CN112986295B - X-ray fluorescence spectrometry pressed sample for asphalt and sample preparation method thereof - Google Patents
X-ray fluorescence spectrometry pressed sample for asphalt and sample preparation method thereof Download PDFInfo
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Abstract
The application provides an X-ray fluorescence spectrometry pressed sample for asphalt, which aims to solve the technical problems of low sample preparation efficiency, difficult cleaning of grinding equipment and high equipment loss risk of the existing asphalt impurity component determination method, and belongs to the field of asphalt impurity component analysis and detection. The pressed sample is convenient to manufacture and high in efficiency, and can not pollute or damage detection equipment in the detection process, so that the efficiency of measuring the asphalt impurity components is effectively improved, and the cost of measuring the asphalt impurity components is reduced. The application also provides a sample preparation method for the X-ray fluorescence spectrometry pressed sample of asphalt.
Description
Technical Field
The application belongs to the field of asphalt impurity component analysis and detection, and particularly relates to an X-ray fluorescence spectrometry pressed sample for asphalt and a sample preparation method thereof.
Background
Asphalt is a black brown mixture composed of hydrocarbon compounds with different molecular weights and derivatives thereof, is an organic cementing material with high viscosity, and has wide application in building materials, road construction, plastics, rubber and carbon industries. Graphite electrodes used in the steel industry, electrolytic cell cathodes used in the aluminum industry and prebaked anodes all need coal pitch as a binder and an impregnant; coal pitch is also a raw material for producing pitch coke, and pitch coke which is easy to graphitize is also an important raw material for artificial graphite; besides, asphalt is widely used as a raw material for producing asphalt-based carbon fibers and asphalt plastics.
In asphalt application, the content of metal impurity elements except carbon, hydrogen, oxygen and nitrogen is an important aspect of attention, because the electrochemical consumption of carbon electrodes can be promoted, the physical performance of the asphalt is reduced, the physical performance of the asphalt is harmful impurities, related products have index requirements of the content of the impurity metal elements, and meanwhile, limit requirements of heavy metal elements of the asphalt are set due to environmental protection or health factors, so that the content of the impurity metal elements in the asphalt has stricter control requirements in the fields of electrode production, carbon manufacturing for aluminum, graphite or asphalt plastic production and the like, and therefore, the determination of the impurity elements in the asphalt is an important work.
Currently, the method for measuring the asphalt impurity elements mainly comprises an inductively coupled plasma emission spectrometry (ICP-AES method) and an X-ray fluorescence spectrometry (XRF method). Inductively coupled plasma emission spectrometry measurement belongs to wet chemistry analysis: ma Liangbang and Ge Ying are used for measuring trace impurity metal elements in the solid asphalt by using an ICP-AES method, wang Hao, zhang Ying and the like are used for measuring elements such as calcium, iron, sodium, nickel, vanadium and the like in the petroleum asphalt by using the ICP-AES method, and Zhang Ning is used for measuring 6 elements such as silicon, sodium, calcium, vanadium, iron, nickel and the like in the coal asphalt by using the ICP-AES method. In wet chemical measurement, volatile matters are required to be removed at a low temperature (about 200 ℃) in advance for preventing loss caused by asphalt boiling, ash treatment is required to be carried out at 800-1000 ℃, acid-base dissolution (or melting) is required to be carried out on ash, the ash treatment is required to consume 4-8 hours, more than 1 hour is required for the post-treatment and standing process of acid dissolution, and more than 6 hours is required for the overall pretreatment; the asphalt processed by the microwave digestion technology is not easy to be completely decomposed, if black slag remains, suspension is easy to be formed, and suspension injection has great pollution to equipment, equipment is easy to be damaged, and the measurement accuracy is influenced; meanwhile, the sample weighing amount of the method is about 0.5g, on one hand, the asphalt has poor uniformity and is not representative, in addition, the asphalt impurity content is low, and the operation of low sample weighing amount greatly reduces the concentration of the solution, so that part of elements are lower than the detection limit of equipment.
The method for measuring the asphalt by using the X-ray fluorescence spectrometry belongs to direct and rapid analysis, but is reported and less at present, zhang Aifen, ma Huixia and the like are used for measuring trace elements in the asphalt by using the X-ray fluorescence spectrometry, and manual grinding is adopted for direct tabletting measurement, but in the sample grinding process, the conditions that the asphalt is seriously adhered to a mortar and a grinding rod are unavoidable, and the asphalt is required to be cleaned for many times, so that the cleaning is difficult, meanwhile, in the XRF measurement, the accident that the asphalt pollutes and damages a light pipe is very easy to occur, the current industry has a plurality of examples that the asphalt damages the light pipe due to the measurement, and the price of the X-ray light pipe is generally more than 30 ten thousand, which is also an important reason that the current XRF measurement of the impurity elements of the asphalt is not widely popularized and applied.
Disclosure of Invention
In order to solve the technical problems of low sample preparation efficiency, difficult cleaning of detection equipment and high equipment loss risk of the existing asphalt impurity component determination method, the application provides an X-ray fluorescence spectrum determination pressed sample for asphalt, which is convenient to manufacture and high in efficiency, and can not pollute or damage detection equipment in the detection process, so that the asphalt impurity component determination efficiency is effectively improved, and the asphalt impurity component determination cost is reduced.
The application also provides a sample preparation method for the X-ray fluorescence spectrometry pressed sample of asphalt.
The application is realized by the following technical scheme:
the application provides an X-ray fluorescence spectrometry tabletting sample of asphalt, which comprises an additive and asphalt, wherein the mass ratio of the additive to the asphalt is more than or equal to 1/5, and the additive comprises at least one of boric acid, lithium carbonate, lithium boron compound, high molecular hydrocarbon compound and high molecular carbohydrate.
Preferably, the mass ratio of the additive to the asphalt is 1/5-5.
Optionally, the lithium boron compound includes at least one of lithium borate, lithium tetraborate, and lithium metaborate.
Optionally, the high molecular hydrocarbon compound comprises at least one of polyethylene, polyvinyl chloride, polyvinylidene fluoride powder, polypropylene powder and polystyrene.
Optionally, the high molecular carbohydrate includes at least one of starch, methylcellulose, and natural rubber. Optionally, the asphalt comprises at least one of coal asphalt, petroleum asphalt, natural asphalt, wood asphalt, shale asphalt, and artificially modified asphalt.
A method for preparing a pressed sample by X-ray fluorescence spectrometry of asphalt, the method comprising:
mixing and grinding the additive and asphalt to obtain a mixture;
tabletting the mixture to obtain a tabletting sample;
wherein the mass ratio of the additive to the asphalt is more than or equal to 1/5;
the additive comprises at least one of boric acid, lithium carbonate, lithium boron compound, high molecular hydrocarbon compound and high molecular carbohydrate.
Optionally, the lithium boron compound comprises at least one of lithium borate, lithium tetraborate, and lithium metaborate;
the high molecular hydrocarbon compound comprises at least one of polyethylene, polyvinyl chloride, polyvinylidene fluoride powder, polypropylene powder and polystyrene.
The high molecular carbohydrate includes at least one of starch, methylcellulose and natural rubber.
Optionally, the mixing and grinding the additive and the asphalt to obtain a mixture specifically comprises:
mixing and grinding the additive and asphalt to obtain the mixture with the particle size of 0.1-3.0 mm.
Optionally, the step of tabletting the mixture to obtain a tabletting sample specifically includes:
tabletting the mixture to obtain a tabletting sample;
wherein, the way of the tabletting is any one of direct tabletting, powder cushion bottom tabletting and nested tabletting;
the powder material of the powder cushion bottom tablet comprises at least one of boric acid, polyethylene, lithium borate, lithium metaborate, starch and methyl cellulose;
the nesting material of the nesting tablet comprises any one of a plastic ring, a metal ring and a metal sleeve disk.
One or more technical schemes of the application have at least the following technical effects or advantages:
1. according to the X-ray fluorescence spectrometry pressed sample for asphalt, the additive is added into the pressed sample for asphalt, the addition of the additive with high melting point can raise the softening point of asphalt from 45 ℃ to 110 ℃ to above 110 ℃, so that the phenomenon that the pressed sample for asphalt is melted after being irradiated by X-rays in an optical chamber for 5min to 10min to cause pollution damage accidents of light pipes in XRF measurement is avoided, and huge property loss is avoided; therefore, the pressed sample disclosed by the application is convenient to prepare, high in efficiency, and free from polluting or damaging detection equipment in the detection process, so that the efficiency of measuring the asphalt impurity components is effectively improved, and the cost of measuring the asphalt impurity components is reduced.
2. According to the X-ray fluorescence spectrometry pressed sample for asphalt, the mass ratio of the additive of the pressed sample to the asphalt is more than or equal to 1/5, the bonding degree of the asphalt can be effectively reduced, the softening point of the asphalt can be improved, if the mass ratio of the additive to the asphalt is less than 1/5, the softening point of the pressed sample can not be ensured to be more than 110 ℃, the safety of XRF measurement of the pressed sample can not be ensured, and the additive can not be ensured to be at least one of boric acid, lithium carbonate, lithium boron compound, high molecular hydrocarbon compound and high molecular carbohydrate, so that the softening point of the pressed sample of the asphalt can be improved, and meanwhile, the additive can not interfere with the XRF measurement result of the asphalt.
3. According to the sample preparation method for the asphalt X-ray fluorescence spectrometry pressed sample, disclosed by the application, the additive is added in the asphalt sample preparation process for grinding, on one hand, the addition of the additive can reduce the asphalt bonding degree, is beneficial to grinding in the asphalt sample preparation process, improves the sample preparation efficiency, and simultaneously can overcome the problem that a mortar is not easy to clean after grinding, on the other hand, the addition of the additive with high melting point can raise the asphalt softening point from 45-110 ℃ to above 110 ℃, so that the asphalt pressed sample is prevented from being melted after being irradiated by X-rays in an optical room for 5-10 min during XRF (X-ray) measurement, and the light pipe pollution damage accident is caused, and further, huge property loss is avoided.
The foregoing description is only an overview of the present application, and is intended to be implemented in accordance with the teachings of the present application in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present application more readily apparent.
Drawings
In order to more clearly illustrate the technical solutions of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a sample preparation method of the present application;
FIG. 2 is an external view of the mixture according to example 3 of the present application;
FIG. 3 is an external view of a mixture prepared in comparative example 3 of the present application;
FIG. 4 is an external view showing a pressed sample obtained in example 3 of the present application after being placed in an oven at 110℃for 10 minutes;
FIG. 5 is an external view showing a pressed sample sheet obtained in comparative example 3 according to the present application after being placed in an oven at 110℃for 10 minutes.
Detailed Description
The advantages and various effects of the present application will be more clearly apparent from the following detailed description and examples. It will be understood by those skilled in the art that these specific embodiments and examples are intended to illustrate the application, not to limit the application.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In case of conflict, the present specification will control.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
It should be noted that in this document, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions.
The technical scheme provided by the application aims to solve the technical problems, and the general idea is as follows:
currently, in sample preparation for determining asphalt impurity components by an X-ray fluorescence spectrometry, manual grinding is generally adopted, and then direct tabletting is adopted for sample preparation, and the prepared sample is directly subjected to XRF determination. However, the sample has extremely high cohesiveness and serious cohesiveness, so that the mortar is not easy to clean, and meanwhile, the applicant discovers that in XRF measurement, a sample wafer needs to be irradiated by X-rays for 5-10 min in an optical chamber, the temperature can reach 70-100 ℃, the asphalt softening point is extremely low, asphalt is easy to melt for a long time, so that light pipe accidents are caused by pollution and damage, the price of an X-ray light pipe is generally more than 30 ten thousand, and the method is also an important reason that the impurity elements of the asphalt are not widely popularized and applied in the current XRF measurement.
The wet chemical determination of the impurity elements in asphalt is complex in operation, time-consuming and labor-consuming, and can not meet the timeliness requirement, and the conventional method for determining the impurity elements in asphalt by XRF damages an X-ray tube to cause huge property loss. In order to solve the problems, the application realizes rapid, safe and low-cost determination of asphalt impurity elements, and the conventional method for determining asphalt impurity elements based on XRF adds a high-melting-point additive into asphalt for mixed grinding in a tabletting sample preparation process, and the softening point of a sample sheet after mixed grinding is increased to be more than 110 ℃, so that the softening point of a sample prepared from asphalt is greatly increased. The application greatly enhances the safety degree of the XRF measurement of the asphalt sample, avoids huge property loss of a detection mechanism caused by melting of the asphalt sample, and simultaneously improves the application range of the XRF measurement, thereby bringing great convenience for product quality control, environmental protection and the like in the fields of electrode production, carbon manufacturing for aluminum, graphite or asphalt plastic production and the like.
According to an exemplary embodiment of the present application, there is provided an X-ray fluorescence spectrometry tableting sample of asphalt, the tableting sample comprising an additive and asphalt, the mass ratio of the additive to the asphalt being equal to or greater than 1/5, the additive comprising at least one of boric acid, lithium carbonate, a lithium boron compound, a high molecular hydrocarbon compound, and a high molecular carbohydrate.
According to the application, the additive is added into the asphalt tabletting sample, and the addition of the additive with high melting point can raise the asphalt softening point from 45-110 ℃ to above 110 ℃, so that the asphalt tabletting sample is prevented from melting after being irradiated by X-rays in a light room for 5-10 min in XRF measurement, the pollution damage accident of a light pipe is avoided, and huge property loss is further avoided, and on the other hand, the addition of the additive can reduce the bonding degree of asphalt, thereby being beneficial to grinding in the sample preparation process of the asphalt tabletting sample, improving the sample preparation efficiency and simultaneously overcoming the problem that a mortar is difficult to clean after grinding.
According to the application, the mass ratio of the additive to the asphalt of the tabletting sample is more than or equal to 1/5, the bonding degree of the asphalt can be effectively reduced, and the softening point of the asphalt can be improved, if the mass ratio of the additive to the asphalt is less than 1/5, the softening point of the tabletting sample can not be ensured to be more than 110 ℃, the safety of XRF measurement of the tabletting sample can not be ensured, and the additive can be at least one of boric acid, lithium carbonate, lithium boron compound, high molecular hydrocarbon compound and high molecular carbohydrate, so that the softening point of the asphalt tabletting sample can be improved, and the additive can be ensured not to interfere with the XRF measurement result of the asphalt.
As a preferred embodiment, the mass ratio of the additive to the asphalt is 1/5 to 5.
In the application, the mass ratio of the additive to the asphalt is preferably 1/5-5, which has the advantages that the application can meet the requirements of increasing the softening point of various asphalt sample pieces, and if the mass ratio is more than 5, the additive is wasted, and the excessive additive can dilute the concentration of impurity elements in the sample, thereby being unfavorable for XRF measurement.
As an alternative embodiment, the lithium boron compound includes at least one of lithium borate, lithium tetraborate, and lithium metaborate.
In the application, the lithium boron compound comprises at least one of lithium borate, lithium tetraborate and lithium metaborate, and the additive can also select boric acid and lithium carbonate, because the melting point of the compound is far higher than that of asphalt, the melting point and the bonding degree of asphalt can be obviously reduced after the compound is added, and the X fluorescence yields of constituent elements of boron, lithium, carbon, hydrogen and oxygen are extremely low, and the compound belongs to element types which cannot be measured by XRF, and the measurement of impurity components of asphalt is not influenced by the introduction of the compound.
As an alternative embodiment, the high molecular hydrocarbon compound includes at least one of polyethylene, polyvinyl chloride, polyvinylidene fluoride powder, polypropylene powder, and polystyrene.
In the application, the additive can be selected from polyethylene high molecular hydrocarbon compounds, the melting point of the high molecular hydrocarbon compounds is far higher than that of asphalt, the melting point and the bonding degree of the asphalt can be obviously reduced after the high molecular hydrocarbon compounds are added, the X fluorescence yields of constituent elements of carbon, hydrogen and oxygen are extremely low, the high molecular hydrocarbon compounds belong to element types which cannot be detected by XRF, and the detection of impurity components of the asphalt is not influenced by the introduction of the high molecular hydrocarbon compounds.
As an alternative embodiment, the high molecular carbohydrate includes at least one of starch, methyl cellulose, and natural rubber.
In the application, the additive can be selected from high molecular carbohydrates such as starch and methyl cellulose, because the melting point of the high molecular carbohydrates is far higher than that of asphalt, the melting point and the bonding degree of the asphalt can be obviously reduced after the high molecular carbohydrates are added, and the X fluorescence yield of main constituent elements such as carbon, hydrogen and oxygen is extremely low, and the high molecular carbohydrates belong to element types which cannot be detected by XRF, and the detection of impurity components of the asphalt is not influenced by the introduction of the high molecular carbohydrates.
As an alternative embodiment, the asphalt includes at least one of coal asphalt, petroleum asphalt, natural asphalt, wood asphalt, shale asphalt, and artificially modified asphalt.
In the application, asphalt in the tabletting sample can adopt at least one of coal asphalt, petroleum asphalt, natural asphalt, wood asphalt, shale asphalt and artificial modified asphalt, namely, the tablet is applicable to various asphalt with softening point less than 110 ℃, and the application range is wide.
According to another exemplary embodiment of the present application, there is provided a method for preparing a pressed sample by X-ray fluorescence spectrometry of asphalt, as shown in fig. 1, the method comprising:
s1, mixing and grinding the additive and asphalt to obtain a mixture.
According to the application, the additive is added in the asphalt sample preparation process for grinding, so that on one hand, the asphalt bonding degree can be reduced, the grinding in the asphalt sample preparation process is facilitated, the sample preparation efficiency is improved, meanwhile, the problem that a mortar is not easy to clean after grinding can be solved, on the other hand, the additive with high melting point can be added, the asphalt softening point can be raised to be more than 110 ℃ from 45-110 ℃, when an XRF (X-ray) is measured, an asphalt tabletting sample is prevented from being melted after being irradiated for 5-10 min by an X-ray in an optical room, the light pipe is prevented from polluting and damaging, and further huge property loss is avoided.
Wherein the additive comprises at least one of boric acid, lithium carbonate, lithium boron compound, high molecular hydrocarbon compound and high molecular carbohydrate.
The additive disclosed by the application is at least one of boric acid, lithium carbonate, lithium boron compound, high molecular hydrocarbon compound and high molecular carbohydrate, so that the softening point of an asphalt tabletting sample is improved, and meanwhile, the additive can be ensured not to interfere with an XRF (X-ray diffraction) measurement result of asphalt.
The mass ratio of the additive to the asphalt is more than or equal to 1/5.
According to the application, the mass ratio of the additive to the asphalt of the tabletting sample is more than or equal to 1/5, the bonding degree of the asphalt can be effectively reduced, and the softening point of the asphalt can be improved, if the mass ratio of the additive to the asphalt is less than 1/5, the softening point of the tabletting sample can not be ensured to be more than 110 ℃, and the safety of XRF measurement of the tabletting sample can not be ensured.
As an alternative embodiment, the lithium boron compound includes at least one of lithium borate, lithium tetraborate, and lithium metaborate;
the high molecular hydrocarbon compound comprises at least one of polyethylene, polyvinyl chloride, polyvinylidene fluoride powder, polypropylene powder and polystyrene;
the high molecular carbohydrate includes at least one of starch, methylcellulose and natural rubber.
In the application, the additive selects the components, because the melting point of the above compounds is far higher than that of asphalt, the melting point and the bonding degree of asphalt can be obviously reduced after the additive is added, and the X fluorescence yields of main constituent elements of boron, lithium, carbon, hydrogen and oxygen are extremely low, and the additive belongs to the element category which cannot be measured by XRF, and the measurement of the impurity components of asphalt is not influenced by introducing the substances.
As an alternative embodiment, the additive and asphalt are mixed and ground to obtain a mixture with a particle size of 0.1-3.0 mm;
in the application, the particle size of the mixture is 0.1-3.0mm, the uniformity of mixing of samples with the particle size within the range is good, the particle size of the ground samples is usually not lower than 0.1mm due to the cohesiveness of asphalt, and the uniformity of mixing of the additive and the asphalt samples is poor when the particle size of the ground samples is higher than 3.0mm, so that the reproducibility of the measurement result is poor.
In the application, the following mode can be adopted for the mixed grinding of the preparation mixture:
the mixed grinding adopts manual grinding, and the time is more than or equal to 100s;
or, the mixed grinding adopts machine grinding, and the time is less than or equal to 50s.
As a preferred embodiment, the mass ratio of the additive to the asphalt is (1/5-5), and the optimal ratio is 1:1.
S2, tabletting the mixture to obtain a tabletting sample.
As an alternative embodiment, the tabletting the mixture to obtain a tablet sample specifically includes:
tabletting the mixture to obtain a tabletting sample;
wherein, the way of the tabletting is any one of direct tabletting, powder cushion bottom tabletting and nested tabletting;
the powder material of the powder cushion bottom tablet comprises at least one of boric acid, polyethylene, lithium borate, lithium metaborate, starch and methyl cellulose;
the nesting material of the nesting tablet comprises any one of a plastic ring, a metal ring and a metal sleeve disk.
In the application, the asphalt tabletting process can adopt conventional direct tabletting, powder bedding tabletting and nested tabletting, and can also adopt other feasible tabletting processes, and when the tabletting process adopts powder bedding tabletting, the powder material comprises at least one of boric acid, polyethylene, lithium borate, lithium metaborate, starch and methyl cellulose, so as to increase the firmness of the sample; when the tabletting process adopts nested tabletting, the nested material comprises any one of a plastic ring, a metal ring and a metal sleeve disk, and has the advantages of being the most firm relative to the sample tablet prepared by direct tabletting and powder cushion bottom tabletting, and the highest safety degree in measurement.
The X-ray fluorescence spectrometry pressed sample of an asphalt of the present application and the method for preparing the same will be described in detail with reference to examples, comparative examples and experimental data.
Example 1
The sample preparation method for the X-ray fluorescence spectrometry of the asphalt pressed sample specifically comprises the following steps:
(1) 3g of petroleum asphalt sample with a softening point of 40 ℃ are weighed, and high-purity lithium borate particles or powder are added according to the proportion of additive: asphalt=5:1.
(2) And (3) manually mixing and grinding the materials obtained in the step (1) by using an agate mortar, wherein the mixing and grinding time is 150s, the mixture with the particle size of 1.5-3.0 mm is obtained, after grinding, asphalt solids are not bonded on the agate mortar and a grinding rod, and the mortar and the grinding rod are erased by using paper at one time.
(3) Directly tabletting the mixture on a tablet press to prepare a sample wafer with a smooth surface, and placing the sample wafer in a baking oven at 110 ℃ for 10min, wherein the sample wafer is kept intact and is not softened.
Example 2
The sample preparation method for the X-ray fluorescence spectrometry of the asphalt pressed sample specifically comprises the following steps:
(1) 5g of coal tar pitch sample with softening point of 75 ℃ is weighed, and high-purity lithium metaborate particles or powder are added according to the proportion of additive: pitch=4:1.
(2) Mixing and grinding the material obtained in the step (1) on a machine device made of tungsten carbide, wherein the mixing and grinding time is 30s, the mixture with the particle size of 1.0-2.8mm is obtained, after grinding, the surface of the material bowl is simply brushed, no solid is adhered, and the material bowl can be thoroughly cleaned by washing the material bowl with alcohol once.
(3) Tabletting the mixture on a boric acid bedding on a tabletting machine to prepare a sample with a smooth surface, and placing the sample in a baking oven at 110 ℃ for 10min, wherein the sample is kept intact and is not softened.
Example 3
The sample preparation method for the X-ray fluorescence spectrometry of the asphalt pressed sample specifically comprises the following steps:
(1) 10g of an artificially modified asphalt sample with a softening point of 95 ℃ are weighed, and boric acid particles or powder are added according to the proportion of additive: asphalt=2:1.
(2) Mixing and grinding the material obtained in the step (1) on tungsten carbide material machine equipment, wherein the mixing and grinding time is 20s, the mixture with the particle size of 0.1-1.9mm is obtained, after grinding, the surface of the material bowl is simply brushed, no solid is adhered, and the material bowl can be thoroughly cleaned by washing the material bowl with alcohol once.
(3) Directly tabletting the mixture on a tablet press to prepare a sample wafer with a smooth surface, and placing the sample wafer in a baking oven at 110 ℃ for 10min, wherein the sample wafer is kept intact and is not softened.
Example 4
The sample preparation method for the X-ray fluorescence spectrometry of the asphalt pressed sample specifically comprises the following steps:
(1) 12g of an artificially modified asphalt sample with a softening point of 105 ℃ are weighed, and polyethylene powder particles or powder are added according to the proportion of additive: asphalt=2:3.
(2) And (3) mixing and grinding the material obtained in the step (1) on zirconia planetary ball mill equipment, wherein the mixing and grinding time is 50s, so as to obtain a mixture with the particle size of 0.8-2.6mm, after grinding, the surface of the material bowl is simply brushed, no solid is adhered, and the material bowl can be thoroughly cleaned by washing the material bowl with alcohol once.
(3) Directly tabletting the mixture on a tablet press to prepare a sample wafer with a smooth surface, and placing the sample wafer in a baking oven at 110 ℃ for 10min, wherein the sample wafer is kept intact and is not softened.
Example 5
The sample preparation method for the X-ray fluorescence spectrometry of the asphalt pressed sample specifically comprises the following steps:
(1) 15g of an artificially modified asphalt sample with a softening point of 108 ℃ are weighed, and additive particles or powder of lithium tetraborate and lithium metaborate with a mass ratio of 12:22 are added according to a ratio of additive to asphalt with a ratio of 1:5.
(2) Mixing and grinding the material obtained in the step (1) on tungsten carbide material machine equipment for 10s to obtain a mixture with the particle size of 0.9-2.9mm, after finishing grinding, simply brushing a material pot, and thoroughly cleaning the material pot by using alcohol for one time, wherein a very small amount of solid remains on the material pot.
(3) Directly tabletting the mixture on a tablet press to prepare a sample wafer with a smooth surface, and placing the sample wafer in a baking oven at 110 ℃ for 10min, wherein the sample wafer is kept intact and is not softened.
Example 6
The sample preparation method for the X-ray fluorescence spectrometry of the asphalt pressed sample specifically comprises the following steps:
(1) 10g of natural asphalt with a softening point of 109 ℃ are weighed, and lithium carbonate particles or powder are added according to the proportion of additive: asphalt=2:1.
(2) Mixing and grinding the material obtained in the step (1) on tungsten carbide material machine equipment, mixing and grinding for 20s to obtain a mixture with the particle size of 0.5-2.5mm, simply brushing a material pot after grinding, and thoroughly cleaning the material pot by using alcohol for one time after a small amount of solid is remained on the material pot.
(3) And (3) embedding and tabletting the mixture on a plastic ring on a tablet press to prepare a sample wafer with a smooth surface, and placing the sample wafer in a baking oven at 110 ℃ for 10min, wherein the sample wafer is kept intact and is not softened.
Example 7
The sample preparation method for the X-ray fluorescence spectrometry of the asphalt pressed sample specifically comprises the following steps:
(1) Weighing a mixture of 1g of wood asphalt and 4g of shale asphalt, wherein the softening point is 81 ℃, adding additive particles or powder containing starch and methyl cellulose according to the ratio of additive: asphalt=2:1, and the mass ratio of the starch to the methyl cellulose is 1:2.
(2) Mixing and grinding the material obtained in the step (1) on tungsten carbide material machine equipment, wherein the mixing and grinding time is 20s, so as to obtain a mixture with the particle size of 1.5-1.9mm, after grinding, simply brushing a material pot, and cleaning the material pot thoroughly by using alcohol for one time, wherein a very small amount of solid remains on the material pot.
(3) Directly tabletting the mixture on a tablet press to prepare a sample wafer with a smooth surface, and placing the sample wafer in a baking oven at 110 ℃ for 10min, wherein the sample wafer is kept intact and is not softened.
Comparative example 1:
the sample pretreatment method for determining the content of the asphalt impurity element by adopting the wet-process chemical ICP-AES method in the comparative example specifically comprises the following steps:
(1) Ashing coal tar pitch sample with softening point of 95 ℃): weighing 5g of coal tar pitch sample, putting the coal tar pitch sample into a platinum crucible, heating the coal tar pitch sample in an electric plate at about 200 ℃ for about 1 hour until fume is completely dispersed, putting the platinum crucible into a high-temperature furnace at 800 ℃ for heating and burning for 6 hours until the sample is completely ashed, and cooling the coal tar pitch sample to room temperature in a dryer until no black particles or obvious residues (if black residues need to be continuously ashed until the coal tar pitch sample is completely ashed).
(2) Dissolving coal pitch sample ash: taking out the platinum crucible containing ash, dissolving with nitric acid, hydrofluoric acid and perchloric acid solution, heating on an electric heating furnace until smoking is completed, then slightly heating with dilute hydrochloric acid solution until insoluble matters are clarified, and then transferring to a 100mL volumetric flask for constant volume, wherein the whole ash dissolution takes about 1 h.
The whole ashing and dissolving process is within the range of 6-10 h.
Comparative example 2:
the sample preparation method for the X-ray fluorescence spectrometry of the asphalt pressed sample comprises the following specific steps:
(1) 10g of a sample of the artificially modified asphalt having a softening point of 95℃was weighed.
(2) The asphalt sample is manually mixed and ground by an agate mortar for 100 seconds, the grinding sample with the particle size of 0.3-3.2mm is obtained after the grinding is completed, a large amount of asphalt solids are adhered on the agate mortar and a grinding rod, paper cannot be effectively erased, alcohol is added to enable the mortar and the grinding rod to grind each other, the mortar and the grinding rod are difficult to clean, and the grinding sample can be thoroughly cleaned by repeatedly adding three times of alcohol.
(3) Directly tabletting the ground material on a tablet press to prepare a sample wafer with a smooth surface, placing the sample wafer in a baking oven at 110 ℃ for 10min, softening the sample, and deforming the sample wafer by only touching the sample wafer with a cotton glove by hands of an experimenter.
Comparative example 3:
the sample preparation method for the X-ray fluorescence spectrometry of the asphalt pressed sample comprises the following specific steps:
(1) 10g of a sample of the artificially modified asphalt having a softening point of 95℃was weighed.
(2) And mixing and grinding the asphalt sample on tungsten carbide mechanical equipment for 20s. After grinding, a large amount of asphalt is adhered to the tungsten carbide material bowl, and the adhesion is serious, so that the particles with the particle size of 1.0-6.6mm are obtained. Alcohol is added to enable the mortar and the grinding rod to grind each other, so that the mortar is difficult to clean, the mortar can be thoroughly cleaned only by repeatedly adding alcohol for three times, but the inner wall of the cleaned mortar is in a gray black state and cannot be removed.
(3) Directly tabletting the ground material on a tablet press to prepare a sample wafer with a smooth surface, placing the sample wafer in a baking oven at 110 ℃ for 10min, softening the sample, and deforming the sample wafer by only touching the sample wafer with a cotton glove by hands of an experimenter.
Comparative example 4
The sample preparation method for the X-ray fluorescence spectrometry of the asphalt pressed sample comprises the following specific steps:
(1) 10g of a sample of an artificially modified asphalt with a softening point of 84℃were weighed and boric acid additive was added in a ratio of additive: asphalt=1:7.
(2) Mixing and grinding the material obtained in the step (1) on tungsten carbide material machine equipment for 20s to obtain a mixture with the particle size of 0.5-5.2mm, wherein the adhesion is serious. After finishing grinding, the solid is cleaned by adding alcohol for many times, but the inner wall of the material pot is in a gray black state and cannot be removed.
(3) Directly tabletting the mixture on a tablet press to prepare a sample wafer with a smooth surface, placing the sample wafer in a baking oven at 110 ℃ for 10min, softening a sample, and deforming the sample wafer by only touching the sample wafer with a cotton glove by hands of an experimenter.
In each example and comparative example of the present application, the particle size of the sample after grinding was measured by a laser particle sizer, and the particle size in the range of D20 to D80 was selected.
Related experiments:
the properties of the asphalt samples prepared in examples 1 to 7 and comparative examples 1 to 4 were tested, and the test results are shown in Table 1.
The related test method comprises the following steps:
sample preparation time: total time spent from weighing, grinding, washing to tabletting, or total time spent in ICP-AES process.
Sample bonding degree: the degree of adhesion of the asphalt sample during grinding is determined according to the cleaning difficulty.
TABLE 1 Performance data for asphalt samples prepared in examples 1-7 and comparative examples 1-4
As can be seen from Table 1, in the sample preparation process for detecting impurity components by using an XRF method, a certain amount of high-melting-point additive is added, so that the bonding degree of asphalt can be reduced, the grinding in the process of preparing the asphalt sample is facilitated, the sample preparation efficiency is improved, the problem that a mortar is not easy to clean after grinding can be solved, the softening point of the asphalt can be raised to be more than 110 ℃ by adding the high-melting-point additive, the problem that an asphalt tabletting sample is melted during XRF measurement to cause light pipe pollution damage accidents is avoided, and huge property loss is avoided.
Detailed description of the drawings 2-5:
as shown in FIG. 2, the mixture obtained in example 3 of the present application, as can be seen from FIG. 2, has higher uniformity of particle size of the milled sample, and only a small amount of the milled sampleMeasuring amountThe presence of large particles;
as shown in FIG. 3, the mixture prepared in comparative example 3 of the present application, as can be seen from FIG. 3, the ground sample has a large number of large particles and has low uniformity of particle size;
as shown in FIG. 4, the appearance of the pressed sample obtained in example 3 of the present application after being placed in an oven at 110℃for 10 minutes is shown, and as can be seen from FIG. 4, the pressed sample is kept intact without softening.
As shown in FIG. 5, the appearance of the pressed sample sheet of comparative example 3 of the present application after being placed in an oven at 110℃for 10 minutes, it can be seen from FIG. 5 that the pressed sample sheet was softened, and the experimenter merely touched with a cotton glove by hand to cause deformation.
One or more of the technical schemes of the application has at least the following technical effects or advantages:
(1) According to the X-ray fluorescence spectrometry pressed sample for asphalt, the additive is added into the pressed sample for asphalt, the addition of the additive with high melting point can raise the softening point of asphalt from 45 ℃ to 110 ℃ to above 110 ℃, so that the accident of pollution and damage of light pipes caused by the fact that the pressed sample for asphalt is irradiated by X-rays in an optical chamber for 5min to 10min during XRF measurement is avoided, and huge property loss is avoided.
(2) According to the X-ray fluorescence spectrometry pressed sample for asphalt, the mass ratio of the additive of the pressed sample to the asphalt is more than or equal to 1/5, the bonding degree of the asphalt can be effectively reduced, the softening point of the asphalt can be improved, if the mass ratio of the additive to the asphalt is less than 1/5, the softening point of the pressed sample can not be ensured to be more than 110 ℃, the safety of XRF measurement of the pressed sample can not be ensured, and the additive can not be ensured to be at least one of boric acid, lithium carbonate, lithium boron compound, high molecular hydrocarbon compound and high molecular carbohydrate, so that the softening point of the pressed sample of the asphalt can be improved, and meanwhile, the additive can not interfere with the XRF measurement result of the asphalt.
(3) According to the sample preparation method for the asphalt X-ray fluorescence spectrometry pressed sample, disclosed by the application, the additive is added in the asphalt sample preparation process for grinding, on one hand, the addition of the additive can reduce the asphalt bonding degree, is beneficial to grinding in the asphalt sample preparation process, improves the sample preparation efficiency, and simultaneously can overcome the problem that a mortar is not easy to clean after grinding, on the other hand, the addition of the additive with high melting point can raise the asphalt softening point from 45-110 ℃ to above 110 ℃, so that the asphalt pressed sample is prevented from being melted after being irradiated by X-rays in an optical chamber for 5-10 min during XRF (X-ray) measurement, and the light pipe pollution damage accident is caused, and further, huge property loss is avoided.
(4) The application relates to a sample preparation method for an X-ray fluorescence spectrometry pressed sample of asphalt, wherein an additive is at least one of boric acid, lithium carbonate, lithium boron compound, high molecular hydrocarbon compound and high molecular carbohydrate, the melting point of the above compounds is far higher than that of asphalt, the melting point and the bonding degree of asphalt can be obviously reduced after the above compounds are added, and the X-ray fluorescence yield of main constituent elements of boron, lithium, carbon, hydrogen and oxygen is extremely low, and the method belongs to element types which cannot be detected by XRF, so that the detection of asphalt impurity components is not influenced by the introduction of the substances.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present application without departing from the spirit or scope of the application. Thus, it is intended that the present application also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (3)
1. An X-ray fluorescence spectrometry tableted sample of asphalt, characterized in that the tableted sample comprises an additive and asphalt in a mass ratio of 1/5 to 5, the additive comprising at least one of boric acid, lithium carbonate, a lithium boron compound comprising at least one of lithium borate, lithium tetraborate and lithium metaborate, and a high molecular hydrocarbon compound comprising at least one of polyethylene, polyvinyl chloride, polyvinylidene fluoride powder, polypropylene powder and polystyrene, the high molecular carbohydrate comprising at least one of starch, methylcellulose and natural rubber, the asphalt comprising at least one of coal asphalt, petroleum asphalt, natural asphalt, wood asphalt, shale asphalt and artificially modified asphalt;
the sample preparation method for the X-ray fluorescence spectrometry pressed sample of asphalt comprises the following steps:
mixing and grinding the additive and asphalt to obtain a mixture;
tabletting the mixture to obtain a tabletting sample;
the additive can reduce the bonding degree of asphalt and raise the softening point of asphalt to above 110 ℃.
2. An X-ray fluorescence spectrometry tabletted sample of asphalt according to claim 1, wherein the mixing and grinding of the additive and asphalt to obtain a mixture, comprises:
mixing and grinding the additive and asphalt to obtain the mixture with the particle size of 0.1-3.0 mm.
3. An X-ray fluorescence spectrometry tabletted sample of asphalt according to claim 1, wherein said tabletting of said mixture to obtain a tabletted sample comprises:
tabletting the mixture to obtain a tabletting sample;
wherein, the tabletting mode is any one of direct tabletting, powder cushion bottom tabletting and nested tabletting;
the powder material of the powder cushion bottom tablet comprises at least one of boric acid, polyethylene, lithium borate, lithium metaborate, starch and methyl cellulose;
the nesting material of the nesting tablet comprises any one of a plastic ring, a metal ring and a metal sleeve disk.
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