CN1425735A - A group of medium and high temperature heat pump mixed working medium - Google Patents

A group of medium and high temperature heat pump mixed working medium Download PDF

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Publication number
CN1425735A
CN1425735A CN 03100578 CN03100578A CN1425735A CN 1425735 A CN1425735 A CN 1425735A CN 03100578 CN03100578 CN 03100578 CN 03100578 A CN03100578 A CN 03100578A CN 1425735 A CN1425735 A CN 1425735A
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hfc
hcfc
high temperature
temperature heat
moderate
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CN1233780C (en
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王怀信
马利敏
郑臣明
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Tianjin University
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Tianjin University
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Abstract

The serial mixed working mediums for medium and high temperature heat pump are suitable for use as the refrigerant of medium and high temperature heat pump system of condensatino temperature 100-160 deg.c. They are binary and ternary mixtures of eight kinds of matters, including HCFC-123, HCFC-124, HFC-134a, HCFC-142b, HFC-152a, HFC-245fa, HFC236-fa and HC-600a in different mass proportions. The different components in required proportion area mixed physically at normal temperature to form the corresponding mixed working mediums. The working medium have no damage to ozonosphere, lower green house effect, proper thermodynamic parameters and excellent circulation performance. They may be used in the medium and high temperature heat pump system of HCFC22 air compressor.

Description

One group of moderate and high temperature heat mixing medium
Technical field
The invention belongs to the refrigeration agent in heat pump or refrigeration, the air-conditioning system, especially be suitable as condensing temperature and be the refrigeration working medium in 60-120 ℃ the moderate and high temperature heat system.
Background technology
For produce and life in a large amount of that exist, to heat energy grade requirement relatively low (temperature is 60-160 ℃) with can link, adopt the heat pump heat supply technology that the total energy utilising efficiency higher than conventional energy-provision way not only arranged, minimizing CO 2Discharging (thereby reducing Greenhouse effect) also can effectively utilize the low grade heat energy that contains in industrial exhaust heat, Geothermal energy, sun power and the environment (air, soil, surface water or shallow ground water), reduces the thermal pollution that the waste heat discharging causes.Current, high temperature in the heat pump techniques forward (condensing temperature is 80-100 ℃), high temperature (condensing temperature is higher than 100 ℃) heat pump direction develop, and restrict one of key issue of its development, are exactly to lack the cycle fluid that is fit to.The material that in the past once was used as high temperature heat pump system working medium has CFC11, CFC113, CFC114 etc., they are CFC class material, its depletion of the ozone layer gesture (ODP) and global warming potential (GWP) are all very big, and developed country is in forbidding in 1996, and developing country also will be in forbidding in 2010.What application was more at present is the air-conditioning-heat pump of working medium with HCFC22 or its surrogate R407C, R410A etc., the hot water top temperature that can provide is 50-55 ℃, and (high more not only cycle performance worsens, also will cause the accident because of the pressure and the warm upper limit of row that breaks through system), the heat energy of higher temperature level can't be provided.Development environment close friend, the good novel working medium of thermal performance are most important to the development of moderate and high temperature heat technology.
Mixing medium provided by the invention is for condensing temperature is that 60-120 ℃ moderate and high temperature heat system applies is developed, and also can be used as centrifugal refrigerating, air conditioning unit working medium.
Summary of the invention
The purpose of this invention is to provide one group and be suitable for the new working medium that the moderate and high temperature heat unit is used, make its environmental characteristics and cycle performance all good.
Content introduction of the present invention and embodiment: one group of moderate and high temperature heat mixing medium, contain 1,1-two chloro-2,2,2-Halothane (HCFC-123), one chloro-1,2,2,2-Tetrafluoroethane (HCFC-124), 1,1,1,2-Tetrafluoroethane (HFC-134a), a chloro-1,1-C2H4F2 C2H4F2 (HCFC-142b), 1,1-C2H4F2 C2H4F2 (HFC-152a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), Trimethylmethane (HC600a), 1,1,1,3,3,3 ,-HFC-236fa constituent element materials such as (HFC-236fa).The basic parameter of each constituent element material is as shown in table 1.By HFC-134a, HCFC-124, HCFC-142b forms moderate and high temperature heat mixing medium-1, by HFC-152a, HCFC-124, HCFC-123 forms moderate and high temperature heat mixing medium-2, by HFC-152a, HFC-134a, HCFC-123 forms moderate and high temperature heat mixing medium-3, by HFC-134a, HCFC-124, HCFC-123 forms moderate and high temperature heat mixing medium-4, by HFC-152a, HCFC-124, HFC-245fa forms moderate and high temperature heat mixing medium-5, by HCFC-124, HCFC-142b, HFC-152a forms moderate and high temperature heat mixing medium-6, by HFC-134a, HCFC-142b, HCFC-123 forms moderate and high temperature heat mixing medium-7, by HFC-134a, HCFC-124, HFC-245fa forms moderate and high temperature heat mixing medium-8, by HFC-152a, HFC-134a, HFC-236fa forms moderate and high temperature heat mixing medium-9, by HFC-152a, HCFC-124, HFC-236fa forms moderate and high temperature heat mixing medium-10, by HCFC-124, HC-600a forms moderate and high temperature heat mixing medium-11.Its concrete proportioning (mass percent) is:
HFC-134a/HCFC-124/HCFC142-b (moderate and high temperature heat mixing medium-1, when comprising HCFC-142b and be zero component, HFC-134a/HCFC-124 is the binary mixing medium): 5-50/30-90/0-60%,
HFC-152a/HCFC-124/HCFC-123 (moderate and high temperature heat mixing medium-2): 5-30/40-90/20-60%,
HFC-152a/HFC-134a/HCFC-123 (moderate and high temperature heat mixing medium-3): 5-40/30-90/5-70%,
HFC-134a/HCFC-124/HCFC-123 (moderate and high temperature heat mixing medium-4, when comprising HCFC-124 and be zero component, HFC-134a/HCFC-123 is the binary mixing medium): 20-90/0-40/10-80%,
HFC-152a/HCFC-124/HFC-245fa (moderate and high temperature heat mixing medium-5): 5-30/40-90/5-30%,
HCFC-124/HCFC-142b/HFC-152a (moderate and high temperature heat mixing medium-6, when comprising HCFC-142b and be zero component, HCFC-124/HFC-152a is the binary mixing medium): 40-95/0-30/5-30%,
HFC-134a/HCFC-142b/HCFC-123 (moderate and high temperature heat mixing medium-7, when comprising HCFC-123 and be zero component, HFC-134a/HCFC-142b is the binary mixing medium): 20-95/5-50/0-75%,
HFC-134a/HCFC-124/HFC-245fa (moderate and high temperature heat mixing medium-8, when comprising HCFC-124 and be zero component, HFC-134a/HFC-245fa is the binary mixing medium): 30-95/0-70/10-60%,
HFC-152a/HFC-134a/HFC-236fa (moderate and high temperature heat mixing medium-9, when comprising HFC-152a and be zero component, HFC-134a/HFC-236fa is the binary mixing medium): 0-25/20-70/30-80%,
HFC-152a/HCFC-124/HFC-236fa (moderate and high temperature heat mixing medium-10, when comprising HCFC-124 and be zero component, HFC-152a/HFC236-fa is the binary mixing medium): 5-30/0-60/10-95%,
HCFC-124/HC-600a (moderate and high temperature heat mixing medium-11): 90-99/1-10%.
The preparation method of mixing medium of the present invention is each constituent element material to be carried out physical mixed at normal temperatures by its specified quality proportioning get final product.
The present invention has the following advantages and beneficial effect:
(1) compliance with environmental protection requirements: ODP of the present invention equals zero or approaches zero, and the GWP in most mixing mediums is lower, less than 1000.As seen its environmental characteristics is good, meets the requirement of protecting ozonosphere, reducing Greenhouse effect.(2) thermal parameter is suitable: under the moderate and high temperature heat design conditions, and close under the standard air conditioning condition of stress level and HCFC22, row's temperature is lower than row's temperature of HCFC22 compressor and limits.Therefore, can adopt the compressor of air conditioner of HCFC22 in the high temperature heat pump system design, need not to be working medium of the present invention specialized designs compressor separately.(3) cycle performance is good: the present invention is about 4.4 at the heat supply COP under the high temperature heat pump design conditions, the unit mass heat supplied substantially more than 110kJ/kg, the unit volume heat supplied is at 3500kJ/m 3About, cycle performance is good.The interchanger load is close with the HCFC22 air-conditioning system, working medium of the present invention directly can be poured into (some working medium requires more oil change) air conditioning unit in existing HCFC22, be translated into the moderate and high temperature heat unit of new working medium, efficiency and unit main hardware matching degree can guarantee to circulate.
The basic parameter of contained constituent element in the table 1 moderate and high temperature heat mixing medium
T b: normal boiling point, T c: critical temperature, P c: emergent pressure
T b??????T c??????P c
Constituent element title molecular formula molecular weight
ODP???????GWP
℃???????℃???????MPa
HCFC123 1,1-two chloro-CHCl 2CF 3152.93 27.85 183.79 3.674 0.02 90
2,2, the 2-Halothane
HCFC124 one chloro-1,2,2 CHClFCF 3136.48-12.05 122.50 3.634 0.02 440
The 2-Tetrafluoroethane
HFC134a???1，1，1，2-????????????CF 3CH 2F???102.03???????-26.15??101.06???4.056????0?????????1300
Tetrafluoroethane
HCFC142b 1-one chloro-1,1 CClF 2CH 3100.50-9.25 137.1 4.246 0.06 1800
C2H4F2 C2H4F2
HFC152a???1，1-??????????????????CHF 2CH 3???66.05????????-24.15??113.29???4.520????0?????????150
C2H4F2 C2H4F2
HFC245fa 1,1,1,3,3-five fluorine CF 3CH 2CHF 2134.0 15.30 157.50 3.644 0 790
Propane
HFC236fa??1，1，1，3，3，3-??????CF 3CH 2CF 3152.01???????-1.11???130.60???3.177????0?????????6300
HFC-236fa
HC600a Trimethylmethane CH (CH 3) 2CH 358.12-11.8 135.00 3.650 0＜50
Embodiment embodiment 1: get 13 Mass%HFC-134a, 53 Mass%HCFC-124,34 Mass%HCFC-142b carries out after the physical mixed at normal temperatures as refrigeration agent.Embodiment 2: get 24 Mass%HFC-152a, 62 Mass%HCFC-124,14 Mass%HCFC-123 carries out after the physical mixed at normal temperatures as refrigeration agent.Embodiment 3: get 12 Mass%HFC-152a, 52 Mass%HFC-134a, 36 Mass%HCFC-123 carries out after the physical mixed at normal temperatures as refrigeration agent.Embodiment 4: get 67 Mass%HFC-134a, 0 Mass%HCFC-124,33 Mass%HCFC-123 carries out after the physical mixed at normal temperatures as refrigeration agent.Embodiment 5: get 16 Mass%HFC-152a, 70 Mass%HCFC-124,14 Mass%HFC-245fa carries out after the physical mixed at normal temperatures as refrigeration agent.Embodiment 6: get 71 Mass%HCFC-124,17 Mass%HCFC-142b, 12 Mass%HFC-152a carries out after the physical mixed at normal temperatures as refrigeration agent.Embodiment 7: get 55 Mass%HFC-134a, 18 Mass%HCFC-142b, 27 Mass%HCFC-123 carries out after the physical mixed at normal temperatures as refrigeration agent.Embodiment 8: get 9 Mass%HFC-134a, 8 Mass%HCFC-124,83 Mass%HFC-245fa carries out after the physical mixed at normal temperatures as refrigeration agent.Embodiment 9: get 23 Mass%HFC-152a, 7 Mass%HFC-134a, 70 Mass%HFC-236fa carries out after the physical mixed at normal temperatures as refrigeration agent.Embodiment 10: get 23 Mass%HFC-152a, 24 Mass%HCFC-124,53 Mass%HFC-236fa carries out after the physical mixed at normal temperatures as refrigeration agent.Embodiment 11: get 95 Mass%HCFC-124,5 MassCarry out under the %HC-600a, normal temperature after the physical mixed as refrigeration agent.
If the design conditions of heat pump are taken as: average vaporization temperature is 40 ℃, average condensing temperature is 90 ℃, the suction superheat temperature be 5 ℃ (to some working medium, for guaranteeing to avoid wet compression, getting the exhaust superheating temperature is 5 ℃), supercooling temperature is 5 ℃, it is 85% that compression process is decided entropic efficiency, according to cycle calculations, above-mentioned 11 embodiment have related parameter and cycle performance index as shown in table 2.
Table 2 embodiment of the invention performance
Parameter and performance Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Evaporating pressure/MPa ??0.619 ??0.567 ??0.507 ??0.519 ??0.596 ??0.628
Condensing pressure/MPa ??2.018 ??2.018 ??2.029 ??2.071 ??1.998 ??2.072
Pressure ratio ??3.30 ??3.56 ??4.00 ??3.99 ??3.35 ??3.30
Exhaust temperature/℃ ??97.7 ??103.7 ??111.1 ??109.8 ??96.6 ??95.5
??COP ??4.51 ??4.50 ??4.49 ??4.47 ??4.46 ??4.33
Heat supplied/kJ/kg ??121.6 ??141.9 ??164.6 ??152.0 ??124.2 ??118.4
Unit volume heating capacity/kJ/m 3 ??3758 ??3745 ??3694 ??3734 ??3756 ??3793
??ODP ??0.034 ??0.012 ??0.005 ??0.005 ??0.012 ??0.012
??GWP ??1070 ??289 ??767.5 ??997.5 ??400.8 ??654
Parameter and performance Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11
Evaporating pressure/MPa ????0.488 ????0.570 ????0.616 ????0.620 ????0.584
Condensing pressure/MPa ????2.005 ????1.954 ????2.039 ????2.032 ????1.918
Pressure ratio ????4.11 ????3.43 ????3.31 ????3.28 ????3.28
Exhaust temperature/℃ ????108.1 ????96.0 ????96.8 ????96.4 ????95.1
????COP ????4.32 ????4.29 ????4.52 ????4.43 ????4.32
Heat supplied/kJ/kg ????153.1 ????107.4 ????124.0 ????122.1 ????106.7
Unit volume heating capacity/kJ/m 3 ????3469 ????3498 ????3747 ????3769 ????3473
????ODP ????0.016 ????0.016 ????0 ????0.004 ????0.018
????GWP ????1158 ????571.2 ????3440 ????2668 ????＜401

Claims (2)

1. one group of moderate and high temperature heat mixing medium, contain 1,1-two chloro-2,2,2-Halothane (HCFC-123), one chloro-1,2,2,2-Tetrafluoroethane (HCFC-124), 1,1,1,2-Tetrafluoroethane (HFC-134a), one chloro-1,1-C2H4F2 C2H4F2 (HCFC-142b), 1,1-C2H4F2 C2H4F2 (HFC-152a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), Trimethylmethane (HC-600a), 1,1,1,3,3,3-HFC-236fa constituent element materials such as (HFC-236fa), it is characterized in that by HFC-134a, HCFC-124, HCFC-142b forms moderate and high temperature heat mixing medium-1, by HFC-152a, HCFC-124, HCFC-123 forms moderate and high temperature heat mixing medium-2, by HFC-152a, HFC-134a, HCFC-123 forms moderate and high temperature heat mixing medium-3, by HFC-134a, HCFC-124, HCFC-123 forms moderate and high temperature heat mixing medium-4, by HFC-152a, HCFC-124, HFC-245fa forms moderate and high temperature heat mixing medium-5, by HCFC-124, HCFC-142b, HFC-152a forms moderate and high temperature heat mixing medium-6, by HFC-134a, HCFC-142b, HCFC-123 forms moderate and high temperature heat mixing medium-7, by HFC-134a, HCFC-124, HFC-245fa forms moderate and high temperature heat mixing medium-8, by HFC-152a, HFC-134a, HFC-236fa forms moderate and high temperature heat mixing medium-9, by HFC-152a, HCFC-124, HFC-236fa forms moderate and high temperature heat mixing medium-10, by HCFC-124, HC-600a forms moderate and high temperature heat mixing medium-11.
2. according to the described moderate and high temperature heat mixing medium of claim 1, it is characterized in that the concrete proportioning (mass percent) of above-mentioned various constituent element materials is:
HFC-134a/HCFC-124/HCFC-142b (moderate and high temperature heat mixing medium-1): 5-50/30-90/0-60%,
HFC-152a/HCFC-124/HCFC-123 (moderate and high temperature heat mixing medium-2): 5-40/40-90/20-60%,
HFC-152a/HFC-134a/HCFC-123 (moderate and high temperature heat mixing medium-3): 5-40/30-90/5-70%,
HFC-134a/HCFC-124/HCFC-123 (moderate and high temperature heat mixing medium-4): 20-90/0-40/10-80%,
HFC-152a/HCFC-124/HFC-245fa (moderate and high temperature heat mixing medium-5): 5-30/40-90/5-30%,
HCFC-124/HCFC-142b/HFC-152a (moderate and high temperature heat mixing medium-6): 40-95/0-30/5-30%,
HFC-134a/HCFC-142b/HCFC-123 (moderate and high temperature heat mixing medium-7): 20-95/5-50/0-75%,
HFC-134a/HCFC-124/HFC-245fa (moderate and high temperature heat mixing medium-8): 30-95/0-70/10-60%,
HFC-152a/HFC-134a/HFC-236fa (moderate and high temperature heat mixing medium-9): 0-25/20-70/30-80%,
HFC-152a/HCFC-124/HFC-236fa (moderate and high temperature heat mixing medium-10): 5-30/0-60/10-95%,
HCFC-124/HC-600a (moderate and high temperature heat mixing medium-11): 90-99/1-10%.
CN 03100578 2003-01-20 2003-01-20 A group of medium and high temperature heat pump mixed working medium Expired - Fee Related CN1233780C (en)

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CNB2004100779549A CN100389165C (en) 2003-01-20 2003-01-20 Tetrachloroethane(HFC134a) containing middle and high temperature heat pump mixed working substance
CNB2004100779553A CN100400615C (en) 2003-01-20 2003-01-20 Medium-high temperature hot pumping mixed working medium containing HFC-152a
CN 03100578 CN1233780C (en) 2003-01-20 2003-01-20 A group of medium and high temperature heat pump mixed working medium

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CNB2004100779549A Division CN100389165C (en) 2003-01-20 2003-01-20 Tetrachloroethane(HFC134a) containing middle and high temperature heat pump mixed working substance

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CN 03100578 Expired - Fee Related CN1233780C (en) 2003-01-20 2003-01-20 A group of medium and high temperature heat pump mixed working medium
CNB2004100779549A Expired - Fee Related CN100389165C (en) 2003-01-20 2003-01-20 Tetrachloroethane(HFC134a) containing middle and high temperature heat pump mixed working substance
CNB2004100779553A Expired - Fee Related CN100400615C (en) 2003-01-20 2003-01-20 Medium-high temperature hot pumping mixed working medium containing HFC-152a

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CNB2004100779553A Expired - Fee Related CN100400615C (en) 2003-01-20 2003-01-20 Medium-high temperature hot pumping mixed working medium containing HFC-152a

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1328350C (en) * 2004-04-05 2007-07-25 天津大学 Middle and high temperature heat pump mixed working medium containing HFC245fa
CN100387674C (en) * 2005-01-14 2008-05-14 天津大学 Mixed substance containing HCFC-142b(chloro-1,1-difluoroethane) for moderate and high temperature heat pump
CN106566476A (en) * 2016-10-28 2017-04-19 佛山市大芝热泵制冷设备有限公司 Environment-friendly ternary non-azeotropic high-condensing-temperature refrigerant and filling method thereof
CN107603568A (en) * 2017-10-17 2018-01-19 青岛理工大学 Environment-friendly non-azeotropic mixed refrigerant suitable for high-temperature heat pump
CN107603567A (en) * 2017-10-13 2018-01-19 青岛理工大学 Application of HFC-245fa/HFC-134a mixed refrigerant in high-temperature heat pump

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CN100347265C (en) * 2005-09-16 2007-11-07 清华大学 Mixed heat pump work substance with zero ozone layer destroying potential
CN101186807B (en) * 2007-12-01 2011-01-26 广东长菱空调冷气机制造有限公司 Mixed refrigerant
CN111057523B (en) * 2019-11-14 2021-03-16 浙江巨化新材料研究院有限公司 Medium-high temperature heat pump mixed working medium

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AU7470991A (en) * 1990-03-23 1991-10-21 California Institute Of Technology Near azeotropic mixture substitute for dichlorodifluoromethane
JPH07504889A (en) * 1991-12-03 1995-06-01 ユナイテッド　ステーツ　インバイオロンメンタル　プロテクション　エイジェンシー Refrigerant composition and method of use thereof
US5800729A (en) * 1995-07-26 1998-09-01 Electric Power Research Mixtures of pentafluoropropane and a hydrofluorocarbon having 3 to 6 carbon atoms
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1328350C (en) * 2004-04-05 2007-07-25 天津大学 Middle and high temperature heat pump mixed working medium containing HFC245fa
CN100387674C (en) * 2005-01-14 2008-05-14 天津大学 Mixed substance containing HCFC-142b(chloro-1,1-difluoroethane) for moderate and high temperature heat pump
CN106566476A (en) * 2016-10-28 2017-04-19 佛山市大芝热泵制冷设备有限公司 Environment-friendly ternary non-azeotropic high-condensing-temperature refrigerant and filling method thereof
CN107603567A (en) * 2017-10-13 2018-01-19 青岛理工大学 Application of HFC-245fa/HFC-134a mixed refrigerant in high-temperature heat pump
CN107603568A (en) * 2017-10-17 2018-01-19 青岛理工大学 Environment-friendly non-azeotropic mixed refrigerant suitable for high-temperature heat pump

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CN100389165C (en) 2008-05-21
CN1613956A (en) 2005-05-11
CN1629247A (en) 2005-06-22
CN1233780C (en) 2005-12-28

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