CN106840792A - A kind of method of corrosivity chlorinity in detection fire-resistance oil - Google Patents
A kind of method of corrosivity chlorinity in detection fire-resistance oil Download PDFInfo
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Abstract
The invention discloses a kind of method for detecting corrosivity chlorinity in fire-resistance oil, by decomposing and the corrosivity chlorine in fire-resistance oil is separated, it is accurate to calculate the corrosivity chlorinity obtained in fire-resistance oil sample.This method overcomes existing method and can only carry out chloride content detection, fire-resistance oil fresh oil can not pointedly be assessed and oily corrosive shortcoming is run, realize the accurate detection of corrosivity chlorinity in fire-resistance oil, effectively prevent easily to deteriorate, have the fire resistant oil access arrangement of harm, it is accurate to judge whether be subject to corrosivity chlorine pollution during oil product use, ensure the safety in operation of equipment.
Description
Technical field
The invention belongs to electric power chemical analysis field, and in particular to corrosivity chlorinity in one kind detection fire-resistance oil
Method.
Background technology
Fire-resistance oil has the advantages that anti-oxidative stability is good, hydrolytic stability is strong and heat resistant fire-proof is good, extensively
Working media as electrohydaulic speed governor system.However, because the complexity of production technology limitation and use environment causes fire-resistant
Chlorine-bearing compound is inevitably present in oil, raw material (such as POCl3, the catalyst metals villaumite of production residual is generally comprised
Deng), the cl contaminant that touches during byproduct of reaction (such as hydrochloric acid, chloride phosphate) and use (such as neoprene,
The chlorinated solvents such as the chloride encapsulant such as leather, rubber asbestos gasket, equipment cleaning gasoline, chloralkane).The exceeded appearance of chlorinity
It is easily caused fire resistant oil and accelerates hydrolytic degradation and corrosion electro-hydraulic control system metal material, thrashing is made when serious, triggers tight
The security incident of weight.Wherein, butter (hydrochloric acid, metal chloride etc.) and labile organic chloride (such as POCl3,
Chloride phosphate etc.) it is big to the harmfulness of oil quality and system, unite and be classified as corrosivity chlorine, and remaining organic chloride stable in properties
Thing harm is small, is non-aggressive chlorine.However, existing method is to test chlorine after fire-resistance oil is decomposed completely to contain at present
Amount, including：Bomb method (DL/T 433-2015), high-temp combustion small-hole drilling (DL/T 1206-2013), clear up-automatic current potential
Titration (ZL 201410320222.1) etc., or the chlorine element directly tested in fire resistant oil using x-ray fluorescence spectrometry method
Content, these methods can only carry out total content detection (total chlorine) to chlorine-bearing compound, it is impossible to which corrosivity chlorine is made a distinction individually
Detection, its result is used to assess obvious lack of targeted when oil property and its harmfulness to system.Therefore, it is quite necessary to
The detection method of corrosivity chlorinity in fire-resistance oil is set up, for the safe operation of equipment provides reliable guarantee.
The content of the invention
Chloride content can only be detected in traditional fire-resistance oil it is an object of the invention to be directed to, and can not effective table
Levy the present situation of the chlorine extent of injury in fire-resistance oil, there is provided a kind of simple, accurate, test repeatability is good, can accurately judge
Whether corrosivity chlorine pollution is subject to during oil product use, equipment safety in operation is ensured, in Efficient Characterization fire-resistance oil
The method of corrosivity chlorinity in the accurate detection fire-resistance oil of the present situation of the chlorine extent of injury.
To achieve these goals, the solution of the present invention is a kind of detection of corrosivity chlorinity in fire-resistance oil
Method, methods described comprises the following steps：
1) decompose and separate the corrosivity chlorine in fire-resistance oil；
It is 50 according to volume mass ratio that test solution will be decomposed with fire-resistance oil:1-1:3 (mL/mg) mix, and stirring heats up
To 50~100 DEG C, the easy decomposition organic chloride in the corrosivity chlorine in fire-resistance oil is decomposed, be cooled to room temperature, point
Layer, obtains upper strata and decomposes test solution and lower floor's fire-resistance oil, determines upper strata and decomposes chlorinity C in test solution1；
Butter and easy decomposition organic chloride in corrosivity chlorine are most of after decomposing to be tried into upper strata decomposition
In liquid, non-aggressive chlorine is stayed in lower floor's fire-resistance oil；
2) using unmixed fire-resistance oil and step 1) the decomposition test solution of equivalent as blank test solution, to blank
Control test solution is according to step 1) same operation is carried out, then determine its chlorinity C0；
3) mass percentage content of corrosivity chlorine is calculated according to equation below (a) in the nitrate fire resistant oil：
C=(C1-C0)/R (a)
Wherein, C is the mass percent of corrosivity chlorine in fire-resistance oil, and unit is mg/kg；
C1For step 1) upper strata decompose test solution in chlorinity, unit is mg/L；
C0For step 2) blank test solution in chlorinity, unit is mg/L；
R be step 1) in fire-resistance oil with decompose test solution mass volume ratio, unit is kg/L；
Wherein, it is that water, the not chloride acid solution that mass fraction is 0.1%~20% or alkalescence are water-soluble to decompose test solution
Liquid.
In step 1) in, by above-mentioned ingenious control, the easy decomposition chloride in fire-resistance oil on the one hand can be made
Decompose, and enter in decomposition test solution, another aspect butter can also enter in decomposition test solution, so as to effectively pass through a step
Acquire the content of corrosivity chlorine.
Total chlorine includes corrosivity chlorine and non-aggressive chlorine.
Corrosivity chlorine includes butter and easily decomposes organic chloride.
The present invention further includes following preferred technical scheme：
Preferred scheme, further determines distribution coefficient K of the corrosivity chlorine in fire resistant oil and decomposition test solution；
To the inorganic chlorine C for decomposing test solution addition any concentration3, mixed with the not chloride blank fire-resistance oil of same volume
Close, and by step 2) flow processing mixed liquor, after separation test remain in decompose test solution in chlorinity C4, calculate and divided
Distribution coefficient K=(C3-C4)/C4；By (1+K) (C1-C0)/R is calculated the corrosivity chlorinity in fire-resistance oil.
(1+K)(C1-C0)/R(b)
By determining distribution coefficient K, the measurement essence of the corrosivity chlorinity in fire-resistance oil can be further improved
Degree.
Described acid solution is HNO3、H2SO4、H3PO4Or H3BO3Solution, described alkaline solution for LiOH, NaOH or
KOH solution.
Preferred scheme, step 2) in, be layered by being centrifuged, the rotating speed in centrifugation delaminating process for 1000rad/min~
20000rad/min。
Preferred scheme, step 2) in, the centrifugation time is 1min~30min.
Preferred scheme, the corrosivity chlorine includes butter and easily decomposes organic chloride.
Preferred scheme, step 2) in, decomposed into upper strata after butter and the easily decomposition of decomposition organic chloride
In test solution, non-aggressive chlorine is stayed in lower floor's fire-resistance oil.
Preferred scheme, chlorinity is determined by x-ray fluorescence spectrometry method.
Preferred scheme, in detection process, at least carries out three parallel tests, and final result is the flat of three result of the tests
Average.
It is preferred that stirring heats up most 50 DEG C, 65 DEG C, 75 DEG C, 85 DEG C or 100 DEG C.
After stirring heats up, preferably constant 2~24h.
Further preferred constant 4h, 8h, 12h, 16h or 24h.
Heated up by stirring, decompose the corrosivity chlorine in fire-resistance oil sample, phosphoric acid is obtained after being cooled to room temperature
Mixed liquor after the completion of ester fire-resistant oil samples and decomposition test solution reaction, then mixed liquor is poured into centrifuge tube be centrifuged, and is made
Fire-resistance oil sample enters in decomposition test solution with test solution layering, corrosivity chlorine is decomposed, and non-aggressive chlorine stays in lower floor's phosphoric acid
In ester fire resistant oil, layer fire-resistance oil is removed to be measured.
Not chloride acid solution or the mass fraction of alkaline aqueous solution are preferably 0.1%, 0.5%, 2%, 8%, 15%
Or 20%.
The centrifugal rotational speed be preferably 1000rad/min, 3000rad/min, 5000rad/min, 10000rad/min,
15000rad/min or 20000rad/min.
The centrifugation time is preferably 1min, 5min, 10min, 20min or 30min.
Step 1) decomposable process preferably carried out in high temperature high voltage resistant, corrosion-resistant reactor.
The country once had multiple thermal power plants to occur because fire resistant oil inferior quality causes fire resistant oil hydrolytic degradation and metal material
Expect the problem of corrosion, or even occur to change fresh oil, electro-hydraulic control system part and whole system and stopping transport causing the failure of shutdown.
Chloride content meets standard requirement during a lot of fire resistant oils are found in detection, but is contained using corrosivity chlorine in present invention detection discovery oil
Amount ratio is higher, is the main cause for causing above mentioned problem.For this present situation, inventor is finally carried by constantly research
The solution of the present invention is gone out.
Compared with prior art, beneficial effects of the present invention are：
(1) it is present invention firstly provides being measured to the corrosivity chlorinity in fire-resistance oil and of the invention
It is applied widely, fresh oil, run it is oily and it is retired scrap oil can detect.
(2) the corrosivity chlorinity result that the present invention is measured can be used for precise Identification fire-resistance oil confrontation Fuel System
The harmfulness of system equipment metal.
(3) test result of the present invention is accurate, test repeatability is good.
The present invention breaches prior art and can only test the thought and technical limitation of chloride content in fire resistant oil, carries first
Go out and realize by corrosivity chlorinity in simple method Accurate Determining fire resistant oil, so as to examination of being dispatched from the factory to fire-resistance oil
Test, the pollution during material sampling observation and use and deterioration condition are accurately judged, prevent underproof fire resistant oil and enter
Equipment, detects the quality of fire resistant oil in operational outfit in time, ensures production safety.
The present invention can carry out the assessment of more efficient and specific aim to phosphate fuel oil, accurately judge Oil Production and used
Whether corrosivity chlorine pollution is subject in journey.Some chloride contents that are particularly prevented from of the invention are relatively low, but corrosivity chlorinity
Fire resistant oil higher enters system, causes system corrosion and operation troubles, lifting system safe operation stability.It is of the invention to carry
Go out has very important realistic meaning for the industry.
Specific embodiment
To illustrate the invention to the detectability of corrosivity chlorine in different fire-resistance oils, embodiment 1,2 is phosphoric acid
Ester fire resistant oil fresh oil, embodiment 3~5 are that fire-resistance oil runs oil, and embodiment 6,7 is that fire-resistance oil is retired scraps
As test specimen, embodiment 8~10 is using existing methods comparative example to oil.
Embodiment 1
Prepare 0.1% HNO3Aqueous solution 50mL is added in high temperature high voltage resistant and corrosion resistant polytetrafluoroethylene (PTFE) autoclave,
Stirring is warming up to 100 DEG C, constant 12h, is cooled to after room temperature as blank control group.Prepare 0.1% HNO3Aqueous solution 50mL,
Weigh in 1g fire-resistance oils fresh oil addition high temperature high voltage resistant and corrosion resistant polytetrafluoroethylene (PTFE) autoclave, stirring is warming up to
100 DEG C, constant 2h is cooled to after room temperature and obtains fire-resistance oil sample and decompose the mixed liquor after the completion of test solution reaction.Will
Mixed liquor pours into centrifuge tube and 30min is centrifuged with rotating speed 1000rad/min, makes fire-resistance oil sample and decomposes test solution point
Layer, corrosivity chlorine enters in the aqueous solution in fire-resistance oil sample, takes upper strata decomposition test solution to be measured.Then chromatography of ions is used
The chlorinity C of the aqueous solution in instrument analysis margin control group0With chlorinity C in the decomposition test solution after centrifugation1, according to formula (a)
Fire-resistance oil sample etches chlorinity is calculated, five results of parallel test are average chlorine content.Test result is such as
Shown in table 1：
The test result of corrosivity chlorinity in the fire-resistance oil fresh oil of table 1
As can be seen from Table 1, the standard deviation of the corrosivity chlorinity result tested using this method is 0.16mg/kg,
Relative standard deviation is 1.91%, small with error, and standard deviation is low, as a result accurately, the good advantage of test repeatability.
Embodiment 2
Remove in ionized water 30mL addition high temperature high voltage resistants and corrosion resistant polytetrafluoroethylene (PTFE) autoclave, stirring is warming up to 85
DEG C, constant 24h is cooled to after room temperature as blank control group.Ionized water 30mL is removed, 1g fire-resistance oil fresh oils is weighed and is added
Enter in high temperature high voltage resistant and corrosion resistant polytetrafluoroethylene (PTFE) autoclave, stirring is warming up to 85 DEG C, constant 24h, after being cooled to room temperature
Obtain fire-resistance oil sample and decompose the mixed liquor after the completion of test solution reaction.Mixed liquor is poured into centrifuge tube with rotating speed
3000rad/min is centrifuged 10min, fire-resistance oil sample is layered with test solution is decomposed, and corrodes in fire-resistance oil sample
Property chlorine enter decompose test solution in, take upper strata decompose test solution it is to be measured.Then decomposed using in ion chromatograph analysis margin control group
The chlorinity C of test solution0With chlorinity C in the decomposition test solution after centrifugation1, fire-resistance oil sample is calculated according to formula (a)
Product corrosivity chlorinity, five results of parallel test are average chlorine content.Test result is as shown in table 2：
The test result of corrosivity chlorinity in the fire-resistance oil fresh oil of table 2
As can be seen from Table 2, the standard deviation of the corrosivity chlorinity result tested using this method is 0.20mg/kg,
Relative standard deviation is 2.30%, small with error, and standard deviation is low, as a result accurately, the good advantage of test repeatability.
Embodiment 3
1) 0.5% H is prepared2SO4Aqueous solution 20mL adds high temperature high voltage resistant and corrosion resistant polytetrafluoroethylene (PTFE) autoclave
In, stirring is warming up to 50 DEG C, constant 8h, is cooled to after room temperature as blank control group.
2) 0.5% H is prepared2SO4Aqueous solution 20mL, weigh 1g fire-resistance oils operation oil add high temperature high voltage resistant and
In corrosion resistant polytetrafluoroethylene (PTFE) autoclave, stirring is warming up to 50 DEG C, and constant 8h obtains fire-resistance oil after being cooled to room temperature
Mixed liquor after the completion of sample and decomposition test solution reaction.Mixed liquor is poured into centrifuge tube and is centrifuged with rotating speed 10000rad/min
5min, makes fire-resistance oil sample be layered with test solution is decomposed, and corrosivity chlorine enters decomposition test solution in fire-resistance oil sample
In, take upper strata decomposition test solution to be measured.
3) the chlorinity C of test solution and then in use high-temp combustion Microcoulomb instrument analysis margin control group is decomposed0With centrifugation point
Chlorinity C in decomposition test solution after1；
Certain density inorganic chlorine C is added to test solution is decomposed3, mixed with the not chloride blank fire-resistance oil of same volume
Close, and by step 2) flow processing mixed liquor, after separation test remain in decompose test solution in chlorinity C4, calculate and divided
Distribution coefficient K=(C3-C4)/C4；K=0.0989
By (1+K) (C1-C0)/R is calculated the corrosivity chlorinity in fire-resistance oil.
Five results of parallel test are average chlorine content.Test result is as shown in table 3：
The test result of corrosivity chlorinity in the fire-resistance oil of table 3 operation oil
As can be seen from Table 3, the standard deviation of the corrosivity chlorinity result tested using this method is 0.87mg/kg,
Relative standard deviation is 3.49%, small with error, and standard deviation is low, as a result accurately, the good advantage of test repeatability.
Embodiment 4
1) 20% H is prepared3PO4Aqueous solution 10mL is added in high temperature high voltage resistant and corrosion resistant polytetrafluoroethylene (PTFE) autoclave,
Stirring is warming up to 75 DEG C, constant 16h, is cooled to after room temperature as blank control group.
2) 20% H is prepared3PO4Aqueous solution 10mL, weighs 1g fire-resistance oils operation oil and adds high temperature high voltage resistant and resistance to
In the polytetrafluoroethylene (PTFE) autoclave of corrosion, stirring is warming up to 75 DEG C, and constant 16h obtains fire-resistance oil after being cooled to room temperature
Mixed liquor after the completion of sample and decomposition test solution reaction.Mixed liquor is poured into centrifuge tube and is centrifuged with rotating speed 5000rad/min
10min, makes fire-resistance oil sample be layered with test solution is decomposed, and corrosivity chlorine enters decomposition test solution in fire-resistance oil sample
In, take upper strata decomposition test solution to be measured.
3) the chlorinity C of test solution and then in use x-ray fluorescence spectrometry instrument analysis margin control group is decomposed0With centrifugation point
Chlorinity C in decomposition test solution after1,
Certain density inorganic chlorine C is added to test solution is decomposed3, mixed with the not chloride blank fire-resistance oil of same volume
Close, and by step 2) flow processing mixed liquor, after separation test remain in decompose test solution in chlorinity C4, calculate and divided
Distribution coefficient K=(C3-C4)/C4；K=0.0957
By (1+K) (C1-C0)/R is calculated the corrosivity chlorinity in fire-resistance oil.
Five results of parallel test are average chlorine content.Test result is as shown in table 4：
The test result of corrosivity chlorinity in the fire-resistance oil of table 4 operation oil
As can be seen from Table 4, the standard deviation of the corrosivity chlorinity result tested using this method is 0.54mg/kg,
Relative standard deviation is 2.18%, small with error, and standard deviation is low, as a result accurately, the good advantage of test repeatability.
Embodiment 5
1) prepare in 8% LiOH aqueous solution 3mL addition high temperature high voltage resistants and corrosion resistant polytetrafluoroethylene (PTFE) autoclave, stir
Mix and be warming up to 85 DEG C, constant 8h is cooled to after room temperature as blank control group.
2) 8% LiOH aqueous solution 3mL are prepared, 1g fire-resistance oils operation oil is weighed and is added high temperature high voltage resistant and corrosion resistant
In the polytetrafluoroethylene (PTFE) autoclave of erosion, stirring is warming up to 85 DEG C, and constant 8h obtains fire-resistance oil sample after being cooled to room temperature
With the mixed liquor after the completion of decomposition test solution reaction.Mixed liquor is poured into centrifuge tube 1min is centrifuged with rotating speed 15000rad/min,
Fire-resistance oil sample is set to be layered with test solution is decomposed, corrosivity chlorine enters in decomposition test solution in fire-resistance oil sample, takes
It is to be measured that test solution is decomposed on upper strata.
3) the chlorinity C of test solution and then in use potentiometric titrimeter analysis margin control group is decomposed0After centrifugation
Decompose chlorinity C in test solution1。
Certain density inorganic chlorine C is added to test solution is decomposed3, mixed with the not chloride blank fire-resistance oil of same volume
Close, and by step 2) flow processing mixed liquor, after separation test remain in decompose test solution in chlorinity C4, calculate and divided
Distribution coefficient K=(C3-C4)/C4；K=0.0996
By (1+K) (C1-C0)/R is calculated the corrosivity chlorinity in fire-resistance oil.
Five results of parallel test are average chlorine content.Test result is as shown in table 5：
The test result of corrosivity chlorinity in the fire-resistance oil of table 5 operation oil
As can be seen from Table 5, the standard deviation of the corrosivity chlorinity result tested using this method is 0.72mg/kg,
Relative standard deviation is 2.92%, small with error, and standard deviation is low, as a result accurately, the good advantage of test repeatability.
Embodiment 6
1) prepare in 20% KOH aqueous solution 1mL addition high temperature high voltage resistants and corrosion resistant polytetrafluoroethylene (PTFE) autoclave, stir
Mix and be warming up to 50 DEG C, constant 4h is cooled to after room temperature as blank control group.
2) prepare 20% KOH aqueous solution 1mL, weigh 1g fire-resistance oils it is retired scrap oil add high temperature high voltage resistant and
In corrosion resistant polytetrafluoroethylene (PTFE) autoclave, stirring is warming up to 50 DEG C, and constant 4h obtains fire-resistance oil after being cooled to room temperature
Mixed liquor after the completion of sample and decomposition test solution reaction.Mixed liquor is poured into centrifuge tube and is centrifuged with rotating speed 20000rad/min
1min, makes fire-resistance oil sample be layered with test solution is decomposed, and corrosivity chlorine enters decomposition test solution in fire-resistance oil sample
In, take upper strata decomposition test solution to be measured.
3) the chlorinity C of test solution and then in use high-temp combustion Microcoulomb instrument analysis margin control group is decomposed0With centrifugation point
Chlorinity C in decomposition test solution after1。
Certain density inorganic chlorine C is added to test solution is decomposed3, mixed with the not chloride blank fire-resistance oil of same volume
Close, and by step 2) flow processing mixed liquor, after separation test remain in decompose test solution in chlorinity C4, calculate and divided
Distribution coefficient K=(C3-C4)/C4；K=0.0969
By (1+K) (C1-C0)/R is calculated the corrosivity chlorinity in fire-resistance oil.
Five results of parallel test are average chlorine content.Test result is as shown in table 6：
The retired test result for scrapping corrosivity chlorinity in oil of the fire-resistance oil of table 6
As can be seen from Table 6, the standard deviation of the corrosivity chlorinity result tested using this method is 2.26mg/kg,
Relative standard deviation is 3.36%, small with error, and standard deviation is low, as a result accurately, the good advantage of test repeatability.
Embodiment 7
1) in the NaOH aqueous solution 1mL addition high temperature high voltage resistants and corrosion resistant polytetrafluoroethylene (PTFE) autoclave of preparation 15%,
Stirring is warming up to 65 DEG C, constant 2h, is cooled to after room temperature as blank control group.
2) 15% NaOH aqueous solution 1mL are prepared, the retired oil of scrapping of 3g fire-resistance oils is weighed and is added high temperature high voltage resistant
In corrosion resistant polytetrafluoroethylene (PTFE) autoclave, stirring is warming up to 65 DEG C, and constant 2h obtains phosphate fire-resistant after being cooled to room temperature
Mixed liquor after the completion of oil samples and decomposition test solution reaction.Mixed liquor is poured into centrifuge tube and is centrifuged with rotating speed 5000rad/min
10min, makes fire-resistance oil sample be layered with test solution is decomposed, and corrosivity chlorine enters decomposition test solution in fire-resistance oil sample
In, take upper strata decomposition test solution to be measured.
3) the chlorinity C of test solution and then in use x-ray fluorescence spectrometry instrument analysis margin control group is decomposed0With centrifugation point
Chlorinity C in decomposition test solution after1。
Certain density inorganic chlorine C is added to test solution is decomposed3, mixed with the not chloride blank fire-resistance oil of same volume
Close, and by step 2) flow processing mixed liquor, after separation test remain in decompose test solution in chlorinity C4, calculate and divided
Distribution coefficient K=(C3-C4)/C4；K=0.0954；
By (1+K) (C1-C0)/R is calculated the corrosivity chlorinity in fire-resistance oil.
Five results of parallel test are average chlorine content.Test result is with embodiment 1,2 to such as shown in table 7：
The retired test result for scrapping corrosivity chlorinity in oil of the fire-resistance oil of table 7
As can be seen from Table 7, the standard deviation of the corrosivity chlorinity result tested using this method is 2.30mg/kg,
Relative standard deviation is 3.51%, small with error, and standard deviation is low, as a result accurately, the good advantage of test repeatability.
Comparative example 8
Using bomb method, high-temp combustion small-hole drilling, clear up-potentiometric titration and x-ray fluorescence spectrometry method be to embodiment
1st, the fire-resistance oil fresh oil in 2 has carried out chlorinity test, and five results of parallel test are average chlorine content.Its test
Result is as shown in table 8.
The contrast of the test result and embodiment 1,2 of chlorine in the existing method test fire-resistance oil fresh oil of table 8
From the results, it was seen that bomb method, high-temp combustion small-hole drilling, clear up-automatic potentiometric titration and X-ray it is glimmering
The result that the chlorinity value that light spectroscopic methodology is measured is tested apparently higher than this method, illustrates that the corrosivity chlorine in fire-resistance oil is
A part in total chlorine.Decomposing the corrosivity chlorine in fire resistant oil with separating step in the present invention is to measure corrosivity chlorinity
Major reason and essential step.
Comparative example 9
Using bomb method, high-temp combustion small-hole drilling, clear up-potentiometric titration and x-ray fluorescence spectrometry method be to embodiment
In 3~5 fire-resistance oil operation oil carried out chlorinity test, its test result and with embodiment 3~5 to such as table
Shown in 9.
The contrast of the test result and embodiment 1,2 of chlorine in the existing method test fire-resistance oil operation oil of table 9
From the results, it was seen that bomb method, high-temp combustion small-hole drilling, clear up-automatic potentiometric titration and X-ray it is glimmering
The result that the chlorinity value that light spectroscopic methodology is measured is tested apparently higher than this method, illustrates that the corrosivity chlorine in fire-resistance oil is
A part in total chlorine.Decomposing the corrosivity chlorine in fire resistant oil with separating step in the present invention is to measure corrosivity chlorinity
Major reason and essential step.
Comparative example 10
Using bomb method, high-temp combustion small-hole drilling, clear up-potentiometric titration and x-ray fluorescence spectrometry method be to embodiment
6th, the retired oil of scrapping of fire-resistance oil in 7 has carried out chlorinity test, its test result and with embodiment 6,7 to such as
Shown in table 10.
The contrast of the existing method test retired test result for scrapping chlorine in oil of fire-resistance oil of table 10 and embodiment 1,2
From the results, it was seen that bomb method, high-temp combustion small-hole drilling, clear up-automatic potentiometric titration and X-ray it is glimmering
The result that the chlorinity value that light spectroscopic methodology is measured is tested apparently higher than this method, illustrates that the corrosivity chlorine in fire-resistance oil is
A part in total chlorine.Decomposing the corrosivity chlorine in fire resistant oil with separating step in the present invention is to measure corrosivity chlorinity
Major reason and essential step.
Claims (10)
1. it is a kind of detect fire-resistance oil in corrosivity chlorinity method, it is characterised in that：Methods described includes following step
Suddenly：
1) decompose and separate the corrosivity chlorine in fire-resistance oil；
It is 50 according to volume mass ratio that test solution will be decomposed with fire-resistance oil:1-1:3 (mL/mg) mix, and stirring is warming up to 50
~100 DEG C, the easy decomposition organic chloride in the corrosivity chlorine in fire-resistance oil is decomposed, be cooled to room temperature, be layered, obtained
Test solution and lower floor's fire-resistance oil are decomposed to upper strata, upper strata is determined and is decomposed chlorinity C in test solution1；
Butter and easy decomposition organic chloride in corrosivity chlorine are most of after decomposing to be entered in upper strata decomposition test solution,
Non-aggressive chlorine is stayed in lower floor's fire-resistance oil；
2) using unmixed fire-resistance oil and step 1) the decomposition test solution of equivalent as blank test solution, to blank
Test solution is according to step 1) same operation is carried out, then determine its chlorinity C0；
3) mass percentage content of corrosivity chlorine is calculated according to equation below (a) in the nitrate fire resistant oil：
C=(C1-C0)/R (a)
Wherein, C is the mass percent of corrosivity chlorine in fire-resistance oil, and unit is mg/kg；
C1For step 1) upper strata decompose test solution in chlorinity, unit is mg/L；
C0For step 2) blank test solution in chlorinity, unit is mg/L；
R be step 1) in fire-resistance oil with decompose test solution mass volume ratio, unit is kg/L；
Wherein, it is water, the not chloride acid solution or alkaline aqueous solution that mass fraction is 0.1%~20% to decompose test solution.
2. detection method according to claim 1, it is characterised in that：Corrosivity chlorine is further determined in fire resistant oil and decomposition
Distribution coefficient K in test solution；
To the inorganic chlorine C for decomposing test solution addition any concentration3, mix with the not chloride blank fire-resistance oil of same volume, and press
Step 2) flow processing mixed liquor, after separation test remain in decompose test solution in chlorinity C4, calculate and obtain distribution coefficient K
=(C3-C4)/C4；By (1+K) (C1-C0)/R is calculated the corrosivity chlorinity in fire-resistance oil.
3. detection method according to claim 1 and 2, it is characterised in that：Described acid solution is HNO3、H2SO4、
H3PO4Or H3BO3Solution.
4. detection method according to claim 1 and 2, it is characterised in that：Described alkaline solution be LiOH, NaOH or
KOH solution.
5. detection method according to claim 1 and 2, it is characterised in that：After stirring is warming up to 50~100 DEG C, constant 2~
24h。
6. detection method according to claim 1 and 2, it is characterised in that：Step 2) in, it is layered by being centrifuged, centrifugation point
Rotating speed during layer is 1000rad/min~20000rad/min.
7. detection method according to claim 1 and 2, it is characterised in that：Step 2) in, the centrifugation time be 1min~
30min。
8. detection method according to claim 1 and 2, it is characterised in that：By ion chromatograph, potentiometric titrimeter, height
Temperature burning Microcoulomb instrument or x-ray fluorescence spectrometry instrument determine chlorinity.
9. detection method according to claim 1 and 2, it is characterised in that：In detection process, three parallel examinations are at least carried out
Test, final result is three average values of result of the test.
10. detection method according to claim 1 and 2, it is characterised in that：Step 1) decomposable process it is high in high temperature resistant
Carried out in pressure, corrosion-resistant reactor.
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| CN114660159A (en) * | 2022-03-21 | 2022-06-24 | 中国石油化工股份有限公司 | Method for retarding corrosion of rectification system of vinyl acetate device |
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