CN108717106A - The device and its detection method of total sulfur content in a kind of detection natural gas - Google Patents
The device and its detection method of total sulfur content in a kind of detection natural gas Download PDFInfo
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- CN108717106A CN108717106A CN201810568877.9A CN201810568877A CN108717106A CN 108717106 A CN108717106 A CN 108717106A CN 201810568877 A CN201810568877 A CN 201810568877A CN 108717106 A CN108717106 A CN 108717106A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000003345 natural gas Substances 0.000 title claims abstract description 78
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000001514 detection method Methods 0.000 title claims abstract description 41
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 41
- 239000011593 sulfur Substances 0.000 title claims abstract description 41
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 89
- 230000007062 hydrolysis Effects 0.000 claims abstract description 88
- 239000007789 gas Substances 0.000 claims abstract description 58
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 42
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000001741 organic sulfur group Chemical group 0.000 claims abstract description 17
- 238000012546 transfer Methods 0.000 claims abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 238000005259 measurement Methods 0.000 abstract description 10
- 238000001285 laser absorption spectroscopy Methods 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 230000007812 deficiency Effects 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 19
- 239000005864 Sulphur Substances 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002795 fluorescence method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 208000011580 syndromic disease Diseases 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000000041 tunable diode laser absorption spectroscopy Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- PNZVFASWDSMJER-UHFFFAOYSA-N acetic acid;lead Chemical class [Pb].CC(O)=O PNZVFASWDSMJER-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 sulphur compound Chemical class 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/22—Fuels, explosives
- G01N33/225—Gaseous fuels, e.g. natural gas
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
Abstract
The present invention relates to the devices and its detection method of total sulfur content in a kind of detection natural gas.The reaction unit includes gas transfer pipeline and the pipe valve set gradually in gas transfer pipeline, steam-laden device, hydrolysis reactor and hydrogen sulfide measuring device；The pipe valve connects the air inlet of gas transfer pipeline, and gas outlet is arranged in hydrogen sulfide measuring device；Organic sulfur hydrolyst is filled in the hydrolysis reactor, and hydrolysis reactor connects heater.Sulfide in natural gas is hydrolyzed by generation hydrogen sulfide gas using the device, then uses the content of total cure hydrogen in hydrogen sulfide measuring device detection mixing sample to calculate total sulfur content in raw natural gas sample.The detection device of the present invention is simple, detection method mild condition, it is easy to operate it is safer, at low cost, precision is high, the deficiency for being unable to total sulfur content in on-line measurement natural gas using Diode Laser Absorption Spectroscopy is compensated for, is a kind of new effective means for measuring total sulfur in natural gas.
Description
Technical field
The present invention relates to the detection method technical fields of impurity in natural gas, more particularly to total in a kind of detection natural gas
The device and its detection method of sulfur content.
Background technology
Natural gas can greatly alleviate the pressure of current atmosphere pollution exacerbation as a kind of clean energy resource in promoting the use of
Power, the use of China's natural gas at present has become comparable universal, while advantage possessed by natural gas itself makes it make
With having obtained being widely recognized as the public.But the use of natural gas is also there is also some problems in actual life,
Wherein the most main is exactly that the detection technique of natural-gas sulphur content need to be further strengthened, and the sulfur content in natural gas is being fired
Also pollution can be generated during burning to atmospheric environment, therefore can be for the raising of the detection technique of sulfur content in natural gas
Largely environment protection.
Natural gas generally refers to be present in the mixed gas in subsurface rock reservoir based on hydrocarbon, and natural gas is main
Ingredient alkane, wherein methane account for the overwhelming majority, and in addition there are a small amount of ethane, propane and butane, while natural gas generally has sulphur
Change hydrogen, carbon dioxide, nitrogen and aqueous vapor and a small amount of carbon monoxide and micro rare gas, such as helium and argon.Sulphur in natural gas
The constituent of content is more, and this also increases the difficulty that we detect it.
In the prior art in natural gas sulfide detection use more universal method include oxidation small-hole drilling,
Lead acetate paper band method, chromatography flame photometric detector method (FPD), ultraviolet fluorescence method and Laser absorption spectroscopy.
It aoxidizing small-hole drilling and sample is introduced using oxidizing process by cracking tube reaction, measured object is converted into titratable ion, by
Carrier gas is brought into titration cell and is titrated, and the electricity consumed during electrolytic titration is measured, and according to Faraday's law, calculates sample
Total sulfur content.Oxidation small-hole drilling needs to carry carrier gas, and needs to be oxidized cracking, reaction temperature height, to equipment requirement compared with
It is high.
Lead acetate paper is that, by adding hydrogen pyrolytic conversion, other sulfide will be converted to containing the gas of sulfide with method
For H2S is detected again.Analyzed gas is mixed with hydrogen, is heated to 900 degrees Celsius, is converted to H2S gases, be passed into reative cell with
The paper tape of saturated acetic acid lead reacts, and reaction result makes paper tape generate the spot of brown, and the brownish depth of paper is detected by photoelectric method
It is shallow to correspond to H2The concentration of S.Since this method needs to heat the gases to pyrolytic conversion, conversion condition control is tighter, simultaneously
Have an impact to the service life of high temperature reaction stove, needs to be replaced frequently high temperature reaction stove, consumptive material and complicated for operation, severe operational environment.
Chromatography FPD methods are the separation principles using chromatographic column, and gaseous mixture is separated, various sulfide section in different times
It is interior to be detected one by one by FPD, carry out quantitative analysis.When multi-component mixed gas passes through chromatographic column, due to gas molecule
Type is different, generates difference by the speed of pillar, mixed gas, which just has occurred, at column outlet is separated into each component
Phenomenon.Sulfur-containing compound burns in hydrogen-rich-air flame, forms excited state molecule, can be sent out respectively when they return to ground state
The characteristic spectrum of 526nm and 394nm is projected, this luminous intensity is directly proportional to the volume fraction of sulphur compound in sample.This feature
Spectrum is received after optical filter filters by photomultiplier, then is amplified through micro current amplifier, and sample is obtained after signal processing
The content of middle sulfide.Flame photometric detector be to the response of sulfide it is non-linear, the response of conventional FPD and sulfide
Content exponent function relation.For FPD methods by then passing through chromatographic column separation component, interval time of measurement is longer, every six minutes average
A data are obtained, and are not online analytical instruments.
After ultraviolet fluorescence method sample is introduced in high-temperature cracking furnace, pyrolysis oxidization reaction occurs for sample.At 1050 DEG C or so
At a high temperature of, sample is fully vaporized prior and occurs oxicracking, and sulfide therein is quantitatively converted into sulfur dioxide.Reaction gas
It is carried by carrier gas, moisture content therein is sloughed by membrane dryer, into reative cell.Sulfur dioxide is by the ultraviolet of specific wavelength
Line irradiates, and absorbing this ray makes some electrical steering High-Energy Orbits.It is excessive when electronics returns to their original track
Energy just releases in the form of light, and Photoelectric multiplier tube is received by specific wavelength detection, and the fluorescence of transmitting carrys out sulphur
Say to be entirely specific and directly proportional to the content of sulphur in raw sample.Amplify again through micro current amplifier, at computer data
Reason, you can be converted to the electric signal directly proportional to luminous intensity, the sulfur content of respective sample can be calculated by measuring its size.
Ultraviolet fluorescence method needs carrier gas and reaction temperature to be up to 1050 DEG C, and severe reaction conditions are complicated for operation.
Laser absorption spectroscopy is mainly that the laser beam for the process tuning that semiconductor laser goes out passes through tested gas,
It is detected by the photoelectric sensor of receiving unit.Laser beam energy is decayed by tested gas molecules sorb, is received single
The absorbance of member detection meets Lambert-Beer's law with tested gas content, and sulfide content is calculated with this.The technology has existing
The advantages that field measurement, quick response, the scope of application are big, precision is high, reliability is high and maintenance is small.But this method but can only
Detect the content of hydrogen sulfide.
Therefore, it is anxious that searching one is easy to operate, equipment is simple, can detect the detection method of total sulfur content in natural gas
The technical issues of need to solving.
Invention content
The present invention provides a kind of device detecting total sulfur content in natural gas to overcome the above-mentioned deficiency of the prior art
And its detection method, the device and method generate hydrogen sulfide gas by the way that hydrolysis is occurred for the sulfide in natural gas, so
The content for measuring hydrogen sulfide gas in mixed gas afterwards, to which sulphur total amount in natural gas sample be calculated.Apparatus structure letter
Single, easy to operate, method reaction condition is mild, can measure total sulfur content in natural gas.
To achieve the goals above, the present invention is achieved by the following technical solutions：
The device of total sulfur content in a kind of detection natural gas, described device include gas transfer pipeline and in air shooter
Pipe valve, steam-laden device, hydrolysis reactor and the hydrogen sulfide measuring device that road is set gradually；The pipe valve connection
Gas outlet is arranged in hydrogen sulfide measuring device in the air inlet of gas transfer pipeline；Organic sulfur water is filled in the hydrolysis reactor
Catalyst is solved, and hydrolysis reactor connects heater.
Preferably, the hydrolysis reactor is first-stage reactor.
Preferably, the hydrolysis reactor is multistage reactor, the multistage reactor series connection.
Preferably, the air shooter road, the setting turn between pipe valve and the input end of steam-laden device
Subflow gauge.
Preferably, temperature control system is also connected in the hydrolysis reactor, the temperature control system includes temperature sensing
Device and temperature controller, the temperature sensor are arranged on hydrolysis reactor, and the temperature controller connects heater.
Preferably, drier is set on the air shooter road between hydrolysis reactor and hydrogen sulfide measuring device.
Preferably, the gas outlet in hydrogen sulfide measuring device connects a gas concentration unit.
Another object of the present invention is to provide a kind of detection method of total sulfur content in natural gas, which includes
Following steps：
(1) it samples：The injection port of gas transfer pipeline is connected on the sample point of natural gas sample, opens sampling steel cylinder valve
Door is deflated, and opens pipe valve, natural gas is made to enter gas transfer pipeline；
(2) hydrolysis：Hydrolysis production occurs after steam-laden device in hydrolysis reactor for natural gas sample
Unboiled water solution natural gas sample, the hydrolysis make sulfide hydrolysis generate hydrogen sulfide gas and carbon dioxide gas；The day
Right gas sample product charge flow rate is 300~350mL/ minutes；
(3) it detects：The hydrogen sulfide content of hydrolysis natural gas sample in hydrogen sulfide measuring device detecting step (2), calculates total
Sulfur content.
Preferably, drier is introduced into the hydrolysis natural gas sample before hydrogen sulfide measuring device to be dried.
Preferably, the hydrolysis reactor is concatenated multistage reactor, and hydrolysis is multistage hydrolysis, respectively needle
To sulfide different in natural gas, corresponding organic sulfur hydrolyst is placed in corresponding hydrolysis reactor, step by step water
Solve organic sulfur.
Compared with prior art, a kind of device and its detection method detecting total sulfur content in natural gas provided by the invention
Advantageous effect be：
(1) the device combined detection method compensates for that be unable to on-line measurement using Diode Laser Absorption Spectroscopy natural
The deficiency of total sulfur content in gas is a kind of new effective means for measuring total sulfur in natural gas；
(2) it can be carried out under room temperature or low temperature using tempreture organic sulphur hydrolysis, very high temperature need not be heated to, whole
It is simpler in body structure, it is more convenient in operation；
(3) natural gas is inflammable and explosive gas, and the temperature of tempreture organic sulphur hydrolysis is generally in 60-80 degree or so, than other need
The method to be heated at high temperature is safer；
(4) tempreture organic sulphur hydrolysis technology is a very ripe technology in chemical industry at present, and tempreture organic sulphur hydrolysis is urged
There are many type of agent, cheap；It is lower than other detection methods in cost；
(5) tempreture organic sulphur hydrolysis technology combination Diode Laser Absorption Spectroscopy has in terms of natural gas total sulfur on-line measurement
There is higher measurement accuracy.
Description of the drawings
Fig. 1 is the apparatus structure schematic diagram of total sulfur content in detection natural gas in embodiment 1.
Fig. 2 is the apparatus structure schematic diagram of the total sulfur content detection with two-stage hydrolysis reactor.
Specific implementation mode
It shows that example illustrates certain embodiments of the present invention, and should not be construed as the model of the limitation present invention
It encloses.Present disclosure can be improved from material, method and reaction condition simultaneously, all these improvement should all
It falls within the spirit and scope of the present invention.
Embodiment 1：Detect the device of total sulfur content in natural gas
As shown in Figure 1, it is a kind of detection natural gas in sulfide total amount device, the device include gas transfer pipeline and
Pipe valve 1 that gas transfer pipeline is set gradually, spinner flowmeter 2, steam-laden device 3, hydrolysis reactor 4, drier 7
With hydrogen sulfide measuring device 8；Pipe valve 1 connects the air inlet of gas transfer pipeline, and outlet is arranged in hydrogen sulfide measuring device 8
Mouthful；Organic sulfur hydrolyst is filled in the hydrolysis reactor 4, and hydrolysis reactor 4 connects heater 5.Hydrolysis reactor 4
In be also connected with temperature control system 6, the temperature control system 6 includes temperature sensor and temperature controller, and the temperature passes
Sensor is arranged on hydrolysis reactor 4, and the temperature controller connects heater 5.
In the present embodiment, valve 1 and spinner flowmeter 2 carry out throughput for controlling.Steam-laden device 3 is for providing
Steam generator or other equipment can be used to provide vapor for vapor needed for hydrolysis, steam-laden device 3.Hydrolysis
Organic sulfur hydrolyst is filled in reactor 4, the gas for mixing the organic sulfur of vapor is hydrolyzing under the action of catalyst
Hydrolysis occurs in reactor 4；Different for the type of sulfide in different natural gases, hydrolysis reactor 4 can be level-one
Reactor, or multistage reactor；For multistage reactor when, multistage reactor series connection, for wanting water in every stage reactor
The temperature needed for different catalyst and different hydrolysis is arranged in the sulfide of solution.Heater 5 is for adding reactor
Heat provides physical reactions condition for hydrolysis, heater can be used heating tape, heating tube, heating furnace or it is other types of plus
Hot product.Temperature control system 6 includes temperature sensor with temperature controller, temperature sensor acquisition reaction temperature data, temperature
Degree controller controls heater by the data of acquisition and is heated, to realize reaction temperature control.Drier 7 will be extra
Water is dried, and vapor is avoided to enter measuring instrumentss, has damage to instrument.Hydrogen sulfide measuring device 8 is in addition to using semiconductor
Laser absorption spectroscopy measures, and also other means can be taken to measure.It, can be in hydrogen sulfide in the detection device of the present invention
Gas outlet in measuring device connects a gas concentration unit, prevents from causing environmental pollution.
The operation principle of the device of sulfide total amount is in detection natural gas in the present embodiment：Contain volatile sulfur gases
Natural gas is adjusted by valve 1 and spinner flowmeter 2 to desired flow rate of, in hydrolysis reactor 4 after steam-laden device 3
Middle generation hydrolysis, 7 enter H after the drying of drier 72S measuring devices 8 measure.Own in hydrolysis reactor 4
Machine sulphur can be converted into H2S finally measures total H2S contents are to calculate total sulfur content in raw natural gas sample.
Embodiment 2：Sulfide total amount in the right gas sample product of observation
Using the device of embodiment 1, the detection method of sulfide total amount in natural gas, including 3 steps are detected.
1, it samples
The injection port of gas transfer pipeline is connected on the sample point of natural gas sample, is opened sampling steel cylinder valve and is deflated,
It opens pipe valve 1 and spinner flowmeter 2 is adjusted to desired flow rate of, natural gas is made to enter gas transfer pipeline；It is described natural
Gas sample product charge flow rate is 300~350mL/ minutes；
2, hydrolysis
Natural gas sample occurs hydrolysis in hydrolysis reactor after steam-laden device and generates hydrolysis natural gas
Sample, the hydrolysis make sulfide hydrolysis generate hydrogen sulfide gas and carbon dioxide gas.It is arranged in hydrolysis reactor
Catalyst is common organic sulfur hydrolyst.Part tempreture organic sulphur hydrolysis reaction equation is as follows：
COS+H2O=H2S+CO2
CS2+2H2O=2H2S+CO2
By taking COS gas hydrolysis as an example, COS hydrolysis chemical equations are as follows：
COS+H2O=H2S+CO2
Assuming that reaction temperature is 60 DEG C, COS contents 300ppm in natural gas.Corresponding chemical equilibrium constant K=at this time
1.762×105。
(1) 60 DEG C of saturated vapor substance withdrawl syndromes are calculated
60 DEG C of saturated vapour pressures are 19.932 × 103Pa
PV=nRT (1)
It can be obtained according to formula (1)：
N/V=P/RT
=19.932 × 103Pa/(8.31Pa·m3/mol·k×(273+60)k)
=7.2mol/m3
60 DEG C of saturated vapor substance withdrawl syndromes are：7.2mol/m3
(2) the amount concentration of 60 DEG C of COS gaseous matters is calculated
It can be obtained according to formula (1)：
V=nRT/P
=(8.31Pam3/molk × (273+60) k)/101325Ps
=27.3L
The amount concentration of 300ppm COS gaseous matters：0.3/27.3=0.011mol/m3
If COS has converted X mol
COS+H2O=H2S+CO2
Initial concentration：0.011 7.2 0 0
Equilibrium concentration：(0.011-X) (7.2-X) X X
K=X2/ ((0.011-X) (7.2-X))=1.762 × 105
X=0.0109999999999999
Conversion ratio=0.0109999999999999/0.011=99.99999%
Other sulfide such as CS can be calculated using same method2The amount and its conversion ratio of hydrolysis.Theoretically see
Hydrolysis organic sulfur conversion rate is high.At present hydrolysis catalyst experiment have been carried out the conversion ratio 99% of organic sulfur with
On, and reaction speed is exceedingly fast, and Transient transformation can be achieved substantially.So tempreture organic sulphur hydrolysis technology combination semiconductor laser is absorbed
Spectral technique can realize total sulfur on-line measurement in natural gas.
3, it detects
Natural gas sample hydrolyzes sulfide by hydrolysis reactor 4, and the hydrolysis natural gas after hydrolysis passes through drier 7
Water vapour is removed, then mixed gas enters hydrogen sulfide measuring device, and the hydrogen sulfide of natural gas sample is hydrolyzed in detecting step (2)
Content, to calculate total sulfur content.Hydrogen sulfide measuring device 8, can be accurate using Diode Laser Absorption Spectroscopy (TDLAS)
Measure H after reacting2The total amount of S, it is final to obtain total sulfur content in raw natural gas sample.
Sulfide is in addition to hydrogen sulfide, COS, CS in natural gas2Other than three kinds of sulfide, further include mainly carbonyl sulfur, mercaptan,
The diversified forms of thioether, thiophene, thiophane and other sulfide.Therefore, multistage reactor cascaded structure can be used, every grade anti-
The catalyst that different tempreture organic sulphur hydrolysis are placed in device is answered, by organic sulfur stepwise hydrolysis.It is illustrated in figure 2 containing two-stage reactor string
The sulfide detection device of connection, wherein the first hydrolysis reactor 4-1 combines a kind of specific organic sulfur hydrolyst first
A form of sulfide of the lower hydrolysis of heater 5-1 effects, and the second hydrolysis reactor 4-2 combines another tempreture organic sulphur hydrolysis to urge
Agent hydrolyzes another form of sulfide under secondary heater 5-2 effects.According to the method, for specific natural gas
Sample, places corresponding organic sulfur hydrolyst in corresponding hydrolysis reactor, and stepwise hydrolysis organic sulfur finally obtains original
The content for total hydrogen sulfide that sample and hydrolysis generate.
Hydrogen sulfide on-line measurement instrument is using TDLAS technologies, it can be achieved that H2S content on-line measurements, measurement accuracy are
0.5mmp, the reaction time is within 5s.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. it is a kind of detection natural gas in total sulfur content device, which is characterized in that described device include gas transfer pipeline and
Pipe valve (1), steam-laden device (3), hydrolysis reactor (4) and the hydrogen sulfide that gas transfer pipeline is set gradually measure dress
It sets (8)；Gas outlet is arranged on (8) in the air inlet of pipe valve (1) the connection gas transfer pipeline, hydrogen sulfide measuring device；
Organic sulfur hydrolyst, and hydrolysis reactor (4) connection heater (5) are filled in the hydrolysis reactor (4).
2. the device of total sulfur content in a kind of detection natural gas according to claim 1, which is characterized in that the hydrolysis is anti-
It is first-stage reactor to answer device (4).
3. the device of total sulfur content in a kind of detection natural gas according to claim 1, which is characterized in that the hydrolysis is anti-
It is multistage reactor to answer device (4), the multistage reactor series connection.
4. the device of total sulfur content in a kind of detection natural gas according to claim 1, which is characterized in that the gas is defeated
It send on pipeline, spinner flowmeter (2) is set between pipe valve (1) and the input end of steam-laden device (3).
5. the device of total sulfur content in a kind of detection natural gas according to claim 1, which is characterized in that the hydrolysis is anti-
It answers and is also connected with temperature control system (6) in device (4), the temperature control system (6) includes temperature sensor and temperature controller,
The temperature sensor is arranged on hydrolysis reactor (4), the temperature controller connection heater (5).
6. the device of total sulfur content in a kind of detection natural gas according to claim 1, which is characterized in that in hydrolysis
Air shooter road setting drier (7) between device (4) and hydrogen sulfide measuring device (8).
7. the device of total sulfur content in a kind of detection natural gas according to claim 1, which is characterized in that hydrogen sulfide measures
Gas outlet on device connects a gas concentration unit.
8. the detection method of total sulfur content in a kind of natural gas, which is characterized in that include the following steps：
(1) it samples：The injection port of gas transfer pipeline is connected on the sample point of natural gas sample, is opened sampling steel cylinder valve and is put
Gas opens pipe valve, natural gas is made to enter gas transfer pipeline；The natural gas sample charge flow rate is 300~350mL/
Minute；
(2) hydrolysis：Natural gas sample occurs hydrolysis in hydrolysis reactor after steam-laden device and generates water
Natural gas sample is solved, the hydrolysis makes sulfide hydrolysis generate hydrogen sulfide gas and carbon dioxide gas；
(3) it detects：The hydrogen sulfide content of hydrolysis natural gas sample in hydrogen sulfide measuring device detecting step (2), calculates total sulfur and contains
Amount.
9. the detection method of total sulfur content in a kind of natural gas according to claim 8, which is characterized in that enter hydrogen sulfide
Hydrolysis natural gas sample before measuring device is introduced into drier and is dried.
10. the detection method of total sulfur content in a kind of natural gas according to claim 8, which is characterized in that the hydrolysis
Reactor is concatenated multistage reactor, and hydrolysis is multistage hydrolysis, is directed to sulfide different in natural gas respectively,
Corresponding organic sulfur hydrolyst, stepwise hydrolysis organic sulfur are placed in corresponding hydrolysis reactor.
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