CN113447394B - Complex organic mixture simulated distillation device and method based on thermogravimetric analyzer - Google Patents
Complex organic mixture simulated distillation device and method based on thermogravimetric analyzer Download PDFInfo
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Abstract
A complex organic mixture simulated distillation device and method based on a thermogravimetric analyzer comprises a crucible distillation kettle body and a crucible distillation kettle cover which are matched; the crucible distillation kettle cover comprises a cylindrical shell, a through hole column is arranged on the cylindrical shell, the cylindrical shell is communicated with the through hole column, and a first fixing ring is arranged on the outer wall of the bottom of the cylindrical shell; the crucible distillation kettle body is an inserted crucible distillation kettle body or a flat-bottom crucible distillation kettle body; the insert type crucible distillation kettle body or the flat bottom type crucible distillation kettle body is provided with a second fixed ring matched with the first fixed ring. The complex organic mixture is placed in a novel crucible distillation kettle, and a simulated distillation curve of the complex organic mixture is obtained by means of accurate temperature control and quality recording of a thermogravimetric analyzer. The method has the advantages of time and labor saving, small sample consumption, high accuracy and the like, and can be widely used for simulated distillation tests of petroleum, coal tar, biomass/oil shale pyrolysis oil, natural product extracts and the like.
Description
Technical Field
The invention relates to the field of detection of complex organic mixtures, in particular to a complex organic mixture simulated distillation device and method based on a thermogravimetric analyzer.
Background
The complex organic mixture has various kinds, and coal tar, petroleum, liquefied coal oil, organic solvent extraction oil of coal, biomass/oil shale pyrolysis oil, natural product extract and the like are common. They are generally composed of hundreds or even tens of thousands of organic compounds and are characterized by a broad molecular weight distribution. The method for separating the complex organic mixture comprises distillation, extraction, solvent extraction and the like. Distillation is most common in industrial applications.
Distillation is an important means for separating and distilling the enrichment fraction of the complex organic mixture, and is also the first step of extracting the organic compounds in the complex organic mixture, for example, the chemical in coal tar is firstly distilled to obtain the fraction enriched in the chemical, so that the chemical in the complex organic mixture can be effectively separated. In the petroleum crude oil processing process, the petroleum crude oil is separated into naphtha, gasoline, diesel oil fractions and the like by adopting a distillation method. In order to be able to accurately guide the industrial distillation processing of complex organic mixtures, it is first necessary to carry out distillation experiments on complex organic mixtures in a laboratory. At present, the most widely used distillation experiment for complex organic mixtures is the "determination of atmospheric distillation characteristics of Petroleum products". In addition, there is a crude oil simple distillation test method. Since light petroleum products contain mainly chain aliphatic hydrocarbons and small amounts of naphthenes, distillation tests generally follow a better linear relationship, and thus these assays are essentially feasible for distillation tests of light petroleum products, but are not attractive for use with more complex organic mixtures of heavy petroleum products, coal tar, natural products, biomass/oil shale pyrolysis oils, and coal liquefaction oils. Because of the more complex composition of these complex organic mixtures and the association, complexation between compounds, they generally contain aliphatic hydrocarbons, aromatic hydrocarbons, phenols and sulfur-and nitrogen-containing compounds. In addition, the number of compounds in these complex organic mixtures is thousands of, and the content of a single compound is very low.
The current method has the following problems: 1) The flask is too little in sample loading amount, and the component steam escape amount is limited when the complex organic mixture is distilled, so that the temperature fluctuation change is larger; 2) The design of the condensing tube is too long, and the distillate with larger distillation molecular weight can be condensed; 3) When the distillation amount and the distillation temperature are recorded in the test process, human factors are main error sources; 4) The process is complex, and the input manpower and material resources are large; 5) Volatile gases during testing can cause harm to the health of the tester and waste during testing can cause harm to the environment.
In order to solve the problems of the current methods. Patent CN110057924 a discloses a method for determining simulated distillation of coal tar gas chromatography. The method comprises the steps of distilling coal tar by using a chromatographic column under the temperature programming condition, and determining main components in the coal tar by measuring the retention time of a single-component standard sample; the temperature cut ranges of the components in the coal tar are used to define the limits of each component in the chromatogram when the chromatogram simulates distillation. Compared with the existing distillation method, the method overcomes the defects of large sample consumption, long time consumption, fuzzy segmentation among components, low data accuracy and the like of the traditional distillation method. Gas chromatography is also used in the American ASTM D2887-2018 standard to simulate the distillation range of petroleum. The pressure in the gas chromatographic column is not normal pressure, so that the error of simulated distillation of the gas chromatograph is large. For complex oils such as heavy petroleum products, coal tar, natural products, biomass/oil shale pyrolysis oil and coal liquefaction oil, which have higher boiling points, higher viscosities and high content of polycyclic aromatic hydrocarbons, it is difficult to pass through the mobile phase in the standards of patent CN110057924 a and ASTM D2887-2018, while part of higher boiling point compounds remain in the stationary phase of the chromatographic column, jeopardizing the chromatographic column. Whereas for gasoline fractions having a boiling point below 60 c, the ASTM D2887-2018 standard has a major limitation. On the other hand, the standard curve used in the gas chromatography simulated distillation method is based on aliphatic, and the method using normal alkane as an external standard is not suitable for the boiling point determination of the aromatic hydrocarbon-rich oil.
Disclosure of Invention
The invention aims to overcome the defects of the existing distillation device and provide a complex organic mixture simulated distillation device with small sample consumption and high accuracy based on a thermogravimetric analyzer.
The invention further aims to provide a time-saving, labor-saving, accurate and convenient method for carrying out simulated distillation on a complex organic mixture based on a thermogravimetric analyzer, so as to overcome the problems of low accuracy, time and labor consumption, health hazard and environmental pollution existing in the traditional distillation method of the complex organic mixture, and the defects of the traditional method for determining the boiling point range distribution of the complex organic mixture by using gas chromatography simulated distillation.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a complex organic mixture simulated distillation device based on a thermogravimetric analyzer comprises a crucible distillation kettle body and a crucible distillation kettle cover which are matched;
the crucible distillation kettle cover comprises a cylindrical shell, a through hole column is arranged on the cylindrical shell, the cylindrical shell is communicated with the through hole column, and a first fixing ring is arranged on the outer wall of the bottom of the cylindrical shell;
the crucible distillation kettle body is an inserted crucible distillation kettle body or a flat-bottom crucible distillation kettle body; the insert type crucible distillation kettle body or the flat bottom type crucible distillation kettle body is provided with a second fixed ring matched with the first fixed ring.
The invention is further improved in that the outer diameter of the through hole column is 4mm, and the wall thickness is 0.5-1.5 mm; the diameter of the cylindrical shell is 6-12 mm, the height of the cylindrical shell is 5mm, the inner cavity is formed in the cylindrical shell, and the inner diameter of the bottom of the inner cavity is 4-10 mm.
The invention is further improved in that the outer wall of the upper end of the cylindrical shell is subjected to chamfering treatment, and the cylindrical shell and the through hole column are in natural transition.
The invention is further improved in that the diameter of the cylindrical shell of the first fixing ring is 4-11 mm, the height is 1mm, and the thickness is 0.5-1.0 mm.
When the crucible distillation kettle body is an inserted crucible distillation kettle body, the crucible distillation kettle body comprises an upper cylindrical shell and a lower cylindrical shell which are communicated, a reducing transition section is arranged between the upper cylindrical shell and the lower cylindrical shell, a baffle is arranged in the reducing transition section, and a second fixing ring is arranged on the inner wall of the top of the upper cylindrical shell.
The invention is further improved in that the diameter of the upper cylindrical shell is 6-12 mm, the height is 4.5-10 mm, and the wall thickness is 0.7-1.2 mm; the diameter of the lower cylindrical shell is 3-6 mm, the height is 3-6 mm, and the wall thickness is 0.7-1.2 mm; the diameter of the second fixing ring is 5-11 mm, the height is 1mm, and the thickness is 0.5mm.
When the crucible distillation kettle body is a flat-bottom type crucible distillation kettle body, the crucible distillation kettle body comprises a bottom plate, a cylindrical shell is arranged on the bottom plate, and a second fixing ring is arranged on the inner wall of the top of the cylindrical shell.
The invention is further improved in that the diameter of the cylindrical shell is 6-12 mm, the height is 4.5-10 mm, and the wall thickness is 0.7-1.2 mm; the diameter of the bottom plate is 6-12 mm, the height is 0.7-1.5 mm, the diameter of the second fixing ring is 5-11 mm, the height is 1mm, and the thickness is 0.5mm.
The invention is further improved in that the main body of the crucible distillation kettle and the cover of the crucible distillation kettle are made of alumina, zirconia or stainless steel; when the materials of the crucible distillation kettle body and the crucible distillation kettle cover are stainless steel, the surfaces of the crucible distillation kettle body and the crucible distillation kettle cover are subjected to passivation treatment.
A distillation method based on the device, comprising the following steps:
1) The empty crucible distillation kettle body and the crucible distillation kettle cover are arranged in a thermogravimetric analyzer after being mounted, and a blank group test is carried out to generate a blank base line;
2) Transferring the complex organic mixture into a crucible distillation kettle body, covering a crucible distillation kettle cover, and then testing the complex organic mixture by adopting a thermogravimetric analyzer and deducting a blank base line, wherein the temperature rise program of the thermogravimetric analyzer is the same as the temperature rise program used by the blank base line;
3) Obtaining a complex organic mixture simulated distillation curve after testing, and calculating distillation characteristic parameters according to the distillation curve;
wherein, the temperature program when the blank group test and the thermogravimetric analyzer are used for testing the complex organic mixture is: raising the temperature to 35-210 ℃ at 1-10 ℃/min, and initially waiting for 0-30 min; raising the temperature to 210-230 ℃ at 1-10 ℃/min, and staying for 0-10 min; raising the temperature to 230-300 ℃ at 1-10 ℃/min, and staying for 0-10 min; heating to 300-330 ℃ at 1-10 ℃/min, and staying for 0-10 min; heating to 330-360 ℃ at 1-10 ℃/min, and staying for 0-10 min; heating to 360-400 ℃ at 1-10 ℃/min, and staying for 0-10 min; heating to 400 ℃ at 1-10 ℃/min, and staying for 0-10 min.
Compared with the prior art, the invention has the beneficial effects that: the invention can rapidly, simply, accurately and efficiently acquire the distillation curve and the distillation characteristic parameters, solves the problems of low accuracy, time and labor consumption, health hazard and environmental pollution of the traditional distillation device, and has the following advantages:
compared with a distillation flask used in the traditional method, the device reduces the design of an industrial distillation tower, is more similar to and meets the operation requirement of industrial distillation; the distillation crucible cover designed by the device is provided with the through hole column with a certain height, has a certain reflux effect, can play a certain degree of rectification effect, and the longer the through hole column is, the better the rectification effect is, and the different types of distillation crucible covers can be selected according to the complexity degree of the organic mixture; through setting up first solid fixed ring and second solid fixed ring, make crucible distillation cauldron main part and the tight combination of cauldron lid, prevent to produce relative displacement in the measurement process, can reduce the fluctuation of simulated distillation curve.
The method is operated based on the thermogravimetric analyzer, automatically records data after the experiment is started, and is free from being attended by an experimenter, so that the method has the advantages of time and labor saving, small sample consumption, high accuracy and relatively environmental friendliness; the method has lower requirements on samples, can test complex organic mixtures which are high-viscosity liquid and solid at normal temperature, and can be widely used for simulated distillation of petroleum, coal tar, biomass/oil shale pyrolysis oil and natural product extracts.
Drawings
Fig. 1 is a schematic structural diagram of a simulated distillation apparatus according to an embodiment of the present invention. Wherein, (a) is example 1; (b) is example 2; (c) is example 3; (d) is example 4; (e) is example 5; (f) is example 6 and example 7;
FIG. 2 is a schematic diagram of a simulated distillation apparatus according to an embodiment of the present invention. Wherein, (a) is example 1; (b) is example 2; (c) is example 3; (d) is example 4; (e) is example 5; (f) is example 6 and example 7;
FIG. 3 is a graph of simulated distillation of low temperature coal tar in example 1;
FIG. 4 is a graph of simulated distillation of petroleum in example 2;
FIG. 5 is a graph of simulated distillation of biomass pyrolysis oil in example 3;
FIG. 6 is a graph of simulated distillation of low temperature coal tar in example 4;
FIG. 7 is a graph of simulated distillation of petroleum in example 5;
FIG. 8 is a graph of simulated distillation of biomass pyrolysis oil in example 6;
FIG. 9 is a graph of simulated distillation of biomass pyrolysis oil in example 7;
FIG. 10 is a graph of medium and low temperature coal tar TG performed directly with a hot 70. Mu.L crucible.
In the figure, 1 is a crucible distillation kettle cover, and 2 is a crucible distillation kettle main body.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is widely applicable to complex organic mixtures such as: simulated distillation of petroleum, coal tar, biomass/oil shale pyrolysis oil and natural product extracts.
A complex organic mixture simulated distillation apparatus based on a thermogravimetric analyzer, comprising: a crucible distillation kettle body 2 and a crucible distillation kettle cover 1; the crucible distillation kettle cover 1 is of a cover structure with a through hole column, and the through hole column is used for communicating the inner cavity of the crucible distillation kettle main body 2 with the outside; the outer diameters of the crucible distillation kettle body 2 and the crucible distillation kettle cover 1 are the same.
The crucible distillation kettle cover 1 comprises a cylindrical shell, a through hole column is arranged on the cylindrical shell, the cylindrical shell is communicated with the through hole column, and the outer diameter of the through hole column is
The wall thickness is 0.5-1.5 mm; the diameter of the cylindrical shell is
The height is 5mm, the inside of the shell structure is an inner cavity, the inner diameter of the bottom of the inner cavity is 4-10 mm, the outer wall of the upper end of the cylindrical shell is subjected to chamfering treatment, and the cylindrical shell and the through hole column are in natural transition; wherein, the outer wall of the bottom of the cylindrical shell is provided with a diameter of +.>
A first height of 1mm and a thickness of (0.5-1.0) mmAnd a fixing ring.
The crucible distillation kettle body 2 is an inserted crucible distillation kettle body or a flat-bottom crucible distillation kettle body; when the crucible distillation still body 2 is an inserted crucible distillation still body, the crucible distillation still body 2 is of a variable-diameter cylinder structure with openings at the upper end and the lower end, and when the crucible distillation still body 2 is a flat-bottom crucible distillation still body, the crucible distillation still body 2 is of a cylinder structure with an opening at the upper end and a closed bottom.
Further, when the main body 2 of the crucible distillation still has a diameter-variable cylinder structure with openings at the upper end and the lower end, the main body 2 of the crucible distillation still comprises an upper cylinder shell and a lower cylinder shell which are communicated, and the diameter of the upper cylinder shell is that
The height is 4.5-10 mm, and the wall thickness is 0.7-1.2 mm; the diameter of the lower cylindrical shell is +.>
The height is (3-6) mm, and the wall thickness is 0.7-1.2 mm; when the diameters of the upper cylindrical shell and the lower cylindrical shell are different, the upper cylindrical shell and the lower cylindrical shell are in variable-diameter transition through a variable-diameter transition section, and the transition height section is 1-4 mm; a baffle plate with the diameter of 1-2 mm is arranged in the reducing transition section to separate the upper cylindrical shell from the lower cylindrical shell of the main body of the crucible distillation kettle; wherein the inner wall of the top of the upper cylindrical shell is provided with a diameter of +>
And the height is 1mm, the thickness is 0.5mm, and the second fixing ring is used for arranging the crucible distillation kettle cover 1.
Further, when the main body 2 of the crucible distillation still has a cylindrical structure with an open upper end and a closed bottom, the main body 1 of the crucible distillation still comprises a bottom plate, a cylindrical shell is arranged on the bottom plate, and the diameter of the cylindrical shell is
The height is (4.5-10) mm, and the wall thickness is 0.7-1.2 mm; the diameter of the bottom plate is->
The height is (0.7-1.5) mm, wherein the inner wall of the top of the cylindrical shell is provided with a diameter of +.>
A second fixing ring with the height of 1mm and the thickness of 0.5mm.
The crucible distillation kettle body and the kettle cover are tightly combined through the first fixing ring and the second fixing ring, so that relative displacement is prevented in the measurement process, and fluctuation of a simulated distillation curve can be reduced.
Further, the crucible distillation kettle cover has various different sizes, the difference is that the heights of the upper through hole columns are different, and the heights can be designed to be 5-50mm and the like according to the requirements; different sizes, and volumes of 50 mu L-200 mu L and other specifications; wall thickness is different, etc.
Further, the main body of the crucible distillation kettle and the cover of the crucible distillation kettle are made of high-purity alumina, zirconia or 310s stainless steel.
Further, if 310s stainless steel is selected, the surface passivation treatment is performed.
A complex organic mixture simulated distillation determination method based on a thermogravimetric analyzer comprises the following steps:
1) The empty crucible distillation kettle body and the crucible distillation kettle cover are arranged in a thermogravimetric analyzer after being mounted, and a blank group test is carried out to generate a blank base line; wherein the temperature raising program is as follows: raising the temperature to 35-210 ℃ at 1-10 ℃/min, and initially waiting for 0-30 min; raising the temperature to 210-230 ℃ at 1-10 ℃/min, and staying for 0-10 min; raising the temperature to 230-300 ℃ at 1-10 ℃/min, and staying for 0-10 min; heating to 300-330 ℃ at 1-10 ℃/min, and staying for 0-10 min; heating to 330-360 ℃ at 1-10 ℃/min, and staying for 0-10 min; heating to 360-400 ℃ at 1-10 ℃/min, and staying for 0-10 min; heating to 400 ℃ at 1-10 ℃/min, and staying for 0-10 min;
2) Uniformly sampling and dehydrating the complex organic mixture to be tested; if the experiment is not started immediately after the sample preparation is completed, direct sunlight and a heat source are avoided, and the sample is well preserved;
3) Accurately weighing 5-10 mg of processed sample, transferring into a main body of a crucible distillation kettle, and after capping, testing the complex organic mixture by adopting a thermogravimetric analyzer and deducting a blank base line, wherein the temperature rise program of the thermogravimetric analyzer is the same as the temperature rise program used by the blank base line;
4) And obtaining a simulated distillation curve of the complex organic mixture after the test, and calculating corresponding distillation characteristic parameters according to the distillation curve.
Example 1
The upper part of a crucible distillation kettle cover which is matched with a crucible with the thermal weight of 70 mu L is the outer diameter
A through hole cylinder structure with the wall thickness of 1mm, wherein the height of the through hole cylinder is 5mm; lower dimension->
The inner cavity is of a shell structure, the diameter of the bottom of the inner cavity is 4.4mm, the upper end of the outer wall of the lower part is subjected to chamfering treatment, and the upper part and the lower part are naturally transited; wherein the outer wall of the bottom of the crucible distillation kettle cover is provided with a diameter of +.>
Rings 1mm high and 0.8mm thick.
The experimental raw materials are medium-low temperature coal tar, and anhydrous sodium sulfate is used for dehydration.
The TG device was an STA449F3 thermogravimetric analyzer (Netzsch, germany); the method comprises the steps of adopting a 70 mu L crucible, not loading samples, loading a distillation kettle cover matched with the crucible with the thermal weight of 70 mu L onto the crucible, and measuring a blank baseline and N 2 As a protective gas and a reaction gas, wherein the protective gas flow is 20mL/min, and the reaction gas flow is 30mL/min;
heating program: raising the temperature to 35 ℃ at 5 ℃/min, and initially waiting for 10min; then raising the temperature to 210 ℃ at 10 ℃/min, and staying for 0min; raising the temperature to 230 ℃ at 10 ℃/min, and staying for 0min; heating to 300 ℃ at 10 ℃/min, and staying for 0min; heating to 330 ℃ at 10 ℃/min, and staying for 0min; heating to 360 ℃ at 10 ℃/min, and staying for 0min; heating to 400 ℃ at 10 ℃/min, and staying for 0min;
a70 mu L crucible is adopted, 10mg of dehydrated raw oil is filled in the crucible, a distillation kettle cover matched with the crucible with the thermal weight of 70 mu L is arranged on the crucible, a blank base line is loaded, and a simulated distillation experiment is carried out under the same conditions and a temperature-raising program. The subsequent same crucible distillation still and temperature programming experiment can share the same blank base line, and the blank base line has the effective period of 30 days.
The simulated distillation curve obtained is shown in figure 3.
Example 2
In example 2, the through-hole column of the distillation still cover matched with the crucible with the thermal weight of 70 mu L is 10mm, the experimental raw material is petroleum, and the rest conditions are the same as those of example 1. The simulated distillation curve obtained is shown in figure 4.
Example 3
In example 3, the through-hole column of the distillation still cover matched with the crucible with the thermal weight of 70 mu L is 15mm, the experimental raw material is biomass pyrolysis oil, and the rest conditions are the same as those in example 1. The simulated distillation curve obtained is shown in figure 5.
Example 4
The size of the upper end of the main body of the crucible distillation kettle is
The wall thickness is 1mm; the size of the lower end of the main body of the crucible distillation kettle is
The wall thickness is 1mm; the upper end and the lower end of the main body of the crucible distillation kettle are in diameter-variable transition, and the height is 3mm; a baffle plate with the diameter of 1.5mm is arranged in the reducing transition to separate the upper end and the lower end of the main body of the crucible distillation kettle; wherein, the inner wall of the top of the main body of the crucible distillation kettle is provided with one
Rings 0.5mm thick. The upper part of the crucible distillation kettle cover is provided with an outer diameter +.>
A through hole cylinder structure with the wall thickness of 1mm; lower dimension->
The inner cavity is of a shell structure, the diameter of the bottom of the inner cavity is 6mm, the upper end of the outer wall of the lower part is subjected to chamfering treatment, and the upper part and the lower part are naturally transited; wherein, the outer wall of the bottom of the crucible distillation kettle cover is provided with a +.>
A ring of 0.5mm thickness and an upper through-hole column height of 5mm.
The experimental raw materials are medium-low temperature coal tar, and anhydrous sodium sulfate is used for dehydration.
The TG device was an STA449F3 thermogravimetric analyzer (Netzsch, germany); the crucible distillation still is adopted, the sample is not loaded, the crucible distillation still cover is loaded on the crucible, the blank baseline measurement is carried out, and N is N 2 As a protective gas and a reaction gas, wherein the protective gas flow is 20mL/min, and the reaction gas flow is 30mL/min;
heating program: raising the temperature to 35 ℃ at 5 ℃/min, and initially waiting for 10min; raising the temperature to 210 ℃ at 5 ℃/min, and staying for 1min; raising the temperature to 230 ℃ at 5 ℃/min, and staying for 1min; heating to 300 ℃ at 5 ℃/min, and staying for 1min; heating to 330 ℃ at 5 ℃/min, and staying for 1min; heating to 360 ℃ at 5 ℃/min, and staying for 1min; heating to 400 ℃ at 5 ℃/min, and staying for 1min.
The crucible distillation still is adopted, 10mg of dehydrated raw oil is filled in the crucible distillation still, a crucible distillation still cover is arranged on the crucible distillation still, a blank base line is loaded, and a simulated distillation experiment is carried out under the same conditions and with the same temperature rise program. The subsequent same crucible distillation still and temperature programming experiment can share the same blank base line, and the blank base line has the effective period of 30 days.
The simulated distillation curve obtained is shown in figure 6.
Example 5
In example 5, the through-hole column of the crucible distillation kettle cover of the invention is 10mm, the experimental raw material is petroleum, and the other conditions are the same as those of example 4. The simulated distillation curve obtained is shown in figure 7.
Example 6
In example 6, the through hole column of the crucible distillation kettle cover of the invention is 15mm, the experimental raw material is biomass pyrolysis oil, and the rest conditions are the same as those of example 4. The simulated distillation curve obtained is shown in figure 8.
Example 7
In example 6, the through hole column of the crucible distillation kettle cover is 15mm, and the experimental raw material is coal tar heavy oil. Heating program: raising the temperature to 35 ℃ at 5 ℃/min, and initially waiting for 10min; raising the temperature to 210 ℃ at 5 ℃/min, and staying for 1min; raising the temperature to 230 ℃ at 5 ℃/min, and staying for 1min; heating to 300 ℃ at 5 ℃/min, and staying for 1min; heating to 330 ℃ at 5 ℃/min, and staying for 1min; heating to 360 ℃ at 5 ℃/min, and staying for 1min. The other conditions were the same as in example 4. The simulated distillation curve obtained is shown in figure 9.
Calculation method
In the method, the medium and low temperature coal tar, petroleum, biomass pyrolysis oil and coal tar heavy oil are taken as examples, the weight loss is calculated according to a distillation curve, and finally, the accurate distillation characteristic parameters of the complex organic mixture are obtained, and 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% and a dry point are respectively selected as characteristic weight loss points, the temperature of the corresponding weight loss point is recorded, wherein the dry point is the temperature at which the mass of a corresponding sample is not obviously reduced after differentiating the distillation curve, and the inflection point of the differential curve is obtained.
According to the invention, the TG is fully utilized, so that the quality change characteristic of the sample in the temperature rising process can be rapidly analyzed, the thermal weight loss is obtained, and the distillation weight loss condition of the sample under the temperature rising program is accurately judged.
The characteristic parameters of examples 1-7 obtained according to FIGS. 3-9 are shown in Table 1.
TABLE 1 simulation distillation characteristic parameters of complex organic mixtures based on thermogravimetric analyzer examples 1-7
For further judgment, a distillation experiment of national standard GB/T6536-2010 "determination of atmospheric distillation characteristics of Petroleum products" was performed on a part of the complex organic mixture. Meanwhile, in order to judge the complex organic mixture measured by the national standard GB/T6536-2010 petroleum product atmospheric distillation characteristic measurement method and the measurement result of the method, GC-MS component detection is carried out on part of the complex organic mixture.
The contents of the medium-low temperature coal tar components used in example 1 are shown in Table 2. The results of the atmospheric distillation characteristics of the medium and low temperature coal tar, petroleum and biomass pyrolysis oil products are shown in Table 3.
Table 2 Low temperature coal tar GC-MS composition Table (greater than 0.5%)
Table 3 atmospheric distillation characteristics of low temperature coal tar, petroleum and biomass pyrolysis oil
By comparing the simulated distillation results of the inventive examples in Table 1 with the atmospheric distillation characteristics of the complex organic mixtures in Table 3, in combination with the GC-MS composition table in Table 2, it can be seen that the data obtained by the inventive examples are more accurate and more consistent with the boiling point ranges of the components. Whereas conventional atmospheric distillation methods are difficult to accommodate for complex organic mixtures and do not provide for good separation of some components, e.g. the sample contains a certain amount of low boiling compounds, the results of conventional methods are not shown, but the corresponding areas can be found in the simulated distillation curve obtained in the present invention. According to the invention, the simulated distillation of various complex organic mixtures can be realized by changing the height of the through hole column of the crucible distillation kettle cover. Meanwhile, by comparing fig. 10 and fig. 3, it can be found that the common TG experiment, due to the large contact area with the air flow and the lack of the designed crucible distillation kettle cover of the present invention, the lack of the characteristics of separating components and simulating distillation, the obtained data deviate from the actual results.
The simulated distillation of the complex organic mixture of the method is carried out in a novel crucible distillation kettle for a designed thermogravimetric analyzer. The novel crucible distillation kettle completely reduces the design of an industrial distillation tower. The complex organic mixture is placed in a novel crucible distillation kettle, and a simulated distillation curve of the complex organic mixture is obtained by means of accurate temperature control and quality recording of a thermogravimetric analyzer. The method has the advantages of time and labor saving, small sample consumption, high accuracy and the like, and can be widely used for simulated distillation tests of petroleum, coal tar, biomass/oil shale pyrolysis oil, natural product extracts and the like.
The method can simulate distillation of complex organic mixture, has certain value for guiding industrial production, has scientific and reasonable design, simple and easy processing and good use effect, and has high popularization value and wide application prospect.
Claims (6)
1. The complex organic mixture simulated distillation device based on the thermogravimetric analyzer is characterized by comprising a crucible distillation kettle body (2) and a crucible distillation kettle cover (1) which are matched;
the crucible distillation kettle cover (1) comprises a cylindrical shell, a through hole column is arranged on the cylindrical shell, the cylindrical shell is communicated with the through hole column, and a first fixing ring is arranged on the outer wall of the bottom of the cylindrical shell;
the crucible distillation kettle body (2) is an inserted crucible distillation kettle body or a flat-bottom crucible distillation kettle body; the insert type crucible distillation kettle body or the flat bottom type crucible distillation kettle body is provided with a second fixed ring matched with the first fixed ring;
when the crucible distillation kettle main body (2) is a plug-in type crucible distillation kettle main body, the crucible distillation kettle main body (2) comprises an upper cylindrical shell and a lower cylindrical shell which are communicated, a reducing transition section is arranged between the upper cylindrical shell and the lower cylindrical shell, a baffle is arranged in the reducing transition section, and a second fixing ring is arranged on the inner wall of the top of the upper cylindrical shell; the second fixed ring is used for setting a crucible distillation kettle cover (1);
when the crucible distillation kettle main body (2) is a flat-bottom crucible distillation kettle main body, the crucible distillation kettle main body (2) comprises a bottom plate, a cylindrical shell is arranged on the bottom plate, and a second fixing ring is arranged on the inner wall of the top of the cylindrical shell;
the height of the through hole column with the same outer diameter of the crucible distillation kettle main body (2) and the crucible distillation kettle cover (1) is 5-50mm;
chamfering the outer wall of the upper end of the cylindrical shell, and naturally transiting between the cylindrical shell and the through hole column;
the main body of the crucible distillation kettle and the cover of the crucible distillation kettle are made of alumina, zirconia or stainless steel; when the materials of the crucible distillation kettle body and the crucible distillation kettle cover are stainless steel, passivating the surfaces of the crucible distillation kettle body and the crucible distillation kettle cover;
the distillation crucible cover is provided with a through hole column with a certain height, has a certain reflux effect, plays a certain degree of rectification effect, and the longer the through hole column is, the better the rectification effect is.
2. The complex organic mixture simulated distillation apparatus based on a thermogravimetric analyzer as claimed in claim 1, wherein the through-hole column has an outer diameter of 4mm and a wall thickness of 0.5 to 1.5mm; the diameter of the cylindrical shell is 6-12 mm, the height of the cylindrical shell is 5mm, the inner cavity is formed in the cylindrical shell, and the inner diameter of the bottom of the inner cavity is 4-10 mm.
3. The device of claim 1, wherein the first stationary ring cylindrical shell has a diameter of 4-11 mm, a height of 1mm, and a thickness of 0.5-1.0 mm.
4. The device for simulated distillation of complex organic mixture based on thermogravimetric analyzer as claimed in claim 1, wherein said upper cylindrical shell has a diameter of 6-12 mm, a height of 4.5-10 mm and a wall thickness of 0.7-1.2 mm; the diameter of the lower cylindrical shell is 3-6 mm, the height is 3-6 mm, and the wall thickness is 0.7-1.2 mm; the diameter of the second fixing ring is 5-11 mm, the height is 1mm, and the thickness is 0.5mm.
5. The complex organic mixture simulated distillation apparatus based on a thermogravimetric analyzer as claimed in claim 1, wherein the diameter of the cylindrical shell is 6-12 mm, the height is 4.5-10 mm, and the wall thickness is 0.7-1.2 mm; the diameter of the bottom plate is 6-12 mm, the height is 0.7-1.5 mm, the diameter of the second fixing ring is 5-11 mm, the height is 1mm, and the thickness is 0.5mm.
6. A distillation method based on the apparatus according to any one of claims 1-5, characterized by comprising the steps of:
1) The empty crucible distillation kettle body and the crucible distillation kettle cover are arranged in a thermogravimetric analyzer after being mounted, and a blank group test is carried out to generate a blank base line;
2) Transferring the complex organic mixture into a crucible distillation kettle body, covering a crucible distillation kettle cover, and then testing the complex organic mixture by adopting a thermogravimetric analyzer and deducting a blank base line, wherein the temperature rise program of the thermogravimetric analyzer is the same as the temperature rise program used by the blank base line;
3) Obtaining a complex organic mixture simulated distillation curve after testing, and calculating distillation characteristic parameters according to the distillation curve;
wherein, the temperature program when the blank group test and the thermogravimetric analyzer are used for testing the complex organic mixture is: raising the temperature to 35-210 ℃ at 1-10 ℃/min, and initially waiting for 0-30 min; raising the temperature to 210-230 ℃ at 1-10 ℃/min, and staying for 0-10 min; raising the temperature to 230-300 ℃ at 1-10 ℃/min, and staying for 0-10 min; heating to 300-330 ℃ at 1-10 ℃/min, and staying for 0-10 min; heating to 330-360 ℃ at 1-10 ℃/min, and staying for 0-10 min; heating to 360-400 ℃ at 1-10 ℃/min, and staying for 0-10 min; heating to 400 ℃ at 1-10 ℃/min, and staying for 0-10 min.
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