CN109696375A - Using the method for TG-MS combination instrument measurement constituent content - Google Patents
Using the method for TG-MS combination instrument measurement constituent content Download PDFInfo
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- CN109696375A CN109696375A CN201710995887.6A CN201710995887A CN109696375A CN 109696375 A CN109696375 A CN 109696375A CN 201710995887 A CN201710995887 A CN 201710995887A CN 109696375 A CN109696375 A CN 109696375A
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- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder
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- G01N30/8624—Detection of slopes or peaks; baseline correction
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Abstract
The present invention relates to it is a kind of using TG-MS combination instrument measurement constituent content method, this method comprises: A, by quality be m1Calibration object and quality be m sample to be tested be put into TG-MS combination instrument while carrying out thermogravimetric-mass spectrum blob detection, obtain demarcate object caused by marked gas mass spectrum peak area SAWith the mass spectrum peak area S of the gas as produced by element to be measured contained in sample to be testedB；B, the quality m of gas produced by contained element to be measured in sample to be tested is calculated using formula (1)B, formula (1) are as follows:C, the mass content w that the element to be measured accounts for sample to be tested is calculated using formula (2)B, formula (2) are as follows:Method provided by the invention can be influenced without external equipment, test result by instrument state small, applied widely with the content of element in a variety of test substances such as Accurate Determining solid, liquid and solid-liquid mixing sample.
Description
Technical field
The present invention relates to a kind of methods using TG-MS combination instrument measurement constituent content.
Background technique
TG-MS combination instrument is common heat analysis method, can be used for being pyrolyzed molecule and element in emergent gas
Quantitative and semi-quantitative analysis, plays an important role in research and production field.Its main quantitative analysis method including the use of
Pulse gas sample injector injected in situ into TG-MS system marked gas into quantitative (pulse gas quantitation in situ), using solid
Body standard specimen establishes external standard curve (solid etalon sample external standard curve method) and uses three kinds of methods of solid internal standard compound.
The pulse gas quantitation in situ of TG-MS combination instrument is to utilize pulse gas sample injector into TG-MS system
The marked gas in situ that injects is into quantitative method.Document (petroleum journal (PETROLEUM PROCESSING), 2016,32 (3): 622-628) report
With CO2For standard gas, using six-way valve and loop ring the specific time and at a temperature of inject into TG-MS system it is a certain amount of pure
CO2Standard gas, to pyrolysis in sample and the generated CO that burns2Quantitative analysis is carried out, so that carbon in sample be calculated
Content.There are also document (Thermochimica Acta 295 (1997) 167-182；Thermochimica Acta 295
(1997) 95-105) utilize the Pulsed Sampling device (Pusle of German Nai Chi company of commercialization) and pure CO2Standard gas is inquired into
Experimental condition is to the CO being pyrolyzed out in solid sample2Carry out the influence of quantitative analysis.Yu et al. (Thermochimica Acta
451(2006)10-15；Thermochimica Acta 440 (2006) 195-199) using similar method to being pyrolyzed in InN
The N of evolution2Quantitative analysis is carried out, the standard gas used is pure nitrogen gas.It can be seen that the above method is required to one arteries and veins of configuration
Sample injector is rushed, there are expensive, complicated for operation, marked gas to be difficult to the problems such as selecting and saving, and limits its application model
It encloses.
Solid etalon sample external standard curve method is to establish external standard curve progress TG-MS element using solid etalon sample to quantify
The technology of analysis and a kind of widely applied method.Yan Jinding et al. (analytical chemistry 32 (2) (2004) 166-168) and old
The tinkling of pieces of jade red et al. (journal of Zhejiang university (engineering version) 50 (5) (2016) 961-969), which is disclosed, is measured element using this method,
The realization of this method needs to be divided into two stages, and first stage is to establish external standard curve, and a kind of each pair of gas is quantified, just
It needs to find the solid sample that can release the gas, multiple TG-MS test is carried out to it, to establish the mass spectrum of the gas
The paced work curve either external standard curve of peak area and its quality correlation；Second stage is test sample to be tested and obtains
The mass spectrum peak area of the gas is obtained, the mass spectrum peak area and its quality correlation of the gas then obtained using the first stage
External standard curve calculates the quality of the gas in sample to be tested.But due to the mistake of the process and test sample of establishing external standard curve
Journey is completely independent two stages, so being very easy to instrument state variation (vacuum degree variation, pollution of ion source, gas occur
The fluctuation etc. of body flow velocity) caused by systematic bias, error even can be 100% or more.
Yu Huimei et al. (Chinese patent CN 102830130A) et al. utilizes a kind of double flute sample crucible, by sample to be tested,
And the standard solid of same gas can be released and put together, the two is subjected to TG-MS test simultaneously, is then analyzed
With the CO of comparison sample to be tested and the release of standard solid sample2Mass spectrum peak area, to carry out quantitative analysis.This method is one
Determine to overcome the disadvantage of solid etalon sample external standard curve method and pulse gas quantitation in situ respectively in degree, is not needing to increase
While adding expensive attachment device, real time correction can be carried out to instrument state and environmental condition during the test.But
There is also apparent limitations for this method, and as described in patent, internal standard substance and the pyrogenous origin emergent gas of sample to be tested are same
One gas, the mass-to-charge ratio of the characteristic peak of Mass Spectrometer Method is identical, if solid internal standard compound and sample to be tested are at the same temperature
Pyrolysis then will lead to the mass spectral characteristic overlap of peaks for the emergent gas that the two generates, so that quantitative analysis can not be carried out.So
Satisfactory internal standard substance and standard specimen are difficult to find in actual application process, such as: carbon deposit, pitch, coal on catalyst
The sample combustions such as residue release CO2Wider range (150 DEG C -800 DEG C), if using in solid-state described in the patent
Mark substance C aCO3(pyrolysis generates CO2Temperature be 600 DEG C -800 DEG C), then sample to be tested and solid-state internal standard substance CaCO3It generates
CO2Mass spectral characteristic peak will overlapping, quantitative analysis can not be carried out.In addition, if will be using this method to a variety of evolutions
When gas or element carry out quantitative analysis, it is necessary to obtain a greater variety of solid internal standard compounds, such as: Analysis for CO2With regard to needing to obtain
CO must be can produce2Internal standard substance, analyze H2O, which just needs to obtain, can produce H2The internal standard substance of O analyzes SO2It can with regard to needing to obtain
Generate SO2Internal standard substance.On the one hand above-mentioned solid internal standard substance is found to take time and effort；On the other hand it is necessary to ensure that internal standard substance
Between, will not interact between internal standard substance and sample to be tested；Finally also it is necessary to ensure that all internal standard substance pyrolysis ease
Gas temperature is different from sample to be tested out.The above problem causes the application of this method to be extremely limited.
Summary of the invention
The object of the present invention is to provide a kind of method using TG-MS combination instrument measurement constituent content, the present invention is mentioned
The method of confession can be with the content of element in a variety of test substances such as Accurate Determining solid, liquid and solid-liquid mixing sample, without outer
Connect equipment, test result influenced by instrument state it is small, applied widely.
To achieve the goals above, the present invention provides a kind of method using TG-MS combination instrument measurement constituent content,
This method comprises:
It A, is m by quality1Calibration object and quality be m sample to be tested be put into TG-MS combination instrument while carrying out
Thermogravimetric-mass spectrum blob detection obtains the mass spectrum peak area S of marked gas caused by calibration objectAWith by sample to be tested it is contained to
Survey the mass spectrum peak area S of gas produced by elementB；Wherein, the mass-to-charge ratio of mass spectra peak caused by the marked gas with by
The mass-to-charge ratio of the mass spectra peak of gas produced by contained element to be measured is different in sample, quality m1Calibration object caused by mark
The quality for determining gas is mA；
B, the quality m of gas produced by contained element to be measured in sample to be tested is calculated using formula (1)B, formula (1) are as follows:
Wherein, FAB(mB) it is gas produced by contained element to be measured in marked gas caused by calibration object and sample to be tested
Correlation function, obtaining step includes:
S1, by quality be m1' the calibration object be put into TG-MS combination with containing the internal standard compound of the element to be measured
Thermogravimetric-mass spectrum blob detection is carried out simultaneously in instrument, obtains the mass spectrum peak area S of marked gas caused by calibration objectA' and internal standard compound
Contained in gas produced by the element to be measured mass spectrum peak area SB'；Wherein, described to be measured contained in the internal standard compound
The quality of gas produced by element is mB', it demarcates described contained in the mass spectra peak and internal standard compound of marked gas caused by object
The mass spectra peak of gas produced by element to be measured is non-overlapping；The mass-to-charge ratio of mass spectra peak caused by the marked gas with by described interior
The mass-to-charge ratio for marking the mass spectra peak of gas produced by the element to be measured contained in object is different, quality m1' the calibration object
The quality of generated marked gas is mA'；
S2, the element to be measured contained in marked gas caused by calibration object and internal standard compound is calculated using formula (1-1)
The related coefficient a of produced gas, formula (1-1) are as follows:
S3, it repeats step S1 and S2 and changes the quality of the internal standard compound, obtain n related coefficient a；Wherein, n be greater than
2 natural number；
S4, with mB' be abscissa and carry out Function Fitting by ordinate of a, obtain correlation function FAB(mB)；
C, the mass content w that the element to be measured accounts for sample to be tested is calculated using formula (2)B, formula (2) are as follows:
Wherein, x is for the total atom amount of element to be measured in gas produced by contained element to be measured in sample to be tested and to test sample
The ratio of the molecular weight of gas produced by contained element to be measured in product.
Optionally, reaction gas is sent into the thermogravimetric analyzer of the TG-MS combination instrument and in the sample to be tested
Contained element to be measured and calibration object are reacted, and gas produced by contained element to be measured and calibration gas in the sample to be tested are obtained
Body.
Optionally, the reaction gas includes being selected from nitrogen, air, oxygen, helium, argon gas, hydrogen, carbon dioxide and dioxy
Change at least one of sulphur, the flow velocity of the reaction gas is greater than zero to 1000mL/min.
Optionally, gas produced by contained element to be measured is not same in the reaction gas, marked gas and sample to be tested
Kind gas, and the mass signal that three kinds of gases have mass-to-charge ratio different.
Optionally, the calibration object is liquid, solid or solidliquid mixture.
Optionally, the quality of the calibration object is 0.1mg-1000mg.
Optionally, the sample to be tested is liquid, solid or solidliquid mixture.
Optionally, in the TG-MS combination instrument thermogravimetric analyzer Range of measuring temp -2400 DEG C of room temperature DEG C it
Between.
Optionally, in the TG-MS combination instrument thermogravimetric analyzer Range of measuring temp 100 DEG C -1700 DEG C it
Between.
Optionally, the quality of the sample to be tested and internal standard compound is each independently 0.1mg-500g.
It optionally, will be in gas and internal standard compound produced by element to be measured contained in marked gas, sample to be tested by carrier gas
Gas produced by the contained element to be measured is purged from the thermogravimetric analyzer of TG-MS combination instrument to thermogravimetric-mass spectrum connection
With in the mass spectrometer of instrument.
Optionally, in step s 4, the Function Fitting is carried out using Origin software or Excel software.
Compared with prior art, the present invention has the advantage that
1, the present invention has compared with the method for existing injection marked gas and does not need marked gas and injection calibration gas
The advantages of attachment device of body, saves cost, marked gas is avoided to be difficult to the shortcomings that finding and storing；
2, the present invention with it is existing establish the method for external standard curve compared with, instrument state and environmental change bring can be overcome
Deviation；
3, the present invention can overcome internal standard substance and sample to be tested to be pyrolyzed emergent gas matter compared with existing internal standard substance method
The problem of peak overlap, can also carry out simultaneously quantitative analysis to a variety of emergent gas and element；
4, the present invention combines the temperature program(me) of TG, can analyze the pyrolysis amount of each element under different temperatures section；
5, the method for the present invention is simple and efficient, accuracy is high, it is applied widely, without marked gas injection device, can be simultaneously
To a variety of thermal decomposition materials carry out it is quantitative, can the content to thermal decomposition material under different temperatures carry out quantitative analysis.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is a kind of structural schematic diagram of specific embodiment of TG-MS combination instrument provided by the present invention.
Fig. 2A-Fig. 2 B is the fitting function F of the embodiment of the present invention 1AB(mB) coordinate diagram.
Fig. 3 is that comparative example 1 of the present invention utilizes CaCO3The outer marking quantitative curve established as internal standard compound.
Fig. 4 is CaCO in comparative example 23It carries out TG-MS simultaneously with catalyst and tests CO obtained2(m/z=44) mass spectra peak
Spectrogram.
Description of symbols
1 crucible, 2 crucible, 3 sample holder
4 reaction gas, 5 thermogravimetric analyzer furnace body 6 reacts gas bottle
7 mass spectrometer, 8 tail gas
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
As shown in Figure 1, the present invention provides a kind of method using TG-MS combination instrument measurement constituent content, this method
Include:
It A, is m by quality1Calibration object and quality be m sample to be tested be put into TG-MS combination instrument while carrying out
Thermogravimetric-mass spectrum blob detection obtains the mass spectrum peak area S of marked gas caused by calibration objectAWith by sample to be tested it is contained to
Survey the mass spectrum peak area S of gas produced by elementB；Wherein, the mass-to-charge ratio of mass spectra peak caused by the marked gas with by
The mass-to-charge ratio of the mass spectra peak of gas produced by contained element to be measured is different in sample, quality m1Calibration object caused by mark
The quality for determining gas is mA；
B, the quality m of gas produced by contained element to be measured in sample to be tested is calculated using formula (1)B, formula (1) are as follows:
Wherein, FAB(mB) it is gas produced by contained element to be measured in marked gas caused by calibration object and sample to be tested
Correlation function, obtaining step includes:
S1, by quality be m1' the calibration object be put into TG-MS combination with containing the internal standard compound of the element to be measured
Thermogravimetric-mass spectrum blob detection is carried out simultaneously in instrument, obtains the mass spectrum peak area S of marked gas caused by calibration objectA' and internal standard compound
Contained in gas produced by the element to be measured mass spectrum peak area SB'；Wherein, described to be measured contained in the internal standard compound
The quality of gas produced by element is mB', it demarcates described contained in the mass spectra peak and internal standard compound of marked gas caused by object
The mass spectra peak of gas produced by element to be measured is non-overlapping；The mass-to-charge ratio of mass spectra peak caused by the marked gas with by described interior
The mass-to-charge ratio for marking the mass spectra peak of gas produced by the element to be measured contained in object is different, quality m1' the calibration object
The quality of generated marked gas is mA'；
S2, the element to be measured contained in marked gas caused by calibration object and internal standard compound is calculated using formula (1-1)
The related coefficient a of produced gas, formula (1-1) are as follows:
S3, it repeats step S1 and S2 and changes the quality of the internal standard compound, obtain n related coefficient a；Wherein, n be greater than
2 natural number；
S4, with mB' be abscissa and carry out Function Fitting by ordinate of a, obtain correlation function FAB(mB)；
C, the mass content w that the element to be measured accounts for sample to be tested is calculated using formula (2)B, formula (2) are as follows:
Wherein, x is for the total atom amount of element to be measured in gas produced by contained element to be measured in sample to be tested and to test sample
The ratio of the molecular weight of gas produced by contained element to be measured in product.
The present invention obtains function F in the form of ratioAB(mB), to make the mass spectrum of measurement calibration object generation internal standard gas
Produced by the mass spectra peak of gas produced by the element to be measured contained in systematic bias caused by peak and measurement internal standard compound
Systematic bias can cancel out each other, while measurement calibration object generate internal standard gas mass spectra peak and by institute in sample to be tested
Generated systematic bias is also cancelled out each other in the form of ratio when mass spectra peak containing gas produced by element to be measured, to make
Test, which is equivalent to, every time has incidentally done primary correction, so that make to measure every time is not influenced by system deviation, to improve letter
Number FAB(mB) use the time, and expand the scope of application of instrument operating parameter and working condition.In addition, present invention use can produce
The internal standard compound of the raw marked gas different from gas produced by sample to be tested carries out calculating correlation function, there is no calibration object with
The problem of peak overlap caused by sample to be tested is pyrolyzed simultaneously, the scope of application is widened.Further, it is also possible to simultaneously to a variety of to be measured
Emergent gas is quantified, and analysis efficiency is significantly improved, opposite external standard gas injection method, the external standard gas that this method need not be expensive
And special device, it is low in cost.
According to the present invention, TG-MS combination instrument and thermogravimetric-mass spectrum blob detection are well-known to those skilled in the art,
TG-MS combination instrument includes thermogravimetric analyzer and mass spectrometer, and thermogravimetric of the thermogravimetric analyzer for sample to be tested is decomposed simultaneously
Pyrolysis amount is obtained, gas caused by pyrolysis, which enters, carries out Mass Spectrometer Method in mass spectrometer, which is referred to as
Thermogravimetric-Mass Spectrometer Method.
According to the present invention, the substance measured needed for the pyrolysis of calibration object generates marked gas and sample to be tested is in gaseous form
Partially or completely escape, can be nitrogen, air, oxygen, helium, argon gas, hydrogen, carbon dioxide, sulfur dioxide, cyclohexene,
One or more, the contained element to be measured in marked gas and sample to be tested of the inorganic gas such as n-dodecane and/or organic gas
Generated gas is gas with various, and the gas with various is characterized in the mass signal without identical mass-to-charge ratio；Occurred
Evolution process can occur oxidation, volatilization, distillation, reduction or cracking one or more kinds of processes.Pass through above-mentioned evolution
Process can determine that by quality be m1Calibration object caused by marked gas quality mA, such as:
(i), it distils and/or volatilizees: quality m1Calibration object A by distillation and/or volatilization processMarked gas A is generated, then
mA=m1；
(ii), decomposition reaction: quality m1Calibration object AxMyPass through decomposition reactionGenerate marked gas A, then:
In formula: MABAnd MARespectively demarcate object AxMyWith the molal weight of marked gas A；
(iii), metathesis reaction: quality m1Calibration object Q and reaction gas P occur Q (Gu liquid)+P (gas) → A
(gas)+B (Gu liquid) reaction generates marked gas A, then:
In formula: MQAnd MAThe molal weight of object Q and marked gas A are respectively demarcated, x is marked gas A and demarcates object Q's
Molar ratio；
The evolution process is not limited to above three process, and those skilled in the art can be determined with reference to the prior art
The quality m of marked gasA。
According to the present invention, part element to be measured can produce gas under the conditions of thermogravimetric in some calibration objects and sample to be tested
Body, such as calcium carbonate can be decomposed into calcium oxide and carbon dioxide at 780 DEG C, and partially demarcate to be measured in object and sample to be tested
Element is the ZnS in stable state, such as reclaimable catalyst under the conditions of thermogravimetric.In order to make thermal stability preferably demarcate object
With element to be measured generate gas, reaction gas can be sent into the thermogravimetric analyzer of the TG-MS combination instrument with it is described to
Contained element to be measured and calibration object are reacted in sample, obtain gas produced by contained element to be measured in the sample to be tested
And marked gas, the reaction gas may include selected from nitrogen, air, oxygen, helium, argon gas, hydrogen, carbon dioxide and dioxy
Change at least one of sulphur, the flow velocity of the reaction gas is greater than zero to 1000mL/min.
According to the present invention, marked gas and calibration object need to generally meet three conditions, and one is marked gas in thermogravimetric item
Thermostabilization under part is not decomposed or is reacted with sample to be tested and reaction gas；Secondly the boiling point for calibration object is lower than
Room temperature, which is that calibration object needs accurate weighing and keeps stablizing before thermogravimetric is tested, and calibration object can only preferably decompose
A kind of substance of gas out；Thirdly being typically chosen the sample for analyzing the pure or above purity, and/or known composition for calibration object and dividing
The sample of product is solved, such as: analyzing pure CaCO3, the pure ZnS of analysis, the SiO for adsorbing known quantity benzene2Microballoon etc..
According to the present invention, mass spectrum overlap of peaks in order to prevent, it is contained to be measured in the reaction gas, marked gas and sample to be tested
Gas produced by element is not same gas, and the mass signal that three kinds of gases have mass-to-charge ratio different.
Method of the invention can be used for measuring the sample to be tested of various suitable thermogravimetric analysis, such as can be liquid, solid
Body or solidliquid mixture, the internal standard compound can be pure sample or the mixture of known composition, preferably analyze pure or above pure
The quality of the sample of degree, the calibration object can be 0.1mg-1000mg, and the quality of the sample to be tested and internal standard compound is respectively only
It on the spot can be 0.1mg-500g.
According to the present invention, the Range of measuring temp of general thermogravimetric analyzer is between -2400 DEG C of room temperature DEG C, preferably 100
Between DEG C -1700 DEG C, the thermogravimetric for selecting reasonable temperature range to carry out sample to be tested can be carried out by way of temperature programming
It decomposes, temperature control program can be heating, cooling or constant temperature.
According to the present invention, in general, generally pass through carrier gas for element to be measured contained in marked gas, sample to be tested
Thermogravimetric analyzer of the gas produced by the element to be measured contained in produced gas and internal standard compound from TG-MS combination instrument
Middle purging can make all gas that can be filled in mass spectrometer into the mass spectrometer of TG-MS combination instrument
Sorting is surveyed, and carrier gas can be the conventional carrier of TG-MS combination instrument, with marked gas, sample to be tested caused by calibration object
In gas produced by the element to be measured contained in gas and internal standard compound produced by contained element to be measured be gas not of the same race i.e.
Can, for example, can for selected from inorganic gas such as nitrogen, air, oxygen, helium, argon gas, hydrogen, carbon dioxide and sulfur dioxide and
The inert gases such as at least one of organic gas, preferably nitrogen, the flow velocity of carrier gas can be 0.1-1000mL/min.
According to the present invention, in step S4, the Function Fitting can be carried out using Origin software or Excel software, this
Field technical staff can also be fitted using other common mathematical function fitting softwares, which can be linear fit,
It may be nonlinear fitting.Alternatively, may determine that correlation function is constant if the related coefficient repeatedly measured is not much different
Related coefficient is made average value by function.
A kind of embodiment, as shown in Figure 1, calibration object is placed in crucible 1, and internal standard compound is put when testing related coefficient a
It is placed in crucible 2；When testing sample to be tested, calibration object is placed in crucible 1, and sample to be tested is placed in crucible 2.Specific stream
Journey can be with are as follows: calibration object and sample to be tested (internal standard compound) are placed in the crucible 1 on the sample holder 3 of thermogravimetric analyzer furnace body 5
In crucible 2, reaction gas 4 then is passed through from reaction gas bottle 6 and carries out displaced air, generate tail gas 8 and send out thermogravimetric analyzer furnace
Body 5.After furnace body heating, while reaction gas is reacted with calibration object and sample to be tested (internal standard compound), play the role of carrier gas, it will
Generated gas is sent into mass spectrometer 7 and is analyzed.
The present invention will be further illustrated by embodiment below, but the present invention is not therefore subject to any restriction.
Nai Chi company, the model Germany STA449F5+ of TG-MS combined instrument used in the embodiment of the present invention and comparative example
QMS403D and STA409C+QMS403PC.
Carbon and sulfur content are measured using U.S. LECO-600 carbon and sulfur analytical instrument measurement in catalyst.
Embodiment 1
(1) as shown in Figure 1, accurate weighing 14.6mg analyzes pure Salzburg vitriol (CuSO4·5H2O it) is put into for calibration object
In crucible 1,5.26mg H is released in thermal histories2O；
(2) accurate weighing 10mg analyzes pure CaCO3It is put into crucible 2 for internal standard compound, 4.4mg is generated in thermal histories
CO2；
(3) start TG test, be warming up to 900 DEG C at room temperature with the heating rate of 10 DEG C/min, reaction gas (carrier gas) is
Compressed air, flow velocity 100mL/min.Meanwhile with Mass Spectrometer Method matter composition and division in a proportion be 18 (H2) and 44 (CO O2) spectral line, and utilize
Instrument carries software and integrates to the area of above-mentioned spectral peak；
(4) internal standard compound CaCO is calculated using formula (1-1)3It is pyrolyzed the internal standard gas CO generated2With calibration object CuSO4·5H2O
It is pyrolyzed the marked gas H generated2The related coefficient a of O is 1.23；
(5) it weighs 14.6mg and analyzes pure CuSO4·5H2O is that calibration object is put into crucible 1, weighs analyze pure CaCO respectively3
5.0mg, 15.0mg, 20.0mg and 25.0mg are simultaneously respectively put into crucible 2, theoretically can produce internal standard gas CO2 2.2mg、
6.6mg, 8.8mg and 11.0mg；
(6) above-mentioned (1)-(4) are repeated, marked gas H can be obtained2O and internal standard gas CO2Related coefficient a be respectively
1.25,1.22,1.20 and 1.19；
(7) with related coefficient a ordinate, with CO2Quality is abscissa, carries out linear fit, obtains FAB(mB)=
1.263-0.015mB, fitting correlation coefficient R2=0.9868, coordinate diagram is as shown in Figure 2 A；
(8) pure Salzburg vitriol (CuSO is analyzed with 14.6mg4·5H2O it is) calibration object, weighs analytically pure ZnS respectively
5.0mg, 10.0mg, 15.0mg, 20.0mg and 25.0mg are internal standard compound, and oxidative pyrolysis generates internal standard gas SO2 3.30mg、
6.60mg, 9.90mg, 13.20mg and 16.49mg；
(9) step (1)-(4) are repeated, marked gas SO can be obtained2With internal standard gas H2The related coefficient a of O, with SO2Matter
Amount is abscissa, carries out linear fit, obtains FAB(mB)=0.448-0.0055mB, fitting correlation coefficient R2=0.9759, coordinate
Figure is as shown in Figure 2 B；
(10) accurate weighing 14.6mg analyzes pure Salzburg vitriol (CuSO4·5H2O it) is put into crucible 1 for calibration object,
51.5mg catalyst sample to be measured is weighed to be put into crucible 2；
(11) start TG test, be warming up to 900 DEG C at room temperature with the heating rate of 10 DEG C/min, reaction gas is that compression is empty
Gas, flow velocity 100mL/min.Meanwhile with Mass Spectrometer Method matter composition and division in a proportion be 18 (H2O)、44(CO2) and 64 (SO2) spectral line, and benefit
Software is carried with instrument to integrate the area of above-mentioned spectral peak；
(12) respectively by marked gas H2O, pyrogenous origin CO in sample2And SO2Mass spectra peak area substitute into formula respectively
(1)
(13) according to SO2、CO2And H2The chemical formula of O and the quality of sample, using element to be measured in formula (2) calculating sample
ContentThe results are shown in Table 1.
Step (10)-(13) are repeated, difference is that the sample size of catalyst is changed into 20.1mg and 103.5mg, as a result such as
Shown in table 1.
Embodiment 2
The carbon of same sample is measured after carrying out three months of the measurement of embodiment 1 using the correlation function of embodiment 1
With element sulphur mass fraction, measurement result is shown in Table 2.
Comparative example 1
(1) the analytically pure calcium carbonate (CaCO of accurate weighing 5mg, 10mg, 20mg3), respectively in dry air atmosphere into
Row TG-MS test, with the heating rate of 10 DEG C/min from room temperature to 1000 DEG C, carrier gas N2Flow velocity be 20mL/min, instead
Should gas air flow velocity be 30mL/min；
It (2) is 44 (CO with Mass Spectrometer Method matter composition and division in a proportion2) spectral line, calculate separately its spectral peak area；
(3) by spectral peak area and carbon quality association, quantitative model is established, as a result as shown in Figure 3；
(4) TG-MS test is carried out with identical experimental condition to catalyst sample to be measured, while with Mass Spectrometer Method matter
Composition and division in a proportion is 44 (CO2) spectral line, calculate its spectral peak area；
(5) the test spectral peak area of sample to be tested is brought into quantitative model, calculates the mass fraction of its carbon, as a result
It is shown in table 3.
Comparative example 2
(1) the analytically pure calcium carbonate (CaCO of 10mg is weighed3) and 20mg catalyst sample to be measured, the two is respectively charged into two
A Al2O3In small crucible, and by above-mentioned two crucible on thermogravimetric sample holder, then with the heating rate of 10 DEG C/min from room
Temperature is warming up to 1000 DEG C, and the flow velocity of carrier gas compressed air is 20mL/min, and the flow velocity of reaction gas air is 30mL/min；
It (2) is 44 (CO with Mass Spectrometer Method matter composition and division in a proportion2) spectral line, as a result as shown in Figure 4；
(3) due to CaCO3CO can be generated at 600 DEG C -800 DEG C with sample to be tested2Gas, the two mass spectrum overlap of spectral lines, nothing
Method calculates separately respective spectral peak area, so carrying out quantitative test.
Comparative example 3
It is measured after comparing three months of the experiment of example 1 using the quantitative model for the Fig. 3 of comparative example 1 measured
The carbon mass fraction of same sample, measurement result are shown in Table 4.
Carbon and element sulphur quantitative analysis results in 1 embodiment of table, 1 catalyzed samples
1Elemental analyser measurement result.
2The method of the present invention measurement result.
Carbon and element sulphur quantitative analysis results in 2 embodiment of table, 2 catalyzed samples
1Elemental analyser measurement result.
2The method of the present invention measurement result.
Carbon and element sulphur quantitative analysis results in 3 comparative example of table, 1 catalyzed samples
1Elemental analyser measurement result.
2The method of the present invention measurement result.
Carbon and element sulphur quantitative analysis results in 4 comparative example of table, 3 catalyzed samples
1Elemental analyser measurement result.
2The method of the present invention measurement result.
Claims (12)
1. a kind of method using TG-MS combination instrument measurement constituent content, this method comprises:
It A, is m by quality1Calibration object and quality be m sample to be tested be put into TG-MS combination instrument while carrying out thermogravimetric-
Mass spectrum blob detection obtains the mass spectrum peak area S of marked gas caused by calibration objectAWith by element to be measured contained in sample to be tested
The mass spectrum peak area S of produced gasB；Wherein, the mass-to-charge ratio of mass spectra peak caused by the marked gas with by sample to be tested
In gas produced by contained element to be measured mass spectra peak mass-to-charge ratio it is different, quality m1Calibration object caused by marked gas
Quality be mA；
B, the quality m of gas produced by contained element to be measured in sample to be tested is calculated using formula (1)B, formula (1) are as follows:
Wherein, FAB(mB) it is the phase for demarcating marked gas and gas produced by element to be measured contained in sample to be tested caused by object
Function is closed, obtaining step includes:
S1, by quality be m1' the calibration object be put into TG-MS combination instrument with containing the internal standard compound of the element to be measured
Thermogravimetric-mass spectrum blob detection is carried out simultaneously, obtains the mass spectrum peak area S of marked gas caused by calibration objectA' and internal standard compound in institute
The mass spectrum peak area S of gas produced by the element to be measured containedB'；Wherein, the element to be measured contained in the internal standard compound
The quality of produced gas is mB', it demarcates described to be measured contained in the mass spectra peak and internal standard compound of marked gas caused by object
The mass spectra peak of gas produced by element is non-overlapping；The mass-to-charge ratio of mass spectra peak caused by the marked gas with by the internal standard compound
Contained in gas produced by the element to be measured mass spectra peak mass-to-charge ratio it is different, quality m1' the calibration object produced
The quality of raw marked gas is mA'；
S2, it is produced using the element to be measured contained in marked gas caused by formula (1-1) calculating calibration object and internal standard compound
The related coefficient a of angry body, formula (1-1) are as follows:
S3, it repeats step S1 and S2 and changes the quality of the internal standard compound, obtain n related coefficient a；Wherein, n is greater than 2
Natural number；
S4, with mB' be abscissa and carry out Function Fitting by ordinate of a, obtain correlation function FAB(mB)；
C, the mass content w that the element to be measured accounts for sample to be tested is calculated using formula (2)B, formula (2) are as follows:
Wherein, in total atom amount and sample to be tested of the x for element to be measured in gas produced by contained element to be measured in sample to be tested
The ratio of the molecular weight of gas produced by contained element to be measured.
2. according to the method described in claim 1, wherein, reaction gas to be sent into the thermogravimetric analysis of the TG-MS combination instrument
It is reacted in instrument with element to be measured contained in the sample to be tested and calibration object, obtains contained member to be measured in the sample to be tested
Gas and marked gas produced by element.
3. according to the method described in claim 2, wherein, the reaction gas includes being selected from nitrogen, air, oxygen, helium, argon
At least one of gas, hydrogen, carbon dioxide and sulfur dioxide, the flow velocity of the reaction gas are greater than zero to 1000mL/min.
4. according to the method described in claim 2, wherein, contained member to be measured in the reaction gas, marked gas and sample to be tested
Gas produced by element is not same gas, and the mass signal that three kinds of gases have mass-to-charge ratio different.
5. according to the method described in claim 1, wherein, the calibration object is liquid, solid or solidliquid mixture.
6. according to the method described in claim 1, wherein, the quality of the calibration object is 0.1mg-1000mg.
7. according to the method described in claim 1, wherein, the sample to be tested is liquid, solid or solidliquid mixture.
8. according to the method described in claim 1, wherein, the test temperature of thermogravimetric analyzer in the TG-MS combination instrument
Range is between -2400 DEG C of room temperature DEG C.
9. according to the method described in claim 1, wherein, the test temperature of thermogravimetric analyzer in the TG-MS combination instrument
Range is between 100 DEG C -1700 DEG C.
10. according to the method described in claim 1, wherein, the quality of the sample to be tested and internal standard compound is each independently
0.1mg-500g。
11. according to the method described in claim 1, wherein, by carrier gas by element to be measured contained in marked gas, sample to be tested
Thermogravimetric analyzer of the gas produced by the element to be measured contained in produced gas and internal standard compound from TG-MS combination instrument
Middle purging is into the mass spectrometer of TG-MS combination instrument.
12. according to the method described in claim 1, in step s 4, carrying out the letter using Origin software or Excel software
Number fitting.
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