CN109709079A - A kind of ultraviolet fluorescence method measures combustion tube and the application of minim total sulfur content - Google Patents
A kind of ultraviolet fluorescence method measures combustion tube and the application of minim total sulfur content Download PDFInfo
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Abstract
The present invention relates to a kind of combustion tube of ultraviolet fluorescence method measurement minim total sulfur content and application, the measurement of the minim total sulphur content, total nitrogen and chloride content suitable for petrochemical enterprise sample.It discloses the protective sleeve of syringe needle pipe with injection port that insertion is provided with outside combustion tube sample introduction end face, in combustion tube from one partition of setting at injection port end 2/5ths, one combustion chamber is divided into a precombustion section and burning zone, protective sleeve of syringe needle pipe is arranged in precombustion section, the suction line and oxygen intake pipeline of oxygen and argon gas are provided in the precombustion section of combustion tube, the suction line of oxygen and argon gas is being arranged helically at partition, oxygen intake pipeline passes through in the through partition preformed hole of precombustion section, the inner combustion tube with helix tube is provided in the burning zone of combustion tube.The present invention increases the sample volume of sample, extends the burning time of sample, lowering apparatus detectable concentration to 0.1mg/kg, improves analysis speed and accuracy of analysis, extends the service life of quartz ampoule.
Description
Technical field:
The present invention relates to the combustion tubes of total sulfur content in ultraviolet fluorescence method measurement petrochemicals, are suitable for petrochemical industry
The measurement of total sulfur content in enterprise's air-liquid body sample is equally applicable to total nitrogen content in petrochemical enterprise air-liquid body sample
Measurement.
Background technique:
Sulfur content is an important content of analysis of oil, is an important Con trolling index in petrochemicals.Sulphur
Compound is to cause one of the main harm object of equipment burn into catalyst poisoning and engine scuffing, the sulfur content in petroleum refining
Accurate Determining have a very important significance.Currently, the method for measurement sulfur content mainly has small-hole drilling and ultraviolet fluorescence method.
Small-hole drilling influence factor is more, cumbersome, higher to the technical requirements of operator；Ultraviolet fluorescence method is easy to operate, again
Renaturation is good, accuracy is high, is the referee method that sulfur content detects in petrochemicals, but it is only suitable for measuring 1mg/Kg or more
Total sulfur content, be not suitable for 1mg/Kg minim total sulfur content below analysis, and the big portion of total sulfur content in petrochemicals
Divide and be less than 1mg/Kg, causes ultraviolet fluorescence method in the analysis application aspect of minim total sulfur content by biggish limitation.GB/
Although T11141 ultraviolet fluorescence method can measure the sulfur content of 0.2mg/Kg in gas, there is no detailed sulphur quartz ampoule in method
Structure chart and operating condition, it is not very practical, it is micro total in gas there is presently no being measured with domestic Ultraluminescence sulphur content analyzer
The document report of sulfur content.There are interference signals for Ultraluminescence sulphur content analyzer, little to the very high sample effects of sulfur content, to sulphur
The very low sample of content (total sulfur content is less than 0.5mg/Kg), measurement result influences very big.Because sulfide easily adsorbs, the minim total sulphur content
Gas standard specimen prepare and save difficult, be difficult to realize with gas standard specimen school Instrument measuring gaseous sample.Gaseous sample is measured to use
There are systematic error, corresponding technical problems to need to be solved for liquid standard specimen tester.Power & light company, the U.S. was to purple in recent years
Outer fluorescence combustion of sulfur pipe improves, and sample volume is increased to 100 microlitres by traditional 20 microlitres, but analysis time needs 6 minutes,
It is not able to satisfy the middle requirement controlled and quickly analyzed, and expensive equipment, only accessory gas sampler just needs 200,000 yuan or more, use cost
It is high, it is difficult to large-scale popularization application.Also there is the linguistic term to Ultraluminescence combustion of sulfur pipe in the country, mainly imitates U.S.'s thermoelectricity
The structure of combustion of sulfur pipe, problem coking, that analysis time is long and measurement result is inaccurate is still unresolved, and the minim total sulphur content in gas contains
Amount ultraviolet fluorescence method and the result of small-hole drilling the reason of there are larger differences and solution have not been reported.
Summary of the invention:
Goal of the invention is to provide combustion tube and the application of a kind of ultraviolet fluorescence method measurement minim total sulfur content, it can largely into
Sample and sample energy completely burned measure minim total sulfur content in sample rapidly and accurately to will pass through ultraviolet fluorescence method and (are less than
0.5mg/Kg), or by the nitriding that shines the content of micro total nitrogen in sample is rapidly and accurately measured.Establish a kind of liquid mark
The analysis method of minim total sulfur content in the Instrument measuring gaseous sample of sample school.
Technical solution:
The combustion tube of ultraviolet fluorescence method measurement minim total sulfur content of the present invention, to it on the basis of prior art combustion tube
Structure improves, it, which is particularly disclosed, is provided with the syringe needle protection with tubaeform injection port in the centre at combustion tube injection port end
Casing, protective sleeve of syringe needle pipe are inserted into the precombustion section in combustion tube, and a length of 13~15 centimetres of casing, internal diameter is 1~2 millimeter,
The tubaeform injection port head setting is outer 3~3.5 centimetres of combustion tube injection port end face.From injection port end five in combustion tube
One partition is set at/bis-, and the partition will be divided into two parts in combustion tube, a part is precombustion close to injection port end
Section, another part are burning zone close to mixed gas outlet end, and protective sleeve of syringe needle pipe is inserted into the precombustion section in combustion tube；Burning
Pipe injection port end separately has two by-pass lines to penetrate, one is oxygen and Ar inlet pipeline, the oxygen and Ar inlet pipeline are worn
It is arranged to "U" shaped after entering in combustion tube precombustion section, one section of helix tube, oxygen and argon gas is set in " U " word turning lower half
It is 3~4 millimeters that suction line, which is exported from injection port end inner wall,.The second is oxygen intake pipeline, the oxygen intake pipeline is passed through
Precombustion section is gone directly in partition preformed hole.A piece inner combustion tube with helix tube, the interior burning are set in the burning zone
Pipe is arranged to "U" shaped in the mixed gas outlet end close to burning zone, and "U" shaped inner combustion tube one end is connected to partition preformed hole
In, the other end is arranged from 1 centimeters of partition.
The present invention also discloses that a kind of Ultraluminescence rule determines the application of the combustion tube of minim total sulfur content simultaneously.
A) only logical carrier gas (Ar), the flow velocity of the carrier gas are 10~45mL/min in protective sleeve of syringe needle pipe.
B) lead to the gaseous mixture of oxygen and argon gas in oxygen and Ar inlet pipeline, the flow velocity of oxygen is 100~300mL/
Min, argon gas are 0~250mL/min.
C) lead to oxygen in oxygen intake pipeline, the flow velocity of oxygen is 200~500mL/min.
Working principle is to bring combustion tube and oxygen mix by carrier gas after gaseous specimen or liquid sample evaporation and burn,
Middle Determination of Trace Sulfur is largely converted into sulfur dioxide (fraction is converted into sulfur trioxide), and the gas that sample burning generates is removing water
Afterwards by ultraviolet light, the energy that sulfur dioxide absorbs ultraviolet light is converted into the sulfur dioxide (SO of excitation state2 *), when excitation state
Sulfur dioxide emits fluorescence when returning to the sulfur dioxide of stable state, and is detected by photomultiplier tube, is calculated by gained signal value
The sulfur content of sample out.The signal value of instrument with the fluorescence intensity that sulphur emits in addition to having outside the Pass, and there is also interference signal, interference letters
Number size it is related with sample combustion completeness.Because with liquid standard specimen school Instrument measuring gaseous sample, a certain amount of liquid mark
The interference signal of sample should be close with a certain amount of under test gas sample interference signal, and measurement result is just accurate, otherwise, can be because of liquid
The completeness of the gentle sample sample combustion of standard specimen is different, and the interference signal value of generation is different, biggish systematic error as a result occurs,
Leading to the measurement result of ultraviolet fluorescence method and the result of the small-hole drilling of classics, there are biggish deviations.The sample introduction item of liquid standard specimen
Part should be close with the sampling condition of gaseous sample, and the interference signal value of the two should also approach, and is measured with liquid standard specimen tester
Gaseous sample, interference signal value should cancel out each other, and the measurement result of ultraviolet fluorescence method could coincide with the result of small-hole drilling, point
It is just accurate to analyse result.
It is an advantage of the invention that higher or relatively low to minim total sulfur content result in domestic ultraviolet fluorescence method measurement gas (with
Traditional small-hole drilling compares) the reason of analyze and research, according to error Producing reason, targetedly to Ultraluminescence sulphur
The combustion of sulfur pipe and measuring method of analyzer improve, and the sample volume of improved combustion of sulfur pipe (quartz ampoule) sample is micro- from 20
Rising increases to 50 microlitres, and minimum detectable concentration is reduced to 0.1mg/Kg by 1mg/Kg, and analysis time is 90 seconds, than U.S. thermoelectricity
Instrument shortens 270 seconds.Improved method increases the sample volume of sample, extends the burning time of sample, the minimum inspection of lowering apparatus
Concentration is surveyed, the precision of analysis speed and analysis is improved.Quartz ampoule is not easy coking, extends the service life of quartz ampoule.It is improved
Method determines the sample volume of liquid standard specimen and the relationship of under test gas sample injection volume, eliminates standard specimen with caused by sample difference and is
System error, improves the accuracy of analysis.Improved method can measure the micro total of 0.1mg/Kg or more in gas and fluid sample
Sulfur content has biggish application value in petrochemical industry production.
Detailed description of the invention:
Fig. 1, schematic diagram of structure of the invention；
Fig. 2, traditional combustion of sulfur pipe organigram；
The influence of Fig. 3, precombustion section oxygen gas flow rate of the present invention to measurement result；
The influence of Fig. 4, precombustion section argon gas flow velocity of the present invention to measurement result；
The influence of Fig. 5, burning zone oxygen gas flow rate of the present invention to measurement result；
The influence of Fig. 6, sample introduction flow rate of carrier gas of the present invention to measurement result；
The working curve of Fig. 7, fluid present invention standard specimen；
The influence of Fig. 8, gas sample introduction amount of the present invention to measurement result.
Specific embodiment:
According to Fig. 1, closed injection port end and mixed gas outlet 9 in combustion tube on the basis of existing technology, this
Invention is provided in the centre at combustion tube injection port end with tubaeform injection port 1 and protective sleeve of syringe needle pipe 2, protective sleeve of syringe needle pipe 2
It is inserted into the precombustion section 5 in combustion tube, 2 a length of 13~15 centimetres of casing, internal diameter is 1~2 millimeter, the tubaeform injection port
The setting of 1 head is outer 3~3.5 centimetres of quartz ampoule injection port end face, from setting one at injection port end 2/5ths in combustion tube
A partition 6, the partition 6 will be divided into two parts in combustion tube, a part is precombustion section 5, another part close to injection port end
It is burning zone 7 close to mixed gas outlet end, protective sleeve of syringe needle pipe 2 is inserted into the precombustion section 5 in combustion tube；Combustion tube is closed
Injection port end separately has two by-pass lines to penetrate, one is oxygen and Ar inlet pipeline, the oxygen and Ar inlet pipeline 4 penetrate
It is arranged to "U" shaped after in combustion tube precombustion section 5, one section of helix tube is set in " U " word turning lower half, oxygen and argon gas enter
Mouth pipeline outlet is 3~4 millimeters from injection port end inner wall, the second is oxygen intake pipeline 3, the oxygen intake pipeline 3 is passed through
Precombustion section 5 is gone directly in 6 preformed hole of partition, and an inner combustion tube 8 with helix tube is arranged in the burning zone 7, described interior
Combustion tube is arranged to "U" shaped at 9 end of mixed gas outlet close to burning zone 7, and it is pre- that "U" shaped inner combustion tube one end is connected to partition
In boxing out, the other end is arranged from 1 centimeters of partition.The sample volume of the liquid standard specimen of tester and hydrocarbon gas sample to be measured
Sample volume have certain relevance, the sample volume of hydrocarbon gas sample is 250~375 times of liquid standard specimen sample volume.
A kind of application of the combustion tube of ultraviolet fluorescence method measurement minim total sulfur content according to claim 1；1. being institute
Only logical carrier gas (Ar) is stated in protective sleeve of syringe needle pipe, the flow velocity of the carrier gas is 10~45mL/min；
2. being the gaseous mixture for leading to oxygen and argon gas in the oxygen and Ar inlet pipeline, the flow velocity of oxygen is 100~
300mL/min, argon gas are 0~250mL/min；
3. being to lead to oxygen in the oxygen intake pipeline, the flow velocity of oxygen is 200~500mL/min；
4. be the sample volume of liquid standard specimen being 40 microlitres, the sample volume of corresponding hydrocarbon gas sample is 10~15 milliliters,
The volume of the quantitative loop of gas sampler is 10~15 milliliters.
Embodiment 1:
According to Fig. 1, the present invention improves its structure on the basis of prior art combustion tube, it is specifically disclosed
The centre at combustion tube injection port end is provided with the protective sleeve of syringe needle pipe with tubaeform injection port penetrated, protective sleeve of syringe needle pipe
It is inserted into the precombustion section in combustion tube, a length of 14 centimetres of casing, internal diameter is 1.5 millimeters, and the tubaeform injection port head is set
It sets outer 3.3 centimetres of combustion tube injection port end face.It is described from one partition of setting at injection port end 2/5ths in combustion tube
Partition will be divided into two parts in combustion tube, a part is precombustion section close to injection port end, and another part is close to mixed gas outlet
End is burning zone, and protective sleeve of syringe needle pipe is inserted into the precombustion section in combustion tube；Combustion tube injection port end separately has two by-pass lines to wear
Enter, one is oxygen and Ar inlet pipeline, the oxygen and Ar inlet pipeline are arranged after penetrating in quartz ampoule precombustion section
At "U" shaped, one section of helix tube is set in " U " word turning lower half, oxygen and Ar inlet pipeline outlet are from injection port end
Wall is 3.5 millimeters.The second is oxygen intake pipeline, the oxygen intake pipeline is passed through in the through partition preformed hole of precombustion section.
A piece inner combustion tube with helix tube is set in the burning zone, and the inner combustion tube is in the mixed gas outlet close to burning zone
End is arranged to "U" shaped, and "U" shaped inner combustion tube one end is connected in partition preformed hole, and the other end is arranged from 1 centimetre of partition
Place.
Embodiment 2: with embodiment 1, only protective sleeve of syringe needle pipe range is 13 centimetres, and interior through 1 millimeter, injection port head is arranged
Outer 3 centimetres of combustion tube injection port end face, oxygen and Ar inlet pipeline outlet are 3 millimeters from injection port end inner wall.
Embodiment 3: with embodiment 1, only protective sleeve of syringe needle pipe range is 15 centimetres, and interior through 2 millimeters, injection port head is arranged
Outer 3.5 centimetres of combustion tube injection port end face, oxygen and Ar inlet pipeline outlet are 4 millimeters from injection port end inner wall.
Concrete operations of the present invention are as follows:
(1), minim total sulfur content in sample is measured
1 experimental section
1.1 instruments and reagent
Ultraluminescence sulphur content analyzer: ZDS-2000 type fluorescence sulfur determinator, Gaoke Analyzer Co., Ltd., Jiangyan City.
Syringe: 100 milliliters.Gastight syringe: 5mL, An Jielun company.Micro syringe: 20 microlitres, 50 microlitres, Ningbo City Zhenghai
Three love instrument plants.Gas six-way valve: meta analysis Instrument Ltd. on Nanjing；Gas sampler: logical with gas plane six
Valve and polyfluortetraethylene pipe and syringe needle voluntarily assemble, and quantity tube is polyfluortetraethylene pipe, the volume of quantity tube be 5mL,
10mL,12mL,15mL,20mL.The sample inlet of gas sampler connects a No. 7 syringe needle (syringe needles with outlet line
Band side opening), syringe needle is pricked into sample introduction pad, is brought the gaseous sample in quantity tube in combustion of sulfur pipe by carrier gas.It will when sampling
Even in the stainless joint of the syringe needle insertion aluminium foil sampler bag of suction line.Sulphur standard specimen: 0.1mg/L, 0.5mg/L, 1mg/L,
3mg/L, 5mg/L, Ultraluminescence sulphur content analyzer in Jena carries and Research Institute of Petro-Chemical Engineering's production.Sulphur standard gas:
Total sulfur content is 0.93mg/m3COS and 15.0mg/m3H2S, nitrogen are Balance Air, the limited public affairs of the gas of Foshan section
Department.Oxygen: purity is greater than 99.9%, argon gas: purity is greater than 99.9%.Combustion of sulfur pipe: Novel quartz cracking tube, as shown in Figure 1.
1.2 experimental operating conditions
The flow velocity of precombustion section oxygen and argon gas and the flow velocity of burning zone supplemental oxygen are adjusted respectively, are set high-voltage value, are used
50 microlitres of syringe injects 40 microlitres of sulphur standard specimen of 0.5mg/L or 1.0mg/L into combustion of sulfur pipe, measures sulphur under different condition
The integrated value of standard specimen determines their optimum flow rate.It is as follows to be determined by experiment suitable operating condition: high pressure 525V, furnace temperature
It is 900~1050 DEG C, the flow velocity of precombustion section oxygen and argon gas is respectively 100~300mL/min, and argon gas is 0~200mL/
Min, burning zone supplemental oxygen flow velocity be 200~500mL/min, Liquid sample introduction amount be 40 microlitres, gas sampling amount be 10~
15mL, the sample introduction speed of liquid sample feeding device are 2~3 microlitres/second；Gas sample introduction speed is 10~45mL/min mL/min.
1.3 sample analysis
40 microlitres of standard specimens are injected in combustion of sulfur pipe by liquid sample feeding device under the operating conditions described above, instrument is shown automatically
Integrated value, and working curve is established according to the quality and integrated value of sulphur in standard specimen automatically.Fluid sample is injected by identical method,
According to the sample volume of fluid sample, density and integrated value and the working curve of standard specimen, the automatic analysis result for calculating fluid sample.
Gaseous sample is imported 10~15mL gaseous sample in combustion of sulfur pipe by gas sampler, and instrument is according to the density and work of gas
Make the automatic Calculation results of curve.
2 results and discussion
Influence of the structure of 2.1 combustion of sulfur pipes to measurement
Traditional combustion of sulfur pipe is improved, by injection port be changed to can sample introduction protective sleeve of syringe needle pipe；By oxygen and argon
The elbow position of gas pipeline keeps the injection port end face of combustion of sulfur pipe more by being changed to 1 centimetre of extension from stretching 1 centimetre in injection port end face
Put in 2 centimetres of boiler tube；In combustion of sulfur pipe from a partition is increased at injection port end 2/5ths, a combustion chamber is divided into one
Precombustion section and burning zone；Increase outer diameter helix tube reversed for 3 millimeters of U-shaped in burning zone.Entrust river ring analysis instrument
The processing of device Co., Ltd, as shown in Figure 1.
As shown in Fig. 2, traditional combustion of sulfur pipe is relatively simple for structure, there is injection port 10, cuts gas and oxygen intake 12, split
Oxygen entrance 13 is solved, gas economizer bank 14, spout 15, combustion chamber 16, only one combustion of the traditional combustion of sulfur pipe of mixed gas outlet 17. are cut
Room 16 is burnt, the time of sample combustion is shorter, and sample volume is usually 20 microlitres, and sample volume increases, and the tail end of combustion of sulfur pipe can be tied
Charcoal, therefore, traditional ultraviolet fluorescence method can only measure the sulfur content of 1mg/Kg or more in sample.The present invention is to traditional combustion of sulfur
Pipe improves (as shown in Figure 1), and injection port is changed to protective sleeve of syringe needle pipe, and a combustion chamber is changed to a precombustion section 5
With burning zone 7, increase a spiral inner combustion tube in burning zone 7, improved combustion of sulfur pipe makes sample enter pre-burning
It burns in oxygen after burning section 5 and after argon gas mixing, subsequently into burning away in the inner combustion tube 8 in burning zone 7, is burning
7 supplemental oxygens of section, sample further burn, and in this way by three sections of burnings, sample combustion is complete, and the sample volume maximum of sample is reachable
50 microlitres, thus improved method can measure the total sulfur content of 0.1mg/Kg or more in sample.Improved combustion of sulfur pipe sample combustion
The burning time is long, and sample combustion is complete, and combustion tube is not easy coking.Traditional combustion of sulfur pipe burning time is short, and sample volume is greater than 30 millis
Liter is easily coking, and therefore, traditional combustion of sulfur pipe can only measure the total sulfur content of 1mg/Kg or more in sample.Measuring, argon gas
With oxygen elbow position from injection port end face be 1 centimetre when, casing (should be longer than syringe needle) overall length be 5~12.5 centimetres of analysis triphens
Precombustion section can be coking when (benzene,toluene,xylene), and integrated value is small, and measurement result repeatability and accuracy are poor, this is because set
Pipe is too short, and sample preheating time is short, and sample burns in the temperature lower of precombustion section, and sample combustion is incomplete.In order to ensure
The sample of the higher composition containing boiling point such as triphen, catalytic reforming feedstock add and split the completely burneds such as diesel oil, and the length of casing is 13~15cm ratio
It is appropriate, preferably 14 centimetres.The injection port of traditional Ultraluminescence combustion of sulfur pipe is cylinder, is deformed after sample introduction pad is heated,
Easily it is rushed out.Injection port is changed to the injection port (tubaeform) of Microcoulomb instrument quartz ampoule, the inside is big, and outlet is small, and sample introduction pad is stuck in
In injection port, it is difficult to go out.The sample volume of the Ultraluminescence sulphur content analyzer of U.S.'s thermoelectricity is 100 microlitres, in order to keep sample complete
Burning, they increase a blowback lines, supplemental oxygen from the tail portion of combustion of sulfur pipe, and sample introduction speed is very slow, and only sample introduction is time-consuming
Just up to 120 seconds, analysis time is needed 360 seconds.The present invention is total up to 90 seconds improved combustion of sulfur pipe analysis time, than U.S. thermoelectricity
Analysis time shortens 270 seconds, is able to satisfy the middle requirement controlled and quickly analyzed.The injection port oxygen of traditional combustion of sulfur pipe cannot be too big,
Otherwise, add short, the incomplete combustion that splits difficult volatile sample burning times such as diesel oil, measurement result is bigger than normal.Improved combustion of sulfur
The oxygen of pipe precombustion section can increase to 500mL/min, and sample is burnt by after oxygen dilution by three sections, and burning time is long, surveys
Determine result and small-hole drilling coincide.
The influence of 2.2 high pressures
Take the sulphur standard specimen of 40 microlitres of 0.5mg/L with 50 microlitres of micro syringe, measurement high pressure be 500V, 510V,
The integrated value of 520V, 530V, 540V are respectively 524,585,640,732,873, illustrate that high pressure is bigger, and the sensitivity of instrument is got over
Height, integrated value is bigger, but high pressure is too big, and unstability of base line is less reproducible, and high pressure is lower, and baseline is more stable, but sensitivity is got over
It is low.The COS standard gas for being 0.93mg/m3 with total sulfur content, with Dilution air, measurement high pressure is 500V, 510V, 520V, 525V,
The minimum detectable concentration of 530V is respectively 0.5mg/Kg, 0.4mg/Kg, 0.2mg/Kg, 0.1mg/Kg, 0.05mg/Kg.High pressure is
525V measures the COS standard gas of 0.1mg/Kg, integrated value 30, and repeatability preferably, and therefore, high pressure is that 525V is able to satisfy method
With the requirement (Con trolling index of total sulfur content is no more than 1mg/Kg in propylene) of petrochemical industry production, therefore, high pressure optimum value
For 525V.
The influence of 2.3 furnace temperature
Take the sulphur standard specimen of 40 microlitres of 0.5mg/L with 50 microlitres of micro syringe, measurement furnace temperature is 900 DEG C, 950 DEG C,
1000 DEG C, 1050 DEG C of integrated value be respectively 613,538,479,406, illustrate that furnace temperature is higher, sample combustion is more complete, integrated value
It is smaller, but the ingredient of combustion of sulfur pipe is pure quartz, using temperature no more than 1100 DEG C, the otherwise crystal structure meeting of quartz ampoule
It changes, service life can shorten, and therefore, furnace temperature is preferably 1050 DEG C.
The influence that sebific duct adsorbs on 2.4 airbags
Sebific duct on airbag is mainly used for sampling and carry, it has suction-operated to the sulfide in gaseous sample, cannot
It and gas sampler are directly connected to sample introduction, should be sampled using the polyfluortetraethylene pipe that even syringe needle (with side opening) outer diameter is 3mm.
Because syringe needle internal diameter is small, pressure stabilizing and current stabilization can be played, keep constant sample volume, thus measurement result is reproducible.Sampling
When, by the stainless joint of the syringe needle insertion aluminium foil sampler bag of even polyfluortetraethylene pipe, squeeze airbag, sample displacement polytetrafluoro
Ethylene inlet pipe and quantity tube, operation is very easy.Syringe needle band side opening, is not easy to plug.Poly- the four of gas sampler sample export
Vinyl fluoride also connects syringe needle, and syringe needle is inserted into the sample introduction pad of casing, and Sample introduction precombustion section is burnt in sample introduction carrier gas.It can keep away in this way
Exempt to use syringe sampling and sample introduction, frequently pricks the sebific duct of aluminium foil sampler bag and the sample introduction pad of combustion of sulfur pipe, cause sebific duct and sample introduction
Pad gas leakage.
The influence of 2.5 quantitative loops absorption
Most of quantitative loop is stainless steel material, and stainless steel has certain absorption to sulfide, and polyfluortetraethylene pipe is to sulphur
Compound adsorbs very little, therefore, measures the most handy polyfluortetraethylene pipe of quantity tube of minim total sulfur content in gas.
The determination of 2.6 quantitative loop volumes
The accuracy of quantitative loop volume directly affects the accuracy of result.With in vernier caliper measurement polyfluortetraethylene pipe
Diameter and length can determine roughly the volume of quantitative loop.By 10 milliliters of rough calculation of quantitative loop both ends silicon rubber pipe sleeve
Firmly, its quality is weighed, quantitative loop is then connected into tap, fills water, in the same way entangling the both ends of quantitative loop (will
The water-stop of the inside), the water of quantitative loop outer wall is dried, and with being dried with nitrogen, weigh quantitative loop, total matter of silicone rubber tube and water
Amount, the difference of the two is the quality of the water in quantitative loop, according to the quality of water can Accurate Determining quantitative loop volume.After measured
The exact volume of 10 milliliters of quantitative loops of rough calculation is 10.2 milliliters, and calculated result and measured result coincide preferably.
Influence of the 2.7 precombustion section oxygen gas flow rates to measurement result
The sulphur standard specimen of 40 microlitres of 0.5mg/L is taken with 50 microlitres of micro syringe, adjusts the flow velocity of precombustion section oxygen,
The integrated value under different oxygen gas flow rates is measured, as a result such as Fig. 3.
Fig. 3 is influence of the precombustion section oxygen gas flow rate to measurement result.From figure 3, it can be seen that precombustion section oxygen gas flow rate
Bigger, the burning of sulphur standard specimen is more complete, and integrated value is smaller, and precombustion section oxygen gas flow rate is 250mL/min, and sample combustion is complete, after
Continuous to increase oxygen gas flow rate, integrated value varies less, and therefore, the optimum flow rate of precombustion section oxygen is 250mL/min.
Influence of the flow velocity of 2.8 precombustion section argon gas to measurement result
The sulphur standard specimen of 40 microlitres of 0.5mg/L is taken with 50 microlitres of micro syringe, adjusts the flow velocity of precombustion section argon gas,
The integrated value under different argon gas flow velocitys is measured, as a result such as Fig. 4.Fig. 4 is influence of the precombustion section argon gas flow velocity to measurement result.
Figure 4, it is seen that the obstructed argon gas of precombustion section 5, sample combustion is incomplete, and integrated value is larger, is passed through 50mL/
The argon gas of min, integrated value reduce, and illustrate to be passed through argon gas, sample, by argon-dilution, burns more complete in precombustion section 5.Experiment card
The obstructed argon gas of bright precombustion section 5, sample introduction speed is too fast when measuring propylene and butene-1, sample detonation sometimes, and measurement result is inclined
Greatly, the tail end of combustion of sulfur pipe is easily coking, therefore, the preferably logical argon gas of precombustion section.Precombustion section argon gas flow velocity is 150mL/min,
Sample combustion is complete, and integrated value is minimum.Continue the flow velocity of increase argon gas, the burning time of sample is short, and the concentration of oxygen reduces, sample
Product incomplete combustion, SO2It is converted into SO3Small, integrated value increases.Therefore, the optimum flow rate of precombustion section argon gas is 150mL/min.
Influence of the 2.9 burning zone oxygen gas flow rates to measurement result
The sulphur standard specimen of 40 microlitres of 1.0mg/L is taken with 50 microlitres of micro syringe, adjusts the flow velocity of 7 oxygen of burning zone,
The integrated value under different oxygen gas flow rates is measured, as a result such as Fig. 5.Fig. 5 is influence of 7 oxygen gas flow rate of burning zone to measurement result.From
It is smaller that Fig. 5 can be seen that burning zone oxygen gas flow rate, and the burning of sulphur standard specimen is more incomplete, and integrated value is bigger, and burning zone oxygen gas flow rate is got over
Greatly, the burning of sulphur standard specimen is more complete, and integrated value is smaller, in order to ensure sample (such as catalytic reforming feedstock, benzene, toluene, the diformazan of difficult to burn
Benzene adds and splits diesel oil etc.) completely burned, the flow velocity of burning zone oxygen is answered bigger.Burning zone oxygen gas flow rate is bigger, is more not easy to tie
Charcoal, instrument are more stable.The flow velocity of burning zone oxygen is lower than 200mL/min, and peak hangover measures the sample of difficult to burn, combustion of sulfur pipe
Tail portion is easily coking.Burning zone oxygen gas flow rate is 450mL/min, and integrated value is lower, continues the flow velocity for increasing oxygen, integrated value variation
Less, therefore, the optimum flow rate of burning zone oxygen is 450mL/min.
Influence of the 2.10 sample introduction flow rate of carrier gas to measurement result
The domestic syringe sampling of gaseous sample, the easy gas leakage of syringe inner wall, and biggish syringe needle is needed, measurement result repeats
Property is poor.Different sample introduction carrier gas are measured with constant speed, constant pressure and constant Injection volumes with gas sampler herein
The integrated value of butene-1 under flow conditions, as shown in fig. 6, Fig. 6 is influence of the sample introduction flow rate of carrier gas to measurement result.It can from Fig. 6
Find out, sample introduction flow rate of carrier gas is bigger, and integrated value is bigger, this is because sample introduction flow rate of carrier gas is bigger, burning time is shorter, sample combustion
Burn more incomplete, SO2It is converted into SO3Smaller, integrated value is bigger.Sample introduction flow rate of carrier gas cannot be too low, and otherwise peak trails, signal value
Too low, poor repeatability, sample analysis time is long.It is demonstrated experimentally that sample introduction flow rate of carrier gas is 40mL/min, peak shape is symmetrical, repeatability
Good, measurement result and small-hole drilling coincide.Therefore, best sample introduction flow rate of carrier gas is 40mL/min.
2.11 working curve
Taking total sulfur content respectively with 50 microlitres of micro syringes is 0.1mg/L, 0.5mg/L, 1mg/L, 3mg/L, 5mg/L
40 microlitres of liquid standard specimen, be injected into combustion of sulfur pipe, measure its integrated value, with the quality (ng) of sulphur in standard specimen be horizontal seat
Mark, makees working curve by ordinate of integrated value, as shown in Figure 7.As can be seen from Figure 7, the integrated value of liquid standard specimen and sulphur
Quality is in a linear relationship, y=17.85x+363.8, coefficient R2It is 0.999, wherein y is integrated value, and x is the quality of sulphur
(ng).It can be seen from figure 7 that sulfur content linear relationship out of 0.1~5mg/L is good.It is most handy to measure gaseous sample
Gas standard specimen school instrument, to eliminate standard specimen and sample difference bring systematic error.It is quasi- but using propylene or butene-1 as Balance Air
It really prepares total sulfur content and is less than 1mg/m3Gas standard specimen it is relatively difficult, contain because being used to prepare in the propylene or butene-1 of standard gas
Micro sulfide, and trace sulfide is easily adsorbed in standard gas, cannot be saved for a long time.The gas of my commission Foshan section has
The COS standard gas that total sulfur content in propylene is respectively 0.36mg/m3,0.57mg/m3,0.93mg/m3 is prepared by limit company, uses after arrival
The concentration that microcoulomb method measures them is respectively 1.42mg/m3,1.72mg/m3,3.42mg/m3, experiments have shown that (rear producer is also true
Recognize) the propylene sulfur compound with standard gas, producer is seeked advice from, the propylene and butene-1 for being difficult to find not sulfur compound are replied by producer,
Standard gas of the total sulfur content less than 1mg/m3 can not be prepared accurately in propylene and butene-1.Therefore, the gaseous samples such as propylene, butene-1
The measurement of middle total sulfur content can only also use liquid standard specimen tester, cannot use gas standard specimen school instrument.With liquid standard specimen school instrument
Device, measure gaseous sample, because the sample volume of the two, sample injection method, sample introduction speed, medium and sample complete combustibility not
Together, biggish systematic error can be generated, causes minim total sulfur content analytical error in ultraviolet fluorescence method measurement gaseous sample larger,
There are biggish deviations with the measurement result of microcoulomb method, so that domestic Ultraluminescence sulphur content analyzer the minim total sulphur content in measurement gas
It can not be applied when content, the minim total sulfur content being only used in measurement liquid.Usual small-hole drilling analyzes gaseous sample total sulfur
Result be less than 0.5mg/m3, the result of domestic Ultraluminescence sulphur content analyzer is often largely greater than 1mg/m3.From the linear of Fig. 7
Equation can be seen that standard specimen sample volume be 40 microlitres when, constant term 363.8.The sample volume of measuring standard specimen is 20 microlitres
Linear equation are as follows:
When y=31.36x+46.4, i.e. sample volume are 20 microlitres, constant term 46.4 illustrates that sample volume is bigger, and sample is got over
Difficult to burn, constant term is bigger, and sample volume is smaller, and sample gets over easy firing, and constant term is smaller.It follows that constant term is instrument
Interference signal, it is mainly related with the complete combustibility of sample.The gaseous sample of sulfur content very low (total sulfur is less than 0.1mg/m3)
(such as propylene, butene-1) sample volume is bigger, and integrated value is bigger, illustrates that interference signal is bigger, and sample volume is smaller, and integrated value is smaller,
Interference signal is smaller.The sample volume of the very low propylene of measuring sulfur content or butene-1 (total sulfur is less than 0.1mg/m3) is 10~
15 milliliters of integrated value is close to 363.8, and therefore, the volume of liquid standard specimen is that the sample volume of 40 microlitres of corresponding gaseous samples should be
10~15 milliliters.GB/T11141 is not illustrated the ultraviolet fluorescence method reason different with micro-coulometric determination result, does not also mention
The method solved out, GB/T7716-2014 polymerization-grade propylene product standard only illustrate when two methods measurement result has objection with
Subject to ultraviolet fluorescence method, but the selection of ultraviolet fluorescence method operating condition is improper, as a result may inaccuracy.Liquid in GB/T11141
Sample volume is 50 microlitres, and domestic combustion of sulfur pipe is extremely difficult to, and sample volume is largely 20 microlitres, gas in GB/T11141
Sample volume be 10 milliliters or other volumes, have no rationale and experimental verification, the standard be version in 2014 new method, not
Illustrate the sample volume of liquid standard specimen and the corresponding relationship of gas sample introduction amount, not enough rigorously, method may be to introduce foreign side, state
Method, without experimental check.The volume of liquid standard specimen and the volume of gaseous sample should have certain corresponding relationship, otherwise, measure micro-
It is more relatively low than to be less higher be exactly to measure result and the small-hole drilling of total sulfur content, is constantly present certain systematic error, this mistake
It influences less, to be less than 1mg/m for sulfur content when difference is larger for sulfur content3, it is affected.Liquid standard specimen be 20 microlitres, third
The sample volume of alkene gaseous sample is 10 milliliters, and the integrated value that ultraviolet fluorescence method measures total sulfur is 422, result 1.2mg/m3, micro-
The result of acrylonitrile by Coulometry total sulfur is less than 0.5mg/m3, the two difference is larger, this is because 20 microlitres of liquid standard specimen and 10
It is different that completeness is burnt in milliliter gaseous sample burning.Liquid standard specimen is 40 microlitres, and the sample volume of propylene gas sample is 10 milliliters,
The integrated value that ultraviolet fluorescence method measures total sulfur is 422, result 0.3mg/m3, the measurement result of small-hole drilling is less than 0.5mg/
m3, the measurement result of two methods is coincide, this is because 40 microlitres of liquid standard specimen and 10 milliliters of propylene gas sample combustions are complete
Whole degree is identical, and interference signal is cancelled out each other.Thus illustrate, the volume of liquid standard specimen and the sample volume of under test gas sample should have
Certain corresponding relationship.
Influence of 2.12 sample volumes to measurement
The propylene of different volumes is taken with 5 milliliters of An Jielun gastight syringe or the polytetrafluoroethylene (PTFE) quantity tube of different volumes
Sample measures its integrated value, as a result such as Fig. 8.
From figure 8, it is seen that the sample volume of propylene is not in a linear relationship with integrated value, illustrate integrated value in addition to in propylene
Sulfur content have outside the Pass, it is also related with instrument interference signal, and interference signal is related with the completeness of sample combustion, gas sample
Product sample volume is bigger, and burn more incomplete, SO2It is converted into SO3Smaller, integrated value is bigger.Therefore, gas sample introduction amount is bigger,
Measurement result is bigger, and sample volume is smaller, and measurement result is smaller.
When measuring fluid sample sample volume is 20 microlitres, 30 microlitres, 40 microlitres, 50 microlitres, minimum detectable concentration point
Not Wei 1mg/Kg, 0.5mg/Kg, 0.1mg/Kg, 0.05mg/Kg, sample volume is bigger, and minimum detectable concentration is lower, combustion of sulfur Guan Yue
Easily coking, the sample volume of fluid sample is 40 microlitres proper.The sample volume of gaseous sample be 5 milliliters, 10 milliliters, 15 milli
It rises, 20 milliliters, minimum detectable concentration is respectively 1mg/Kg, 0.1mg/Kg, 0.07mg/Kg, 0.05mg/Kg.Thus illustrate, into
Sample amount is bigger, and minimum detectable concentration is smaller, but sample volume is too big, and sample combustion is incomplete, and combustion of sulfur pipe is easily coking, measurement result
(compared with small-hole drilling) bigger than normal.Sample volume is too small, and minimum detectable concentration is bigger, and measurement result is relatively low (being shown in Table 1).Table 1 is 40
Microlitre liquid standard specimen school Instrument measuring propylene in total sulfur content result.As it can be seen from table 1 liquid standard specimen is 40 microlitres,
When the sample volume of gaseous sample is 10 milliliters and 15 milliliters, the result and small-hole drilling of ultraviolet fluorescence method are coincide.40 microlitres of sulphur
Standard specimen (is prepared) with isooctane, is equivalent to isooctane gas 5.6mL, and isooctane contains 7 C-C singly-bounds, the total bond energy of C-C singly-bound
2436kJ；Propylene contains 1 C-C singly-bound and a C=C double bond, and total bond energy of C-C singly-bound and C=C double bond is 963kJ, theoretical
On
5.6mL isooctane gas is suitable with the complete combustibility of 14.2mL propylene (or 10.4mL butylene).It can be with from table 1
Find out, the total sulfur content in Accurate Determining propylene or butene-1 sample, the sample volume of liquid standard specimen is preferably 40 microlitres, gas
The sample volume of sample is preferably 10~15 milliliters, and the sample volume of gaseous sample is 250~375 times of liquid standard specimen sample volume.
Influence of the sample volume of 1 gaseous sample of table to measurement result accuracy
The repeatability of 2.13 methods
The sulphur standard specimen METHOD FOR CONTINUOUS DETERMINATION 5 times integrated values of 40 microlitres of 0.5mg/L are taken to distinguish with 50 microlitres of micro syringe
It is 396,421,398,400,393, average value 402, standard deviation 2.8%.
40 microlitres of benzene are taken with 50 microlitres of micro syringes, measure total sulfur content therein, METHOD FOR CONTINUOUS DETERMINATION 6 with ultraviolet glimmering method
It is secondary, as a result as follows: 0.32mg/Kg, 0.31mg/Kg, 0.34mg/Kg, 0.36mg/Kg, 0.33mg/Kg, 0.30mg/Kg, it is average
Value is 0.33mg/Kg, relative standard deviation 6.6%.The propylene product that 10 milliliters are taken with gas sampler is surveyed with ultraviolet glimmering method
Fixed total sulfur content therein, it is METHOD FOR CONTINUOUS DETERMINATION 6 times, as a result as follows: 0.67mg/Kg, 0.64mg/Kg, 0.67mg/Kg, 0.60mg/
Kg, 0.65mg/Kg, 0.62mg/Kg, average value 0.64mg/Kg, relative standard deviation 4.3%.12 are taken with gas sampler
The butene-1 product of milliliter measures total sulfur content therein with ultraviolet glimmering method, and METHOD FOR CONTINUOUS DETERMINATION 6 times, average value 0.35mg/Kg,
Relative standard deviation is 6.0%.Thus illustrate, measure the minim total sulfur content of liquid or gaseous sample, ultraviolet fluorescence method because into
Sample amount is big, reproducible.Small-hole drilling by quartz ampoule structure because being limited, and sample volume is few, and (Liquid sample introduction amount is 8.4 microlitres, gas
Body sample injection volume is 2 milliliters), measurement less than the sample of 0.5mg/Kg not appearance or lesser lopsided peak, and poor repeatability out,
Result < 0.5mg/Kg can only be reported.
The accuracy of 2.14 methods
40 microlitres of benzene is taken with 50 microlitres of micro syringe, toluene, ethylbenzene, dimethylbenzene, catalytic reforming feedstock, adds and splits scheelite brain
Oil adds and splits diesel oil, light dydrocarbon etc., is injected into Ultraluminescence sulphur content analyzer, measures its integrated value, bent according to the work of liquid standard specimen
The density of line and liquid calculates the total sulfur content of fluid sample, and analyses and compares with small-hole drilling, as a result such as table 2.
Result is analyzed in the comparison of 2 fluid sample of table
With gas sampler take 12 milliliters propylene, butene-1, carbon four, deodorization after liquefied gas, pass through sample introduction carrier gas (Ar)
It is brought into Ultraluminescence sulphur content analyzer, measures its integrated value, according to the density of the working curve of gas standard specimen and gaseous sample,
The total sulfur content of gaseous sample is calculated, and is analysed and compared with small-hole drilling, as a result such as table 3.
Result is analyzed in the comparison of 3 gaseous sample of table
It can be seen that from table 2 and table 3, ultraviolet fluorescence method and micro-coulometric determination result are coincide, the relative deviation of two methods
Less than 15%, in the error range that method allows (repeatability of method is 20%), illustrate that ultraviolet fluorescence method measurement is micro total
Systematic error is not present in sulfur content, as a result accurately.
Be respectively respectively 47 with the total sulfur content in improved combustion of sulfur pipe and traditional combustion of sulfur pipe measurement hydrogenated diesel oil,
60mg/kg, the measurement result of small-hole drilling are 46mg/kg, the measurement result of improved combustion of sulfur pipe and the result of small-hole drilling
It coincide and reproducible, is burnt endless with the total sulfur content in traditional combustion of sulfur pipe measurement hydrogenated diesel oil because sample difficulty is volatilized
Entirely, measurement result is bigger than normal and poor repeatability.
The standard specimen of 0.5mg/kg is added into toluene, the recovery of standard addition for measuring toluene is 98%.Into butene-1 product
The H of a certain amount of 15mg/m3 is added2S standard gas (nitrogen is Balance Air), the sample recovery rate for measuring butene-1 is 104%, by
This explanation, improved method accuracy is high, and measurement result is reliable.
2 conclusions
(1) structure of Ultraluminescence combustion of sulfur pipe is improved, extends the burning time of sample, increase the sample introduction of sample
Amount reduces the minimum detectable concentration of minim total sulfur content in sample, improves the accuracy of analysis.
(2) research ultraviolet fluorescence method measures minim total sulfur content error Producing reason, the complete full journey of confirmatory sample burning
Degree be affected to measurement result, the completeness of liquid standard specimen and gas sample combustion answer it is essentially identical, gaseous sample into
Sample amount should be 250~375 times of liquid standard specimen sample volume.
(3) analysis method with minim total sulfur content in sulphur liquid standard specimen quantitative gas sample, gaseous sample gas are established
Body sample injector sample introduction under constant pressure and constant flow velocity, sample volume is constant, and analysis result is reproducible.Measurement propylene,
Minim total sulfur content relative standard deviation is 4.3%, 6.0% in butene-1 gas, as a result with small-hole drilling coincide compared with
It is good.
(4) ultraviolet fluorescence method instrument stabilizer, disturbing factor is small, and maintenance is simple, easy to operate, and analysis speed is fast, may replace
The total sulfur content of 0.1mg/Kg or more in micro-coulometric determination gas and fluid sample, this method can use cheap domestic equipment
Minim total sulfur content in gas and fluid sample is measured, there is biggish application value in petrochemical enterprise.
(2), the content of micro total nitrogen in sample is measured
With nitrogen standard liquid tester, remaining is identical as the measurement method of sulphur, and improved combustion tube and traditional combustion tube are surveyed
The result for determining total nitrogen is coincide preferably, within the scope of the reproducibility of method.
Claims (2)
1. a kind of combustion tube of ultraviolet fluorescence method measurement minim total sulfur content, it includes closed injection port end and mixed in combustion tube
Gas outlet is closed, it is characterized in that being provided with the protective sleeve of syringe needle pipe with tubaeform injection port, needle in the centre at combustion tube injection port end
Head protection casing is inserted into the precombustion section in combustion tube, and a length of 13~15 centimetres of casing, internal diameter is 1~2 millimeter, the loudspeaker
The setting of shape injection port head is outer 3~3.5 centimetres of quartz ampoule injection port end face, in combustion tube from injection port end 2/5ths at
One partition is set, and the partition will be divided into two parts in combustion tube, a part is precombustion section, another portion close to injection port end
Dividing close to mixed gas outlet end is burning zone, and protective sleeve of syringe needle pipe is inserted into the precombustion section in combustion tube；Combustion tube injection port
End separately has two by-pass lines to penetrate, one is oxygen and Ar inlet pipeline, the oxygen and Ar inlet pipeline penetrate combustion tube
It is arranged to "U" shaped after in precombustion section, one section of helix tube, oxygen and Ar inlet pipeline is set in " U " word turning lower half
Exporting from injection port end inner wall is 3~4 millimeters, the second is oxygen intake pipeline, the oxygen intake pipeline passes through precombustion section
In through partition preformed hole, an inner combustion tube with helix tube is set in the burning zone, and the inner combustion tube is close
The mixed gas outlet end of burning zone is arranged to "U" shaped, and "U" shaped inner combustion tube one end is connected in partition preformed hole, the other end
From 1 centimeters of partition, the sample volume of the sample volume of the liquid standard specimen of tester and hydrocarbon gas sample to be measured has one for setting
Fixed relevance, the sample volume of hydrocarbon gas sample are 250~375 times of liquid standard specimen sample volume.
2. a kind of application of the combustion tube of ultraviolet fluorescence method measurement minim total sulfur content according to claim 1；1. being described
Only logical carrier gas (Ar), the flow velocity of the carrier gas are 10~45mL/min in protective sleeve of syringe needle pipe；
2. being the gaseous mixture for leading to oxygen and argon gas in the oxygen and Ar inlet pipeline, the flow velocity of oxygen is 100~300mL/
Min, argon gas are 0~250mL/min；
3. being to lead to oxygen in the oxygen intake pipeline, the flow velocity of oxygen is 200~500mL/min；
4. be the sample volume of liquid standard specimen being 40 microlitres, the sample volume of corresponding hydrocarbon gas sample is 10~15 milliliters, gas
The volume of the quantitative loop of sample injector is 10~15 milliliters.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112964751A (en) * | 2021-02-05 | 2021-06-15 | 上海元析仪器有限公司 | Double-layer combustion tube for total organic carbon analyzer |
| CN114965853A (en) * | 2021-02-20 | 2022-08-30 | 中国石油化工股份有限公司 | Combustible gas combustion reaction device and concentration detection system of hydrogen sulfide in hydrogen |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51146889A (en) * | 1975-06-11 | 1976-12-16 | Rikagaku Kenkyusho | Oxygen content measurement method for organic compound |
| CN201569645U (en) * | 2009-12-31 | 2010-09-01 | 吴振伟 | Quartz combustion tube |
| CN103604904A (en) * | 2013-11-13 | 2014-02-26 | 江苏东华分析仪器有限公司 | High-capacity quartz combustion tube for oil product analysis |
| CN106546655A (en) * | 2015-09-18 | 2017-03-29 | 中国石油化工股份有限公司 | The quartz ampoule and its assay method of total sulfur or chloride content in a kind of oxidation micro-coulometric determination sample |
-
2017
- 2017-10-26 CN CN201711012567.0A patent/CN109709079A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51146889A (en) * | 1975-06-11 | 1976-12-16 | Rikagaku Kenkyusho | Oxygen content measurement method for organic compound |
| CN201569645U (en) * | 2009-12-31 | 2010-09-01 | 吴振伟 | Quartz combustion tube |
| CN103604904A (en) * | 2013-11-13 | 2014-02-26 | 江苏东华分析仪器有限公司 | High-capacity quartz combustion tube for oil product analysis |
| CN106546655A (en) * | 2015-09-18 | 2017-03-29 | 中国石油化工股份有限公司 | The quartz ampoule and its assay method of total sulfur or chloride content in a kind of oxidation micro-coulometric determination sample |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112964751A (en) * | 2021-02-05 | 2021-06-15 | 上海元析仪器有限公司 | Double-layer combustion tube for total organic carbon analyzer |
| CN114965853A (en) * | 2021-02-20 | 2022-08-30 | 中国石油化工股份有限公司 | Combustible gas combustion reaction device and concentration detection system of hydrogen sulfide in hydrogen |
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