CN108931584A - Arsenic phosphorus sulphur impurity on-line monitoring method in a kind of liquefaction hydrocarbon raw material - Google Patents
Arsenic phosphorus sulphur impurity on-line monitoring method in a kind of liquefaction hydrocarbon raw material Download PDFInfo
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- CN108931584A CN108931584A CN201710379197.8A CN201710379197A CN108931584A CN 108931584 A CN108931584 A CN 108931584A CN 201710379197 A CN201710379197 A CN 201710379197A CN 108931584 A CN108931584 A CN 108931584A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
Abstract
The invention discloses arsenic phosphorus sulphur impurity on-line monitoring methods in a kind of liquefaction hydrocarbon raw material, including：Establish on-line monitoring system comprising：Equipped with the main box of gas chromatograph-mass spectrometer (GC-MS), system purge gas tank, sample interface case, carrier gas interface case, emptying clack box, power interface and communication interface；Activation system is monitored the arsenic phosphorus sulphur impurity in liquefaction hydrocarbon raw material, obtains monitoring data；According to the monitoring data, the inlet amount of regulation liquefaction hydrocarbon raw material.The on-line monitoring to arsenic phosphorus sulphur impurity in liquefaction hydrocarbon raw material not only may be implemented in the method for the present invention, and according to obtained arsenic phosphorus sulfur content, the inlet amount of regulation liquefaction hydrocarbon raw material.
Description
Technical field
The present invention relates to a kind of on-line monitoring method of arsenic phosphorus sulphur impurity in liquefaction hydrocarbon raw material, more particularly to one kind are industrial
Impurity on-line monitoring technique and data processing method in polymer grade liquefaction hydrocarbon raw material, belong to petrochemical materials and test and analyze neck
Domain.
Background technique
Ethylene, propylene in Liquefied Hydrocarbon are most important production polyethylene, polyacrylic starting monomer in polyolefin industry,
Purity and impurity content directly affect the activity of polyolefin catalyst and the material property of polyolefin resin, therefore monitor analysis liquid
Changing the impurity content in hydrocarbon raw material is to prevent polyolefin catalyst inactivation from guaranteeing the premise that polyolefin steadily produces.
Arsenic hydride, hydrogen phosphide, carbonyl sulfur are in petroleum refining process as the catalytic cracking of petroleum enters Liquefied Hydrocarbon
In raw material, especially terrestrial facies, marine facies are easy to containing a large amount of arsenides, phosphide, sulfide with petroleum in the crude oil of oil
Refining resolve into small molecule arsenic hydride, hydrogen phosphide, carbonyl sulfur enter liquefaction hydrocarbon raw material in.Arsenic hydride, hydrogen phosphide, carbonyl
Sulphur can directly make with the titanium magnesium activated centre reaction bonded of polyolefin catalyst its loss of activity therefore its must be monitored point
Analysis while strict control content.
Chinese patent CN105233806A proposes adsorbent that is a kind of while purifying hydrogen sulfide, hydrogen phosphide, arsenic hydride
Preparation method, this patent relate generally to arsenic hydride, hydrogen phosphide sorbent preparation method rather than at monitoring technology and data
Reason method.Chinese patent CN203437020U proposes a kind of phosphine gas monitoring device and phosphine gas purification system
System, this patent relate generally to the monitoring and automatic control of hydrogen phosphide purification tail gas, improve the purification efficiency of hydrogen phosphide.Patent text
Part CN101450302A discloses a kind of C 4 olefin desulfurization absorbent and preparation method and application.It is related to liquid currently without domestic patent
Change arsenic hydride in hydrocarbon raw material, hydrogen phosphide, the application of carbonyl sulphur impurity monitoring technology and data processing method and openly.
In addition to patent, there is also following disadvantages for existing arsenic hydride, hydrogen phosphide, carbonyl sulfur research and application technology：(1) can only
For arsenic hydride, hydrogen phosphide, a kind of species analysis of carbonyl sulfur cannot analyze simultaneously three kinds of substances (2) can only offline sampling analysis not
It can accomplish on-line real time monitoring, it cannot be guaranteed that personnel safety and sample representativeness.(3) data processing needs artificial calculating or correction
It is unable to automatic processing data result, while result can not automation remote transmission.Therefore, against the above technical problems, have
Necessity provides arsenic hydride, hydrogen phosphide, carbonyl sulphur impurity real-time online detection technique and data processing side in a kind of liquefaction hydrocarbon raw material
Method is to overcome drawbacks described above.(4) arsenic hydride, hydrogen phosphide, carbonyl sulfur monitoring analysis precision are inadequate, and polyolefin catalyst requires liquefaction
Arsenic hydride, hydrogen phosphide, COS content control are in 30mL/m in hydrocarbon raw material3, but present analysis technology is difficult to accomplish 30mL/m3's
Arsenic hydride, hydrogen phosphide, carbonyl sulfur monitoring analysis.
Summary of the invention
The purpose of the present invention is provide in view of the deficiencies of the prior art it is a kind of liquefaction hydrocarbon raw material in arsenic phosphorus sulphur impurity it is online
The on-line monitoring to arsenic hydride, hydrogen phosphide and carbonyl sulphur impurity in liquefaction hydrocarbon raw material not only may be implemented in monitoring method, the present invention,
Producers are allow to be accurately obtained the content of arsenic hydride, hydrogen phosphide and carbonyl sulfur in liquefaction hydrocarbon raw material in real time；May be used also simultaneously
According to arsenic hydride, hydrogen phosphide and COS content in obtained liquefaction hydrocarbon raw material, the inlet amount of regulation liquefaction hydrocarbon raw material, with regulation
The performance of the polymer of preparation guarantees the even running of polymer generating means.
Purpose according to the present invention provides arsenic phosphorus sulphur impurity on-line monitoring method in a kind of liquefaction hydrocarbon raw material, including：
Step A：Establish arsenic phosphorus sulphur impurity on-line monitoring system in liquefaction hydrocarbon raw material comprising：
Gas chromatograph-mass spectrometer (GC-MS) is arranged inside in main box, for receiving liquefaction hydrocarbon gasification raw material and to therein
Arsenic phosphorus sulphur impurity is detected；
The system purge gas tank being external on the main tank body sidewall, import connect inert gas source, outlet institute
Main box is stated, for conveying inert gas into the main box；
The sample interface case being external on the main tank body sidewall, material inlet connect Liquefied Hydrocarbon feed side line interface,
Material outlet connects the main box, for receiving liquefaction hydrocarbon raw material and being vaporized to obtain Liquefied Hydrocarbon gasified raw material, then send
Enter the main box；
The carrier gas interface case being external on the main tank body sidewall, import connect carrier gas source, and outlet connects the main tank
Body, for the delivery of carrier gas into the main box；
The emptying clack box being external on the main tank body sidewall, main box described in inlet communication, outlet emptying, for arranging
The intracorporal gas of the main tank out；
Step B：Activation system monitors the arsenic phosphorus sulphur impurity in liquefaction hydrocarbon raw material on-line, obtains liquefaction hydrocarbon raw material
The monitoring data of middle arsenic phosphorus sulphur impurity content.
According to certain embodiments of the present invention, gas chromatograph-mass spectrometer (GC-MS), computer number are equipped in the main box
According to processing system and for the pipeline of connection.
According to a preferred embodiment of the present invention, for the shape of the main box, there is no particular limitation, preferably
Cuboid.In some specific embodiments, the size range of the main box is being not more than 200cm × 150cm × 100cm.
According to the preferred embodiment of the present invention, inert gas is filled with by system purge gas tank in the main box, with
Prevent explosion.
Gas chromatograph-mass spectrometer (GC-MS) of the present invention, Salbutamol Selected Ion Monitoring mode (arsenic hydride selects characteristic ion m/z=76,
Hydrogen phosphide selects characteristic ion m/z=34, and carbonyl sulfur selects ion m/z=60), use stationary phase for polystyrene-divinyl
The PLOT capillary column of base benzene class can satisfy μ L/m in liquefaction hydrocarbon raw material3The monitoring of rank arsenic hydride, hydrogen phosphide, carbonyl sulfur
Demand.
According to a preferred embodiment of the present invention, the injection port of the gas chromatograph-mass spectrometer (GC-MS) connects the sample
The outlet of product interface box, for being detected to the Liquefied Hydrocarbon gasified raw material from the sample interface case.
According to certain embodiments of the present invention, one end of the computer data processing system and the gas-chromatography-
Mass spectrometer is connected, and the other end is via communication interface linking parsing system, for the inspection according to gas chromatograph-mass spectrometer (GC-MS)
Measure detection data.
According to a preferred embodiment of the present invention, the intracorporal inert gas pressure of system purge main tank is 0.5-
2.0MPa。
In some specific embodiments, the inert gas includes nitrogen.
According to the preferred embodiment of the present invention, the sample interface case includes：
The filter device being connect with the material inlet, for receiving the liquid from the Liquefied Hydrocarbon feed side line interface
Change hydrocarbon raw material, and is filtered processing to it；
Constant-voltage equipment is depressurized, for receiving the liquefaction hydrocarbon raw material from the filter device, and is vaporized, obtains liquid
Change hydrocarbon gasification raw material；
The decompression constant-voltage equipment connects the injection port of the gas chromatograph-mass spectrometer (GC-MS) via the material outlet.
In some specific embodiments, the liquefaction hydrocarbon raw material enters the sample interface case via material inlet, first
It is first filtered via filter device, removes particulate matter therein；Subsequently into decompression constant-voltage equipment, vacuum flashing processing is carried out,
Gasification forms Liquefied Hydrocarbon gasified raw material；Finally, Liquefied Hydrocarbon gasified raw material via outlet enter gas chromatograph-mass spectrometer (GC-MS) into
Sample mouth, is detected.
According to a preferred embodiment of the present invention, atmosphere exhaust-valve and chromatography in main box are equipped in the emptying clack box
Instrument carrier gas unstripped gas exhaust-valve.
According to some embodiments of the present invention, main box described in the inlet communication of atmosphere exhaust-valve in the main box, out
Mouth emptying, for the intracorporal gas of the main tank to be discharged.
According to some embodiments of the present invention, gas phase color described in the inlet communication of the chromatograph carrier gas unstripped gas exhaust-valve
The outlet of spectrum-mass spectrometer, outlet emptying, for the gas of the gas chromatograph-mass spectrometer (GC-MS) to be discharged.
Preferred real mode according to the present invention, arsenic phosphorus sulphur impurity on-line monitoring system further includes in the liquefaction hydrocarbon raw material：
The power interface being external on the main tank body sidewall, one end connect power supply, and the other end is distinguished by connecting line
It is connect with the power interface of each instrument, for powering to each instrument；
The communication interface being external on the main tank body sidewall, one end connect the main box, other end linking parsing
System, for obtained detection data to be transmitted to analysis system.
According to certain embodiments of the present invention, the system also includes analysis system, each device of the system passes through
Pipeline is connect with analysis system, and by analysis system obtained data are analyzed and controlled with the operation of each device.According to this
The preferred embodiment of invention, the step B include：
Activation system makes liquefaction hydrocarbon raw material enter the system via Liquefied Hydrocarbon feed side line interface, to liquefaction hydrocarbon raw material
In arsenic phosphorus sulphur impurity monitored on-line, obtain monitoring data.
According to a preferred embodiment of the present invention, the step B is specifically included：
Activation system, liquefaction hydrocarbon raw material enter the sample interface case via Liquefied Hydrocarbon feed side line interface, successively carry out
Filtering and reduced pressure treatment；Meanwhile the valve opening of system purge gas tank, inert gas is sent to main box, in main box
Inert gas atmosphere is formed, atmosphere exhaust-valve in the main box in clack box is vented and opens, flow inert gas in main tank；It carries
The valve opening of gas interface box send carrier gas to gas chromatograph-mass spectrometer (GC-MS)；Gasify in liquefaction hydrocarbon samples through sample interface case
Before, carrier gas first purges the gas chromatograph-mass spectrometer (GC-MS)；Liquefied Hydrocarbon gasified raw material sample interface case export into
Enter the gas chromatograph-mass spectrometer (GC-MS), qualitative and quantitative detection is carried out to arsenic phosphorus sulphur impurity therein, detection data is via institute
Computer processing system is stated to obtain；The gas of the chromatograph discharge is via emptying clack box discharge.
According to certain embodiments of the present invention, the analysis condition of the gas chromatograph-mass spectrometer (GC-MS) is as follows：
Carrier gas：Purity is greater than 99.999% helium, hydrogen or other gas that can be used for gas chromatograph-mass spectrometer (GC-MS)
Body.Analysis condition：Gas chromatography mass spectrometry condition：The PLOT capillary column of polystyrene-divinylbenzene class；Column length 10-60m；Internal diameter
0.25-0.32mm；Column temperature：20-50 DEG C of initial temperature, 100-200 DEG C of maximum temperature, 1-20 DEG C of heating rate/min, split ratio：
1-10:1；Flow rate of carrier gas 1.0-10.0mL/min, constant current mode.Mass spectrum：Quadrupole rod temperature：100-150 DEG C, ion source temperature：
200-300 DEG C, select ion (SIM) mode, ion sequence：Hydrogen phosphide (34), arsenic hydride (76), carbonyl sulfur (60).
According to a preferred embodiment of the present invention, the qualitative analysis includes：Gas chromatography-mass spectrometry is using guarantor
Time and selection characteristic ion two ways is stayed to carry out arsenic hydride, hydrogen phosphide qualitative analysis.The retention time of hydrogen phosphide is in 3min-
6min selects characteristic ion m/z=34, arsenic hydride retention time 3.5min-6.5min, selects characteristic ion m/z=76.Carbonyl
Sulphur retention time 6min-9min selects characteristic ion m/z=60.
According to the preferred embodiment of the present invention, the quantitative analysis includes：With arsenic hydride, hydrogen phosphide, carbonyl sulfur infiltration
Pipe or calibrating gas are standard substance, draw external standard calibration curve and the control correction to program table of integrals, and three kinds of measured object corrections are bent
The linearly dependent coefficient of line requires to be greater than 0.999.In Liquefied Hydrocarbon sample analysis using the base table of calibration curve to arsenic hydride,
Hydrogen phosphide, carbonyl sulfur measured object carry out quantitative correction integral, obtain the exact level of three kinds of measured objects.
Preferred embodiment in accordance with the present invention, the method also includes step C：According to the monitoring data, regulation liquefaction
The inlet amount of hydrocarbon raw material.
A preferred embodiment according to the present invention, the charging that liquefaction hydrocarbon raw material is regulated and controled according to the monitoring data
Amount includes：
When arsenic hydride, hydrogen phosphide, COS content are less than 0.03mL/m3When, liquefaction hydrocarbon raw material and catalyst are by normal ratio
Example mixing；
When arsenic hydride, hydrogen phosphide, COS content are in 0.03mL/m3~0.10mL/m3When, do not change liquefaction hydrocarbon raw material into
Catalyst amount increases by 20%~80% and mixes with liquefaction hydrocarbon raw material in the case where sample amount；
When arsenic hydride, hydrogen phosphide, COS content are greater than 0.10mL/m3When, stop liquefaction hydrocarbon raw material charging.
According to the preferred embodiment of the present invention, the normal rates are that the liquefy mass ratio of hydrocarbon raw material and catalyst is
(30000-40000):1, polymerization multiple at this time is usually 30000-200000 times.
Of the invention is a little as follows with advantageous effects：
(1) arsenic phosphorus sulphur impurity on-line monitoring system can by having carried out technological processing for explosion protection feature in the liquefaction hydrocarbon raw material that the present invention establishes
To be directly connected to process units side line, compared with the existing technology by being then sent through lab analysis detection after manual sampling, reduce
Sample secondary pollution ensure that the representative while more real-time accurate of sample, also avoid the risk of artificial field sampling.
(2) it can satisfy by the Optimal Development of gas chromatograph-mass spectrometer (GC-MS) to 30mL/m in liquefaction hydrocarbon raw material3Arsenic
Change hydrogen, hydrogen phosphide, carbonyl sulfur monitoring analysis, relative to existing analysis method and analytical technology arsenic hydride, hydrogen phosphide, carbonyl sulfur
Detection limit it is lower, be able to satisfy requirement of the polyolefin catalyst of new generation to Liquefied Hydrocarbon raw material impurity content.
(3) gas chromatograph-mass spectrometer (GC-MS) used in only needs to use high-purity helium for carrier gas, greatlies simplify on-line analysis
System technological processing for explosion protection feature grade and the design of carrier gas interface exhaust port.Existing chromatography class, spectral class analytical technology are required to provide more
The combustion gas such as road-load gas even hydrogen and oxygen propose on-line analysis system technological processing for explosion protection feature grade and the design of carrier gas interface exhaust port
It is difficult to reach requirement out.
(4) impurity data that arsenic phosphorus sulphur impurity on-line monitoring system measures in the liquefaction hydrocarbon raw material that the present invention establishes is accurate,
By obtained monitoring data can the liquefy inlet amount of hydrocarbon raw material of direct regulation and control guaranteed with regulating and controlling the performance of the polymer of preparation
The even running of polymer generating means.
Detailed description of the invention
Fig. 1 is the flow chart of arsenic phosphorus sulphur impurity on-line monitoring method in present invention liquefaction hydrocarbon raw material；
Fig. 2 is the front view of arsenic phosphorus sulphur impurity on-line monitoring system in present invention liquefaction hydrocarbon raw material；
Fig. 3 is the right view of arsenic phosphorus sulphur impurity on-line monitoring system in present invention liquefaction hydrocarbon raw material；
Fig. 4 is the top view of arsenic phosphorus sulphur impurity on-line monitoring system in present invention liquefaction hydrocarbon raw material；
Fig. 5 is according to the arsenic hydride of one embodiment of the invention, hydrogen phosphide and carbonyl sulfur qualitative analysis total ion current figure；
Fig. 6 is the external standard song that present invention arsenic hydride quantitative analysis according to an embodiment of the invention corrects that the table of integrals is drawn
Line；
Fig. 7 is the external standard song that present invention hydrogen phosphide quantitative analysis according to an embodiment of the invention corrects that the table of integrals is drawn
Line；
Fig. 8 is the external standard song that present invention carbonyl sulfur quantitative analysis according to an embodiment of the invention corrects that the table of integrals is drawn
Line；
Fig. 9 is the data communication structure chart of arsenic phosphorus sulphur impurity on-line monitoring system and method in present invention liquefaction hydrocarbon raw material.
Description of symbols：1, main box；2, system purge gas tank；3, sample interface case；4, carrier gas interface case；5, it is vented
Clack box；6, power interface；7, communication interface.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be described.
Arsenic phosphorus sulphur impurity on-line monitoring method includes in this lotionization hydrocarbon raw material：；
Step A：Arsenic phosphorus sulphur impurity on-line monitoring system in liquefaction hydrocarbon raw material as in Figure 2-4 is established, including：Main box
1, system purge gas tank 2, sample interface case 3, carrier gas interface case 4, emptying clack box 5, power interface 6 and communication interface 7；
Wherein, equipped with gas chromatography-mass spectrometry, computer data processing system and for connecting in the main box 1
Pipeline.The injection port of gas chromatography-mass spectrometry connects the outlet of the sample interface case, for from the sample
The Liquefied Hydrocarbon gasified raw material of product interface box is detected.One end of computer data processing system and the gas chromatography-mass spectrum
It is connected with instrument, the other end is via communication interface linking parsing system, for being obtained according to the detection of gas chromatography-mass spectrometry
Detection data, and it is transmitted to analysis system.In embodiments of the present invention, main box 1 is cuboid, and size range is being not more than
200cm×150cm×100cm.In embodiments of the present invention, support leg, the support are equipped between the main box and ground
The number of foot is 4, is located at the quadrangle on the main box ground.
The import of the system purge gas tank 2 connects inert gas source, and main box described in outlet is used for the master
Inert gas is conveyed in cabinet 1, makes to form inert gas atmosphere in main box, thus explosion-proof.In embodiments of the present invention, system
The inert gas pressure purged in gas tank is 0.5-2.0MPa, and inert gas is preferably nitrogen.
The sample interface case 3 includes：The filter device being connect with the material inlet, for receiving from the liquid
Change the liquefaction hydrocarbon raw material of hydrocarbon raw material side line interface, and is filtered processing to it；Constant-voltage equipment is depressurized, for receiving from institute
The liquefaction hydrocarbon raw material of filter device is stated, and is vaporized, Liquefied Hydrocarbon gasified raw material is obtained；The decompression constant-voltage equipment is via described
Material outlet connects the injection port of the gas chromatography-mass spectrometry.
The import of the carrier gas interface case 4 connects carrier gas source, and outlet connects the main box, for into the main box
Delivery of carrier gas.
Atmosphere exhaust-valve and chromatograph carrier gas unstripped gas exhaust-valve in main box are equipped in the emptying clack box 5.In cabinet
Main box described in the inlet communication of atmosphere exhaust-valve, outlet emptying, for the intracorporal gas of the main tank to be discharged.Chromatograph carrier gas
The outlet of gas chromatography-mass spectrometry described in the inlet communication of unstripped gas exhaust-valve, outlet emptying, for the gas phase to be discharged
The gas of chromatograph-mass spectrometer.
One end of the power interface 6 connects power supply, and the other end is connected with the power interface of each instrument respectively by connecting line
It connects, for powering to each instrument.
One end of the communication interface 7 connects the main box, other end linking parsing system, the detection for will obtain
Data are transmitted to analysis system.
Step B：Activation system, liquefaction hydrocarbon raw material enters the sample interface case via Liquefied Hydrocarbon feed side line interface, first
It is first filtered via filter device, removes particulate matter therein；Subsequently into decompression constant-voltage equipment, vacuum flashing processing is carried out,
Gasification forms Liquefied Hydrocarbon gasified raw material；Meanwhile the valve opening of system purge gas tank, inert gas is sent to main box,
Inert gas atmosphere is formed in main box, is vented atmosphere exhaust-valve in the main box in clack box and is opened, makes inert gas in main tank
Interior flowing；The valve opening of carrier gas interface case send carrier gas to gas chromatograph-mass spectrometer (GC-MS)；In liquefaction hydrocarbon samples through sample
Before interface box gasification, carrier gas first purges the gas chromatography-mass spectrometry；Liquefied Hydrocarbon gasified raw material sample connects
The outlet of mouth case enters the gas chromatography-mass spectrometry, carries out qualitative and quantitative detection, detection to arsenic phosphorus sulphur impurity therein
Data are obtained via the computer processing system；The gas of the gas chromatography-mass spectrometry discharge is via emptying clack box row
Out.
Step C：According to the monitoring data, the inlet amount of regulation liquefaction hydrocarbon raw material：
When arsenic hydride, hydrogen phosphide, COS content are less than 0.03mL/m3When, liquefaction hydrocarbon raw material and catalyst are by normal ratio
(mass ratio of liquefaction hydrocarbon raw material and catalyst is (30000-40000) for example mixing:1), usually polymerization multiple is 30000-
200000 times；
When arsenic hydride, hydrogen phosphide, COS content are in 0.03mL/m3~0.10mL/m3When, do not change liquefaction hydrocarbon raw material into
Catalyst amount increases by 20%~80% and mixes with liquefaction hydrocarbon raw material in the case where sample amount；
When arsenic hydride, hydrogen phosphide, COS content are greater than 0.10mL/m3When, stop liquefaction hydrocarbon raw material charging.
Embodiment 1
The on-line monitoring of arsenic phosphorus sulphur impurity in liquefaction hydrocarbon raw material：
(1) arsenic phosphorus sulphur impurity on-line monitoring system in liquefaction hydrocarbon raw material is established, which specifically includes main box 1, system
Purge gas tank 2, sample interface case 3, carrier gas interface case 4, emptying clack box 5, power interface 6 and communication interface 7；Wherein, the master
Gas chromatography-mass spectrometry, computer data processing system and the pipeline for connection are equipped in cabinet 1.Gas-chromatography-matter
The injection port of spectrum combined instrument connects the outlet of the sample interface case, one end of computer data processing system and the gas phase color
It composes mass spectrometer to be connected, the other end connects the analysis system via the communication interface；The size of main box 1 is 188cm
×138cm×91cm；The import of system purge gas tank 2 connects source nitrogen, main box described in outlet, in system purge gas tank
Nitrogen pressure be 1.1MPa.It is equipped in sample interface case 3 and the sequentially connected filter device of material inlet and decompression constant pressure dress
It sets, the decompression constant-voltage equipment connects the injection port of gas chromatography-mass spectrometry via the material outlet；Carrier gas interface case 4
Import connect carrier gas source, outlet connection main box；It is vented in clack box 5 and is equipped with atmosphere exhaust-valve and chromatograph carrier gas in main box
Unstripped gas exhaust-valve, the inlet communication main box of atmosphere exhaust-valve in cabinet, outlet emptying；Chromatograph carrier gas unstripped gas exhaust-valve
Inlet communication gas chromatography-mass spectrometry outlet, outlet emptying；One end of power interface 6 connects power supply, and the other end is logical
Connecting line is crossed to connect with the power interface of each instrument respectively；One end of communication interface 7 connects main box, other end linking parsing system
System.
(2) activation system, the hydrocarbon raw material that makes to liquefy via Liquefied Hydrocarbon feed side line interface enter sample interface case, through filtering and
Vacuum flashing processing, forms Liquefied Hydrocarbon gasified raw material；Meanwhile the valve opening of system purge gas tank, nitrogen is sent to main box
It is interior, nitrogen atmosphere is formed in main box, is vented atmosphere exhaust-valve in the main box in clack box and is opened, flows nitrogen in main tank
It is dynamic；The valve opening of carrier gas interface case send carrier gas to gas chromatography-mass spectrometry；In liquefaction hydrocarbon samples through sample interface case
Before gasification, carrier gas first purges gas chromatography-mass spectrometry；
(3) Liquefied Hydrocarbon gasified raw material sample interface case outlet enters gas chromatography-mass spectrometry, to arsenic phosphorus sulphur therein
Impurity carries out qualitative and quantitative detection：
Chromatographiccondition：PLOT class capillary column；Column length 60m；Internal diameter 0.32mm；Column temperature：40 DEG C of initial temperature, highest
150 DEG C of temperature, 10 DEG C/min of heating rate, split ratio：5:1；Flow rate of carrier gas 2.0mL/min, constant current mode.Quadrupole rod temperature：
150 DEG C, ion source temperature：230 DEG C, select ion (SIM) mode, ion sequence：Hydrogen phosphide (34), arsenic hydride (76), carbonyl
Sulphur (60)；
Qualitative analysis condition：Gas chromatograph-mass spectrometer is qualitative using retention time progress hydrogen phosphide, arsenic hydride, carbonyl sulfur
Analysis.The retention time of hydrogen phosphide is 4.854, and arsenic hydride retention time 5.285min, carbonyl sulfur retention time 6.849min are (such as
Shown in Fig. 5)；
Quantitative analysis condition：Different content hydrogen phosphide, arsenic hydride, carbonyl sulfur calibrating gas are on gas chromatograph-mass spectrometer
Response obtain corresponding checking list, external standard calibration curve is drawn according to checking list, further obtains external standard correction equation (as schemed
6, shown in 7,8)；Tested liquefaction hydrocarbon raw material sample enters gas chromatograph-mass spectrometer and detects that hydrogen phosphide, arsenic hydride, carbonyl sulfur are rung
Should be worth according to appearance calibration curve or appearance correction equation obtain hydrogen phosphide in sample, arsenic hydride, carbonyl sulfur exact level；
1 hydrogen phosphide checking list of table
2 arsenic hydride checking list of table
3 carbonyl sulfur checking list of table
(4) according to measured hydrogen phosphide, arsenic hydride, COS content data, the inlet amount of regulation liquefaction hydrocarbon raw material, following table
Technological parameter is bulk propylene tank polymerization operating condition.
3 bulk propylene tank polymerization operating condition of table
| PH3Content (mL/m3) | 0.030 | 0.055 | 0.030 | 0.020 | 0.030 | 0.114 | 0.030 | 0.154 |
| AsH3Content (mL/m3) | 0.020 | 0.020 | 0.062 | 0.030 | 0.268 | 0.030 | 0.020 | 0.063 |
| COS content (mL/m3) | 0.020 | 0.030 | 0.010 | 0.058 | 0.020 | 0.030 | 0.577 | 0.079 |
| Liquefied Hydrocarbon raw material dosage/kg | 1550 | 1550 | 1550 | 1550 | 0 | 0 | 0 | 0 |
| Catalyst amount/g | 54 | 73 | 77 | 70 | 0 | 0 | 0 | 0 |
Any numerical value mentioned in the present invention, if between any minimum and any highest value be there are two
The interval of unit then includes each all values for increasing a unit from minimum to peak.For example, if stating one kind
The value of the state-variables such as the amount of component, or temperature, pressure, time is 50-90, in the present specification it means that specific
List 51-89,52-88 ... and the numerical value such as 69-71 and 70-71.For the value of non-integer, can with due regard to
0.1,0.01,0.001 or 0.0001 is a unit.This is only some special examples indicated.In this application, with similar side
The all possible combinations of formula, the numerical value between cited minimum and peak are considered to have disclosed.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (10)
1. arsenic phosphorus sulphur impurity on-line monitoring method in a kind of liquefaction hydrocarbon raw material, including：
Step A：Establish arsenic phosphorus sulphur impurity on-line monitoring system in liquefaction hydrocarbon raw material comprising：
Gas chromatograph-mass spectrometer (GC-MS) is arranged inside in main box, for receiving liquefaction hydrocarbon gasification raw material and to arsenic phosphorus sulphur therein
Impurity is detected；
The system purge gas tank being external on the main tank body sidewall, import connect inert gas source, master described in outlet
Cabinet, for conveying inert gas into the main box；
The sample interface case being external on the main tank body sidewall, material inlet connect Liquefied Hydrocarbon feed side line interface, raw material
Outlet connects the main box, for receiving liquefaction hydrocarbon raw material and being vaporized to obtain Liquefied Hydrocarbon gasified raw material, is then fed into institute
State main box；
The carrier gas interface case being external on the main tank body sidewall, import connect carrier gas source, and outlet connects the main box, use
In the delivery of carrier gas into the main box；
The emptying clack box being external on the main tank body sidewall, main box described in inlet communication, outlet emptying, for being discharged
State the intracorporal gas of main tank；
Step B：Activation system monitors the arsenic phosphorus sulphur impurity in liquefaction hydrocarbon raw material on-line, obtains arsenic in liquefaction hydrocarbon raw material
The monitoring data of phosphorus sulphur impurity content.
2. the method according to claim 1, wherein the main box in be equipped with gas chromatograph-mass spectrometer (GC-MS),
Computer data processing system and pipeline for connection.
3. method according to claim 1 or 2, which is characterized in that the injection port of the gas chromatograph-mass spectrometer (GC-MS) connects
The outlet for connecing the sample interface case, for being detected to the Liquefied Hydrocarbon gasified raw material from the sample interface case.
4. method described in any one of -3 according to claim 1, which is characterized in that the computer data processing system warp
It is connected by pipeline with the gas chromatograph-mass spectrometer (GC-MS), for being counted according to the detection of gas chromatograph-mass spectrometer (GC-MS)
According to.
5. method described in any one of -4 according to claim 1, which is characterized in that the intracorporal pressure of main tank is 0.5-
2.0MPa；And/or the inert gas includes nitrogen.
6. method described in any one of -5 according to claim 1, which is characterized in that the sample interface case includes：
The filter device being connect with the material inlet, for receiving the Liquefied Hydrocarbon from the Liquefied Hydrocarbon feed side line interface
Raw material, and processing is filtered to it；
Constant-voltage equipment is depressurized, for receiving the liquefaction hydrocarbon raw material from the filter device, and is vaporized, obtains Liquefied Hydrocarbon
Gasified raw material；
The decompression constant-voltage equipment connects the injection port of the gas chromatograph-mass spectrometer (GC-MS) via the material outlet.
7. method described in any one of -6 according to claim 1, which is characterized in that be equipped with main box in the emptying clack box
Interior atmosphere exhaust-valve and chromatograph carrier gas unstripped gas exhaust-valve, main tank described in the inlet communication of atmosphere exhaust-valve in the main box
Body, outlet emptying, for the intracorporal gas of the main tank to be discharged；The inlet communication institute of the chromatograph carrier gas unstripped gas exhaust-valve
State the outlet of gas chromatograph-mass spectrometer (GC-MS), outlet emptying, for the gas of the gas chromatograph-mass spectrometer (GC-MS) to be discharged.
8. method according to any one of claims 1-7, which is characterized in that the step B includes：Activation system,
So that liquefaction hydrocarbon raw material is entered the system via Liquefied Hydrocarbon feed side line interface, the arsenic phosphorus sulphur impurity in liquefaction hydrocarbon raw material is carried out
On-line monitoring, obtains monitoring data.
9. method described in any one of -8 according to claim 1, which is characterized in that the method also includes step C：According to
The monitoring data, the inlet amount of regulation liquefaction hydrocarbon raw material.
10. method described in any one of -9 according to claim 1, which is characterized in that described according to the monitoring data tune
The inlet amount of draining hydrocarbon raw material includes：
When arsenic hydride, hydrogen phosphide, COS content are less than 0.03mL/m3When, liquefaction hydrocarbon raw material and catalyst are mixed by normal rates
It closes；
When arsenic hydride, hydrogen phosphide, COS content are in 0.03mL/m3~0.10mL/m3When, do not change liquefaction hydrocarbon raw material sample volume
In the case where catalyst amount increase by 20%~80% with liquefy hydrocarbon raw material mix；
When arsenic hydride, hydrogen phosphide, COS content are greater than 0.10mL/m3When, stop liquefaction hydrocarbon raw material charging.
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