WO2000015730A1

WO2000015730A1 - Heat transfer fluids

Info

Publication number: WO2000015730A1
Application number: PCT/US1999/017870
Authority: WO
Inventors: Robert A. Damiani; Michael R. Damiani
Original assignee: Damiani Robert A; Damiani Michael R
Priority date: 1998-09-17
Filing date: 1999-08-06
Publication date: 2000-03-23
Also published as: AU5549599A; CA2344276C; MXPA01002760A; EP1114114A4; CA2344276A1; EP1114114A1; TW495546B

Abstract

A heat transfer fluid having high heat capacity, high thermal loading capacity, low viscosity and low freezing point includes diphenyl oxide and 1,1 diphenyl ethane in broad proportions.

Description

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 capacity and adequate thermal stability 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% diphenyl oxide and 27% biphenyl commonly known as DowthermA,

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 dibenzyl 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 capability, or a

combination of both. Disclosure of Invention

It is the object of the present invention to overcome any disadvantages of the prior art heat transfer fluids and to eliminate the use of biphenyls to obviate the need for spill reportage under

the EPA regulations. It is also an object 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 diphenyl oxide (DPO) sometimes referred to as diphenyl ether, which has

a structural formula of C₆H₅OC₆H₅ and 1,1 diphenyl ethane (DPE) having a structural formula

of CH3CH(C₆H₅)₂ in varying amounts but generally a larger amount of either diphenyl oxide

or 1 , 1 diphenyl ethane to substantially equal amounts of diphenyl oxide and 1 , 1 diphenyl ethane. In other words, fluid with an excess of 1 ,1 diphenyl ethane over diphenyl oxide and vice versa

provides a useful heat transfer fluid. However, the preferred ratios of about 5 to 50% 1 , 1 diphenyl ethane to 95-50% diphenyl 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 that the performance of this material is unexpected and even synergistic.

Best Mode for Carrying Out the Invention

The present invention is a mixture in broad proportions of diphenyl oxide (DPO), which

has a structural formula of C₆H₅OC₆H₅ and 1,1 diphenyl ethane (DPE) having a structural

formula of CH₃CH(C₆H₅)₂. The preferred ratios of about 5 to 50% 1,1 diphenyl ethane to 95- 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 diphenyl ethane and diphenyl oxide, as outlined above, is the

preferred embodiment of the invention, it is known to one of ordinary skill in the art that certain

impurities and/or isomers can be added in small quantities to this preferred heat transfer mixture

without affecting the performance characteristics of the invention, as discussed more fully below. In particular, it is known that XCELTHERM XT, a commercially available product consisting

essentially of a mixture of 92-95% 1,1 diphenyl ethane, 7-4% 1,2 diphenyl ethane, and 1%

diphenyl methane can be substituted for the pure 1,1 diphenyl ethane material of the preferred

heat transfer mixture without essentially affecting the overall heat transfer characteristics of the

resultant mixture when compared to the expected performance characteristics of the preferred embodiment of the invention. The XCELTHERM XT product is processed by the assignee of

this patent, Radco Industries, Inc. of LaFox, Illinois. Accordingly, it is known that a material

consisting essentially of 1,1 diphenyl ethane and smaller amounts of other impurities and/or

isomers can be substituted for the pure 1,1 diphenyl ethane of the preferred composition.

Thermal stability tests of mixtures of 1,1 diphenyl ethane and diphenyl 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, diphenyl ether and 1 , 1 diphenyl ethane. The combinations that have been tested are terphenyls, dibenzyl toluene, the diphenyl 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 "diphenyl ether," "diphenyl oxide" and "DPO" will be used throughout this specification as indicating the same chemical component while "DPE" will be used as indicating l,l,diphenyl/ethane.

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 two broad classifications:

1. Liquid phase fluids-characterized by low vapor pressure with heat transfer occurring in the liquid phase.

2. Liquid/vapor 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%o diphenyl oxide/27% biphenyl mixture - a liquid/vapor phase fluid.

2. Hydrogenated terphenyl\quatraphenyl mixture - a liquid phase fluid.

3. Dibenzyl Toluene - a liquid phase fluid.

The primary factors which define a fluid's use range are:

1. Thermal Stability.

2. Pour/cry stalizing point.

The primary factor which defines its effectiveness within it's operating range is:

1. Heat transfer coefficient - the ability 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. 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.

DPO/BIP:

1. High pour/crystallizing point - results in system shutdown problems especially in colder climates.

2. 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/vapor phase with

acceptable thermal stability to 700 °F offering a sufficiently low pour/crystallizing 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 with 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 1 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 the DPO is in excess

of or equal to the DPE.

Table 2 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.

The following Tables 1A-1E 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-

DPE/DPO relative to the indicated product. (-)% shows the percentage decrease in heat transfer coefficient of DPO/DPE-DPE/DPO relative to the indicated product.

Pour Point/Crystallizine Point was determined for the various fluids utilizing ASTM D97. Table

3 represents a comparison of Pour Points/Crystallizine Points of the various fluids.

Thermal stability 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 industry standard for the testing of relative

thermal stability between heat transfer fluids Although there is no standard ASTM-type Ampule

Test defined, the data generated by such testing has proven reliable over the course of many 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 given system.

The procedure for the Ampule Test is as follows: Purpose: To determine relative thermal stability by measuring the thermal decomposition

of heat transfer fluids under like conditions in the absence of oxygen.

A. SAMPLE PREPARATION

1. Cut 6 inch lengths of clean, dry 316 ss tubing (^lΔ 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 1 A, IB, etc.

B. SAMPLE PREPARATION

1. Place 5ml of each sample into individual ampules (sample #1 - 5ml into

Ampule marked 1A, 5ml into Ampule marked IB, etc.) and note the product name of the sample and its designated Ampule.

2. Retain 5ml 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. C. OXYGEN 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 with 1/8" tubing.

4. Install a board as a work surface.

5. 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 sparging tube (30 PSI nitrogen) into each tube for 1 minute.

10. Cap each tube immediately after sparging with nitrogen.

D. THERMAL STRESS

1. Place the prepared tube rack of ampules in an oven capable of holding the

selected temperature at ± 1 °F and with no more than ± ^lΛ°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 Weeks).

3. At the end of the time period shut down the oven and allow Ampules to cool for 24 hours undisturbed.

E. ANALYSIS

1. Uncap each ampule and decant into a properly labeled 15ml glass vial. 2. Analyze each retained reference sample and its appropriate processed

samples utilizing using ASTMD2997 Simdis Gas Chromatography Methodology.

3. Calculate the % highMow 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 types of heat transfer

fluids is shown in Table 4.

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 5.

Thus, the tests of these various chemical compositions demonstrate that the diphenyl ether or oxide/1 ,1 diphenyl ethane mixture is superior insofar as heat transfer coefficient and thermal

stability is concerned with respect to teφhenyl and dibenzyl toluene and equivalent or superior

in heat transfer coefficient to the eutectic mixture of diphenyl 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

ClaimsWhat is claimed is:

1. A heat transfer fluid comprising a mixture of diphenyl oxide and 1 , 1 diphenyl ethane.

2. The heat transfer fluid of claim 1 wherein said 1,1 diphenyl ethane is comprised of a mixture of 1,1 diphenyl ethane and 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 wherein said 1,1 diphenyl ethane consists essentially of a mixture of 1,1 diphenyl ethane, 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 diphenyl 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 fluid 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 fluid of Claim 8 wherein said diphenyl oxide is present in about 85% by weight of said mixture and said 1 , 1 diphenyl ethane is present in about 15% by weight of said mixture.

1 1. 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.

AMENDED CLAIMS

[received by the International Bureau on 17 January 2000 (17.01.00); original claims 1 and 8 amended; remaining claims unchanged (1 page)]

What is claimed is:

1. A heat biphenyl-free transfer fluid comprising a mixture of diphenyl oxide and 1 , 1 diphenyl ethane.

2. The heat transfer fluid of claim 1 wherein said 1,1 diphenyl ethane is comprised of a mixture of 1 ,1 diphenyl ethane and 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 wherein said 1 ,1 diphenyl ethane consists essentially of a mixture of 1 ,1 diphenyl ethane, 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 1 wherein said diphenyl 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.