CN108072676A - A kind of emulation nuclear magnetic resonance spectroscopy system and its application - Google Patents
A kind of emulation nuclear magnetic resonance spectroscopy system and its application Download PDFInfo
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- 238000005481 NMR spectroscopy Methods 0.000 title claims abstract description 97
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000004458 analytical method Methods 0.000 claims abstract description 56
- 238000003860 storage Methods 0.000 claims abstract description 44
- 238000004140 cleaning Methods 0.000 claims abstract description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000003921 oil Substances 0.000 claims description 37
- 239000010779 crude oil Substances 0.000 claims description 25
- 238000012360 testing method Methods 0.000 claims description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000003350 kerosene Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000000034 method Methods 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000012300 Sequence Analysis Methods 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
- G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
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- Physics & Mathematics (AREA)
- High Energy & Nuclear Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The present invention provides a kind of emulation nuclear magnetic resonance spectroscopy system, including with valvular nitrogen storage device 1, the sample jar 2 with heating unit, on-line NMR analyzer 3, sump tank 4, the 5, circulating pump 6 that cleans the storage with heating unit, triple valve 7 and 8 and pipeline 9.The present invention also provides application of the emulation nuclear magnetic resonance spectroscopy system in off-line analysis petrochemical industry oil product, concrete operation step includes：Shimming, measure and cleaning.The emulation nuclear magnetic resonance spectroscopy system of the present invention allows online NMR analyzers to apply offline, ceiling restriction when breaching online use to analysis sample type, the use scope of NMR analyzers is expanded, the application for making NMR analyzers is more flexible, improves its utilization rate.
Description
Technical field
The invention belongs to petrochemical industries and analytical chemistry field, and in particular to it is a kind of emulation nuclear magnetic resonance spectroscopy system and its
Application in off-line analysis petrochemical industry oil product.
Background technology
With the promotion of enlargement and the overall technology equipment of China's oil chemical plant installations, with to it is energy-saving,
Quality, pollution treatment emission reduction and the increasingly pursuit of safety in production are improved, uses the Dynamic matrix control skill using multivariable predictive control as representative
Art (APC), using process real-time optimization as the Optimized-control Technique (RT-OPT) of core come improve the operation of process units, control water
The flat heat subject for having become current petrochemical enterprise in China.And these control means all be unable to do without mass parameter, these quality ginseng
Several ingredients and physical data then provided from on-line analysis.Therefore, the importance of online analytical instrument and usage amount and day
It is all to increase.Laboratory Instruments is substituted with online analytical instrument, automatization level can be improved, reduce cost of labor, realize production
Precision management, and the basis as intelligent factory construction and important step.
Due to magnetic resonance analysis system can the lighttight sample such as Direct Analysis crude oil, also directly can accurately detect
Sticky aqueous various hydrocarbon mediums are analyzed, so magnetic resonance analysis technology, which becomes, disclosure satisfy that various Jie of oil refining process
The first choice that matter quickly tests and analyzes.On-line NMR analyzer has obtained answering than wide in foreign oil petrochemical industry
With.Since equipment price is expensive (general ten thousand/platforms of 300-400), the application of the online NMR analytical instrument of China's petrochemical industry is detected in
Dushanzi refinery and Yanshan Petrochemical.
Online analytical instrument is the analytical equipment at a set of technique scene, is related to the process interface condition of production, electrically
Interface condition, communication interface condition, analysis interface condition, instrumentation tap condition, public work environmental interface condition and technique dress
Put interior construction.On-line analysis medium is once it is determined that cannot change；It such as to change, it is necessary to original each interface pipeline
It removes, the redesign of stringing and progress process conditions, very cumbersome again.Due to the complexity of petrochemical iy produced, it is related to a variety of
Various technique and device, intermediate product are also that species is various.But the standard configuration of online NMR analyzers is served only for less than 6 at present
The sequence analysis of a different process medium；If covering entire Petrochemical process production, more online NMR analyses are needed to configure
Instrument, entreprise cost pressure are larger.Further, since the property of different material is different, it is necessary to the object analyzed in advance needs
Material carries out analog simulation test, obtains enough information.On the one hand submit necessary information for online analytical instrument buying demonstration
And evidence, in-line analyzer is preferably run after on the other hand can ensureing.
Obviously, the NMR analyzers in laboratory can not solve the above problems.
The content of the invention
For above-mentioned technical problem existing in the prior art, the present invention provides a kind of emulation nuclear magnetic resonance spectroscopy system.It should
System allows online NMR analyzers to apply offline, and ceiling restriction when breaching online use to analysis sample type is expanded
The big use scope of NMR analyzers, the application for making NMR analyzers is more flexible, improves its utilization rate.
In order to realize foregoing invention purpose, present invention employs following technical solutions：
A kind of emulation nuclear magnetic resonance spectroscopy system, including with valvular nitrogen storage device 1, the sample with heating unit
Product tank 2, on-line NMR analyzer 3, sump tank 4, the 5, circulating pump 6 that cleans the storage with heating unit, triple valve 7 and 8,
With pipeline 9；Wherein, the nitrogen storage device 1, sample jar 2, triple valve 7, on-line NMR analyzer 3,8 and of triple valve
Sump tank 4 is linked in sequence by pipeline 9, the 5, circulating pump 6 that cleans the storage, triple valve 7,3 and of on-line NMR analyzer
Triple valve 8 is made up of the circuit of closing pipeline 9；The sample introduction end of the online nmr analysis instrument 3 by triple valve 7 respectively and sample
Product tank 2 and circulating pump 6 connect, the sample outlet end of online nmr analysis instrument 3 by triple valve 8 respectively with sump tank 4 and clean the storage
Connection.
Preferably, the nitrogen storage device 1 is nitrogen cylinder.
Preferably, the heating unit is water bath heating device.
Preferably, the on-line NMR analyzer 3 is Aspect AI-60 on-line NMR analyzers.
Preferably, the volume of the sample jar 2 is 1~3L, more preferably 2L.
Preferably, it is described clean the storage 5 volume for 3~6L, more preferably 5L.
It is also an object of the present invention to provide above-mentioned emulation nuclear magnetic resonance spectroscopy system in off-line analysis petrochemical industry
Application in oil product.
Preferably, the application specifically comprises the following steps：
I. shimming
Will cleaning oil add in described in clean the storage 5, be heated to the temperature of setting, switching three-way valve 7 and 8 makes to clean the storage
5th, circulating pump 6 and on-line NMR instrument 3 form loop by pipeline 9, and open the circulation pump 6, cleaning oil is in the cleaning
It is cycled between oil tank 5 and the Nuclear Magnetic Resonance 3, nuclear magnetic signal is looked in reference test, and shimming behaviour is carried out if condition is unsatisfactory for
Make, until the stable magnetic field of the magnetic nuclear resonance analyzer；
II. measure
Sample to be tested is added in into sample jar 2, is heated to the temperature of setting, switching three-way valve 7 and 8 makes nitrogen storage device
1st, sample jar 2, on-line NMR analyzer 3 and sump tank 4 form access；The valve of nitrogen storage device 1 is opened, uses nitrogen
Make the sample to be tested into the magnetic nuclear resonance analyzer 3 and stop 25~35 seconds, nuclear magnetic scanning 5 times is averaged output
Spectrogram and analysis data；Then sample to be tested flows into the sump tank 4 from the magnetic nuclear resonance analyzer 3；
III. clean
After the completion of measure, sample jar 2 is vented, closes the valve of nitrogen storage device, disconnects nitrogen；Switch the triple valve
7 and 8, make to clean the storage 5, circulating pump 6, on-line NMR instrument 3 are connected with sump tank 4 by pipeline 9, and the cleaning oil starts
The on-line NMR analyzer 3 is cleaned, then flows into the sump tank 4.
Preferably, after the completion of the cleaning step, the triple valve 8 can also be switched, make cleaning oil in the cleaning oil
It cycles between tank 5 and the on-line NMR analyzer 3, prepares for test next time.
Preferably, after the completion of the cleaning step, the cleaning of sample jar 2 is further included.
Preferably, the cleaning oil is aviation kerosine.
Preferably, the temperature of the setting refers to that the sample to be tested is reached by heating, sample to be tested passes through pipeline 9
Into the magnetic nuclear resonance analyzer 3 Nuclear Magnetic Resonance 3 is made to reach the temperature of operating temperature.
Preferably, the magnetic nuclear resonance analyzer 3 is Aspect AI-60 on-line NMR analyzers.
It is described to clean the storage 5 when the magnetic nuclear resonance analyzer is Aspect AI-60 on-line NMR analyzers
Volume for 5L, the volume of the sample jar 2 is 2L；The design temperature of the cleaning oil and sample to be tested is 70 DEG C ± 5 DEG C；Institute
The pressure for stating sample to be tested into the Aspect AI-60 on-line NMR analyzers is 0.08~0.1MPa.
Preferably, the sample to be tested is in crude oil, diesel oil hydrogenation raw material, catalytically cracked material and hydrocracking raw material
One or more.
Above-mentioned offline application, obtained analysis data include the crude oil API, sulfur content, water content, C/Hratio, nitrogen and contain
Amount, carbon residue, boiling range, freezing point, Cetane number, pour point and acid value.
Magnetic resonance analyzer is to meet the head that the various media of oil refining process quickly test and analyze because analysis is accurate, quick
Choosing.And the single factor for influencing magnetic resonance analysis system results is exactly the stability of temperature.Inside magnetic nuclear resonance analyzer device just
Normal operating temperature is 45 DEG C or so.Online in use, maintaining the operating temperature of NMR analyzers with online sample to be tested.
In petrochemical iy produced flow during application on site NMR analyzers, the amount of sample is big, can be sample by valve and control signal
Stability of flow per hour control in 70~100kg.So sample of big flow can be incited somebody to action by discharging or absorbing heat
The temperature of NMR analyzers in itself maintains 45 DEG C of requirement or so of operating temperature.But online NMR analyzers offline should
Used time, the amount of sample to be tested are very limited, it is impossible to as it is online when, there is lasting sample to be tested to enter nmr analysis instrument.
In the present invention, sample to be tested only 2L or so of magnetic nuclear resonance analyzer can be entered.Since crude oil and heavy end are in low temperature
Under the conditions of mobility it is bad, the sample nuclear magnetic resonance relaxation time of different phase is entirely different.Nuclear magnetic resonance under cryogenic conditions
Signal cannot meet the requirement of quality inspection analysis；Under hot conditions due in sample to be tested light components it is volatile, cause into core
The amount of the sample to be tested of magnetic analyzer is again inadequate.Therefore, the present invention must solve the problems, such as to be how through finite quantity (as above
The 2L stated) heat of sample to be tested radiates to meet the operating temperature requirements of NMR analyzers.
Inventor has carried out following experiment, and the heating temperature of sample to be tested is studied：
Under the temperature conditionss of following settings, walked using emulation nuclear magnetic resonance spectroscopy system of the present invention and above application
Suddenly, measure respectively with a collection of crude oil.
1st, (room temperature) is not heated in crude oil and cleaning oily (aviation kerosine)；
2nd, crude oil and cleaning oily (aviation kerosine) are both heated to 50 DEG C；
3rd, crude oil and cleaning oily (aviation kerosine) are not heated to 70 DEG C；
4th, crude oil and cleaning oily (aviation kerosine) are both heated to 90 DEG C.
It the results are shown in Table 1.
Magnetic nuclear resonance analyzer measurement result under 1 different temperatures of table
Interpretation of result：
1. heating temperature is 90 DEG C, the pressure significant changes of sample jar show that light component is volatilized completely in crude oil.
Therefore, heating temperature cannot be 90 DEG C.
2. resolution ratio is higher, obtained sample component information is more complete, and the physical property characterized based on spectrogram information is also
It is more accurate.As can be seen from the table, when crude oil sample is heated to 70 DEG C, the resolution ratio of crude oil collection of illustrative plates is best；And the temperature of sample
Even if degree raises (to 90 DEG C) again, resolution ratio does not also improve significantly again, low boiler cut from crude oil is given steam instead
Out, the precision of analysis result is influenced.
In addition, during the experiment, when sample temperature is at 30 DEG C, viscosity is larger, viscous wall power is stronger, has used high temperature item
Lower 5 times of part or more cycles oil mass, the cleaning performance of recycle oil when just reaching 70 DEG C of sample；Equally, 50 DEG C when, recycle oil cleaning sample
The dosage when dosage of product is also greater than 70 DEG C of sample, is a very big waste to recycle oil, uneconomical；Also increase transportation cycle
The labor intensity of oil.
Accordingly, it is preferred that the heating temperature of cleaning oil and sample to be tested is 70 DEG C.In practical application, heating temperature can be with
It is floated, 70 ± 5 DEG C can all meet test request.
Online NMR analyzers are applied to offline inspection by the present invention for the first time, are no longer made test sample quantity by online use
Limitation, expand the application ranges of NMR analyzers, the whole process of petrochemical iy produced can be flexibly applied to, from raw material,
Intermediate products are to final products at different levels.By being compared with laboratory NMR analyzers, standard deviation is less than 1, illustrates that the present invention's is offline
Using being successful.
Description of the drawings
Below in conjunction with the accompanying drawings, the present invention is described further.
Fig. 1 is the structure diagram of the online nmr analysis system of emulation of the present invention, wherein 1 represents nitrogen storage device, 2
The sample jar with heating unit is represented, 3 represent on-line NMR analyzer, and 4 represent sump tank, and 5 represent with heating dress
Put clean the storage, 6 represent circulating pump, 7 and 8 and represent triple valve respectively, 9 represent pipeline.
Fig. 2 is illustrated that 15 test samples of emulation nuclear magnetic resonance spectroscopy system and lab analysis of embodiment 2 obtain
API values trend comparison figure, wherein "-◆-" represent the obtained data of lab analysis, "-■-" represents emulation nmr analysis
The data that system testing obtains.
Fig. 3 is illustrated that 15 test samples of emulation nuclear magnetic resonance spectroscopy system and lab analysis of embodiment 2 obtain
Sulfur content value trend comparison figure, wherein "-◆-" represent the obtained data of lab analysis, "-■-" represents emulation nuclear-magnetism
The data that analysis system is tested.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.It should be understood that the present invention is not restricted to down
State embodiment.
A kind of emulation nuclear magnetic resonance spectroscopy system of embodiment 1
It is described emulation nuclear magnetic resonance spectroscopy system structure diagram, see Fig. 1, including the nitrogen storage device 1 with valve,
Sample jar 2 with heating unit, Aspect AI-60 on-line NMRs analyzer 3, sump tank 4, with heating unit
Clean the storage 5, circulating pump 6, triple valve 7 and 8 and pipeline 9；Wherein, nitrogen storage device 1, sample jar 2, triple valve 7, online
Magnetic nuclear resonance analyzer 3, triple valve 8 and sump tank 4 are linked in sequence by pipeline 9, the 5, circulating pump 6 that cleans the storage, triple valve 7,
On-line NMR analyzer 3 and triple valve 8 are made up of the circuit of closing pipeline 9；The sample introduction end of online nmr analysis instrument 3 leads to
It crosses triple valve 7 to connect with sample jar 2 and circulating pump 6 respectively, the sample outlet end of online nmr analysis instrument 3 is respectively and useless by triple valve
Oil tank 4 and the connection that cleans the storage.
In the present embodiment, the nitrogen storage device 1 is nitrogen cylinder.
Wherein, the sample jar 2 and clean the storage 5 heating unit be water bath heating device.The volume of the sample jar
For 2L, the volume to clean the storage is 5L.
Embodiment 2 emulates application of the nuclear magnetic resonance spectroscopy system in off-line analysis crude oil sample
Using the emulation nuclear magnetic resonance spectroscopy system of embodiment 1, off-line analysis crude oil sample, concrete operation step is：
I. shimming
Using aviation kerosine as cleaning oil, will 5L cleaning oil add in described in clean the storage 5, be heated to 70 ± 5 DEG C, switching three-way
Valve 7 and 8, makes to clean the storage 5, circulating pump 6 and Aspect AI-60 on-line NMRs instrument 3 forms loop by pipeline 9,
Open the circulation pump, cleaning oil are cycled in described clean the storage between 5 and the Nuclear Magnetic Resonance 3, and reference test looks for nuclear-magnetism to believe
Number, because being unsatisfactory for condition, shimming operation is carried out, until the stable magnetic field of the magnetic nuclear resonance analyzer；
II. measure
2L crude oil samples to be measured are added in into sample jar 2, are heated to 70 DEG C, switching three-way valve 7 and 8 makes nitrogen cylinder 1, sample
Tank 2, on-line NMR analyzer 3 and sump tank 4 form access；The valve of nitrogen cylinder is opened, it is 0.08 to adjust nitrogen pressure
~0.1MPA makes the sample to be tested into the magnetic nuclear resonance analyzer with nitrogen and stops 25~35 seconds, nuclear magnetic scanning 5
It is secondary, it is averaged output spectrogram and analysis data；Then sample to be tested flows into sump tank 4；
III. clean
After the completion of measure, sample jar is vented, closes the valve of nitrogen cylinder, disconnects nitrogen；Switch the triple valve 7 and 8, make
Clean the storage 5, circulating pump 6, on-line NMR instrument 3 is connected with sump tank 4 by pipeline 9, and the cleaning oil starts to clean institute
On-line NMR analyzer 3 is stated, oil stream is then cleaned and enters sump tank 4.Switch the triple valve 8, make cleaning oil described clear
It is cycled between oil-washing tank 5 and the on-line NMR analyzer 3, while cleaning sample tank, it prepares for test next time.
According to aforesaid operations step, 15 crude oil samples are determined.
In addition, laboratory also determines API and sulfur content respectively to same batch crude oil sample；Wherein, it is automatically close with DMA48
The API of crude oil is calculated after degree analyzer measurement density, is GB/T 1884-2000 according to analytical standard, uses x-
Supreme8000 fluorescence constant sulphur appliance measures sulfur content, and analytical standard is GB/T 17040-2008.
To emulate nmr analysis system directly measure obtained crude oil API and sulfur content and with the data of experimental determination into
Row compares, and calculates deviation and standard deviation, the results are shown in Table 2 and table 3；The API and sulfur content result that two kinds of analysis methods obtain become
Gesture compares figure, sees Fig. 2 and Fig. 3 respectively.
The crude oil API values that 2 two kinds of analysis methods of table obtain
The sulfur content in crude oil value that 3 two kinds of analysis methods of table obtain
From it is shown in table 2 and 3 as a result, and tendency chart shown in Fig. 2 and Fig. 3 can be seen that the emulation nuclear-magnetism of the present invention
Crude oil API that resonance analyzing system testing obtains and sulfur content as a result, consistent with Analytical Laboratory Results, standard deviation is small.
Illustrate that the emulation nuclear magnetic resonance spectroscopy system test result of the present invention is accurate.
Embodiment 3Emulate application of the nuclear magnetic resonance spectroscopy system in off-line analysis hydrogenated diesel oil material sample
Using the emulation nuclear magnetic resonance spectroscopy system of embodiment 1, bavin is hydrogenated with according to the identical step off-line analysis of embodiment 2
Oily material sample, the difference is that test sample is hydrogenated diesel oil raw material.
In addition, laboratory determines the carbon content and hydrogen of same batch sample using varioEL-cube carbon and hydrogen analysis meter,s
Content, analytical standard SH/T0656-1998.
Two methods measurement result is shown in Table 4.
The hydrogenated diesel oil feed carbon content and hydrogen content that 4 two kinds of analysis methods of table measure
a：Carbon content standard deviation value=2.4；b：Hydrogen content standard deviation value=0.78.
Table 4 the results show that the carbon of hydrogenated diesel oil raw material that the emulation nuclear magnetic resonance spectroscopy system testing of the present invention obtains
Content and hydrogen content as a result, consistent with Analytical Laboratory Results, standard deviation is small.Illustrate the emulation nuclear magnetic resonance point of the present invention
Analysis system test result is accurate.
Embodiment 4Emulate application of the NMR analysis systems in off-line analysis catalytically cracked material sample
Using the emulation nuclear magnetic resonance spectroscopy system of embodiment 1, split according to the identical step off-line analysis catalysis of embodiment 2
Change material sample, the difference is that test sample is catalytically cracked material.
In addition, laboratory also determines the carbon residue content and nitrogen content of same batch sample；Wherein, carbon residue content laboratory is surveyed
Surely using JSR3602 automatic fine carbon residue determinators, analytical standard is GB/T17144-1997 (2004)；Nitrogen content laboratory point
Using trace SN cube sulphur nitrogen analysis instrument, analytical standard is SH/T 0657-2007 for analysis
Two methods measurement result is shown in Table 5.
The catalytically cracked material residual carbon content and nitrogen content that 5 two kinds of analysis methods of table measure
a：Residual carbon content standard deviation value=0.51；b：Nitrogen content standard deviation value=0.0642.
Table 5 the results show that the carbon of catalytically cracked material that the emulation nuclear magnetic resonance spectroscopy system testing of the present invention obtains
Content and nitrogen content as a result, consistent with Analytical Laboratory Results, standard deviation is small.Illustrate the emulation nuclear magnetic resonance point of the present invention
Analysis system test result is accurate.
Embodiment 5Emulate application of the NMR analysis systems in off-line analysis hydrocracking raw material sample
With the emulation nuclear magnetic resonance spectroscopy system of embodiment 1, it is hydrocracked according to the identical step off-line analysis of embodiment 2
Material sample, the difference is that test sample is hydrocracking raw material.
In addition, laboratory also determines the 50 DEG C of viscosity and sulfur content of same batch sample；Wherein, experimental determination uses
The full-automatic viscosity determinators of FDT-0471 measure 50 DEG C of viscosity, and analytical standard is GB/T 8929-2006；X-supreme8000 is glimmering
Light constant sulphur appliance measures sulfur content, and standard is GB/T 17040-2008.
Two methods measurement result is shown in Table 6.
The catalytically cracked material residual carbon content and nitrogen content that 6 two kinds of analysis methods of table obtain
a：Viscosity (50 DEG C) standard deviation value is<3%；b：Sulfur content standard deviation value=0.051.
Table 6 the results show that the emulation nuclear magnetic resonance spectroscopy system testing of the present invention obtain the 50 of hydrocracking raw material
DEG C viscosity and sulfur content as a result, consistent with Analytical Laboratory Results, standard deviation is small.Illustrate the emulation nuclear magnetic resonance of the present invention
Analysis system test result is accurate.
In short, the present invention provide it is a kind of emulation nuclear magnetic resonance spectroscopy system, it is achieved thereby that on-line NMR instrument from
Line application, so as to expand the reference scope of on-line NMR analyzer and utilization ratio.
Claims (10)
1. a kind of emulation nuclear magnetic resonance spectroscopy system, including with valvular nitrogen storage device (1), the sample with heating unit
Product tank (2), on-line NMR analyzer (3), sump tank (4), cleaning the storage (5) with heating unit, circulating pump (6),
Triple valve (7) and (8) and pipeline (9)；Wherein, the nitrogen storage device (1), sample jar (2), triple valve (7), in line core
Magnetic resonance analyzer (3), triple valve (8) and sump tank (4) are linked in sequence by pipeline (9), described to clean the storage (5), cycle
It pumps (6), triple valve (7), on-line NMR analyzer (3) and triple valve (8) and the circuit closed is formed by pipeline (9)；Institute
The sample introduction end of online nmr analysis instrument (3) is stated to connect with sample jar (2) and circulating pump (6) respectively by triple valve (7), it is described
The sample outlet end of line core magnetic analyzer (3) by triple valve (8) respectively with sump tank (4) and clean the storage (5) connect.
2. emulation nuclear magnetic resonance spectroscopy system according to claim 1, which is characterized in that the nitrogen storage device (1)
For nitrogen cylinder；
Preferably, the heating unit is water bath heating device.
3. emulation nuclear magnetic resonance spectroscopy system according to claim 1 or 2, which is characterized in that the on-line NMR
Analyzer (3) is Aspect AI-60 on-line NMR analyzers.
4. emulation nuclear magnetic resonance spectroscopy system according to any one of claim 1 to 3, which is characterized in that the sample
The volume of tank (2) is 1~3L, more preferably 2L；
Preferably, the described volume for cleaning the storage (5) is 3~6L, more preferably 5L.
5. emulation nuclear magnetic resonance spectroscopy system any one of Claims 1-4 is in off-line analysis petrochemical industry oil product
Application；
Preferably, the application specifically comprises the following steps：
I. shimming
Will cleaning oil add in described in clean the storage (5), be heated to the temperature of setting, switching three-way valve (7) and (8) make cleaning oil
Tank (5), circulating pump (6) and on-line NMR instrument (3) form loop, open the circulation pump (6), cleaning by pipeline (9)
Oil is cycled in described clean the storage (5) between the Nuclear Magnetic Resonance (3), and nuclear magnetic signal is looked in reference test, if being unsatisfactory for item
Part then carries out shimming operation, until the stable magnetic field of the magnetic nuclear resonance analyzer；
II. measure
Sample to be tested is added in into sample jar (2), is heated to the temperature of setting, switching three-way valve (7) and (8) fill nitrogen storage
It puts (1), sample jar (2), on-line NMR analyzer (3) and sump tank (4) and forms access；Open nitrogen storage device (1)
Valve, with nitrogen make the sample to be tested into the magnetic nuclear resonance analyzer (3) and stop 25~35 seconds, nuclear magnetic scanning 5
It is secondary, it is averaged output spectrogram and analysis data；Then sample to be tested flows into the waste oil from the magnetic nuclear resonance analyzer (3)
Tank (4)；
III. clean
After the completion of measure, the sample jar (2) is vented, closes the valve of nitrogen storage device, disconnects nitrogen；Switch the threeway
Valve (7) and (8) make to clean the storage (5), circulating pump (6), on-line NMR instrument (3) and sump tank (4) pass through pipeline (9) even
Logical, the cleaning oil starts to clean the on-line NMR analyzer (3), then flows into the sump tank (4).
6. application according to claim 5, which is characterized in that after the completion of the cleaning step, described three can also be switched
Port valve (8) makes cleaning oil be cycled in described clean the storage (5) between the on-line NMR analyzer (3), is surveyed for next time
Have a fling at preparation；
Preferably, after the completion of the cleaning step, the cleaning of the sample jar (2) is further included.
7. according to the application of claim 5 or 6, which is characterized in that the cleaning oil is aviation kerosine.
8. application according to any one of claims 5 to 7, which is characterized in that the temperature of the setting refers to described treat
Sample by heating reach, by pipeline (9) into the magnetic nuclear resonance analyzer (3) make the Nuclear Magnetic Resonance (3)
Reach the temperature of operating temperature.
9. the application according to any one of claim 5 to 8, which is characterized in that the magnetic nuclear resonance analyzer (3) is
Aspect AI-60 on-line NMR analyzers；
Preferably, when the magnetic nuclear resonance analyzer is Aspect AI-60 on-line NMR analyzers, the cleaning oil
The volume of tank (5) is 5L, and the volume of the sample jar (2) is 2L；The design temperature of the cleaning oil and sample to be tested is 70 DEG C
±5℃；The pressure of the sample to be tested into the Aspect AI-60 on-line NMR analyzers is 0.08~0.1MPa.
10. the application according to any one of claim 5 to 9, which is characterized in that the sample to be tested is selected from crude oil, bavin
One or more in oily hydrogenating materials, catalytically cracked material and hydrocracking raw material；
Preferably, the analysis data obtained include the crude oil API, sulfur content, water content, C/Hratio, nitrogen content, residual
Charcoal, boiling range, freezing point, Cetane number, pour point and acid value.
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