CN100347265C - Mixed heat pump work substance with zero ozone layer destroying potential - Google Patents
Mixed heat pump work substance with zero ozone layer destroying potential Download PDFInfo
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- CN100347265C CN100347265C CNB2005100864334A CN200510086433A CN100347265C CN 100347265 C CN100347265 C CN 100347265C CN B2005100864334 A CNB2005100864334 A CN B2005100864334A CN 200510086433 A CN200510086433 A CN 200510086433A CN 100347265 C CN100347265 C CN 100347265C
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- Prior art keywords
- heat pump
- hfc
- present
- ozone layer
- working substance
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000000126 substance Substances 0.000 title abstract 7
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims abstract description 28
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 claims abstract description 17
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000001273 butane Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 239000007791 liquid phase Substances 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 239000003507 refrigerant Substances 0.000 abstract description 4
- ZXVZGGVDYOBILI-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoropropane Chemical compound FC(F)C(F)(F)C(F)F ZXVZGGVDYOBILI-UHFFFAOYSA-N 0.000 abstract 1
- -1 and 1 Chemical compound 0.000 abstract 1
- 238000005057 refrigeration Methods 0.000 description 10
- FYIRUPZTYPILDH-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoropropane Chemical compound FC(F)C(F)C(F)(F)F FYIRUPZTYPILDH-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000006378 damage Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000004781 supercooling Methods 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical group FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000589248 Legionella Species 0.000 description 1
- 208000007764 Legionnaires' Disease Diseases 0.000 description 1
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to heat pump mixed working substance with zero ozone layer destroying potential, particularly to mixed refrigerant working substance used for a middle and high temperature water source heat pump unit. The working substance contains three kinds of substance, such as 1, 1, 1, 2-tetrafluoro ethane, 1, 1, 1, 2, 3, 3, 3-heptafluoro propane, and 1, 1, 2, 3, 3-hexafluoro propane, or the three kinds of components and butane form quaternary mixed working substance. The present invention has a preparing method that various components are physically mixed according to the corresponding proportion under a liquid phase state. The present invention does not break an ozone layer and accords with the requirement of the environmental protection, the present invention is innoxious and nonflammable, and thermal performance and thermal parameters are better. The present invention can be directly used in an HFC-134a heat pump unit, and the main parts of a compressor and a system do not need changing; the heat pump unit using the mixing refrigerant working substance can provided hot water with a middle and high temperature of about 80 DEG C.
Description
Technical field
The present invention relates to the hybrid refrigeration working medium that a kind of middle heat pump of high-temp water source unit uses, the heat pump fluid of particularly a kind of do not damage the ozone layer fully (being ozone layer destroying potential ODP=0).
Background technology
Water source heat pump technology is to utilize low temperature Lowlevel thermal energy resources such as GEOTHERMAL WATER, underground water, surface water (river, lake water, seawater), trade effluent, and employing heat pump principle, by a spot of electric energy input Lowlevel thermal energy is shifted to high level heat, thereby realize a kind of energy-conserving and environment-protective technology of heating and cooling.Characteristics such as that water resource heat pump has is energy-efficient, stable and reliable operation, obvious environment benefit, a tractor serves several purposes.Since water resource heat pump have higher efficient, again be subjected to hardly envrionment temperature in each in season influence, can effectively utilize characteristics such as the waste heat energy, be a main direction of studying of present refrigeration, air conditioner industry therefore.
The middle and high temperature refrigerant that in the past was used as water resource heat pump usually is CFC-11 and CFC-114 etc.But because CFC-11 and CFC-114 all belong to CFC class material, the latent value ODP of its ozone depletion is respectively 1.0 and 0.85, atmospheric ozone layer there is serious destruction, and the influence of their Greenhouse effect is also very big, its chamber effect potential value GWP is respectively 4600 and 9800, developed country is in forbidding in 1996, and developing country also will be in forbidding in 2010.So it is very necessary developing environment amenable water resource heat pump middle and high temperature refrigerant, the heat pump fluid of particularly need not damage the ozone layer fully (being ODP=0).
In order to satisfy radiator heating and prevent that germ (as legionella etc.) from growing, and often needs to provide the hot water about 80 ℃ in the domestic hot-water.
Present existing heat pump fluid, or leaving water temperature(LWT) low excessively (fluorine Lyons-22 and 1,1,1,2-Tetrafluoroethane), or atmospheric ozone layer had destruction (being that ODP is non-vanishing), or leaving water temperature(LWT) is too high are to such an extent as to make original compressor can't works better.So being badly in need of not damaging the ozone layer fully and can using has the heat pump fluid that compressor provides 80 ℃ of left and right sides hot water now.
Summary of the invention
The present invention is intended to research and develop the new working medium of mixing that is applicable to middle heat pump of high-temp water source unit, and it can not damaged the ozone layer, and satisfies the environmental requirement that reduces Greenhouse effect; Have thermal parameter and thermal property preferably again, safety, reliable; And compatible with existing HFC-134a handpiece Water Chilling Units equipment with refrigeration oil, but connect and charge, connect under normal temperature water source in the utilization (about the 40 ℃) condition at , the middle high-temperature-hot-water about 80 ℃ can be provided.
Technical scheme of the present invention is as follows:
A kind of ozone layer destroying potential provided by the invention is zero heat pump mixed working medium, and it is characterized in that: this mixing medium closes 1,1,1,2-Tetrafluoroethane, 1,1,1,2,3,3,3-heptafluoro-propane and 1,1,1,2,3, three kinds of materials of 3-HFC-236fa, this content of quality percentage of each component is respectively:
1,1,1,2-Tetrafluoroethane 10～80%
1,1,1,2,3,3,3-heptafluoro-propane 5～80%
1,1,1,2,3,3-HFC-236fa 15～80%.
Can also add butane in above-mentioned three kinds of components, the mass percentage content of its component is respectively:
1,1,1,2-Tetrafluoroethane 10～80%
1,1,1,2,3,3,3-heptafluoro-propane 5～80%
1,1,1,2,3,3-HFC-236fa 13～80%
Butane 2～10%
Refrigeration working medium provided by the invention, its preparation method are above-mentioned various components to be carried out physical mixed by its corresponding mixture ratio get final product under liquid phase state.
In the said components 1,1,1,2-Tetrafluoroethane (HFC-134a), its molecular formula is CH
2FCF
3, molar mass is 102.03, and normal boiling point is-26.1 ℃, and critical temperature is 101.1 ℃, and emergent pressure is 4.06MPa.
1,1,1,2,3,3,3-heptafluoro-propane (HFC-227ea), its molecular formula are CF
3CHFCF
3, molar mass is 170.03, and normal boiling point is-15.6 ℃, and critical temperature is 102.8 ℃, and emergent pressure is 2.98MPa.
1,1,1,2,3,3-HFC-236fa (HFC-236ea), its molecular formula are CHF
2CHFCF
3, molar mass is 152.04, and normal boiling point is 6.2 ℃, and critical temperature is 139.3 ℃, and emergent pressure is 3.50MPa.
Butane (HC-600), its molecular formula are CH
3CH
2CH
2CH
3, molar mass is 58.12, and normal boiling point is-0.5 ℃, and critical temperature is 152.0 ℃, and emergent pressure is 3.80MPa.
The present invention has the following advantages and beneficial effect:
A. environmental performance:
Its ozone layer destroying potential of refrigeration agent of the present invention (ODP) is zero, and its Greenhouse effect coefficient (GWP) is also lower, approximate HFC-134a.The present invention meets the protection ozonosphere fully, reduces the environmental protection requirement of Greenhouse effect.
B. thermal parameter:
The HFC-134a refrigeration agent is under normal temperature heat pump operating mode (5 ℃ of 27 ℃ of vaporization temperatures, 71 ℃ of condensing temperatures, 5 ℃ of supercooling temperatures and temperature of superheat), and evaporating pressure is that 706.2MPa, condensing pressure are that 2168.3MPa, compression ratio are 3.07, exhaust temperature is 87.9 ℃.And the present invention is when being used for high temperature design conditions (10 ℃ of 40 ℃ of vaporization temperatures, 83 ℃ of condensing temperatures, 2 ℃ of supercooling temperatures and temperature of superheat), evaporating pressure and condensing pressure all with HFC-134a close under middle normal temperature heat pump operating mode.Illustrated that but the present invention meets the system that charges in crude HFC-134a, and need not change other parts, higher leaving water temperature(LWT) (about 80 ℃) just can be provided.
C. thermal property:
The present invention is about 4.8 at the heat supply COP under the above-mentioned design conditions, the volume heat supplied is 5100kJ/m
3About, thermal property is better.
In sum, the present invention does not damage the ozone layer, and can reduce the Greenhouse effect influence, compliance with environmental protection requirements; And nontoxic, not flammable, thermal property and thermal parameter are all better, but connect and utilize the HFC-134a heat pump that middle high-temperature-hot-water (about 80 ℃) is provided, the major parts in compressor and the system need not changed, production line need not transformed.
Embodiment
Embodiment 1: the HFC-134a with 10%, 10% HFC-227ea and 80% HFC-236ea carry out physical mixed under liquid phase.
Embodiment 2: the HFC-134a with 45%, 25% HFC-227ea and 30% HFC-236ea carry out physical mixed under liquid phase.
Embodiment 3: the HFC-134a with 80%, 5% HFC-227ea and 15% HFC-236ea carry out physical mixed under liquid phase.
Embodiment 4: the HFC-134a with 10%, 5% HFC-227ea, 80% HFC-236ea and 5% HC-600 carry out physical mixed under liquid phase.
Embodiment 5: the HFC-134a with 53%, 20% HFC-227ea, 20% HFC-236ea and 7% HC-600 carry out physical mixed under liquid phase.
Embodiment 6: the HFC-134a with 80%, 5% HFC-227ea, 13% HFC-236ea and 2% HC-600 carry out physical mixed under liquid phase.
Under design conditions, promptly under 10 ℃ of 40 ℃ of vaporization temperatures, 83 ℃ of condensing temperatures, 2 ℃ of supercooling temperatures and the temperature of superheat, the thermal property of the foregoing description refrigeration working medium is listed in the table 1.Also listed the parameter of HFC-134a in the table 1, so that this is now.
By table 1 as seen, with HFC-134a mutually this, condensing pressure is low, exhaust temperature is suitable, COP and heat supplied under the heat supply operating mode are suitable, illustrate and can utilize existing HFC-134a heat pump compressor to form heat pump set fully, (about 40 ℃) can provide the hot water about 80 ℃ under middle normal temperature water condition.In addition, can find out also from table 1 that the ODP value of refrigeration agent of the present invention all is zero, GWP is lower than or is similar to HFC-134a.It should be noted that the GWP value of the quaternary refrigeration working medium that proposes in this patent is littler than corresponding ternary refrigeration working medium owing to added HC-600.Therefore, integrated environment better performances.
Table 1 embodiment thermal property and environmental properties
| Embodiment | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | HFC134a |
| Evaporating pressure kPa | 419.5 | 728.1 | 902.8 | 423.4 | 795.6 | 915.8 | 1018.2 |
| Condensing pressure kPa | 1338.4 | 2129.2 | 2545.6 | 1333.6 | 2255.9 | 2562.9 | 2802.4 |
| Pressure ratio | 3.19 | 2.92 | 2.82 | 3.15 | 2.84 | 2.80 | 2.75 |
| Exhaust temperature ℃ | 93.3 | 98.6 | 102.1 | 93.6 | 99.2 | 101.9 | 103.2 |
| Heat supply COP | 4.97 | 4.74 | 4.69 | 4.98 | 4.70 | 4.67 | 4.62 |
| Heat supplied kJ/kg | 130.07 | 126.15 | 138.64 | 139.72 | 135.98 | 139.62 | 142.15 |
| Volume heat supplied kJ/m 3 | 3250.4 | 4956.5 | 5924.9 | 3256.7 | 5216.6 | 5936.0 | 6470.0 |
| ODP | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| GWP | 1104 | 1586 | 1317 | 883 | 1344 | 1276 | 1300 |
Claims (3)
1. an ozone layer destroying potential is zero heat pump mixed working medium, and wherein the mass percent sum of each constituent element is 100%, it is characterized in that: this mixing medium contains 1,1,1,2-Tetrafluoroethane, 1,1,1,2,3,3,3-heptafluoro-propane and 1,1,1,2,3, three kinds of materials of 3-HFC-236fa, this content of quality percentage of described three kinds of components is respectively:
1,1,1,2-Tetrafluoroethane 10～80%
1,1,1,2,3,3,3-heptafluoro-propane 5～80%
1,1,1,2,3,3-HFC-236fa 20～80%.
2. be zero heat pump mixed working medium according to the described ozone layer destroying potential of claim 1, it is characterized in that: described mixing medium also contains butane, and this content of quality percentage of butane is:
1,1,1,2-Tetrafluoroethane 10～80%
1,1,1,2,3,3,3-heptafluoro-propane 5～80%
1,1,1,2,3,3-HFC-236fa 20～80%
Butane 2～10%.
3. be zero heat pump mixed working medium according to the described a kind of ozone layer destroying potential of claim 1, it is characterized in that: this mixing medium is only by 1,1,1,2-Tetrafluoroethane, 1,1,1,2,3,3,3-heptafluoro-propane and 1,1,1,2,3, three kinds of materials of 3-HFC-236fa are formed, and the mass percentage content of each component is respectively:
1,1,1,2-Tetrafluoroethane 10～80%
1,1,1,2,3,3,3-heptafluoro-propane 5～80%
1,1,1,2,3,3-HFC-236fa 30～80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100864334A CN100347265C (en) | 2005-09-16 | 2005-09-16 | Mixed heat pump work substance with zero ozone layer destroying potential |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100864334A CN100347265C (en) | 2005-09-16 | 2005-09-16 | Mixed heat pump work substance with zero ozone layer destroying potential |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1740263A CN1740263A (en) | 2006-03-01 |
| CN100347265C true CN100347265C (en) | 2007-11-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100864334A Expired - Fee Related CN100347265C (en) | 2005-09-16 | 2005-09-16 | Mixed heat pump work substance with zero ozone layer destroying potential |
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| Country | Link |
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| CN (1) | CN100347265C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460479C (en) * | 2006-07-10 | 2009-02-11 | 浙江蓝天环保高科技股份有限公司 | Environment-friendly type heat pump mixed working medium |
| CN101407713A (en) * | 2007-10-12 | 2009-04-15 | 霍尼韦尔国际公司 | Blend working fluid and uses thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280166A (en) * | 2000-07-28 | 2001-01-17 | 清华大学 | Refrigerant |
| US6231781B1 (en) * | 1998-12-23 | 2001-05-15 | Korea Institute Of Science And Technology | Refrigerant mixture comprising difluoromethane and 1,1,1-trifluoroethane |
| US6524495B1 (en) * | 1999-11-10 | 2003-02-25 | Korea Institute Of Science And Technology | Refrigerant mixture comprising difluromethane, pentafluroethane and 1,1,1-trifluoroethane |
| US6692653B2 (en) * | 2001-02-16 | 2004-02-17 | Korea Institute Of Science And Technology | Refrigerant composition |
| CN1563255A (en) * | 2004-04-05 | 2005-01-12 | 天津大学 | A group of mixed working media containing HFCs and HPCs for mid-high temperature heat pump |
| CN1629247A (en) * | 2003-01-20 | 2005-06-22 | 天津大学 | Tetrachloroethane(HFC134a) containing middle and high temperature heat pump mixed working substance |
-
2005
- 2005-09-16 CN CNB2005100864334A patent/CN100347265C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6231781B1 (en) * | 1998-12-23 | 2001-05-15 | Korea Institute Of Science And Technology | Refrigerant mixture comprising difluoromethane and 1,1,1-trifluoroethane |
| US6524495B1 (en) * | 1999-11-10 | 2003-02-25 | Korea Institute Of Science And Technology | Refrigerant mixture comprising difluromethane, pentafluroethane and 1,1,1-trifluoroethane |
| CN1280166A (en) * | 2000-07-28 | 2001-01-17 | 清华大学 | Refrigerant |
| US6692653B2 (en) * | 2001-02-16 | 2004-02-17 | Korea Institute Of Science And Technology | Refrigerant composition |
| CN1629247A (en) * | 2003-01-20 | 2005-06-22 | 天津大学 | Tetrachloroethane(HFC134a) containing middle and high temperature heat pump mixed working substance |
| CN1563255A (en) * | 2004-04-05 | 2005-01-12 | 天津大学 | A group of mixed working media containing HFCs and HPCs for mid-high temperature heat pump |
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|---|---|
| CN1740263A (en) | 2006-03-01 |
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