INTRODUCED by Gosstandart of Russia

2. ADOPTED by the Interstate Council for Standardization, Metrology and Certification (Protocol No. 6-94 of October 21, 1994)

State name	Name of the national standardization body
The Republic of Azerbaijan	Azgosstandart
Republic of Armenia	Armgosstandard
Republic of Belarus	Belgosstandart
Republic of Georgia	Gruzstandart
The Republic of Kazakhstan	Gosstandart of the Republic of Kazakhstan
Republic of Kyrgyzstan	Kyrgyzstandard
The Republic of Moldova	Moldovastandard
Russian Federation	Gosstandart of Russia
The Republic of Uzbekistan	Uzgosstandart
	State Standard of Ukraine

3. This standard represents the complete authentic text of ISO 7404-5-85 “Bituminous and anthracite coal. Methods of petrographic analysis. Part 5. Method for microscopic determination of vitrinite reflectance indicators" and contains additional requirements reflecting the needs of the national economy

4. IN REPLACE GOST 12113-83

Date of introduction 1996-01-01

This standard applies to brown coals, bituminous coals, anthracite coals, coal mixtures, solid dispersed organic matter and carbonaceous materials and establishes a method for determining reflectance indicators.

The vitrinite reflectance index is used to characterize the degree of metamorphism of coals during their search and exploration, mining and classification, to establish the thermogenetic transformation of solid dispersed organic matter in sedimentary rocks, as well as to determine the composition of coal mixtures during beneficiation and coking.

Additional requirements reflecting the needs of the national economy are highlighted in italics.

1. PURPOSE AND SCOPE OF APPLICATION

This standard specifies a method for determining minimum, maximum and arbitrary reflectance using an oil immersion microscope. and in the air on polished surfaces polished briquettes and sanded specimens vitrinite component of coal.

GOST 12112-78 Brown coals. Method for determining petrographic composition

GOST 9414.2-93 Hard coal and anthracite. Methods of petrographic analysis. Part 2. Method for preparing coal samples

3. ESSENCE OF THE METHOD

The essence of the method is to measure and compare electric currents arising in a photomultiplier tube (PMT) under the influence of a light flux reflected from the polished surfaces of macerals or submacerals of the test sample and standard samples (standards) with an established reflectance index.

4. SAMPLING AND SAMPLE PREPARATION

4.1. Sampling for the preparation of polished briquettes is carried out according to GOST 10742.

4.2. Polished briquettes are produced according to GOST 9414.2.

From the samples intended for measuring reflection indicators with the construction of reflectograms, two polished briquettes with a diameter of at least 20 mm are made.

4.3. To prepare polished briquettes from rocks with inclusions of solid dispersed organic matter, the crushed rock is first enriched, for example by flotation, by chemical decomposition of the constituent inorganic part of the rocks, and others.

4.4. To prepare polished specimens of coal, samples are taken from the main formation-forming lithotypes with a size of at least 30×30×30 mm. When taking samples from drill hole cores, it is allowed to take samples measuring 20×20×20 mm.

4.5. To prepare polished specimens from rocks with inclusions of solid dispersed organic matter, samples are selected in which inclusions of solid organic matter are visible microscopically or their presence can be assumed based on the type of deposits. The size of the samples depends on the sampling opportunity (natural outcrops, mine workings, drill cores).

4.6. The preparation of polished samples consists of three operations: impregnation in order to give the samples strength and solidity for subsequent grinding and polishing.

4.6.1. Synthetic resins, carnauba wax, rosin with xylene, etc. are used as impregnating agents.

For some types of coals and rocks with inclusions of solid dispersed organic matter, it is sufficient to immerse the sample in an impregnating agent.

If the sample has sufficient strength, the surface perpendicular to the layering plane is lightly ground.

Samples of weakly compacted sandy-clayey rocks containing small scattered organic inclusions are dried in an oven at a temperature of 70 °C for 48 hours before soaking in rosin and xylene.

The samples are tied with wire, to the end of which a label with a passport is attached, and placed in one layer in a porcelain cup, pour rosin into it, crushed into grains ranging from 3 to 7 mm in size, and fill it with xylene (3 cm 3 per 1 g of rosin) so that so that the samples are completely covered with the solution.

Impregnation is carried out in a fume hood while heating on a closed tile for 50 - 60 minutes until the xylene has completely evaporated. The samples are then removed from the dish and cooled to room temperature.

4.6.2. Grind two mutually parallel planes of the impregnated sample, perpendicular to the layering, and polish one of them.

Grinding and polishing are carried out in accordance with GOST R 50177.2 and GOST 12113.

4.7. When studying polished briquettes and polished specimens that have been stored for a long time, as well as previously measured samples, it is necessary to grind them down by 1.5 - 2 mm and repolish them before measuring the reflection index.

5. MATERIALS AND REAGENTS

5.1. Calibration Standards

5.1.1. Reflectance standards, which are samples with a polished surface, satisfy the following requirements:

a) are isotropic or represent the main cross section of uniaxial minerals;

b) durable and corrosion-resistant;

c) save constant indicator reflections for a long time;

d) have a low absorption rate.

5.1.2. The standards must be more than 5 mm thick or have the shape triangular prism (30/60°) to avoid more light entering the lens than that reflected from its upper (working) surface.

A polished edge is used as a working surface to determine the reflectance index. Base and sides of the standard covered with an opaque black varnish or placed in a durable opaque frame.

The beam path of a wedge-shaped standard embedded in black resin during photometric reflectance measurements is shown in Figure 1.

5.1.3. When carrying out measurements, at least three standards are used with reflectance indices close to or overlapping the area of ​​measurement of the reflectance indices of the samples under study. To measure a coal reflectance of 1.0%, standards with reflectances of approximately 0.6 should be used; 1.0; 1.6%.

The average refractive and reflective indices for commonly used standards are given in Table 1.

5.1.4. The true values ​​of the reflectance index of the standards are determined in special optical laboratories or calculated from the refractive index.

Knowing the refractive index n and absorption rate? (if significant) of the standard at a wavelength of 546 nm, the reflectance can be calculated ( R) as a percentage according to the formula

If the refractive index is not known or it is suspected that the surface properties may not exactly correspond to the nominal fundamental properties, the reflectance is determined by careful comparison with a standard of known reflectance.

5.1.5. The zero standard is used to eliminate the influence of the dark current of the photomultiplier tube and scattered light in the optical system of the microscope. K8 optical glass can be used as a zero standard or a polished briquette made from coal with a particle size of less than 0.06 mm and having a recess in the center with a diameter and depth of 5 mm, filled with immersion oil.

Figure 1 - Beam path in a wedge-shaped standard embedded in black resin,
in photometric measurements of the reflectance index

Table 1

Average reflective refractive indices for commonly used standards

5.1.6. When cleaning standards, care should be taken not to damage the polished surface. Otherwise, it is necessary to re-polish its working surface.

5.2. Immersion oil that meets the following requirements:

non-corrosive;

does not dry out;

with a refractive index at a wavelength of 546 nm 1.5180 ± 0.0004 at 23 °C;

with temperature coefficient dn/dt less than 0.005 K -1 .

The oil must not contain toxic components and its refractive index must be checked annually.

5.3. Rectified alcohol,

5.4. Absorbent cotton wool, fabric for optics.

5.5. Slides and plasticine for fixing the samples under study.

6. EQUIPMENT

6.1. Monocular or a binocular polarizing microscope with a photometer to measure the indicator in reflected light. The optical parts of the microscope used to measure reflectance are shown in Figure 2. The components are not always arranged in the specified sequence.

6.1.1. Light source A. Any light source with stable radiation can be used; A 100W quartz halogen lamp is recommended.

6.1.2. Polarizer D- polarizing filter or prism.

6.1.3. An aperture for adjusting light, consisting of two variable apertures, one of which focuses the light on the rear focal plane of the lens (illuminator) IN), the other is on the surface of the sample (field diaphragm E). It must be possible to center with respect to the optical axis of the microscope system.

6.1.4. Vertical illuminator - Berek prism, coated plain glass plate or Smith illuminator (combination of a mirror with a glass plate Z). Types of vertical illuminators are shown in Figure 3.

6.1.6. Eyepiece L - two eyepieces, one of which is equipped with crosshairs, which can be scaled so that the total magnification of the objective, eyepieces and in some cases the tube is from 250° to 750°. A third eyepiece may be required M on the path of light to the photomultiplier tube.

A- lamp; B- collecting lens; IN- illuminator aperture; G- thermal filter;
D- polarizer; E- field diaphragm; AND- focusing lens of the field diaphragm;
Z- vertical illuminator; AND- lens; R - sample; TO- table; L- eyepieces;
M - third eyepiece; N- measuring aperture, ABOUT- 546 nm interference filter;
P- photomultiplier

Figure 2 - Optical parts of a microscope used to measure reflectance

6.1.7. Microscope tube having the following accessories:

a) measuring aperture N, which allows you to adjust the light flux reflected into the photomultiplier from the surface of the sample R, area less than 80 microns 2. The aperture should be centered with the crosshairs of the eyepiece;

b) devices for optical isolation of eyepieces to prevent excess light from entering during measurements;

c) necessary blackening to absorb scattered light.

Note - Using precautions, part of the light flux can be directed to the eyepiece or television camera for continuous observation when measuring the reflectance index.

6.1.8. Filter ABOUT with a maximum transmission band at (546 ± 5) nm and a half-width of the transmission band less than 30 nm. The filter should be located in the path of the light flux directly in front of the photomultiplier tube.

A- filament; B- collecting lens; IN - illuminator aperture (position of filament reflection);
G- field diaphragm; D- focusing lens of the field diaphragm; E- Berek prism;
AND- reverse focal plane of the lens (position of the filament image and the illuminator aperture);
Z- lens; AND- sample surface (position of the visual field image);

A- vertical illuminator with Berek prism; b- illuminator with glass plate; V- Smith's illuminator

Figure 3 - Diagram of vertical illuminators

6.1.9. Photomultiplier P, fixed in a nozzle mounted on the microscope and allowing the light flux to enter the photomultiplier window through the measuring aperture and filter.

The photomultiplier tube must be of the type recommended for measuring light fluxes of low intensity, must have sufficient sensitivity at 546 nm and low dark current. Its characteristic must be linear in the measurement range, and the signal must be stable for 2 hours. Typically, a direct multiplier with a diameter of 50 mm with an optical input at the end having 11 diodes is used.

6.1.10. Microscope stage TO, capable of rotating 360° perpendicular to the optical axis, which can be centered by adjusting the stage or lens. The rotating table is connected to a sample driver, which ensures movement of the sample, with a step of 0.5 mm in the directions X And Y, equipped with a device that allows for slight adjustment of movements in both directions within 10 microns.

6.2. Stabilizer direct current for a light source. The characteristics must satisfy the following conditions:

1) the lamp power should be 90 - 95% of the norm;

2) fluctuations in lamp power should be less than 0.02% when the power source changes by 10%;

3) pulsation at full load less than 0.07%;

4) temperature coefficient less than 0.05% K -1.

6.3. DC voltage stabilizer for photomultiplier.

The characteristics must satisfy the following conditions:

1) voltage fluctuations at the output must be at least 0.05% when the voltage of the current source changes by 10%;

2) ripple at full load less than 0.07%;

3) temperature coefficient less than 0.05% K -1 ;

4) a change in load from zero to full should not change the output voltage by more than 0.1%.

Note - If during the measurement period the power supply voltage drops by 90%, an autotransformer should be installed between the power source and both stabilizers.

6.4. A indicating device (display) consisting of one of the following devices:

1) a galvanometer with a minimum sensitivity of 10 -10 A/mm;

2) recorder;

3) digital voltmeter or digital indicator.

The instrument must be adjusted so that its full-scale response time is less than 1 s and its resolution is 0.005% of the reflectance. The device must be equipped with a device for removing the small positive potential that arises during the discharge of the photomultiplier and due to the dark current.

Notes

1. The digital voltmeter or indicator should be able to clearly distinguish the values ​​of the maximum reflectance when the sample is rotated on the stage. Individual reflectance values ​​can be stored by electronic equipment or recorded on magnetic tape for subsequent processing.

2. To amplify the photomultiplier signal when feeding it to the indicating device, you can use an amplifier with a low noise level.

6.5. Device to give the polished surface of the test sample or standard a position parallel to the glass slide (press).

7. MEASUREMENTS

7.1. Preparation of equipment (in 7.1.3 and 7.1.4, letters in parentheses refer to Figure 2).

7.1.1. Initial Operations

Make sure the room temperature is (23 ± 3) °C.

Includes sources of current, light and other electrical equipment. Set the voltage recommended for this photomultiplier by its manufacturer. To stabilize the equipment, wait 30 minutes before starting measurements.

7.1.2. Adjusting the microscope to measure reflectance.

If an arbitrary reflectance is measured, the polarizer is removed. If maximum reflectance is being measured, the polarizer is set to the zero position when using a glass plate or Smith illuminator, or at an angle of 45° when using a Berek prism. If a polarizing filter is used, it is checked and replaced if it produces significant discoloration.

7.1.3. Lighting

A drop of immersion oil is applied to the polished surface of a polished briquette mounted on a glass slide and leveled and placed on the microscope stage.

Check that the microscope is adjusted correctly for Köhler illumination. Adjust the illuminated field using the field diaphragm ( E) so that its diameter is about 1/3 of the entire field. Illuminator aperture ( IN) are adjusted to reduce glare without unduly reducing the luminous flux. Subsequently, the size of the adjusted aperture is not changed.

7.1.4. Adjusting the optical system. The image of the field diaphragm is centered and focused. Center the lens ( AND) but in relation to the axis of rotation of the object stage and regulate the center of the measuring aperture ( N) so that it coincides either with the crosshairs of the threads or with a given point in the field of view of the optical system. If the measurement aperture image cannot be seen on the sample, select a field containing a small shiny inclusion, such as a pyrite crystal, and align it with the crosshairs. Adjust the centering of the measuring aperture ( N) until the photomultiplier tube gives the highest signal.

7.2. Reliability check and equipment calibration

7.2.1. Equipment stability.

The standard with the highest reflectance is placed under a microscope and focused in immersion oil. The photomultiplier voltage is adjusted until the reading on the display matches the reflectance of the reference (for example, 173 mV corresponds to a reflectance of 173%). The signal should be constant, changes in readings should not exceed 0.02% within 15 minutes.

7.2.2. Changes in readings when rotating the reflectance standard on the stage.

Place a standard with an oil reflectance of 1.65 to 2.0% on the stage and focus it in immersion oil. Slowly rotate the table to ensure that the maximum change in indicators is less than 2% of the reflectance of the taken standard. If the deviation is higher than this value, it is necessary to check the horizontal position of the standard and ensure that it is strictly perpendicular to the optical axis and rotates in the same plane. If after this the fluctuations do not become less than 2%, the mechanical stability of the stage and the geometry of the microscope must be checked by the manufacturer.

7.2.4. Photomultiplier signal linearity

Measure the reflectance of other standards at the same constant voltage and the same light aperture setting to verify that the measurement system has a linear relationship within the measured limits and the standards correspond to their calculated values. Rotate each standard so as to bring the readings as close as possible to the calculated value. If the value for any of the standards differs from the calculated reflectance by more than 0.02%, the standard should be cleaned and the standardization process repeated. The standard must be polished again until the reflectance differs from the calculated value by more than 0.02%.

If the reflectance of the standards does not produce a linear diagram, check the linearity of the photomultiplier signal using standards from other sources. If they do not give a linear plot, check the signal linearity again by applying several neutral density calibration filters to reduce the light flux to a known amount. If the photomultiplier signal is confirmed to be non-linear, replace the photomultiplier tube and carry out further testing until signal linearity is obtained.

7.2.5. Equipment calibration

Having established the reliability of the equipment, it is necessary to ensure that the indicating device gives correct readings for the zero standard and three reflection standards of the coal being tested, as specified in 7.2.1 - 7.2.4. The reflectance of each standard shown on the display should not differ from the calculated value by more than 0.02%.

7.3. Measurement of vitrinite reflectance index

7.3.1. General provisions

The method for measuring maximum and minimum reflectance is given in 7.3.2, and arbitrary in 7.3.3. In these subclauses, the term vitrinite refers to one or more submacerals of the vitrinite group.

As stated in Section 1, the choice of submacerals on which measurements are made determines the result and, therefore, it is important to decide on which submacerals the reflectance measurements should be taken and note them when reporting the results.

7.3.2. Measuring the maximum and minimum reflectance of vitrinite in oil.

Install the polarizer and check the equipment in accordance with 7.1 and 7.2.

Immediately after calibration of the equipment, a leveled polished preparation made from the test sample is placed on a mechanical table (preparation guide), which allows measurements to be made starting from one corner. Immersion oil is applied to the surface of the sample and focusing is performed. Move the sample slightly with the slide until the crosshairs are focused on the appropriate vitrinite surface. The surface on which measurements are made should not have cracks, polishing defects, mineral inclusions or relief and should be at some distance from the boundaries of the maceral.

Pass light through a photomultiplier tube and rotate the table 360° at a speed of no more than 10 min -1 . Record the highest and lowest values ​​of the reflectance index, which are noted when the stage is rotated.

Note: By rotating the specimen 360°, ideally two identical maximum and minimum readings can be obtained. If the two readings are very different, the cause should be determined and the error corrected. Sometimes the error may be caused by air bubbles in the oil entering the area being measured. In this case, the readings are not taken into account and air bubbles are eliminated by lowering or raising the microscope stage (depending on the design). The front surface of the objective lens is wiped with an optical cloth, a drop of oil is again applied to the surface of the sample, and focusing is performed.

The sample is moved in the direction X(step length 0.5 mm) and take measurements when the crosshair hits a suitable vitrinite surface. To ensure that measurements are taken at the appropriate site of vitrinite, the sample can be moved with a slider to a distance of up to 10 µm. At the end of the path, the sample moves to the next line: the distance between the lines is at least 0.5 mm. The distance between the lines is chosen such that the measurements are distributed evenly on the surface of the section. Continue to measure the reflectance using this testing procedure.

Every 60 min, check again the calibration of the equipment against the standard that is closest to the highest reflectance (7.2.5). If the reflectance of the standard differs by more than 0.01% from the theoretical value, discard the last readings and perform them again after recalibrating the equipment against all standards.

Reflectance measurements are made until the required number of measurements is obtained. If the polished briquette is prepared from coal of one layer, then 40 to 100 measurements and more are made (see table 3 ). The number of measurements increases with increasing degree of vitrinite anisotropy. In each measured grain, the maximum and minimum reading values ​​are determined when the microscope stage is rotated. Average maximum and minimum reflectances are calculated as the arithmetic average of the maximum and minimum reports.

If the sample used is a mixture of coals, then 500 measurements are made.

On each polished specimen, 10 or more vitrinite sections should be measured, depending on the degree of anisotropy of the sample under study and the objectives of the study.

Before starting measurements, the polished specimen is positioned so that the layering plane is perpendicular to the incident beam of the microscope optical system. At each measured point, the position of the maximum reading is found, and then readings are recorded every 90° of rotation of the microscope stage as it rotates 360°.

Maximum and minimum reflectance (R 0, max and R 0, min) calculated as the arithmetic average of the maximum and minimum samples, respectively.

7.3.3. Measurement of an arbitrary reflectance index of vitrinite in immersion oil (R 0, r)

Apply the procedure described in 7.3.2, but without the polarizer and rotation of the sample. Perform calibration as described in 7.2.5

The vitrinite reflectance is measured until the required number of measurements is recorded.

On each sanding briquette it is necessary to perform from 40 to 100 or more measurements (table 3 ) depending on the homogeneity and degree of anisotropy of the sample under study.

The number of measurements increases with increasing heterogeneity in the composition of the group of huminite and vitrinite, as well as with pronounced anisotropy hard coals and anthracite.

The number of measurements for samples containing solid dispersed organic matter is determined by the nature and size of these inclusions and can be significantly lower.

To establish the composition of coal mixtures from reflectograms, it is necessary to carry out at least 500 measurements on two samples of the coal sample under study. If the participation of coals of varying degrees of metamorphism included in the charge cannot be established unambiguously, another 100 measurements are carried out and further until their quantity is sufficient. Limit number of measurements - 1000.

On each polished sample, up to 20 measurements are performed in two mutually perpendicular directions. To do this, the grinding specimen is installed so that the layering plane is perpendicular to the incident beam of the microscope optical system. The areas for measurements are selected so that they are located evenly over the entire surface of the vitrinite of the polished specimen under study.

Arbitrary reflectance index (R 0, r ) is calculated as the arithmetic mean of all measurements.

7.3.4. Airborne reflectance measurements.

Definitions of maximum, minimum and arbitrary reflection indices (R a, max, R a, min And R a, r) ​​can be carried out for a preliminary assessment of the stages of metamorphism.

Measurements in air are carried out similarly to measurements in immersion oil at lower values ​​of the aperture diaphragm, illuminator voltage and PMT operating voltage.

On the polished briquette under study, it is necessary to perform 20 - 30 measurements, on polished specimen - 10 or more.

8. PROCESSING OF RESULTS

8.1. Results can be expressed as a single value or as a series of numbers at 0.05% reflectance intervals (1/2 V-step) or at intervals of 0.10% of the reflection index ( V-step). Average reflections and standard deviation are calculated as follows:

1) If individual readings are known, then the average reflectance and standard deviation are calculated using formulas (1) and (2), respectively:

(2)

Where ?R- average maximum, average minimum or average arbitrary reflection indicator, %.

Ri- separate indication (measurement);

n- number of measurements;

Standard deviation.

2) If the results are presented as a series of measurements in 1/2 V-step or V-step, use the following equations:

Where Rt- average value 1/2 V-step or V-step;

X- number of reflection indicator measurements in 1/2 V-step or V-step.

The submacerals of vitrinitis, to which the values ​​relate, are recorded ?R regardless of what reflection indicator was measured, the maximum, minimum or arbitrary, and the number of measurement points. Percentage of vitrinite for each 1/2 V-step or V-step can be represented in the form of a reflectogram. An example of expressing the results is given in Table 2, the corresponding reflectogram is in Figure 4.

Note - V-step has a range of 0.1 reflectance index, and 1/2 - 0.05%. To avoid overlapping reflectance values ​​expressed to the second decimal place, value intervals are presented, for example, as follows:

V- step - 0.60 - 0.69; 0.70 - 0.79, etc. (incl.).

1 / 2 V- pitch: 0.60 - 0.64; 0.65 - 0.69, etc. (incl.).

The average value of the series (0.60 - 0.69) is 0.645.

The average value of the series (0.60 - 0.64) is 0.62.

8.2. If necessary, an arbitrary reflectance index (R 0, r ) are calculated from the average values ​​of the maximum and minimum reflection indices using the formulas:

for grinding material R 0, r = 2 / 3 R 0, max + 1 / 3 R 0, min

for polished briquettes

Magnitude occupies an intermediate position between R 0, max and R 0, min And associated with the orientation of the grain in the polished briquette.

8.3. As an additional parameter, the reflection anisotropy index (AR) is calculated using the formulas:

8.4. Processing of measurement results in ordinary and polarized light in air using polished briquettes and sanded specimens is carried out similarly to the processing of measurement results in immersion oil (8.1 ).

Figure 4 - Reflectogram compiled from the results of Table 2

table 2

The measured reflectance is arbitrary

Submacerals vitrinitis telocollinitis and desmocollinitis

Reflectance index	Number of observations	Percentage of observations

Total number of measurements n = 500

Average reflectance ?R 0, r = 1.32%

Standard deviation? = 0.20%

9. ACCURACY

9.1. Convergence

Convergence of definitions of average values ​​of maximum, minimum or arbitrary reflectance is the value by which two separate readings made with the same number of measurements by the same operator on the same specimen using the same apparatus differ at 95% confidence level.

Convergence is calculated using the formula

Where? t- theoretical standard deviation.

Convergence depends on a number of factors including:

1) limited accuracy of calibration using reflectance standards (6.2.5);

2) permissible calibration offset during measurements (6.3.2);

3) the number of measurements taken and the range of reflectance values ​​for vitrinite of one coal seam.

The overall effect of these factors can be expressed by a standard deviation of the average reflectance of up to 0.02% for a sample of one individual coal from one seam. This corresponds to a convergence of up to 0.06%.

9.2. Reproducibility

The reproducibility of determinations of the average values ​​of the maximum, minimum or arbitrary indicators is the value by which the values ​​of two determinations made with the same number of measurements by two different operators on two different preparations made from the same sample and using different equipment differ, with a confidence level 95%.

Reproducibility is calculated using the formula

Where? 0 is the actual standard deviation.

If operators are adequately trained to identify vitrinitis or related submacerals and the reflectance of the standard is reliably known, the standard deviations of mean reflectance determinations by different operators in different laboratories are 0.03%. The reproducibility is thus 0.08%

9.3. The permissible differences between the results of the average values ​​of the reflection indicators of the two definitions are indicated in the table 3 .

Table 3

Reflection index, %	Permissible differences % abs.		Number of measurements
	in one laboratory	in different laboratories
Up to 1.0 incl.

10. TEST PROTOCOL

The test report must include:

2) all details necessary to identify the sample;

3) total number of measurements;

4) type of measurements taken, i.e. maximum, minimum or arbitrary reflectance index;

5) the type and ratio of vitrinite submacerals used in this definition;

6) the results obtained;

7) other features of the sample noticed during the analysis and which may be useful in using the results.

Vitrinite group: a - colinite (homogeneous gray) with cutinite (black). Reflected light. Immersions b - colinite (homogeneous gray), corpocolinite (dark gray oval body on the left), thelinite (uneven stripe in the center). White spherulites are pyrite. Reflected polarized light. State of extinction; c - vitrodetrinitis. Reflected light. Immersion g - colinitis (top), telinitis (bottom).

Telinite (gray), resinite (black). Reflected light. Immersions.

Crushed fragments of a vitrinite nature are very common in coal. They form the desmocolinite groundmass clarita and trimacerita. As a rule, when examined in normal reflected light using oil immersion, these fragments cannot be distinguished from each other. In this case, they are combined under the name “desmocolinitis”. Only methylene iodide immersion makes it possible to clearly distinguish them in coal with a high yield of volatile substances. In reflected light using oil immersion, vitrodetrinite particles can only be seen when they are surrounded by components that have a different reflectivity (for example, clay minerals in carbonaceous shales or inertinite in shales).

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FEDERAL AGENCY FOR TECHNICAL REGULATION AND METROLOGY

NATIONAL

STANDARD

RUSSIAN

FEDERATION

MEDICAL PRODUCTS FOR DIAGNOSTICS

IN VITRO

Information provided by the manufacturer with in vitro diagnostic reagents used for biological staining

In vitro diagnostic medical devices - Information supplied by the manufacturer with in vitro diagnostic reagents for staining in biology (IDT)

Official publication

Standardinform

Preface

Goals and principles of standardization in Russian Federation installed Federal law dated December 27, 2002 No. 184-FZ “On technical regulation”, and the rules for the application of national standards of the Russian Federation - GOST R 1.0-2004 “Standardization in the Russian Federation. Basic provisions"

Standard information

1 PREPARED by the Laboratory of Clinical and Laboratory Diagnostics Research Institute of Public Health and Health Care Management of the State Budgetary educational institution higher vocational education First Moscow State medical University them. I. M. Sechenov" of the Ministry of Health of the Russian Federation based on its own authentic translation into Russian international standard specified in paragraph 4

2 INTRODUCED by the Technical Committee for Standardization TC 380 “Clinical laboratory tests and medical devices for in vitro diagnostics”

3 APPROVED AND ENTERED INTO EFFECT by Order Federal agency on technical regulation and metrology dated October 25, 2013 No. 1201-st.

4 This standard is identical to the international standard ISO 19001:2002 “In vitro diagnostic medical devices. Information supplied by the manufacturer with in vitro diagnostic reagents for staining in biology" (ISO 19001:2002 "/l vitro diagnostic medical devices - Information supplied by the manufacturer with in vitro diagnostic reagents for staining in biology").

The name of this standard has been changed relative to the name of the specified international standard to bring it into compliance with GOST R 1.5 (subsection 3.5).

5 INTRODUCED FOR THE FIRST TIME

The rules for applying this standard are established in GOST R 1.0-2012 (section 8). Information about changes to this standard is published in the annually published information index “National Standards”, and the text of changes and amendments is published in the monthly published information index “National Standards”. In case of revision (replacement) or cancellation of this standard, the corresponding notice will be published in the monthly published information index “National Standards”. Relevant information, notices and texts are also posted in the public information system - on the official website of the Federal Agency for Technical Regulation and Metrology on the Internet (gost.ru)

© Standardinform, 2014

This standard cannot be fully or partially reproduced, replicated or distributed as an official publication without permission from the Federal Agency for Technical Regulation and Metrology

A.4.2.3.3 Staining procedure

A.4.2.3.3.1 Deparaffinize and rehydrate tissue sections; carry out a change in antigen (see the above staining procedure)

A.4.2.3.3.2 Incubate with hydrogen peroxide mass fraction 3% in distilled water for 5

A.4.2.3.3.3 Wash with distilled water and place in TBS for 5 minutes.

A.4.2.3.3.4 Incubate with monoclonal mouse anti-human estrogen receptor, optimally diluted in TBS (see A.4.2.3), for 20 - 30 minutes.

A.4.2.3.3.5 Rinse with TBS and place in a TBS bath for 5 minutes.

A.4.2.3.3.6 Incubate with a working solution of biotinylated goat anti-mouse/rabbit immunoglobulin antibody for 20 - 30 minutes.

A.4.2.3.3.7 Rinse with TBS and place in a TBS bath for 5 minutes.

A.4.2.3.3.8 Incubate with the working solution of the StreptAvidin-biotin/horseradish peroxidase complex for 20 - 30 minutes.

A.4.2.3.3.9 Rinse with TBS and place in a TBS bath for 5 minutes.

A.4.2.3.3.10 Incubate with the DAB solution for 5-15 minutes (use gloves when handling DAB).

A.4.2.3.3.11 Wash with distilled water.

A.4.2.3.3.12 Conduct contrast staining with hematoxylin solution for 30 s.

A.4.2.3.3.13 Rinse with tap water for 5 minutes.

A.4.2.3.3.14 Rinse with distilled water for 5 minutes.

A.4.2.3.3.15 Dehydrate with ethanol at a volume fraction of 50% for 3 minutes, then for 3 minutes at a volume fraction of 70%, and finally for 3 minutes at a volume fraction of 99%.

A.4.2.3.3.16 Wash in two xylene changes, 5 minutes each. A.4.2.3.3.17 Extract into a synthetic hydrophobic resin.

A.4.2.3.4 Suggested dilutions

Optimal staining can be obtained by diluting the antibody in TBS pH = 7.6 mixed by volume from (1 + 50) to (1 + 75) µl when examined on formaldehyde-fixed paraffin sections of human breast cancer. The antibody can be diluted with TBS, mixed in volumes from (1 + 50) to (1 + 100) µl, for use in APAAP technology and avidin-biotin methods in the study of acetone-fixed sections of frozen breast cancer tissue.

A.4.2.3.5 Expected results

The antibody intensively labels the nuclei of cells known to contain a large number of estrogen receptors, such as uterine epithelial and myometrial cells and normal and hyperplastic mammary epithelial cells. Staining is predominantly localized to the nuclei with no cytoplasmic staining. However, cryostat sections containing small or undetectable amounts of estrogen receptor (eg, intestinal epithelium, cardiac muscle cells, brain cells, and connective tissue) show negative results with the antibody. The antibody targets breast carcinoma epithelial cells that express the estrogen receptor.

Fabric dyeing depends on the handling and processing of the fabric prior to dyeing. Improper fixation, freezing, thawing, washing, drying, heating, cutting, or contamination with other tissues or fluids may cause artifacts or false-negative results.

A.5 Demonstration of 7-cells by flow cytometry

WARNING - The reagent contains sodium azide (15 mmol/L). NaN 3 can react with lead or copper to form explosive metal azides. When removing, rinse with plenty of water.

A.5.1 Monoclonal mouse anti-human G cells

The following information applies to monoclonal mouse anti-human 7-knots:

a) product identity: monoclonal mouse anti-human 7-klet, CD3;

b) clone: ​​UCHT;

c) immunogen: human pediatric thymocytes and lymphocytes from a patient with Sezary disease;

d) antibody source: purified mouse monoclonal antibodies;

e) specificity: the antibody reacts with T cells in the thymus, bone marrow, peripheral lymphoid tissue and blood. Most T-cell tumors also express CD3 antigen, but it is absent in non-T-cell lymphoid tumors. Consistent with the model of antigen synthesis in normal thymocytes, the earliest site of detection in tumor cells is the cell cytoplasm;

f) composition:

0.05 mol/l Tris/HCI buffer, 15 mmol/l NaN 3, pH = 7.2, bovine serum albumin, mass fraction 1

IgG isotype: IgGI;

lg purification: protein A sepharose column;

Purity: mass fraction approximately 95%;

Conjugate molecule: fluorescein isothiocyanate isomer 1 (FITC);

- (NR)-ratio: £ 495 nm/£ 278 nm = 1.0 ± 0.1, corresponding to a molar ratio of FITC/protein of approximately 5;

e) handling and storage: stable for three years after isolation at temperatures from 2 °C to 8

A.5.2 Intended use

A.5.2.1 General

The antibody is intended for use in flow cytometry. The antibody can be used for qualitative and quantitative detection of T cells.

A.5.2.2 Type(s) of material

The antibody can be applied to suspensions of fresh and fixed cells, acetone-fixed cryostat sections, and cell smears.

A.5.2.3 Procedure for testing antibody reactivity for flow cytometry

Details of the methodology used by the manufacturer are as follows:

a) Collect venous blood into a test tube containing an anticoagulant.

b) Isolate mononuclear cells by centrifugation on a separation medium; otherwise, the red blood cells are lysed after the incubation step specified in d).

c) Wash mononuclear cells twice with RPMI 1640 or phosphate buffered saline (PBS) (0.1 mol/L phosphate, 0.15 mol/L NaCl, pH = 7.4).

d) To 10 μl of FITC-conjugated monoclonal mouse anti-human T cells, CD3 reagent, add a cell suspension containing 1 to 10 e cells (usually about 100 ml) and mix. Incubate in the dark at 4°C for 30 min [for double staining, R-phycoerythrin (RPE)-conjugated antibody should be added at the same time].

f) Wash twice with PBS + 2% bovine serum albumin; resuspend the cells in an appropriate fluid for analysis on a flow cytometer.

f) Use another FITC (fluorescein isothiocyanate) conjugated monoclonal antibody as a negative control.

e) Fix the precipitated cells by mixing with 0.3 ml of paraformaldehyde with a mass fraction of 1% in PBS. When stored in the dark at 4°C, fixed cells can be kept for up to two weeks.

h) Perform analysis on a flow cytometer.

A.5.2.4 Proposed dilution

The antibody should be used for flow cytometry in concentrated form (10 µl/gest). For use on cryostat sections and cell smears, the antibody must be mixed with a suitable diluent in a volume ratio of (1 + 50) µl.

A.5.2.5 Expected results

The antibody detects the CD3 molecule on the surface of T cells. When assessing the staining of cryostat sections and cell smears, the reaction product should be localized on the plasma membrane.

Fabric dyeing depends on the handling and processing of the fabric prior to dyeing. Improper fixation, freezing, thawing, washing, drying, heating, sectioning, or contamination with other tissues or fluids may cause artifacts or false-negative results.

Appendix YES (reference)

Information on the compliance of reference international and European regional standards with the national standards of the Russian Federation

Table DA.1

Designation of the reference international standard compliance Designation and name of the corresponding national standard *There is no corresponding national standard. Before approval, it is recommended use Russian translation the language of this international standard. Translation of this international standard is in the Federal information center technical regulations and standards.

NATIONAL STANDARD OF THE RUSSIAN FEDERATION

MEDICAL DEVICES FOR IN VITRO DIAGNOSTICS Information provided by the manufacturer with in vitro diagnostic reagents used for staining in biology

In vitro diagnostic medical devices. Information supplied by the manufacturer with in vitro diagnostic reagents for staining in biology

Date of introduction - 2014-08-01

1 area of ​​use

This standard specifies requirements for information provided by manufacturers with reagents used for staining in biology. The requirements apply to manufacturers, suppliers and traders of dyes, dyes, chromogenic reagents and other reagents used for staining in biology. The requirements for information provided by manufacturers specified in this standard are a necessary condition obtaining comparable and reproducible results in all areas of staining in biology.

This standard uses Normative references to the following international and European regional standards:

ISO 31-8, Quantities and units. Part 8. Physical chemistry and molecular physics (ISO 31-8, Quantities and units - Part 8: Physical chemistry and molecular physics)

EH 375:2001 Information to be provided by the manufacturer with in vitro diagnostic reagents for professional use(EN 375:2001, Information supplied by the manufacturer with in vitro diagnostic reagents for professional use)

EH 376:2001, Information supplied by the manufacturer with in vitro diagnostic reagents for self-testing

Note - When using this standard, it is advisable to check the validity of the reference standards in the public information system - on the official website of the Federal Agency for Technical Regulation and Metrology on the Internet or using the annual information index “National Standards”, which was published as of January 1 of the current year, and on issues of the monthly information index “National Standards” for the current year. If an undated reference standard is replaced, it is recommended that the current version of that standard be used, taking into account any changes made to that version. If a dated reference standard is replaced, it is recommended to use the version of that standard with the year of approval (adoption) indicated above. If, after the approval of this standard, a change is made to the referenced standard to which a dated reference is made that affects the provision referred to, it is recommended that that provision be applied without regard to that change. If the reference standard is canceled without replacement, then the provision in which a reference to it is given is recommended to be applied in the part that does not affect this reference.

3 Terms and definitions

This standard uses the following terms with their corresponding definitions:

3.1 information supplied by the manufacturer: All printed, written, graphical or other information supplied or accompanying the in vitro diagnostic reagent.

3.2 label: Any printed, written or graphic information applied to packaging.

Official publication

3.3 in vitro diagnostic reagent: A reagent, used alone or in combination with other in vitro diagnostic medical devices, intended by the manufacturer for in vitro studies of substances of human, animal or plant origin in order to obtain information relevant to the detection, diagnosing, monitoring or treating a physiological condition, health condition or disease or congenital anomaly.

3.4 staining: Adding color to a material by reaction with a dye or chromogenic reagent.

3.5 dye (dye): A colored organic compound which, when dissolved in a suitable solvent, is capable of imparting color to a material.

Note - The physical nature of color is selective absorption (and/or emission) in the visible region of the electromagnetic spectrum between 400 and 800 nm. Dyes are molecules with large systems delocalized electrons (connected TT-electron systems). The light absorption characteristics of colorants are represented by an absorption spectrum in the form of a diagram that compares light absorption and wavelength. The spectrum and wavelength at maximum absorption depend on the chemical structure of the dye, the solvent and the spectral measurement conditions.

3.6 dye, paint (stain): A solution of one or more coloring substances in certain concentrations in a certain solvent, used for coloring.

NOTE The paint may be prepared by directly dissolving the coloring matter in a solvent or by diluting the prepared stock solution with suitable agents.

3.6.1 stock solution of stain: A stable, defined solution of one or more dyes in a higher concentration than that used in dyeing.

NOTE Stability means the constancy of the properties of a coloring matter even in the presence of other coloring substances.

3.7 chromogenic reagent: A reagent that reacts with chemical groups present or induced in cells and tissues to form a colored compound in situ.

Example - Typical chromogenic reagents:

a) diazonium salt;

b) Schiff's reagent.

3.8 fluorochrome: A reagent that emits visible light when irradiated with exciting light of a shorter wavelength.

3.9 antibody (antibody): A specific immunoglobulin formed by B lymphocytes in response to exposure to an immunogenic substance and capable of binding to it.

Note - The molecule of an immunogenic substance contains one or more parts with a characteristic chemical composition, an epitope.

3.9.1 polyclonal antibody: A mixture of antibodies capable of reacting specifically with a specific immunogenic substance.

3.9.2 monoclonal antibody: An antibody capable of specifically reacting with a single epitope of a specific immunogenic substance.

3.10 nucleic acid probe: A single-stranded oligonucleotide or polynucleotide of a certain length, complementary to a specific nucleic acid nucleotide sequence.

3.11 lectin: A protein of non-immunogenic origin with two or more binding sites that recognizes and binds to specific saccharide residues.

4 Requirements for information provided by the manufacturer

4.1 General requirements

4.1.1 Information provided by the manufacturer with reagents used for staining in biology

Information provided by the manufacturer with reagents used for staining in biology should be in accordance with ISO 31-8, ISO 1000, EN 375 and EN 376. Particular attention should be paid to the warnings given in EN 375. In addition, where applicable, the requirements specified in 4.1.2, 4.1.3 and 4.1.4, should be applied to various reagents used for staining in biology.

4.1.2 Product name

The product name must include registration number in CAS and the name and index number of the dye, if applicable.

Note1— CAS registration numbers are Chemical Reference Service (CAS) registration numbers. They are numeric code numbers for substances assigned an index by the Chemical Reference Service to chemical substances.

Note2 - The paint index gives a 5-digit number, C.I. number. and a specially compiled name for most coloring substances.

4.1.3 Description of the reagent

The reagent description must include relevant physical and chemical data, accompanied by information specific to each batch. The data must contain at least the following information:

a) molecular formula including counterion;

b) molar mass (g/mol) precisely indicated, with or without the inclusion of a counter-ion;

c) permissible limits of interfering substances;

For colored organic compounds the data should include:

d) molar absorbance (the content of the pure colorant molecule may be given instead, but not the content of the total colorant);

e) wavelength or number of waves at maximum absorption;

f) thin layer chromatography, high performance liquid chromatography or high performance thin layer chromatography data.

4.1.4 Intended use

A description should be provided that provides guidance on biological staining and quantitative and qualitative procedures (if applicable). The information should include information regarding the following:

a) type(s) of biological material, handling and processing prior to staining, for example:

1) whether cell or tissue samples can be used;

2) whether frozen or chemically fixed material can be used;

3) protocol for tissue handling;

4) what fixing medium can be used;

b) details of the appropriate reaction procedure used by the manufacturer to test the reactivity of a dye, dye, chromogenic reagent, fluorochrome, antibody, nucleic acid probe or lectin used for staining in biology;

c) the result(s) expected from the reaction procedure on the intended type(s) of material in the manner intended by the manufacturer;

d) notes on appropriate positive or negative tissue controls and interpretation of the result(s);

4.2 Additional requirements for specific types of reagents

4.2.1 Fluorochromes

Regardless of the type of application, fluorochromes offered for staining in biology must be accompanied by the following information:

a) selectivity, for example, describing the target(s) that can be demonstrated using specific conditions; wavelengths of excitation and emission light; for antibody-bound fluorochromes, the fluorochrome/protein (F/P) ratio.

4.2.2 Metal salts

Where metal-containing compounds are proposed for use in metal-absorbing staining techniques in biology, the following additional information must be provided:

systematic name; purity (no impurities).

4.2.3 Antibodies

Antibodies proposed for staining in biology must be accompanied by the following information:

a) description of the antigen (immunogenic substance) against which the antibody is directed and if the antigen is defined by a cluster of the differentiation system - CD number. The description should include, if appropriate, the type of macromolecule being detected, part of which is to be detected, the cellular localization and the cells or tissues in which it is found, and any cross-reactivity with other epitopes;

b) for monoclonal antibodies - clone, method of production (tissue culture supernatant or ascitic fluid), immunoglobulin subclass and light chain identity;

c) for polyclonal antibodies, the host animal and whether whole serum or immunoglobulin fraction is used;

a description of the form (solution or lyophilized powder), the amount of total protein and specific antibody, and for a solution, the nature and concentration of the solvent or medium;

f) if applicable, a description of any molecular binders or excipients added to the antibody;

statement of purity, purification technique, and methods for detecting impurities (e.g., Western blotting, immunohistochemistry);

4.2.4 Nucleic acid probes

Nucleic acid probes proposed for staining in biology must be accompanied by the following information:

the sequence of bases and whether the probe is single- or double-helical; molar mass of the probe or number of bases and, if appropriate, number of fractions (in percent) of guanine-cytosine base pairs;

the marker used (radioactive isotope or non-radioactive molecule), point of attachment to the probe (3" and/or 5") and the percentage of the substance labeled on the probe; detectable gene target (DNA or RNA sequence);

e) a description of the form (lyophilized powder or solution) and amount (pg or pmol) or concentration (pg/ml or pmol/ml), if applicable, and, in the case of a solution, the nature and concentration of the solvent or medium;

f) a statement of purity, purification procedures, and methods for detecting impurities, such as high-performance liquid chromatography;

Appendix A (reference)

Examples of information provided by the manufacturer with reagents commonly used

in biological staining techniques

A.1 General provisions

The following information represents examples of procedures and should not be construed as the only way a procedure should be performed. These procedures can be used by a manufacturer to test the reactivity of colorants and illustrate how a manufacturer can provide information to comply with this standard.

A.2 Methyl green dye-pyronine Y A.2.1 Methyl green dye

Information regarding methyl green dye is as follows:

a) product identity:

Methyl green (synonyms: double green SF, light green);

CAS registration number: 22383-16-0;

Name and color index number: basic blue 20, 42585;

b) composition:

Molecular formula including counterion: C 2 bH33M 3 2 + 2BF4";

Molar mass with (or without) counterion: 561.17 g mol" 1 (387.56 g

Mass fraction (content) of methyl green cation: 85%, determined using absorption spectrometry;

Permissible limits of interfering substances, given as mass fractions:

1) water: less than 1%;

2) inorganic salts: less than 0.1%;

3) detergents: not present;

4) colored impurities, including violet crystals: not detectable by thin layer chromatography;

5) indifferent compounds: 14% soluble starch;

d) thin layer chromatography: only one main component is present, corresponding

methyl green;

e) Handling and storage: Stable when stored in a carefully sealed brown bottle at room temperature (18°C to 28°C).

A.2.2 Ethyl green dye

The information relating to the ethyl green dye is as follows:

a) product identity:

1) ethyl green (synonym: methyl green);

2) CAS registration number: 7114-03-6;

3) name and index number of the paints: the name is not included in the paint index, 42590;

b) composition:

1) molecular formula including a counterion: C27H 3 5N 3 2+ 2 BF4";

2) molar mass with (or without) counterion: 575.19 g mol" 1 (401.58 g mol" 1);

3) mass fraction of ethyl green cation: 85%, determined using absorption spectrometry;

Water: less than 1%;

Detergents: none;

c) wavelength of maximum absorption of the dye solution: 633 nm;

d) thin layer chromatography: only one major component is present, which is ethyl green;

A.2.3 Pyronine Y dye

The following information applies to the dye pyronin Y:

a) product identity:

1) pyronine Y (synonyms: pyronine Y, pyronine G, pyronine G);

2) CAS registration number: 92-32-0;

3) name and number in the paint index: the name is not in the paint index, 45005;

b) composition:

1) molecular formula including counterion: Ci7HigN20 + SG;

2) molar mass with (or without) counterion: 302.75 g mol" 1 (267.30 g mol" 1);

3) mass fraction of pyronin Y cation: 80%, determined using absorption spectrometry;

4) permissible limits interfering substances, given as mass fractions:

Water: less than 1%;

Inorganic salts: less than 0.1%;

Detergents: none;

Colored impurities, including violet crystals: not detectable by thin layer chromatography;

Indifferent compounds: 19% soluble starch;

c) wavelength of maximum absorption of the dye solution: 550 nm;

d) thin layer chromatography: only one main component is present, coinciding with pyronin Y;

e) Handling and storage: Stable when stored in a well-closed brown glass bottle at room temperature between 18°C ​​and 28°C.

A.2.4 Intended application of the methyl green-pyronine Y staining method

A.2.4.1 Type(s) of material

Methyl green-pyronine Y dye is used for dyeing fresh-frozen, paraffin-waxed or plastic sections of various types of tissue.

A.2.4.2 Handling and treatment before painting Possible fixatives include:

Carnoy's liquid [ethanol (99% by volume) + chloroform + acetic acid (99% by volume), mixed in volumes of (60 + 30 + 10) ml] or

Formaldehyde (mass fraction 3.6%), phosphate buffered (pH = 7.0); routine drying, cleaning, soaking and paraffin coating, routine section preparation using a microtome.

A.2.4.3 Working solution

Prepare a solution of ethyl green or methyl green from an amount corresponding to the mass of 0.15 g of pure dye, calculated as a colored cation (in the above examples, 0.176 g in each case) in 90 ml of hot (temperature 50 ° C) distilled water.

Dissolve an amount corresponding to the mass of 0.03 g of pyronin Y, calculated as a colored cation (0.038 g in the example above) in 10 ml of 0.1 mol/l phthalate buffer (pH = 4.0). Mix the last solution with a solution of ethyl green or methyl green.

A.2.4.4 Stability

The working solution is stable for at least one week when stored in a tightly sealed brown glass bottle at room temperature between 18°C ​​and 28°C.

A.2.4.5 Staining procedure A.2.4.5.1 Dewax the sections.

A.2.4.5.2 Wet the sections.

A.2.4.5.3 Stain sections for 5 min at room temperature about 22 °C in a working

solution.

A.2.4.5.4 Wash the sections in two changes of distilled water, from 2 to 3 s in each.

A.2.4.5.5 Shake off excess water.

A.2.4.5.6 Activate in three changes of 1-butanol.

A.2.4.5.7 Transfer directly from 1-butanol to a hydrophobic synthetic resin.

A.2.4.6 Expected result(s)

The following results are expected with the types of materials listed in A.2.4.1:

a) for nuclear chromatin: green (Karnov fixative) or blue (formaldehyde fixative); a) for nucleoli and cytoplasm rich in ribosomes: red (Karnov fixative) or lilac-red (formaldehyde fixative);

c) for cartilage matrix and mast cell granules: orange;

d) for muscles, collagen and red blood cells: unstained.

A.3 Feulgen-Schiff reaction

A.3.1 Pararosaniline dye

WARNING -For R 40: possible risk irreversible effects.

For S 36/37: Protective clothing and gloves are required.

The following information applies to the dye pararosaniline.

a) product identity:

1) pararosaniline (synonyms: basic ruby, parafuchsin, paramagenta, magenta 0);

2) CAS registration number: 569-61-9;

3) name and index number of paints: main red 9, 42500;

b) composition:

1) molecular formula including counterion: Ci9Hi 8 N 3 + SG;

2) molar mass with (and without) the antiion: 323.73 g mol" 1 (288.28 g mol" 1);

3) mass fraction of pararosaniline cation: 85%, determined using absorption spectrometry;

4) permissible limits of interfering substances, given as mass fractions:

Water: less than 1%;

Inorganic salts: less than 0.1%;

Detergents: not present;

Colored impurities: methylated homologues of pararosaniline may be present in trace amounts, determined by thin layer chromatography, but acridine is not present;

Indifferent compounds: 14% soluble starch;

c) wavelength of maximum absorption of the dye solution: 542 nm;

d) thin layer chromatography: there is one main component corresponding to

pararosaniline; methylated homologs of pararosaniline in trace amounts;

e) Handling and storage: Stable when stored in a carefully sealed brown bottle at room temperature between 18°C ​​and 28°C.

A.3.2 Intended use of the Feulgen-Schiff reaction

A.3.2.1 Type(s) of material

The Feulgen-Schiff reaction is used for paraffin or plastic sections of various types of tissues or cytological material (smear, tissue print, cell culture, monolayer):

A.3.2.2 Handling and treatment before painting

A.3.2.2.1 Possible fixing agents

Possible fixatives include:

a) histology: formaldehyde (mass fraction 3.6%), phosphate buffered (pH = 7.0);

b) cytology:

1) liquid fixing material: ethanol (volume fraction 96%);

2) air dried material:

Formaldehyde (mass fraction 3.6%), phosphate buffered;

Methanol + formaldehyde (mass fraction 37%) + acetic acid (mass fraction 100%), mixed in volumes (85 +10 + 5) ml.

The material fixed in Buina's fixative is unsuitable for this reaction.

Details of the manufacturer's procedure for testing the reactivity of the chromogenic reagent are given in A.3.2.2.2 to A.3.2.4.

A.3.2.2.2 Pararosaniline-Schiff reagent

Dissolve 0.5 g of pararosaniline chloride in 15 ml of 1 mol/l hydrochloric acid. Add 85 ml aqueous solution K 2 S 2 0 5 (mass fraction 0.5%). Wait 24 hours. Shake 100 ml of this solution with 0.3 g of charcoal for 2 minutes and filter. Store the colorless liquid at a temperature not lower than 5 °C. The solution is stable for at least 12 months in a tightly sealed container.

A.3.2.2.3 Wash solution

Dissolve 0.5 g of K 2 S 2 O s in 85 ml of distilled water. Add 15 ml of 1 mol/l hydrochloric acid. The solution is ready for immediate use and can be used within 12 hours.

A.3.2.3 Staining procedure

A.3.2.3.1 Dewax the paraffin sections in xylene for 5 min, then wash for 2 min, first in ethanol with a volume fraction of 99%, and then in ethanol with a volume fraction of 50%.

A.3.2.3.2 Wet plastic sections, dewaxed paraffin sections and cytological material in distilled water for 2 minutes.

A.3.2.3.3 Hydrolyze the material in 5 mol/l hydrochloric acid at a temperature of 22 °C for 30 to 60 minutes (the exact hydrolysis time depends on the type of material).

A.3.2.3.4 Rinse with distilled water for 2 minutes.

A.3.2.3.5 Stain with pararosaniline reagent for 1 hour.

A.3.2.3.6 Wash in three successive changes of washing solution for 5 minutes each.

A.3.2.3.7 Rinse twice with distilled water, for 5 minutes each time.

A.3.2.3.8 Dehydrate in ethanol with a volume fraction of 50%, then with 70% and finally in 99% ethanol, for 3 minutes each time.

A.3.2.3.9 Wash twice in xylene, for 5 minutes each time.

A.3.2.3.10 Extract into a synthetic hydrophobic resin.

A.3.2.4 Expected results

The following results are expected with the types of materials listed in A.3.2.1:

For cell nuclei (DNA): red.

A.4 Immunochemical demonstration of estrogen receptors

WARNING - Reagent containing sodium azide (15 mmol/L). NaN 3 can react with lead or copper to form explosive metal azides. When removing, rinse with plenty of water.

A.4.1 Monoclonal mouse anti-human estrogen receptor

The following information applies to monoclonal mouse anti-human estrogen receptor.

a) product identity: monoclonal mouse anti-human estrogen receptor, clone 1D5;

b) clone: ​​1D5;

c) immunogen: recombinant human estrogen receptor protein;

d) antibody source: mouse monoclonal antibody supplied in liquid form as tissue culture supernatant;

e) specificity: the antibody reacts with the L-terminal domain (A/B region) of the receptor. When immunoblotted, it reacts with a 67 kDa polypeptide chain obtained by transforming Escherichia coli and transfecting COS cells with plasmid vectors expressing the estrogen receptor. In addition, the antibody reacts with cytosolic extracts of luteal endometrium and MCF-7 human breast cancer cells;

f) cross-reactivity: the antibody reacts with rat estrogen receptors;

e) composition: tissue culture supernatant (RPMI 1640 medium containing fetal calf serum), dialyzed against 0.05 mmol/L Tris/HCI, pH = 7.2, containing 15 mmol/L NaN3.

Ig concentration: 245 mg/l;

Ig isotype: IgGI;

Light chain identity: kappa;

Total protein concentration: 14.9 g/l;

h) handling and storage: stable for up to three years at storage temperatures between 2 °C and 8 °C.

A.4.2 Intended use

A.4.2.1 General

The antibody is used for qualitative and semi-quantitative detection of estrogen receptor expression (eg, breast cancer).

A.4.2.2 Type(s) of material

The antibody can be applied to formalin-fixed paraffin sections, acetone-fixed frozen sections, and cell smears. In addition, the antibody can be used to detect antibodies by enzyme-linked immunosorbent assay (ELISA).

A.4.2.3 Staining procedure for immunohistochemistry

A.4.2.3.1 General

A variety of sensitive staining technologies are used for formalin-fixed paraffin tissue sections, including immunoperoxidase, APAAP (alkaline phosphatase anti-alkaline phosphatase) and avidin-biotin methods, such as LSAB (Labeled StreptAvidin-Biotin) methods. Antigen changes, such as heating in 10 mmol/L citrate buffer, pH = 6.0, are mandatory. Slides should not be allowed to dry during this processing or during the subsequent immunohistochemical staining procedure. The APAAP method has been proposed for staining cell smears.

Details of the procedure used by the manufacturer on formalin-fixed paraffin tissue sections to examine antibody reactivity for immunohistochemistry are given in A.4.2.3.2 to A.4.2.3.4.

A.4.2.3.2 Reagents

A.4.2.3.2.1 Hydrogen peroxide, mass fraction 3% in distilled water.

A.4.2.3.2.2 Tris buffer saline (TBS), consisting of 0.05 mol/l Tris/HCI and 0.15 mol/l NaCI at pH =

A.4.2.3.2.3 Primary antibody consisting of monoclonal mouse anti-human estrogen receptor, optimally diluted in TBS (see A.4.2.3.4).

A.4.2.3.2.4 Biotinylated goat anti-mouse/rabbit immunoglobulin antibody, working

Prepare this solution at least 30 minutes, but not earlier than 12 hours before use, as follows:

5 ml TBS, pH = 7.6;

50 µl of biotinylated, affinity-isolated goat anti-mouse/rabbit immunoglobulin antibody in 0.01 mol/l phosphate buffer solution, 15 mmol/l N3, in sufficient quantity to bring the final concentration to 10 - 20 mg/ml.

A.4.2.3.2.5 StreptAvidin-biotin/horseradish peroxidase complex (StreptABComplex/HRP), working

Prepare this solution as follows:

5 ml TBS, pH = 7.6;

50 µl StreptAvidin (1 mg/l) in 0.01 mol/l phosphate buffer solution, 15 mmol/l NaN 3 ;

50 μl of biotinylated horseradish peroxidase (0.25 mg/l) in 0.01 mol/l phosphate buffer solution, 15 mmol/l NaN 3 ;

A.4.2.3.2.6 Diaminebenzidine substrate (DAB) solution

Dissolve 6 mg of 3,3"-diaminebenzidine tetrahydrochloride in 10 ml of 0.05 mol/l TBS, pH = 7.6. Add 0.1 ml of hydrogen peroxide with a mass fraction of 3% in distilled water. If precipitation occurs, filter.

A.4.2.3.2.7 Hematoxylin

Dissolve 1 g of hematoxylin, 50 g of aluminum potassium sulfate, 0.1 g of sodium iodate and 1.0 g of citric acid in 750 ml of distilled water. Make up to 1000 ml with distilled water.

Knowledge of the basics of coal formation processes and the conditions for the applicability of solid fuels in metallurgy allows you to flexibly manage technological processes And economic efficiency production of iron and steel.

The use of fossil fuels in metallurgy dates back one hundred years. The source material and conditions of formation of fossil fuels became the reason for their species diversity. Modern metallurgy presents high requirements to the quality of raw materials, incl. to coke and blown additives. Knowledge of the basics of coal formation processes and the conditions for the applicability of solid fuels in metallurgy allows you to flexibly manage technological processes and the economic efficiency of iron and steel production.

Composition and structure of the original plant material

The currently established theory of coal formation implies the origin of combustible fossils from plant mass that has undergone a certain metamorphism over a long period of time.

A variety of plants, from single-celled algae to trees, took part in the formation of the source material for all fossil fuels. According to modern concepts, the structure of plants contains substances of the following chemical groups: fats, waxes, resins, carbohydrate complexes (cellulose and pectin substances), lignin, proteins.

Fats widely distributed in plants: they contain about 1,700 different types of fats. According to their chemical composition, fats are esters of trihydric alcohol - glycerol - and saturated and unsaturated fatty acids (monocarboxylic acids, with a normal carbon chain and an even number of carbon atoms). Fats are insoluble in water, but easily soluble in diethyl ether, carbon disulfide, gasoline, and aromatic hydrocarbons.

Waxes are esters of higher monocarboxylic acids and higher primary monohydric alcohols of normal structure. Waxes in plants cover the stems, leaves, and spore shells with a thin layer, protecting them from external influences. Waxes have a high melting point for organic materials (70...72 °C). They are extremely stable substances and, due to their stability, are almost always present in coals.

Resins. Plant resins are a mixture of various organic compounds (acids, esters, alcohols, phenols and hydrocarbons). Resins are inherent higher plants, in which they are found in solutions of essential oils (balms). In plants, resin passages are filled with balsams. When a plant is damaged, resin concentrates are released abundantly, which quickly thicken in air as a result of the evaporation of essential oils, as well as due to partial polymerization of resin substances. Such clots of solid resin come to us in the form of resin nodules embedded in the organic part of coal.

Cellulose(C6H10O5) – main construction material plant tissues, giving plants mechanical strength.

Hemicelluloses(heteropolysaccharides) are complex organic compounds, the hydrolysis of which produces the simplest sugars (pentoses, hexoses, etc.).

Pectic substances– perform a supporting function in the walls of plant cells, young fruits and tissues.

Lignin is a polymer of aromatic nature. Participates in the formation of plant cell walls. The formation of lignin is characteristic only of vascular plants. During the period of evolution (plants reached land), vascular plants acquired the ability to produce enzymes capable of forming lignin from carbohydrates. Lignin plays the role of a cementitious substance, gluing together bundles of cellulose fibers, and thus makes up the main part of wood. The approximate content of lignin in some plants (% wt.) is: beech - 22, spruce - 27, tree alfalfa - 23, clubmoss - 37, cuckoo flax - 38, sphagnum (a special genus of moss) - 4.5.

Squirrels– natural products of macromolecular structure that are converted during hydrolysis into alpha amino acids. One of the most important properties of proteins, which is absent in other plant chemical groups, is specificity.

The elemental composition of coal formers is given in Table. 1:

Table 1. Elemental composition of coal formers

Quantitative content of chemical groups of substances in various types plants are given in table. 2.

Table 2. Content of main groups of chemical substances in plants, % (wt.)

Initial plant material and its transformations during coal formation processes

Depending on the composition of the original plant material, coals are divided into humus, sapropelite, liptobiolite and mixed.

Humus coals are formed from land plants.

Liptobiolite coals are also formed from terrestrial vegetation, but from the most persistent plant components in natural conditions - integumentary tissues (cuticles, bark, resins, spores, pollen).

Sapropelite coals are formed exclusively from accumulations of algae - green, blue-green.

Mixed coals They are a product of joint transformations of various terrestrial and aquatic vegetation.

Along with the source material, the composition and properties of coals are also influenced by the physical and geographical conditions under which the accumulation of plant material occurred. This concept covers the landscape environment, divided into lake, swamp, sea, lagoon, etc., and its physical and chemical (hydrochemical and microbiological) features, including salinity, flow, stagnation, etc.

The most important condition ensuring the possibility of the formation of coal is the lack of access to the source material of atmospheric oxygen. The formation conditions and types of coals are given in Table. 3.

Table 3. Formation conditions and types of coals

The initial substance of coals (main mass)	Conditions of formation at the stage of diagenesis	Coal classification
Lignin and cellulose	Regenerative environment of stagnant groundwater, enriched with humic acids. Alkaline phenolic environment. Presence of sphagnum.	Humus coals	Claren (vitren, micrinite, fusain) Duren (from Latin duris (solid)	Banded coal (Splint or “anthraxylon” from anthrax (coal) and xylon (wood)
Cuticles		Liptobiolite coals		Non-banded coal (“attritus” lat. attritys (worn out)
Sapropelites (remains of lower plants, algae - from the Greek sapros- (rotten) and pelos- (dirt)	Accumulation in closed lake and lagoon reservoirs.	Sapropelite coals	Kennel, Boghead, Torbanite, Shales

Only humic, banded coals can be coking, i.e. Claren coals:

• Claren (Latin clarus - shiny) is a coal composed of components rich in carbon and microimpurities: vitrain, micrinite and fusain.
• vitren, vitritis, vitrinite (Latin vitrum - glass) - black shiny, hydrocarbon-rich plant tissue - the main carrier of sintering properties. Forms “lenses” and “layers” in the bulk of coal.
• micrinite is a matte black component made from plant spores.
• fusain, fusinite (French fusain - lens) - black powdery, similar charcoal with a silky shine.

Classification of coals by degree of metamorphism

Differences in the source material, the degree of water content of peatlands, the chemical composition of the environment and the facial conditions of sedimentation and peat accumulation, which determine the direction and intensity of oxidative and reductive microbiological processes, created the basis in the peat stage for the formation of various genetic types of coals. Peat formation and peat accumulation culminated in the overlapping of the peat bog with sediments forming roof rocks. Diagenetic (compaction, dehydration of sediments, gas release) and biochemical processes of a reducing nature that occurred at relatively low temperatures and pressure led to the transformation of peat into brown coal.

Coals containing weakly decomposed woody remains cemented by earthy coal, called lignites.

Brown coals- one of the varieties of coals - are widespread. The share of brown coal and lignite reserves in world coal reserves is 42%. The shallow location and high thickness of coal seams make it possible to widely use open method development, the economic and technical advantages of which largely compensate for the relatively low quality of raw materials.

As a result of prolonged exposure elevated temperatures and pressure, brown coals are transformed into hard coals, and the latter into anthracite. The irreversible process of gradual change in the chemical composition (primarily in the direction of carbonization), physical and technological properties of organic matter in transformations from peat to anthracite is called carbonification. Coalification at the stages of transformation of brown coals into hard coals and the latter into anthracites, caused by processes occurring in the earth's crust, is called coal metamorphism. There are three main types of coal metamorphism:

• regional, caused by the influence of the internal heat of the Earth and the pressure of the overlying rock strata when coals are immersed deep in the earth’s crust;
• thermal - under the influence of heat generated by magmatic bodies that overlap or penetrate into the coal-bearing strata, or into the underlying sediments;
• contact - under the influence of the heat of igneous rocks that have penetrated into coal seams or crossed them directly; problematically, metamorphism of coals is recognized as possible due to increased temperatures in areas of manifestation of tectonic compressive and shearing forces - dynamometamorphism.

The structural and molecular rearrangement of organic matter during coal metamorphism is accompanied by a consistent increase in the relative carbon content in them, a decrease in the oxygen content, and the release of volatile substances; in certain patterns with extreme values ​​at the middle stages of coalification, the hydrogen content, heat of combustion, hardness, density, fragility, optical, electrical, etc. change. physical properties coals. To determine these stages, the following are used: the yield of volatile substances, carbon content, microhardness and other features of the chemical composition and physical properties of coals. The most effective method for determining the stage of coalification is by the reflectivity of vitrinite.

Stone coals at the middle stages of metamorphism, they acquire sintering properties - the ability of gelified and lipoid components of organic matter to transform when heated under certain conditions into a plastic state and form a porous monolith - coke. The relative amount of coal reserves with high caking ability is 10...15% of the total reserves of hard coal, which is associated with a higher intensity of transformation of organic matter in the middle stages of metamorphism. Caking coals occur at temperatures from approximately 130 to 160...180 °C with a general range of temperatures that determine the occurrence of coal metamorphism, from 70...90 °C for long-flame coals to 300...350 °C for anthracites. The highest quality caking coals were formed in basins that experienced regional metamorphism during deep dive coal-bearing strata. During thermal and contact metamorphism, due to a sharp change in temperature and low pressure, the transformation of organic matter proceeds unevenly and the quality of coal is characterized by inconsistent technological properties. Rocks of coal-bearing formations, along with coal metamorphism, undergo catagenetic transformations.

In aeration zones and active action Underground water near the Earth's surface, coals undergo oxidation. In terms of its effect on the chemical composition and physical properties of coals, oxidation has the opposite direction compared to metamorphism: coals lose their strength properties (before they are converted into a sooty substance) and caking ability; the relative oxygen content in them increases, the amount of carbon decreases, humidity and ash content increase, and the heat of combustion sharply decreases. The depth of coal oxidation, depending on the modern and ancient topography, the position of the groundwater table, the nature of climatic conditions, the material composition and metamorphism of coals, ranges from 0 to 100 m vertically.

Differences in the material composition and degree of metamorphism led to a great differentiation of the technological properties of coals. To establish the rational direction of industrial use of coals, they are divided into grades and technological groups; This division is based on parameters characterizing the behavior of coals during thermal exposure. The boundary between brown and hard coals is taken to be the highest calorific value of the working mass of ash-free coal, equal to 5700 kcal/kg (23.86 MJ).

The leading indicator when using coal for energy purposes is lower heat combustion - in terms of working fuel, it fluctuates within the range (kcal/kg): 2000...5000 (8.372...20.930 MJ) for brown coals, 4100...6900 (17.162...28.893 MJ) for hard coals and 5700 ...6400 (23.86...26.79 MJ) for anthracite. The reduced value of this indicator in brown coals is explained by the low degree of carbonization of organic matter, weak compaction of the material and, accordingly, their high natural moisture content, varying in the range of 15...58%. Based on the working moisture content, brown coals are divided into technological groups: B1 with Wp > 40%, B2 with Wp 30...40% and B3 with Wp< 30%.
The industrial marking of bituminous coals is based on indicators characterizing the results of their high-temperature dry distillation (coking): the yield of volatile substances formed during the decomposition of organic mass (partially inorganic material - sulfides, carbonates, hydrated minerals), and the characteristics of the ashless combustible residue - coke in terms of caking properties . The weight yield of volatile substances from coals consistently decreases with increasing degree of carbonification from 45 to 8% for hard coals and to 8...2% for anthracites.

In the USSR, the caking ability of coals is determined in a laboratory apparatus by the plastometric method proposed in 1932 by Soviet scientists L. M. Sapozhnikov and L. P. Bazilevich, based on the thickness of the plastic layer formed during heating (y) taking into account shrinkage (x), expressed in mm. The highest sintering ability is characterized by coals of the middle stages of coalification with a plastic layer thickness of 10...35 mm (grades K and Zh). With a decrease and increase in the degree of metamorphism, the caking ability of coals decreases. Coals of grades D and T are characterized by a slightly baked powdery non-volatile residue. In table Table 4 shows the values ​​of the main indicators of coal quality at various stages of coalification in relation to grades in accordance with GOST.

Table 4. Main quality indicators of graded coals

Coal grades	Letter designation of brands	Average values ​​of indicators for coals consisting predominantly of vitrinite			Reflectivity of vitrinite in oil immersion R0, %
		Yield of volatile substances Vg, %		Heat of combustion Qgb, kcal/kg
		41 or more	76 or less
Long flame		39 or more
Coke
Lean-sintering
Anthracites			91 or more

In addition to those indicated in the table, in some basins there are intermediate grades: gas fatty (GZh), coke fatty (KZh), coke second (K2), low-caking (SS). Coals of grades G, GZh, Zh, KZh, K and OS are divided into technological groups according to their sintering ability; to indicate the technological group, a number is added to the letter designation of the brand indicating lowest value thickness of the plastic layer (y) in these coals, for example G6, G17, KZh14, etc. For coals from specific basins, the values ​​of classification indicators (VG and y) are regulated by GOST. To produce metallurgical coke, a mixture of different grades of coal is used - a charge, the main component of which is coal with high sintering properties.

The division of coal into brown, bituminous and anthracite is accepted in most European countries (in some, with additional separation of lignites). The International System of Classification of Hard Coals, adopted in 1956 by the UN Economic Commission for Europe, is also based on the yield of volatile substances for coals with V >33% - the higher calorific value of the wet ash-free mass, caking ability and coking ability. The type of coal is indicated by a three-digit code number, the first digit of which indicates the class of coal (by volatility or heat of combustion), the second - the group (by sintering ability, determined by the Rog method or the swelling index in the crucible), the third - the subgroup (by coking ability, determined by Odiber methods). Arnoux or Gray-King). In the USA and some other countries, coals are divided into lignites, subbituminous, bituminous coals and anthracites; classification parameters are adopted: for lignites, subbituminous and bituminous (with a volatile yield >31%) coals - the heat of combustion of the ash-free mass, for bituminous with volatile<31% и антрацитов – выход летучих веществ и содержание связанного углерода.

Coal marking, reflecting a complex of certain technological properties of coal varieties, is used as the main criterion in the practice of industrial use of coal. For specific areas of consumption, additional technical requirements are established. A sharp decrease in the thermal effect of coal combustion and the economic indicators of their use due to ballast (ash and moisture) determines the need for briquetting coals with high natural humidity and preliminary enrichment of high-ash coals. The maximum ash content of coals sent for layer combustion should not exceed 20...37%, for pulverized combustion - 45%.

For coking, low-ash (enriched) caking coals are used, in which the content of sulfur and phosphorus is limited. For semi-coking, gasification, production of liquid fuel, rock wax and other areas of consumption, caking ability, sulfur content, ash content, lumpiness, thermal resistance, resin content, bitumen content and other quality indicators are standardized.

The main coal basins of the Russian Federation are sources of coking coals

Donetsk basin. One of the largest European coal basins. On the territory of the Rostov region there is only the extreme eastern part of the basin, where anthracite is predominantly distributed. Coking coals are available in three out of seven regions - Kamensko-Gundorovsky, Belokalitvensky, Tatsinsky - and are characterized by easy and medium washability. Coals from the Donetsk basin are characterized by high sulfur content.

Kuznetsk basin. It is located on the territory of the Kemerovo and Novosibirsk regions and covers an area of ​​27 thousand km2 (110 x 350 km). Of the 25 geological-industrial regions, coking coal is developed in 20. The washability of coal is light and medium with a concentrate yield of 70 to 90%. Coals from the Kuznetsk basin are characterized by low sulfur content. All grades of coking coal are mined in the basin. Favorable mining and geological conditions for the occurrence of coals and the shallow depth of their mining make the use of these coals economically feasible throughout almost the entire territory of Russia.

Pechora pool. It is part of the Northern region and is located on the territory of the Komi Republic and the Nenets Autonomous Okrug of the Arkhangelsk region. The basin area is 90 km2. Coking coals are common in the Vorkuta, Vorgashorskoye and Khalmeryuskoye deposits. Coals are mainly medium-enriched (the concentrate yield is from 70 to 85% (wt.), coals of the GZhO, K, Zh grades are easily enriched (the concentrate yield is 85-93% wt.). Fatty and gaseous fatty coals of the Vorkutinskoye and Vorgashorskoye deposits can be taken into as a lean additive up to 50% of lean coals with a significant increase in coke strength.Coal grade K from the Khalmeryu deposit during coking produces strong metallurgical coke of high quality.

Karaganda basin. It is a source of coking coal for enterprises in the East of Russia; it is located in Central Kazakhstan on the territory of the region of the same name. Its area is 3000 km2 (30 x 100 km). Coals are difficult to enrich, because mineral components are very finely distributed in the organic mass of coal. The concentrate yield ranges from 15 to 65% (wt).

Quality indicators of coking coals

The quality of coals is determined by their technological and petrographic indicators.

Volatile yield (V)– products, excluding moisture, released from coal in the form of gas and steam. They are formed during the decomposition of coal under heating conditions without air access. They are determined to be dry (dry - Vd) or dry ash free (Vdaf). Together with sinterability, it determines the suitability of coals for coking. It is this indicator that is key when compiling a coal charge and considering the possibility of replacing coal in the charge.

Ash content (A)– content of non-combustible inorganic material in coal. Defined as the residue formed when coal is heated as a result of combustion of the entire combustible mass. Determined for dry condition (dry – Ad).

Sulfur (S)– sulfur content in coal. Contained in the form of sulfides, sulfates, organic compounds and elemental sulfur. Determined for dry condition (dry – Sd).

Vitrinit (Vt)– one of the types of organic matter (macerals) that forms a mass of coal. In addition to vitrinite, liptinite and inertinite are distinguished. Vitrinite is the most valuable maceral.

Vitrinite reflectance index (R0)– the reflectivity of vitrinite is an indicator of the degree of metamorphism of coals (the more, the older the coal). To characterize the degree of carbonization, the average reflectance of vitrinite in ordinary monochromatic light is determined.

Plastic layer thickness (y)– one of the main indicators of coal caking, characterizing the assessment of the quality of coking coals. Defined as the maximum distance between the interface surfaces “coal - plastic mass - semi-coke”, determined during plastometric tests.

Fixed carbon (FC)- the part of carbon that remains when coal is heated in a closed vessel until volatile substances are completely removed (i.e., this is the non-volatile part minus ash).

Total Moisture (TM)– moisture contained in fossil coal, including free, surface and bound. During coking, moisture negatively affects the bulk density of the coal charge, energy consumption for crushing and heat for coking; When the humidity is more than 8%, it becomes difficult to transport the charge in coal preparation shops.

Gray King coking index– this indicator is the main characteristic of coal coking ability; Gray-King coke type is determined according to the reference scale: A, B, C, D, E, F, G1, G2,..., G12; coke type "A" indicates that the coal does not coke, types "B", "C", "D" indicate low coking properties,..., types "G5" - "G12" indicate high coking properties of coals, Moreover, the higher the number, the better the coking ability.

Crucible Swelling Number (CSN)/Free Swelling Index (FSI)– the main characteristic by which the caking ability of coals around the world is assessed; Caking ability is one of the most important classification indicators for coals used for coking; the sinterability of the coal charge must be sufficient to ensure high strength of the coke substance (as a rule, the higher the CSN value, other things being equal, the better).

Maximum fluidity according to Gieseler (Gieseler Max Fluidity)– well-caking coals are determined using the Gieseler method; This parameter is very important for coking coals, because low-fluidity coals are not able to independently participate in the coking process (they require the addition of high-fluidity coals for binding); to compare this parameter, a logarithmic (ordinal scale) is used.

Grindability Index (Hardgrove Index)– empirical index achieved by grinding a coal sample. Grinding of narrowly classified coal weighing 50 g is carried out in a ring ball mill for 60 revolutions. The index is determined based on the particle size distribution of crushed coal.

Classification of coking coals

In Russia and the CIS there is a Unified Classification of Coals according to GOST 25543-88. According to this classification, coal is divided into the following grades:

• B – brown;
• D – long-flame;
• DG – long-flame gas;
• G – gas;
• GZhO – gas fatty lean;
• GZh – gas fatty;
• F – fat;
• KZh – coke fatty;
• K – coke;
• KO – coke-leaned;
• KSN – low-metamorphosed sintered coke;
• KS – low-caking coke;
• OS – lean sintering;
• TS – skinny caking;
• SS – low-caking;
• T – skinny;
• A – anthracite.

The world classification divides coals into Hard Coking Coal (HCC), Semi-soft Coking Coal (SSCC), Pulverised Coal for Injection (PCI), Thermal Coal/Steam Coal (Fig. 1):

Figure 1 - World classification of coals

The ratio of world coal reserves and directions of their use depending on carbon and moisture content is shown in Fig. 2:

Figure 2 - Ratio of world coal reserves

PUT – pulverized coal fuel

History of the development of pulverized coal fuel injection technology

The technology of blast furnace smelting using pulverized coal fuel has been known since 1831. The industrial application of pulverized coal injection technology began only in the middle of the 20th century, and this technology became widespread in the 80s of the 20th century. The long period of development of pulverized coal technology can be explained by the need to develop complex and expensive equipment for the preparation and injection of pulverized coal, as well as successful competition from fuel oil and natural gas.

The first patent for the injection of crushed solid fuel into a blast furnace through tuyeres was issued in England in 1831. A similar patent was issued in Germany in 1877. Data on the beginning of the practical use of pulverized coal vary: according to some sources, the first attempts at injection were made in 1840, according to others, the first injection of crushed coal into a shaft furnace was carried out in Canada during the smelting of blister copper in 1911.

Large-scale experimental work on pulverized coal injection began in the 50-60s of the twentieth century in the USA. At that time, fuel oil played a leading role in fuel injection technology.
In 1955 in the USSR at the metallurgical plant named after. Dzerzhinsky conducted experiments on injecting coal dust through a tuyere into a blast furnace with a volume of 427 m3 during the smelting of ferrosilicon. These experiments marked the beginning of research into the blast furnace process using pulverized fuel in industrial blast furnaces of the USSR.

It was only after the energy crisis in the 70s that attention turned to coal as a more reasonable economic alternative. The practice of injecting fuel oil and other oil derivatives used in the 70s of the twentieth century ensured coke consumption at the level of 400 kg/t of pig iron. The second oil crisis forced the abandonment of liquid injection and sharply increased coke consumption.

The 1980s saw a period of rapid growth in the construction of pulverized coal injection plants around the world, mainly in Europe and Asia. In North America, injection of natural gas together with other types of liquid and solid fuels has become popular. By the end of the 80s, pulverized fuel injection significantly replaced other types of fuel in the United States.

Due to the opposite direction of the impact of the processes of injection of pulverized coal and natural gas on the operation of a blast furnace, it became obvious to combine the injection of these types of fuel for a milder effect on the operation of the furnace. In the USA, this technology has become widely used (Table 5):

Table 5. Use of various blown additives in US blast furnaces

The popularity of this solution is explained by the fact that the combination of the two materials provides, under less stringent conditions, the maximum possible coke savings.
To date, as a result of improvements, the technology of pulverized coal injection has found wide practical application. The use of pulverized coal injection technology makes it possible to reduce the specific coke consumption to 325...350 kg/t of cast iron. The leader in specific consumption of pulverized coal is the Netherlands (Fig. 3,). Recently, technology has been actively developing in China ().

Figure 3. PUF injection level

Necessary conditions for the successful implementation of pulverized coal injection technology

To implement the technology of pulverized coal injection into blast furnace smelting, it is necessary to perform a set of the following measures:

• improve coke quality in terms of CSR to 62% or more;
• reduce the ash content of the coking charge to 7.5%;
• ensure high stability of the quality indicators of the charge for coking;
• use coals with an ash content of 6.0-8.5% and a sulfur content of less than 0.5% for pulverized coal;
• ensure the stability of the quality indicators of coals used for pulverized coal;
• ensure the stability of the quality of iron ore charge components;
• reduce the fines content in iron ore raw materials to 3...5%;
• increase the blast temperature to 1200...1250 °C;
• increase the oxygen content in the blast to 28...33%.

In parallel with the reduction in coke consumption when injecting large quantities of pulverized coal, the requirements for coke quality first of all increase ( see section "Download/Supporting literature"), since coke is the only solid material below the cohesive zone of the blast furnace and is consumed here at a slower rate, i.e. is subjected to longer exposure to high temperatures and the weight of the charge column. In this regard, coke must be stronger physically and resistant to chemical attack in order to ensure high gas permeability of the charge.

The strength of coke after reacting with carbon dioxide (CSR - coke stretch reactivity) largely depends on the chemical composition of the ash, which affects the reactivity of the coke.

The composition of blast furnace slag also affects the efficiency of pulverized coal injection - researchers have found a significant moderating effect on the increase in pressure loss resulting from the use of iron ore raw materials with low Al2O3 content.

Features of the combustion of coal dust in the tuyere hearths of a blast furnace

The most important defining requirement of the new technology is to ensure complete combustion of fuel within the tuyere zone of the blast furnace. The release of pulverized coal fuel particles beyond the tuyere zone causes a decrease in the coke replacement coefficient, a deterioration in the viscosity of the slag and the gas permeability of the lower part of the blast furnace.
Complete combustion of coal dust particles in tuyere hearths is determined by the fractional composition of coal, volatile content, temperature of the tuyere zone and oxygen content in the blast.

Based on theoretical and practical research, it has been shown that particles less than 200...100 microns can completely burn within the tuyere zones. The negative side of reducing the size of the injected coal is a significant increase in the costs of preparing pulverized coal, a decrease in the productivity of grinding equipment, an increase in coal losses, etc.
The combustion process of coal particles can be divided into three stages:

1. heating and release of volatile substances;
2. ignition of volatile substances and degassing;
3. combustion of carbon residue and melting of inorganic elements of coal.

The first stage involves heating a coal particle from ambient temperature to 450 °C, proceeds almost instantly and takes no more than 5% of the total combustion time of the particle. The heating time is directly proportional to the particle diameter and inversely proportional to the temperature around the particle. Moreover, the influence of particle diameter on the heating rate is more significant.

In reality, the degassing process and the third stage - combustion of the carbon residue - do not occur strictly sequentially, but overlap each other. That is, combustion of the carbonaceous residue begins before the degassing process is completed. The burning time is determined by the formula:

where ρ is the particle density, g/cm3; d – particle diameter, mm; β is the substance transfer number (cm/s), determined by the Rantz and Marshall equation; C_O2 – oxygen concentration in the gas space, mol/cm3. The combustion of coke residue occupies a significant part of the process, and the combustion time is directly proportional to the diameter of the particles, inversely proportional to the oxygen content and at this stage does not depend on the ambient temperature.

The presented description gives a qualitative description of the combustion process of coal particles in the tuyere hearth. In reality, the combustion process of particles is more complex - during combustion, particles change their speed relative to the flow, the size and shape of particles change, and the coefficients of thermal and thermal diffusivity change. The temperature of the gas environment and the oxygen content in it are also variable quantities.

It should be noted that in the tuyere hearth of a blast furnace the conditions for the combustion of coal dust are more favorable:

• dust is fed into a stream of hot blast with a temperature of 1100...1250 °C, moving at high speed, as a result of which the dust is well heated and dispersed;
• in front of the blast furnace tuyeres there is a significant space with a low concentration of circulating pieces of coke and a high concentration of oxygen - in this volume the flare process of coal dust combustion is developed;
• Unburnt dust particles falling on pieces of heated coke with a film of melt can stick to them and, returning to the tuyere zone, burn.

However, even under such conditions, some of the coal dust may not burn. Reducing the size of the coal particles and increasing the temperature reduces the time required for complete combustion. In this case, an increase in temperature has a greater effect on the completeness of the process than the particle size.

The calculations made show that when particles of 100 microns in size are blown into the tuyere zone and a blast temperature of 1000 °C, during the time the particle is in the tuyere zone (0.01...0.04 s), about 60...80% of the coal will burn, and the rest will reach the zone boundaries in the form of degassed particles. The further behavior of unburned particles can develop according to one of the scenarios:

• secondary gasification of dust carbon using CO2;
• oxidation of coal dust carbon using liquid phase oxides (FeO, SiO2, MnO, etc.);
• trapping of particles in the charge with transition to the lower layers of the blast furnace, followed by combustion in the tuyere hearths.

According to calculations, regardless of the consumption of injected coal, 66% of all unburned coal is carried out through the top, 23% is consumed in the carbon gasification reaction, and the remaining 11% ends up in the central zone of the blast furnace hearth.

A study of the composition of flue dust for the carbon content of coke and blown coal showed that in dry dust the carbon content is about 55%, of which 90% is coke carbon, and 10% is semi-coke carbon from coal dust. Based on the total removal of flue dust, the removal of coal dust through the flue is about 1% of the injected coal.

Coal reactivity, low ash content, low flash point and minimal volatile matter content are the most favorable combination. The content of sulfur and phosphorus is limited by specific smelting conditions and requirements for the content of these elements in cast iron. Thus, with regard to the qualitative characteristics of pulverized coal and the parameters of a blast furnace, the efficiency of its injection is determined by the following fundamental features:

• use of low-ash coals for pulverized coal (5...14%);
• grinding pulverized coal up to 22...75 microns;
• acceptable coal grindability index (HGI);
• uniform supply of pulverized coal to the blast furnace tuyeres (unevenness ±4...10%).

World practice of using coal for pulverized coal

The characteristics of the coals used as pulverized coal are given in Table. 6.

Table 6. Characteristics of coals for pulverized coal

Manufacturer					Caking ability (CSN index)	Fluidity according to Gieseler
	Bayswater No3 PCI
	South Blackwater PCI
Helensburgh Coal	Metropolitan PCI
Australian Premium Coals
Australian Premium Coals

For injection purposes, coals with low coking properties are used - CSN index less than 4 units, fluidity within 200 ddpm. Sulfur content is limited to 0.6%, ash content – ​​no more than 10%.

It should be noted that coals with a high volatile content (32...38%) and low volatile coals (15...20%) are mainly used for injection:

Figure 4 - Content of volatile substances in coals for pulverized coal

Coals with low volatile matter content are characterized by high carbon content, which greatly increases the coke replacement rate. At the same time, high volatile coal has a low coke replacement rate but has good combustion efficiency. In addition, the use of coals with a high content of volatile substances for injection promotes the reduction reaction due to the higher hydrogen content in such coals.

In many cases, in order to improve the technological controllability of the process, coal mixtures of high- and low-volatile coals are used in order to regulate the content of volatile substances and the ash content of the injected pulverized coal. In addition, with the joint injection of pulverized coal and natural gas, for economic efficiency, it is possible to increase the proportion of highly volatile coals in mixtures during periods of increasing natural gas prices. This makes it possible to partially compensate for the reducing ability of the resulting gases due to the hydrogen of volatile substances.

On the curve of the relationship between coal type and plastic properties, coals for injection as pulverized coal (PCI) occupy extreme positions:

Figure 5 - Relationship between coal type and plastic properties

This position of coals for pulverized coal directly affects their price. PCI coal is a category of coals unsuitable for coking. This coal is inferior in price to premium brands of coking coal (-31% on average for the year). But the use of pulverized coal injection technology allows saving expensive coke, which results in superior price over coking coals of the Semi Soft category (+12% on average per year). The dynamics of price changes are shown in Fig. 6.

Figure 6 - Ratio of metallurgical coal quotes

Implementation of pulverized coal injection technology in the Russian Federation

Despite the fact that the first experiments in pulverized coal injection in the USSR date back to the middle of the 20th century, this technology has not yet found wide application at Russian enterprises. Causes:

• availability of excess natural gas reserves;
• complex infrastructure for the preparation, storage and supply of pulverized coal;
• unresolved problems with the supply of pulverized coal to blast furnaces (tuyere design, uniformity of distribution);
• the need for parallel investments in improving the quality of coke and iron ore raw materials.

The last attempt to introduce pulverized coal injection technology in the Russian Federation was the implementation of a project at Tulachermet in 1992...1993. During the experiment, it was not possible to resolve issues related to the supply of pulverized coal to the blast furnace.

Until now, interest in pulverized coal injection technology has been of an academic nature. But changing economic conditions led to a revision of the development strategy of the domestic metallurgy. The current trend of increasing the cost of natural gas for industrial enterprises has pushed the leading metallurgical companies of the Russian Federation to implement projects for the injection of pulverized coal (NLMK, Evraz ZSMK, Evraz NTMK). Taking into account the more complex technical and technological conditions of Russian enterprises (Table 7, see section "Download/Supporting literature") and the quality of the domestic coal base, the implementation of pulverized coal injection projects will be associated with known difficulties, and achieving high indicators in the amount of pulverized coal injected and the coke replacement rate is unlikely.

Table 7. Technological conditions of blast furnaces

However, the transition to new technology is an obvious step towards optimizing the cost of cast iron through a combination of various technological substitutes for coke.

If we talk about the coal base for coal coal in the Russian Federation, then it seems possible to use for these purposes coals with low coking properties (GZhO, SS, TS) and grades of thermal coals bordering on coking (G, T). The combination of highly volatile (G, GZhO) and low-volatile (SS, TS, T) grades will make it possible to create controlled coal mixtures for use as pulverized coal.

The quality and directions of use of coals are largely determined by the composition of the original plant material and the degree of metamorphism. A description of the main qualitative characteristics of metallurgical coals is given. A special place is occupied by coals for use as pulverized coal fuel (PCF). The requirements for the successful implementation of pulverized coal injection technology are listed, the features of pulverized coal combustion in a blast furnace and the features of the implementation of pulverized coal injection technology in the Russian Federation are reflected. Requirements for coals for use as pulverized coal are given and grades of coals for use as pulverized coal are listed.

• pulverized coal fuel
• quality of coals for pulverized coal
• PUT price
• requirements for ITB

Main literature:

Supporting literature:

• Pulverized coal injection on the threshold of a new century ("NChMZR" 02.2001)
• Improving the quality of raw materials when injecting pulverized coal ("NChMZR" 03.2001)
• Requirements for coke quality for blast furnaces with high consumption of pulverized coal ("Steel" 06.2009)
• Prospects for the use of pulverized coal in DCs in Ukraine and Russia ("Steel" 02.2008)

where coefficient k characterizes the capture rate, and the exponent m is the order of the reaction. The value of k varies from 0 to oo. In this case, when Kg is a coefficient taking into account the quality of the base; I is the height of free fall of coal, m.

where P is the angle of inclination of the reflecting surface, degree; W+5~ - content of class larger than 6 mm, %.

Both the nature of the impacts and the external mechanical loads that occur during changes in traffic flow are determined by the design parameters of reloading devices and means of transport: the height of the difference, the rigidity and angle of inclination of the reflective surface, the speed and inclination angle of the feed conveyor and other factors.

growth at an angle and to the horizon from a height h onto the reflecting surface, which in turn is inclined at an angle P. At the point of collision of the reflecting surface and anthracite, the speed of its fall can be decomposed into normal vn and tangential vr components with respect to the reflecting surface. The kinetic energy of the collision is determined by the normal component Y„, which can be determined by the formula

The current classifications consider coal mainly as an energy fuel, so they do not sufficiently reflect the properties important for chemical processing processes. Currently, in many countries, research is underway to develop methods for unambiguously assessing the suitability of any coal for various areas of its technological use, including for processing into motor fuels. In recent years, in the Soviet Union, the development of such a unified classification has been completed: coal days based on their genetic and technological parameters. According to this classification, the petrographic composition of coal is expressed by the content of fusinized microcomponents. The stage of metamorphism is determined by the reflection index of vitrinite, and the degree of reduction is expressed by a complex indicator: for brown coals - by the yield of semi-coking tar, and for bituminous coals - by the yield of volatile substances and sintering ability. Each of the classification parameters reflects certain features of the material composition and molecular structure of coals.

Until 1989, each coal basin had its own classification, established by the corresponding GOST. The basis of these classifications for dividing coals into grades and within each grade into groups were: the yield of volatile substances, the thickness of the plastic layer and the characteristics of the non-volatile residue when determining the yield of volatile substances. Since 1991, the Unified Classification of Hard Coals has been introduced. According to the standard, which provides for new classification parameters, coals are divided into types, depending on the value of the vitrinite reflectance, heat of combustion and the release of volatile substances into brown, stone and anthracite.

Kevich and Yu.A. Zolotukhin tried to develop a method for predicting the strength of coke taking into account the petrographic composition and reflectance of vitrinite. The heterogeneity of coals in the charges in terms of the degree of metamorphism and microlithotype composition was taken into account. The thickness of the plastic layer was also taken into account, as well as the ash content of the predicted charge, calculated by additivity.

As can be seen, within each pair of charges differentiated by batteries there are no noticeable differences in ash content, total sulfur content, or sinterability. The yield of volatile substances is slightly lower for the charges intended for coke oven battery No. 1-bis. The values ​​of complex indicators for all options correspond to or are close to the optimal median values; some preference can still be given to the charges for battery No. 1-bis. In table Figure 6 shows sinterability characteristics confirming this position. Petrographic characteristics of the experimental charges, including the average values ​​of the vitrinite reflectance and the distribution of various stages of metamorphism within the vitrinite component of the coal charges, are presented in Table. 7.

Charge options Vitrinite reflectance index р О/ "0, /О Stage of vitrinite metamorphism, %

petrographic;

The stage of metamorphism is determined by the reflectivity of vitrinite. The essence of the method is to measure and compare the electric currents arising in the photomultiplier tube when light is reflected from the polished surfaces of the sample and the reference sample. The reflectance index of vitrinite for hard coals ranges from 0.40 to 2.59.

Low-rank coals are considered to be coals with a higher calorific value of less than 24 MJ/kg and an average vitrinite reflection index of less than 0.6%;

Coals of a higher rank are considered coals with a higher calorific value equal to or more than 24 MJ/kg, as well as with a higher calorific value of less than 24 MJ/kg, provided that the average vitrinite reflectance is equal to or exceeds 0.6%.

Average vitrinite reflection index, K, "% - two digits

The first two digits of the code indicate the reflectivity of vitrinite corresponding to the lower limit of the 0.1% range of values ​​for the average vitrinite reflectance multiplied by 10;