US2901320A - Process for forming nitrogen oxides - Google Patents

Process for forming nitrogen oxides Download PDF

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US2901320A
US2901320A US529234A US52923455A US2901320A US 2901320 A US2901320 A US 2901320A US 529234 A US529234 A US 529234A US 52923455 A US52923455 A US 52923455A US 2901320 A US2901320 A US 2901320A
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detonation
nitrogen
charge
oxygen
nitrogen oxides
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US529234A
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John F Haller
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Olin Corp
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Olin Corp
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/24—Nitric oxide (NO)
    • C01B21/30—Preparation by oxidation of nitrogen

Definitions

  • a detonation or shock wave through a gaseous mixture comprising nitrogen and oxygen produces nitrogen oxides.
  • a make charge of a gaseousmixture comprising nitrogen and oxygen is introduced into a portion of a reaction space and a detonatable material is introduced into the remaining portion.
  • the detonatable material is detonated and the detonation Wave impinges on the make charge causing reaction between the nitrogen and oxygen and formation of nitrogen oxides.
  • the nitrogen oxides produced are suitable for use in making the corresponding acids.
  • the detonatable or explosive material can be any which is adaptable to detonation by spark or other suitable ignition means to produce a detonation or shock wave. It is advantageous to choose one which is compatible with the reactants and products of the reacting section.
  • the use of a mixture of hydrogen and oxygen in this invention is particularly advantageous as the water formed in the explosive reaction is utilized for the hydrolysis of the nitrogen oxides, while any excess is easily condensed from unreacted nitrogen and oxygen thus permitting their efficient recycling.
  • Other suitable explosive mixtures such as ethylene and oxygen or acetylene and oxygen can be used.
  • the reactants are used in stoichiometric amounts. Air can be used instead of oxygen. Explosive substances such as chlorine dioxide or hydrazoic acid can also be used.
  • the make charge consists of a gaseous mixture comprising nitrogen and oxygen.
  • the reaction chamber 1 is a nickel pipe, e.g. a pipe seven feet in length and one inch in diameter.
  • the reactor can be operated under elevated or reduced pressure. Elevated or reduced pressures are advantageous depending on Le Chateliers principle of volume change. Thus where the volume of the reactants is greater than that of the products, the use of elevated pressures is advantageous. Increased pressures also increase equipment capacity and permit the use of more intense detonation waves.
  • Approximately the upper three feet of the reactor tube are filled with, for example, hydrogen and oxygen gas in a ratio of about 2:1, while the remaining lower portion is filled with nitrogen and oxygen gas in a 1:1 ratio.
  • the lower' portion is filled through inlets 2 and 3.
  • the gases pass through gas mixer 4 and through the coiled copper tubing 6 which protects the rest of the apparatus from the effect of the detonation wave.
  • the sidearm of mixer 4 has a flexible connection to coil 6.
  • the filling of the upper portion of the tube is done through inlets 7 and 8 and is controlled by the electric hosecock 9.
  • Both tubes 7 and 8 pass through hosecock 9 and both tubes are closed ice simultaneously by the operation of the bar of the hosecock.
  • the purpose of the hosecock is to cause intermittent flow of the explosive gases and thus prevent their continuous burning.
  • the product is emitted from the exit tube 10, fitted with an electrically controlled stopcock 11.
  • the operation of the ignition by the spark plug 12, the electrical hosecock 9, and the stopcock 11 is automatically controlled by means of the electrical circuit 13.
  • the timing is controlled by a series of relays, the central relay consisting essentially of a small synchronous motor whose rotating axle makes and breaks the circuit.
  • the reactor suitable for use in the process is of a size suitable to produce a detonation wave.
  • Laffite et al., Compt. rend. 183, 283 (1926) have shown that an oxygen-hydrogen explosion must travel for at least 70 cm. in a tube of at least one inch in diameter before a shock wave is produced.
  • the size of the reactor can vary over a considerable range.
  • the reaction is carried out in a confined reaction space as, for example, the reactor of the drawing which is a closed tube.
  • confined I mean to include, however, reactors which are open at the end opposite the explosion end.
  • the explosion end of the tube must be closed but the opposite end of the reactor can be open or closed.
  • the tube can open into a larger volume where the gaseous products are collected.
  • the reaction space is elongated.
  • the reaction portion i.e. the nitrogen-oxygen reaction portion
  • the reaction portion of the tube of the drawing need not be cylindrical, but can taper to an appropriately smaller diameter, or it can widen, in which case the whole tube assumes a funnel shape.
  • the former variation is valuable when carrying out an endothermic reaction, which would consume the energy of the shock wave at a greater rate than usual.
  • the tapering permits the wave to pass through the entire length of the reactants with undiminished intensity.
  • an exothermic reaction would increase the intensity of the wave.
  • the reaction section of the tube can funnel out, thus nullifying any increase in intensity and permitting the use of a larger volume of reactants.
  • the length of this section should be as long as possible to obtain good yields, but is limited by the distance through which the shock wave will travel substantially undiminished in the specific reactants used.
  • the reactor is preferably positioned vertically with that end at the top which contains the less dense gas mixture but the reaction portion can be extended horizontally. This tends to prevent mixing of the reacting and exploding components.
  • the detonation charge and make charge can be separated in the reactor by a separating medium such as, for example, a rupturable diaphragm, e.g. a cellophane diaphragm, or a narrow zone of inert gas.
  • a separating medium such as, for example, a rupturable diaphragm, e.g. a cellophane diaphragm, or a narrow zone of inert gas.
  • the separation provides more certain ignition of the detonation charge as it insures its uncontamination and thus provides closer control over the process.
  • the separation medium is particularly useful when the detonation charge and make charge are not compatible.
  • compatible gas mixtures thus avoiding the use of a diaphragm between the detonation charge and the make charge, such a diaphragm can be used pro vided it is of exceedingly low inertia so as not to decrease the shock intensity.
  • An important advantage of a diaphragm is

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Description

Aug. 25, 1959 J. F. HALLER PROCESS FOR FORMING NITROGEN OXIDES Filed Aug. 18, 1955 INVENTOR.
John F.Hol1er BY WWI/9&
ATTORNEYS United States Patent PROCESS FOR FORMING NITROGEN OXIDES John Haller, Mount Carmel, Conn., assignor to Olin Mathieson Chemical Corporation, a corporation of Virginia Application August 18, 1955, Serial No. 529,234
9 Claims. (Cl. 23163) My invention relates to the novel application of detonation or shock waves to bring about chemical reactions.
I have found that passing a detonation or shock wave through a gaseous mixture comprising nitrogen and oxygen produces nitrogen oxides. According to my invention, a make charge of a gaseousmixture comprising nitrogen and oxygen is introduced into a portion of a reaction space and a detonatable material is introduced into the remaining portion. The detonatable material is detonated and the detonation Wave impinges on the make charge causing reaction between the nitrogen and oxygen and formation of nitrogen oxides. The nitrogen oxides produced are suitable for use in making the corresponding acids.
The detonatable or explosive material can be any which is adaptable to detonation by spark or other suitable ignition means to produce a detonation or shock wave. It is advantageous to choose one which is compatible with the reactants and products of the reacting section. The use of a mixture of hydrogen and oxygen in this invention is particularly advantageous as the water formed in the explosive reaction is utilized for the hydrolysis of the nitrogen oxides, while any excess is easily condensed from unreacted nitrogen and oxygen thus permitting their efficient recycling. Other suitable explosive mixtures such as ethylene and oxygen or acetylene and oxygen can be used. The reactants are used in stoichiometric amounts. Air can be used instead of oxygen. Explosive substances such as chlorine dioxide or hydrazoic acid can also be used. The make charge consists of a gaseous mixture comprising nitrogen and oxygen.
My invention will be further illustrated by reference to the accompanying drawing which is a diagrammatic drawing of one suitable form of apparatus for conducting the process of the invention.
The reaction chamber 1 is a nickel pipe, e.g. a pipe seven feet in length and one inch in diameter. The reactor can be operated under elevated or reduced pressure. Elevated or reduced pressures are advantageous depending on Le Chateliers principle of volume change. Thus where the volume of the reactants is greater than that of the products, the use of elevated pressures is advantageous. Increased pressures also increase equipment capacity and permit the use of more intense detonation waves. Approximately the upper three feet of the reactor tube are filled with, for example, hydrogen and oxygen gas in a ratio of about 2:1, while the remaining lower portion is filled with nitrogen and oxygen gas in a 1:1 ratio. The lower' portion is filled through inlets 2 and 3. The gases pass through gas mixer 4 and through the coiled copper tubing 6 which protects the rest of the apparatus from the effect of the detonation wave. The sidearm of mixer 4 has a flexible connection to coil 6. The filling of the upper portion of the tube is done through inlets 7 and 8 and is controlled by the electric hosecock 9. Both tubes 7 and 8 pass through hosecock 9 and both tubes are closed ice simultaneously by the operation of the bar of the hosecock. The purpose of the hosecock is to cause intermittent flow of the explosive gases and thus prevent their continuous burning. The product is emitted from the exit tube 10, fitted with an electrically controlled stopcock 11.
The operation of the ignition by the spark plug 12, the electrical hosecock 9, and the stopcock 11 is automatically controlled by means of the electrical circuit 13. The timing is controlled by a series of relays, the central relay consisting essentially of a small synchronous motor whose rotating axle makes and breaks the circuit.
The reactor suitable for use in the process is of a size suitable to produce a detonation wave. For example, Laffite et al., Compt. rend. 183, 283 (1926), have shown that an oxygen-hydrogen explosion must travel for at least 70 cm. in a tube of at least one inch in diameter before a shock wave is produced. The size of the reactor can vary over a considerable range. The reaction is carried out in a confined reaction space as, for example, the reactor of the drawing which is a closed tube. By the term confined I mean to include, however, reactors which are open at the end opposite the explosion end. The explosion end of the tube must be closed but the opposite end of the reactor can be open or closed. Advantageously, the tube can open into a larger volume where the gaseous products are collected. Preferably, the reaction space is elongated.
Certain modifications of the reactor can be advantageous for dilferent reactions. For example, the reaction portion, i.e. the nitrogen-oxygen reaction portion, of the tube of the drawing need not be cylindrical, but can taper to an appropriately smaller diameter, or it can widen, in which case the whole tube assumes a funnel shape. The former variation is valuable when carrying out an endothermic reaction, which would consume the energy of the shock wave at a greater rate than usual. The tapering permits the wave to pass through the entire length of the reactants with undiminished intensity. Conversely, an exothermic reaction would increase the intensity of the wave. In this case the reaction section of the tube can funnel out, thus nullifying any increase in intensity and permitting the use of a larger volume of reactants. The length of this section should be as long as possible to obtain good yields, but is limited by the distance through which the shock wave will travel substantially undiminished in the specific reactants used.
The reactor is preferably positioned vertically with that end at the top which contains the less dense gas mixture but the reaction portion can be extended horizontally. This tends to prevent mixing of the reacting and exploding components.
The detonation charge and make charge can be separated in the reactor by a separating medium such as, for example, a rupturable diaphragm, e.g. a cellophane diaphragm, or a narrow zone of inert gas. The separation provides more certain ignition of the detonation charge as it insures its uncontamination and thus provides closer control over the process. The separation medium is particularly useful when the detonation charge and make charge are not compatible. Although it is preferable to use compatible gas mixtures, thus avoiding the use of a diaphragm between the detonation charge and the make charge, such a diaphragm can be used pro vided it is of exceedingly low inertia so as not to decrease the shock intensity. An important advantage of a diaphragm is to prevent diffusion of the reaction gases into the detonation gases with consequent loss of wave intensity. A soap bubble film, for example, can be used as a diaphragm.
The mechanism of the process is not clearly understood; ut -the reaction adiabatic heating and cooling which is produced by the shock Wave.
is probably-"due to the rapid Myinvention willebe further illustratedb y the follow ing'ex-amples conducted with the apparatus of the drawing. v I z ;..E mp.
The gas flow and the electrical circuit was arranged so thattheigases filled the tube in 54 seconds. This re-- quired-310 cc. of-H and-155 cc.- of- O in the'upper section of the'tube, and 309cc. of leach O and N in theolowerpotrion of i the tube.--The= electrical hoseco'ck then stoppedthe flow of H and O'g'forsix-seonds and thekexplosio'n wasproduced.--- The gases formed -Were' led into 25 cc. of Water with a pH of 5.50. Afterex plosi'o'nstook place (over aperiodof "20 minutes)-" the pH.-of-1 the-'-water dropped to 3-;20.- This Was due to the formation of nitric acid in water.
Exzrntp le Since water was being continuously condensed on the inner wall of tube during its operation, a portion" of the nitrogen oxides was dissolved therein. This did' not have-s'uflicienttime to drain (as would be the casein an applied, eontinuous operation of-this apparatus) during the short-runs-of these experiments. -'To determine the amount of acid retainedin the tube, it wasflushed with" water; after a run of 3 detonations.- This'rinse: 'Water Wasad ded to the waterin which the effluent gases'were collected-.--A tot-a1 of-1340 cc. of 'water was" collected." j The original pH of the waterwas 5.15,. Thecombined;
sentially of nitrogen and oxygen, confining in anotheri portion of the reaction space a detonation charge of a material which will detonate "upon"ignition; igniting 'tli' detonation charge, impinging the resulting detonation wave against the make charge whereby the nitrogen and oxygen of the make charge are caused to react.
2. The process of claim 1 in which the material which will detonate on ignition is a mixture of oxygen and hydrogen. v
3. The process of claim 1 in which the reaction space is an elongated reaction space. we: w n
4;. The process:ofJ-claimr 1 in=whihc the reaction space is a confined elongated reaction space.
5. Theprocess of claim 1 in which the reaction space isaclosedtube. i A N 6. The process O'fitclairr'i ilin which a separating medium is interposed between the make charge and detonation charge.
7. The process of claim 1, the proportion of nitrogen and oxygen present in the make charge being such as to cause combination of nitrogen and oxygen to form said nitrogen oxides.
8. The process ofclaim 1 wherein nitrogen and oxyi gen present in the make charge are in about stoichiometric amounts.
The process of claim-,1 in which the material- I which will detonate on ignition is a gaseous material.
References Cited file ot-this patent UNITED STATES PATENTS 961,350 7 V 1,639,584 Bone Aug. 16, 1921? 2,690,960 Kistiakowsky et al. .OCt.fT5, 1954" 2,832,665 Hertzberg et a1. Apr. 29, 1958 I FOREIGN PATENTS :ffi. 26,728 Great Britain AD. 1905 OTHER REFERENCES" Lessing: Scientific American, No. 5, vol. 1 88, pages v 29 to 35, May 1953.
' Hausser June1 4,1 91(

Claims (1)

1. A PROCESS FOR THE PRODUCTION OF NITROGEN OXIDES WHICH COMPRISES CONFINING IN ONE PORTION OF A REACTION SPACE A MAKE CHARGE OF A GASEOUS MIXTURE CONSISTING ESSENTIALLY OF NITROGEN AND OXYGEEN, CONFINING IN ANOTHER PORTION OF TTHE REACTION SPACE A DETONATION CHARGE OF A MATERIAL WHICH WILL DETONATE UPON IGNITION, IGNITING THE DETONATION CHARGE, IMPINGING THE RESULTING DETONATION WAVE AGAINST THE MAKE CHARGE WHEREBY THE NITROGEN AND OXYGEEN OF THE MAKE CHARGE ARE CAUSED TO REACT.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3268432A (en) * 1960-10-31 1966-08-23 Richfield Oil Corp Treatment of hydrocarbons with shock waves
US4367130A (en) * 1970-11-30 1983-01-04 Lemelson Jerome H Chemical reaction

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB190526728A (en) * 1905-12-21 1906-05-24 Rudolf Pawlikowski An Improved Process of and Apparatus for Producing Endothermic Chemical Compounds.
US961350A (en) * 1906-05-31 1910-06-14 Friedrich Haeusser Process of making nitric acid.
US1639584A (en) * 1923-02-28 1927-08-16 Bone William Arthur Production of activated nitrogen and of oxides of nitrogen therefrom
US2690960A (en) * 1951-05-09 1954-10-05 Cabot Godfrey L Inc Detonation process of making carbon black
US2832665A (en) * 1954-12-23 1958-04-29 Cornell Aeronautical Labor Inc Method and apparatus for carrying out gas phase reactions which require a high temperature to promote the reaction and rapid cooling to preserve the reaction product

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB190526728A (en) * 1905-12-21 1906-05-24 Rudolf Pawlikowski An Improved Process of and Apparatus for Producing Endothermic Chemical Compounds.
US961350A (en) * 1906-05-31 1910-06-14 Friedrich Haeusser Process of making nitric acid.
US1639584A (en) * 1923-02-28 1927-08-16 Bone William Arthur Production of activated nitrogen and of oxides of nitrogen therefrom
US2690960A (en) * 1951-05-09 1954-10-05 Cabot Godfrey L Inc Detonation process of making carbon black
US2832665A (en) * 1954-12-23 1958-04-29 Cornell Aeronautical Labor Inc Method and apparatus for carrying out gas phase reactions which require a high temperature to promote the reaction and rapid cooling to preserve the reaction product

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3268432A (en) * 1960-10-31 1966-08-23 Richfield Oil Corp Treatment of hydrocarbons with shock waves
US4367130A (en) * 1970-11-30 1983-01-04 Lemelson Jerome H Chemical reaction

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