US3774393A - Method of generating power - Google Patents

Method of generating power Download PDF

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Publication number
US3774393A
US3774393A US00172513A US3774393DA US3774393A US 3774393 A US3774393 A US 3774393A US 00172513 A US00172513 A US 00172513A US 3774393D A US3774393D A US 3774393DA US 3774393 A US3774393 A US 3774393A
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Prior art keywords
isomers
condenser
mixture
boiler
difluorobenzene
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Expired - Lifetime
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US00172513A
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English (en)
Inventor
M Bechtold
C Tullock
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
    • F01K25/08—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/208—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being MX
    • 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
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa

Definitions

  • This invention relates to a method of generating power using the Rankine cycle. More particularly, this invention relates to the use of novelpower fluids in Rankine cycle engines.
  • the present invention can be defined as a method of generating power in which a working substance is heated and vaporized, does work in a prime mover and after doing said work is condensed. andv recycled,
  • the working substance consists essentially of at least one halogenated benzene compound having the formula sm b obtained as the products of synthesis.
  • the working substance consists essentially of at least one halogenated benzene compound having the formula sm b obtained as the products of synthesis.
  • all of the isomers of a given compound boil in a narrowrange of temperatures (about 2C) and such mixtures generally exhibit a lower melting point than the pure isomers, while is of advantage in operating the engine.
  • FIG. 1 is a diagram showing the various stages of a Rankine cycle including an optional regeneration step to optimize the efficiency.
  • FIG. 2 is a temperature-entropy diagram for a mixture of isomers of trichlorodifluorobenzene.
  • This boiler can be any conventional form of boiler. Boilers of the rotating type wherein the liquid is distributed over a large surface by centrifugal force are particularly efficient thermally and produce high quality vapor. Such boilers are preferred for use with the working substances of the present invention.
  • the vapor then passes to a prime mover such asa turbine 2 when it expands in the turbine nozzles and is employed to a condenser 3 when it is condensed back to the liquid phase.
  • the liquid is then pumped back to the boiler l by pump 4 and thus recycled.
  • small air-cooled condensers of high efficiency can be employed.
  • Expansion of the vapor in the prime mover is essentially isentropic.
  • the vapor of the working substances of this invention becomes superheated upon expansion.
  • the efficiency of the cycle can, therefore, be improved by passing the exhaust from the turbine employed as a primemover through a regenerator 5 wherein the excess heat is removed from the vapor and transferred to the boiler feed as taught by U.S. Pat. No. 3,040,528.
  • FIG. 2 there is shown the temperature-entropy diagram for a mixture of isomers of trichlorodifluorobenw zene, one of the compositions useful as working fluids in Rankine cycle engines accordingv to the present invention.
  • This mixture contains:
  • Power is generated by expansion of the mixture from vapor at a temperature of 621F, psia, point 11 on the diagram, in a turbine. Expansion is-essentially isentropic and the working fluid is cooled, following the line from 11 to 12 to a temperature of433F and 3 psia.
  • the condenser pressure is then cooled at 3 psia, pressure from 433 to 296.8F, the condenser temperature following the line from i2 to 13.
  • the cooling can be conducted in thecondenser, butisprefera bly conducted inaregenerator.
  • the vapor is then condensed to liquid in the'condenser, following the line from 13 to 14 in FIG. 2.
  • the indicated Rankine cycle thermal efficiency (n cycle) is given by wherein r is the regeneration factor, i.e., the fraction of heat recovered by regeneration. With no regeneration, the above mixture of trichlorodifluorobenzenes has an efficiency in Rankine cycle engines given by With 70 percent regeneration, the Rankine cycle efficiency is increased to
  • the above mixture of isomers of trichlorodifluorobenzene can be made by heating pentachlorobenzene with potassium fluoride in sulfolane (tetramethylene sulfone). The mixture has a critical temperature of 427C (800.7F), a critical pressure of 522.4 p.s.i.a., a boiling point of 203C (397.4F) and a freezing point of about 40C (40F).
  • the pure isomers can be isolated from the mixture by conventional methods of separation. All of the isomers have essentially the same boiling point and critical temperature. The melting points, however, vary: isomer [1 melts at -13C and isomer IV melts at about 25C. isomer I melts at 155C, 11] at 28C, V at 505C and isomer V] at C.
  • the novel compound 1V 1,2,5- trichloro-3,4-difluorobenzene which has the lowest melting point, also has exceptional heat stability.
  • the working fluids of the present invention have surprising thermal stability and are suitable for use at boiler temperatures of 350C.
  • the working fluids are preferably such that inhalation of vapors from accidental breakage or spills should not be damaging to health.
  • the working fluids of the present invention are essentially non-toxic in acute inhalation tests.
  • the working fluids of the present invention are essentially non-toxic in acute inhalation tests.
  • ChR-CD male rats each weighing 250300 grams, were exposed to the test material in a 20-liter exposure chamber for 4 hours.
  • the test material was metered at a uniform rate by a syringe drive into a stainless steel T tube heated to l50175C through which air was passed to give a concentration of about 1245 ppm and fed to the exposure chamber.
  • the exposed rats were kept 14 days after treatment for observation. During treatment the rats exhibited lachrimation and salivation, with face pawing and gasping. After exposure the rats had a normal weight gain (against a control of untreated rats) over the 14 day observation period. No rats died during this period.
  • the flammability of the fluids should be as low as possible to minimize the risks of tire.
  • the working fluids of the resent invention do not support combustion.
  • High Molecular Weight High molecular weight is particularly beneficial in the construction of low horsepower (i;e., 1000 h.p.) turbine engines, since it permits operation with a single stage turbine at reasonable speeds.
  • the molecular weight should be at least 150.
  • the liquids employed in the present invention all have molecular weights of a least 165. and the preferred class of compounds have a molecular weight of at least 199.5.
  • Boiling Point A particularly severe problem in the design of Rankine cycle engines which are intended to be portable, is in providing efficient condensation.
  • the working fluids of the present invention boil at temperatures in the range of about to 245C, and for the preferred class of fluids from about 200 to 245C. The above ranges are suitable for use with small, air-cooled condensers. Further the compounds can be employed in efficient, subcritical Rankine cycles where the boiler pressure is relatively low so that relatively light weight engines can be constructed.
  • rotary boilers in which the working substance is maintained in the liquid state on an extended cylindrical surface by centrifugal force are particularly useful for small Rankine cycle engines.
  • Rotary condensers which have smaller diameter than the boiler and rotate therewith can be employed with advantage, and the centrifugal force employed to pump the liquid (operationally through a regenerator) from the condenser to the boiler.
  • the greater the liquid density of the working substance the smaller the diameter of the boiler (and consequently of the small engine) which is required at a given speed of rotation or conversely, for a given size of boiler and condenser the slower the rate of rotation required to achieve efficient operation.
  • the working fluids of the present invention have liquid densities of about 1.4 to 1.7 and are suited for use in rotary boilers and condensers.
  • the freezing point of fluids employed as working substances in Rankine cycle engines must be well below the operating temperature of the condenser.
  • the fluids should be liquid at ambient temperature, although, in contrast to water which expands on freezing, organic fluids contract on freezing and thus will not cause rupture of the condenser tubes.
  • a mixture of the desired products can be obtainedby heating pentachlorobenzene with potassium fluoride in a polar organic solvent such as sulfolane, methyl sulfone, dimethylformamide, l-methyl-Z-pyrrolidone and the like.
  • a polar organic solvent such as sulfolane, methyl sulfone, dimethylformamide, l-methyl-Z-pyrrolidone and the like.
  • Another method is to heat the pentachlorobenzene 25 .with potassium fluoride in the absence of a solvent.
  • Yet another method is to chlorinate partially fluorinated benzenes by refluxing with SO Cl
  • Compounds containing more than one hydrogen can also be'made by partial replacement of the chlorine in the corresponding chloro compound with fluorine by potassium fluoride H H H 01 H 01 H F H Cl 01 fgg g F 01 01 01 C1 conversion 01 c1
  • Pure l,2,4-trichloro-3,S-difluorobenzene may be prepared by the reported literature procedure, G. G. Yakobson, V. E. Platonov, A. K. Petrov, V. S. Kryukova, N. A. Geishtein and N. N. Yorozhtsov, Jr., Zh. Obshch. Khim 36, 2l33 (1966); English translation:
  • EXAMPLE A Preparation of a mixture of isomers of C HCl F
  • a 2 liter round-bottom flask equipped with a reflux condenser and protected from atmospheric moisture with a tube of Drierito there were placed 300 gm. of pentachlorobenzene, 366 gm. of anhydrous potassium fluoride and 450, ml. of sulfolane (tetramethylene sulfone).
  • the mixture was heated for 4 hours under reflux.
  • the initial pot temperature of 255 C. slowly dropped to 233C. during the heating period.
  • the reflux condenser was then replaced with a short still heat and the crude product was removed by distillation at 200-260C.
  • the column was packed with diatomaceous earth [Chromasorb W(NAW)] of 45-60 mesh with 25 percent octylphenoxy polyethylene glycol (Triton X 305
  • the temperature of the column was 150C. and a helium flow of 300 mL/minute was employed.
  • the sample was injected in an amount of 0.5 mL/pass.
  • the first peak with a retention time of 42.2 minutes, consisted of essentially pure 1,2,5-trichloro3,4-difluorobenzene.
  • a second peak with a retention time of 54.6 minutes consisted of 75 percent l,2,4-trichloro-3,S-difluorobenzene, percent l,3,5- tn'chloro-2,4-difluorobenzene and 10 percent of 1,2,3- trichlori4,S-difluorobenzene.
  • a third peak with a retention time of 59.7 minutes consisted of essentially pure 2,3 ,4-trichloro-l ,S-difluorobenzene.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Engine Equipment That Uses Special Cycles (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)
US00172513A 1971-08-17 1971-08-17 Method of generating power Expired - Lifetime US3774393A (en)

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US17251371A 1971-08-17 1971-08-17

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US (1) US3774393A (it)
JP (1) JPS5629088B2 (it)
CA (1) CA969975A (it)
DE (1) DE2240503C3 (it)
FR (1) FR2150123A5 (it)
GB (1) GB1401063A (it)
IT (1) IT964044B (it)
NL (1) NL7211257A (it)
SE (1) SE381314B (it)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3944494A (en) * 1973-05-30 1976-03-16 E. I. Du Pont De Nemours And Company Stabilization of trichlorodifluoro benzenes
US20120006024A1 (en) * 2010-07-09 2012-01-12 Energent Corporation Multi-component two-phase power cycle

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES8605328A1 (es) * 1983-06-13 1986-04-01 Mendoza Rosado Serafin Un procedimiento de generacion de energia mecanica trabajando con una mezcla de fluidos de distintos puntos de ebullicion.
CN112630257B (zh) * 2020-12-28 2024-03-22 宁波铭瑞中兴电子科技有限公司 一种玻璃水水箱监控方法、系统、智能终端以及存储介质

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3040528A (en) * 1959-03-22 1962-06-26 Tabor Harry Zvi Vapor turbines
US3234734A (en) * 1962-06-25 1966-02-15 Monsanto Co Power generation
US3366699A (en) * 1965-01-04 1968-01-30 Imp Smelting Corp Ltd Preparation of highly fluorinated aromatic compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3040528A (en) * 1959-03-22 1962-06-26 Tabor Harry Zvi Vapor turbines
US3234734A (en) * 1962-06-25 1966-02-15 Monsanto Co Power generation
US3366699A (en) * 1965-01-04 1968-01-30 Imp Smelting Corp Ltd Preparation of highly fluorinated aromatic compounds

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3944494A (en) * 1973-05-30 1976-03-16 E. I. Du Pont De Nemours And Company Stabilization of trichlorodifluoro benzenes
US20120006024A1 (en) * 2010-07-09 2012-01-12 Energent Corporation Multi-component two-phase power cycle

Also Published As

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DE2240503C3 (de) 1981-10-22
DE2240503A1 (de) 1973-02-22
FR2150123A5 (it) 1973-03-30
CA969975A (en) 1975-06-24
JPS5629088B2 (it) 1981-07-06
SE381314B (sv) 1975-12-01
IT964044B (it) 1974-01-21
GB1401063A (en) 1975-07-16
DE2240503B2 (de) 1981-03-12
NL7211257A (it) 1973-02-20
JPS4829688A (it) 1973-04-19

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