US3342545A - Method of removing propane and other hydrocarbons from gases - Google Patents

Method of removing propane and other hydrocarbons from gases Download PDF

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Publication number
US3342545A
US3342545A US505096A US50509665A US3342545A US 3342545 A US3342545 A US 3342545A US 505096 A US505096 A US 505096A US 50509665 A US50509665 A US 50509665A US 3342545 A US3342545 A US 3342545A
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air
ozone
hydrocarbons
catalyst
propane
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US505096A
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English (en)
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Jaeger Karl
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Linde GmbH
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Linde GmbH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/08—Separating gaseous impurities from gases or gaseous mixtures or from liquefied gases or liquefied gaseous mixtures
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/40—Air or oxygen enriched air, i.e. generally less than 30mol% of O2

Definitions

  • FIGURE 4 a 50 M0 N0 20H 250 lm K Temperature 1 Z" of Air OXIDATIVE DECOMPOSITION OF 60 IO PPM PROPANE IN AIR UNDER VARYING CONDITIONS Curve 1 Manganese dioxide fig without ozone Curve II Ozone without manganese dioxide Ozone and manganese dioxide KARL U'MEGER ATTORNEY United States Patent Ofifice 3,342,545 Patented Sept. 19, 1967 3,342,545 METHOD OF REMOVING PRCWANE AND OTHER HYDROCARBQNS FROM GASES Karl Jaeger, Kunststoff, Germany, assignor to Linde A.G., Wieshaden, Germany Filed Oct. 13, 1965, Ser. No.
  • the present invention relates in general to the removal of organic molecules from a gas, more particularly, to a process for removing hydrocarbons from air prior to the separation of the air into its major components by a low temperature rectification process.
  • a still further object is to remove organic molecules from contaminated air in general, for example, from engine exhaust gases.
  • a system is provided based on the discovery that contaminated air can be purified at relatively moderate temperatures, by destroying the organic molecules therein by treatment with ozone in the presence of a catalyst.
  • one embodiment of the process of the present invention essentially comprises initially compressing the air which is to be separated to the pressure necessary for introducing the air into the rectification installation.
  • the compressed air is then passed into a chamber containing a catalyst and which is connected with a source of ozone.
  • This ozone can be produced in a manner known per se from pure oxygen and then blown into the stream of compressed air.
  • the ozone can also be produced from the oxygen contained in the compressed air.
  • the quantity of ozone is at least 1.5 times, preferably about five times, the stoichiometric quantity necessary for effecting the reaction.
  • reaction equation is represented by the following:
  • manganese dioxide is preferred because of its low cost and good efficiency even at relatively low temperatures.
  • catalyst cost is not so important for a particular application, use can also be made of noble metal catalysts such as, for example, palladium or platinum in their conventional catalytic forms.
  • catalysts functioning in a substantially equivalent manner can also be employed.
  • activated charcoal is most disadvantageous in this respect. Activated charcoal is known to dissipate ozone very quickly, so if organic molecules are passed over activated charcoal together with ozone, the latter is dissipated in so short a time that an appreciable oxidation of organic molecules cannot take place.
  • This invention is broadly applicable for the oxidation of all types of organic molecules, particularly those having up to about 10 carbon atoms to yield reaction products of CO and H 0, with NO, N0 and S0 also being possible-depending on the constitution of the organic molecule.
  • the invention is particularly useful for the oxidation of saturated hydrocarbons having 1-l0 carbon atoms, which are ordinarily more diflicult to oxidize, especially propane, at relatively moderate temperatures.
  • the process of this invention can be conducted by treating the contaminated air with the catalyst and ozone at preferably 25280 C.
  • the upper limit is more preferably about 200 C.
  • the upper limit is advantageously about 150 C. for the manganese dioxide catalyst, and about C. for the noble metal catalysts. It is important to note at this point that it is only by treating the impurities with ozone in the presence of a catalyst that a suflicient percentage of the impurities can be destroyed at such relatively low maximum temperatures.
  • minimum reaction temperatures for the removal of hydrocarbons from air about 25 C. is preferred for noble metal catalysts, whereas for manganese dioxide, a minimum temperature of about 30, preferably at least 70 and more preferably at least 80 C., and most preferably a reaction temperature of about 90l30 C. can be used.
  • this invention is useful for destroying organic molecules in varying concentrations in all types of gases ranging from low concentrations in ordinary air to high concentrations in exhaust gases. As a rule of thumb, the contaminants will not exceed by volume of the gas.
  • this invention is of particular value when the concentration of each hydrocarbon impurity does not exceed ppm, the usual concentration being about 2 ppm.
  • the reaction between the impurity and ozone in the presence ofa catalyst takes place very quickly, the desired contact time being only on the order of seconds.
  • the process can be repeated several times. This can be done by adding fresh ozone to the hot stream of air after the air has 7 passed the catalyst. It is particularly eifective to mix the air containing hydrocarbons and the ozone in the presence of the catalyst or within the catalytic material itself. In other words, it is preferred that a substantial percentage, advantageously at least 40%, more beneficially at least 60%, and desirably 100% of the decomposition reaction takes place in the presence of the catalyst.
  • the residual ozone (about 0.1 to 10% of the starting concentration) is dissipated by passing the air over a suitable material such as a bed of iron ore, activated charcoal, or platinum black.
  • a suitable material such as a bed of iron ore, activated charcoal, or platinum black.
  • the temperature range for the residual ozone decomposition reaction is from room temperature up to the temperature at which the' oxidation of the organic molecules is performed.
  • a suitable substance for decomposing the ozone may be added to the washing agent.
  • the air can be heated to a higher temperature after it has been compressed.
  • the gas leaving the turbocompressor has a temperature of 90 to 100 C.
  • FIGURE 1 is a schematic view of the apparatus of the present invention showing the air separation installation and a single oxidation stage;
  • FIGURE 2 is a schematic view similar to that of FIG- URE 1 but showing three oxidation stages combined in a single unit;
  • FIGURE 3 is a schematic view of a modification of the present invention wherein the air is further heated after being compressed.
  • FIGURE 4 is a graph which illustrates the synergistic effect achieved when oxidizing propane with ozone in the presence of :manganese dioxide.
  • FIGURE 1 the air which is to be separated by the low temperature rectification process is entered through a conduit 1 and compressed in a compressor 2 to the pressure necessary for the air separation installation which is connected in series there with.
  • the compressed air is then passed into ozone chamber 3 which is connected to a source of ozone through the conduit 9.
  • a contact chamber 4 having manganese dioxide therein as a catalyst is then connected in series to the chamber 3.
  • a bed of iron ore 5 is con- 4- nected to the contact chamber 4 and a recooler 6 connected to the bed 5.
  • a conduit 7 then connects the recooler 6 with a conventional low temperature rectification air separation installation 8.
  • the air is compressed in compressor 2 to a pressure of approximately 6 atmospheres and accordingly is heated to a temperature of about C.
  • This air contains, for example, 2 ppm. each of acetylene, propane, propylene, and butane.
  • the compressed air is then passed into the ozone chamber into which ozone is introduced through the conduit 9 to be mixed with the heated air.
  • the ozone is conventionally produced by passing a silent electrical discharge through pure oxygen or by the action of ultraviolet radiation.
  • For the aforementioned quantity of hydrocarbons in the air approximately 350 p.p.m. of ozone are introduced.
  • the quantity of ozone is about five times the stoichiometric quantity necessary for effecting the reaction.
  • the contact chamber 4 contains manganese dioxide (MnO- in a quantity corresponding to a space velocity (weight rate of flow per hour and volume of contact) of approximately 4000 Nm. /h./m. More than of the aforementioned hydrocarbons are burned at the end of the contact chamber 4.
  • MnO- manganese dioxide
  • the air is then passed over the bog iron ore bed 5 to remove the excess ozone therein.
  • the air is then passed through the recooler 6 and through the conduit 7 into the low temperature air separation installation 8.
  • This installation may be operated by means of reversible heatexchangers or regenerators in order to further cool the air to be separated and to remove carbon dioxide and water from the air. If desired, the air may also be washed for removing the impurities therefrom before entering the installation 8.
  • a sodium sulfite solution may be added to the washing agent to also effectively decompose any excess ozone contained in the air.
  • FIGURE 2 The apparatus illustrated in FIGURE 2 is essentially the same as that shown in FIGURE 1 except that the ozone chamber, the contact chamber and the iron ore bed are combined in a single unit indicated at 10.
  • the compressed air discharged from the compressor 2 is alternatingly passed through ozone chambers 13 and contact chambers 14 having catalytic material therein.
  • a bed of bog iron ore 15 is provided after the last contact chamber.
  • electrical discharge gaps are provided in the ozone chamber whereby the ozone is produced in the chambers from the oxygen contained in the air. It is, of course, possible to introduce ozone into the chambers 13 from an external source of ozone as described in the embodiment of FIGURE 1.
  • FIGURE 3 there is shown an apparatus according to the present invention wherein the air is heated to a higher temperature after the air has been compressed.
  • this apparatus provides two regenerators whose functions can be reversed so that the entire process is continuous although the regenerators alternatingly perform their functions.
  • the various components of the installation are interconnected by valves 11 and 12 with the valves 11 being shown in the open position for fiow of the air through one regenerator and the valves 12 being shown in the closed position.
  • the air is discharged from the compressor 2 into a regenerator 16 which has a bed of bog iron ore 15 or rusty iron at the one end thereof for dissipating excess ozone.
  • the air then flows through a reheater 18, an ozone chamber 13 and a catalyst contact chamber 4.
  • the heated air from which the hydrocarbons have been removed then flows through the regenerator 17 and is further cooled in the recooler 6.
  • the cooled air is then conducted through the conduit 7 to the low temperature air separation installation.
  • the present invention provides a process and apparatus for the elfective removal of hydrocarbons, particularly saturated hydrocarbons such as propane, from air.
  • a process of gas purification which comprises treating a contaminated gaseous stream with ozone in the presence of a catalyst selected from the group consisting essentially of manganese dioxide, said gaseous stream containing contaminants comprising propane, said propane being decomposed to essentially CO and H 0, said catalyst functioning to increase the rate of decomposition of said propane.
  • a process for removing propane from air by combustion prior to the separation of air by low temperature rectification comprising the steps of compressing air containing propane to the pressure at which the air is to enter a low temperature rectification installation to raise the temperature of the air, mixing ozone with the heated air, and burning the mixture of heated air and ozone at 30*15 0 C. in the presence of manganese dioxide catalyst.
  • a process as defined by claim 10, comprising the further step of treating the resultant air having burned hydrocarbons therein with a substance different from said catalyst and capable of dissipating any residual ozone.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Treating Waste Gases (AREA)
  • Processing Of Solid Wastes (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
US505096A 1960-10-14 1965-10-13 Method of removing propane and other hydrocarbons from gases Expired - Lifetime US3342545A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEG30704A DE1117617B (de) 1960-10-14 1960-10-14 Verfahren und Vorrichtung zum Entfernen von Kohlenwasserstoffen aus Luft vor deren Zerlegung durch Tieftemperaturrektifikation

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4213947A (en) * 1977-10-13 1980-07-22 Champion International Corporation Emission control system and method
FR2483781A1 (fr) * 1980-06-10 1981-12-11 Charbonnages De France Procede d'epuration d'effluents gazeux malodorants
US4343776A (en) * 1980-12-22 1982-08-10 Engelhard Corporation Ozone abatement catalyst having improved durability and low temperature performance
US4378048A (en) * 1981-05-08 1983-03-29 Gulf Research & Development Company Substoichiometric combustion of low heating value gases using different platinum catalysts
US20070059229A1 (en) * 2000-03-03 2007-03-15 Temple Stephen R Method and apparatus for use of reacted hydrogen peroxide compounds in industrial process waters
US20190168159A1 (en) * 2017-12-04 2019-06-06 Ricardo Inc. Pollutant treatment process and apparatus
US10525410B2 (en) 2013-01-22 2020-01-07 Stephen R. Temple Methods and equipment for treatment of odorous gas steams
US10881756B2 (en) 2012-06-28 2021-01-05 Stephen R. Temple Methods and equipment for treatment of odorous gas streams from industrial plants
US10898852B2 (en) 2016-08-15 2021-01-26 Stephen R. Temple Processes for removing a nitrogen-based compound from a gas or liquid stream to produce a nitrogen-based product
US11389763B2 (en) 2019-08-28 2022-07-19 Stephen R. Temple Methods for absorbing a targeted compound from a gas stream for subsequent processing or use

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009020750B4 (de) * 2009-05-11 2014-01-09 Nt Ablufttechnik Gmbh Reinigung von Abluft

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1602404A (en) * 1924-09-23 1926-10-12 Joseph C W Frazer Oxidizing catalyst
US2700648A (en) * 1951-01-19 1955-01-25 Air Reduction Ozone stabilization
US2809881A (en) * 1954-12-20 1957-10-15 Welsbach Corp Processes for the catalytic purification of oxygen employing o3
US2965439A (en) * 1957-09-09 1960-12-20 Engelhard Ind Inc Removal of acetylene from air
US3151943A (en) * 1958-04-07 1964-10-06 Toyo Koatsu Ind Inc Method for purifying exit oxygen from the ozonolysis of fatty acids

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE693357C (de) * 1938-08-17 1940-07-06 Linde Eismasch Ag Verfahren zur Beseitigung des Ozons

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1602404A (en) * 1924-09-23 1926-10-12 Joseph C W Frazer Oxidizing catalyst
US2700648A (en) * 1951-01-19 1955-01-25 Air Reduction Ozone stabilization
US2809881A (en) * 1954-12-20 1957-10-15 Welsbach Corp Processes for the catalytic purification of oxygen employing o3
US2965439A (en) * 1957-09-09 1960-12-20 Engelhard Ind Inc Removal of acetylene from air
US3151943A (en) * 1958-04-07 1964-10-06 Toyo Koatsu Ind Inc Method for purifying exit oxygen from the ozonolysis of fatty acids

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4213947A (en) * 1977-10-13 1980-07-22 Champion International Corporation Emission control system and method
FR2483781A1 (fr) * 1980-06-10 1981-12-11 Charbonnages De France Procede d'epuration d'effluents gazeux malodorants
WO1981003623A1 (fr) * 1980-06-10 1981-12-24 Charbonnages De France Procede d'epuration d'effluents gazeux malodorants
US4343776A (en) * 1980-12-22 1982-08-10 Engelhard Corporation Ozone abatement catalyst having improved durability and low temperature performance
US4378048A (en) * 1981-05-08 1983-03-29 Gulf Research & Development Company Substoichiometric combustion of low heating value gases using different platinum catalysts
US7550123B2 (en) * 2000-03-03 2009-06-23 Steen Research, Llc Method and apparatus for use of reacted hydrogen peroxide compounds in industrial process waters
US20070059229A1 (en) * 2000-03-03 2007-03-15 Temple Stephen R Method and apparatus for use of reacted hydrogen peroxide compounds in industrial process waters
US10881756B2 (en) 2012-06-28 2021-01-05 Stephen R. Temple Methods and equipment for treatment of odorous gas streams from industrial plants
US10525410B2 (en) 2013-01-22 2020-01-07 Stephen R. Temple Methods and equipment for treatment of odorous gas steams
US10898852B2 (en) 2016-08-15 2021-01-26 Stephen R. Temple Processes for removing a nitrogen-based compound from a gas or liquid stream to produce a nitrogen-based product
US20190168159A1 (en) * 2017-12-04 2019-06-06 Ricardo Inc. Pollutant treatment process and apparatus
US10780395B2 (en) * 2017-12-04 2020-09-22 Ricardo Inc. Pollutant treatment process and apparatus
US11305231B2 (en) 2017-12-04 2022-04-19 Ricardo Uk Limited Pollutant treatment process and apparatus
US11389763B2 (en) 2019-08-28 2022-07-19 Stephen R. Temple Methods for absorbing a targeted compound from a gas stream for subsequent processing or use

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Publication number Publication date
FR1303265A (fr) 1962-09-07
DE1117617B (de) 1961-11-23

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