed working medium is different from that of propane by comparing the single working medium with the propane. And further comparing the heat exchange curve of the mixed working medium and the propane during the heat exchange with the LNG with the output power of the Rankine cycle power generation system, wherein the result is shown in FIG. 2 and Table 1.
TABLE 1 turbine output power comparison of mixed working fluids with propane
| Working medium | Output power kW |
| Propane | 4782 |
| Example 1 | 5189 |
| Example 2 | 5369 |
| Example 3 | 5073 |
| Example 4 | 5289 |
| Example 5 | 5330 |
| Example 6 | 5546 |
As can be seen from FIG. 2, the temperature difference of the heat exchange curve of the mixed working medium and the LNG is smaller, the mixed working medium is more fit, and the heat exchange effect is better; as can be seen from Table 1, the output power of the mixed working medium of the invention is higher than that of propane, which shows that the mixed working medium not only improves the safety of the system, but also improves the utilization rate of LNG cold energy.
The above embodiments are only used for illustrating the design idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention accordingly, and the protection scope of the present invention is not limited to the above embodiments. Therefore, all equivalent changes and modifications made in accordance with the principles and concepts disclosed herein are intended to be included within the scope of the present invention.
Claims (3)
1. A safe and efficient mixed working medium suitable for LNG cold energy utilization is characterized by comprising a first component and a second component, wherein the first component is R290, and the second component is one of R23, R116 and R32; by mass percentage, the proportion of R290 in the mixed working medium is 65-99%, and the proportion of R23 is 1-35%;
or the proportion of R290 in the mixed working medium is 35-99 percent, and the proportion of R116 is 1-65 percent;
or the proportion of R290 in the mixed working medium is 68-99 percent, and the proportion of R32 is 1-32 percent;
or said first component is R125 and said second component is R1270; in percentage by mass, the proportion of R125 in the mixed working medium is 40-99%, and the proportion of R1270 is 1-60%;
or said first component is R161 and said second component is R116; by mass percentage, the proportion of R161 in the mixed working medium is 30-65%, and the proportion of R116 is 35-70%.
2. A mixed working medium suitable for LNG cold energy utilization according to claim 1, characterized in that the mixed working medium is formed by mixing a first component and a second component in a normal pressure liquid phase state.
3. A preparation method of a mixed working medium suitable for LNG cold energy utilization, as claimed in claim 1, characterized in that the first component and the second component are physically mixed according to a mass ratio under a normal pressure liquid phase state to obtain a binary mixed working medium.
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| CN1029625C (en) * | 1990-12-17 | 1995-08-30 | 纳幕尔杜邦公司 | Constant boiling compositions of fluorinated hydrocarbons |
| US5234613A (en) * | 1991-09-30 | 1993-08-10 | E.I. Du Pont De Nemours And Company | Substantially constant boiling compositions of difluoromethane and propane |
| ES2174872T3 (en) * | 1993-02-05 | 2002-11-16 | Du Pont | COMPOSITIONS OF A HYDROFLUOROCARBIDE AND A HYDROCARBON N. |
| CN1083474C (en) * | 1995-10-24 | 2002-04-24 | 顾雏军 | Improved non-azeotropic operating medium using in thermal circulation |
| EP1123959B8 (en) * | 1998-06-06 | 2006-04-26 | Nihon Freezer Co., Ltd. | Coolant for super low temperature cooling |
| FR2892125B1 (en) * | 2005-10-14 | 2010-07-30 | Arkema | COMPOSITION BASED ON HYDROFLUOROCARBONS |
| CN101302423B (en) * | 2008-06-27 | 2010-06-02 | 北京工业大学 | Working substance for thermal syphon type energy recovery apparatus |
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| CN104449580B (en) * | 2013-09-24 | 2018-01-26 | 中化蓝天集团有限公司 | A kind of composition containing HFC 161 and stabilizer |
| CN107556969B (en) * | 2016-06-30 | 2020-09-08 | 中石化洛阳工程有限公司 | Working medium for liquefied natural gas cold energy organic Rankine cycle power generation |
| CN109852348B (en) * | 2019-01-10 | 2020-10-23 | 珠海格力电器股份有限公司 | Environment-friendly mixed working medium |
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