CA2344276C - Heat transfer fluids - Google Patents
Heat transfer fluids Download PDFInfo
- Publication number
- CA2344276C CA2344276C CA002344276A CA2344276A CA2344276C CA 2344276 C CA2344276 C CA 2344276C CA 002344276 A CA002344276 A CA 002344276A CA 2344276 A CA2344276 A CA 2344276A CA 2344276 C CA2344276 C CA 2344276C
- Authority
- CA
- Canada
- Prior art keywords
- heat transfer
- mixture
- diphenyl
- dpo
- ethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
A heat transfer fluid having high heat capacity, high thermal loading capacity, low visces~ and low freezine point includes diphenyl oxide and 1.1 diphenyl ethane in broad proportions.
Description
wo oorisi3o PcrNS~n~s~o HEAT TRANSFER FLUIDS
' Technical Field . Heat transfer fluids, sometimes referred to as heat transfer media. are heat transfer agents which are used in cooling and heating circuits and in heat recovery units.
There may be other uses for such fluids and as such, they are required or expected to have a high heat transfer capacity, high thermal loading capaciy and adequate thermal stabilin~ for the operating range. It is also desirable to have fluids which can stand very high heat and yet have a low freezing point while being inert.
Background Art There have been prior art heat transfer fluids which have some of the proper characteristics at high temperatures and at low temperatures and are chemically inert. The eutectic mixture of 73°~o Biphenyl oxide and 27°.~o biphenyl commonly known as Dow~thermA, is currently one of the largest volume heat transfer fluids sold worldwide.
Other widely used fluids are a mixture of hydrogenated terphenyl and quatraphenyl and dibertzyl toluene.
It has, however, become desirable to get away from the available heat transfer fluids which have previously been used for a number of reasons, one of which is the current requirements of the EPA as to reportable spill quantity for biphenyl. It is also desirable to provide a heat transfer fluid which has a higher resistance to heat and a lower freezing capabiliy, or a combination of both.
Disclosure of Invention It is the object of an aspect of the present invention to overcome any disadvantage~~ of the prior art heat transfer fluids and to eliminate the use of biphenyls to ~~bviate the need for spill reportage under the EPA regulations.
It is also an object of an aspect of the present invention to provide a more useful heat transfer fluid insofar as heat levels and freezing points are concerned and to additionally create heat transfer fluids having better stability under various conditions.
To achieve the objects of this invention, therefore, it has been discovered that a mixture: in broad proportions of Biphenyl oxide (DPO) sometimes referred to as Biphenyl ether, which has a structural formula of C~HSOC~HS and 1,1 Biphenyl ethane (DPE) having a structural formula of CH3CH(C~,HS)2 in varying amounts but generally a larger amount of either Biphenyl oxide or 1,1 Biphenyl ethane to substantially equal amounts of Biphenyl oxide and l,l Biphenyl ethane. In other words, fluid with an excess of 1,1 Biphenyl ethane over Biphenyl oxide and vice versa provides a useful heat transfer fluid. However, the preferred ratios of about S
to 50% 1,1 Biphenyl ethane to 95-50% Biphenyl oxide provides a heat transfer fluid with remarkable improvements over the prior art fluids, i.e., higher heat transfer coefficients and lower freezing points as well as greater thermal stability.
The composition recited above though similar to the prior art compositions already mentioned, is not shown in the prior art, has not been used, and as previously stated, is remarkably better than the prior art compositions so much so that it may be considered th~it the performance of~this material is unexpected and even synergistic.
According to one aspect of the invention, there is provided a heat biphenyl-free transfer fluid comprising a mixture of Biphenyl oxide and 1,1 Biphenyl ethane.
Best Mode for Carrying Out the Invention The present invention is a mixture in broad proportions of Biphenyl oxide (DPO), which has a structural formula of C6HSOC6H5, and 1,1 Biphenyl ethane (DPE) having a structural formula of C',H3CH(C6H5)Z. The preferred ratios of about to 50% 1,1 cliphenyl ethane to 95- -WO 00/15730 PC'TNS99/17870 50% diphenyl oxide provides a heat transfer fluid having high heat transfer coefficients, low freezing points and good thermal stability.
Although a mixture of 1,1 Biphenyl ethane and Biphenyl oxide, as outlined above, is the preferred embodiment of the invention, it is know to one of ordinarv~ skill in the art Lhat certain impurities and.~or isomers can be added in small quantities to this preferred heat transfer mixture without affecting the performance characteristics ofthe invention, as discussed more i;.:lly below.
In particular, it is know that XCELTHERM XT, a commercially available product consisting essentially of a mixture of 92-95°~0 1,1 Biphenyl ethane, 7-4°~0 1,2 Biphenyl etha.~:, and I
Biphenyl methane can be substituted for the pure 1,1 Biphenyl ethane material of the preferred heat transfer mia-ture without essentially affecting the overall heat transfer character:_tics of the resultant mixture when compared to the etpected performance characteristics of the preferred embodiment of the invention. The XCELTHERIvi XT product is processed by the assignee of this patent, Radco Industries, Inc. of LaFox, Illinois. ?accordingly. it is l:no~~n that a material consisting essentially of 1,1 Biphenyl ethane and smaller amounts of other impurities and/or isomers can be substituted for the pure 1.1 Biphenyl ethane of the preferred composition.
Thermal stability tests of mixtures of 1,1 Biphenyl ethane and Biphenyl oxide alone have been conducted. However, in view of all of the materials that have been used prior to the development of the heat transfer fluid of this invention, it has been decided to run confirmatory tests as to the novelty and unexpected improvement provided by the heat transfer fluid combination of this invention, namely, Biphenyl ether and 1,1 Biphenyl ethane.
The combinations that have been tested are terphenyls, dibenzyl toluene, the Biphenyl oxide-biphenyl mixture and the compositions of the invention to determine which fluid provides the best heat transfer results.
It should be noted here that the terms "Biphenyl ether," ''Biphenyl oxide" and "DPO" gill be used throughout this specification as indicating the same chemical component while "DPE" will be used as indicating l,l,diphenyhethane.
Many industrial production processes require the use of a heat transfer fluid in the temperature range of 600°F - 700°F. The heat transfer fluids used in this temperature range fall into t~~o broad classifications:
1. Liquid phase fluids-characterized by low vapor pressure y ith heat transfer occurring in the liquid phase.
2. Liquid,wapor phase fluids-characterized by higher vapor pressures with heat transfer occurring in the liquid or vapor phase.
Three distinct chemistries, all aromatic, define the most widely used fluids worldwide in this temperature classification.
1. 73% diphenyl oxide.'?7°ro biphenyl mixture - a liquid/vapor phase fluid.
2. Hydrogenated terphenvl'.quatraphenyl mixture - a liquid phase fluid.
3. Dibertzyl Toluene - a liquid phase fluid.
The primary factors which define a fluid's use range are:
1. Thermal Stabiliy.
2. Pour!crystalizing point.
The primary factor which defines its effectiveness within it's operating range is:
1. Heat transfer coefficient - the abiliy to upload, transfer, and download heat/unit time-area at a given temperature.
A major factor in a fluid's use is its environmental impact - whether it is regulated as a hazardous chemical. Since these fluids may from time-to-time leak from the system or be subject to the over-the-road spillage, those fluids regarded as "hazardous" by the EPA incur additional potential liabilities, and therefore expense, in their use.
' Technical Field . Heat transfer fluids, sometimes referred to as heat transfer media. are heat transfer agents which are used in cooling and heating circuits and in heat recovery units.
There may be other uses for such fluids and as such, they are required or expected to have a high heat transfer capacity, high thermal loading capaciy and adequate thermal stabilin~ for the operating range. It is also desirable to have fluids which can stand very high heat and yet have a low freezing point while being inert.
Background Art There have been prior art heat transfer fluids which have some of the proper characteristics at high temperatures and at low temperatures and are chemically inert. The eutectic mixture of 73°~o Biphenyl oxide and 27°.~o biphenyl commonly known as Dow~thermA, is currently one of the largest volume heat transfer fluids sold worldwide.
Other widely used fluids are a mixture of hydrogenated terphenyl and quatraphenyl and dibertzyl toluene.
It has, however, become desirable to get away from the available heat transfer fluids which have previously been used for a number of reasons, one of which is the current requirements of the EPA as to reportable spill quantity for biphenyl. It is also desirable to provide a heat transfer fluid which has a higher resistance to heat and a lower freezing capabiliy, or a combination of both.
Disclosure of Invention It is the object of an aspect of the present invention to overcome any disadvantage~~ of the prior art heat transfer fluids and to eliminate the use of biphenyls to ~~bviate the need for spill reportage under the EPA regulations.
It is also an object of an aspect of the present invention to provide a more useful heat transfer fluid insofar as heat levels and freezing points are concerned and to additionally create heat transfer fluids having better stability under various conditions.
To achieve the objects of this invention, therefore, it has been discovered that a mixture: in broad proportions of Biphenyl oxide (DPO) sometimes referred to as Biphenyl ether, which has a structural formula of C~HSOC~HS and 1,1 Biphenyl ethane (DPE) having a structural formula of CH3CH(C~,HS)2 in varying amounts but generally a larger amount of either Biphenyl oxide or 1,1 Biphenyl ethane to substantially equal amounts of Biphenyl oxide and l,l Biphenyl ethane. In other words, fluid with an excess of 1,1 Biphenyl ethane over Biphenyl oxide and vice versa provides a useful heat transfer fluid. However, the preferred ratios of about S
to 50% 1,1 Biphenyl ethane to 95-50% Biphenyl oxide provides a heat transfer fluid with remarkable improvements over the prior art fluids, i.e., higher heat transfer coefficients and lower freezing points as well as greater thermal stability.
The composition recited above though similar to the prior art compositions already mentioned, is not shown in the prior art, has not been used, and as previously stated, is remarkably better than the prior art compositions so much so that it may be considered th~it the performance of~this material is unexpected and even synergistic.
According to one aspect of the invention, there is provided a heat biphenyl-free transfer fluid comprising a mixture of Biphenyl oxide and 1,1 Biphenyl ethane.
Best Mode for Carrying Out the Invention The present invention is a mixture in broad proportions of Biphenyl oxide (DPO), which has a structural formula of C6HSOC6H5, and 1,1 Biphenyl ethane (DPE) having a structural formula of C',H3CH(C6H5)Z. The preferred ratios of about to 50% 1,1 cliphenyl ethane to 95- -WO 00/15730 PC'TNS99/17870 50% diphenyl oxide provides a heat transfer fluid having high heat transfer coefficients, low freezing points and good thermal stability.
Although a mixture of 1,1 Biphenyl ethane and Biphenyl oxide, as outlined above, is the preferred embodiment of the invention, it is know to one of ordinarv~ skill in the art Lhat certain impurities and.~or isomers can be added in small quantities to this preferred heat transfer mixture without affecting the performance characteristics ofthe invention, as discussed more i;.:lly below.
In particular, it is know that XCELTHERM XT, a commercially available product consisting essentially of a mixture of 92-95°~0 1,1 Biphenyl ethane, 7-4°~0 1,2 Biphenyl etha.~:, and I
Biphenyl methane can be substituted for the pure 1,1 Biphenyl ethane material of the preferred heat transfer mia-ture without essentially affecting the overall heat transfer character:_tics of the resultant mixture when compared to the etpected performance characteristics of the preferred embodiment of the invention. The XCELTHERIvi XT product is processed by the assignee of this patent, Radco Industries, Inc. of LaFox, Illinois. ?accordingly. it is l:no~~n that a material consisting essentially of 1,1 Biphenyl ethane and smaller amounts of other impurities and/or isomers can be substituted for the pure 1.1 Biphenyl ethane of the preferred composition.
Thermal stability tests of mixtures of 1,1 Biphenyl ethane and Biphenyl oxide alone have been conducted. However, in view of all of the materials that have been used prior to the development of the heat transfer fluid of this invention, it has been decided to run confirmatory tests as to the novelty and unexpected improvement provided by the heat transfer fluid combination of this invention, namely, Biphenyl ether and 1,1 Biphenyl ethane.
The combinations that have been tested are terphenyls, dibenzyl toluene, the Biphenyl oxide-biphenyl mixture and the compositions of the invention to determine which fluid provides the best heat transfer results.
It should be noted here that the terms "Biphenyl ether," ''Biphenyl oxide" and "DPO" gill be used throughout this specification as indicating the same chemical component while "DPE" will be used as indicating l,l,diphenyhethane.
Many industrial production processes require the use of a heat transfer fluid in the temperature range of 600°F - 700°F. The heat transfer fluids used in this temperature range fall into t~~o broad classifications:
1. Liquid phase fluids-characterized by low vapor pressure y ith heat transfer occurring in the liquid phase.
2. Liquid,wapor phase fluids-characterized by higher vapor pressures with heat transfer occurring in the liquid or vapor phase.
Three distinct chemistries, all aromatic, define the most widely used fluids worldwide in this temperature classification.
1. 73% diphenyl oxide.'?7°ro biphenyl mixture - a liquid/vapor phase fluid.
2. Hydrogenated terphenvl'.quatraphenyl mixture - a liquid phase fluid.
3. Dibertzyl Toluene - a liquid phase fluid.
The primary factors which define a fluid's use range are:
1. Thermal Stabiliy.
2. Pour!crystalizing point.
The primary factor which defines its effectiveness within it's operating range is:
1. Heat transfer coefficient - the abiliy to upload, transfer, and download heat/unit time-area at a given temperature.
A major factor in a fluid's use is its environmental impact - whether it is regulated as a hazardous chemical. Since these fluids may from time-to-time leak from the system or be subject to the over-the-road spillage, those fluids regarded as "hazardous" by the EPA incur additional potential liabilities, and therefore expense, in their use.
wo oons~3o PcrNS99n~s~o Disadvantages of the various types of fluids:
Terphenyls:
1. Can only be used to 650°F due to lower thermal stability 2. Relatively low heat transfer coefficient.
3. Can only be used in the liquid phase.
Dibenzyl Toluene:
1. Can only be used to 660°F due to lower thermal stability.
2. Relatively low heat transfer coefficient.
3. Can only be used in the liquid phase.
DPOBIP:
1. High pour!crystallizing point - results in system shutdoNn problems especially in colder climates.
'_'. Contains biphenyl - environmentally hazardous quantity in spills of over 100 lbs. of biphenyl.
The objective is to provide a single fluid that will operate in either the liquid,rapor phase with acceptable thermal stabiliy to 700°F offering a sufficiently low pour,'crystallizine point, high heat transfer coefficient. and minimal environmental exposure.
The heat transfer coefficient is a primary measure of the ability of a heat transfer medium to transfer heat. Therefore, a fluid having a higher heat transfer coefficient at a given temperature may be expected to transfer more heat/unit heat exchange surface area than another 7th a lower heat transfer coefficient at the same temperature. As such, a higher production rate or a decrease in production time is possible with the fluid having the higher heat transfer coefficient.
Table l represents a comparison of the heat transfer coefficients of the common ypes of heat transfer fluids with the heat transfer coefficients of this invention when the DPO is in excess of or equal to the DPE.
Comparison of Hcat Transfer Coefiictenu Table I
HEAT TRANSFER
COEFFICIENTS
Schedule 40 2' pipe (2 066' IDl ~a' 7 fl'sec flow rate TEMP(F) TcrphrnyltDBT' 73!'''795,'5 8:'15 75~: 5p;5C
DPO~BIPDPO.~DPEDPO,DPEDPO'DPEDPODPE
500 360 66 369 645 452 16 447 sa3 s.s2 86 65 24 79 =3 625 365 a6 377 444 454 05 469 445 u4 -;
52 77 45 a, 650 369 05 385 44..68455 37 45G 44' t45 29 36 S3 c8 675 NIAt N/Av 438 457 06 4: t aa~ ass 85 3 i 8. 83 700 N/A~ !~J/A'433 dS6 35 450 468 441 68 49 16 4e ~-Mactmum use temperature re;ammcnded by fluid suppler is 6S0'F
'-Mammum use temperature recemmendcd by fluid supplier is 660F
Heat transfer coefPtctent is a mcasurt of the ability of a fiend to uptake, uansport.
and download BTU The higher the heat uansfer coefficient r heat relative per to another unrt product the greater the ability of the tlutd girth the higher heat transfer coeCCtctem to uansie area of heat exchange surface Table ? represents a comparison of the heat transfer coefficients of the common types of heat transfer fluids with the heat transfer coefficients of this invention when DPE is in excess of DPO.
Comparison oC Hcat Transfer CoefTicten~s Table 2 HEAT TRANSFER
Schedule 40 2"
pipe (2.066' IDi ~u~
7 fUsec Oow nee TEMP (F) TerphenyltDBT2 73I?7 9515 85115 75..5 DPO/HIP DPE1DP0 DPE'DPO DPE:'DPO
600 360 66 369 86 445 65 415 1 a 19 1 4?3 08 ? I
62S 365.46 377.52 444.77 416 55 d20 55 424 59 650 369 05 385.29 442 68 441 .1 450 14 u7 67 t - Maximum use temperature recommended by fluid supplier is 650F.
2 - Maximum use temperature recommended by fluid supplier a 660F
Heat transfer coefTtctent is a metuure of the ab~lm~
of a fluid to uptake.
uansport and download BTU. The hteher the heat uansfcr eoePfteient relative to another product the greater the ability of the fluid uoh the higher heat uansfer coeft'tctent to uansfer heat per unrt area of heat exchange surface.
WO OOI15730 PCT/US99/c 7870 The following Tables 1 A-1 E and 2A-2C are derived from heat transfer coefficients in Tables 1 and 2. (+)% shows the percentage increase in heat transfer coefficient of DPO/DPE-DPElDPO relative to the indicated product. (-)% shows the percentage decrease in heat transfer coefficient of DPO/DPE-DPE/DPO relative to the indicated product.
Table 1 A
o C0~1PARISON
OF HEAT TRANSFER
COEFFICIENTS
Product 9S/5 8S/I S 7S ~5 SO~SO
DPO-'DPE DPOIDPE DPODPE DPODPE
Terphenyt -25.37 +24.01 23.OS +22.62 Dibenryl t22.2S 120.92 + 19.99 19.57 Toluene 73!27 1.46 +0.36 -0.42 _0.77 DPOBIP
Table 1B
,b COMPARISON
OF HEAT TRANSFER
COEFFICIENTS
Product 95/5 8S.1 S 75!?S 50/SO
DPO~~DPE DPOr'DpE DPO~DPE DPO:'DPE
Terphenyl 24.24 22.98 -2 I .89 21.69 Dibenryl +20.27 + 19.OS + t 8.00 17.80 Toluene 7327 2.09 +1.OS -0. I6 -0.01 DPOBIP
Table 1C
COMPARISON
OF HEAT TRANSFER
COEFFICIENTS
Product 9S/S 85/ 15 7Sr2S SOlSO
DPOIDPE DPO/DPE DPO/DPE DPOr'DPE
Terphenyl +23.39 +22.03 +21.27 20.76 Dibenryl + 18.19 ;16.89 ~ 16.15 - I 5.67 Toluene 73r27 +2.87 +1.73 + I .11 +0.68 DPOBIP
Table ID
~o COMPARISON
OF HEAT TRANSFER
COEFFICIENT'S
Product 9515 8S!15 755 50.50 DPO~DPE DPO-'DPE DPO~'DPE DPO'DPE
Terphenyl N/A~ NIA N/A N.'A
Dibenryl N!A' N/A N;A N;A
Toluene 73,27 -4. I 5 +2.84 +2.05 +3.36 DPO-BI P
Manufacturer recommends highest use temperature of 650F.
'Manufacturer recommends highest use temperature of 660F.
Table 1 E
,o CO'~IPARISON
OF HEAT TRANSFER
COEFFICIE',vTS
',00'F
Product 95; 5 85 15 75/25 50,'50 DPO'DPE DPO'DPE DPOIDPE DPODPE
Terphenyl N/A ~ N'A N, A NI A
Dibenzvl h'A~ N/A N/A NIA
Toluene 73/27 5.23 +3.88 +3.35 t .79 DPOBIP
Manufacturer recommends highest use temperature of 650F.
ZManufacturer recommends highest use temperature of 660F.
wo oon sr3o PcrnJS99n ~a~o Table COMPARISON
OF HEAT
TRANSFER
COEFFICIENTS
600'F
Product 95/5 85/15 75r25 DPE/DPO DPE/DPO DPEIDPO
Terpheny ~ I 5.11 ~ I 6.30 -17.3 I
1 ~
Dibenzyl'+12.25 +13.32 +14.39 Toluene 73:'27 -7.34 -6.33 -5.06 DPO:BIP
~i~fanufacturer recommends highest use temperature of 650F.
''Manufacturer recommends highest use temperature of 660F.
Table o CO~1PAR1SON
OF HEAT
TRANSFER
COEFFICIENTS
Product 95/5 8515 75125 DPElDPO DPE:DPO DPE/DPO
Terphenyl~T13.98 -15.07 +16.18 Dibenryl'+ I 0.34 1 1.40 t 12.47 Toluene -6.77 -5.76 -4.75 DPO~BIP
~hlanufacturer recommends highest use temperature of 650F.
rlanufacturer recommends highest use temperature of 660'F.
Table ,o COMPARISON
OF HEAT
TRANSFER
COEFFICIENTS
Product 9515 85i 15 75r'?5 DPE/DPO DPE,~DPO DPEJDPO
Terphenyl+ 19.55 X21.97 121.30 ~
Dibenryl''+14.51 116.83. +16.19 Toluene 73"_'7 -0.33 +1.68 -1.12 DPOBIP
Manufacturer recommends highest use temperature of 650'F.
ZManufacturer recommends highest use temperature of 660F.
Pour Point/Crvstallizine Point was determined for the various fluids utilizing .4STM D97. Table 3 represents a comparison of Pour Points/Crvstallizine Points of the various fluids.
Comparison of Pour Points/Crystallizing Points of the various fluids Table 3 ~
POUR/CRYST,4LLIZf~G
POINTS
Product Temp F
Terphenyl -15 Dibenzvl Toluene -50 95,'5 DPO/DPE 54 85;15 DPO/DPE 40 75!''5 DPO,'DPE ?7 95.5 DPEJDPO -30 75x25 DPE/DPO -13 ~ASTM D97 Testing Method Thermal stabilit<~ may be defined as the resistance of chemical bonds to thermal cracking.
A fluid exhibiting greater thermal stability relative to another at any given temperature will provide increased fluid life and a decreased potential for system fouling caused by thermal degradation by products.
The Thermal stability tests were conducted using the Ampule Test Procedure.
The Ampule Test is generally accepted as an industy standard for the testing of relative thermal stability between heat transfer fluids Although there is no standard ASTM-ype Ampule Test defined, the data generated by such testing has proven reliable over the course of many wo oonsz3o Pcrnrs~n~s~o years. Variations between methods exist as to the composition and diameter of the ampules, the method by which the oxygen is removed from the ampule, the sample size, and the temperature run. However, with the exception of those methods which do not properly provide for oxygen removal. the relative results are reliable as long as uniform temperatures are maintained across the oven. The data serves to define the thermal stability performance differences between fluids in any gi~~en s~~stem.
The procedure for the Ampule Test is as follows:
Purpose: To determine relative thermal stabiliy by measuring the thermal decomposition of heat transfer fluids under like conditions in the absence of oxygen.
A. SA'vIPLE PREPAR4TION
1. Cut 6 inch lengths of clean, dry 31b ss tubing (!! OD x 5 16 ID) in sufficient number for two samples of each fluid to be tested.
2. Wash the insides of the tubes with Xylol followed by Acetone. air blow and allow to dry.
3. Utilizing stainless steel swagelok fittings. cap one end of each tube.
4. Utilizing a metal etching tool. label the tubes lA, 1B, etc.
B. SAMPLE PREPARATION
I . Place ~ml of each sample into individual ampules (sample # 1 - Sml into Ampule marked lA, Sml into Ampule marked 1B, etc.) and note the product name of the sample and its designated Ampule.
2. Retain Sml of each sample in a glass vial and set aside as a reference.
3. Place the filled ampules vertically in a metal tube rack placing the samples on either side of the rack.
WO 00/15730 PC'TNS99/17870 C. OX~'GE:~1 REMOVAL
Tube Sparging Procedure 1. Place filled, uncapped tubes (in the rack) into the glove box.
2. Place caps and required tools into the glove box.
3. Connect nitrogen line to deflated bag W th 1/8" tubing.
4. Install a board as a work surface.
Start nitrogen at 60 PSI on the regulator.
6. After the bag begins to inflate, seal the open end with tape as per instructions.
7. After bag is fully inflated. open vent valve.
8. Reduce pressure from the regulator to 30 PSI.
9. After bag has inflated place the spargin~ tube (30 PSI nitrogenl into each tube for 1 minute.
10. Cap each tube immediately after sparging with nitrogen.
D. THER'viAL STRESS
1. Place the prepared tube rack of ampules in an oven capable of holding the selected temperature at t 1 ° F and with no more than t ~/ ° F
temperature gradient across the oven.
2. Bring the oven to the desired temperature and maintain this temperature under the parameters defined above the 336 hrs. (Two V'eeks).
3. At the end of the time period shut dow the oven and allow Ampules to cool for 24 hours undisturbed.
E. ANALYSIS
1. Uncap each ampule and decant into a properly labeled l5ml glass vial.
wo oons~o Pcrius~n~s~o 2. Analyze each retained reference sample and its appropriate processed samples utilizing using ASTMD2997 Simdis Gas Chromatography Methodology.
3. Calculate the % high\low boiler of each sample relative to the reference sample The results of the Thermal Stability Test are as follows:
Thermal Stability - Resistance of chemical bonds to thermal cracking at any given temperature when DPO is in excess of or equal to DPE as compared to the common ypes of heat transfer fluids is shown in Table 4.
Comparison of Thermal Stability Table 336 Hour Ampule Test THERMAL
DECOMPOSITION
TEMP Terphenyl'DBT' 73!17 9515 85J15 80120 75~=S 0/50 ('F) DPOBIP DPO1DPEDPO/DPEDPO/DPEDPO~'DPEDPOIpPE
600 0 87 0 59 0 004 0 002 0 00? 0 01 0 01 0.004 625 1 36 0.99 0 Ol 0 01 0 01 0 02 0 03 0 03 650 3 50 2 29 0 04 0.03 0 06 0. l2 0 15 0 22 675 NIA' NJA' 0. I 0. l3 0.37 0 60 0 88 1.60 l 700 H~.,' NJA~ 0 49 0.48 1 67 2 89 a.5o 7 s2 !-Maximum use temperature recommended by fluid supplier is 650F.
2-Maximum use temperature recommended by fluid supplier is 660F.
3-Maximum use temperature recommended by fluid supplier is 750F.
-Sample analysis by ASTM
WO 00/15730 PC'T/US99/17870 Thermal Stability-Resistance of chemical boards to thermal cracking at any given temperature when DPE is in excess of DPO as compared to the common types of heat transfer fluids is shown in Table S.
Comparison of Thermal Stability Table 336 Hour Ampule Test THERMAL
DECOMPOSITION
TEMP(F) Terphenyl~DBT~ 73'27 95'5 85 IS 75'25 DPOBIP DPE:'DPO DPE DPO DPE:DPO
600 0.87 0.59 0.004 0.09 0.01 0.01 625 1.36 0.99 0.01 0.27 0.1 ~ 0.09 650 3.50 2.29 0.04 1.40 1.02 0.85 I-Maximum use temperature recommended by fluid supplier is 6~0'F.
2-Maximum use temperature recommended by fluid supplier is 660F.
3-Maximum use temperature recommended by fluid supplier is 750F.
4-Sample analysis by ASTM
Thus. the tests of these various chemical compositions demonstrate that the Biphenyl ether or oxide/1,1 Biphenyl ethane mixture is superior insofar as heat transfer coefficient and thermal stability:' is concerned with respect to terphenyl and dibenzyl toluene and equivalent or superior in heat transfer coefficient to the eutectic mixture of Biphenyl oxide and biphenyl while providing lower pour point and lastly, avoids the use of biphenyl which is now important in the industry.
Various features of the invention have been particularly shown and described in connection with the illustrated embodiments of the invention, however, it must be understood that these particular arrangements merely illustrate and that the invention is to be given its fullest interpretation within the terms of the appended claims.
Terphenyls:
1. Can only be used to 650°F due to lower thermal stability 2. Relatively low heat transfer coefficient.
3. Can only be used in the liquid phase.
Dibenzyl Toluene:
1. Can only be used to 660°F due to lower thermal stability.
2. Relatively low heat transfer coefficient.
3. Can only be used in the liquid phase.
DPOBIP:
1. High pour!crystallizing point - results in system shutdoNn problems especially in colder climates.
'_'. Contains biphenyl - environmentally hazardous quantity in spills of over 100 lbs. of biphenyl.
The objective is to provide a single fluid that will operate in either the liquid,rapor phase with acceptable thermal stabiliy to 700°F offering a sufficiently low pour,'crystallizine point, high heat transfer coefficient. and minimal environmental exposure.
The heat transfer coefficient is a primary measure of the ability of a heat transfer medium to transfer heat. Therefore, a fluid having a higher heat transfer coefficient at a given temperature may be expected to transfer more heat/unit heat exchange surface area than another 7th a lower heat transfer coefficient at the same temperature. As such, a higher production rate or a decrease in production time is possible with the fluid having the higher heat transfer coefficient.
Table l represents a comparison of the heat transfer coefficients of the common ypes of heat transfer fluids with the heat transfer coefficients of this invention when the DPO is in excess of or equal to the DPE.
Comparison of Hcat Transfer Coefiictenu Table I
HEAT TRANSFER
COEFFICIENTS
Schedule 40 2' pipe (2 066' IDl ~a' 7 fl'sec flow rate TEMP(F) TcrphrnyltDBT' 73!'''795,'5 8:'15 75~: 5p;5C
DPO~BIPDPO.~DPEDPO,DPEDPO'DPEDPODPE
500 360 66 369 645 452 16 447 sa3 s.s2 86 65 24 79 =3 625 365 a6 377 444 454 05 469 445 u4 -;
52 77 45 a, 650 369 05 385 44..68455 37 45G 44' t45 29 36 S3 c8 675 NIAt N/Av 438 457 06 4: t aa~ ass 85 3 i 8. 83 700 N/A~ !~J/A'433 dS6 35 450 468 441 68 49 16 4e ~-Mactmum use temperature re;ammcnded by fluid suppler is 6S0'F
'-Mammum use temperature recemmendcd by fluid supplier is 660F
Heat transfer coefPtctent is a mcasurt of the ability of a fiend to uptake, uansport.
and download BTU The higher the heat uansfer coefficient r heat relative per to another unrt product the greater the ability of the tlutd girth the higher heat transfer coeCCtctem to uansie area of heat exchange surface Table ? represents a comparison of the heat transfer coefficients of the common types of heat transfer fluids with the heat transfer coefficients of this invention when DPE is in excess of DPO.
Comparison oC Hcat Transfer CoefTicten~s Table 2 HEAT TRANSFER
Schedule 40 2"
pipe (2.066' IDi ~u~
7 fUsec Oow nee TEMP (F) TerphenyltDBT2 73I?7 9515 85115 75..5 DPO/HIP DPE1DP0 DPE'DPO DPE:'DPO
600 360 66 369 86 445 65 415 1 a 19 1 4?3 08 ? I
62S 365.46 377.52 444.77 416 55 d20 55 424 59 650 369 05 385.29 442 68 441 .1 450 14 u7 67 t - Maximum use temperature recommended by fluid supplier is 650F.
2 - Maximum use temperature recommended by fluid supplier a 660F
Heat transfer coefTtctent is a metuure of the ab~lm~
of a fluid to uptake.
uansport and download BTU. The hteher the heat uansfcr eoePfteient relative to another product the greater the ability of the fluid uoh the higher heat uansfer coeft'tctent to uansfer heat per unrt area of heat exchange surface.
WO OOI15730 PCT/US99/c 7870 The following Tables 1 A-1 E and 2A-2C are derived from heat transfer coefficients in Tables 1 and 2. (+)% shows the percentage increase in heat transfer coefficient of DPO/DPE-DPElDPO relative to the indicated product. (-)% shows the percentage decrease in heat transfer coefficient of DPO/DPE-DPE/DPO relative to the indicated product.
Table 1 A
o C0~1PARISON
OF HEAT TRANSFER
COEFFICIENTS
Product 9S/5 8S/I S 7S ~5 SO~SO
DPO-'DPE DPOIDPE DPODPE DPODPE
Terphenyt -25.37 +24.01 23.OS +22.62 Dibenryl t22.2S 120.92 + 19.99 19.57 Toluene 73!27 1.46 +0.36 -0.42 _0.77 DPOBIP
Table 1B
,b COMPARISON
OF HEAT TRANSFER
COEFFICIENTS
Product 95/5 8S.1 S 75!?S 50/SO
DPO~~DPE DPOr'DpE DPO~DPE DPO:'DPE
Terphenyl 24.24 22.98 -2 I .89 21.69 Dibenryl +20.27 + 19.OS + t 8.00 17.80 Toluene 7327 2.09 +1.OS -0. I6 -0.01 DPOBIP
Table 1C
COMPARISON
OF HEAT TRANSFER
COEFFICIENTS
Product 9S/S 85/ 15 7Sr2S SOlSO
DPOIDPE DPO/DPE DPO/DPE DPOr'DPE
Terphenyl +23.39 +22.03 +21.27 20.76 Dibenryl + 18.19 ;16.89 ~ 16.15 - I 5.67 Toluene 73r27 +2.87 +1.73 + I .11 +0.68 DPOBIP
Table ID
~o COMPARISON
OF HEAT TRANSFER
COEFFICIENT'S
Product 9515 8S!15 755 50.50 DPO~DPE DPO-'DPE DPO~'DPE DPO'DPE
Terphenyl N/A~ NIA N/A N.'A
Dibenryl N!A' N/A N;A N;A
Toluene 73,27 -4. I 5 +2.84 +2.05 +3.36 DPO-BI P
Manufacturer recommends highest use temperature of 650F.
'Manufacturer recommends highest use temperature of 660F.
Table 1 E
,o CO'~IPARISON
OF HEAT TRANSFER
COEFFICIE',vTS
',00'F
Product 95; 5 85 15 75/25 50,'50 DPO'DPE DPO'DPE DPOIDPE DPODPE
Terphenyl N/A ~ N'A N, A NI A
Dibenzvl h'A~ N/A N/A NIA
Toluene 73/27 5.23 +3.88 +3.35 t .79 DPOBIP
Manufacturer recommends highest use temperature of 650F.
ZManufacturer recommends highest use temperature of 660F.
wo oon sr3o PcrnJS99n ~a~o Table COMPARISON
OF HEAT
TRANSFER
COEFFICIENTS
600'F
Product 95/5 85/15 75r25 DPE/DPO DPE/DPO DPEIDPO
Terpheny ~ I 5.11 ~ I 6.30 -17.3 I
1 ~
Dibenzyl'+12.25 +13.32 +14.39 Toluene 73:'27 -7.34 -6.33 -5.06 DPO:BIP
~i~fanufacturer recommends highest use temperature of 650F.
''Manufacturer recommends highest use temperature of 660F.
Table o CO~1PAR1SON
OF HEAT
TRANSFER
COEFFICIENTS
Product 95/5 8515 75125 DPElDPO DPE:DPO DPE/DPO
Terphenyl~T13.98 -15.07 +16.18 Dibenryl'+ I 0.34 1 1.40 t 12.47 Toluene -6.77 -5.76 -4.75 DPO~BIP
~hlanufacturer recommends highest use temperature of 650F.
rlanufacturer recommends highest use temperature of 660'F.
Table ,o COMPARISON
OF HEAT
TRANSFER
COEFFICIENTS
Product 9515 85i 15 75r'?5 DPE/DPO DPE,~DPO DPEJDPO
Terphenyl+ 19.55 X21.97 121.30 ~
Dibenryl''+14.51 116.83. +16.19 Toluene 73"_'7 -0.33 +1.68 -1.12 DPOBIP
Manufacturer recommends highest use temperature of 650'F.
ZManufacturer recommends highest use temperature of 660F.
Pour Point/Crvstallizine Point was determined for the various fluids utilizing .4STM D97. Table 3 represents a comparison of Pour Points/Crvstallizine Points of the various fluids.
Comparison of Pour Points/Crystallizing Points of the various fluids Table 3 ~
POUR/CRYST,4LLIZf~G
POINTS
Product Temp F
Terphenyl -15 Dibenzvl Toluene -50 95,'5 DPO/DPE 54 85;15 DPO/DPE 40 75!''5 DPO,'DPE ?7 95.5 DPEJDPO -30 75x25 DPE/DPO -13 ~ASTM D97 Testing Method Thermal stabilit<~ may be defined as the resistance of chemical bonds to thermal cracking.
A fluid exhibiting greater thermal stability relative to another at any given temperature will provide increased fluid life and a decreased potential for system fouling caused by thermal degradation by products.
The Thermal stability tests were conducted using the Ampule Test Procedure.
The Ampule Test is generally accepted as an industy standard for the testing of relative thermal stability between heat transfer fluids Although there is no standard ASTM-ype Ampule Test defined, the data generated by such testing has proven reliable over the course of many wo oonsz3o Pcrnrs~n~s~o years. Variations between methods exist as to the composition and diameter of the ampules, the method by which the oxygen is removed from the ampule, the sample size, and the temperature run. However, with the exception of those methods which do not properly provide for oxygen removal. the relative results are reliable as long as uniform temperatures are maintained across the oven. The data serves to define the thermal stability performance differences between fluids in any gi~~en s~~stem.
The procedure for the Ampule Test is as follows:
Purpose: To determine relative thermal stabiliy by measuring the thermal decomposition of heat transfer fluids under like conditions in the absence of oxygen.
A. SA'vIPLE PREPAR4TION
1. Cut 6 inch lengths of clean, dry 31b ss tubing (!! OD x 5 16 ID) in sufficient number for two samples of each fluid to be tested.
2. Wash the insides of the tubes with Xylol followed by Acetone. air blow and allow to dry.
3. Utilizing stainless steel swagelok fittings. cap one end of each tube.
4. Utilizing a metal etching tool. label the tubes lA, 1B, etc.
B. SAMPLE PREPARATION
I . Place ~ml of each sample into individual ampules (sample # 1 - Sml into Ampule marked lA, Sml into Ampule marked 1B, etc.) and note the product name of the sample and its designated Ampule.
2. Retain Sml of each sample in a glass vial and set aside as a reference.
3. Place the filled ampules vertically in a metal tube rack placing the samples on either side of the rack.
WO 00/15730 PC'TNS99/17870 C. OX~'GE:~1 REMOVAL
Tube Sparging Procedure 1. Place filled, uncapped tubes (in the rack) into the glove box.
2. Place caps and required tools into the glove box.
3. Connect nitrogen line to deflated bag W th 1/8" tubing.
4. Install a board as a work surface.
Start nitrogen at 60 PSI on the regulator.
6. After the bag begins to inflate, seal the open end with tape as per instructions.
7. After bag is fully inflated. open vent valve.
8. Reduce pressure from the regulator to 30 PSI.
9. After bag has inflated place the spargin~ tube (30 PSI nitrogenl into each tube for 1 minute.
10. Cap each tube immediately after sparging with nitrogen.
D. THER'viAL STRESS
1. Place the prepared tube rack of ampules in an oven capable of holding the selected temperature at t 1 ° F and with no more than t ~/ ° F
temperature gradient across the oven.
2. Bring the oven to the desired temperature and maintain this temperature under the parameters defined above the 336 hrs. (Two V'eeks).
3. At the end of the time period shut dow the oven and allow Ampules to cool for 24 hours undisturbed.
E. ANALYSIS
1. Uncap each ampule and decant into a properly labeled l5ml glass vial.
wo oons~o Pcrius~n~s~o 2. Analyze each retained reference sample and its appropriate processed samples utilizing using ASTMD2997 Simdis Gas Chromatography Methodology.
3. Calculate the % high\low boiler of each sample relative to the reference sample The results of the Thermal Stability Test are as follows:
Thermal Stability - Resistance of chemical bonds to thermal cracking at any given temperature when DPO is in excess of or equal to DPE as compared to the common ypes of heat transfer fluids is shown in Table 4.
Comparison of Thermal Stability Table 336 Hour Ampule Test THERMAL
DECOMPOSITION
TEMP Terphenyl'DBT' 73!17 9515 85J15 80120 75~=S 0/50 ('F) DPOBIP DPO1DPEDPO/DPEDPO/DPEDPO~'DPEDPOIpPE
600 0 87 0 59 0 004 0 002 0 00? 0 01 0 01 0.004 625 1 36 0.99 0 Ol 0 01 0 01 0 02 0 03 0 03 650 3 50 2 29 0 04 0.03 0 06 0. l2 0 15 0 22 675 NIA' NJA' 0. I 0. l3 0.37 0 60 0 88 1.60 l 700 H~.,' NJA~ 0 49 0.48 1 67 2 89 a.5o 7 s2 !-Maximum use temperature recommended by fluid supplier is 650F.
2-Maximum use temperature recommended by fluid supplier is 660F.
3-Maximum use temperature recommended by fluid supplier is 750F.
-Sample analysis by ASTM
WO 00/15730 PC'T/US99/17870 Thermal Stability-Resistance of chemical boards to thermal cracking at any given temperature when DPE is in excess of DPO as compared to the common types of heat transfer fluids is shown in Table S.
Comparison of Thermal Stability Table 336 Hour Ampule Test THERMAL
DECOMPOSITION
TEMP(F) Terphenyl~DBT~ 73'27 95'5 85 IS 75'25 DPOBIP DPE:'DPO DPE DPO DPE:DPO
600 0.87 0.59 0.004 0.09 0.01 0.01 625 1.36 0.99 0.01 0.27 0.1 ~ 0.09 650 3.50 2.29 0.04 1.40 1.02 0.85 I-Maximum use temperature recommended by fluid supplier is 6~0'F.
2-Maximum use temperature recommended by fluid supplier is 660F.
3-Maximum use temperature recommended by fluid supplier is 750F.
4-Sample analysis by ASTM
Thus. the tests of these various chemical compositions demonstrate that the Biphenyl ether or oxide/1,1 Biphenyl ethane mixture is superior insofar as heat transfer coefficient and thermal stability:' is concerned with respect to terphenyl and dibenzyl toluene and equivalent or superior in heat transfer coefficient to the eutectic mixture of Biphenyl oxide and biphenyl while providing lower pour point and lastly, avoids the use of biphenyl which is now important in the industry.
Various features of the invention have been particularly shown and described in connection with the illustrated embodiments of the invention, however, it must be understood that these particular arrangements merely illustrate and that the invention is to be given its fullest interpretation within the terms of the appended claims.
Claims (13)
1. A heat transfer fluid comprising a mixture of diphenyl oxide and 1,1 diphenyl ethane.
2. The heat transfer fluid of claim 1 further including one or more impurities.
3. The heat transfer fluid of claim 2 wherein said one or more impurities can be selected from the group consisting of diphenyl methane and 1,2 diphenyl ethane.
4. The heat transfer fluid of claim 1 further including 1,2 diphenyl ethane and diphenyl methane.
5. The heat transfer fluid of claim 4 wherein said 1,1 diphenyl ethane is about 92 to 95 weight percent of said mixture, said 1,2 diphenyl ethane is about 7 to 4 weight percent of said mixture, and said diphenyl methane is about 1 weight percent of said mixture.
6. The heat transfer fluid of claim 1 wherein the amount of said 1,1 diphenyl ethane ranges from an excess to equal to said diphenyl oxide.
7. The heat transfer fluid of claim 1 wherein the amount of said diphenyl oxide ranges from an excess to equal to said 1,1 diphenyl ethane.
8. The heat transfer fluid of claim 7 wherein said dipheny oxide is present from 95-5% by weight of said mixture and said 1,1 diphenyl ethane is present from 5-50% by weight of said mixture.
9. The heat transfer of Claim 8 wherein said diphenyl oxide is present in about 95% by weight of said mixture and said 1,1 diphenyl ethane is present in about 5% by weight of said mixture.
10. The heat transfer of claim 8 wherein said diphenyl oxide is present in about 85% by weight of said mixture and said 1,1 diphneyl ethane is present in about 15% by weight of said mixture.
11. The heat transfer fluid of claim 8 wherein said diphenyl oxide is present in about 75% by weight of said mixture and said 1,1 diphenyl ethane is present in about 25% by weight of said mixture.
12. The heat transfer fluid of claim 8 wherein said diphenyl oxide is present in about 50% by weight of said mixture and said 1,1 diphenyl ethane is present in about 50% by weight of said mixture.
13. The heat transfer fluid of claim 1 wherein said fluid has a high heat transfer coefficient, a low freezing point, and a good thermal stability.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15674498A | 1998-09-17 | 1998-09-17 | |
| US09/156,744 | 1998-09-17 | ||
| US09/231,435 US6022488A (en) | 1998-09-17 | 1999-01-14 | Heat transfer fluid containing 1,1-diphenyl ethane and diphenyl oxide |
| US09/231,435 | 1999-01-14 | ||
| PCT/US1999/017870 WO2000015730A1 (en) | 1998-09-17 | 1999-08-06 | Heat transfer fluids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2344276A1 CA2344276A1 (en) | 2000-03-23 |
| CA2344276C true CA2344276C (en) | 2004-10-19 |
Family
ID=26853469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002344276A Expired - Fee Related CA2344276C (en) | 1998-09-17 | 1999-08-06 | Heat transfer fluids |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1114114A4 (en) |
| AU (1) | AU5549599A (en) |
| CA (1) | CA2344276C (en) |
| MX (1) | MXPA01002760A (en) |
| TW (1) | TW495546B (en) |
| WO (1) | WO2000015730A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013095850A1 (en) * | 2011-12-20 | 2013-06-27 | Dow Global Technologies Llc | Methods for alcohol dehydration |
| CN104364226A (en) * | 2012-05-31 | 2015-02-18 | 陶氏环球技术有限责任公司 | Catalytic dehydration of aryl alcohols to diaryl ethers |
| CN104271544B (en) * | 2012-05-31 | 2017-12-26 | 陶氏环球技术有限责任公司 | Aryl alcohol catalytic dehydration is into diaryl ether |
| EP2872249A1 (en) | 2012-08-30 | 2015-05-20 | Dow Global Technologies LLC | Catalysts and methods for alcohol dehydration |
| EP2872250A1 (en) * | 2012-08-30 | 2015-05-20 | Dow Global Technologies LLC | Catalysts and methods for alcohol dehydration |
| EP2943277A1 (en) * | 2013-03-21 | 2015-11-18 | Dow Global Technologies LLC | Catalysts and methods for alcohol dehydration |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3888777A (en) * | 1971-04-02 | 1975-06-10 | Dow Chemical Co | Heat transfer agents |
| US4011274A (en) * | 1973-01-13 | 1977-03-08 | Asahi-Dow Limited | 1,1-diphenyl ethane process |
| US4622160A (en) * | 1985-10-23 | 1986-11-11 | The Dow Chemical Company | Heat-transfer fluid |
-
1999
- 1999-08-06 AU AU55495/99A patent/AU5549599A/en not_active Abandoned
- 1999-08-06 CA CA002344276A patent/CA2344276C/en not_active Expired - Fee Related
- 1999-08-06 EP EP99942030A patent/EP1114114A4/en not_active Withdrawn
- 1999-08-06 MX MXPA01002760A patent/MXPA01002760A/en not_active IP Right Cessation
- 1999-08-06 WO PCT/US1999/017870 patent/WO2000015730A1/en active Application Filing
- 1999-09-15 TW TW88115938A patent/TW495546B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP1114114A1 (en) | 2001-07-11 |
| EP1114114A4 (en) | 2007-10-24 |
| WO2000015730A1 (en) | 2000-03-23 |
| CA2344276A1 (en) | 2000-03-23 |
| MXPA01002760A (en) | 2002-04-24 |
| AU5549599A (en) | 2000-04-03 |
| TW495546B (en) | 2002-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2344276C (en) | Heat transfer fluids | |
| Beattie | Olivine-melt and orthopyroxene-melt equilibria | |
| Kim et al. | Vapor–liquid equilibria for the carbon dioxide+ propane system over a temperature range from 253.15 to 323.15 K | |
| Higashi et al. | Measurements of the vapor-liquid coexistence curve for the binary R12+ R22 system in the critical region | |
| CN105378024A (en) | Dielectric or heat-transfer fluid compositions and uses of same | |
| US6022488A (en) | Heat transfer fluid containing 1,1-diphenyl ethane and diphenyl oxide | |
| Leu et al. | Equilibrium phase properties of the n-butane-hydrogen sulfide and isobutane-hydrogen sulfide binary systems | |
| Barrick et al. | Solubilities of carbon dioxide in naphthalene, phenanthrene, and pyrene at pressures to 10.6 MPa and temperatures from 373 to 433 K | |
| AU645911B2 (en) | Heat-transfer medium compositions | |
| Leu et al. | The equilibrium phase properties of the methanol-hydrogen sulfide binary system | |
| Glasgow et al. | Compounds involved in production of synthetic rubber | |
| Moradinia et al. | Solubilities of solid n-octacosane, n-triacontane and n-dotriacontane in supercritical ethane | |
| Schaeffer | Gas chromatographic analysis of traces of light hydrocarbons. A review of different systems in practice | |
| EP0980410B1 (en) | Thermal fluid blends containing 1,2,3,4-tetrahydro(1-phenylethyl)naphthalene | |
| NO300380B1 (en) | Use of substituted biphenyls as heat transfer fluid | |
| Kay et al. | Critical-locus curves and liquid-vapor equilibria in the binary systems of benzene with carbon dioxide and sulfur dioxide | |
| Okada et al. | Surface tension of HFC refrigerant mixtures | |
| CN209927695U (en) | Simulation test device for corrosion of petrochemical equipment by oil containing organic matters | |
| CN113484454A (en) | Headspace/gas chromatography method for volatile petroleum hydrocarbon in water | |
| Kumagai et al. | Measurements of PVTx properties for the binary refrigerant HCFC 142b+ HCFC 22 system | |
| CN106967916B (en) | The liquid alloy and the preparation method and application thereof of alternative mercury | |
| US7910017B2 (en) | Low temperature heat transfer fluid composition comprising alkylbenzene and dibutyl ether | |
| Howard et al. | A laboratory evaluation of the suitability of cesium acetate brines as completion, workover, suspension, and packer fluids for extreme/ultra HPHT wells–results of an extensive corrosion testing program | |
| SI9400163A (en) | Composition consisting of hydrogenated fluorocarbons | |
| Vigh et al. | Combined electron-spin-resonance, X-ray-diffraction studies on phospholipid vesicles obtained from cold-hardened wheats: I. An attempt to correlate electron-spin-resonance spectral characteristics with frost resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |