Mode of measuring of a common concentration of carbon and hydrocarbon oxides in oxygen with the aid of spectrometry of mobility of ions

IPC classes for russian patent Mode of measuring of a common concentration of carbon and hydrocarbon oxides in oxygen with the aid of spectrometry of mobility of ions (RU 2273847):

H01J49 - Particle spectrometers or separator tubes (for measuring gas pressure H01J0041100000)

G01N27/64 - using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber

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FIELD: the invention refers to the field of quantitative analysis of contents of admixtures in oxygen- oxides of carbon and hydrocarbon.

SUBSTANCE: the mode includes the following operations: transformation of carbon and hydrocarbon oxide present in the flow of oxygen into dioxide; measuring of the concentration of carbon dioxide in oxygen after transformation; determination according to the results of measuring in accordance with the previous operation of the common initial concentration of carbon and hydrocarbon oxide.

EFFECT: increases accuracy.

6 cl, 1 dwg

This invention relates to a method of measuring the total concentration of carbon monoxide and hydrocarbons in oxygen using mobility spectrometry ion.

Oxygen is widely used as a reactive gas in the manufacture of integrated circuits in order to create the oxide layers, which mainly act as electrical insulation between the various active parts of the circuit. As is known, in the manufacture of such devices purity of all materials used is of particular importance; in fact, impurities that may be present in the reagents or reaction medium, can get into a solid device, thus, changing their electrical characteristics and increasing waste production. Specifications purity gases used in the production processes can vary depending on the manufacturer and specific process that uses gas. Typically, the gas is considered to be acceptable for production purposes, if the content of impurities does not exceed 10 ppm (parts per million, namely molecule impurities on 10⁹gas molecules); preferably, the content of impurities should be less than 1 h/million Thus, the ability to accurately and reproducibly measure very low concentrations of impurities in gases becomes very important.

A technique that can be used is camping for this purpose, is the ion mobility spectrometry, known in the art by the acronym PIES; the same abbreviation used to denote a device which implements this technique, meaning in this case "spectrometer to determine the mobility of ions". Interest in this technique is due to its extremely high sensitivity, and limited the size and cost of the device; in suitable conditions, it is possible to define types, in the gas or vapor phase, in the gas environment in quantities of the order of picograms (PG, 10^-12g) or in concentrations as low as parts per trillion (h/tln, equivalent to one molecule of the analyte on the 10¹²gas molecules). SPI-devices and methods of analysis with which they are described, for example, in U.S. patents 5457316 and 5955886, assigned by an American firm PCP Inc.

Physico-chemical fundamentals of methods very difficult as the interpretation of the results of PIES. To explain these principles and results, you can refer to the book "Ion Mobility Spectrometry", the authors G.A. Eiceman and Z. Karpas, published in 1994 CRC Press.

Briefly, LIST the device mainly consists of the reaction zone, the separation zone and collector of charged particles.

Inside the reaction zone of the ionization of the samples, including the analyzed gases or vapours in the gas-carrier, usually with what amewu β radiation emitted by the⁶³Ni. Ionization occurs mainly in gas-carrier with the formation of the so-called "ion-reagents", a charge which is then distributed to those present species depending on their affinity to the electron or proton or from their ionization potentials.

The reaction zone is separated from the separation zone bars that when maintaining a suitable potential prevents the penetration of ions obtained in the reaction zone, a separation zone. Analytical "zero point" is set at the time when the lattice potential is cancelled, allowing the ions in the separation area.

The separation zone comprises a series of electrodes that generate such an electric field in which the ions are directed from the lattice to the manifold. In this zone, which is supported by atmospheric pressure, a gas flow having a direction opposite to the movement of ions. Countercurrent gas (called in the art "drifting gas") is a highly pure gas, which can either comply with gas, which is determined by the presence of impurities or other gas. The speed of the ions depends on the electric field and cross section of the same ions in a gaseous medium, so that different ions require different time crossing the separation zone and getting into the collector particles. The time elapsed since the "zero moment" before getting into the collector particles, called "time". The collector is connected to processing the signals to the system that turns the current values obtained as a function of time, in the final graph, in which the peaks corresponding to different ions, shown as a function of "time of flight"; defining the time and knowing the conditions of the test, you can detect the presence of substances that are the subject of analysis, while based on the peak areas can be calculated by applying the appropriate algorithms for computing the concentration of the respective molecules.

Most often SLEEP-analysis is performed for molecules with a positive charge. On the contrary, the analysis of oxygen in the reaction zone also produces negatively charged molecules. In such conditions (negative mode) SPI-analysis may be sensitive only to the species, the electron affinity which is higher than that of oxygen, and which, therefore, can receive a charge from the gas; this usually occurs for carbon dioxide, CO₂. Therefore, the analysis of impurities in the oxygen limited. Among the molecules whose concentration of oxygen may be of interest, can be named, for example, carbon monoxide, CO, and hydrocarbons, in particular methane, CH₄.

The object of this and the finding is a way of measuring the total concentration of CO and hydrocarbons in oxygen using mobility spectrometry ion.

According to this invention the specified object is a method including the following operations:

a) the conversion of carbon monoxide and hydrocarbons present in the stream of oxygen, carbon dioxide;

b) measuring the concentration of carbon dioxide in oxygen after the conversion in accordance with paragraph (a); and

(C) determining the measurement results in accordance with paragraph (b) total initial concentration of carbon monoxide and hydrocarbons.

According to the second variant of the method according to the invention is used for oxygen, already the source containing carbon dioxide as an impurity (this condition must be set using the preliminary assessment carried out for oxygen, not praterinsel conversion of CO and hydrocarbons). In this case, when conducting IPN-analysis get the concentration value corresponding to the amount of the original present CO₂and CO₂obtained by conversion of CO and hydrocarbons. In this case, apply a variant of the method according to the invention, comprising the following operations:

a) the conversion of carbon monoxide and hydrocarbons present in the stream of oxygen, carbon dioxide;

b) measuring the concentration of carbon dioxide in oxygen after the conversion in accordance with paragraph (a);

b') the concentration measurement dioxide is glared in the flow of oxygen, endured the operation of the conversion in accordance with paragraph (a);

(C) determining on the comparison of the concentrations of carbon dioxide in accordance with paragraphs (b) and (b') the initial concentration of carbon monoxide and hydrocarbons.

The invention is described below using the single drawing, which schematically shows a system for the practical implementation of the method according to the invention.

According to the method in accordance with the invention, CO and hydrocarbons, which are molecules that are not defined in the oxygen when using a standard SPI-analysis quantitatively converted into carbon dioxide, CO₂that unlike the previous is determined by the analysis of the form of molecules.

The method according to the invention can be implemented in practice with the use of gas treatment systems, shown schematically in the drawing. The system 10 consists of the inlet 11, which moves the analyzed gas; along the line 11 installed system 12, which converts CO and hydrocarbons in the CO₂system 10 also includes two trautwig distributor, V₁and V₂above and below the system 12, which separates the system 12 from the gas stream, directing the latter along the secondary line 11'. Below system 12 or line 11' is SLEEP analyzer 13; he SOS is the RTO from the reaction zone 14, separated from the separation zone 15 bars 16; in the end zone 15, opposite the zone 14 is the collector particles 17 (details such as input and output openings for "drifting gas, not shown); the collector is connected electrically to the device 18, which has an electronic section, which converts the electrical impulses coming from the manifold 17, in numerical data and calculation section (for example, a microprocessor) for processing the received data; the device 18 may be physically integrated with the device SLEEP; finally, the device 18 outputs the result of the analysis range 19, in which the recorded peaks, corresponding to different chemical species defined as a function of the time of their passing in the device 13.

In the first variant of the method according to the invention the flow of oxygen fed to the system 10, is sent to the system 12 for turning, switching valves V₁and V₂relevant provisions, carry out the conversion of CO and hydrocarbons, and the treated gas is sent to SLEEP analyzer 13 for analysis.

In the second variant of the method according to the invention the operation b) are the same as in the first embodiment, and the operation b') hold, directing the flow of oxygen fed to the system 10, the analyzer 13 via line 11', separating it from the system 12 switching races is realitly V ₁and V₂at the corresponding position.

12 system for the conversion of CO and hydrocarbons CO₂contains at least an oxidation catalyst; continuous recovery of such compounds is favorable that CO and hydrocarbons are present in trace amounts in the atmosphere composed almost completely of oxygen. The catalysts used for this transformation, represents, for example, oxides of some noble metals such as ruthenium, rhodium, palladium and platinum; preferred is palladium oxide, PdO. The optimal operating temperature PdO is from about 200 to about 350°C. the palladium Oxide or even prepared systems for the conversion of CO and hydrocarbons containing this compound is commercially available and sold, for example, by the applicant, the German firm Degussa-Hüls AG and American company Engelhard Co.

1. The method of measuring the concentration of carbon monoxide and hydrocarbons in oxygen using spectrometry mobility of ions, comprising the following operations:

a) the conversion of carbon monoxide and hydrocarbons present in the stream of oxygen, carbon dioxide;

b) measuring the concentration of carbon dioxide in oxygen after the conversion in accordance with paragraph (a), and

c) determining the measurement results in accordance with paragraph (b) General outcome of the Oh concentration of carbon monoxide and hydrocarbons.

2. The method according to claim 1 which further includes an operation b'), which enables measurement of the concentration of carbon dioxide in the stream of oxygen, endured the operation of the conversion in accordance with paragraph (a); and operation) is conducted by comparing the concentrations of carbon dioxide, measured in accordance with the operations (b) and (b').

3. The method according to claim 1, wherein operation (a) is carried out with the use of the system (10) for processing gas including inlet line (11) for the test gas, the system (12) for converting carbon monoxide and hydrocarbons, SLEEP analyzer (13) and defining and processing data unit (18), and the entire gas flow filed in the specified system (10) processing, refer to the system (12) for converting carbon monoxide and hydrocarbons switch in position two trautwig distributors (V₁; V₂located above and below the specified system (12) transformation.

4. The method according to claim 2, in which the operation (b) is carried out with the use of the system (10) for processing gas including inlet line (11) for the test gas, the system (12) for converting carbon monoxide and hydrocarbons, SLEEP analyzer (13) and defining and processing data unit (18), and the entire gas flow filed in the specified system (10) processing, is sent to the analyzer through the secondary line (11), avoiding passing is specified via the system (12) the conversion of carbon monoxide and hydrocarbons, switch in position two trautwig distributors (V₁; V₂located above and below the specified system (12) transformation.

5. The method according to any of PP and 4, where the system (12) the conversion of carbon monoxide and hydrocarbons comprises at least one catalyst used for oxidation of hydrocarbons selected from the oxides of the noble metals.

6. The method according to claim 5, in which the specified catalyst is palladium oxide.

7. The method according to claim 6, in which the temperature of the palladium oxide during surgery b) support in the range of 200-350°C.