Process Mass Spectrometryspbinno.ibdk.ru/s/upload/files/6d5fc71cc0c7d22a619b5… · · 2013-04-12- Mud Gas Logging; - Isotope Analysis; ... - The rack of gas probe conditioning

Process Mass Spectrometry

МЕТТЕК — the research-and-production company with twenty years'

experience of innovations in process mass spectrometry and

introduction the EMG industrial gas analysis system for continuous

(on-line) and discrete measurements.

The company is the leader in Russia on introduction the gas analysis

systems and complexes on the base of time-of-flight mass

spectrometers for various analytical application in oil and gas, nuclear

and metallurgical industries, geology, high purity and rare gases

production, emissions monitoring, scientific researches.

Process mass spectrometry, being the most powerful analytical method, it is intended

for continuous operation in hazard working conditions for control, operating and

optimization of technological process, maintenance of industrial and ecological safety,

quality assurance of raw materials and let out production.

METTEK actively introduces the innovations and know-how in the field of the mass

spectrometry, high-speed digital signal processing, the vacuum technologies, protected

by own patents, and offers to Customers a wide spectrum of analytical applications on

the basis of process mass spectrometers EMG.

Beginning from the sample probe, finishing software METTEK carries out all kinds of

works: from designing of gas analysis systems taking into account individual requirements of the Customer, to the object delivery in operation with the subsequent

supervision, including personnel training, guarantee and service. Applied technical

decisions and universality of the software allow to adapt gas analysis complexes for

work in systems of automation of leading manufacturers of the equipment and system

integrators: Siemens, Rockwell Automation (Allen Bradley), etc.

WWW.METTEK.RU JSC «METTEK», Saint-Petersburg, Russia

http://www.mettek.ru/

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The EMG process mass-spectrometer

provide real-time, fast, accurate, comprehensive

gas analysis.

OPERATIONAL CHARACTERISTICS

- Modular configuration, fast replacement of

blocks for maintenance service and repair;

- IP54 protective execution;

- Continuous working 24 hours during 6 – 12

months without of servicing of vacuum system;

- Automatic algorithm of working with the functions of diagnostics, adjustment, calibration

and operative control of measurements

accuracy.

Mass-spectrometer EMG-20-7

H2, D2, T2, He, CH4, H2O, Ne, N2, CO, O2, Ar, CO2, SO2, Kr, Xe 200 ns

C2H6, C3H8, C4H10, C5H12, C6H14, C6H6, C7H8

Depending on the analytical applications the

process mass spectrometers EMG are equipped with various modifications of Sample Conditioning

System.

SAMPLE CONDITIONING SYSTEM SPECIFICATIONS

- Continuous of gas probe sampling under conditions: Temperature up to 1200 °С;

Dust content up to 30 г/м3;

Pressure (10-3 3) bar;

Presence of a condensate, aggressive gases; - Step by step cleaning of gas probe, dust, condensate removal, cooling;

- Switching from various points of sampling and gas probe transportation on the mass spectrometer input;

- Automatic control of the operating parameters (temperature, pressure, volume flow) and self-diagnostics of the Sample Conditioning System.

Industrial Sample Conditioning Block

20 years experience of innovations

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ANALYTICAL APPLICATIONS

METALLURGY

- Basic Oxygen Steel process (converter);

- Blast Furnace Optimization; - Steel Vacuum Processing (VOD, RH);

- Air separation (analysis of blowing oxygen purity); - Emissions Monitoring and Pilot Plant Gas Analysis for non-ferrous metallurgy.

GEOLOGY

- Mud Gas Logging; - Isotope Analysis; - Gas Measuring;

- Fluid Inclusions Gas Analysis (geochemistry investigations).

OIL AND GAS INDUSTRY

- LNG production;

- Natural gas processing; - Hydro-cracking process;

- High-temperature cracking furnace optimization; - Process of the catalyst regeneration; - The chemical analysis of technological gases: recycle hydrogen, fuel, inert.

ATOMIC ENERGETIC

- Chemical and isotope analysis of H2-He-T2 fuel gas mixtures (International project "ITER" - experimental thermonuclear reactor);

- Chemical and isotope analysis of gas phase of the fuel elements cover; - Monitoring of hydrogen and other gases migration during the atomic

reactor stress testing.

HIGH-PURITY GAS PRODUCTION

- He, Ne, Ar, Kr, Xe, H2, N2, O2

ALTERNATIVE ENERGETIC

- Plasma gasification of the solid waste with reception of synthesis-gas for power and chemical industry; - Optimize of hydrogen reformer and catalyst efficiency for fuel cells

development and testing.

INVESTIGATIVE ANALYSIS

- Monitoring of the gas phase for thermal, termogravimetric analysis; - The elemental analysis (C, N, O), quantity determination of the

dissolved gases in metals; - Pilot plant gas analysis of the metallurgical processes.

Express Multicomponent Gas Analysis

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Process Mass Spectrometry in Iron and Steel

STEEL VACUUM PROCESSING

Improvement of quality of steel and release of special steels — the main purpose of investments of the modern metallurgical enterprises in

building of installations for vacuum processing of metal at modernization of technological processes.

Vacuum processing allows to delete effectively the dissolved gases in metal: H2, N2,

O2, and also С by reaction with O2 at pressure decline. Vacuum processing of a steel

reduces quantity of nonmetallic inclusions and impurity (S, Mn, Pb, Zn, Сu), raises

mechanical and technological properties of an end-product.

Installations for vacuum processing of steel Tianjin Pipe Corporation (TPCO), Tianjin, China

Steel Vacuum Processing

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Technologies of Vacuum Processing of Steel:

1) Premise of a ladle with metal in the vacuum chamber, metal hashing by inert gas;

input of deoxidants and alloying additives from the bunker which is in the vacuum

chamber; a method "pumping out in a ladle".

2) Pumping out at a modulation from a ladle in a ladle or from a ladle in a mold; the

method of "jet pumping out" or "stream pumping out".

3) DH-process, it is developed by German firm "Dortmund-Horder Hiittenunion" —

vacuum processing of the fused metal by its repeated absorption from a ladle in the

portions in the vacuum chamber.

4) RH-process, is developed by German firms "Ruhrstahl AG" and "Heraeus" — vacuum processing of the fused metal by its continuous receipt from a ladle in the

vacuum chamber on one branch pipe and the return plum in a ladle on other branch

pipe.

Process VOD can be used for various variants of technology of vacuum processing of

a steel and is intended for reception of low carbonaceous steels, highly alloyed chrome

containing steels, the heat resisting alloys containing nickel, cobalt, the chrome,

special steels and alloys.

In figure various updatings of VOD-process are shown:

а) RH-process б) pumping out in a ladle


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The technology of vacuum processing provides:

- Steel homogenization in a ladle;

- Exact finishing on a chemical composition before steel plum;

- Decrease concentration of sulfur in a steel < 50 ppm;

- Reception of a steel with the carbon concentration < 0,003 %; - Decrease concentration of nonmetallic inclusions in a steel < 0,002 %;

- Decrease concentration of nitrogen in a steel < 40 ppm;

- Decrease concentration of hydrogen in a steel < 1,5 ppm;

- Decrease the oxygen concentration in a steel < 30 ppm.

Examples of steel marks became received by means of vacuum processing:

- An automobile steel with a low limit of fluidity for punching of details with

difficult configuration (concentration in metal: C < 0,003 %, N < 0,004 %); - Electrotechnical steels (concentration in metal: C, N < 0,001 %, H < 0,0001 %);

- Low carbonaceous, highly alloyed steels, heat resisting, special steels.

Built in installation of vacuum processing of steel and connected with Automated Control System the EMG gas analysis mass spectrometer system provides real-time,

fast, accurate, multicomponent (H2, CO, N2, O2, Ar, CO2) gas analysis.

The diagram of the gas analysis of steel vacuum processing

(RH-process)


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Introduction of the Gas Analysis System on the Basis of the EMG Process Mass Spectrometer Allows:

- To operate of technological process, to optimize working parameters, to obtain the

data for mathematical modeling;

- To control efficiency of degassing of metal and to receive steel with the set

parameters, chemical composition error on impurity and dissolved gases 1 ppm; - To reduce time and material inputs at expansion of an assortment of a let out steel,

perfection and modernization of technological processes;

- Use pulse injection He or Xe in the pipe allows to count correctly the volume flow

of departing gases at various pressure that gives the necessary data for complete

control of steel vacuum processing.

Platform with Block of Commutation in the place of gas probe sampling

The equipment of the EMG-20-1 gas analysis systems in the room of gas analysis

The main shutter of the vacuum pump (A place of dump of gas probe)

The main control panel on the installation of vacuum processing of steel

EMG-20-1 gas analysis system for control and operating of steel vacuum

processing (VOD), Baosteel, Shanghai, China


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Specification of Gas Analysis Systems on the Basis of the EMG Process Mass Spectrometer for Steel Vacuum Processing

1. Process time-of-flight mass spectrometer with operating controler, vacuum system

on the basis of magnito-charging or turbomolecular vacuum pump.

2. Control station on the basis of industrial PC.

3. Graphic station on the basis of industrial PC.

4. Sample Conditioning System, includind:

- Heat-resistant sampling probes, Тmax = 1200 C, ceramic-metal filters for primary clearing of gas probe;

- The block of Commutation with elements of gas probe cleaning of 2nd step;

- The rack of gas probe conditioning with the block of operating and elements of

gas probe cleaning of 3rd step;

- Warmed gas lines for gas probe transportation; - Vacuum pumps for prorolling of gas probe.

5. The software of gas analysis systems: a package of applied programs for the gas

analysis (for built in industrial controler EMG-20-1, the block of operating Sample

Conditioning System, Control and Graphic stations).

6. The complete set of calibration and test gas mixes in cylinders.

7. The complete set of the control-measuring equipment, spare parts and expendable

materials.

The pneumatic scheme of gas analysis systems for

control and operating of vacuum processing of steel


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BASIC OXYGEN STEEL MAKING

Molten iron from the blast furnace is decarburized at the steel plant when

pure oxygen is blown at supersonic speeds through a water-cooled retractable lance. This process reduces the carbon content by oxidization. Furnaces used for

this process are often referred to as converters, basic oxygen furnaces (BOF), or the basic oxygen process (BOP).

During the basic oxygen steel process, the ladle is charged with 20% scrap. Molten

iron is added to achieve the required charge balance. Before the lance is lowered, the

typical chemistry is 4% carbon, 0.5% silicon, 0.1% phosphorous and 0.02% sulfur.

Once the lance is lowered, the carbon is burned to form CO and CO2. The temperature

rises to +1700 °C, melting the scrap and lowering the carbon content. At this point,

fluxes are fed into the vessel to form slag which absorbs impurities. In addition, the

CO helps to purge N2 from the steel.

The structure diagram of the gas analysis complex on the basis of the EMG-20-1

process mass spectrometer for control of the basic oxygen steel process

Basic Oxygen Steel Making

The EMG-20-1 process mass

spectrometers provide the accuracy

of definition CO and CO2 at level of

0,05 % vol. that allows to predict

composition of the let out steel on

carbon with accuracy of 0,01 %.

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The EMG-20-1 process mass spectrometer provides the continuous analysis of the

departing gases composition, blowing oxygen, gas in the mode of argon purges that

allows to reduce consumption of power and material resources, to raise safety of technological process, to increase productivity and quality of the let out steel.

The information collected and processed by the gas analysis complex allows the

operator on the control panel the converter:

- to define the moment of the smelting "ignition";

- on the curve of the CO concentration recession to define the time of the

termination of the oxygen blowing;

- to supervise the degree of a lime mastering;

- on the curve of the O2 concentration to supervise tightness of the pipe of

departing gases;

- on the curve of the H2 concentration to fix the moment of infringement of the

water cooled lance integrity.

The diagram of the gas analysis of the basic oxygen steel processing

Basic Oxygen Steel Making

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BLAST FURNACE OPTIMIZATION

The blast furnace is charged with iron oxide bearing sinter pellets (FeO),

flux and coke which are loaded into the furnace through a rotating distributor or chute. To achieve correct distribution of these materials, the feed rate and the

order that the materials are fed into the top must be controlled.

Indirect reduction of the iron ore by carbon monoxide takes place inside the top of the

blast furnace stack between +300 °C to +1400 °C:

3Fe2O3 + CO 2Fe3O4 + CO2

Fe3O4 + CO 3FeO + CO2

FeO + CO Fe + CO2

At higher temperatures, direct reduction takes place:

FeO + C Fe + CO

The optimum coke rate is achieved when direct reduction is maximized.

The structure diagram of the gas analysis complex on the basis of the EMG-20-1

process mass spectrometer for technological process control of the blast furnace

Blast Furnace Optimization

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The EMG-20-1 process mass spectrometer provides accurate measurement of CO,

CO2, N2, H2 and other gases. If there is too much CO in the top gas, chemical heat will

leave the furnace and coke consumption will be too high. If the CO2 is too high, heat

will be carried from the furnace by the exothermic reaction: 2CO C + CO2.

The N2 measurement is an important parameter for the on-line kinetic process models

that are used for deriving mass balance, heat balance, fuel capacity and hot metal

production.

H2 is measured for safety reasons. If the reading is too high, it indicates water is

leaking into the furnace, creating a dangerous situation that can result in explosions.

Gas composition measurement is particularly important during the end-of-campaign

blow down that takes place prior to rebuilds and relines because explosive gas

mixtures can be generated.

Burden probes are often used to collect periodic temperature and gas composition

profiles. These data points are used to monitor burden distribution.

The time diagram of the gas analysis for process control of the blast furnace

Blast Furnace Optimization

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Specification of the EMG-20-1 Mass Spectrometer

Range of registered masses, Da. 1 150

Resolution at 10 % level, M/ M 150 Measured components:

H2, He, CO, N2, Ar, O2, CO2, CH4, SO2, H2S, NOХ

Dynamic range, % vol. 0,01 100 Detection limits, ppm

- Analog mode of the registration system 50

- Count mode of the registration system 5

Speed, scan/s 20000

Duration of the analysis cycle, s, no more 1

Quantity of simultaneously measured components 16

The built in calibrations for analyzed gas mixes

Mass spectrometer EMG-20-1

МЕТТЕК has introduced gas analysis systems for control and operating of the steel

vacuum processing on the largest metallurgical enterprises of China entering in the

TOP-30 of the world steel manufacturers: Baosteel, WISCO, Shandong Iron & Steel

Group, Anyang Iron & Steel Group, TPCO.

METTEK

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Process Mass Spectrometry in Geology

MUD GAS LOGGING

Mud gas logging – investigation method of composition of hydrocarbonic and other gases in the chisel solution, it is direct in the course of drilling and at sampling of discrete probe.

Mud gas logging – direct method of the revealing and estimation of the productive oil

and gas layers characteristics and the other geological objects in a cut of a hole in the

course of operational and prospecting drilling on the oil and gas.

Modern technologies of building of the oil and gas

holes, including high-speed drilling (> 50 m/h),

drilling of the leaning position-directed and

horizontal holes, carrying out of complex geologo-

technological researches directly in the course of

drilling without carrying out descent-elevating

operations, define necessity to application of the

more informative analytical methods for mud gas

logging:

- quantity of measured components; - simultaneous definition organic and

inorganic components;

- wide dynamic range;

- high speed of measurements;

- isotope analysis.

Mud Gas Logging

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Mass spectrometer EMG-20-7.

The device has been developed by request of

the JSC "Surgutneftegaz", for work as a part

of the stations for geologo-technological

investigations. Mass spectrometer provides

the mud gas logging at prospecting and

operational drilling on the oil and gas. The

simultaneous analysis of the methane

homologies (С1-С6), aromatic (benzene,

toluene) hydrocarbons and inorganic components, 2-3 seconds for 1 cycle of

measurement, the wide dynamic range of

measurements, low detection limits, allows

authentically, with split-hair accuracy on the

depth of drilling to reveal the oil pools and to

carry out the forecast of efficiency of layers-

collectors.

The software of the EMG-20-7 mass spectrometer supports the international

protocols WITS/WITSML and allows to carry out function of the remote access and

control with display of the current information on the mud gas logging, to working

parameters and a device condition. By means of modern wire and satellite Internet

technologies it is possible to provide diagnostics, adjustment, mass spectrometer

calibration in the real-time mode, to supervise process and data quality of mud gas

logging.

The diagram of the mud gas logging adhered to depth of the drilling.

EMG-20-7 mass spectrometer

Mud Gas Logging

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The EMG-20-7 mass spectrometer allows to register contrastly the oil and gas

layers capacity from 0,5 meters, authentically and precisely to define the gas -oil

contact at horizontal drilling at capacity of a layer to 5 meters that is important taking

into account of the full development of the basic deposits in Western Siberia and the

European part of Russia. The information received by means of the mass spectrometer: stratification on

the depth and characteristics of the all oil layers, including low-power, allows is

proved to make a choice for application of the punching operations, the hydraulic

rupture of layers, drillings of lateral horizontal trunks for increase and restoration of

the oil return at the operation and after major repairs of holes.

Important function of the EMG gas analysis complex as a part of station of the

geological and technological investigations is safety of the drilling: high performance

of the mass spectrometer allows to predict operatively possible emissions of gas

(allocation and the forecast of zones with abnormal high sheeted pressure), and also to

register toxic gases: hydrogen sulfide, carbon oxide.

Having passed check of reliability of the work in the cruel conditions on the

operating chisel (vibration and shock influences, difference of temperatures), the

EMG-20-7 mass spectrometer is the compact and mobile device with transportation

possibility automobile and helicopter transport in cross-country conditions, low temperatures. Now it is maintained more than 50 mass spectrometers which used for

mud gas logging at prospecting and technological drilling of holes on the deposits of

Western Siberia.

Placing of the EMG-20-7 mass

spectrometer in station of geologo-

technological in "Razrez-2".

Mud Gas Logging

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Metrological Characteristic of the EMG-20-7 Mass Spectrometer

Component

Concentration, % vol. Deviation,

% vol. SD, % vol.

Data of standard gas mixture

Data of measurements

CH4 10,31 0,01 10,297 0,013 0,042

C2H6 1,99 0,09 2,075 0,085 0,004

C3H8 0,99 0,03 1,024 0,034 0,0012

C4H10 0,533 0,050 0,583 0,050 0,0002

i-C4H10 0,054 0,006 0,048 0,006 0,0005

C5H12 0,0098 0,0006 0,00989 0,00009 0,00004

C6H14 0,000117 0,00007 0,00118 0,00001 0,00001

Metrological characteristics of the EMG-20-7 mass spectrometer were checked on the

basis of the State primary standard of the mass concentration of the gas components

GET 154-2001, D.I. Mendeleyev Metrological Institute, St.-Petersburg.

Application of the EMG-20-7 mass spectrometer is especially actual at the

prospecting drilling: the device allows to provide the isotope analysis in field

conditions, helium registration — as a natural marker of oil and gas deposits. The

system of input of gas sample allows to spend both the continuous analysis in the

course of the drilling, and the discrete analysis of the chisel solution and core samples by the thermo-vacuum degassing and the thermal analysis.

Analytical application of the EMG-20-7 mass spectrometer in geology:

- mud gas logging at prospecting and technological drilling on the oil and gas;

- gas shooting (hydrocarbons, carbon dioxide, sulphurous gases, helium,

hydrogen, etc.) by search of the oil, gas and ore deposits for revealing of

perspective areas and decrease of the expenses for prospecting drilling;

- the analysis of fluid inclusion in the sample of the firm breed, the isotope

analysis of gases at geochemical researches, superdeep drilling.

Mud Gas Logging

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Range of registered masses, Da 1 200


СH4, С2H6, C3H8, i-C4H10, C4H10, C5H12, C6H14,

H2, He, N2, Ar, O2, CO2, H2S, SO2

Dynamic range, % vol. 0,0001 100 Detection limits, ppm

- Count mode of the registration system: 0,5

Speed, scan/s 20000


Chanel of the registration system:

- analog mode 16

- count mode 16 Automated self-calibration

Automated correction of the base line


Mud Gas Logging

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Process Mass Spectrometry in Nuclear Industry

ATOMIC ENERGETIC

Atomic engineering safety one of the actual problems at designing,

technological tests of the equipment, working off and optimization of scenarios of the design failures course, algorithms of the safety systems operations.

At the A.P. Aleksandrov research institute within the limits of the project to design of

the new generation of atomic power stations of average capacity with the 640 MVt

reactor creates the large-scale integrated stand including model of the reactor

installation with electro-heated simulators of the fuel elements and a protective cover.

This Stand is the unique stand in Russia, intended for reception of representative experimental data on the heat and weight carrying over processes, on the hydrogen

distribution, carrying over of the gases and aerosols in volumes of the atomic power

station.

Large-scale integrated stand,

A.P. Aleksandrov research institute, Sosnovy Bor

Atomic Reactors Stress Testing

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The Stand is intended for carrying out of the complex experimental researches of

interconnected thermo-hydraulic, physical, chemical and thermo-mechanical

processes in reactor installation, in passive systems of safety and in volume of the

atomic power station at "through" modeling transitive and emergency regimes.

Built in the Stand the automated gas analysis complex on the basis of the EMG-20-7

process mass spectrometer allows to spend measurements of volume concentration of

the hydrogen, helium and air components in premises of the atomic power station.

The analysis of gas samples is carried out from 11 points of sampling, on automatic

algorithm or on the operator's command.

Distinctive characteristics of the given gas analysis complex is the block principle of

configuration and equipment placing: the analytical rack settles down in the dangerous

zone, and the block of operating of the mass spectrometer and sampling system in a

safe zone with total length of cable connections ~ 50 m.

Data of the gas analysis serves for a quantitative estimation of the following modeling

processes in the Stand.

The Convection of the steam and gas.

Thermal and concentration stratification of the environment.

Distribution and hydrogen accumulation to premises.

Distribution and localization of aerosols (on simulators).

The structure diagram of the gas analysis complex at the Stand

Atomic Reactors Stress Testing

EMG-20-7

mass spectrometer

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Analysis of the Chemical Composition and Isotopes Structure of the Gas Phase of the Irradiated Fuel Elements by Mass Spectrometry

At operating of the fuel elements the fission products -inert gases (He and Kr)

leave fuel into the specially provided free volumes which intended for indemnification

(decrease) of gas pressure. Migration of the fuel components and nuclides, chemical transformations leading to the products formation with smaller density promote

occurrence of stoppers in a fuel column, impenetrable for gas that can lead to increase

of gas pressure to inadmissible limits and to lead to destruction of a protective cover

and exit of the fuel element out of operation

For definition of the gas permeability of the fuel column and the stopper location,

impenetrable for gas, at Scientific research institute of nuclear reactors, Dimitrovgrad,

has been developed the experimental method. This method is consisting in consecutive

infringement and restoration of the protective cover of the fuel element on its length

with the chosen step and simultaneous measurement of the parameters of gas phase,

change of the parameters allows to define the stopper location, impenetrable for gas.

Infringement and restoration of the protective cover of the fuel element carry out

in the remote way by means of the optical laser working in modes of a puncture and

tea leaves of the formed aperture in the protective cover. Pressure and composition of

the gases which have left the fuel element at a puncture of the cover, define manometrical and mass spectrometer methods.

By request of the Institute of nuclear reactors METTEK together with Physico -

technical institute A.F. Ioffe of the Russian Academy of Sciences and «INTEK

Vacuum» has designed the EMG-20-8 mass spectrometer for realization of the given

experimental method for tests of the fuel elements.

Scientific research institute of nuclear reactors,

State corporation "Rosatom", Dimitrovgrad

Chemical and Isotope Analysis. Fuel Elements

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Mass-spectrum of Xe isotopes.

EMG-20-8 mass spectrometer.

The EMG-20-8 mass spectrometer has the V-shaped time-of-flight mass analyzer and

the differential vacuum pumping out of the ionic source. The device has original

sampling system with possibility of testing of the samples in the tight ampoules at the

lowered pressure (up to 100 mm Hg).

Results of the mass spectrometer chemical analysis of the gas phase of the fuel

elements; - reference data, - data of measurements by EMG-20-8.


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Resolution at 10 % level, M/ M 500 Dynamic range, 8 orders of magnitude

Detection limits, ppm: 0,5

Speed, scan/s 20000

Minimal duration of the analysis cycle, s, no more 1

Analytical chanel of the registration system:

- analog mode 16

- count mode 16

Automated self-adjustment of the mass-spectrum:

choice of the analytical spectral lines;

optimum parameters for the maximum spectral permission; intervals of the signal integration (maximum of measurements sensitivity)



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Analysis of the Chemical Composition and Isotopes Structure of the H2-He-T2 Fuel Gas Mixes by Mass Spectrometry

The decision of the problem of the precision, continuous chemical and isotope

analysis of the H2-He-T2 fuel gas mixtures is necessary for creation of the

thermonuclear rectors. Impurity in the fuel mixture are hydrogen-1, helium-3, helium-4, oxygen and oxides, nitrogen and its derivatives, neon, argon, hydrocarbons.

Concentration of impurity in a fuel gas mixture are in a range from 0,001 1 vol. %.

At realization of the International project ITER (the International Thermonuclear

Experimental Reactor) by request of the Russian Federal Nuclear Center, Sarov, with the assistance of the Research institute D.V.Efremov and the Physico-technical

institute A.F.Ioffe of the Russian Academy of Sciences METTEK has designed and

constructed the specialized time-of-flight mass spectrometer EMG-40-2 with the

raised mass-spectral resolution in the field of the light masses.

Resolution of the mass spectrometer, M/ M, for the full isotope analysis of the all components of the hydrogen-helium gas mixture should be not less than 3000, thus the

doublet tritium - helium-3 would not be resolved. However, for the practical problems

decision for analysis of these mixtures is enough the spectral permission, M/ M for

10 % of peak-height, not less than 500 which is required for resolution of the doublets 3He - HD and

4He — D2.

Requirements to the mass-spectral resolution of the mass spectrometer for the

isotope analysis in the field of the light masses

Chemical and Isotope Analysis of H2-He-T2 Fuel Gas Mixes

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Resolution at 10 % level, M/ M 600

Dynamic range, % vol. 0,001 100 Detection limits, ppm: 1,0

Speed, scan/s 50000

Minimal duration of the analysis cycle, s, no more 1

Quantity of simultaneously measured components 16

EMG-40-2 mass-spectrometer.

Mass-analyzer combined with vacuum system

Chemical and Isotope Analysis of H2-He-T2 Fuel Gas Mixes

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Process Mass Spectrometry in High Purity Gas Production

HIGH PURITY GAS PRODUCTION

The modern technologies in radio-electronics, cryogenic, laser,

space techniques, medicine demand more and more high-purity gases, making thus more and more strict requirements under the concentration of

the micro impurities. The technology of production of high-purity gases demands modern analytical methods both for operative control of

technological process, and for quality assurance of raw materials, intermediate and end-products.

The process mass spectrometry is the method which allows to solve problems of

analytical control at all stages of the high-purity gases production. The basic

advantages of a method:

High speed of the analysis — operative control of the technological process in

the several points by one device;

The simultaneous multi-component analysis in the wide dynamic range —

determination of the basic components and micro impurities of the gas mixture

for the one cycle of measurements;

Low detection limits — determination of micro impurity and ultra micro

impurity without the enrichments stages;

The isotope analysis — control of the technological process of the gases of spectral cleanliness production.

EMG-20-9 mass spectrometer. Determination of the micro impurities,

high purity neon production (99,9999 %), «IceBlick», Odessa

High Purity Gas Production

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Process Mass Spectrometry in High Purity Gas Production




He, Ne, Ar, Kr, Xe, H2, N2, O2, CO, CO2, CXHY

Dynamic range, % vol. 0,00005 100 Detection limits, ppm: 0,1

Speed, scan/s 20000


Chanel of the registration system:

- analog mode 16

- count mode 16

Automated self-calibration

Automated correction of the base line


High Purity Gas Production

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Process Mass Spectrometry in Alternative Energetics

PLASMA GASIFICATION OF THE SOLID WASTE

Plasma and plasma chemical technologies in the modern world find

various applications in the different branches and fields of the human activity from metallurgy and high-temperature synthesis of new substances

to medicine — surgical operations by means of the plasma scalpel which provides the cutting and repairing of the blood vessels at the same time.

Research of the plasma gasification of the solid waste — applied science area where

Russia keeps in the lead positions in the world. According to F.G. Rutberg, the

academician of the Russian Academy of Sciences, the director of Institute of electro -

physics and electric power industry of the Russian Academy of Sciences, the winner of

the international award «Global energy» for 2011 — "In the world in 10-15 years

plasma application will be more than metallurgy and chemistry together taken".

Experimental installation of plasma gasification of the solid waste at the Institute of

electro-physics and electric power industry, St.-Petersburg. In the foreground Sampling

and Sample Conditioning System of the gas analysis complex on the basis of the

EMG-20-1 process mass spectrometer EMG-20-1, produced METTEK.

Plasma gasification

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At the Institute of electro-physics and electric power of the Russian Academy of

Sciences the experimental installation of plasma gasification of the solid waste is

exploited. With help of this experimental installation are developing the technologies

of recycling of various kinds of the solid waste, production of the synthesis-gas which

can be used in the energetic or as raw materials for the chemical industry.

The Installation of plasma gasification consists of following basic components: the

reactor for gasification, generators of plasma with power supply systems, an

afterburner, system of cooling and clearing of departing gases. High-voltage plasma

generators of an alternating current of industrial frequency with capacity up to 50 kW

and using the environment air for formation of plasma are applying.

The main principle of the installation action consists in the following: high-

temperature plasma gasification with possible reception of the electric power or

recycling of residual heat, with the subsequent multistage clearing of smoke gases

according to the norms of environment protection.

Chemical reaction of the plasma gasification, process temperature - 1200 1500 C

(C, CxHy) + Air + H2O

H2 + CO + CO2 + N2 + O2 + H2O + Ar + CH4 + NOx + SO2 + H2S

The block diagram of installation of plasma gasification of the solid waste

with built in the gas analysis complex on the basis of the EMG-20-1

process mass spectrometer.

Plasma gasification

30


Process Parameters of the Plasma Gasification

Parameters Value for different kinds of the recycling waste

Wood RDF* Waste of tires

Specific heat of combustion, МJ/kg 16 15 33

Consumption on the 1 kg of waste:

gas for plasma formation, kg 1,44 1,51 2,88

Secondary blasting (water steam), kg - - 1,33

Power consumption, kW h/kg 1,0 1,06 1,85

Mode of plasma generator, МJ/kg 2,25 2,27 2,08

Plasma temperature, C 1950 2000 1800

Specific output of synthesis-gas, m3/kg 2,48 2,46 5,03

Component of synthesis-gas, % vol.

hydrogen (H2) 24,5 26,3 30,6

carbon oxide (CO) 31,4 27,5 24,0

carbon dioxide (CO2) 3,5 3,2 5,2

water (H2O) 4,9 4,9 4,9

nitrogen (N2) 35,7 37,8 35,1

Specific heat of gas combustion, МJ/m3 6,16 5,88 5,89

* RDF - Refuse-Derived Fuel.

The installation of plasma gasification of the solid waste allows to solve

simultaneously two problems: recycling of the waste of wood, coal, plastic, RDF,

automobile tires and produce of energy from renewed sources (alternative energetic).

Process of plasma gasification spent at the temperature more than 1200 °С allows to

avoid occurrence in the synthesis-gas of liquid fractions (pitches) which are formed in

the considerable quantities at lower temperatures that excludes necessity of their

further recycling. High temperature of the process provides destruction of toxic and

difficultly decomposed components of the waste completely and, in the presence of

chlorine-containing components in the waste, excludes synthesis of secondary

especially toxic substances.

The received synthesis-gas can go on burning to a gas boiler-house and serve as partial

replacement of natural gas or it is exposed to additional conditioning (cleaning) for the

further use as raw materials in the chemical industry.

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31


Structure and Purpose of the Mass Spectrometry Gas Analysis System for

Process Control of Plasma Gasification of the Waste

The gas analysis system on the basis of the EMG-20-1 process mass spectrometer,

produced METTEK, built in the installation of plasma gasification of the solid waste

allows to control of technological process, to spend optimization of working

parameters, to supervise overall performance of the departing gases cleaning system,

to carry out the monitoring of harmful substances emissions to atmosphere.

Change of temperature in the time at work of the installation of

plasma gasification of the solid waste

Determined components, ranges of measured concentration, values of concentration of departing gases at the plasma gasification (product-gas) at the stage of working process

(the stationary operating mode of the installation)

Component Range of measured concentration, % vol.

Concentration at the stationary operating mode, % vol.

Hydrogen, H2 0,01 50,0 25,0 30,0

Carbon oxide, CO 0,01 50,0 25,0 30,0

Nitrogen, N2 0,01 80,0 35,0 40,0

Carbon dioxide, CO2 0,01 10,0 1,0 5,0

Oxygen, O2 0,01 25,0 1,0 2,0

Argon, Ar 0,01 2,0 0,8 1,0

Methane, CH4 0,01 5,0 1,0 2,0

Water, H2O 0,1 5,0 1,0 5,0

Nitrogen oxides, NOX 0,0005 1,0 < 0,5

Sulfur dioxide, SO2 0,0005 1,0 < 0,01

Hydrogen sulphid, H2S 0,0005 1,0 < 0,01

Plasma gasification

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Sampling block:

- heat-resistant sampling

probes, Тmax = 1200 C; - ceramic-metal filters for

primary cleaning of the gas

sample with the return purge;

- automated operating

electro-magnetic valves;

- gages of pressure, temperatures.

Industrial rack of sample conditioning and

gas-flow commutation:

- block for valve operating ;

- components of sample conditioning:

filtration, condensate removal;

- system for working parameters control

(pressure, temperature, volume gas-flow)

- panel of heating with a temperature

regulator.

EMG-20-1 process mass spectrometer:

- Instrument rack – the industrial rack, IP54,

with stabilization of a temperature mode;

- Mass analyzer (mass-reflectron) complete

with modules of ionic optics, the generator of

rectangular impulses, the broadband amplifier,

system of temperature stabilization;

- Vacuum system on the basis of the turbo-

molecular vacuum pump, productivity: 70 l/s;

- Sampling System for input of testing and calibration gas mixtures with automatically

operated valve-gate;

- The block of electronics with modular

configuration of components for simplicity

of servicing, diagnostics and repairing.

Plasma gasification

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Process Mass Spectrometry in Scientific Investigation

THERMOGRAVIMETRIC ANALYSIS

For the characteristic of thermo-physical properties, structure and

stability of various substances and materials methods of the thermal analysis are widely used. Especially wide application finds the

thermogravimetric analysis in which loss of weight of the sample is registered continuously during programmed heating.

The thermogravimetric analysis is a recognized method of the testing by prodicing of

polymeric materials, in the chemical industry, in pharmaceutics, is applied also to

research of properties of ceramic materials, minerals and metals, foodstuff, glues,

varnishes and paints.

The most powerful analytical means for scientific researches in the thermogravimetry are the systems of synchronous TG-DTA/DSC analysis combined with a mass

spectrometer for control of a gas phase composition.

Gas analysis by the EMG-20-8

mass-spectrometer at the

thermogravimetric analysis.

The installation of TG-DTA/DSC

analysis «Setsys Evolution»,

SETARAM, France.

Institute «Gipronickel»,

Saint-Petersburg,

«MMC «Norilsky nickel».

Investigative Analysis

34


At the synchronous TG-DTA/DSC analysis change of a thermal flow and weight of the sample as function from temperature and time is simultaneously measured at

controllable atmosphere. The given method of the thermogravimetric analysis not only

increases productivity of measurements, but also simplifies interpretation of the

results, thanks to possibility to separate the processes with various thermal effects

(positive or negative) which are not accompanied by change of weight (for example,

phase transitions) from at what there is a weight change (for example, a desorption,

degradation).

Gas analysis by mass spectrometry (MS) allows to receive more detailed information on the composition and the thermo-physical properties of investigated samples and to

interpret the results of measurements authentically.

The sample at the thermogravimetric analysis (TGA) is in the set both controllable conditions and environment (speed of heating, gas atmosphere, volume flow, etc.).

Method TGA combined with mass spectrometer system for the gas analysis is used, for

example, for quantitative definition of composition of a polymeric composition or any

mixtures. Weight loss in the atmosphere of inert gas, for example, can result from

allocation chemically or physically connected water (behavior at drying). Allocation of

the solvents and softeners or decomposition of polymers, are divided in time

depending on its thermal stability. After switching of the inert gas atmosphere on the oxidizing atmosphere (air, oxygen) the added soot, for example, burns down to carbon

dioxide. Inorganic additives, such as talc or fiber glass in the field of temperatures to

1000°C form the rest in the form of ashes.

Investigations at the synchronous TG-DTA/DSC analysis, combined with МS:

Decomposition

• allocation of water

• stability

• residual solvent • pyrolysis

Heterogeneous reactions solid - gas

• combustion

• oxidation

• corrosion • adsorption

• desorption

The analysis of composite

materials

• composition of polymers

• the technical analysis

• burning out of the binding

• destruction of paraffin • definition of the ashes rest

Identification

• composition of gas mixtures

• under the mass spectrum form

("A fingerprint" method)

• patial pressure

• fragments • reactions gas-solid phase


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Specialized EMG-20-8 mass spectrometer for scientific investigations as a part of installation of the thermogravimetric analysis has high-temperature (up to 450 °С)

input of the gas sample, the automated adjustment of a mass spectrum and a choice of

the analytical spectral lines: 16 analytical lines in the analog and 16 in the count modes

of system registration operating.

Defined components by mass spectrometer for investigations for development of new technologies , optimization of parameters of technological processes of copper -nickel

producing in the "MMC" Norilsky nickel":

H2, N2, O2, CO, Ar, SO2, H2S, CH4, NH3, COS, CS2

Range of measured concentration: 0,0001 100 % vol.,

is minimum reached detection limit – 0,01 ppm.

Before scientific researches the system of TG-DTA/DSC and mass spectrometer gas analysis is tested by means of standard samples with the known chemical composition

and thermo-physical properties. The obtained data of the gas analysis is compared to

reference values by means of the balance method.

The time diagram of the gas analysis of reference sample of the copper-nickel

concentrate. The EMG-20-8 mass spectrometer.


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