CN108460243B - Small sample industrial analysis and calculation element analysis method using coal - Google Patents

Small sample industrial analysis and calculation element analysis method using coal Download PDF

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CN108460243B
CN108460243B CN201810108671.8A CN201810108671A CN108460243B CN 108460243 B CN108460243 B CN 108460243B CN 201810108671 A CN201810108671 A CN 201810108671A CN 108460243 B CN108460243 B CN 108460243B
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CN108460243A (en
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陈宇
陈献春
石吉银
林拱光
蒋孝科
朱畅
张民赦
蓝德智
刘周扬
杨永概
林志炜
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Fujian Zhongshisuo Electric Power Industry Co ltd
State Grid Corp of China SGCC
Electric Power Research Institute of State Grid Fujian Electric Power Co Ltd
State Grid Fujian Electric Power Co Ltd
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Fujian Zhongshisuo Electric Power Industry Co ltd
State Grid Corp of China SGCC
Electric Power Research Institute of State Grid Fujian Electric Power Co Ltd
State Grid Fujian Electric Power Co Ltd
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Abstract

The invention relates to an industrial analysis and calculation element analysis method for a small sample by utilizing coal. In the case of a small sample, the carbon content of the coal is calculated according to the corresponding relation between the element analysis of the coal and the industrial analysis through the industrial analysis data of the coalCHydrogen content ofHOxygen contentONitrogen content ofNAnd sulfur contentS，Thereby completing the elemental analysis of the coal. The invention carries out mathematical treatment on the coal quality with small sample number, and the obtained coal has good element analysis precision, and the analysis method has low cost.

Description

Small sample industrial analysis and calculation element analysis method using coal
Technical Field
The invention relates to a method for analyzing and calculating elements by utilizing the industrial analysis of coal, which is used for analyzing basic data required by the test, energy-saving evaluation, environmental protection analysis, off-line and on-line performance analysis of a coal-fired power plant, in particular to a small-sample method for analyzing and calculating the elements by utilizing the industrial analysis of the coal.
Background
The elemental analysis of coal is more elaborate and costly than industrial analysis, but is extremely important data for coal facilities.
The main method for obtaining the elemental analysis of coal at present is chemical analysis, but the method has high cost and low cost of industrial analysis of coal, and most coal-fired power plants are equipped with equipment for industrial analysis of coal at present to carry out daily tests on the coal used. Most coal fired power plants are not equipped with expensive, cost effective, and less efficient equipment for elemental analysis of coal. However, many calculations and evaluations require elemental analysis of coal, which is indispensable data.
The element analysis of the coal has close relation with the industrial analysis, the relation can be evaluated by a mathematical method, although the relation is not actually measured, the precision is higher, and the method can be applied to certain occasions.
The meaning of the mathematical method is not only calculation, but also reveals the relationship between the coal element analysis and the industrial analysis, and further expresses the physical and chemical meanings.
In fact, the analysis of coal may cause deviation due to sampling, assaying, transcription, etc., which may cause the result to deviate from the actual situation, and if the result is checked by a mathematical method, the problems can be found.
Work has been done in mathematical terms and good results have been obtained.
Disclosure of Invention
The invention aims to provide a high-precision and low-cost method for analyzing and calculating elements by utilizing industrial analysis of coal by using small samples.
In order to achieve the purpose, the technical scheme of the invention is as follows: a small sample industrial analysis calculation element analysis method using coal, for industrial analysis, FCad + Mad + Aad + Vad is 100%, for element analysis, Cad + Had + Oad + Nad + Sad + Mad + Aad is 100%, for industrial analysis, the data of industrial analysis is used, the components of element analysis are calculated by using equation system, including calculation by using fixed carbon, moisture and ash, and for calcium element, the method comprises the following steps:
Figure BDA0001567944820000011
wherein: subscripts 1, 2,3, 4 are sets of data 1, 2,3, 4, respectively; subscript t is test data; FCad is air-dry based fixed carbon; mad is air drying base moisture; aad is an air-drying base ash; cad is the carbon content of the air drying base; the cFCMA0, the cFCMA1, the cFCMA2 and the cFCMA3 are coefficient groups needing to be determined through calculation; the sum of 4 industrial analysis components is 100%, so that only any 3 of the components are selected for calculation; wherein, the industrial analysis and the element analysis adopt an air drying base;
if the number of the samples is more than 4, a plurality of equation sets can be formed through combination to be calculated so as to generate a plurality of coefficient sets, and then an average value is taken;
after the calculation is finished, performing precision verification to confirm the calculation effect;
under the condition that a plurality of equation sets are calculated, if the coefficient deviates far from the average value, analysis is needed to be carried out, abnormal test data are eliminated, the elimination method is that each group of element analysis is calculated by the coefficient set after averaging and is compared with the test data, and the abnormal data are obtained if the difference is large.
In one embodiment of the present invention, in the case of an industrial analysis with only 2 variables, the calorific value can be introduced such that 3 variables participate in the calculation; in the case of 3 variables in the industrial analysis, the heat value can also be introduced, so that 4 variables participate in the calculation, the calculation method is the same as that of the 3 variables, and the accuracy of the calculation without the heat value can be compared through checking to determine which algorithm to select.
In one embodiment of the present invention, in the case of only 2 variables in the industrial analysis, the elemental analysis test value of sulfur can be introduced into the calculation so that 3 variables are calculated; under the condition that the industrial analysis has 3 variables, the element analysis test value can be introduced, so that 4 variables are calculated, the calculation method is the same as that of 3 variables, only 5 samples are needed for each group of data, and the accuracy of the element analysis calculation without adding sulfur can be compared through checking to determine which algorithm is selected.
Compared with the prior art, the invention has the following beneficial effects: the invention carries out mathematical treatment on the coal quality with small sample number, and the obtained coal has good element analysis precision, and the analysis method has low cost.
Detailed Description
The following specifically describes the technical means of the present invention.
The invention relates to a small sample industrial analysis calculation element analysis method using coal, which comprises the following steps of (1) for industrial analysis, wherein FCad + Mad + Aad + Vad is 100%, for element analysis, Cad + Had + Oad + Nad + Sad + Mad + Aad is 100%, and for the element analysis, calculating the element analysis components by using an equation system by using industrial analysis data, wherein the method comprises the following steps of calculating by using fixed carbon, water and ash, and for calcium element:
Figure BDA0001567944820000021
wherein: subscripts 1, 2,3, 4 are sets of data 1, 2,3, 4, respectively; subscript t is test data; FCad is air-dry based fixed carbon; mad is air drying base moisture; aad is an air-drying base ash; cad is the carbon content of the air drying base; the cFCMA0, the cFCMA1, the cFCMA2 and the cFCMA3 are coefficient groups needing to be determined through calculation; the sum of 4 industrial analysis components is 100%, so that only any 3 of the components are selected for calculation; wherein, the industrial analysis and the element analysis adopt an air drying base;
if the number of the samples is more than 4, a plurality of equation sets can be formed through combination to be calculated so as to generate a plurality of coefficient sets, and then an average value is taken;
after the calculation is finished, performing precision verification to confirm the calculation effect;
under the condition that a plurality of equation sets are calculated, if the coefficient deviates far from the average value, analysis is needed to be carried out, abnormal test data are eliminated, the elimination method is that each group of element analysis is calculated by the coefficient set after averaging and is compared with the test data, and the abnormal data are obtained if the difference is large.
In the case of an industrial analysis with only 2 variables, the calorific value can be introduced so that 3 variables participate in the calculation; in the case of 3 variables in the industrial analysis, the heat value can also be introduced, so that 4 variables participate in the calculation, the calculation method is the same as that of the 3 variables, and the accuracy of the calculation without the heat value can be compared through checking to determine which algorithm to select.
In the case of an industrial analysis with only 2 variables, the elemental analysis test value of sulfur can be introduced into the calculation so that 3 variables are calculated; under the condition that the industrial analysis has 3 variables, the element analysis test value can be introduced, so that 4 variables are calculated, the calculation method is the same as that of 3 variables, only 5 samples are needed for each group of data, and the accuracy of the element analysis calculation without adding sulfur can be compared through checking to determine which algorithm is selected.
The following is a specific embodiment of the present invention.
The following are specific examples of the present invention.
The invention relates to a small sample industrial analysis and calculation element analysis method by using coal, which is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
step S01: if there are N samples with complete industrial analysis and elemental analysis, the method can be used when N is a small sample (the distinction between large and small samples is not strict, if the number of samples is too small, regression, artificial neural network, etc. cannot be used, but if the number of samples is large, the method can be used as well, and N is usually less than or equal to 10), if any 4 samples of the N samples are combined, i.e. there is N |! /((N-4)! 4!) combinations where N is a finite integer ≧ 4, for example, 4 sets of sample data as follows:
FCad1、Mad1、Aad1、Vad1、Cad1、Had1、Oad1、Nad1、Sad1
FCad2、Mad2、Aad2、Vad2、Cad2、Had2、Oad2、Nad2、Sad2
FCad3、Mad3、Aad3、Vad3、Cad3、Had3、Oad3、Nad3、Sad3
FCad4、Mad4、Aad4、Vad4、Cad4、Had4、Oad4、Nad4、Sad4
wherein subscripts 1, 2,3, 4 are set of data 1, 2,3, 4 respectively, FCad is air-drying-based fixed carbon, Mad is air-drying-based moisture, Aad is air-drying-based ash, Vad is air-drying-based volatile matter, Cad is air-drying-based carbon content, Had is air-drying-based hydrogen content, Oad is air-drying-based oxygen content, Nad is air-drying-based nitrogen content, Sad is air-drying-based sulfur content;
step S02: for industrial analysis, FCad + Mad + Aad + Vad is 100%, the individual parameters are 3, or the degree of freedom is 3,
for elemental analysis, there is 100% Cad + Had + Oad + Nad + Sad + Mad + Aad, 6 independent parameters, or 6 degrees of freedom.
Because Mad and Aad in the complete elemental analysis (i.e. all the items are added to be 1) are the same as the values in the industrial analysis, only the carbon content Cad, the hydrogen content Had, the oxygen content Oad, the nitrogen content Nad and the sulfur content Sad need to be calculated, some units have the testing capability of the sulfur content Sad, if testing is carried out, the calculation can not be carried out, the calculation result of the sulfur content Sad can be used as a reference, and even the test result of the Sad can be used for calculating other elemental analysis components, so that the calculation accuracy is improved;
it is considered that any one of the components in the elemental analysis can be expressed by industrial analysis, and for example, the carbon content Cad can be estimated as follows:
Figure BDA0001567944820000041
in the formula: FCad, t, Mad, t, Aad, t are air drying base fixed carbon, moisture, ash content test values participating in calculation, and volatile components are removed because independent parameters are 3; after the constant term is added, there are 4, namely: the cFCMA0, cFCMA1, cFCMA2, cFCMA3 require constants determined by calculation.
For the minimum sample case when N is 4, the 3 independent parameters in the industrial analysis form the following system of equations:
Figure BDA0001567944820000042
setting:
Figure BDA0001567944820000043
then there are:
FFCMA*cFCMA＝Cad
i.e., cFCMA ═ FFCMA-1*Cad
The cFCMA determination can be used to calculate Cad, i.e., an estimate of air-dried base carbon as:
Figure BDA0001567944820000044
in the formula: FCad, n, Mad, n, Aad, n are air-dried fixed carbon, moisture, ash test values not taking part in the above calculation (i.e. prediction needed) of the coefficient vector cFCMA, since both the industrial analysis and the elemental analysis data taking part in the calculation are known, if moisture is removed:
the industrial analysis matrix is
Figure BDA0001567944820000051
Then there are:
Figure BDA0001567944820000052
Figure BDA0001567944820000053
the air-dry based carbon estimates were:
Figure BDA0001567944820000054
in the formula: FCad, n, Aad, n, Vad, n are air dry basis fixed carbon, ash, volatile test values not participating in the above-mentioned calculated coefficient vector cfcacv.
Or the ash content:
Figure BDA0001567944820000055
then there are:
Figure BDA0001567944820000056
the air-dry based carbon estimates were:
Figure BDA0001567944820000057
or the fixed carbon:
Figure BDA0001567944820000058
then there are:
Figure BDA0001567944820000059
Figure BDA00015679448200000510
the air-dry based carbon estimates were:
Figure BDA00015679448200000511
although different calculation coefficients can be obtained by using different industrial analysis combinations, the estimated value
Figure BDA00015679448200000512
Should be the same.
Similarly, for the calculation of hydrogen element, after removing volatile component, there are
Figure BDA0001567944820000061
The following can be obtained:
hFCMA＝FFCMA-1Had
the estimated air-dry basis hydrogen was:
Figure BDA0001567944820000062
after the water is removed, the
Figure BDA0001567944820000063
Then there are:
Figure BDA0001567944820000064
Figure BDA0001567944820000065
the estimated air-dry basis hydrogen was:
Figure BDA0001567944820000066
after ash is removed, has
Figure BDA0001567944820000067
Then there are:
Figure BDA0001567944820000068
the estimated air-dry basis hydrogen was:
Figure BDA0001567944820000069
after fixed carbon is removed, have
Figure BDA00015679448200000610
Then there are:
Figure BDA00015679448200000611
Figure BDA00015679448200000612
the estimated air-dry basis hydrogen was:
Figure BDA00015679448200000613
for the calculation of the oxygen element, after removal of the volatiles there are:
Figure BDA0001567944820000071
the following can be obtained:
oFCMA＝FFCMA-1Oad
the air-dry basis oxygen estimates were:
Figure BDA0001567944820000072
after removing water
Figure BDA0001567944820000073
Then there are:
Figure BDA0001567944820000074
Figure BDA0001567944820000075
the air-dry basis oxygen estimates were:
Figure BDA0001567944820000076
after ash removal
Figure BDA0001567944820000077
Then there are:
Figure BDA0001567944820000078
the air-dry basis oxygen estimates were:
Figure BDA0001567944820000079
after removing fixed carbon
Figure BDA00015679448200000710
Then there are:
Figure BDA00015679448200000711
Figure BDA00015679448200000712
the air-dry basis oxygen estimates were:
Figure BDA00015679448200000713
for the calculation of nitrogen, after removing the fixed carbon, there are
Figure BDA0001567944820000081
The following can be obtained:
nFCMA＝FFCMA-1Nad
the air-drying based nitrogen estimates were:
Figure BDA0001567944820000082
after removing water
Figure BDA0001567944820000083
Then there are:
Figure BDA0001567944820000084
Figure BDA0001567944820000085
the air-drying based nitrogen estimates were:
Figure BDA0001567944820000086
after ash removal
Figure BDA0001567944820000087
Then there are:
Figure BDA0001567944820000088
the air-drying based nitrogen estimates were:
Figure BDA0001567944820000089
after removing fixed carbon
Figure BDA00015679448200000810
Then there are:
Figure BDA00015679448200000811
Figure BDA00015679448200000812
the air-drying based nitrogen estimates were:
Figure BDA00015679448200000813
for the calculation of elemental sulfur, there are
Figure BDA0001567944820000091
The following can be obtained:
sFCMA＝FFCMA-1Sad
the estimated air-drying based sulfur was:
Figure BDA0001567944820000092
after removing water
Figure BDA0001567944820000093
Then there are:
Figure BDA0001567944820000094
Figure BDA0001567944820000095
the estimated air-drying based sulfur was:
Figure BDA0001567944820000096
after ash removal
Figure BDA0001567944820000097
Then there are:
Figure BDA0001567944820000098
the estimated air-drying based sulfur was:
Figure BDA0001567944820000099
after removing fixed carbon
Figure BDA00015679448200000910
Then there are:
Figure BDA00015679448200000911
Figure BDA00015679448200000912
the estimated air-drying based sulfur was:
Figure BDA00015679448200000913
as characteristics of elemental analysis, there must be:
Cad+Had+Oad+Nad+Sad+Mad+Aad＝100％
however, both the test and the calculated data are difficult to satisfy, and when testing, one can leave one and do not test, and the last result can be obtained by subtracting all tested results by 100%, thus reducing the test cost. For the calculated results, such a method may be adopted, but in order to reduce the error, correction may be performed after all the results are calculated, as follows:
Figure BDA0001567944820000101
namely:
Figure BDA0001567944820000102
due to the importance of environmental protection, sulfur element analysis Sad can be tested in a plurality of coal-using units and a plurality of power plants, but the testing cost is high, the economical efficiency of daily testing is poor, the workload of testing can be reduced by utilizing calculation, and under the condition that the coal quality is not changed greatly, the calculation can be used for more purposes, and the testing is performed less. If the coal quality is changed greatly, more tests can be performed at the moment of the change, and the tests can be reduced later. In the case of insufficient parameters of the industrial analysis (for example, only 2 parameters), the calculation can be performed instead of the missing parameters, and the missing parameters of the industrial analysis can be calculated, for example, in the case of FCad (air drying based fixed carbon) and Mad (air drying based moisture) only, there are:
Figure BDA0001567944820000103
in calculating Had (air drying basis carbon content) there are:
Figure BDA0001567944820000104
at calculation Oad (air dry basis oxygen content) there were:
Figure BDA0001567944820000105
at calculation of Nad (air dry basis nitrogen content) there are:
Figure BDA0001567944820000106
also, for the case of FCad (air drying based fixed carbon) and Aad (air drying based ash) alone, there are:
Figure BDA0001567944820000111
in calculating Had (air dry basis hydrogen content) there are:
Figure BDA0001567944820000112
in calculating Had (air dry basis oxygen content) there were:
Figure BDA0001567944820000113
in calculating Had (air dry basis nitrogen content) there are:
Figure BDA0001567944820000114
for FCad (air drying based fixed carbon) and Vad (air drying based volatile) only, when calculating Cad (air drying based carbon content) there are:
Figure BDA0001567944820000115
in calculating Had (air dry basis hydrogen content) there are:
Figure BDA0001567944820000116
at calculation Oad (air dry basis oxygen content) there were:
Figure BDA0001567944820000121
at calculation of Nad (air dry basis nitrogen content) there are:
Figure BDA0001567944820000122
for the case of Mad (air drying base moisture) and Aad (air drying base ash) alone, there are:
Figure BDA0001567944820000123
in calculating Had (air dry basis hydrogen content) there are:
Figure BDA0001567944820000124
at calculation Oad (air dry basis oxygen content) there were:
Figure BDA0001567944820000125
at calculation of Nad (air dry basis nitrogen content) there are:
Figure BDA0001567944820000126
for the case of Mad (air drying base moisture) and Vad (air drying base volatile) only, when calculating Cad (air drying base carbon content) there are:
Figure BDA0001567944820000131
in calculating Had (air dry basis hydrogen content) there are:
Figure BDA0001567944820000132
at calculation Oad (air dry basis oxygen content) there were:
Figure BDA0001567944820000133
at calculation of Nad (air dry basis nitrogen content) there are:
Figure BDA0001567944820000134
for the case of only Aad (air drying basis moisture) and Vad (air drying basis volatile), when calculating Cad (air drying basis carbon content) there are:
Figure BDA0001567944820000135
in calculating Had (air dry basis hydrogen content) there are:
Figure BDA0001567944820000136
in calculating Had (air dry basis oxygen content) there were:
Figure BDA0001567944820000137
in calculating Had (air dry basis nitrogen content) there are:
Figure BDA0001567944820000141
the calculation formula and normalization method are the same as those in the case of calculation using industrial analysis.
In fact, in the absence of one of the industrial analyses of the assay (i.e. only 2), Sad (elemental sulphur analysis) can be used to calculate the parameters of its absence, in this case in fact two, the sum of only 4 being 100%, which makes the independent parameters 3, for example in the calculation of Aad (air dry basis ash) in the case of known FCad (air dry basis fixed carbon) and Mad (air dry basis moisture):
Figure BDA0001567944820000142
air-dry base ash estimated before normalization:
Figure BDA0001567944820000143
wherein: aFCMS0, aFCMS1, aFCMS2, aFCMS3 are constants.
When calculating Vad (air drying base volatiles) there are:
Figure BDA0001567944820000144
air drying base volatiles estimated before normalization:
Figure BDA0001567944820000145
wherein: vFCMS0, vFCMS1, vFCMS2, vFCMS3 are constants.
The two values above need to be corrected because the normalization requirements need to be met, namely:
Figure BDA0001567944820000146
determination of the coefficient fcms:
Figure BDA0001567944820000147
if:
Figure BDA0001567944820000148
then there are:
Figure BDA0001567944820000149
the ash content and the volatile component also have a simpler calculation method, namely, the calculation is not corrected, only one of the matrixes is used for calculating, but the calculation precision can be influenced:
if already calculated using the matrix
Figure BDA0001567944820000151
A simple calculation of the air drying base volatiles may be:
Figure BDA0001567944820000152
if already calculated using the matrix
Figure BDA0001567944820000153
A simple calculation of the air-drying based ash may be:
Figure BDA0001567944820000154
in the case of known FCad (air drying based fixed carbon) and Aad (air drying based ash) there are when Mad (air drying based moisture) is calculated:
Figure BDA0001567944820000155
estimated air drying base moisture:
Figure BDA0001567944820000156
when calculating Vad (air drying base volatiles) there are:
Figure BDA0001567944820000157
estimated air drying base volatiles:
Figure BDA0001567944820000158
the two values above need to be corrected:
Figure BDA0001567944820000159
determination of the coefficient fcas:
Figure BDA00015679448200001510
if:
Figure BDA00015679448200001511
then there are:
Figure BDA00015679448200001512
the moisture and the volatile components also have a simpler calculation method, namely, the correction is not carried out, and only one of the calculation methods is calculated by using a matrix:
if already calculated using the matrix
Figure BDA00015679448200001513
A simple calculation of the air drying base volatiles may be:
Figure BDA0001567944820000161
if already calculated using the matrix
Figure BDA0001567944820000162
A simple calculation of the air drying base moisture may be:
Figure BDA0001567944820000163
in the case of known FCad (air drying based fixed carbon) and Vad (air drying based ash) there are when Mad (air drying based moisture) is calculated:
Figure BDA0001567944820000164
calculated air drying base moisture:
Figure BDA0001567944820000165
mad (air dry basis ash) was calculated as:
Figure BDA0001567944820000166
calculated air-dry basis ash:
Figure BDA0001567944820000167
the two values above need to be corrected:
Figure BDA0001567944820000168
determination of the coefficient fcvs:
Figure BDA0001567944820000169
if:
Figure BDA00015679448200001610
then there are:
Figure BDA00015679448200001611
the moisture and the volatile components also have a simpler calculation method, namely, the correction is not carried out, and only one of the calculation methods is calculated by using a matrix:
if already calculated using the matrix
Figure BDA00015679448200001612
A simple calculation of the air-drying based ash may be:
Figure BDA00015679448200001613
if already calculated using the matrix
Figure BDA00015679448200001614
A simple calculation of the air-drying based ash may be:
Figure BDA0001567944820000171
given Mad (air drying based fixed carbon) and Aad (air drying based ash) there are when calculating FCad (air drying based moisture fixed carbon):
Figure BDA0001567944820000172
calculated air dry based fixed carbon:
Figure BDA0001567944820000173
when calculating Vad (air drying base volatiles) there are:
Figure BDA0001567944820000174
calculated air drying base volatiles:
Figure BDA0001567944820000175
the two values above need to be corrected:
Figure BDA0001567944820000176
determination of the coefficient mas:
Figure BDA0001567944820000177
if:
Figure BDA0001567944820000178
then there are:
Figure BDA0001567944820000179
fixed carbon and volatile components also have a simpler calculation method, i.e. no correction is made, only one of them is calculated by a matrix:
if already calculated using the matrix
Figure BDA00015679448200001710
A simple calculation of the air drying base volatiles may be:
Figure BDA00015679448200001711
if already calculated using the matrix
Figure BDA00015679448200001712
A simple calculation of the air-drying based ash may be:
Figure BDA00015679448200001713
in the case of known Mad (air drying based moisture) and Vad (air drying based volatile) there are when calculating FCad (air drying based fixed carbon):
Figure BDA0001567944820000181
calculated air dry based fixed carbon:
Figure BDA0001567944820000182
calculation Aad (air dry basis ash) had:
Figure BDA0001567944820000183
calculated air-dry basis ash:
Figure BDA0001567944820000184
the two values above need to be corrected:
Figure BDA0001567944820000185
determination of the coefficient mvs:
Figure BDA0001567944820000186
if:
Figure BDA0001567944820000187
then there are:
Figure BDA0001567944820000188
fixed carbon and ash also have a simpler calculation method, i.e. no correction is made, only one of them is calculated by matrix:
if already calculated using the matrix
Figure BDA0001567944820000189
A simple calculation of the air-drying based ash may be:
Figure BDA00015679448200001810
if already calculated using the matrix
Figure BDA00015679448200001811
A simple calculation of the air-dried based fixed carbon may be:
Figure BDA00015679448200001812
in the calculation of FCad (air-dry based fixed carbon) with known Aad (air-dry based ash) and Vad (air-dry based volatile) are:
Figure BDA00015679448200001813
calculated air dry based fixed carbon:
Figure BDA0001567944820000191
when Mad (air drying base moisture) is calculated:
Figure BDA0001567944820000192
calculated air drying base moisture:
Figure BDA0001567944820000193
the two values above need to be corrected:
Figure BDA0001567944820000194
determination of the coefficient mvs:
Figure BDA0001567944820000195
if:
Figure BDA0001567944820000196
then there are:
Figure BDA0001567944820000197
fixed carbon and ash also have a simpler calculation method, i.e. no correction is made, only one of them is calculated by matrix:
if already calculated using the matrix
Figure BDA0001567944820000198
A simple calculation of the air-drying based ash may be:
Figure BDA0001567944820000199
if already calculated using the matrix
Figure BDA00015679448200001910
A simple calculation of the air-dried based fixed carbon may be:
Figure BDA00015679448200001911
if the industrial analysis is complete, elemental analysis of sulfur can also be used to reduce computational errors, for example, volatile components are removed in the industrial analysis, and when calculating the air-dried carbon-based elemental analysis Cad, the following formula can be calculated:
Figure BDA00015679448200001912
volatile components were removed in the industrial analysis, and the air-drying base hydrogen elemental analysis Had was calculated:
Figure BDA0001567944820000201
volatile components were removed from the industrial analysis and the calculated air-dried oxygen element analysis Oad:
Figure BDA0001567944820000202
volatiles were removed from the industrial analysis and the air-dry based nitrogen analysis was calculated Nad:
Figure BDA0001567944820000203
ash is removed in industrial analysis, and air drying base carbon element analysis Cad is calculated
Figure BDA0001567944820000204
The ash content is removed in industrial analysis, and the air drying base hydrogen element analysis Had time is calculated
Figure BDA0001567944820000205
Ash is removed from the industrial analysis and calculated for air-drying oxygen element analysis Oad
Figure BDA0001567944820000206
Ash is removed from industrial analysis and air dry basis nitrogen analysis is calculated Nad
Figure BDA0001567944820000211
Removing water in industrial analysis, calculating air drying base carbon element analysis Cad
Figure BDA0001567944820000212
Removing water in industrial analysis, calculating air-drying base hydrogen element analysis Had
Figure BDA0001567944820000213
Moisture was removed from the industrial analysis and the calculated air-drying oxygen analysis Oad
Figure BDA0001567944820000214
Moisture was removed from the industrial analysis and air-dry based nitrogen analysis was calculated Nad
Figure BDA0001567944820000215
Removing fixed carbon content in industrial analysis, and calculating air drying base carbon element analysis Cad
Figure BDA0001567944820000216
Removing fixed carbon component in industrial analysis, calculating air drying base hydrogen element analysis Had
Figure BDA0001567944820000221
Removal of fixed carbon in the Industrial analysis, calculation of air-drying oxygen elemental analysis Oad
Figure BDA0001567944820000222
Removal of fixed carbon in industrial analysis, calculation of air-dried base nitrogen analysis Nad
Figure BDA0001567944820000223
Calorific value is a common parameter that is routinely assayed in some coal-using units, especially power plants. In the case of two industrial analyses, which can be used instead of one parameter in the industrial analysis, the higher calorific value, air drying Qgr, ad, should be used, in this case the removal of the volatile components Vad, in the following way:
for the case of calculating air-dry based carbon:
Figure BDA0001567944820000224
Figure BDA0001567944820000225
Figure BDA0001567944820000226
Figure BDA0001567944820000231
Figure BDA0001567944820000232
Figure BDA0001567944820000233
the order of FCad, Mad, Aad, Vad, Qgr, ad in the matrix does not affect the result of the computation.
The calculations for the other elemental analyses are the same as described above.
The above method is based on the case when N is 4,
when N >4, a method of taking 4 samples out of N samples may be employed, which is done with N! A combination of (N-4) | 4 |, for the case where N ═ 5, when calculating the air drying based carbon:
removing the group 5 data
Figure BDA0001567944820000234
Removing the 4 th group of data
Figure BDA0001567944820000235
Removing the group 3 data
Figure BDA0001567944820000236
Removing the data of group 2
Figure BDA0001567944820000241
Removing the group 1 data
Figure BDA0001567944820000242
That is, for 5 sets of data, for ease of expression, the case of data being removed is:
5，4，3，2，1
for 6 groups of data, 2 samples need to be removed, and the methods for removing the sample combination include:
1, 2; 1, 3; 1, 4; 1, 5; 1, 6; 2, 3; 2, 4; 2, 5; 2, 6; 3, 4; 3, 5; 3, 6; 4, 5; 4, 6; 5,6. There are 15 combinations in total.
For the case of 7 samples, 3 samples need to be removed, and the combination method includes:
1, 2, 3; 1, 2, 4; 1, 2, 5; 1, 2, 6; 1, 2, 7; 1, 3, 4; 1, 3, 5; 1, 3, 6; 1, 3, 7; 1, 4, 5; 1, 4, 6; 1, 4, 7; 1, 5, 6; 1, 5, 7; 1, 6, 7; 2,3, 4; 2,3, 5; 2,3, 6; 2,3, 7; 2,4, 5; 2,4, 6; 2,4, 7; 2,5, 6; 2,5, 7; 2,6, 7; 3,4, 5; 3,4, 6; 3,4, 7; 3, 5, 6; 3, 5, 7; 3, 6, 7; 4, 5, 6; 4, 5, 7; 4, 6, 7; 5,6,7. There are 35 combinations in total.
Similarly, for the case of 8 samples, there are a total of 70 combinations.
The number of combinations z is related to the number of samples n by:
Z＝n！/((n-4)！4！)
if the number of samples is large, the number of combining methods is greatly increased, and the calculation amount is also greatly increased, so that the method is mainly adopted when the number of samples is not large.
It is also possible to select only a part of the data for calculation, rather than all, as long as the number of occurrences of each set of data is the same after selection, for example, for 6 sets of data, the combination is:
1, 3; 1, 4; 1, 5; 1, 6; 2, 3; 2, 4; 2, 5; 2, 6; 3, 5; 3, 6; 4, 5; 4,6. There are a total of 12 combinations, or:
1, 4; 1, 5; 1, 6; 2, 3; 2, 4; 2, 6; 3, 5; 3, 6; 4,5. There are 9 combinations in total, or:
1, 5; 1, 6; 2, 3; 2, 4; 3, 6; 4,5. There are 6 combinations in total.
For the case of 7 samples, 7, 14, 21, and 28 samples need to be removed, and the combination mode after 7 samples are removed is as follows:
1, 2, 3; 1, 2, 5; 1, 2, 6; 1, 2, 7; 1, 3, 4; 1, 3, 6; 1, 3, 7; 1, 4, 6; 1, 4, 7; 1, 5, 6; 1, 5, 7; 1, 6, 7; 2,3, 4; 2,3, 5; 2,3, 6; 2,3, 7; 2,4, 5; 2,4, 6; 2,4, 7; 2,5, 7; 3,4, 5; 3,4, 6; 3, 5, 6; 3, 5, 7; 4, 5, 6; 4, 5, 7; 4, 6, 7; 5,6,7. There are 28 combinations in total.
The combination mode after 14 are removed is as follows:
1, 2, 3; 1, 2, 5; 1, 2, 6; 1, 3, 7; 1, 4, 6; 1, 4, 7; 1, 5, 6; 1, 5, 7; 1, 6, 7; 2,3, 4; 2,3, 6; 2,3, 7; 2,4, 5; 2,4, 7; 2,5, 7; 3,4, 5; 3,4, 6; 3, 5, 6; 3, 5, 7; 4, 5, 6; 4,6,7. There are 21 combinations in total.
The combination mode after 21 are removed is as follows:
1, 2, 3; 1, 2, 5; 1, 4, 6; 1, 4, 7; 1, 5, 6; 1, 6, 7; 2,3, 4; 2,3, 7; 2,4, 7; 2,5, 7; 3,4, 6; 3, 5, 6; 3, 5, 7; 4,5,6. There are 14 combinations in total.
The combination mode after 28 are removed is as follows:
1, 2, 3; 1, 2, 5; 1, 6, 7; 2,4, 7; 3,4, 6; 3, 5, 7; 4,5,6. There are 7 combinations in total.
Other sample numbers can be selected in the same way,
step S03: the average value and the error of each coefficient are calculated,
from the calculation result of step S02, it is possible to obtain
Coefficient average of each element
Figure BDA0001567944820000251
Where z is the number of times the same element is counted, i.e., 1, 2,3, …, i, …, z. If there are 4 sets of data, there are only 1 result, if there are 5 sets of data, there may be 5 results, if there are 6 sets of data, there may be 15 results at the maximum, if there are 7 sets of data, there may be 35 results at the maximum, if there are 8 sets of data, there may be 70 results at the maximum, and if there are more data, the greater the number of results calculated.
And from the average, the error of each coefficient
Figure BDA0001567944820000252
Step S04:
the method comprises the following steps: setting threshold values delta c, delta h, delta o, delta n and delta s of each element according to an acceptable error range; judging and comparing the magnitude between each coefficient error and a set threshold, and if all the coefficient errors of the coefficient (one of delta ci, delta hi, delta oi, delta ni and delta si) of one element are smaller than the threshold, considering the coefficient average value as the final calculation result; if the error of one coefficient is larger than the threshold value, the coefficient of which the error is larger than the threshold value is eliminated, and the average value of the coefficient and the coefficient error are recalculated until all the errors in the coefficient are smaller than the threshold value.
The second method comprises the following steps: if data with abnormally large data exists in the calculation results of the Δ Ci, the Δ Hi, the Δ Oi, the Δ Ni and the Δ Si, it is required to confirm that the samples cause error increase, and samples with obvious abnormality are removed, and in the case that the number of the samples is 5, the samples can be removed as long as the error is obviously reduced after the samples do not participate in the calculation.
The calculation method can also be used for verifying the reasonability of the test result, and if the error after calculation is obviously abnormal, the defect of the test process is possible.
The third method comprises the following steps: for the situation that the number of samples is greater than 5, the number of samples which do not participate in calculation is greater than 1, at this time, the judgment on abnormal samples is not intuitive, and the judgment can be carried out according to the correlation condition between the calculation of the samples participating in the calculation and the result, because the number of samples calculated each time is only 4, generally, if the error is obvious and abnormal, the abnormal calculation result is usually more than one (if the error is the condition of 4 samples, only one calculation is carried out, at this time, the error is abnormal, only data cannot be calculated), the occurrence frequency of the samples which participate in the calculation when the error is abnormal is counted, the samples with the largest occurrence frequency are removed, then the calculation is carried out, and if the error is still abnormal, the samples are continuously reduced by the same method until the requirement of the error is met.
The method four comprises the following steps: when there are a plurality of coal qualities, different coal qualities may be calculated separately in order to improve calculation accuracy, but it is preferable to calculate the mixed coal at the same time, and if the difference is not large, it may be considered to perform the calculation by one method.
The method five comprises the following steps: for the case that the number of samples is large and the calculation result is also large, some statistical methods can be applied, for example, the distribution of errors can be drawn, and the accuracy of the test and calculation data can be evaluated by methods such as normal distribution. The abnormal samples can be eliminated by the method, and the calculation quality is guaranteed.
The above are preferred embodiments of the present invention, and all changes made according to the technical scheme of the present invention that produce functional effects do not exceed the scope of the technical scheme of the present invention belong to the protection scope of the present invention.

Claims (3)

1. A small sample industrial analysis computational elemental analysis method using coal, for industrial analysis FCad + Mad + Aad + Vad is 100%, for elemental analysis Cad + Had + Oad + Nad + Sad + Mad + Aad is 100%, characterized in that: the method adopts industrial analysis data, utilizes an equation system to calculate the components of elemental analysis, and comprises the following steps of calculating by adopting fixed carbon, moisture and ash, and comprises the following steps of:
Figure FDA0003176913660000011
wherein: subscripts 1, 2,3, 4 are sets of data 1, 2,3, 4, respectively; subscript t is test data; FCad is air-dry based fixed carbon; mad is air drying base moisture; aad is an air-drying base ash; cad is the carbon content of the air drying base; vad is an air drying base volatile; had is the hydrogen content of the air-drying base, Oad is the oxygen content of the air-drying base, Nad is the nitrogen content of the air-drying base, and Sad is the sulfur content of the air-drying base; the cFCMA0, the cFCMA1, the cFCMA2 and the cFCMA3 are coefficient groups needing to be determined through calculation; because the sum of the 4 industrial analysis components is 100%, only any 3 of the 4 industrial analysis components are selected for calculation in the equation set calculation; wherein, air drying base is adopted for industrial analysis and element analysis;
if the number of the samples is more than 4, forming a plurality of equation sets through combination to calculate so as to generate a plurality of coefficient sets, and then averaging;
after the calculation is finished, performing precision verification to confirm the calculation effect;
under the condition that a plurality of equation sets are calculated, if the coefficient deviates far from the average value, analysis is needed to be carried out, abnormal test data are eliminated, the elimination method is that each group of element analysis is calculated by the coefficient set after averaging and is compared with the test data, and the abnormal data are obtained if the difference is large.
2. The method of claim 1, wherein the method comprises the steps of: in the case of only 2 variables for industrial analysis, the calorific value is introduced so that 3 variables participate in the calculation; in the case of 3 variables in the industrial analysis, the calorific value is introduced so that 4 variables participate in the calculation, the calculation method is the same as that in the case of 3 variables, and the accuracy in the case of no addition of the calorific value calculation is compared by checking to determine which algorithm to select.
3. The method of claim 1, wherein the method comprises the steps of: introducing the element analysis test value of sulfur into calculation under the condition that the industrial analysis has only 2 variables, so that 3 variables are calculated; under the condition that 3 variables exist in industrial analysis, the element analysis test value is introduced, so that 4 variables are calculated, the calculation method is the same as that of 3 variables, only 5 samples are needed for each group of data, and the accuracy of the element analysis calculation without adding sulfur is compared through checking to determine which algorithm is selected.
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