Трансформаторы: эксплуатация, диагностирование, ремонт и продление срока службы
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Table 8
New degassed oil sample spiked with hydrogen only
Spiked, µl/l Measured concentration, µl/l Corrected, µl/l
PAES GC
H
2
101 82 120 48
CH
4
0 1 0 0
C
2
H
6
0 1 0 0
C
2
H
4
0 1 0 0
C
2
H
2
0 0 0 0
CO 0 2 0 0
CO
2
0 67 55 22
H
2
CH
4
C
2
H
6
C
2
H
4
C
2
H
2
CO CO
2
Fig. 1. Correlation between 50 µl/l spiked samples and instrument readings
H
2
CH
4
C
2
H
6
C
2
H
4
C
2
H
2
CO CO
2
Fig. 2. Correlation between 100 µl/l spiked samples and instrument readings
81
H
2
CH
4
C
2
H
6
C
2
H
4
C
2
H
2
CO CO
2
Fig. 3. Correlation between 200 µl/l spiked samples and instrument readings
H
2
CH
4
C
2
H
6
C
2
H
4
C
2
H
2
CO CO
2
Fig. 4. Correlation between 250 µl/l spiked samples and instrument readings
Photo-acoustic spectroscopy provided consistent good quality correlation betw-
een spiked and measured results of gas in oil when analysing standard quantitative
gassed samples. It was observed that, while the GC was extremely repeatable there
was a large deviation between spiked gas quantity and gas-in-oil results reported.
Correction generally improved this although Carbon Monoxide (CO) and Carbon
Dioxide (CO
2
) are still significantly deviant from expected, possibly due to a known
weaknesses in linearity of any methanizer used in GC for detection of these gases.
4. Conclusions
Gas Chromatography is today the reference method for Dissolved Gas Analysis.
Normally, gas chromatographs should be calibrated by commercially available, or
in-house prepared, gas-in-oil standards that take into account some, but not all, po-
ssible error sources that may influence the quality of the final result. Unfortunately,
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it does not exist an absolute method permitting to carry out such calibrations with
standards of absolutely known gas concentrations.
In addition, there are some laboratories world wide that do not strictly follow
the analytical procedure described in International Standards, including corrections
for temperature, pressure and, specially when the head space extraction method is
used, to equate gas-phase to oil-phase results.
In this study, PAS has proved to be accurate and precise at a range of concentr-
ations and using different oils as demonstrated by testing known standard gas-in-oil
samples. One exception is the indication of small quantities of hydrogen when none
are present. This false positive may be due to slight cross sensitivity of the solid-
state hydrogen sensor to acetylene. Practically however transformer oil will always
contain significant quantities of hydrogen whenever acetylene is present so this
cross sensitivity will have little or no effect on any possible diagnosis being made.
When the GC results are corrected for partition coefficient and volumetric ratio
they are generally more accurate and compare relatively well to Photo-Acoustic
Emission Spectroscopy.
1. Bucholz M. The Bucholz protective system and its practical applications // Elektrotec. Z. (Germany),
1928. Vol. 49. P. 1257–1261.
2. IEC 60599:2007 – Mineral oil-impregnated equipment in service- interpretation of dissolved and free
gases analysis.
3. IEEE Std C57.104:2008 – Guide for the Interpretation of Gases Generated in Oil-Immersed Transf-
ormers.
4. Moelmann A., Pahlavanpour B. New Guidelines for Interpretation of Dissolved Gas Analysis in Oil-
Filled Transformers // Electra. 1999. ¹ 186, Oct.
5. CIGRE. Life management techniques for power transformers // Technical Brochure. 2003. ¹ 227.
6. Duval M. Dissolved Gas Analysis: It Can Safe Your Transformer; IEEE Electrical Insulation Maga-
zine. 1989. Vol. 5, no. 6.
7. De Pablo A. Unpublished results.
ÑÎÏÎÑÒÀÂÈÒÅËÜÍÎÅ ÈÑÑËÅÄÎÂÀÍÈÅ ÕÐÎÌÀÒÎÃÐÀÔÈÈ ÃÀÇÀ
È ÔÎÒÎÀÊÓÑÒÈ×ÅÑÊÎÉ ÈÍÔÐÀÊÐÀÑÍÎÉ ÑÏÅÊÒÐÎÑÊÎÏÈÈ
Â. Ñîêîëîâ
, Ä. Ñêåëëè, À. äå Ïàáëî, Ó. Ôåðãþñîí, GE Energy
Ââåäåíèå
Òðàíñôîðìàòîðû – ýòî áàçîâîå îáîðóäîâàíèå ýíåðãîïðåäïðèÿòèÿ. Ìíî-
ãèå ýíåðãîïðåäïðèÿòèÿ èìåþò óñòàðåâàþùèé ïàðê òðàíñôîðìàòîðîâ, êîòîðûå
óñòàíàâëèâàëèñü ïî ìåðå ðàçâèòèÿ è ðàñøèðåíèÿ ñèñòåìû. Âî ìíîãèõ ñëó÷àÿõ
òðàíñôîðìàòîðû íàõîäÿòñÿ â ýêñïëóàòàöèè â òå÷åíèå ìíîãèõ ëåò ïî èñòå÷åíèè
îæèäàåìîãî ñðîêà ñëóæáû â 25 èëè 40 ëåò. Òàê êàê ïîòðåáíîñòè â ýëåêòðî-
ýíåðãèè óâåëè÷èëèñü, â íåêîòîðûõ ðåãèîíàõ òðàíñôîðìàòîðû íåñóò íàãðóçêó
ñâåðõ íîìèíàëüíîé ìîùíîñòè. Ãåíåðàòîðíûå òðàíñôîðìàòîðû çíà÷èòåëüíî íà-
ãðóæàþòñÿ, òàê êàê îïåðàòîðû ñòðåìÿòñÿ ìàêñèìàëüíî óâåëè÷èòü äîõîäû è óäî-
âëåòâîðèòü ïîòðåáíîñòè â ýíåðãèè. Â íåêîòîðûõ îòðàñëÿõ, íàïðèìåð â ïëàâêå
àëþìèíèÿ èëè íà ñòàëåïëàâèëüíûõ çàâîäàõ, òðàíñôîðìàòîðû òàêæå ÿâëÿþòñÿ
íåîòúåìëåìîé ÷àñòüþ ïðîèçâîäñòâà. Ïîòåðÿ òðàíñôîðìàòîðà íà ýíåðãîïðåä-
83
ïðèÿòèè, ãåíåðèðóþùåé ñòàíöèè èëè â ïðîöåññå ïðîèçâîäñòâà ìîæåò ïðèâå-
ñòè ê ïîòåðå ìèëëèîíîâ äîëëàðîâ â çàâèñèìîñòè îò âðåìåíè ïðîñòîÿ. Çàìåíà
òðàíñôîðìàòîðà – äîðîãîñòîÿùèé è òðóäîåìêèé ïðîöåññ. Â ïîñëåäíèå ãîäû
âîçðîñ ñïðîñ íà òðàíñôîðìàòîðû è ñûðüå, ÷òî ïðèâåëî ê óâåëè÷åíèþ ñòîèìî-
ñòè è âðåìåíè âûïîëíåíèÿ çàêàçà íà ïîñòàâêó íîâîãî òðàíñôîðìàòîðà.
Ôàêò, ÷òî ïëîõî ôóíêöèîíèðóþùèé òðàíñôîðìàòîð ïîðîæäàåò ãàçû, èçâå-
ñòåí åùå ñ 1920-õ ãã. [1], îäíàêî îòñëåæèâàíèå è äèàãíîñòèêà òðàíñôîðìàòîðîâ
ïîñðåäñòâîì àíàëèçà ðàñòâîðåííîãî ãàçà íà÷àëèñü ñ 1950-õ ãã.
Àíàëèç ðàñòâîðåííîãî ãàçà (ÀÐÃ) – ýòî, áåçóñëîâíî, ëó÷øèé ñïîñîá îáíà-
ðóæèòü íåèñïðàâíîñòè â ðàáîòå òðàíñôîðìàòîðîâ. Õîðîøî èçâåñòíûå ïðàâèëà
èíòåðïðåòàöèè ãàçîâ [2–4] ÿñíî ïîêàçûâàþò, êàê âûÿâèòü íåèñïðàâíûå òðàíñ-
ôîðìàòîðû è êàêèå ïîâðåæäåíèÿ ìîãóò ïðîèçîéòè. Èñõîäÿ èç îïûòà, ÀÐÃ ìî-
æåò âûÿâëÿòü è ïðåäóïðåæäàòü 70 % ñàìûõ ÷àñòûõ ñëó÷àåâ îòêàçà ñèëîâûõ
òðàíñôîðìàòîðîâ [5].
Òðàäèöèîííî ÀÐÃ âûïîëíÿåòñÿ ñëåäóþùèì îáðàçîì: èç òðàíñôîðìàòî-
ðà áåðóò îáðàçåö ìàñëà, êîòîðûé ïîñûëàþò â ëàáîðàòîðèþ è îæèäàþò ðå-
çóëüòàòîâ. Îäíàêî íàðóøåíèå ïðîöåäóðû îòáîðà îáðàçöà ìîæåò ïðèâåñòè ê
çíà÷èòåëüíûì îøèáêàì ïðè àíàëèçå. Íàïðèìåð, ïðè íåïðàâèëüíîì îòáîðå
îáðàçöà â ìàñëî ìîãóò ïîïàñòü çàãðÿçíÿþùèå âåùåñòâà, à íåïðàâèëüíîå õðà-
íåíèå ìîæåò ïðèâåñòè ê ïîòåðå ãàçà â ìàñëå â ïåðèîä ìåæäó îòáîðîì îáðàçöà
è àíàëèçîì åãî â ëàáîðàòîðèè. Ðåçóëüòàòû ìîãóò âàðüèðîâàòüñÿ îò ëàáîðà-
òîðèè ê ëàáîðàòîðèè è äàæå ìîãóò îòëè÷àòüñÿ ó ðàçëè÷íûõ ïîëüçîâàòåëåé
îäíîãî îáîðóäîâàíèÿ. Íåçàâèñèìûå èñïûòàíèÿ ÑÈÃÐÝ [6] ïîêàçàëè ðàçíèöó
â äàííûõ, äîñòèãàþùóþ íåñêîëüêèõ ñîòåí ïðîöåíòîâ ìåæäó îáðàçöàìè, ïðî-
òåñòèðîâàííûìè â ðàçëè÷íûõ ëàáîðàòîðèÿõ ïðè èñïîëüçîâàíèè ðàçíûõ ìåòî-
äîâ äèàãíîñòèêè (òàáë. 1).
Òàáëèöà 1
Ñòàòèñòè÷åñêèå äàííûå àíàëèçîâ õðîìàòîãðàôèè ãàçà [6]
Íàèìåíîâàíèå ïîêàçàòåëÿ Îòêëîíåíèå îò çíà÷åíèÿ, %
Îáðàçåö A Îáðàçåö B
Âàêóóìíûé îäèíàðíûé õîä 13 40
Âàêóóìíûé ìíîæåñòâåííûé õîä 23 35
Äåñîðáöèÿ 22 27
Ëó÷øàÿ ëàáîðàòîðèÿ 7 14
Õóäøàÿ ëàáîðàòîðèÿ 39 70
Õóäøåå îòêëîíåíèå íà îäèí ãàç 150 400
Îáðàçåö A: óãëåâîäîðîäû 6–60 ppm; CO, CO
2
: 100–500 ppm.
Îáðàçåö B: óãëåâîäîðîäû 1–10 ppm; CO, CO
2
: 30–100 ppm.
Äðóãàÿ âîçìîæíàÿ ïðè÷èíà ýòîãî ñîñòîèò â òîì, ÷òî õðîìàòîãðàôû ãàçà íà-
ñòðàèâàþòñÿ ñ ïîìîùüþ âíóòðåííèõ ãîòîâûõ ñòàíäàðòîâ ðàñòâîðåííûõ ãàçîâ â
ìàñëå èëè, ÷àùå, ñìåñåé ãàçîâ, äåéñòâèòåëüíîå ñîäåðæàíèå êîòîðûõ òî÷íî íå
óñòàíîâëåíî. Ýòî ìîæåò ïðèâåñòè ê íåîïðåäåëåííîñòè ïðè îöåíêå ðåçóëüòà-
òîâ, îñîáåííî ïðè àíàëèçå òåíäåíöèè êîíöåíòðàöèè ãàçà.
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Èëëþñòðàöèåé ýòîìó ÿâëÿåòñÿ òàáë. 2, â êîòîðîé ïðåäñòàâëåíû ðåçóëüòàòû
ÀÐÃ, ìåòîäà âûäåëåíèÿ ïàðà íàñîñîì Òîïëåðà íà ïðèìåðå íåñêîëüêèõ äåéñòâó-
þùèõ òðàíñôîðìàòîðîâ 400 ê ýíåðãåòè÷åñêîé ñèñòåìû, èìåþùèõ ðàçëè÷íîå
ñîäåðæàíèå ãàçà [7].
Òàáëèöà 2
Ðåçóëüòàòû ÀÐÃ äåéñòâóþùèõ òðàíñôîðìàòîðîâ
Vs,
ml
Vg,
ml
%g H
2
O
2
N
2
CH
4
CO CO
2
C
2
H
4
C
2
H
6
C
2
H
2
Σg %R
49 0,7 1,46 6 1777 10 272 1 40 98 0 1 0 12 195 83,5
49 1,1 2,24 6 2537 14 880 8 25 443 2 10 0 17 911 80,0
70 2,1 3,00 5 2278 21 858 6 232 1499 0 1 0 25 879 86,3
63 2,6 4,13 7 6173 29 105 30 45 1096 6 17 0 36 479 88,3
46 2,9 6,30 11 8963 46 078 5 181 1439 1 2 0 56 680 90,0
41 3,0 7,32 16 6950 52 848 62 182 3691 39 116 0 63 904 87,3
45 3,7 8,22 8 6837 52 998 70 0 1003 63 118 0 61 097 74,3
35 3,3 9,43 22 10 561 60 833 121 175 9736 7 172 0 81 627 86,6
48 5,2 10,83 14 9156 59 969 70 120 31 469 0 125 0 100 923 93,2
48 5,7 11,88 6 12 568 68 396 29 800 22 251 0 11 0 104 061 87,6
Vs – îáúåì îáðàçöà, Vg – îáúåì ãàçà, %g – ïðîöåíòíîå ñîäåðæàíèå ãàçà, Σg – ñóììà âñåõ ïðî-
àíàëèçèðîâàííûõ ãàçîâ, % R – ïðîöåíòíîå ñîäåðæàíèå èçâëå÷åííûõ ãàçîâ.
Ïðîöåäóðà ýêñïåðèìåíòà
Ñîïîñòàâëåíèå ëàáîðàòîðíîé õðîìàòîãðàôèè ãàçà è ôîòîàêóñòè÷åñêîé
ñïåêòðîñêîïèè ïðîâîäèëîñü â ñîîòâåòñòâèè ñî ñòàíäàðòàìè ðàñòâîðåííûõ ãà-
çîâ â ìàñëå, ïîäãîòîâëåííûìè ñîãëàñíî ASTM 3612. Õðîìàòîãðàô ãàçà – ýòî
ñîâðåìåííûé Agilent®. Äàííûé õðîìàòîãðàô ãàçà èñïîëüçóåò äåòåêòîð èîíèçà-
öèè ïëàìåíè, äåòåêòîð òåïëîâîé ïðîâîäèìîñòè è ìåòàíàòîð äëÿ îïðåäåëåíèÿ
êîëè÷åñòâà CO è CO
2
. Òðàíñïîðòèðóþùèì ãàçîì ÿâëÿåòñÿ àðãîí. Âûäåëåíèå
ãàçà èç ìàñëà îñóùåñòâëÿåòñÿ ïðè èñïîëüçîâàíèè ìåòîäà ðàâíîâåñíîãî ñîñòîÿ-
íèÿ òàêæå ïðè ïîìîùè Agilent. Ôîòîàêóñòè÷åñêèé ñïåêòðîñêîï – TRANSPORT
X®, èçãîòîâëåííûé êîìïàíèåé GE Energy. Èñïîëüçóåìûé TRANSPORT X áûë
ñòàíäàðòíûì óñòðîéñòâîì.
Õðîìàòîãðàôèþ ãàçà âûïîëíèëà âíåøíÿÿ ëàáîðàòîðèÿ, ñïåöèàëèçèðóþùà-
ÿñÿ íà àíàëèçå ìàñëà. Ôîòîàêóñòè÷åñêèé ñïåêòðîìåòð èñïîëüçîâàëè ñïåöèàëè-
ñòû GE Energy.
Ñòàíäàðòíûå êîëè÷åñòâåííûå îáðàçöû ðàñòâîðåííûõ ãàçîâ â ìàñëå áûëè ñîç-
äàíû ïóòåì èçâëå÷åíèÿ èç äåãàçèðîâàííîãî òðàíñôîðìàòîðíîãî ìàñëà èçâåñòíûõ
êîíöåíòðàöèé ãàçîâ ðàçëîæåíèÿ. Â äîïîëíåíèå áûëè ñîçäàíû îáðàçöû ñ èñïîëü-
çîâàíèåì ñîñòàðåííîãî ìàñëà, à òàêæå áûëè ïîëó÷åíû îòäåëüíûå îáðàçöû, ñî-
äåðæàùèå òîëüêî âîäîðîä (èç-çà ïðàêòè÷åñêèõ òðóäíîñòåé â ïîëó÷åíèè ñìåñè
ãàçîâ, ñîäåðæàùåé âñå ãàçû ðàçëîæíåíèÿ è âîäîðîä, äëÿ ïðîâåðêè òî÷íîñòè îáíà-
ðóæåíèÿ âîäîðîäà áûë ïðîèçâåäåí îòäåëüíûé îáðàçåö ðàñòâîðèìîñòè âîäîðîäà â
ìàñëå). Âñå ýòè îáðàçöû áûëè ñîçäàíû â ñîîòâåòñòâèè ñ ASTM 3612 Appendix 1.
Ìíîãî÷èñëåííûå îáðàçöû áûëè ñîçäàíû ñ ðàçëè÷íûìè êîíöåíòðàöèÿìè.
85
Õðîìàòîãðàô ãàçà áûë îòêàëèáðîâàí ïðè ïîìîùè ñåðèéíî ïîñòàâëÿåìûõ
ñòàíäàðòíûõ ãàçîâ. Ôîòîàêóñòè÷åñêèé ñïåêòðîñêîï TRANSPORT X áûë îòêà-
ëèáðîâàí ïðîèçâîäèòåëåì ñ èñïîëüçîâàíèåì ìíîæåñòâåííûõ ñòàíäàðòîâ ãàçà è
áûë ïðîâåðåí â ñîîòâåòñòâèè ñ èçâåñòíûìè ñòàíäàðòàìè ðàñòâîðèìîñòè ãàçà â
ìàñëå.
Ðåçóëüòàòû è îáñóæäåíèå
Ðåçóëüòàòû ïîêàçûâàþò ñëàáóþ êîððåëÿöèþ ìåæäó ìåòîäàìè ëàáîðàòîð-
íîé õðîìàòîãðàôèè ãàçà è ôîòîàêóñòè÷åñêîé ñïåêòðîñêîïèè, íåñìîòðÿ íà ñîîò-
âåòñòâèå îòäåëüíûõ ðåçóëüòàòîâ.
Ýòè äàííûå äåìîíñòðèðóþò, ÷òî ðåçóëüòàòû õðîìàòîãðàôèè ãàçà, ïðåäñòàâ-
ëåííûå êàê ðàñòâîðèìîñòü ãàçà â ìàñëå, ìîãóò â äåéñòâèòåëüíîñòè ñîîòâåòñòâî-
âàòü ìàññå ãàçà â µl/l, ïðè÷åì â ýòîò ðåçóëüòàò íå ââåäåíà ïîïðàâêà ñ ó÷åòîì
îáúåìíîãî îòíîøåíèÿ è êîýôôèöèåíòîâ ðàñïðåäåëåíèÿ, ÷òî òðåáóåòñÿ â ñî-
îòâåòñòâèè ñ ìåòîäîì ðàâíîâåñíîãî ñîñòîÿíèÿ. Ïî ñóùåñòâó, ýòè ðåçóëüòàòû
ÿâëÿþòñÿ íåîáðàáîòàííûìè äàííûìè â ãàçîâîé ôàçå è íå ìîãóò èñïîëüçîâàòüñÿ
äëÿ ôàçû ìàñëà òðàíñôîðìàòîðà. Êðîìå òîãî, âåðîÿòíî, ÷òî ðåçóëüòàòû õðîìà-
òîãðàôèè ãàçà íå áûëè îòêîððåêòèðîâàíû ñ ó÷åòîì íîðìàëüíîé òåìïåðàòóðû è
äàâëåíèÿ (çäåñü, îäíàêî, íå áûëî ïîïûòêè ñäåëàòü êîððåêöèþ íà íîðìàëüíóþ
òåìïåðàòóðó è äàâëåíèå).
 òàáë. 3–8 è ðèñ. 1–4 ïðåäñòàâëåíû ðåçóëüòàòû ôîòîàêóñòè÷åñêîé ñïåê-
òðîñêîïèè, õðîìàòîãðàôèè ãàçà è ðÿä îòêîððåêòèðîâàííûõ ðåçóëüòàòîâ õðî-
ìàòîãðàôèè ãàçà, äîïóñêàþùèõ, ÷òî óêàçàííîå âûøå óòâåðæäåíèå âåðíî.
Ïîïðàâî÷íûé êîýôôèöèåíò áûë âçÿò íåïîñðåäñòâåííî èç ASTM 3612. Îòêîð-
ðåêòèðîâàííûå ðåçóëüòàòû ïîêàçûâàþò óëó÷øåíèå ïî ñðàâíåíèþ ñ íåèñïðàâ-
ëåííûì ðåçóëüòàòîì îòíîñèòåëüíî àáñîëþòíîé òî÷íîñòè.
Òàáëèöà 3
Íîâûé îáðàçåö äåãàçèðîâàííîãî ìàñëà,
íàñûùåííîãî ñìåñüþ ãàçà 50
µl/l
Ãàç Èçâëå÷åíî,
µl/l
Èçìåðåííàÿ êîíöåíòðàöèÿ,
µl/l
Îòêîððåêòèðîâàíî µl/l
PAES GC
H
2
0 9 0 0
CH
4
47 50 40 31
C
2
H
6
46 51 15 36
C
2
H
4
46 47 19 34
C
2
H
2
50 47 20 25
CO 49 48 38 17
CO
2
46 97 164 221
86
Òàáëèöà 4
Íîâûé îáðàçåö äåãàçèðîâàííîãî ìàñëà, íàñûùåííîãî ñìåñüþ ãàçà 100 µl/l
Ãàç Èçâëå÷åíî,
µl/l
Èçìåðåííàÿ êîíöåíòðàöèÿ,
µl/l
Îòêîððåêòèðîâàíî µl/l
PAES GC
H
2
0 10 0 0
CH
4
94 98 73 56
C
2
H
6
92 101 29 70
C
2
H
4
92 90 36 65
C
2
H
2
101 96 42 53
CO 97 97 76 34
CO
2
92 140 127 171
Òàáëèöà 5
Íîâûé îáðàçåö äåãàçèðîâàííîãî ìàñëà, íàñûùåííîãî ñìåñüþ ãàçà 200 µl/l
Ãàç Èçâëå÷åíî,
µl/l
Èçìåðåííàÿ êîíöåíòðàöèÿ, µl/l Îòêîððåêòèðîâàíî, µl/l
PAES GC
H
2
0 12 0 0
CH
4
202 190 144 111
C
2
H
6
197 202 60 145
C
2
H
4
197 180 75 135
C
2
H
2
216 194 91 115
CO 208 191 176 79
CO
2
197 228 247 333
Òàáëèöà 6
Íîâûé îáðàçåö äåãàçèðîâàííîãî ìàñëà, íàñûùåííîãî ñìåñüþ ãàçà 250
µl/l
Ãàç Èçâëå÷åíî,
µl/l
Èçìåðåííàÿ êîíöåíòðàöèÿ, µl/l Îòêîððåêòèðîâàíî, µl/l
PAES GC
H
2
0 61 0 0
CH
4
253 242 175 135
C
2
H
6
246 245 75 182
C
2
H
4
246 226 93 167
C
2
H
2
270 252 115 145
CO 260 246 218 98
CO
2
246 232 282 381
87
Òàáëèöà 7
Èñïîëüçîâàííûé îáðàçåö äåãàçèðîâàííîãî ìàñëà, íàñûùåííîãî ñìåñüþ ãàçà
Ãàç Èçâëå÷åíî,
µl/l
Èçìåðåííàÿ êîíöåíòðàöèÿ, µl/l Îòêîððåêòèðîâàíî, µl/l
PAES GC
H
2
0 32 0 0
CH
4
189 212 149 115
C
2
H
6
183 206 60 145
C
2
H
4
183 190 74 133
C
2
H
2
201 194 90 113
CO 194 224 197 89
CO
2
183 286 297 401
Òàáëèöà 8
Íîâûé îáðàçåö äåãàçèðîâàííîãî ìàñëà, íàñûùåííîãî òîëüêî âîäîðîäîì
Ãàç Èçâëå÷åíî,
µl/l
Èçìåðåííàÿ êîíöåíòðàöèÿ, µl/l Îòêîððåêòèðîâàíî, µl/l
PAES GC
H
2
101 82 120 48
CH
4
0 1 0 0
C
2
H
6
0 1 0 0
C
2
H
4
0 1 0 0
C
2
H
2
0 0 0 0
CO
0 2 0 0
CO
2
0 67 55 22
H
2
CH
4
C
2
H
6
C
2
H
4
C
2
H
2
CO CO
2
Показания
Ðèñ. 1. Êîððåëÿöèÿ ìåæäó îáðàçöàìè, íàñûùåííûìè 50 µl/l, è ïîêàçàíèÿìè ïðèáîðîâ
88
H
2
CH
4
C
2
H
6
C
2
H
4
C
2
H
2
CO CO
2
Показания
Ðèñ. 2. Êîððåëÿöèÿ ìåæäó îáðàçöàìè, íàñûùåííûìè 100 µl/l, è ïîêàçàíèÿìè ïðèáîðîâ
H
2
CH
4
C
2
H
6
C
2
H
4
C
2
H
2
CO CO
2
Показания
Ðèñ. 3. Êîððåëÿöèÿ ìåæäó îáðàçöàìè, íàñûùåííûìè 200 µl/l, è ïîêàçàíèÿìè ïðèáîðîâ
H
2
CH
4
C
2
H
6
C
2
H
4
C
2
H
2
CO CO
2
Показания
Ðèñ. 4. Êîððåëÿöèÿ ìåæäó îáðàçöàìè, íàñûùåííûìè 250 µl/l, è ïîêàçàíèÿìè ïðèáîðîâ
89
Ôîòîàêóñòè÷åñêàÿ ñïåêòðîñêîïèÿ îáåñïå÷èëà âûñîêóþ ïîâòîðÿþùóþñÿ
êîððåëÿöèþ ìåæäó êîëè÷åñòâîì âûäåëåííîãî ãàçà è ðåçóëüòàòàìè èçìåðåíèé
ðàñòâîðèìîñòè ãàçà â ìàñëå ïðè àíàëèçå ñòàíäàðòíûõ êîëè÷åñòâåííûõ îáðàçöîâ
ñ ñîäåðæàíèåì ãàçà. Áûëî âûÿâëåíî, ÷òî â òî âðåìÿ êàê àíàëèç õðîìàòîãðàôèè
ãàçà äàâàë ïîâòîðÿåìûå ðåçóëüòàòû, èìåëî ìåñòî çíà÷èòåëüíîå ðàñõîæäåíèå
ìåæäó êîëè÷åñòâîì âûäåëåííîãî ãàçà è ïîëó÷àåìûìè ðåçóëüòàòàìè ðàñòâî-
ðèìîñòè ãàçà â ìàñëå. Êîððåêöèÿ â öåëîì ïîïðàâèëà ýòî, õîòÿ ñîäåðæàíèå
óãàðíîãî ãàçà (CO) è óãëåêèñëîãî ãàçà (CO
2
) âñå åùå çíà÷èòåëüíî îòêëîíÿåòñÿ
îò îæèäàåìûõ çíà÷åíèé, âîçìîæíî, èç-çà èçâåñòíûõ íåäîñòàòêîâ ëèíåéíîñòè
ëþáîãî ìåòàíàòîðà, èñïîëüçóåìîãî â õðîìàòîãðàôèè ãàçà äëÿ âûÿâëåíèÿ ýòèõ
ãàçîâ.
Âûâîäû
Ñåãîäíÿ õðîìàòîãðàôèÿ ãàçà – ýòî âñïîìîãàòåëüíûé ìåòîä äëÿ àíàëèçà
ðàñòâîðåííîãî ãàçà. Êàê ïðàâèëî, õðîìàòîãðàôû íóæíî íàñòðàèâàòü ñ ó÷åòîì
ñòàíäàðòîâ ðàñòâîðåííûõ ãàçîâ â ìàñëå, êîòîðûå ÿâëÿþòñÿ äîñòóïíûìè äëÿ
ïðèîáðåòåíèÿ èëè ïîäãîòàâëèâàþòñÿ â ðàìêàõ ñîáñòâåííîãî ïðîèçâîäñòâà; ýòè
ñòàíäàðòû ó÷èòûâàþò íåêîòîðûå, íî íå âñå âîçìîæíûå èñòî÷íèêè ïîãðåøíî-
ñòåé, êîòîðûå ìîãóò ïîâëèÿòü íà êà÷åñòâî êîíå÷íîãî ðåçóëüòàòà. Ê ñîæàëåíèþ,
íå ñóùåñòâóåò àáñîëþòíîãî ìåòîäà, êîòîðûé áû ïîçâîëÿë âûïîëíÿòü òàêóþ íà-
ñòðîéêó ñî ñòàíäàðòàìè àáñîëþòíî èçâåñòíûõ êîíöåíòðàöèé ãàçà.
Êðîìå òîãî, ïî âñåìó ìèðó ñóùåñòâóþò íåñêîëüêî ëàáîðàòîðèé, êîòîðûå
ñòðîãî íå ñëåäóþò àíàëèòè÷åñêîé ïðîöåäóðå, îïèñàííîé â ìåæäóíàðîäíûõ
ñòàíäàðòàõ, âêëþ÷àÿ ïîïðàâêè íà òåìïåðàòóðó, äàâëåíèå, îñîáåííî êîãäà èñ-
ïîëüçóåòñÿ ìåòîä ðàâíîâåñíîãî ñîñòîÿíèÿ, ÷òîáû óðàâíÿòü ðåçóëüòàòû ãàçîâîé
è ìàñëÿíîé ôàç.
 äàííîì èññëåäîâàíèè ìåòîä ôîòîàêóñòè÷åñêîé ñïåêòðîñêîïèè äàë òî÷íûå
è ïðàâèëüíûå ðåçóëüòàòû ïî ðÿäó êîíöåíòðàöèé è ñ èñïîëüçîâàíèåì ðàçëè÷íûõ
ìàñåë ïóòåì èñïîëüçîâàíèÿ èçâåñòíûõ ñòàíäàðòíûõ îáðàçöîâ ðàñòâîðèìîñòè
ãàçà â ìàñëå. Åäèíñòâåííûì èñêëþ÷åíèåì ÿâëÿåòñÿ âûÿâëåíèå ìàëîãî êîëè÷å-
ñòâà âîäîðîäà, êîãäà îí â äåéñòâèòåëüíîñòè îòñóòñòâóåò. Ýòîò îøèáî÷íûé ïî-
ëîæèòåëüíûé ðåçóëüòàò ìîæåò áûòü âûçâàí áûñòðîé ðåàêöèåé ñåíñîðà òâåðäî-
òåëüíîãî âîäîðîäà íà àöåòèëåí. Íà ïðàêòèêå æå ìàñëî òðàíñôîðìàòîðà âñåãäà
áóäåò ñîäåðæàòü çíà÷èòåëüíîå êîëè÷åñòâî âîäîðîäà, åñëè ïðèñóòñòâóåò àöåòè-
ëåí, òàê ÷òî ýòà ÷óâñòâèòåëüíîñòü ñåíñîðà áóäåò èìåòü ëèáî íåçíà÷èòåëüíûé
ýôôåêò, ëèáî âîîáùå íå ïîâëèÿåò íà ïðîâîäèìóþ äèàãíîñòèêó.
Ïîñëå òîãî êàê ðåçóëüòàòû õðîìàòîãðàôèè ãàçà îòêîððåêòèðîâàíû ñ ó÷å-
òîì êîýôôèöèåíòà ðàñïðåäåëåíèÿ è îáúåìíîãî îòíîøåíèÿ, îíè, êàê ïðàâèëî,
áîëåå òî÷íû è âïîëíå ñîïîñòàâèìû ñ ðåçóëüòàòàìè ôîòîàêóñòè÷åñêîé ñïåêòðî-
ñêîïèè.
1. Bucholz M. The Bucholz protective system and its practical applications // Elektrotec. Z. (Germa-
ny). 1928. Vol. 49. P. 1257–1261.
2. IEC 60599:2007 – Mineral oil-impregnated equipment in service- interpretation of dissolved and
free gases analysis.