CN101865868B - Differential thermal-gas chromatography combined analysis device - Google Patents
Differential thermal-gas chromatography combined analysis device Download PDFInfo
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- CN101865868B CN101865868B CN 200910093342 CN200910093342A CN101865868B CN 101865868 B CN101865868 B CN 101865868B CN 200910093342 CN200910093342 CN 200910093342 CN 200910093342 A CN200910093342 A CN 200910093342A CN 101865868 B CN101865868 B CN 101865868B
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Abstract
The invention provides a differential thermal-gas chromatography combined analysis device which belongs to the field of analysis instruments and relates to an intermittent combination device of a differential thermal analyzer and a gas chromatographic analyzer. The differential thermal-gas chromatography combined analysis device comprises the differential thermal analyzer (1) and the gas chromatographic analyzer (2); a gas sampling component (3) and a temperature sensor are arranged at a gas outlet of the different thermal analyzer (1), wherein the output of the gas sampling component (3) is connected to a sampling port of the gas chromatographic analyzer (2) through an automatic air inlet control mechanism. In the invention, the gas sampling component (3) and the automatic air inlet control mechanism are arranged on the basis of the traditional differential thermal-gas chromatography intermittent combined analysis device, a differential thermal signal, a furnace temperature signal and a temperature signal at a tail gas outlet of the differential thermal analyzer (1) are acquired in real time, and the predicting discrimination is carried out according to a time sequence curve of all signals so as to control that tail gas is guided into the gas chromatographic analyzer (2) to carry out ingredient separation and detection. The differential thermal-gas chromatography combined analysis device can realize automated operation and is suitable for operations without manual supervision.
Description
Technical field
The present invention is a differential thermal-gas chromatography combined analysis device, belongs to field of analytic instrument, relates to the combined apparatus at intermittence of differential thermal analyzer and gas chromatographicanalyzer.
Background technology
Differential thermal-gas chromatography intermittently combined analysis device came across for the 1970's, and (being also referred to as DTA, is under temperature program(me) control, the temperature T of measurement of species to utilize differential thermal analysis (DTA)
sTemperature T with reference substance
rA kind of technology of temperature difference and temperature relation), be used for the composition of amalyzing substances pyrolytic process effusion gas, its gordian technique is to detect the generation moment of effusion gas.Traditional differential thermal-gas chromatography combined analysis device is through directly importing thermal conductance sensing chamber with differential thermal analyzer tail gas; Through comparing with the thermal conductance value of the protection gas that feeds differential thermal analyzer; Judge the release moment of pyrolytic process effusion gas; And by hand differential thermal analyzer tail gas is switched in the gasometry pipe through six-way valve, after being full of, quantity tube should carry out component separating and detection in the quantitative tail gas importing gas chromatograph.Said method and device also are not suitable for the automation mechanized operation of Instrument crosslinking.In fact, the differential thermal signal of differential thermal analyzer output has reflected physical-chemical reactions such as heat absorption in the material thermal decomposition process, heat release, decomposition, crystallization, can draw the generation whether effusion gas is arranged indirectly.Therefore utilize the differential thermal signal and attach temperature variation, be the generation state that to judge effusion gas, thereby can guide the exhaust gas flow direction gas chromatograph to carry out the separation and the detection of composition with differential thermal analyzer tail gas.
Summary of the invention
The object of the present invention is to provide a kind of automation mechanized operation analytical equipment of differential thermal-gas chromatography coupling at intermittence of amalyzing substances pyrolysis product; Utilize the differential thermal signal and attach temperature variation with differential thermal analyzer tail gas; Judge the generation state of effusion gas, thereby guiding exhaust gas flow direction gas chromatograph carries out the separation and the detection of composition.
To achieve these goals; The present invention has taked following technical scheme: on the basis of traditional differential thermal-gas chromatography combined analysis device at intermittence; Gas sampling parts and automatic inlet control mechanism promptly are installed between differential thermal analyzer and gas chromatograph; At said differential thermal analyzer gas outlet gas sampling parts and temperature sensor are installed; The output of gas sampling parts is received the thief hatch of gas chromatograph through automatic inlet control mechanism, and differential thermal analyzer and gas chromatograph are placed on respectively on different platforms or the support platform.Wherein, the gas sampling parts can be manual sealed-regulating valves, and temperature sensor is arranged on this variable valve exit.This manual sealed-regulating valve adopts criss-cross four-way flow regulation chamber; Its four mouths are respectively: with the air intake opening of differential thermal analyzer gas vent socket; The mouth that manual spool be installed relative with air intake opening; Temperature sensor mounted hole as point for measuring temperature, the venthole that receive manual spool Control Flow relative with point for measuring temperature.Wherein, Manually spool is a hand screw that can in valve pocket, move, and this screw rod is provided with the bipassage ring connected in star, is with the O RunddichtringO that agrees with valve pocket chamber wall on it respectively; The end that screw rod is positioned at the chamber is provided with the O RunddichtringO of end, and an end that is positioned at outside the chamber is provided with manual rotating handle.And the mouth that manual spool is installed is provided with the end cap that prevents that hand screw from screwing out.
Temperature sensor in manually place, the hole installation of sealed-regulating valve point for measuring temperature adopts micro-sheathed thermocouple.
The hole of the point for measuring temperature in four-way flow regulation chamber and venthole are respectively equipped with two cutting ferrule seal members, realize sealing radially.
Automatic inlet control mechanism in this programme is made up of the controller of high temperature resistant three-way solenoid valve and head-space sampler and control three-way solenoid valve; This three-way solenoid valve import connects the gas sampling knockdown export, two controlled outlets, and one as evacuation port, and another connects the head-space sampler inlet through the insulation kapillary; This head-space sampler outlet connects the thief hatch of gas chromatograph through the insulation kapillary; This controller can be gathered the temperature of the point for measuring temperature of differential thermal analyzer and gas sampling parts; And judge whether the differential thermal analysis (DTA) process gas of overflowing occurs; When judging that effusion gas appears in the differential thermal analysis (DTA) process, the selection of control three-way solenoid valve two outlets and the action of head-space sampler.Controller wherein can adopt computing machine, judge that the differential thermal analysis (DTA) process gas that whether occurs overflowing can adopt certain algorithm to realize through computing machine, and the step of the action of the selection of control three-way solenoid valve two outlets and head-space sampler is:
1) trigger the headspace sampling device and get into " auto injection " state, and begin the accumulative total timing,
2) after 1 second of time-delay, trigger three-way solenoid valve and open, make differential thermal analyzer and headspace sampling device UNICOM,
3) delay time after 4 seconds, the headspace sampling device is quantitatively air-breathing and gas squeezed in the gas chromatograph again, keep three-way solenoid valve to open for 10 seconds after, close the triggering three-way solenoid valve, make the direct emptying of differential thermal analyzer tail gas,
4) after sample introduction finished, the headspace sampling device got into " hand sampling " state.。
In addition, accurate for what guarantee to detect, the electric device in this programme adopts the power conditioner that connects common civil power as power supply.
Above-mentioned judge that differential thermal analysis (DTA) process whether occur the overflowing algorithm of gas is:
1) gather current time differential thermal analyzer heating-up temperature and differential temperature signal value, and preset current time differential thermal signal value is in " decline passway ";
2) judge that whether the differential thermal analyzer heating-up temperature is more than or equal to design temperature;
3) when differential thermal analyzer heating-up temperature during, preserve current heating-up temperature and differential temperature signal value less than design temperature, and time-delay 1-15 second, get back to step 2;
4) when differential thermal analyzer heating-up temperature during more than or equal to design temperature, up-to-date interval heating-up temperature and the differential temperature signal value of being preserved in the input step 3 of certain heating-up temperature.
5) the Gauss's second order derived function sequence of different σ and differential temperature signal value sequence difference convolution algorithm;
6) convolution sequence of calculating different σ is respectively crossed the zero crossing number and is crossed the corresponding heating-up temperature of zero cross point with each;
7) be benchmark with the zero cross point temperature excessively on the minimum σ, different σ gone up the nearest zero cross point temperature of crossing link with the chain sheet form.
8) the scanning heating-up temperature is interval, with the chained list pairing of identical chain length;
9) it is right to select the chained list the longest and vice-minister;
10) current time differential temperature signal value and the nearest chained list of selecting compare the pairing differential temperature signal value of right-hand point, confirm that current time differential temperature signal value is in " rising " perhaps " decline " passage;
Whether the tunnel condition that 12) relatively calculates is identical with the setting tunnel condition;
13) when the tunnel condition that calculates is identical with the setting tunnel condition, effusion gas do not occur, upgrade present channel status, delay time 1-15 second, get back to step 4;
14) when tunnel condition that calculates and setting tunnel condition were inequality, relatively whether differential thermal analyzer exhaust ports temperature fluctuation range was identical with setting range;
15) when differential thermal analyzer exhaust ports temperature fluctuation range is identical with setting range, effusion gas do not occur, upgrade present channel status, delay time 1-15 second, get back to step 4;
16) when differential thermal analyzer exhaust ports temperature fluctuation range and setting range are inequality, effusion gas occurs, revise channel status, time-delay 1-15 second, get back to step 4.
The implication of each noun is following in the above step:
Differential temperature signal value sequence refers to the time series that the temperature difference signal is formed in the differential thermal analysis (DTA) that differential thermal analyzer obtains at regular intervals, is called for short differential temperature signal value sequence.
Gauss's second order derived function refers to the second order derived function of gauss of distribution function, and gauss of distribution function wherein is for stochastic variable x, and its probability density function can be expressed as
It is distributed as Gaussian distribution or claims normal distribution, is designated as N (μ, σ
2), wherein μ and σ are the expectation value and the variance yields of Gaussian distribution.
Gauss's second order derived function sequence of different σ refers to gauss of distribution function expectation value μ and variances sigma that to relate to two parameters be Gaussian distribution; Different σ values; Can produce different Gaussian distribution second order derived function curves; Discrete x value can obtain one group of Gaussian distribution second order derived function sequence, and different σ values will obtain several groups of different Gaussian distribution second order derived function sequences.Gauss's second order derived function sequence and differential temperature signal value sequence that a certain σ value constitutes are carried out convolution algorithm, and the corresponding differential temperature signal of zero cross point of crossing of its convolution sequence has just constituted the differential temperature signal value sequence under a certain σ value.
Chain length refers to single-track link table length, and chained list is a computer data structure, is a kind of linear list, can't be by the sequential storage data of linearity, but in each node, deposit the pointer of next node, chained list length just constitutes the node number of chained list.
Chained list is to the chained list of the identical or approaching different temperatures of a pair of chained list length that refers to reflection appearance in the temperature chain chart.
" rising passway " or " decline passway " refers to that a certain hop count value in the differential temperature signal value sequence presents the trend of increasing or decreasing in the same way.
Certain heating-up temperature interval refers to because differential temperature signal value sequence and Gauss's derived function sequence are made convolution algorithm; Therefore result's convolution sequence need consider that near the hop count value the differential temperature signal value sequence of interval left margin (being the incipient stage) receives the error that the influence of Gauss's derived function sequence number brings when carrying out convolution algorithm; Especially begin the heating initial stage from room temperature, the so many temperature of Gauss's second order derived function sequence number that convolution algorithm need adopt surmounting also continue just can carry out after one section temperature (20 ℃-30 ℃) again.
In step 9, utilized the principle of judging peak valley; This principle is following: with the σ value hour convolution sequence cross the head node of each corresponding temperature of zero cross point as every single-track link table; Direction along the increase of σ value; Look for convolution sequence under each σ value and cross the corresponding nearest temperature of zero cross point, constitute many unidirectional temperature chained lists.Gauss's second order derived function sequence and the convolution algorithm of differential temperature signal value sequence are equivalent to differential temperature signal value sequence is done the low-pass filtering treatment of different threshold values under the different σ values; The curve that the big more convolution sequence of σ value constitutes is level and smooth more, thereby the length of every temperature chained list has also just reflected the degree that the convolution sequence curve can continue under different σ values.If little fluctuation appears in original differential temperature signal value sequence, will smoothly be fallen through train wave after several σ values is moving, being reflected in the temperature chained list length that just constitutes on the temperature nodes number can be very not long.If material is heated physical-chemical reaction has taken place, significant tendency direction will take place and change in its original differential temperature signal value sequence, is reflected on the temperature chained list length very big numerical value can occur exactly.Because what differential temperature signal value sequence was adopted is that Gauss's second order derived function sequence is carried out convolution, so convolution sequence reflects is the knee characteristic that differential temperature signal value sequence generation directivity changes.The chained list that in temperature chain chart, can reflect into the identical or approaching different temperatures of a pair of chained list length of appearance is right; The linked list head node is just meaned between two temperature of pairing height at this directivity variation has taken place differential temperature signal value sequence curve, just exists the peak value (maximal value) or the valley (minimum value) of a differential temperature signal value.
Apparatus of the present invention are on the basis of traditional differential thermal-gas chromatography combined analysis device at intermittence; Install gas sampling parts and automatic inlet control mechanism additional; Gather the temperature signal in differential thermal signal, temperature signal and the differential thermal analyzer tail gas exit of differential thermal analyzer in real time; Time-serial position through to these signals is predicted differentiation; Judge whether there is effusion gas in the differential thermal analyzer tail gas, discovery is opened the headspace sampling device after effusion gas is arranged automatically, quantitative tail gas is imported in the gas chromatograph carry out component separating and detection.This cover combined analysis device can be realized automation mechanized operation, is fit to the operation under the unmanned nurse environment.
Description of drawings
Fig. 1 is a workflow synoptic diagram of the present invention;
Fig. 2 is a gas sampling modular construction synoptic diagram of the present invention;
The algorithm flow chart of effusion gas appears in Fig. 3 for computer judges differential thermal analysis (DTA) process among the present invention;
Fig. 4 is headspace sampling device breakdown action process flow diagram among the present invention.
Among the figure: 1, differential thermal analyzer, 2, gas chromatograph, 3, the gas sampling parts, 4, three-way solenoid valve, 5, head-space sampler; 6, reference substance pallet, 7, the test specimens pallet, 8, tail gas outlet point for measuring temperature, 9, hand screw, 10, the insulation kapillary; 11, chromatographic column, 12, thermal conductivity detector (TCD), 13, trip bolt, 14, end cap; 15, waist O-ring seals, 16, the end O-ring seals, 17, two cutting ferrule seal member, 18 four-way flow regulation chambeies.
Embodiment
The ability instance is on the basis of traditional differential thermal-gas chromatography combined analysis device at intermittence; Install gas sampling parts 3, automatic inlet control mechanism additional; Utilize the temperature signal at differential thermal signal, furnace temperature signal and differential thermal analyzer 1 tail gas exit point 8 places of computer real-time acquisition differential thermal analyzer 1; Time-serial position through to these signals is predicted differentiation; Judge in differential thermal analyzer 1 tail gas whether have effusion gas, discovery is opened the headspace sampling device after effusion gas is arranged automatically, quantitative tail gas is imported in the gas chromatograph 2 carry out component separating and detection.This cover combined analysis device can be realized automation mechanized operation, is fit to the operation under the unmanned nurse environment.
Below in conjunction with Fig. 1-Fig. 4 the present invention is elaborated:
High-purity protection gas (like nitrogen or argon gas) from the high pressure gas cylinder after decompression, voltage stabilizing are handled; Behind spinner-type flowmeter adjustment flow, feed in the differential thermal analyzer 1; Thermal decomposition to the differential thermal analysis (DTA) sample plays the inert gas shielding effect, promptly under protective atmosphere, carries out the pyrolytic reaction of sample.
Place in the reference substance pallet 6 in differential thermal analyzer 1 heating furnace and fill micro-reference substance (like α-Al
2O
3Powder) heat-resisting crucible is placed the heat-resisting crucible of equivalent that fills the equivalent specimen on the test specimens pallet 7, have the differential thermal thermopair to link to each other between the tray bottom, is used to measure the differential thermal gesture.The differential temperature signal of temperature and sample and reference substance is all exported with the analog quantity form in the stove; This combined apparatus needs the identical output telltale of two cover output signal content; One cover supplies differential thermal analyzer 1 control use, and a cover supplies to judge signal time sequence monitoring use.
The gas sampling parts 3 of a may command air output partly are installed at the escape pipe of differential thermal analyzer 1 heating furnace; These parts are four-way flow regulation chamber; Be installed in the escape pipe top, adopt resistant to elevated temperatures O-ring seals sealing, reveal to prevent tail gas with differential thermal analyzer 1 junction.The hand screw 9 of a control exhaust flow is arranged above gas sampling parts 3, and the bottom of hand screw 9 is embedded with a resistant to elevated temperatures end O-ring seals 15.When hand screw 9 screws in gas sampling parts 3 fully, hand screw 9 bottom end faces will be sealed the outlet of differential thermal analyzer 1 work tail gas fully, and end O-ring seals 15 plays the bottom seals effect; When hand screw 9 was turned on outside gas sampling parts 3, tail gas can flow out gas outlet (as shown in Figure 2), and rotation hand screw 9 may command differential thermal analyzers 1 work tail gas flows out the size in cross section.Embedded 15 pairs of differential thermal analyzers of waist O-ring seals, the 1 work tail gas of two annular grooves on the dependence hand screw 9 possibly revealed vertically and seal.When differential thermal analyzer 1 work tail gas flows out the cross section when maximum, hand screw 9 stops to stretch out, and what stop that this extension relies on is the end cap 14 of gas sampling parts 3 top end and fixing three trip bolts 13 of end cap 14.At the place, gas outlet a tail gas outlet point for measuring temperature 8 is set, measures the endpiece temperature of differential thermal analyzer 1 work tail gas, adopt micro-sheathed thermocouple to detect the temperature of this place's gas, adopt two cutting ferrule seal members 17 to realize the sealing of point for measuring temperature and venthole.
Differential thermal analyzer 1 work tail gas flows out the back along gas sampling parts 3 ventholes and feeds in one section insulation kapillary 10, and this insulation kapillary 10 connects the import of resistant to elevated temperatures three-way solenoid valve 4.Two controlled outlets of three-way solenoid valve 4, one as evacuation port, and another connects head-space sampler 5 inlets through insulation kapillary 10.The selection of 4 liang of outlets of three-way solenoid valve is by computer control, and the temperature and the differential temperature signal of sample and reference substance and the temperature signal in differential thermal analyzer 1 tail gas exit are received this computing machine in the stove, supplies to judge signal time sequence monitoring use.Above three-way solenoid valve 4, head-space sampler 5, computing machine constituted the automatic inlet control mechanism of this combined apparatus, and the outlet of this mechanism is that the outlet of head-space sampler 5 connects gas chromatograph 2.Introduce the course of work (like Fig. 3, Fig. 4) of automatic inlet control mechanism below:
In computer Recognition judgement tail gas, do not occur under the situation of effusion gas, solenoid valve will be worked tail gas by the direct emptying of exhausr port; When computer Recognition is judged when occurring effusion gas in the tail gas, the solenoid valve tail gas of will working inserts the exhausr port that another connects headspace sampling equipment.Judge whether exist effusion gas to rely on following rule to carry out in the tail gas: at first computer real-time receives heating-up temperature and the sample differential temperature signal that differential thermal analyzer 1 sends; And the sample differential temperature signal of (temperature window) in certain heating-up temperature scope carried out signal Processing; The time interval that sort signal is handled can be adjusted according to different type of heating in advance, generally whenever between 1 second to 15 seconds, is carrying out once.Concrete way is that the differential temperature signal time sequence of a certain temperature range and specific Gauss's second order derived function are done process of convolution; Convolution results is carried out zero passage and is judged; So not only eliminated the interference that signal changes peak valley under different scale, also than being easier to find out in this temperature range the corresponding temperature spot of peak and valley in the differential temperature signal time sequence.Near this differential temperature time series sequence these temperature spots is increased progressively the calculation process of successively decreasing, thereby confirm the peak of the concrete representative of the corresponding differential temperature signal of each temperature spot and the characteristic of paddy.The differential temperature signal development trend that to handle last temperature of living in addition specifically identifies out; Promptly according to differential temperature signal time sequence in the end the numerical value at temperature spot place do next time and to handle the prediction setting of differential temperature number of signals value constantly; When signal Processing next time the contrast actual numerical value and last time predicted numerical value relation, i.e. the development trend of decidable differential temperature signal time sequence in such time interval and the peak valley state that possibly occur.Differential temperature peak value in the differential temperature signal time sequence is represented heat release generally speaking; The lowest point representative heat absorption; Follow this physical-chemical reaction the gas of overflowing can occur, at this moment also need the temperature signal of cooperating tail gas monitoring to change to judge wherein whether have effusion gas to exist in gas sampling parts 3 exits.When effusion gas occurring in the work tail gas, tangible fluctuation can take place in the temperature of potpourri.Computing machine combines above-mentioned algorithm to discern whether effusion gas exists in the judgment task tail gas.
When computer Recognition is judged when having effusion gas in the work tail gas; The supervisory control comuter program of Instrument crosslinking device will at first be noted differential thermal analyzer 1 heating-up temperature of this moment; Thereby secondly will send a control signal triggering headspace sampling device start-up routine and switch to automatic running status, and then another control signal of transmission switches to another exhausr port with the solenoid valve duty that kapillary connects by the normal open evacuation port in the second subsequently.After headspace sampling device start-up routine switched to automatic running status, the control signal of headspace sampling device was with the logging program operation of automatic trigger gas chromatography 2.After the supervisory control comuter program of Instrument crosslinking device is sent two control signals after one or two second; The headspace sampling device just can be accomplished predefined warming-up exercise; To open asepwirator pump automatically subsequently; From another exhausr port suction work tail gas of solenoid valve; And suck paced work tail gas by itself 1mL counter-tube decision, after this through headspace sampling device inner six-way valve and the vaporizer of control system, the separation of realization combination gas in the chromatographic column 11 in the post case with quantitative work tail gas inject gas chromatograph 2; And the composition through various permanent gass in TCD (being thermal conductance detecting device 12) the testing tail gas, and calibrate the concentration of every kind of permanent gas composition through the normal mixture body for preparing in advance.The headspace sampling device is accomplished once sampling injection automatically needs ten second time; Supervisory control comuter program of Instrument crosslinking device will be sent a control signal once more the solenoid valve duty that kapillary connects will be switched to the normal open evacuation port by another exhausr port after this, and the headspace sampling device can revert to artificial state by auto state automatically.
The curve numerical value of the curve numerical value of 2 fens segment records of gas chromatograph and differential thermal analyzer 1 omnidistance record all can be kept in the specific file catalogue of Instrument crosslinking assembly monitor computing machine before the instrument end of run separately; The supervisory control comuter program can be carried out data fusion and mapping through by hand these two group records data being obtained the back in the supervisory control comuter program; Process the demonstration chart of DTA-GC, supply the pyrolysis under differential thermal reaction different temperatures of the different samples of research to discharge the composition of effusion gas and the Changing Pattern of constituent concentration thereof.
The air intake duct of headspace sampling device and snorkel all adopt kapillary to process; And through accompanying pipe heating and insulation to handle; Make kapillary volume inside Controllable Temperature built in temperature and the accuracy rating set; The work tail gas that can avoid like this getting into not reason temperature decrease makes and some composition gas generation condensation reaction wherein causes local the obstruction in kapillary inside, forms the dead volume of transmission.The air intake duct of headspace sampling device and the temperature of snorkel are set the temperature of keeping watch on differential thermal analyzer 1 gas sample tube exit should be consistent.
Being electrically connected of differential thermal-gas chromatography combined analysis device provides after the common civil power of employing connects power conditioner, can guarantee the electrical isolation of differential thermal analyzer 1, headspace sampling device, gas chromatograph 2, direct voltage drive power supply and supervisory control comuter electricity consumption and the shock resistance of electric current and voltage, anti-fluctuation like this.Differential thermal analyzer 1 adopts different placement platform or support platform with gas chromatograph 2; Thereby form good vibration isolation; To avoid the ventilation of gas chromatograph 2 post casees to add the influence of the fan vibrations of thermosetting, avoid the continued jitters of differential thermal signal on small scale to differential thermal analyzer 1 inner tray stability.
Claims (9)
1. differential thermal-gas chromatography combined analysis device; Comprise differential thermal analyzer and gas chromatograph; It is characterized in that: gas sampling parts and temperature sensor are installed at said differential thermal analyzer gas outlet; The output of gas sampling parts is received the thief hatch of gas chromatograph through automatic inlet control mechanism, and differential thermal analyzer and gas chromatograph are placed on the different platforms respectively;
Automatic inlet control mechanism wherein is made up of the controller of high temperature resistant three-way solenoid valve and head-space sampler and control three-way solenoid valve; This three-way solenoid valve import connects the gas sampling knockdown export, two controlled outlets, and one as evacuation port, and another connects the head-space sampler inlet through the insulation kapillary; This head-space sampler outlet connects the thief hatch of gas chromatograph through the insulation kapillary; This controller can be gathered the temperature of the point for measuring temperature of differential thermal analyzer and gas sampling parts; And judge whether the differential thermal analysis (DTA) process gas of overflowing occurs; When judging that effusion gas appears in the differential thermal analysis (DTA) process, control three-way solenoid valve and head-space sampler auto injection, its controlled step is:
1) trigger the headspace sampling device and get into " auto injection " state, and begin the accumulative total timing,
2) after 1 second of time-delay, trigger three-way solenoid valve and open, make differential thermal analyzer and headspace sampling device UNICOM,
3) delay time after 4 seconds, the headspace sampling device is quantitatively air-breathing and gas squeezed in the gas chromatograph again, keep three-way solenoid valve to open for 10 seconds after, close the triggering three-way solenoid valve, make the direct emptying of differential thermal analyzer tail gas,
4) after sample introduction finished, the headspace sampling device got into " hand sampling " state.
2. differential thermal-gas chromatography combined analysis device according to claim 1 is characterized in that: said gas sampling parts are a manual sealed-regulating valve, and point for measuring temperature is established in this variable valve exit.
3. differential thermal-gas chromatography combined analysis device according to claim 2; It is characterized in that: said manual sealed-regulating valve adopts criss-cross four-way flow regulation chamber (18); Its four mouths are respectively: with the air intake opening of differential thermal analyzer gas vent socket; The mouth that manual spool be installed relative with air intake opening, temperature sensor mounted hole, the venthole that receive manual spool Control Flow relative with point for measuring temperature as point for measuring temperature.
4. differential thermal-gas chromatography combined analysis device according to claim 3; It is characterized in that: said manual spool is a hand screw (9) that can in valve pocket, move; This screw rod is provided with the bipassage ring connected in star; Be with the O RunddichtringO that agrees with valve pocket chamber wall on it respectively, the end that screw rod is positioned at the chamber is provided with the O RunddichtringO of end, and an end that is positioned at outside the chamber is provided with manual rotating handle.
5. differential thermal-gas chromatography combined analysis device according to claim 4 is characterized in that: the said mouth that manual spool is installed is provided with the end cap (14) that prevents that hand screw (9) from screwing out.
6. differential thermal-gas chromatography combined analysis device according to claim 3 is characterized in that: said point for measuring temperature place is equipped with micro-sheathed thermocouple.
7. differential thermal-gas chromatography combined analysis device according to claim 3 is characterized in that: the hole of the point for measuring temperature in the said four-way flow regulation chamber (18) and venthole are respectively equipped with two cutting ferrule seal members (17).
8. differential thermal-gas chromatography combined analysis device according to claim 1 is characterized in that: said controller adopts computing machine.
9. differential thermal analysis (DTA) process whether occur the overflowing method of gas of judging in the differential thermal-gas chromatography combined analysis device according to claim 1 is characterized in that:
1) gather current time differential thermal analyzer heating-up temperature and differential temperature signal value, and preset current time differential temperature signal value is in " decline passway ";
2) judge that whether the differential thermal analyzer heating-up temperature is more than or equal to design temperature;
3) when differential thermal analyzer heating-up temperature during, preserve current heating-up temperature and differential temperature signal value less than design temperature, and time-delay 1-15 second, get back to step 2;
4) when differential thermal analyzer heating-up temperature during more than or equal to design temperature, up-to-date interval heating-up temperature and the differential temperature signal value of being preserved in the input step 3 of certain heating-up temperature,
5) the Gauss's second order derived function sequence of different σ and differential temperature signal value sequence difference convolution algorithm;
6) convolution sequence of calculating different σ is respectively crossed the zero crossing number and is crossed the corresponding heating-up temperature of zero cross point with each;
7) be benchmark with the zero cross point temperature excessively on the minimum σ, different σ gone up the nearest zero cross point temperature of crossing link with the chain sheet form;
8) the scanning heating-up temperature is interval, with the chained list pairing of identical chain length;
9) it is right to select the chained list the longest and vice-minister;
10) current time differential temperature signal value and the nearest chained list of selecting compare the pairing differential temperature signal value of right-hand point, confirm that current time differential temperature signal value is in " rising passway " perhaps " decline passway ";
Whether the tunnel condition that 12) relatively calculates is identical with the setting tunnel condition;
13) when the tunnel condition that calculates is identical with the setting tunnel condition, effusion gas do not occur, upgrade present channel status, delay time 1-15 second, get back to step 4;
14) when tunnel condition that calculates and setting tunnel condition were inequality, relatively whether differential thermal analyzer exhaust ports temperature fluctuation range was identical with setting range;
15) when differential thermal analyzer exhaust ports temperature fluctuation range is identical with setting range, effusion gas do not occur, upgrade present channel status, delay time 1-15 second, get back to step 4;
16) when differential thermal analyzer exhaust ports temperature fluctuation range and setting range are inequality, effusion gas occurs, revise channel status, time-delay 1-15 second, get back to step 4;
In the above step:
Differential temperature signal value sequence refers to the time series that the temperature difference signal is formed in the differential thermal analysis (DTA) that differential thermal analyzer obtains at regular intervals, is called for short differential temperature signal value sequence;
Gauss's second order derived function refers to the second order derived function of gauss of distribution function, and gauss of distribution function wherein is for stochastic variable x, and its probability density function can be expressed as
It is distributed as Gaussian distribution or claims normal distribution, is designated as N (μ, σ
2), wherein μ and σ are the expectation value and the variance yields of Gaussian distribution;
Gauss's second order derived function sequence of different σ refers to gauss of distribution function expectation value μ and variances sigma that to relate to two parameters be Gaussian distribution; Different σ values; Can produce different Gaussian distribution second order derived function curves; Discrete x value can obtain one group of Gaussian distribution second order derived function sequence; Different σ values will obtain several groups of different Gaussian distribution second order derived function sequences, and Gauss's second order derived function sequence and differential temperature signal value sequence that a certain σ value constitutes are carried out convolution algorithm, and the corresponding differential temperature signal of zero cross point of crossing of its convolution sequence has just constituted the differential temperature signal value sequence under a certain σ value;
Chain length refers to single-track link table length, and chained list is a computer data structure, is a kind of linear list, can't be by the sequential storage data of linearity, but in each node, deposit the pointer of next node, chained list length just constitutes the node number of chained list;
Chained list is to the chained list of the identical or approaching different temperatures of a pair of chained list length that refers to reflection appearance in the temperature chain chart;
" rising passway " or " decline passway " refers to that a certain hop count value in the differential temperature signal value sequence presents the trend of increasing or decreasing in the same way;
Certain heating-up temperature interval refers to because differential temperature signal value sequence and Gauss's derived function sequence are made convolution algorithm; Therefore result's convolution sequence need consider that near the hop count value the differential temperature signal value sequence of interval left margin receives the error that the influence of Gauss's derived function sequence number brings when carrying out convolution algorithm; Especially begin the heating initial stage from room temperature, the so many temperature of Gauss's second order derived function sequence number that convolution algorithm need adopt surmounting and continue 20 ℃-30 ℃ of one section temperature again after just can carry out.
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| CN 200910093342 CN101865868B (en) | 2009-09-28 | 2009-09-28 | Differential thermal-gas chromatography combined analysis device |
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| CN104020237B (en) * | 2014-06-24 | 2016-01-20 | 武汉矽感科技有限公司 | Can with the FastGC post modifying device of ionic migration spectrometer coupling |
| CN105203713A (en) * | 2015-09-29 | 2015-12-30 | 张雪梅 | Intelligent automatic air sampling device used for occupational health |
| CN110057855A (en) * | 2019-04-30 | 2019-07-26 | 内蒙古科技大学 | Eliminate the device that environmental fluctuating influences simultaneous thermal analysis curve |
| CN112268288A (en) * | 2020-10-16 | 2021-01-26 | 重庆渝久环保产业有限公司 | Waste gas detection system |
Citations (3)
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| US6406918B1 (en) * | 1999-01-25 | 2002-06-18 | University Of Massachusetts | Thermal analysis for detection and identification of explosives and other controlled substances |
| CN2893698Y (en) * | 2006-05-11 | 2007-04-25 | 北京科技大学 | Visual differential thermal analysis instrument |
| CN201548505U (en) * | 2009-09-28 | 2010-08-11 | 中国林业科学研究院木材工业研究所 | Differential-thermal-gas chromatography combined analyzing device |
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|---|---|---|---|---|
| US6406918B1 (en) * | 1999-01-25 | 2002-06-18 | University Of Massachusetts | Thermal analysis for detection and identification of explosives and other controlled substances |
| CN2893698Y (en) * | 2006-05-11 | 2007-04-25 | 北京科技大学 | Visual differential thermal analysis instrument |
| CN201548505U (en) * | 2009-09-28 | 2010-08-11 | 中国林业科学研究院木材工业研究所 | Differential-thermal-gas chromatography combined analyzing device |
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