Molecular sieve trap for nitrogen compound detection

• US 4,301,114 A
• Filed: 06/30/1980
• Issued: 11/17/1981
• Est. Priority Date: 06/30/1980
• Status: Expired due to Term

• Current Assignee: Thermedics, Inc. (Thermo Fisher Scientific Incorporated)
• Original Assignee: Thermo Electron Corporation (Thermo Fisher Scientific Incorporated)
• Inventors: Rounbehler, David P., Reisch, John W.
• Primary Examiner(s): Serwin, Ronald
• Application Number:
  US06/164,476
• Time in Patent Office: 505 Days
• Field of Search: 23/230 PC, 422/52, 422/78, 422/80, 422/89, 55/68, 55/75
• US Class Current: 422/52
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: G01N 21/766 of gases
• CPC Class Codes: Y10T 436/170769 N-Nitroso containing [e.g., nitrosamine, etc.]
• CPC Class Codes: Y10T 436/179228 Both nitrogen oxide and dioxide

Abstract

A molecular sieve trap is disclosed for selective trapping of substances in a gas stream, the trap being particularly useful in systems for detecting nitrogen compounds such as N-nitrosamines or nitrogen oxides in a sample. The trap comprises a cartridge containing a packing of a granular adsorbent molecular sieve material with a carefully controlled pore size of about ten angstroms and a preference for adsorbing polar substances. The packing readily passes NO and NO₂ gases in a gas stream directed through the trap while trapping and retaining larger and/or more polar molecules such as those of double-bonded carbon compounds and sulfur compounds which could otherwise interfere with subsequent measurement of the NO or NO_x content of the gas stream. An N-nitroso compound detection system incorporating the molecular sieve trap is described wherein the molecular sieve trap is interposed between a pyrolyzer and a chemiluminescent NO detector to selectively trap substances in the reactor effluent. Also disclosed is a NO_x detection system having a molecular sieve trap in a sample inlet line of a NO_x detector.

Claims

1. Apparatus for selectively trapping substances in a gas stream comprising a cartridge having an inlet at one end for receiving a gas stream, an outlet at the end opposite said inlet end, and a shell defining a chamber between said inlet and said outlet, said chamber containing a packing of a granular molecular sieve material permeable to the flow therethrough of NO gas and adapted to trap and hold substances therein which might otherwise interfere with measurement of the NO gas which has passed through said packing.

2. Apparatus as in claim 1 wherein said molecular sieve material has a nominal pore diameter of about 10 angstroms.

3. Apparatus as in claim 1 or 2 wherein said molecular sieve material is a crystalline sodium alumino-silicate material.

4. Apparatus as in claim 1 wherein said chamber contains, in addition to said packing of granular molecular sieve material, a second packing of a drying agent between said inlet and said packing of granular molecular sieve material, said drying agent being permeable to the flow therethrough of NO gas and adapted to remove water from the gas stream.

5. Apparatus as in claim 4 wherein said drying agent is a granular material selected from the group consisting of sodium sulfate, calcium sulfate, phosphorous pentachloride, aluminum silicates, and combinations thereof.

6. Apparatus as in claim 1 further including porous retainer means adjacent to the inlet and outlet of said cartridge for holding said packing in said chamber.

7. Apparatus as in claim 1 and 2 wherein said particles are of 60 to 80 mesh size.

8. Apparatus for measuring in a sample the amount of predetermined nitrogen compounds comprising:

a chromatograph for receiving said sample and producing an effluent including, at separate intervals of time, a first portion containing said predetermined nitrogen compounds and a second portion without said compounds;

a reactor for selectively liberating NO gas from the nitrogen compounds of said first portion, thereby producing a reactor effluent containing NO gas;

a NO detector for measuring the amount of NO gas liberated in said reactor; and

a trap between said reactor and said detector for selectively trapping substances from said reactor effluent, said trap including a packing of a granular molecular sieve material permeable to the flow therethrough of NO gas and effective to trap and hold substances whose presence in said detector might interfere with measurement of the NO gas liberated by said reactor.

9. Apparatus as in claim 8 wherein said predetermined nitrogen compounds are N-nitroso compounds having the general formula ##STR2## wherein R₁ and R₂ are the same or different organic radicals, including those radicals which together with the non-nitroso N of the depicted N--NO bond constitute a nitrogen heterocyclic radical;

and wherein said reactor is operable to selectively liberate NO gas from said N-nitroso compounds by breaking the N--NO bonds of said N-nitroso compounds.

10. Apparatus as in claim 9 wherein said reactor comprises a pyrolyzer for heating the N-nitroso compounds with an amount of thermal energy effective to break the N--NO bonds thereof.

11. Apparatus as in claim 8 wherein said molecular sieve material comprises particles having pores with a nominal diameter of about 10 angstroms.

12. Apparatus as in claim 11 wherein said molecular sieve material is a crystalline sodium alumino-silicate material.

13. Apparatus as in claim 8 wherein said particles are of 60 to 80 mesh size.

14. Apparatus as in claim 8 wherein said chromatograph comprises a gas chromatograph including a column and means for driving a mixture of said sample and a carrier gas through said column.

15. Apparatus as in claim 8 wherein said trap comprises a cartridge having an inlet for receiving said reactor effluent, an outlet, and a cylindrical shell defining a chamber between said inlet and said outlet, said chamber containing said packing of molecular sieve material and also containing, between said inlet and said packing of molecular sieve material, a second packing of a drying agent permeable to the flow therethrough of NO gas and adapted to remove water from said reactor effluent.

16. Apparatus for measuring in a gaseous sample the concentration of at least one oxide of nitrogen comprising:

a reaction chamber for permitting a chemiluminescent reaction therein of a selected constituent of the sample with a reagent;

means for supplying said reagent and said gaseous sample to the reaction chamber;

means for detecting the light produced in said chamber during a chemiluminescent reaction; and

a trap for selectively removing substances from said gaseous sample prior to entry of said sample into said reaction chamber, said trap comprising a packing of a granular molecular sieve material permeable to the flow therethrough of NO and NO₂ gases and effective to trap and hold substances whose presence in said reaction chamber might interefere with measurement of NO or NO₂ gas in said sample.

17. Apparatus as in claim 16 wherein said molecular sieve material comprises particles having pores with a nominal diameter of about 10 angstroms.

18. Apparatus as in claim 16 wherein said reagent is ozone and said selected constituent of the sample is NO gas.

19. Apparatus as in claim 16 wherein said molecular sieve material comprises particles of a crystalline sodium alumino-silicate material of 60 to 80 mesh size.

20. Apparatus as in claim 19 wherein said trap further comprises a packing of a drying agent permeable to the flow therethrough of NO and NO₂ gases and operable to remove water from said sample prior to passage of said sample through said packing of molecular sieve material.

21. Apparatus as in claim 16 further including an NO₂ converter between, and in fluid communication with, said trap and said reaction chamber for converting NO₂ gas in said sample to NO gas, thereby to permit measurement of the total concentration of NO gas and NO₂ gas of said gaseous sample.