CN102192959A - Thermal cracker, thermal cracking gas chromatograph and thermal cracking analysis method - Google Patents
Thermal cracker, thermal cracking gas chromatograph and thermal cracking analysis method Download PDFInfo
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Abstract
The invention relates to a thermal cracker, a thermal cracking gas chromatograph and a thermal cracking analysis method, which relate to the technical field of thermal cracking gas chromatography. The thermal cracker comprises a sample feeding device, a thermal cracking chamber, an electrical heating furnace, a carrier gas circuit and a control system, wherein the sample feeding device is connected with the thermal cracking chamber; the carrier gas circuit is connected with the upper end of the thermal cracking chamber; the electrical heating furnace is arranged at the periphery of the thermal cracking chamber; a sample carrying element is arranged in the thermal cracking chamber; the sample feeding device comprises a sample cup for containing a sample to be tested and a control button; and the control system is connected with the electrical heating furnace and used for controlling the temperature and the time of the electrical heating furnace. The sample feeding passage of the sample feeding device of the thermal cracker is vertical to a horizontal plane, so that secondary reaction can be minimized, the reproducibility of a chromatogram can be ensured, and the difference caused by manual operation can be eliminated maximally. The thermal cracking gas chromatograph comprises a capillary gas chromatographic column, wherein the outlet of the thermal cracker is connected with the capillary gas chromatographic column.
Description
Technical field
The present invention relates to the thermal cracking gas chromatography technical field, relate in particular to the thermal cracking gas chromatography instrument and the pyrolytic cracking analytical method thereof of a kind of heat cracker and this heat cracker of employing.
Background technology
The thermal cracking gas chromatography technology grows up on thermal cracking and two kinds of technical foundation of gas chromatography.Thermal cracking chromatographic technique application extends to material analysis, petrochemical industry plasticizing, the QC of criminal/scene of a fire evaluation, photoelectricity/semiconductor, product/product are protected, food industries or the like, mainly be applied in polymkeric substance widely at present, adjuvant, coating/ink analysis, cloth, cosmetics, lubricating oil, during the surface contaminant of paper and relevant product subject matter insured pipe detects, become the important means of macromolecular material analysis.
Pyrolysis technology is a kind of sample pre-treatments technology, utilizes thermal energy to decompose, and macromolecular polymer unwinds can be become micromolecule, make it can enter gas chromatograph and separate, and the effect of arrival qualitative and quantitative; If the collocation mass spectrometer more can be analyzed the composition of qualitative the unknown as detecting device, reach the effect of " prescription is confirmed " or " prescription cracks ".The pyrolysis technology core is the control of cracking temperature and cracking time, accurate temperature control and fast heating rate the accuracy of pyrolysis product and repeatability are promoted significantly.Aspect thermal cracker, occurred in succession that heated filament (band) cracker, Curie point cracking go, tube furnace pyrolyzer and laser pyrolyzer, the appearance of new-type cracker and the raising of performance thereof have promoted the development of heat cracker.This technology has the monopolization of external manufacturer substantially at present, mainly contains the CSD5000 series cracking instrument of the CSD company of the U.S., adopts the platinum wire heating means; The Curie point heating pyrolyze instrument (JHP-4) of Japan JHP company; Australian SGE high temperature pyrolysis device (Pyrojector II) adopts the gravity type heating.And domestic production has only the heat cracker of the R200 of Shanghai Kechuang instrument company, and uses traditional heated filament heating means in 60-70 age, exists the rate of heat addition slow, and the temperature degree is low, thereby has the shortcoming of the poor reproducibility of sample analysis.
Cracking (Pyrolysis) only refers to and by heat energy the chemistry that sample changes another kind of or several materials into is crossed reason.The result of cracking usually is that molecular weight reduces, but also may make molecular weight increase (as cross-linking reaction) by various intermolecular reactions, and cracking is also referred to as thermal cracking or pyrolysis sometimes.
Concerning superpolymer, before handling spectrogram, usually need main spectrum peak in addition qualitatively, by qualitative, compose ownership and definite characteristic peak at peak.Characteristic peak is meant the spectrum peak that those have definite corresponding relation with the chemical composition and the structure of sample, and the component of its concentration and sample (or microstructure) contains the hole single funtcional relationship.For example, the monomer peak of superpolymer characterizes the chemical composition of sample; Keyed jointing structure and sequence that oligomer, assorted oligomer characterize multipolymer distribute; Some isomery hydro carbons sign has the olefin polymer of side chain and stereoregular structure etc.
The atlas analysis method of this thermal cracking gas chromatography has two kinds: (1) " fingerprint image " counter point: different samples, under certain test conditions, have the spectrogram of the mutual difference of feature, and just as people's fingerprint, be called " fingerprint image ".The known latent figure that the spectrogram of unknown sample is coexisted under the same terms compares and is identified.This method requires the necessary strict conformance of experiment condition.(2) " rod figure " counter point: spectrogram is handled again, peak height (or peak area) and retention time thereof with the highest spectrum peak are made benchmark (respectively as 100 and 1), relative value is got at its residue spectral peak, make the graph of a relation of relative peak height (or peak area), be called " rod figure " with relative retention.By the comparison of " rod figure ", unknown sample is identified.Also can make interior mark, make benchmark, obtain roughly the same " rod figure " with a certain characteristic peak replacement top of internal standard compound with adding known substance.The advantage of " rod figure " method is needn't be strict with unanimity to experiment condition, and qualification result is reliable, is suitable for material qualitative of a certain veriety.
Along with the continuous progress of science and technology, material processing technique, the foundation level of domestic analytical instrument and development ability have had long-term technological accumulation; And breakthrough progress has been arranged in heating means, meet the technical conditions of core technology high temperature heating in the heat cracker substantially.Therefore, it is fast to have possessed a kind of firing rate of exploitation, the thermal cracker that temperature is high, and combine with domestic gas chromatograph, on the basis that keeps chromatogram detector testing result repeatability, repeatability, make moderate cost, be convenient to user's acceptance, become condition with leading domestic pyrolysis gas chromatography instrument.
Summary of the invention
One aspect of the present invention provides a kind of heat cracker that is applicable to existing gas chromatograph structure, is lower than like product on its cost of manufacture, and controlled temperature range is wide, improves a lot than prior art in repeatability, the repeatability of testing result.
To achieve these goals, technical scheme of the present invention is:
A kind of heat cracker, comprise sampling device, the thermal cracking chamber, electric furnace, carrier gas gas circuit and control system, sampling device is connected with the thermal cracking chamber, the carrier gas gas circuit is connected with the upper end of thermal cracking chamber, electric furnace be arranged on the thermal cracking chamber around, the indoor sample load elements that is provided with of thermal cracking, sampling device comprises the sample cup and the control knob that are used to hold testing sample, control system is connected with electric furnace and is used to control the temperature and time that arrives after the intensification of electric furnace, and the sample intake passage of the sampling device of wherein said heat cracker is perpendicular to the surface level setting.
Aforesaid heat cracker, its cracking room internal layer is tapered quartz or glass tube, the upper end of this thermal cracking chamber is connected with the carrier gas gas circuit.Wherein carrier gas gas circuit is once shunted before capillary gas chromatographic column, presses before control flow rate of carrier gas and the post.
Aforesaid heat cracker, wherein said heating furnace adopt the direct current heating, and temperature controlling range is 300-1000 degree centigrade.
Aforesaid heat cracker wherein is provided with the cooling gas circuit around described electric furnace.
Another aspect of the present invention has provided and a kind ofly can detect a kind of thermal cracking gas chromatography instrument that makes natural or synthetic macromolecular compound.
Aforesaid thermal cracking gas chromatography instrument comprises capillary gas chromatographic column, data handling system, detecting device and aforesaid heat cracker.The thermal cracking chamber of the heat cracker in this thermal cracking gas chromatography instrument possesses the function of vaporizer simultaneously, and the cracking probe is that the sample load elements inserts the thermal cracking chamber, has reduced the dead volume of system greatly.
Aforesaid thermal cracking gas chromatography instrument, also comprise a back-blowing device, be connected the tail end of capillary gas chromatographic column, be arranged on capillary gas chromatographic column and the passage that detecting device is connected, the blowback air device that increases can be behind sample introduction the time open, can prevent that to a certain extent post from polluting, and can prevent that air from entering capillary gas chromatographic column simultaneously.The advantage of blowback air device is the separation efficiency that has improved system, can prevent that also air from entering capillary gas chromatographic column simultaneously.Aforesaid thermal cracking gas chromatography instrument; its optimal design is for also being connected with a guard column between heat cracker and capillary gas chromatographic column; be filled with in this post with capillary gas chromatographic column in identical filler; can in time change its inner filler and be used to protect capillary gas chromatographic column, this guard column and capillary gas chromatographic column coated outside have thermal insulation material to be used for insulation.
Aforesaid thermal cracking gas chromatography instrument, wherein said detecting device are one or more the series connection wherein of flame ionization detector, thermal conductivity detector (TCD), electron capture detector, flame photometric detector (FPD), nitrogen phosphorous detector.
Aforesaid thermal cracking gas chromatography instrument, wherein preferred flame ionization detector, i.e. fid detector.
Aforesaid thermal cracking gas chromatography instrument also comprises an attemperator, is arranged on the exterior circumferential of described capillary gas chromatography and heat cracker interface channel, is used to make the temperature constant of capillary gas chromatographic column injection port.
Utilize the thermal cracking gas facies analysis detection method of above-mentioned thermal cracking gas chromatography instrument, may further comprise the steps:
Sample introduction: will contain sample vertical direction sample introduction in heat cracker of component to be measured, sample falls to the thermal cracking chamber through acceleration of gravity.
(1) sample introduction: will contain sample vertical direction sample introduction in heat cracker of component to be measured, the sample process acceleration of gravity sample introduction that contains component to be measured is to the thermal cracking chamber;
(2) Pintsch process: contain behind the sample feeding of component to be measured heating furnace thermal cracking, under the carrying of gas of carrier gas the sample that contains component to be measured after this thermal cracking brought into the analysis of carrying out next step after capillary gas chromatographic column chromatographic column is separated through 300～1000 ℃;
(3) detecting device analysis: detecting device will detect through the sample that contains component to be measured that separates in the last step, and generates chromatogram by the data handling system that connects that links to each other with detecting device;
(4) data analysis: the content or the purity that calculate the component to be measured in the sample that contains component to be measured according to the result of chromatogram.
The present invention is owing to adopted above-mentioned technology, and the good effect that makes it compared with prior art to have is:
Because adopt vertical sample introduction, in the frame process of acceleration of gravity, distance is certain, so that sample fix in each time that enters heat cracker, just can make the time of sample introduction constant, eliminate manually-operated error, improve reappearance with the gas chromatography of this heat cracker.
2. heat cracker is connected with the GC instrument and just can carries out the thermal cracking gas chromatography analysis.The expense of heat cracker only is about 15% of a GC instrument, and the heat cracker operation and maintenance is also fairly simple, and therefore concerning general gas phase analysis laboratory, it is convenient feasible and with low cost carrying out the thermal cracking gas chromatography analysis.
3. the pyrolysis product to complexity can effectively separate, for the compound of structural similarity, the fine difference between the macromolecular compound especially, the microcomponent in the polymeric material, can both on cracking pattern, reflect delicately, find corresponding feature.
4. employing flame ionization detector is so there is very high sensitivity.Amount of samples is generally microgram to the milligram magnitude, if use sample solution, sample size can reach 0.1～1.0 μ L.And the precision height of quantitative test, this is to the judicial inspection advantageous particularly.
5. analysis speed is fast, contains much information, and typical analytical cycle is half an hour, according to experimental result, can not only carry out structure, splitting mechanism, thermal stability and the reaction kinetics of qualitative evaluation and quantitative test and energy study sample.
Description of drawings
Fig. 1 is the vertical face analysis structural drawing of heat cracker of the present invention.
Fig. 2 is a thermal cracking gas chromatography instrument structural drawing of the present invention.
Fig. 3 is the thermal cracking gas chromatography instrument structural drawing that has back-blowing device after the present invention reequips.
Fig. 4 is the feed naphtha made with thermal cracking gas chromatography instrument of the present invention at 860 ℃ cracking collection of illustrative plates.
Fig. 5 is the chromatogram with the polystyrene of detected standard diagram of thermal cracking gas chromatography instrument of the present invention and unknown content.
Fig. 6 is the thermal cracking gas chromatography instrument detected standard diagram of polystyrene in routine.
Embodiment
Describe the specific embodiment of the present invention in detail below in conjunction with accompanying drawing.
Heat cracker of the present invention:
Fig. 1 is the structural representation of heat cracker of the present invention.
Reference numeral note among Fig. 1: 100: heat cracker, 11: the button of injection port, 12: cooling gas circuit, 13: thermal cracking chamber, 14: electric furnace, 15: sample load elements, 16: sample cup, 17: heat cracker control system, 18 carrier gas gas circuits.
Thermal cracking control system 17 is connected with electric furnace 14 and is used to control the temperature and time of heat cracker as shown in Figure 1, earlier sample is joined the sample cup 16 that is used for holding sample by injection port, when thermal cracking chamber 13 temperature reach the equilibrium temperature of setting, press the button 11 of injection port, sample cup 16 unclamps, so the sample cups in the sample cup 16 drop to rapidly on the sample load elements 15 in the thermal cracking chamber 13.Sample (liquid, gaseous state or solid-state) carries out sample introduction by acceleration of gravity, so each sample injection time all is the reappearance that the same, such design has improved thermal cracking gas chromatography greatly.Sample arrives 13 backs, thermal cracking chamber in constant thermal cracking temperature cracking of following moment, thereby guaranteed that resulting macromolecule sample cleaved fragment keeps more stable after generating, secondary reaction is reduced to minimum degree, make chromatogram spectrogram guarantee certain reappearance, eliminate manual operation difference to greatest extent.
Carrier gas in the carrier gas gas circuit 18 as shown in FIG. can be a high pure nitrogen, also can be high-purity helium.Under the carrying of gas of carrier gas, the product after the macromolecular compound cracking after the thermal cracking is transported to the bottom of thermal cracking chamber 13, is transported to the thermal cracking gas chromatography instrument by the interface channel with capillary gas chromatographic column.
On the electric furnace 14 of this heat cracker, be provided with cooling gas circuit 12 as shown in the figure, this cooling gas circuit 12 can be very fast to electric furnace 14 coolings, can realize fast different temperature requirements, reduce the experimental implementation time in the experimentation, accelerate job schedule.And this heating furnace adopts direct supply electric heating, has well prolonged the serviceable life of electric furnace 14.
Table one:
| Kind | Hot wire type's heat cracker | Curie's point type heat cracker | This heat cracker |
| TRT | 5-25s | 1-1.5s | 0.2s below |
Thermal cracking gas chromatography instrument of the present invention:
Be illustrated in figure 2 as the thermal cracking gas chromatography instrument that utilizes above-mentioned heat cracker and make.
The 201-carrier gas source, 202-reduction valve, 203-pressure maintaining valve, the 204-flowmeter, 205-carrier gas stream, 100-cracker, 206-fills out pre-column, the 207-shunt, and 208-shunts gas circuit, the 209-damper tube, the 211-capillary gas chromatographic column, 212-detecting device, 213-ion amplifier, the 214-data handling system, the 215-Instrument shell.
In the carrier gas source 201 high pure nitrogen is housed, this nitrogen is along carrier gas gas circuit 205 process reduction valve 202, pressure maintaining valve 203 and flowmeters 204, entered heat cracker 100, heat cracker 100 has a thermal cracking chamber 13, this structure has possessed in traditional gas chromatograph the function of corresponding vaporizer and thermal cracking chamber simultaneously, reduced the dead volume of system greatly, connect by passage between heat cracker 100 and the gas chromatograph, the interface volume of interface channel is as far as possible little, is beneficial to reduce dead volume, inhibition secondary reaction, the raising separation efficiency of total system.The same with the described principle of Fig. 1, after sample enters thermal cracking chamber 13, product is taken to the quartz ampoule bottom of taper by carrier gas, and be accelerated and sweep capillary gas chromatographic column 211, if carrier gas flux be 10mL/min so the linear flow speed of quartz ampoule bottom be exactly 12.4cm/s, heating-up time is about 0.25s (50 μ g samples rise to 600 ℃), and duplicate detection below experiment showed, that the realization reappearance of heat cracker 100 of the present invention has improved 4 times than traditional heat cracker.
The sample of process thermal cracking is successively through filling out pre-column 206 (being also referred to as guard column) and shunt 207; shunt 207 can be controlled split ratio; press before being used to control post, a part of gas after the shunting arrives extraneous emptying by shunting gas circuit 208 through damper tube 209 backs.Enter capillary gas chromatographic column 211 again through the carrier gas that contains after the thermal cracking after the shunting, capillary gas chromatographic column 211 can be with their separation of big young pathbreaker according to polarity of the sample after the thermal cracking, behind this sample process detecting device 212 and ion amplifier 213 through separation, carry out data processing by data handling system 214, there are Instrument shell 215 parcels the instrument outside.
The present invention connect before capillary gas chromatographic column 211 fills out pre-column 206, and used immobile liquid is identical with capillary gas chromatographic column 211.Like this, some pollutants will be trapped within to be filled out in the pre-column 206, as long as often change pre-particulate filler, just can protect capillary gas chromatographic column 211 not contaminated effectively, also can improve the separation efficiency of chromatographic system simultaneously.With just having eliminated pollution behind the guard column, guaranteed capillary gas chromatographic column 211 performances, both can prolong 211 life-spans of capillary gas chromatographic column, reduce analysis cost, can guarantee the reappearance of thermal cracking stratographic analysis again.
Be illustrated in figure 3 as the thermal cracking gas chromatography instrument structural drawing that has back-blowing device after the improvement; Reference numeral note wherein is:
The 201-carrier gas source, 202-reduction valve, 203-pressure maintaining valve, 204-flowmeter 205-carrier gas stream, the 100-heat cracker, 206-fills out pre-column, the 207-shunt, 208-shunts gas circuit, 209-damper tube, 211-capillary gas chromatographic column 212-detecting device, 213-ion amplifier, the 214-data handling system, 215-Instrument shell, 216-blowback air transfer valve.
Increased the blowback air device on the thermal cracking gas chromatography instrument of specific embodiment after this optimization in Fig. 2; promptly the tail end of the specific embodiment capillary gas chromatographic column 211 in Fig. 2 is connected with a blowback air transfer valve 216; they are connected by passage; when blowback air transfer valve 216 is connected carrier gas source 201, can reverse feeding blanket gas.This reverse gas has increased the atmospheric pressure of thermal cracking gas chromatography instrument channel interior, makes extraneous gas such as air be not easy to infiltrate instrument channel inside, has eliminated X factor and external interference.The blowback air transfer valve 212 that increases can be opened behind sample introduction, can prevent effectively that capillary gas chromatographic column 211 from polluting.The advantage of blowback air device is the separation efficiency that has improved system, can prevent that also air from entering capillary gas chromatographic column simultaneously.
Heat cracker is connected by passage with gas chromatograph, the interface outer setting at the passage place before capillary gas chromatographic column 211 injection ports attemperator, guaranteed the temperature of injection port.Make the carrier gas stream between heat cracker 100 and capillary gas chromatographic column 211 injection ports not have cold spot to produce, make higher-boiling compound (as C
4The higher-boiling compound of O and so on) and the compound of polarity can transfer to separating column effectively, and in sample flow path, be not adsorbed; And the interface of the interface channel between heat cracker 100 and the gas chromatograph injection port adopts no dead volume structure, and lysate sample gas is directly entered in the capillary gas chromatographic column 211, improves sample separation efficient, avoids the generation of secondary reaction.
The thermal cracking chromatograph advantage of specific embodiments of the invention is effectively to protect capillary gas chromatographic column 211, because the pollution of capillary gas chromatographic column 211 is to influence the thermal cracking chromatograph to test reproducible key factor.The tradition solution is regularly at high temperature aging again capillary gas chromatographic column 211, perhaps uses solvent cleaning.The method is complicated operation, time-consuming not only, and still can exist by some pollutants, is difficult to remove.Interface between the heat cracker 100 of thermal cracking gas chromatography instrument and the gas chromatograph injection port adopts no dead volume structure, and lysate sample gas is directly entered in the capillary gas chromatographic column 211, improves sample separation efficient, avoids the generation of secondary reaction.
Thermal cracking specific embodiment among the present invention has overcome hot wire type's cracker, Curie's point type cracker poor reproducibility, and high boiling substance is the defective of loss easily.This thermal cracking gas chromatography instrument can be connected with instrument such as MS, separates at GC, under MS identifies, can analyze any macromolecular compound, multipolymer is formed and end-group structure etc.
To detect through the component to be measured that kapillary chromatography of gases post 211 separates, and generating chromatogram by the data handling system 214 that is connected with detecting device, the result according to chromatogram calculates component content to be measured or the purity in the sample that contains component to be measured according to " fingerprint image " counter point or " rod figure " counter point then.
Among specific embodiment Fig. 1 of thermal cracking gas chromatography instrument among the present invention and Fig. 2 detecting device can be flame ionization detector (FID), thermal conductivity detector (TCD) (TCD), electron capture detector (ECD), flame photometric detector (FPD) (FPD) or nitrogen phosphorous detector (NPD).FID uses maximum detecting devices in the gas chromatography, the non-constant width of the dynamic range of this detecting device, and not only the range of linearity is wide, and sensitivity is also high, and is also more durable, but it is to some mineral compound, as CO, CO
2, NO, NO
2, H
2O etc. do not have response, and detect these materials just needs thermal conductivity detector (TCD) (TCD), although the sensitivity of TCD is lower, to CO, CO
2, NO, NO
2, H
2O etc. also must use TCD.Another advantage of TCD is not destroy measured object, and promptly so-called non-destructive detector, FID then are destructive detectors.Sometimes in order to obtain the pyrolysis product more information, need to adopt the series connection of two kinds of detecting devices, at this moment cooperate with other detecting device with TCD often, for example TCD connects with FID, can obtain two pyrograms simultaneously.Electron capture detector (ECD) in the cracking of halogen-containing sample of great use.Other selective detector such as flame photometric detector (FPD) (FPD), nitrogen phosphorous detector (NPD) are also having application.
The comparative example:
Embodiment 1:
Present industrial production ethene is many makes raw material with heavy oil, behind the heavy oit pyrolysis, has both produced ethene, also produces the bigger propylene of molecular weight, diolefin and aromatic hydrocarbon, therefore significant in ethylene industry is produced to the evaluation of raw material.Classical evaluation method is by the ratio of component in the pilot scale efficiency test pyrolysis product, as the ratio of paraffin wax hydrocarbon, alkene, cyclic hydrocarbon, aromatic hydrocarbons.Though this method is useful, cost is high and time-consuming. and utilize traditional gas chromatograph not analyze to this product, because naphtha needs cracking fully at high temperature.Thermal cracking gas chromatography instrument in when utilizing this can easily he estimates raw material.
As Fig. 4 is a kind of cracking pattern of producing the feed naphtha of ethene, and it can embody than the incomparable advantage of existing conventional gas-phase chromatogram with each component of feed naphtha under 860 ℃ thermal cracking condition.
Embodiment 2:
Contrast experiment: instrument: the GC-MS combined instrument, capillary gas chromatography tubing string 30m * 0.32mm * 0.25 μ m,
Reagent: polystyrene powder (to be measured), toluene, ethylbenzene, polystyrene standards.
Condition of work: carrier gas: nitrogen, flow: 2-4mL/min prepares toluene respectively, ethylbenzene, cinnamic standard solution uses DMF as standard solution.
Experimental technique: just carry out the drafting of standard brick empirical curve with internal standard method, the solution of preparing with the polyethylene powders of accurate weighing carries out identical sample introduction operation at every turn then, carries out time parallel laboratory test, then each analysis data result is measured.The result shows RSD＜5.6% of above-mentioned 6 groups of data.
Be illustrated in figure 6 as the analysis collection of illustrative plates of under this condition, drawing: 1. propylene, 2. propane, 3.1-butylene, 4. n-butene, 5. pentane, 6. toluene, 7. styrene, 8.C
2H
5-C (Ph)=CH
2, 9.C
4H
9-CH
2CH
2-Ph, 10.C
4H
9-C (Ph)=CH
2, 11.C
4H
9-CH=(Ph) CH
3, 12. styrene dimer bodies, 13. styrene tripolymers, RSD＜5.6%.
With identical experimental technique and experiment reagent, detecting device is FID, carries out operation repetitive 6 times with thermal cracking gas phase spectrometer of the present invention, and the result handles to data, and the result shows RSD＜1.6% of 6 groups of data, is far smaller than existing gas chromatography.Analyze collection of illustrative plates as shown in Figure 5.
Conclusion: compare with existing gas chromatography, the subsidiary reaction of using heat cracker of the present invention to produce is few, and it is more accurate to analyze.By the relative error of different several times testing results, analytical error is done contrast, and with existing gas chromatography RSD＜5.6% contrast, the reappearance of the RSD of this thermal cracking gas chromatography＜1.6% is obviously better.Embodied good repeatability.
The above only is a better embodiment of the present invention; protection scope of the present invention is not exceeded with above-mentioned embodiment; as long as the equivalence that those of ordinary skills do according to disclosed content is modified or changed, all should include in the protection domain of putting down in writing in claims.
Claims (10)
1. heat cracker, comprise sampling device, the thermal cracking chamber, electric furnace, carrier gas gas circuit and control system, sampling device is connected with the thermal cracking chamber, the carrier gas gas circuit is connected with the upper end of thermal cracking chamber, electric furnace be arranged on the thermal cracking chamber around, the indoor sample load elements that is provided with of thermal cracking, sampling device comprises the sample cup and the control knob that are used to hold testing sample, control system is connected with electric furnace and is used to control the temperature and time of electric furnace, it is characterized in that: be provided with a sample introduction product passage in the described sampling device, it is perpendicular to the surface level setting.
2. heat cracker as claimed in claim 1 is characterized in that: the indoor layer of described thermal cracking is tapered quartz or glass tube.
3. heat cracker as claimed in claim 1 is characterized in that: described electric furnace adopts the direct current heating, and temperature controlling range is 300-1000 degree centigrade.
4. heat cracker as claimed in claim 1 is characterized in that: be provided with the cooling gas circuit and be used to cool off this electric furnace on described electric furnace.
5. thermal cracking gas chromatography instrument that adopts heat cracker as claimed in claim 1, comprise capillary gas chromatographic column, data handling system, detecting device, data handling system and detecting device join, and it is characterized in that: the outlet of described heat cracker is connected with capillary gas chromatographic column.
6. thermal cracking gas chromatography instrument as claimed in claim 5; it is characterized in that: between heat cracker and capillary gas chromatographic column, be connected with guard column; be filled with in this post with capillary gas chromatographic column in identical filler, this guard column and chromatographic column coated outside have thermal insulation material.
7. thermal cracking gas chromatography instrument as claimed in claim 5 is characterized in that, described detecting device comprises following a kind of at least: flame ionization detector, thermal conductivity detector (TCD), electron capture detector, flame photometric detector (FPD), nitrogen phosphorous detector.
8. thermal cracking gas chromatography instrument as claimed in claim 5, it is characterized in that: described thermal cracking gas chromatography instrument also comprises an attemperator, be arranged on the exterior circumferential of described capillary gas chromatographic column and heat cracker interface channel, be used to make the temperature constant of capillary gas chromatographic column injection port.
9. thermal cracking gas chromatography instrument as claimed in claim 5, it is characterized in that: also comprise a back-blowing device, be connected the tail end of capillary gas chromatographic column, be arranged on the interface channel of capillary gas chromatographic column and detecting device, be used to control the switch of blowback air-flow.
10. a pyrolytic cracking analytical method that utilizes the described heat cracker gas chromatograph of claim 5 is characterized in that, this method may further comprise the steps:
Step 1, sample introduction: will contain sample vertical direction sample introduction in heat cracker of component to be measured, the sample process acceleration of gravity sample introduction that contains component to be measured is to the thermal cracking chamber;
Step 2, Pintsch process: contain behind the sample feeding of component to be measured thermal cracking, separate bringing the sample that contains component to be measured after this thermal cracking into the capillary gas chromatographic column under the carrying of gas of carrier gas through 300～1000 ℃;
Step 3, the detecting device analysis: detecting device will detect through the sample that contains component to be measured that separates, and generates chromatogram by the data handling system that connects that links to each other with detecting device;
Step 4, data analysis: content or the purity of calculating the component to be measured in the sample that contains component to be measured according to the analysis meter of chromatogram.
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| CN113512433A (en) * | 2021-07-26 | 2021-10-19 | 东南大学 | Biomass pyrolysis gasification real-time monitoring and particle temperature measuring device and method |
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| CN113945659A (en) * | 2021-10-13 | 2022-01-18 | 江苏天瑞仪器股份有限公司 | Gas path operation adjusting method for rapid thermal cracking RoHS detector |
| CN114199666A (en) * | 2021-11-22 | 2022-03-18 | 中国石油大学(北京) | Design, construction and debugging of efficient and controllable online microwave reaction system |
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| CN102721590A (en) * | 2012-06-28 | 2012-10-10 | 中国石油天然气股份有限公司 | Continuous lossless whole rock natural gas generation simulation method |
| CN107228789A (en) * | 2017-07-31 | 2017-10-03 | 郝东辉 | A kind of heat cracker and a kind of mercury analyzer with temperature measurement function |
| CN107228789B (en) * | 2017-07-31 | 2023-09-08 | 郝东辉 | Thermal cracker with temperature measurement function and mercury analyzer |
| CN110824026A (en) * | 2018-08-10 | 2020-02-21 | 中国石油化工股份有限公司 | Evaluation method of contact agent for heavy oil contact cracking |
| CN110824026B (en) * | 2018-08-10 | 2023-09-05 | 中国石油化工股份有限公司 | Evaluation method of contact agent for heavy oil contact cracking |
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| CN114199666A (en) * | 2021-11-22 | 2022-03-18 | 中国石油大学(北京) | Design, construction and debugging of efficient and controllable online microwave reaction system |
| CN114199666B (en) * | 2021-11-22 | 2023-08-15 | 中国石油大学(北京) | Design, construction and debugging of efficient and controllable online microwave reaction system |
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