WO2014059729A1 - Siloxane-contained mixed working medium for rankine cycle system - Google Patents

Siloxane-contained mixed working medium for rankine cycle system Download PDF

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WO2014059729A1
WO2014059729A1 PCT/CN2012/085431 CN2012085431W WO2014059729A1 WO 2014059729 A1 WO2014059729 A1 WO 2014059729A1 CN 2012085431 W CN2012085431 W CN 2012085431W WO 2014059729 A1 WO2014059729 A1 WO 2014059729A1
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working medium
rankine cycle
mixed working
mixed
siloxane
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李家俊
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天津大学
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the invention belongs to a circulating working medium in a thermal system, and particularly relates to a working fluid in a solar self-complexing Rankine cycle system with an evaporation temperature of 190-270 °C.
  • Solar energy is a renewable energy source that can be directly utilized.
  • solar power generation technology has been widely concerned and studied.
  • solar thermal power generation technology using organic Rankine cycle can not only effectively utilize solar energy resources, reduce CO 2 emissions, and reduce greenhouse effect. It can effectively reduce manufacturing costs.
  • the development of organic Rankine cycle technology is to improve the efficiency of the system, because the self-complexing Rankine cycle can recycle the exhaust steam of the expander more efficiently than the single-stage Rankine cycle, so the system efficiency can be improved.
  • it will limit the popularization and application of organic Rankine cycle solar thermal power generation technology. Therefore, the development of an environmentally friendly, excellent thermal performance, evaporation temperature is
  • a mixed working fluid containing siloxane and used in a Rankine cycle system the mixed working medium consisting of octamethylcyclotetrasiloxane (C 8 H 24 0 4 S i4 ) and ten a composition of a cyclopentasiloxane (C 1() H 3 .0 5 Si 5 ); or an octamethylcyclotetrasiloxane (C 8 H 24 0 4 S i4 ) and octamethyltrisiloxane ( C 8 H 24 0 2 SI 3 ) Composition, the mass percentages are respectively: C 8 H 24 0 4 S i4 / C 10 H 3 o0 6 Si 6 : 20-80/80-20%; C 8 H 24 0 4 S i4 /C 8 H 24 0 2 SI 3 : 60-80/40-20%.
  • the sum of the mass percentages of the respective components of the above mixed working medium is 100%
  • each component substance is physically mixed at a normal temperature in a specified mass ratio.
  • Tb normal boiling point
  • Tc critical temperature
  • Pc critical pressure
  • High safety Silicone is characterized by low toxicity, low flammability and high thermal stability.
  • Suitable for thermal parameters Under the design conditions, the pressure level is low, so the pressure bearing capacity and sealing requirements of the system equipment are lower, which can reduce the system cost.
  • Excellent cycle performance The Rankine cycle efficiency under design conditions is greater than 30%, and the net work output per unit mass cycle is above 43kJ/k g .
  • High cycle heat utilization rate The mixed working fluid is a binary non-azeotropic working medium, and there is temperature slip during the phase change process, which can reduce the internal irreversible loss. When there is an internal heat exchanger in the system, Effectively improve the recovery and utilization rate of the residual steam of the expander, thereby improving the thermal efficiency of the system.
  • the component components of the mixed working fluid in the following examples all refer to the mass percentage.
  • the self-cascading solar high temperature Rankine cycle system features a two-stage solar collector.
  • Example 1 20% C 8 H 24 0 4 S i4 and 80% C 10 H 3 o0 6 Si 6 were taken and mixed as a circulating working medium at normal temperature.
  • Example 2 30% C 8 H 24 0 4 S i4 and 70% C 10 H 3 o0 6 Si 6 were taken and mixed at normal temperature to obtain a circulating working medium.
  • Example 3 40% C 8 H 24 0 4 S i4 and 60% C 10 H 3 o0 6 Si 6 were taken and mixed as a circulating working medium at normal temperature.
  • Example 4 50% C 8 H 24 0 4 S i4 and 50% C 10 H 3 o0 6 Si 6 were taken and mixed as a circulating working medium at normal temperature.
  • Example 5 60% C 8 H 24 0 4 S i4 and 40% C 10 H 3 o0 6 Si 6 were taken and mixed as a circulating working medium at normal temperature.
  • Example 6 60% C 8 H 24 0 4 S i4 and 40% C 8 H 24 0 2 SI 3 were taken and mixed as a circulating working medium at normal temperature.
  • Example 7 70% C 8 H 24 0 4 S i4 and 30% C 8 H 24 0 2 SI 3 were taken and mixed as a circulating working medium at room temperature.
  • Example 8 75% C 8 H 24 0 4 S i4 and 25% C 8 H 24 0 2 SI 3 were taken and mixed as a circulating working medium at normal temperature.
  • Example 9 80% C 8 H 24 0 4 S i4 and 20% C 8 H 24 0 2 SI 3 were taken and mixed as a circulating working medium at normal temperature.
  • the design conditions of the circulation system are as follows: the first stage collector outlet temperature is 190 ° C, the second stage collector outlet temperature is 270 ° C, the condensation temperature is 50 ° C, the working medium pump compression and the expander expansion process are equal. Entropy process. According to the cycle calculation, the relevant parameters and cycle performance indicators of the above nine embodiments are shown in Table 2.

Abstract

A siloxane-contained mixed working medium for a Rankine cycle system is formed by octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, or is formed by octamethylcyclotetrasiloxane and octamethyltrisiloxane. Components are physically mixed according to a specific ratio in a normal temperature to obtain the mixed working medium. The mixed working medium is suitable for a solar self-healing auto-cascade Rankine cycle system with an evaporation temperature 190-270ºC. In the present invention, the siloxane of the mixed working medium has characteristics of low toxicity, low flammability, and high heat stability; under designed working conditions, the present invention has low requirements for the pressure, and has low requirements for the bearing capacity and sealability of a system device, the Rankine cycle efficiency is higher than 30%, and the unit mass cycle net work output is basically higher than 43kJ/kg. The mixed working medium is a binary non-azeotropic working medium, has temperature shift in a phase change process, can reduce the internal irreversible loss, and can effectively improve the recycling rate of dead steam waste heat of an expander when an internal heat exchanger exists in the system, thereby improving the heat efficiency of the system.

Description

含有硅氧烷并用于朗 # 环系统的混合工质  Mixture containing siloxane and used in the Lang # ring system
技术领域  Technical field
本发明属于热力系统中的循环工质， 具体涉及到蒸发温度为 190-270 °C的太阳能自复 叠朗肯循环系统中的工质。  The invention belongs to a circulating working medium in a thermal system, and particularly relates to a working fluid in a solar self-complexing Rankine cycle system with an evaporation temperature of 190-270 °C.
背景技术  Background technique
太阳能属于可直接利用的可再生能源， 其中太阳能发电技术一直受到广泛关注和研 究， 例如采用有机朗肯循环的太阳能热发电技术， 不仅可有效利用太阳能资源， 减少 C02 排放， 降低温室效应， 还可以有效地降低制造成本。 有机朗肯循环技术的方向发展在于提 高系统的效率， 因为自复叠朗肯循环要比单级朗肯循环能更有效地回收利用膨胀机的乏 汽， 所以其系统效率可得到提高。 但如果缺乏适合的循环工质， 则限制了有机朗肯循环太 阳能热发电技术的推广应用。 因此开发一种环境友好、 热力性能优良、 蒸发温度为Solar energy is a renewable energy source that can be directly utilized. Among them, solar power generation technology has been widely concerned and studied. For example, solar thermal power generation technology using organic Rankine cycle can not only effectively utilize solar energy resources, reduce CO 2 emissions, and reduce greenhouse effect. It can effectively reduce manufacturing costs. The development of organic Rankine cycle technology is to improve the efficiency of the system, because the self-complexing Rankine cycle can recycle the exhaust steam of the expander more efficiently than the single-stage Rankine cycle, so the system efficiency can be improved. However, if there is no suitable circulating working fluid, it will limit the popularization and application of organic Rankine cycle solar thermal power generation technology. Therefore, the development of an environmentally friendly, excellent thermal performance, evaporation temperature is
190-270 。C , 适用于太阳能自复叠朗肯循环系统的工质具有重要意义。 190-270. C. It is of great significance to apply to the working fluid of solar self-complexing Rankine cycle system.
发明内容  Summary of the invention
本发明的目的是， 提供一组适用于自复叠太阳能高温朗肯循环系统、 含有硅氧烷的混 合工质， 以使其具有较高的热力循环性能。  SUMMARY OF THE INVENTION It is an object of the present invention to provide a set of mixed working fluids suitable for self-capping solar high temperature Rankine cycle systems containing siloxanes to provide high thermodynamic cycling performance.
本发明内容介绍及实施例： 含有硅氧烷并用于朗肯循环系统的混合工质， 所述混合工 质由八甲基环四硅氧烷 （C8H2404Si4) 和十甲基环五硅氧烷 （C1()H3。05Si5) 组成； 或由八甲基 环四硅氧烷（C8H2404Si4)和八甲基三硅氧烷（C8H2402SI3)组成，其质量百分比分别为： C8H2404Si4/ C10H3o06Si6: 20-80/80-20%； C8H2404Si4/C8H2402SI3: 60-80/40-20%。 以上混合工质其各自组元 物质质量百分数之和为 100%。 SUMMARY OF THE INVENTION AND EXAMPLES: A mixed working fluid containing siloxane and used in a Rankine cycle system, the mixed working medium consisting of octamethylcyclotetrasiloxane (C 8 H 24 0 4 S i4 ) and ten a composition of a cyclopentasiloxane (C 1() H 3 .0 5 Si 5 ); or an octamethylcyclotetrasiloxane (C 8 H 24 0 4 S i4 ) and octamethyltrisiloxane ( C 8 H 24 0 2 SI 3 ) Composition, the mass percentages are respectively: C 8 H 24 0 4 S i4 / C 10 H 3 o0 6 Si 6 : 20-80/80-20%; C 8 H 24 0 4 S i4 /C 8 H 24 0 2 SI 3 : 60-80/40-20%. The sum of the mass percentages of the respective components of the above mixed working medium is 100%.
各组元物质的基本参数如表 1所示。  The basic parameters of each component are shown in Table 1.
本发明的制备方法是， 将各组元物质按其指定的质量配比在常温下进行物理混合。  In the preparation method of the present invention, each component substance is physically mixed at a normal temperature in a specified mass ratio.
表 1混合工质各组元基本参数  Table 1 Basic parameters of each component of mixed working fluid
其中 ： Tb: 正常沸点， Tc: 临界温度， Pc: 临界压力  Where: Tb: normal boiling point, Tc: critical temperature, Pc: critical pressure
组元名称 分子式 分 Tb °C Tc Pc  Component name Molecular formula Tb °C Tc Pc
子量 ( °C ) (MPa) 八甲基环四 C8H24O4S 29 175. 313 1. 33 硅氧烷 i4 6. 62 00 . 35 2  Sub-quantity ( °C ) (MPa) Octamethylcyclotetraene C8H24O4S 29 175. 313 1. 33 Siloxane i4 6. 62 00 . 35 2
十甲基环五 C10H30O5 37 210. 346 1. 16 硅氧烷 Si5 0. 77 95 . 00 Decamethylcyclopenta C10H30O5 37 210. 346 1. 16 Siloxane Si 5 0. 77 95 . 00
八甲基三硅 C8H24O2S 23 152. 290 1. 41 6. 53 53 94 本发明具有以下几点有益效果： Octamethyltrisiloxane C8H24O2S 23 152. 290 1. 41 6. 53 53 94 The present invention has the following beneficial effects:
( 1 ) 安全性高： 硅氧烷具有毒性低、 可燃性低及热稳定性高的特点。 （2 ) 热工参数 适宜： 在设计工况下， 压力水平较低， 因此对系统设备的承压能力与密封性要求较低， 可 以减少系统成本。 （3 ) 循环性能优良： 在设计工况下的朗肯循环效率大于 30%， 单位质量 循环净功输出量基本为 43kJ/kg以上。 （4) 循环热利用率较高： 该混合工质为二元非共沸 工质， 在相变过程中存在温度滑移， 可减少内部不可逆损失， 当系统中存在内部换热器时， 可以有效提高膨胀机乏汽余热的回收利用率， 从而提高系统热效率。 (1) High safety: Silicone is characterized by low toxicity, low flammability and high thermal stability. (2) Suitable for thermal parameters: Under the design conditions, the pressure level is low, so the pressure bearing capacity and sealing requirements of the system equipment are lower, which can reduce the system cost. (3) Excellent cycle performance: The Rankine cycle efficiency under design conditions is greater than 30%, and the net work output per unit mass cycle is above 43kJ/k g . (4) High cycle heat utilization rate: The mixed working fluid is a binary non-azeotropic working medium, and there is temperature slip during the phase change process, which can reduce the internal irreversible loss. When there is an internal heat exchanger in the system, Effectively improve the recovery and utilization rate of the residual steam of the expander, thereby improving the thermal efficiency of the system.
具体实 式  Specific form
以下实施例中混合工质的各组元组分均指质量百分数。 自复叠太阳能高温朗肯循环系 统设有两级太阳能集热器。  The component components of the mixed working fluid in the following examples all refer to the mass percentage. The self-cascading solar high temperature Rankine cycle system features a two-stage solar collector.
实施例 1： 取 20% C8H2404Si4 、 80% C10H3o06Si6, 常温下进行混合后作为循环工质。 Example 1: 20% C 8 H 24 0 4 S i4 and 80% C 10 H 3 o0 6 Si 6 were taken and mixed as a circulating working medium at normal temperature.
实施例 2： 取 30% C8H2404Si4 、 70% C10H3o06Si6, 常温下进行混合后作为循环工质。 Example 2: 30% C 8 H 24 0 4 S i4 and 70% C 10 H 3 o0 6 Si 6 were taken and mixed at normal temperature to obtain a circulating working medium.
实施例 3： 取 40% C8H2404Si4 、 60% C10H3o06Si6, 常温下进行混合后作为循环工质。 Example 3: 40% C 8 H 24 0 4 S i4 and 60% C 10 H 3 o0 6 Si 6 were taken and mixed as a circulating working medium at normal temperature.
实施例 4: 取 50% C8H2404Si4 、 50% C10H3o06Si6, 常温下进行混合后作为循环工质。 Example 4: 50% C 8 H 24 0 4 S i4 and 50% C 10 H 3 o0 6 Si 6 were taken and mixed as a circulating working medium at normal temperature.
实施例 5： 取 60% C8H2404Si4 、 40% C10H3o06Si6, 常温下进行混合后作为循环工质。 Example 5: 60% C 8 H 24 0 4 S i4 and 40% C 10 H 3 o0 6 Si 6 were taken and mixed as a circulating working medium at normal temperature.
实施例 6： 取 60% C8H2404Si4 、 40% C8H2402SI3， 常温下进行混合后作为循环工质。 Example 6: 60% C 8 H 24 0 4 S i4 and 40% C 8 H 24 0 2 SI 3 were taken and mixed as a circulating working medium at normal temperature.
实施例 7： 取 70% C8H2404Si4 、 30% C8H2402SI3， 常温下进行混合后作为循环工质。 Example 7: 70% C 8 H 24 0 4 S i4 and 30% C 8 H 24 0 2 SI 3 were taken and mixed as a circulating working medium at room temperature.
实施例 8： 取 75% C8H2404Si4 、 25% C8H2402SI3， 常温下进行混合后作为循环工质。 Example 8: 75% C 8 H 24 0 4 S i4 and 25% C 8 H 24 0 2 SI 3 were taken and mixed as a circulating working medium at normal temperature.
实施例 9: 取 80% C8H2404Si4 、 20% C8H2402SI3， 常温下进行混合后作为循环工质。 Example 9: 80% C 8 H 24 0 4 S i4 and 20% C 8 H 24 0 2 SI 3 were taken and mixed as a circulating working medium at normal temperature.
循环系统设计工况取为:第一级集热器出口温度 190°C，第二级集热器出口温度 270°C， 冷凝温度 50°C， 工质泵压縮与膨胀机膨胀过程为等熵过程。 根据循环计算， 上述 9个实施 例的有关参数和循环性能指标如表 2所示。  The design conditions of the circulation system are as follows: the first stage collector outlet temperature is 190 ° C, the second stage collector outlet temperature is 270 ° C, the condensation temperature is 50 ° C, the working medium pump compression and the expander expansion process are equal. Entropy process. According to the cycle calculation, the relevant parameters and cycle performance indicators of the above nine embodiments are shown in Table 2.
表 2 九个实施例循环性能 循环性能 实施例 实施例 实施例 实施例 实施例 参数 1 2 3 4 5 蒸发压力 73. 626 81. 421 88. 967 98. 296 107. 397 Table 2 Nine Examples Cycle Performance Cycle Performance Examples Examples Examples Examples Examples Parameters 1 2 3 4 5 Evaporation pressure 73. 626 81. 421 88. 967 98. 296 107. 397
(KPa) 冷凝压力 0. 335 0. 397 0. 450 0. 497 0. 539 (KPa) 分离器进 0. 761 0. 760 0. 809 0. 779 0. 785 口干度 气相回路 0. 230/0 0. 341/0 0. 437/0 0. 545/0 0. 642/0 组分比 . 770 . 659 . 563 . 455 . 358 液相回路 0. 103/0 0. 170/0 0. 242/0 0. 341/0 0. 448/0 组分比 . 897 . 830 . 758 . 659 . 552 循环输出 47. 98 38. 08 43. 46
Figure imgf000004_0001
53. 84 净功（kj/kg) 朗肯循环 31. 50 31. 65 30. 40 32. 20 32. 85 效率 ％ 续表 2 循环性能参数 实施例 实施例 实施例 实施例 (KPa) Condensing pressure 0. 335 0. 397 0. 450 0. 497 0. 539 (KPa) Separator into 0. 761 0. 760 0. 809 0. 779 0. 785 Dryness gas phase loop 0. 230/0 0. 341/0 0. 437/0 0. 545/0 0. 642/ 0 composition ratio . 770 . 659 . 563 . 455 . 358 liquid phase circuit 0. 103 / 0 0. 170 / 0 0. 242 / 0 0. 341 / 0 0. 448 / 0 composition ratio . 897 . 758 . 659 . 552 Cyclic output 47. 98 38. 08 43. 46
Figure imgf000004_0001
53. 84 net work (kj/kg) Rankine cycle 31. 50 31. 65 30. 40 32. 20 32. 85 efficiency % continued Table 2 Cycle performance parameters Examples Embodiments Examples
6 7 8 9 蒸发压力（KPa) 188. 385 177. 695 172. 411 166. 192 冷凝压力（KPa) 1. 517 1. 365 1. 280 1. 187 分离器进口干度 0. 836 0. 817 0. 796 0. 877 气相回路组分比 0. 581/0 0. 681/0 0. 731/0 0. 790/0  6 7 8 9 Evaporation pressure (KPa) 188. 385 177. 695 172. 411 166. 192 Condensation pressure (KPa) 1. 517 1. 365 1. 280 1. 187 Separator inlet dryness 0. 836 0. 817 0 796 0. 877 Gas phase loop composition ratio 0. 581/0 0. 681/0 0. 731/0 0. 790/0
. 449 . 319 . 269 . 210 液相回路组分比 0. 695/0 0. 784/0 0. 824/0 0. 869/0  449 . 319 . 269 . 210 liquid phase composition ratio 0. 695/0 0. 784/0 0. 824/0 0. 869/0
. 306 . 216 . 176 . 131 循环输出净功 46. 21 43. 46 47. 98 38. 75 (kj/kg) 朗肯循环效率 ％ 32. 11 32. 69 33. 47 30. 91  306 . 216 . 176 . 131 Recycling net work 46. 21 43. 46 47. 98 38. 75 (kj/kg) Rankine cycle efficiency % 32. 11 32. 69 33. 47 30. 91

Claims

权利要求书 Claim
1. 含有硅氧烷并用于朗肯循环系统的混合工质，其特征是所述混合工质由八甲基环四 硅氧烷（ C8H2404Si4 )和十甲基环五硅氧烷（ C1()H3。05S i5 )组成；或由八甲基环四硅氧烷（ C8H2404Si4 ) 和八甲基三硅氧烷 ( C8H2402SI3 ) 组成， 其质量百分比分别为： C8H2404Si4/ C10H3o06Si6: 20-80/80-20%； C8H2404Si4/C8H2402SI3: 60-80/40-20%； 以上混合工质其各自组元物质质量百 分数之和为 100%。 A mixed working fluid containing siloxane and used in a Rankine cycle system, characterized in that the mixed working substance is composed of octamethylcyclotetrasiloxane (C 8 H 24 0 4 S i4 ) and decamethylcyclopentane Composition of siloxane (C 1() H 3 .0 5 S i 5 ); or octamethylcyclotetrasiloxane (C 8 H 24 0 4 S i4 ) and octamethyltrisiloxane (C 8 H 24 0 2 SI 3 ) Composition, the mass percentages are: C 8 H 24 0 4 S i4 / C 10 H 3 o0 6 Si 6 : 20-80/80-20%; C 8 H 24 0 4 S i4 /C 8 H 24 0 2 SI 3 : 60-80/40-20%; The sum of the mass percentages of the respective components of the above mixed working medium is 100%.
PCT/CN2012/085431 2012-10-16 2012-11-28 Siloxane-contained mixed working medium for rankine cycle system WO2014059729A1 (en)

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