CN1563255A - A group of mixed working media containing HFCs and HPCs for mid-high temperature heat pump - Google Patents

A group of mixed working media containing HFCs and HPCs for mid-high temperature heat pump Download PDF

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CN1563255A
CN1563255A CN 200410018831 CN200410018831A CN1563255A CN 1563255 A CN1563255 A CN 1563255A CN 200410018831 CN200410018831 CN 200410018831 CN 200410018831 A CN200410018831 A CN 200410018831A CN 1563255 A CN1563255 A CN 1563255A
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high temperature
mixing medium
moderate
temperature heat
hfc134a
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CN1255504C (en
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王怀信
马利敏
郑臣明
张宇
杨强
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Tianjin University
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Tianjin University
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Abstract

A grou of mixed working media being used suitable as refrigerant for heat pump with condensing temperature of 60-120 deg.c contains eight component materials of R1311, 1,1,2-HFC 134a, CHF2OCHF2(HFE134), CH2FOCHF2(HFE143), 1,1-HF(152a, 1,1,2,2,3-HF (245ca, 1,1,2,2-HFC254cb and 1,1,1,2,3,3-HFC 236ea for forming binary and ternary mixture as per different mass ratio.

Description

One group of moderate and high temperature heat mixing medium that contains HFCs and HFEs
Technical field
The invention belongs to the refrigeration agent in heat pump or refrigeration, the air-conditioning system, referring more particularly to as condensing temperature is 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 (the high again cycle performance that not only makes of temperature worsens, if surpassing the pressure and the warm upper limit of row of system causes the accident easily), 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: one group of moderate and high temperature heat mixing medium that contains HFCs (hydrogen fluorohydrocarbon class) and HFEs (hydrogen fluorine ethers), contain CF3I (R13I1), 1,1,1,2-Tetrafluoroethane (HFC134a), CHF 2OCHF 2(HFE134), CH 2FOCHF 2(HFE143), 1,1-C2H4F2 C2H4F2 (HFC152a), 1,1,2,2,3-pentafluoropropane (HFC245ca) (HFC254cb) waits the constituent element material.The basic parameter of each constituent element material is as shown in table 1.By HFC134a, HFC152a, HFC254cb forms the moderate and high temperature heat mixing medium-a that contains HFCs, by HFC134a, R13I1, HFC254cb forms the moderate and high temperature heat mixing medium-b that contains HFCs, by HFC152a, R13I1, HFC254cb forms the moderate and high temperature heat mixing medium-c that contains HFCs, by HFC134a, HFC152a, HFC245ca forms the moderate and high temperature heat mixing medium-d that contains HFCs, by HFC134a, R13I1, HFC245ca forms the moderate and high temperature heat mixing medium-e that contains HFCs, by HFC152a, R13I1, HFC245ca forms the moderate and high temperature heat mixing medium-f that contains HFCs, by HFC134a, HFC152a, HFC236ea forms the novel moderate and high temperature heat mixing medium-g that contains HFCs, HFC134a, R13I1, HFC236ea forms the moderate and high temperature heat mixing medium-h that contains HFCs, by R13I1, HFC152a, HFC236ea forms the moderate and high temperature heat mixing medium-i that contains HFCs, by HFC134a, HFC152a, HFE134 forms the moderate and high temperature heat mixing medium-1 that contains HFCs and HFEs, by HFC152a, R13I1, HFE134 forms the moderate and high temperature heat mixing medium-2 that contains HFCs and HFEs, by HFC134a, R13I1, HFE134 forms the moderate and high temperature heat mixing medium-3 that contains HFCs and HFEs, by HFC134a, R13I1, HFE143 forms the moderate and high temperature heat mixing medium-4 that contains HFCs and HFEs, by HFC134a, HFC152a, HFE143 forms the moderate and high temperature heat mixing medium-5 that contains HFCs and HFEs, by R13I1, HFC152a, HFE143 forms the moderate and high temperature heat mixing medium-6 that contains HFCs and HFEs.
The concrete proportioning (mass percent) of above-mentioned each mixing medium is:
HFC134a/HFC152a/HFC254cb (the moderate and high temperature heat mixing medium-a that contains HFCs, when comprising HFC152a and be zero component, HFC134a/HFC254cb is the binary mixing medium): 40-96/0-30/4-60%,
HFC134a/R13I1/HFC254cb (the moderate and high temperature heat mixing medium-b that contains HFCs, when comprising HFC134a and be zero component, R13I1/HFC254cb is the binary mixing medium): 0-60/40-95/5-60%,
HFC152a/R13I1/HFC254cb (the moderate and high temperature heat mixing medium-c that contains HFCs, when comprising R13I1 and be zero component, HFC152a/HFC254cb is the binary mixing medium): 5-45/45-85/10-55%,
HFC134a/HFC152a/HFC245ca (the moderate and high temperature heat mixing medium-d that contains HFCs, when comprising HFC152a and be zero component, HFC134a/HFC245ca is the binary mixing medium): 45-90/0-40/10-55%,
HFC134a/R13I1/HFC245ca (the moderate and high temperature heat mixing medium-e that contains HFCs, when comprising HFC134a and be zero component, R13I1/HFC245ca is the binary mixing medium): 0-40/62-98/2-38%,
HFC152a/R13I1/HFC245ca (contain the moderate and high temperature heat mixing medium of HFCs-f): 4-37/60-95/3-36%,
HFC134a/HFC152a/HFC236ea (the moderate and high temperature heat mixing medium-g that contains HFCs, when comprising HFC152a and be zero component, HFC134a/HFC236ea is the binary mixing medium): 10-95/0-30/5-90%
HFC134a/R13I1/HFC236ea contains moderate and high temperature heat mixing medium-h of HFCs, and when comprising HFC134a and be zero component, R13I1/HFC236ea is the binary mixing medium): 0-60/30-95/10-70%
R13I1/HFC152a/HFC236ea (the moderate and high temperature heat mixing medium-i that contains HFCs, when comprising R13I1 and be zero component, HFC152a/HFC236ea is the binary mixing medium): 0-57/5-38/5-62%
HFC134a/HFC152a/HFE134 (the moderate and high temperature heat mixing medium-1 that contains HFCs and HFEs, when comprising HFC152a and be zero component, HFC134a/HFE134 is the binary mixing medium): 40-90/0-45/10-60%,
HFC152a/R13I1/HFE134 (the moderate and high temperature heat mixing medium-2 that contains HFCs and HFEs, when comprising HFC152a and be zero component, R13I1/HFE134 is the binary mixing medium): 3-35/60-92/5-45%,
HFC134a/R13I1/HFE134 (the moderate and high temperature heat mixing medium-3 that contains HFCs and HFEs): 1-40/20-98/1-40%,
HFC134a/R13I1/HFE143 (the moderate and high temperature heat mixing medium-4 that contains HFCs and HFEs, when comprising R13I1 and be zero component, HFC134a/HFE143 is the binary mixing medium): 45-95/0-50/5-55%,
HFC134a/HFC152a/HFE143 (the moderate and high temperature heat mixing medium-5 that contains HFCs and HFEs): 45-90/5-40/5-50%,
R13I1/HFC152a/HFE143 (the moderate and high temperature heat mixing medium-6 that contains HFCs and HFEs, when comprising HFC152a and be zero component, R13I1/HFE143 is the binary mixing medium): 50-98/0-35/2-50%.
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, and the GWP in most mixing mediums is lower.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 moderate and high temperature heat system design, need not to be working medium of the present invention specialized designs compressor separately.(3) cycle performance is good: the heat supply COP of the present invention under the moderate and high temperature heat design conditions substantially about 4, the unit mass heat supplied substantially more than 110kJ/kg, the unit volume heat supplied is at 3600kJ/m 3More than, 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
Molecule T bT cP c
Constituent element title molecular formula ODP GWP
Amount ℃ ℃ MPa
R13I1 CF3I CF 3L 195.9-21.83 123.29 3.953 0-
HFC134a??1，1，1，2-??????CF 3CH 2F??102.03??-26.15??101.06??4.056????0????1300
Tetrafluoroethane
HFE134???????????????????????????CHF 2OCHF 2?????118.00????4.67????153.4????3.751????0????-
HFE143???????????????????????????CH 2FOCHF 2?????100.0?????30.06???186.83???4.141????0????-
HFC152a???1，1-??????????????????CHF 2CH 3???????66.05?????-24.15??113.29???4.520????0????150
C2H4F2 C2H4F2
HFC245ca 1,1,2,2,3-five fluorine CF 2HCF 2CH 2F 134.0 25.00 178.40 3.885 0-
Propane
HFC254cb 1,1,2,2-tetrafluoro CF2HCF2CH3 116.03-0.78 146.10 3.753 0-
Propane
HFC236ea 1,1,1,2,3,3-hexafluoro CF 3CHFCHF 2152.01 6.50 141.10 3.533 0-
Propane
Embodiment
Embodiment 1: get 43 Mass%HFC134a, 3 Mass%HFC152a, 54 Mass%HFC254cb carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 2: get 6 Mass%HFC134a, 72 Mass%R13I1,22 Mass%HFC254cb carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 3: get 7 Mass%HFC152a, 70 Mass%R13I1,23 Mass%HFC254cb carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 4: get 49 Mass%HFC134a, 13 Mass%HFC152a, 38 Mass%HFC245ca carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 5: get 14 Mass%HFC134a, 40 Mass%R13I1,46 Mass%HFC245ca carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 6: get 8 Mass%HFC152a, 70 Mass%R13I1,22 Mass%HFC245ca carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 7: get 21 Mass%HFC134a, 11 Mass%HFC152a, 68 Mass%HFC236ea carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 8: get 12 Mass%HFC134a, 62 Mass%R13I1,26 Mass%HFC236ea carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 9: get 31 Mass%R13I1,21 Mass%HFC152a, 48 Mass%HFC236ea carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 10: get 49 Mass%HFC134a, 6 Mass%HFC152a, 45 Mass%HFE134 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 11:: get 79 Mass%R13I1,21 Mass%HFE134 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 12: get 32 Mass%HFC134a, 31 Mass%R13I1,37 Mass%HFE134 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 13: get 13 Mass%HFC134a, 71 Mass%R13I1,16 Mass%HFE143 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 14: get 62 Mass%HFC134a, 7 Mass%HFC152a, 31 Mass%HFE143 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 15: get 74 Mass%R13I1,9 Mass%HFC152a, 17 MassCarry out under the %HFE143, 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, get suitable exhaust superheating temperature to guarantee to avoid wet compression,), supercooling temperature is 5 ℃, it is 75% that compression process is decided entropic efficiency, according to cycle calculations, above-mentioned 15 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
Evaporating pressure/MPa ??0.605 ??0.617 ??0.618 ??0.519 ??0.347
Condensing pressure/MPa ??2.062 ??1.963 ??1.968 ??1.955 ??1.341
Pressure ratio ??3.41 ??3.18 ??3.18 ??3.77 ??3.87
Exhaust temperature/℃ ??97.7 ??101.2 ??106.1 ??112.3 ??107.2
???COP ??3.90 ??4.00 ??4.06 ??4.14 ??4.35
Heat supplied/kJ/kg ??137.0 ??88.5 ??98.6 ??177.3 ??138.9
Unit volume heating capacity/kJ/m 3 ??3894 ??3916 ??4014 ??3951 ??2839
Parameter and performance Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10
Evaporating pressure/MPa ??0.493 ??0.513 ??0.608 ??0.563 ??0.611
Condensing pressure/MPa ??1.717 ??1.883 ??2.027 ??1.960 ??2.110
Pressure ratio ??3.48 ??3.67 ??3.33 ??3.48 ??3.45
Exhaust temperature/℃ ??109.8 ??97.8 ??101.6 ??102.0 ??111.1
????COP ??4.20 ??3.93 ??3.92 ??3.99 ??4.23
Heat supplied/kJ/kg ??113.2 ??131.1 ??89.0 ??124.7 ??154.6
Unit volume heating capacity/kJ/m 3 ??3620 ??3528 ??3911 ??3826 ??4218
Parameter and performance Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15
Evaporating pressure/MPa ????0.565 ????0.583 ????0.481 ????0.497 ????0.472
Condensing pressure/MPa ????1.807 ????1.978 ????1.715 ????1.917 ????1.674
Pressure ratio ????3.20 ????3.39 ????3.57 ????3.86 ????3.54
Exhaust temperature/℃ ????111.1 ????110.6 ????116.7 ????117.5 ????118.4
????COP ????4.36 ????4.28 ????4.42 ????4.39 ????4.46
Heat supplied/kJ/kg ????91.6 ????127.5 ????120.4 ????199.2 ????127.8
Unit volume heating capacity/kJ/m 3 ????3821 ????4023 ????3628 ????3925 ????3601

Claims (2)

1. one group of moderate and high temperature heat mixing medium that contains HFCs and HFEs contains CF3I (R13I1), and 1,1,1,2-Tetrafluoroethane (HFC134a), CHF 2OCHF 2(HFE134), CH 2FOCHF 2(HFE143), 1,1-C2H4F2 C2H4F2 (HFC152a), 1,1,1,2,3,3-HFC-236fa (HFC236ea), 1,1,2,2,3-pentafluoropropane (HFC245ca), 1,1,2,2-tetrafluoropropane constituent element materials such as (HFC254cb), it is characterized in that by HFC134a, HFC152a, HFC254cb forms the moderate and high temperature heat mixing medium-a that contains HFCs, by HFC134a, R13I1, HFC254cb forms the moderate and high temperature heat mixing medium-b that contains HFCs, by HFC152a, R13I1, HFC254cb forms the moderate and high temperature heat mixing medium-c that contains HFCs, by HFC134a, HFC152a, HFC245ca forms the moderate and high temperature heat mixing medium-d that contains HFCs, by HFC134a, R13I1, HFC245ca forms the moderate and high temperature heat mixing medium-e that contains HFCs, by HFC152a, R13I1, HFC245ca forms the moderate and high temperature heat mixing medium-f that contains HFCs, by HFC134a, HFC152a, HFC236ea forms the novel moderate and high temperature heat mixing medium-g that contains HFCs, HFC134a, R13I1, HFC236ea forms the moderate and high temperature heat mixing medium-h that contains HFCs, by R13I1, HFC152a, HFC236ea forms the moderate and high temperature heat mixing medium-i that contains HFCs, by HFC134a, HFC152a, HFE134 forms the moderate and high temperature heat mixing medium-1 that contains HFCs and HFEs, by HFC152a, R13I1, HFE134 forms the moderate and high temperature heat mixing medium-2 that contains HFCs and HFEs, by HFC134a, R13I1, HFE134 forms the moderate and high temperature heat mixing medium-3 that contains HFCs and HFEs, by HFC134a, R13I1, HFE143 forms the moderate and high temperature heat mixing medium-4 that contains HFCs and HFEs, by HFC134a, HFC152a, HFE143 forms the moderate and high temperature heat mixing medium-5 that contains HFCs and HFEs, by R13I1, HFC152a, HFE143 forms the moderate and high temperature heat mixing medium-6 that contains HFCs and HFEs.
2. according to the described moderate and high temperature heat mixing medium that contains HFCs and HFEs of claim 1, it is characterized in that the concrete proportioning (mass percent) of above-mentioned various constituent element materials is:
HFC134a/HFC152a/HFC254cb (the moderate and high temperature heat mixing medium-a that contains HFCs, when comprising HFC152a and be zero component, HFC134a/HFC254cb is the binary mixing medium): 40-96/0-30/4-60%,
HFC134a/R13I1/HFC254cb (the moderate and high temperature heat mixing medium-b that contains HFCs, when comprising HFC134a and be zero component, R13I1/HFC254cb is the binary mixing medium): 0-60/40-95/5-60%,
HFC152a/R13I1/HFC254cb (the moderate and high temperature heat mixing medium-c that contains HFCs, when comprising R13I1 and be zero component, HFC152a/HFC254cb is the binary mixing medium): 5-45/45-85/10-55%,
HFC134a/HFC152a/HFC245ca (the moderate and high temperature heat mixing medium-d that contains HFCs, when comprising HFC152a and be zero component, HFC134a/HFC245ca is the binary mixing medium): 45-90/0-40/10-55%,
HFC134a/R13I1/HFC245ca (the moderate and high temperature heat mixing medium-e that contains HFCs, when comprising HFC134a and be zero component, R13I1/HFC245ca is the binary mixing medium): 0-40/62-98/2-38%,
HFC152a/R13I1/HFC245ca (contain the moderate and high temperature heat mixing medium of HFCs-f): 4-37/60-95/3-36%,
HFC134a/HFC152a/HFC236ea (the moderate and high temperature heat mixing medium-g that contains HFCs, when comprising HFC152a and be zero component, HFC134a/HFC236ea is the binary mixing medium): 10-95/0-30/5-90%
HFC134a/R13I1/HFC236ea contains moderate and high temperature heat mixing medium-h of HFCs, and when comprising HFC134a and be zero component, R13I1/HFC236ea is the binary mixing medium): 0-60/30-95/10-70%
R13I1/HFC152a/HFC236ea (the moderate and high temperature heat mixing medium-i that contains HFCs, when comprising R13I1 and be zero component, HFC152a/HFC236ea is the binary mixing medium): 0-57/5-38/5-62%
HFC134a/HFC152a/HFE134 (the moderate and high temperature heat mixing medium-1 that contains HFCs and HFEs, when comprising HFC152a and be zero component, HFC134a/HFE134 is the binary mixing medium): 40-90/0-45/10-60%,
HFC152a/R13I1/HFE134 (the moderate and high temperature heat mixing medium-2 that contains HFCs and HFEs, when comprising HFC152a and be zero component, R13I1/HFE134 is the binary mixing medium): 3-35/60-92/5-45%,
HFC134a/R13I1/HFE134 (the moderate and high temperature heat mixing medium-3 that contains HFCs and HFEs): 1-40/20-98/1-40%,
HFC134a/R13I1/HFE143 (the moderate and high temperature heat mixing medium-4 that contains HFCs and HFEs, when comprising R13I1 and be zero component, HFC134a/HFE143 is the binary mixing medium): 45-95/0-50/5-55%,
HFC134a/HFC152a/HFE143 (the moderate and high temperature heat mixing medium-5 that contains HFCs and HFEs): 45-90/5-40/5-50%,
R13I1/HFC152a/HFE143 (the moderate and high temperature heat mixing medium-6 that contains HFCs and HFEs, when comprising HFC152a and be zero component, R13I1/HFE143 is the binary mixing medium): 50-98/0-35/2-50%.
CN 200410018831 2004-04-05 2004-04-05 A group of mixed working media containing HFCs and HPCs for mid-high temperature heat pump Expired - Fee Related CN1255504C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100347265C (en) * 2005-09-16 2007-11-07 清华大学 Mixed heat pump work substance with zero ozone layer destroying potential
CN102504764A (en) * 2011-11-08 2012-06-20 天津大学 Environment-friendly refrigerant applicable to heat pump system of gas engine

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100347265C (en) * 2005-09-16 2007-11-07 清华大学 Mixed heat pump work substance with zero ozone layer destroying potential
CN102504764A (en) * 2011-11-08 2012-06-20 天津大学 Environment-friendly refrigerant applicable to heat pump system of gas engine

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