Method and device for measuring content of volatile sulfur-containing compounds in asphalt

Abstract

The invention discloses a method and a device for measuring the content of volatile sulfur-containing compounds in asphalt, and relates to the field of compound analysis and detection. The measuring device comprises an inert gas storage tank, a gas flow controller, a heating thermostat, a glass fiber filtering device, a liquid trap, a hydrogen sulfide analyzer, a gas chromatograph and an upper computer. The determination method comprises the following steps: detecting the sulfur-containing compound volatilized from asphalt by using a hydrogen sulfide analyzer under the protection of high-temperature inert gas, and associating the electron transfer amount with the gas concentration by using the electron transfer rule of the sulfur-containing compound gas in the hydrogen sulfide analyzer in the oxidation reaction process; and then calculating the content of each component of the volatile sulfur-containing compound in the asphalt sample, and obtaining the content of the sulfur-containing compound in the asphalt sample through the average relative molecular mass. The method abandons the use of a solvent, avoids the interference caused by the solvent at a high temperature, and has the advantages of high detection precision and wide measurement range.

Description

Technical Field

[0001] The present invention relates to the technical field of compound analysis and detection, and particularly relates to a method and a device for determining the content of volatile sulfur-containing compounds in asphalt. Background Art

[0002] In recent years, with the rapid development of the road transportation industry, the demand for asphalt has been increasing day by day, resulting in a year-on-year increase in the apparent consumption of asphalt. However, volatile substances will be generated during the high-temperature construction or normal-temperature use of asphalt, thus endangering human health and the atmospheric environment. With the increasing attention paid to environmental protection and energy conservation and emission reduction by all sectors of society, the impact of volatile substances in asphalt on the human body and the environment has attracted wide attention. However, the total amount of asphalt fumes is small, the types are numerous, and the activity is strong, making it difficult to qualitatively and quantitatively analyze them. Current domestic and foreign research on asphalt fumes shows that their main components are a large number of volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), and a mixture composed of a small amount of sulfur, nitrogen, and oxygen, which mainly exist in the form of aerosols in the air; and there are almost no reports on the analysis of volatile sulfur-containing substances in asphalt fumes.

[0003] The sulfur-containing substances in asphalt are divided into organic sulfur-containing substances and inorganic sulfur-containing substances. Not all sulfur-containing compounds will volatilize into asphalt fumes. The typical inorganic substance that can enter asphalt fumes is hydrogen sulfide; macromolecular organic sulfur-containing compounds have low volatility and do not enter asphalt fumes in gaseous form during heating. Only when asphalt is heated to a relatively high temperature, they enter asphalt fumes in the form of organic solid particles or organic liquid particles, and organic solid particles and organic liquid particles can be removed by filtration. Small-molecule organic sulfur-containing compounds, such as small-molecule mercaptans and thioethers, belong to low-boiling organic compounds and will volatilize into asphalt fumes; at different temperatures, the volatilization characteristics of sulfur-containing compounds in different components of asphalt are also different. The volatile components of small-molecule organic sulfur-containing compounds cannot be purified by filtration, which is the main reason for the formation of the stinky (strange) smell characteristics and harmful properties of asphalt.

[0004] Currently, there are few domestic and foreign research reports on volatile sulfur-containing compounds in asphalt fumes. Some are only for the determination of mercaptan sulfur or hydrogen sulfide in fuel oil, such as the national standard GB / T34101-2017 "Rapid Liquid Phase Extraction Method for the Determination of Hydrogen Sulfide Content in Fuel Oil", the national standard GB / T1792-2015 "Potentiometric Titration Method for the Determination of Mercaptan Sulfur in Gasoline, Kerosene, Jet Fuel and Distillate Fuel", etc. There is a lack of a method that can detect the total sulfur content of volatile sulfur-containing compounds in asphalt. Summary of the Invention

[0005] The object of the present invention is to provide a method and a device for determining the content of volatile sulfur-containing compounds in asphalt, which are used to overcome the technical problems in the prior art that only the mercaptan sulfur or hydrogen sulfide in fuel oil can be determined, the total amount of sulfur-containing compounds cannot be determined, and the accuracy interference caused by solvent dissolution, etc.

[0006] The technical solution adopted by the present invention to solve the technical problems is as follows:

[0007] A device for determining the content of volatile sulfur-containing compounds in asphalt according to the present invention includes:

[0008] An inert gas storage tank for storing inert gas;

[0009] A gas flow controller for controlling the flow rate of the inert gas introduced into the heating thermostat;

[0010] A heating thermostat for receiving the inert gas and heating the asphalt under the protection of the inert gas to volatilize the sulfur-containing compound gas in the asphalt;

[0011] A fiberglass filtering device for filtering out solid particles in the sulfur-containing compound gas;

[0012] A liquid trap for filtering out liquids and heavy vapors in the sulfur-containing compound gas;

[0013] A hydrogen sulfide analyzer for receiving the sulfur-containing compound gas treated by the liquid trap and measuring the concentration of hydrogen sulfide;

[0014] A gas chromatograph for receiving the sulfur-containing compound gas treated by the liquid trap and performing chromatographic analysis on it to obtain the relative content of the amount of substance of each component in the sulfur-containing compound gas;

[0015] An upper computer for receiving the hydrogen sulfide concentration measured by the hydrogen sulfide analyzer and performing integral processing to obtain the amount of substance of the sulfur-containing compound gas; for correcting the amount of substance of the sulfur-containing compound gas to obtain the corrected amount of substance of the sulfur-containing compound gas; for calculating the average relative molecular mass of the sulfur-containing compound gas according to the relative content of the amount of substance of each component in the sulfur-containing compound gas and the relative molecular mass; for calculating the mass of the sulfur-containing compound gas according to the corrected amount of substance of the sulfur-containing compound gas and the average relative molecular mass of the sulfur-containing compound gas; for calculating the content of sulfur-containing compounds in asphalt according to the mass of asphalt and the mass of the sulfur-containing compound gas.

[0016] As a preferred embodiment, the inert gas is nitrogen, argon or a mixture of nitrogen and argon.

[0017] As a preferred embodiment, a heat transfer medium is added to the heating thermostat.

[0018] A method for determining the content of volatile sulfur compounds in asphalt according to the present invention is realized by using the device for determining the content of volatile sulfur compounds in asphalt described above. This method includes the following steps:

[0019] Step S1: Under the condition of inert gas protection, use a heating thermostat to heat asphalt with a mass of m0 to a certain temperature. The sulfur compound gas volatilized is sequentially passed through a fiberglass filter device and a liquid trap, and then enters a hydrogen sulfide analyzer and a gas chromatograph respectively;

[0020] Step S2: Read the indication of the hydrogen sulfide analyzer through the upper computer and perform integral processing to obtain the amount of substance n' of the sulfur compound gas, and use a correction coefficient k to correct the amount of substance n' of the sulfur compound gas to obtain the corrected amount of substance n of the sulfur compound gas, where n = k * n';

[0021] Step S3: Use the gas chromatograph to perform chromatographic analysis on the sulfur compound gas to obtain the relative content a of the amount of substance of each component in the sulfur compound gas i , and upload it to the upper computer;

[0022] Step S4: According to the relative content a of the amount of substance of each component in the sulfur compound gas i and the relative molecular mass M i calculate to obtain the average relative molecular mass M of the sulfur compound gas 平均 ;

[0023] Step S5: According to the corrected amount of substance n of the sulfur compound gas and the average relative molecular mass M of the sulfur compound gas 平均 calculate to obtain the mass m of the sulfur compound gas, where m = n * M 平均 ;

[0024] Step S6: Calculate the content ω of sulfur compounds in asphalt according to the mass m0 of asphalt and the mass m of sulfur compound gas, where ω = m / m0.

[0025] As a preferred embodiment, in step S1, the inert gas protection conditions are as follows:

[0026] First, purge with an inert gas, then heat up under the condition of maintaining a slightly positive pressure with a small flow rate of the inert gas, and finally, carry out the sulfur compound gas with a certain flow rate of the inert gas.

[0027] As a preferred embodiment, in step S1, the flow rate of the inert gas is 80 ml / min - 120 ml / min.

[0028] As a preferred embodiment, in step S1, use the heating thermostat to heat the asphalt to 150°C - 200°C.

[0029] As a preferred embodiment, in step S2, the correction coefficient k = 1 / (1 - a 硫醇 / 2), where a 硫醇 is the relative molar content of mercaptan substances in the sulfur-containing compound gas.

[0030] As a preferred embodiment, in step S4, the average relative molecular mass M of the sulfur-containing compound gas 平均 = a1M1 + a2M2 +... + a i M i , where a1, a2,..., a i are the relative molar contents of components 1, 2,..., i in the sulfur-containing compound gas, and M1, M2,..., M i are the relative molecular masses of components 1, 2,..., i in the sulfur-containing compound gas.

[0031] The beneficial effects of the present invention are as follows:

[0032] The method and device for determining the content of volatile sulfur-containing compounds in asphalt provided by the present invention detect the sulfur-containing compounds volatilized from asphalt by using a hydrogen sulfide analyzer under the protection of high-temperature inert gas, abandoning the use of solvents and avoiding the interference caused by solvents at higher temperatures; at the same time, by using the law of electron transfer during the oxidation reaction of sulfur-containing compound gas in the hydrogen sulfide analyzer, the electron transfer amount is related to the gas concentration, and at the same time, it is corrected by using a correction coefficient, and then the contents of various components of volatile sulfur-containing compounds in the asphalt sample are calculated, and the sulfur-containing compound content of the asphalt sample is obtained through the average relative molecular mass, which has high detection accuracy and can detect multiple components in the sulfur-containing compound gas, and has the advantage of a wide measurement range. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 is a schematic structural composition diagram of a device for determining the content of volatile sulfur-containing compounds in asphalt according to the present invention;

[0034] Figure 2 is a flowchart of a method for determining the content of volatile sulfur-containing compounds in asphalt according to the present invention;

[0035] Figure 3 is a gas chromatogram of volatile sulfur-containing compounds in asphalt A;

[0036] Figure 4 is a gas chromatogram of volatile sulfur-containing compounds in asphalt B;

[0037] Figure 5 is a gas chromatogram of volatile sulfur-containing compounds in asphalt C;

[0038] Figure 6 It is the gas chromatogram analysis chart of volatile sulfur compounds in asphalt D;

[0039] Figure 7 It is the gas chromatogram analysis chart of volatile sulfur compounds in asphalt E.

[0040] In the figure, 1 is an inert gas storage tank, 2 is a gas flow controller, 3 is a heating thermostat, 4 is a fiberglass filter device, 5 is a liquid trap, 6 is a hydrogen sulfide analyzer, 7 is a gas chromatograph, 8 is a host computer, 9 is a heat transfer medium, 10 is an asphalt container, and 11 is an asphalt sample. Specific embodiments

[0041] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention and are not used to limit the present invention.

[0042] In the first aspect, the present invention provides a device for measuring the content of volatile sulfur compounds in asphalt.

[0043] See Figure 1 For illustration, a device for measuring the content of volatile sulfur compounds in asphalt according to the present invention mainly consists of an inert gas storage tank 1, a gas flow controller 2, a heating thermostat 3, a fiberglass filter device 4, a liquid trap 5, a hydrogen sulfide analyzer 6, a gas chromatograph 7 and a host computer 8. Among them, the inert gas storage tank 1, the gas flow controller 2, the heating thermostat 3, the fiberglass filter device 4, the liquid trap 5 and the hydrogen sulfide analyzer 6 are connected in sequence. That is, the inert gas storage tank 1 is connected to the gas flow controller 2 through a pipeline, the gas flow controller 2 is connected to the heating thermostat 3 through a pipeline, the heating thermostat 3 is connected to the fiberglass filter device 4 through a pipeline, the fiberglass filter device 4 is connected to the liquid trap 5 through a pipeline, the liquid trap 5 is respectively connected to the hydrogen sulfide analyzer 6 and the gas chromatograph 7 through pipelines, and both the hydrogen sulfide analyzer 6 and the gas chromatograph 7 are connected to the host computer 8 through cable wires.

[0044] Among them, the inert gas storage tank 1 stores inert gas, and the inert gas can be nitrogen, argon or their mixture, but is not limited thereto. The inert gas storage tank 1 is mainly used to provide inert gas to the heating thermostat 3 to form an inert gas protection condition, so as to facilitate the heating treatment of asphalt by the heating thermostat 3.

[0045] Among them, the gas flow controller 2 is mainly used to control the flow rate of the inert gas in the inert gas storage tank 1. By using the gas flow controller 2 for control, the inert gas in the inert gas storage tank 1 can flow into the heating thermostat 3 through the pipeline at a suitable flow rate.

[0046] In addition, a heat transfer medium 9 is added to the heating thermostat 3. The heat transfer medium 9 can be a heat-conducting oil, such as dimethyl silicone oil, etc., but is not limited thereto. The heating thermostat 3 is mainly used to heat the asphalt, so as to volatilize the sulfur-containing compound gas in the asphalt. Specifically, a certain mass of asphalt sample 11 can be placed in the asphalt container 10, and then the asphalt container 10 is placed in the heating thermostat 3 for heating.

[0047] In the present invention, the fiberglass filtering device 4 is mainly used to filter out solid particles in the sulfur-containing compound gas, so as to improve the accuracy of the final measurement result.

[0048] Moreover, the liquid trap 5 is mainly used to filter out liquids and heavy vapors in the sulfur-containing compound gas, so as to improve the accuracy of the final measurement result.

[0049] In the present invention, the hydrogen sulfide analyzer 6 is mainly used to receive the sulfur-containing compound gas processed by the liquid trap 5 and measure the concentration of hydrogen sulfide, and then upload the measured concentration of hydrogen sulfide to the host computer 8. In addition, the accuracy of the hydrogen sulfide analyzer 6 is preferably 0.1 ppm or more.

[0050] In the present invention, the gas chromatograph 7 is mainly used to receive the sulfur-containing compound gas processed by the liquid trap 5 and perform chromatographic analysis on the sulfur-containing compound gas, so as to obtain the relative amount of substance a of each component in the sulfur-containing compound gas i , and upload it to the host computer 8. In addition, in the present invention, there are no special limitations on the type, model, and source of the gas chromatograph 7, as long as the corresponding detection results can be achieved.

[0051] In the present invention, the host computer 8 is mainly used to read the indication of the hydrogen sulfide analyzer 6 and perform integration processing to obtain the amount of substance of the sulfur-containing compound gas; and, to correct the amount of substance of the sulfur-containing compound gas to obtain the corrected amount of substance of the sulfur-containing compound gas; and, to calculate the average relative molecular mass of the sulfur-containing compound gas according to the relative amount of substance and relative molecular mass of each component in the sulfur-containing compound gas; and, to calculate the mass of the sulfur-containing compound gas according to the corrected amount of substance of the sulfur-containing compound gas and the average relative molecular mass of the sulfur-containing compound gas; and, to calculate the content of sulfur-containing compounds in the asphalt according to the mass of the asphalt and the mass of the sulfur-containing compound gas.

[0052] In a second aspect, the present invention provides a method for measuring the content of volatile sulfur-containing compounds in asphalt.

[0053] Referring to Figure 2 For illustration, a method for measuring the content of volatile sulfur-containing compounds in asphalt according to the present invention mainly includes the following steps:

[0054] Step S1: First, the inert gas in the inert gas storage tank 1 is controlled by the gas flow controller 2 to be transported to the heating thermostat 3 at a certain flow rate. Under the condition of inert gas protection, the asphalt with a mass of m0 is heated to a certain temperature by the heating thermostat 3. The sulfur-containing compound gas volatilized by heating will pass through the fiberglass filter device 4 and the liquid trap 5 in sequence and then enter the hydrogen sulfide analyzer 6 and the gas chromatograph 7 respectively. Among them, after being processed by the fiberglass filter device 4, the solid particles in the sulfur-containing compound gas can be filtered out. After being processed by the liquid trap 5, the liquid and heavy steam in the sulfur-containing compound gas can be filtered out. Through the combined action of the fiberglass filter device 4 and the liquid trap 5, the accuracy of the final measurement result can be improved.

[0055] Preferably, the inert gas protection condition is as follows: First, purge with inert gas, then heat up under the condition of maintaining a slightly positive pressure with a small flow rate of inert gas, and finally carry out the sulfur-containing compound gas with a certain flow rate of inert gas.

[0056] Preferably, the flow rate of the inert gas is 80 ml / min - 120 ml / min; more preferably, the flow rate of the inert gas is 100 ml / min.

[0057] The so-called inert gas generally refers to a gas that does not react with the substances in the system, such as noble gases, nitrogen, etc. In the present invention, preferably, the inert gas is nitrogen, argon or a mixture thereof, and more preferably, the inert gas is high-purity nitrogen.

[0058] The functions of introducing inert gas in the present invention are as follows: Firstly, it provides an inert reaction environment to prevent the sulfur-containing compounds in the asphalt from being oxidized after volatilization, resulting in inaccurate detection results; Secondly, the inert gas pipeline extends deep into the melted asphalt, and the generated bubbles / bubbling can effectively promote the release of sulfur-containing compounds; Thirdly, the content of sulfur-containing compounds in the asphalt is relatively small, and the gas generated solely by the sulfur-containing compounds cannot effectively make all of them enter the hydrogen sulfide analyzer 6. The introduction of inert gas can play a carrier role, thereby carrying the sulfur-containing compound gas into the hydrogen sulfide analyzer 6.

[0059] In addition, preferably, the heating temperature of the heating thermostat 3 is 150°C - 200°C, and more preferably, the heating temperature of the heating thermostat 3 is 180°C. At this heating temperature, the sulfur-containing compounds in the asphalt can be effectively volatilized. Below 150°C, the volatilization temperature cannot be reached, while above 200°C, a variety of other impurities (non-sulfur-containing compounds) will volatilize and mix into the gas, resulting in inaccurate results.

[0060] Step S2: Read the readings of the hydrogen sulfide analyzer 6 through the host computer 8 and perform integration processing to obtain the amount of substance n' of the sulfur-containing compound gas. Correct the amount of substance n' of the sulfur-containing compound gas with the correction coefficient k to obtain the corrected amount of substance n of the sulfur-containing compound gas, where n = k * n'.

[0061] Preferably, the integration processing can be performed using data processing software.

[0062] Among them, the correction coefficient k = 1 / (1 - a 硫醇 / 2), where a 硫醇 is the relative content of the amount of substance of mercaptan substances in the sulfur-containing compound gas.

[0063] In the present invention, the reason for using the correction coefficient k for correction is mainly as follows: The probe principle of the hydrogen sulfide analyzer 6 is that sulfur in the sulfur-containing compound gas undergoes an oxidation reaction in the electrolytic cell, generating electron transfer, and the amount of electron transfer is proportional to the gas concentration. Therefore, the concentration of the sulfur-containing compound gas can be calculated by measuring the amount of electron transfer. When constructing the electrolytic cell system of the organic sulfur compound sensor, a weak oxidation environment can be selected, that is, the organic sulfur compound is oxidized to organic disulfide; in a weak oxidation environment, for every mole of S in hydrogen sulfide 2- is oxidized to sulfur with a valence of 0, and 2 moles of electrons need to be transferred; for every mole of sulfur in thioether, the sulfur with a valence of +2 is oxidized to sulfoxide with a valence of +4, and 2 moles of electrons need to be transferred; for every mole of sulfur in carbonyl sulfide, the sulfur with a valence of -2 is oxidized to sulfur with a valence of 0, and 2 moles of electrons need to be transferred; for every mole of sulfur in carbon disulfide, the sulfur with a valence of -2 is oxidized to sulfur with a valence of 0, and 2 moles of electrons need to be transferred; for every mole of S in mercaptan 2- is oxidized to sulfur with a valence of -1, and 1 mole of electrons needs to be transferred; oxidizing a certain amount of sulfur will generate a corresponding amount of electron transfer. Utilizing the oxidation-reduction conditions in the electrolytic cell, the electron transfer process forms an electric current, and then by quantifying the magnitude of the electric current, the amount of sulfur reaction can be quantified, and finally the amount of substance of the sulfur-containing compound in the gas can be quantified. From the above description, it can be known that the valence change of most sulfur-containing compounds such as hydrogen sulfide, thioether, carbonyl sulfide, and carbon disulfide is +2 during the oxidation-reduction reaction process, but the valence change of mercaptan is +1, which leads to a deviation if calculated based on 2 moles of electrons transferred per mole of sulfur-containing compound. Therefore, the present invention introduces the correction coefficient k for mercaptan to effectively eliminate this deviation and ensure the accuracy of the detection result.

[0064] Step S3: Perform chromatographic analysis on the sulfur-containing compound gas using a gas chromatograph 7 to obtain the relative content a i of the amount of substance of each component in the sulfur-containing compound gas, and upload it to the host computer 8.

[0065] Preferably, the test conditions of the gas chromatograph 7 are as follows: initial temperature 35°C, hold for 10 min, increase to 260°C at a rate of 5°C / min, hold for 10 min, for a total of 65 min; the detector is SCD; the chromatographic column is PONA, with a specification of 50 m × 200 μm × 0.5 μm; the carrier gas is nitrogen, and the carrier gas flow rate is 0.5 mL / min.

[0066] Through gas chromatography testing of the present invention, it is possible to measure which components are contained in the sulfur-containing compound gas and the relative content of the corresponding amount-of-substance components (i.e., the ratio of the amount of substance of a certain component to the total amount of substance of all gases).

[0067] Step S4: After obtaining the relative amount-of-substance content a of each component in the sulfur-containing compound gas i the host computer 8 calculates the average relative molecular mass M of the sulfur-containing compound gas according to the relative amount-of-substance content a of each component in the sulfur-containing compound gas i and the relative molecular mass M i M = a1M1 + a2M2 +... + a 平均 M i ; where a1, a2,..., a i are the relative amount-of-substance contents of components 1, 2,..., i in the sulfur-containing compound gas, and M1, M2,..., M i i are the relative molecular masses of components 1, 2,..., i in the sulfur-containing compound gas.

[0068] Since the gas chromatograph 7 can measure the specific types of each component in the sulfur-containing compound gas, the relative molecular mass of a certain determined component or compound is a known parameter, which is well-known to those skilled in the art. The product of the relative amount-of-substance content of each component and the relative molecular mass, and finally the sum is the average relative molecular mass of the sulfur-containing compound gas.

[0069] Step S5: After obtaining the average relative molecular mass M of the sulfur-containing compound gas 平均 the host computer 8 calculates the mass m of the sulfur-containing compound gas according to the amount of substance n of the sulfur-containing compound gas after correction and the average relative molecular mass M of the sulfur-containing compound gas 平均 m = n * M 平 均 .

[0070] The present invention calculates the mass m of the sulfur-containing compound gas according to the amount of substance n of the sulfur-containing compound gas after correction and the average relative molecular mass M of the sulfur-containing compound gas 平均 m = n * M 平均 ​; After the calculations in the previous steps S2 to S4, multiply the obtained amount of substance n (mol) of the sulfur compound gas after correction and the average relative molecular mass M 平均 (g / mol) of the sulfur compound gas to obtain the mass m (g) of the sulfur compound.

[0071] Step S6: The host computer 8 calculates the content ω of the sulfur compound in the asphalt based on the mass m0 of the asphalt and the mass m of the sulfur compound gas, that is, ω = m / m0, which means dividing the mass m of the sulfur compound gas by the mass m0 of the asphalt to obtain the content ω of the sulfur compound in the asphalt.

[0072] Among them, since the content of the sulfur compound in the asphalt is relatively low, generally trace, the content ω of the sulfur compound in the asphalt is generally expressed in μg / g.

[0073] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0074] To better illustrate the technical solution of the present invention, the present invention also provides the following specific embodiments. It should be understood that the raw materials used in the following embodiments are all commercially available raw materials unless otherwise specified.

[0075] Examples 1-5 show the final results obtained after 5 different asphalt samples are measured using the measurement method of the present invention.

[0076] Example 1

[0077] This example provides a method for measuring the content of volatile sulfur compounds in asphalt, and the specific steps are as follows:

[0078] S1. Under the condition of nitrogen protection at 100 ml / min, put 30.5758 g (m0) of asphalt A into the 180 °C heating thermostat 3. The volatilized sulfur compound gas passes through the fiberglass filter device 4 and the liquid trap 5 in sequence and then enters the hydrogen sulfide analyzer 6 and the gas chromatograph 7 respectively;

[0079] S2. Read the indication of the hydrogen sulfide analyzer 6 through the host computer 8 and perform integral processing on the data using data processing software to obtain 20.4×10 -6 mol (n') of sulfur compound gas, and use the correction coefficient 1.218 (k) to correct the amount of substance 20.4×10 of the sulfur compound gas -6Calibrate mol(n’), and the amount of substance n of the sulfur-containing compound gas after calibration is obtained as n = k * n’ = 24.8472 * 10 -6 mol;

[0080] S3. Analyze the sulfur-containing compound gas by gas chromatography using a gas chromatograph 7. The test conditions for gas chromatography are as follows: initial temperature 35°C, hold for 10 min, increase to 260°C at a rate of 5°C / min, hold for 10 min, for a total of 65 min; the detector is SCD; the chromatographic column is PONA, with a specification of 50 m × 200 um × 0.5 um; the carrier gas is nitrogen, and the carrier gas flow rate is 0.5 mL / min; the gas chromatography analysis results are as Figure 3 shown; the relative content a of the amount of substance of each component in the sulfur-containing compound gas is obtained i (see Table 1 for details);

[0081] Table 1 Detection results of volatile sulfur-containing compounds in asphalt A

[0082] Name <![CDATA[Content (*10 -6 mol)]]> Relative content (%) Hydrogen sulfide 5.96 29.24 Carbonyl sulfide 1.10 5.40 Methyl mercaptan 2.87 14.08 Ethyl mercaptan 2.67 13.10 Carbon disulfide 5.49 26.90 2-Propanethiol 1.31 6.43 2-Methyl-2-propanethiol 0.25 1.22 1-Propanethiol 0.40 1.97 Thiophene 0.11 0.56 Isopropyl methyl sulfide 0.03 0.14 2-Methyl-1-propanethiol 0.04 0.18 1-Butanethiol 0.02 0.08 Dimethyl disulfide 0.14 0.70

[0083] S4. Calculate the average relative molecular mass M of the sulfur-containing compound gas based on the relative molecular mass M i and the relative content a of the amount of substance i of each component in the sulfur-containing compound gas, and the average relative molecular mass M of the sulfur-containing compound gas is obtained 平均 = a1M1 + a2M2 +... + a 13 M 13 = 57.6 g / mol;

[0084] S5. Calculate the mass m of the sulfur-containing compound gas based on the amount of substance n of the sulfur-containing compound gas after calibration and the average relative molecular mass M of the sulfur-containing compound gas 平均 m = n * M 平均 ;

[0085] S6. Calculate the content ω of the sulfur-containing compound in the asphalt based on the mass m0 of the asphalt and the mass m of the sulfur-containing compound gas, ω = m / m0 = 46.77 ug / g.

[0086] Example 2

[0087] This example provides a method for determining the content of volatile sulfur-containing compounds in asphalt, and the specific steps are as follows:

[0088] S1. Under the condition of nitrogen protection at 100 ml / min, put 30.7515 g (m0) of asphalt B into a 180°C heating thermostat 3. The sulfur-containing compound gas volatilized passes through a glass fiber filter device 4 and a liquid trap 5 for treatment and then enters a hydrogen sulfide analyzer 6 and a gas chromatograph 7 respectively;

[0089] S2. Read the readings of the hydrogen sulfide analyzer 6 through the host computer 8 and perform integral processing on the data using data processing software to obtain 52.6×10 -6 mol (n’) of sulfur-containing compound gas, and use the correction coefficient 1.01 (k) to correct the amount of substance 52.6×10 -6 mol (n’) of sulfur-containing compound gas to obtain the corrected amount of substance n = k×n’ = 53.126×10 -6 mol;

[0090] S3. Perform chromatographic analysis on the sulfur-containing compound gas using a gas chromatograph 7. The test conditions of the gas chromatography are as follows: initial temperature 35°C, hold for 10 min, increase to 260°C at a rate of 5°C / min, hold for 10 min, for a total of 65 min; the detector is SCD; the chromatographic column is PONA, with a specification of 50 m×200 μm×0.5 μm; the carrier gas is nitrogen, and the carrier gas flow rate is 0.5 mL / min; the gas chromatography analysis results are as Figure 4 shown; obtain the relative content of the amount of substance a i (see Table 2 for details);

[0091] Table 2 Detection results of volatile sulfur-containing compounds in asphalt B

[0092]

[0093]

[0094] S4. Calculate the average relative molecular mass M i of the sulfur-containing compound gas according to the relative molecular mass M i and the relative content of the amount of substance a 平均 of the sulfur-containing compound gas, M = a1M1 + a2M2 +... + a9M9 = 36.05 g / mol;

[0095] S5. Calculate the mass m = n×M 平均 of the sulfur-containing compound gas according to the corrected amount of substance n of the sulfur-containing compound gas and the average relative molecular mass M 平均 of the sulfur-containing compound gas;

[0096] S6. Calculate the content ω = m / m0 = 62.3 μg / g of the sulfur-containing compound in the asphalt according to the mass m0 of the asphalt and the mass m of the sulfur-containing compound gas.

[0097] Example 3

[0098] This example provides a method for determining the content of volatile sulfur-containing compounds in asphalt, and the specific steps are as follows:

[0099] S1. Under the condition of nitrogen protection at 100 ml / min, 30.79 g (m0) of asphalt C is placed in a heating thermostat 3 at 180 °C. The sulfur-containing compound gas volatilized passes through a fiberglass filter device 4 and a liquid trap 5 in sequence, and then enters a hydrogen sulfide analyzer 6 and a gas chromatograph 7 respectively;

[0100] S2. Read the indication of the hydrogen sulfide analyzer 6 through a host computer 8 and perform integral processing on the data using data processing software to obtain 16.13×10 -6 mol (n’) of sulfur-containing compound gas, and use a correction factor of 1.19 (k) to correct the amount of substance 16.13×10 -6 mol (n’) of sulfur-containing compound gas to obtain the corrected amount of substance n of sulfur-containing compound gas = k×n’ = 19.1947×10 -6 mol;

[0101] S3. Perform chromatographic analysis on the sulfur-containing compound gas using a gas chromatograph 7. The test conditions of the gas chromatograph are: initial temperature 35 °C, retention for 10 min, rising to 260 °C at a rate of 5 °C / min, retention for 10 min, for a total of 65 min; the detector is SCD; the chromatographic column is PONA, with a specification of 50 m×200 μm×0.5 μm; the carrier gas is nitrogen, and the carrier gas flow rate is 0.5 mL / min; the gas chromatographic analysis results are as Figure 5 shown; obtain the relative content a of the amount of substance of each component in the sulfur-containing compound gas i (see Table 3 for details);

[0102] Table 3 Detection results of volatile sulfur-containing compounds in asphalt C

[0103] Name <![CDATA[Content (*10 -6 mol)]]> Relative content (%) Hydrogen sulfide 0.41 2.55 Carbonyl sulfide 2.27 14.08 Methyl mercaptan 3.84 23.78 Ethyl mercaptan 0.83 5.13 Carbon disulfide 7.78 48.22 2-Propanethiol 0.37 2.30 1-Propanethiol 0.22 1.36 Thiophene 0.07 0.46 2-Methyl-1-propanethiol 0.01 0.08 Dimethyl disulfide 0.33 2.04

[0104] S4. Calculate the average relative molecular mass M of the sulfur-containing compound gas according to the relative molecular mass M i and the relative content a of the amount of substance of each component in the sulfur-containing compound gas i M 平均 = a1M1 + a2M2 +... + a 10 M 10 = 65.834 g / mol;

[0105] S5. Calculate the mass m of the sulfur-containing compound gas according to the amount of substance n of the corrected sulfur-containing compound gas and the average relative molecular mass M 平均 of the sulfur-containing compound gas, m = n×M 平均 ;

[0106] S6. Calculate the content ω of sulfur-containing compounds in asphalt based on the mass m0 of asphalt and the mass m of sulfur-containing compound gas, ω = m / m0 = 41.06 μg / g.

[0107] Example 4

[0108] This example provides a method for determining the content of volatile sulfur-containing compounds in asphalt, and the specific steps are as follows:

[0109] S1. Under the condition of nitrogen protection at 100 ml / min, put 32.8065 g (m0) of asphalt D into the 180 °C heating thermostat 3. The sulfur-containing compound gas volatilized passes through the fiberglass filter device 4 and the liquid trap 5 for treatment respectively, and then enters the hydrogen sulfide analyzer 6 and the gas chromatograph 7.

[0110] S2. Read the indication of the hydrogen sulfide analyzer 6 through the upper computer 8 and perform integral processing on the data with data processing software to obtain 16.5×10 -6 mol (n’) of sulfur-containing compound gas, and use the correction coefficient 1.09 (k) to correct the amount of substance 16.5×10 -6 mol (n’) of sulfur-containing compound gas to obtain the corrected amount of substance n of sulfur-containing compound gas, n = k×n’ = 17.985×10 -6 mol;

[0111] S3. Perform chromatographic analysis on the sulfur-containing compound gas with the gas chromatograph 7. The test conditions of the gas chromatography are as follows: initial temperature 35 °C, retention for 10 min, rising to 260 °C at a rate of 5 °C / min, retention for 10 min, a total of 65 min; the detector is SCD; the chromatographic column is PONA, with a specification of 50 m×200 μm×0.5 μm; the carrier gas is nitrogen, and the carrier gas flow rate is 0.5 mL / min; the gas chromatography analysis results are as Figure 6 shown; obtain the relative content a i of the amount of substance of each component in the sulfur-containing compound gas (see Table 4 for details);

[0112] Table 4 Detection results of volatile sulfur-containing compounds in asphalt D

[0113] Name <![CDATA[Content (*10 -6 mol)]]> Relative content (%) Carbonyl sulfide 7.59 46.03 Methyl mercaptan 1.75 10.60 Ethyl mercaptan 0.88 5.31 Carbon disulfide 5.78 35.00 Dimethyl disulfide 0.51 3.06

[0114] S4. Calculate the average relative molecular mass M i of the sulfur-containing compound gas according to the relative molecular mass M i and the relative content a 平均 of the amount of substance of each component in the sulfur-containing compound gas, M = a1M1 + a2M2 +... + a5M5 = 65.58 g / mol;

[0115] S5. Calculate the mass m of the sulfur-containing compound gas based on the corrected amount of substance n of the sulfur-containing compound gas and the average relative molecular mass M of the sulfur-containing compound gas 平均 The mass m of the sulfur-containing compound gas is calculated as m = n * M 平均 ;

[0116] S6. Calculate the content ω of the sulfur-containing compound in the asphalt based on the mass m0 of the asphalt and the mass m of the sulfur-containing compound gas, where ω = m / m0 = 35.97 μg / g

[0117] Example 5

[0118] This example provides a method for determining the content of volatile sulfur-containing compounds in asphalt, and the specific steps are as follows

[0119] S1. Under the condition of nitrogen protection at 100 ml / min, put 31.3829 g (m0) of asphalt E into a 180 °C heating thermostat 3. The sulfur-containing compound gas volatilized passes through a glass fiber filter device 4 and a liquid trap 5 for treatment respectively, and then enters a hydrogen sulfide analyzer 6 and a gas chromatograph 7

[0120] S2. Read the indication of the hydrogen sulfide analyzer 6 through a host computer 8 and perform integral processing on the data using data processing software. After processing, 12.0 * 10 -6 mol (n') of sulfur-containing compound gas is obtained, and the amount of substance 12.0 * 10 -6 mol (n') of the sulfur-containing compound gas is corrected using a correction factor 1.34 (k) to obtain the corrected amount of substance n of the sulfur-containing compound gas, where n = k * n' = 16.08 * 10 -6 mol;

[0121] S3. Perform chromatographic analysis on the sulfur-containing compound gas using a gas chromatograph 7. The test conditions of the gas chromatography are as follows: initial temperature 35 °C, retention for 10 min, rising to 260 °C at a rate of 5 °C / min, retention for 10 min, for a total of 65 min; the detector is SCD; the chromatographic column is PONA, with a specification of 50 m × 200 μm × 0.5 μm; the carrier gas is nitrogen, and the carrier gas flow rate is 0.5 mL / min; the gas chromatography analysis results are as Figure 7 shown; the relative content a of the amount of substance of each component in the sulfur-containing compound gas is obtained i (see Table 5 for details);

[0122] Table 5 Detection results of volatile sulfur-containing compounds in asphalt E

[0123]

[0124]

[0125] S4. Calculate the average relative molecular mass M of the sulfur-containing compound gas based on the relative molecular mass M i and the relative content a of the amount of substance i of each component in the sulfur-containing compound gas, and obtain the average relative molecular mass M 平均 of the sulfur-containing compound gas = a1M1 + a2M2 +... + a 11 M 11 = 68.88 g / mol;

[0126] S5. Calculate the mass m of the sulfur-containing compound gas based on the amount of substance n of the sulfur-containing compound gas after correction and the average relative molecular mass M 平均 of the sulfur-containing compound gas, and obtain m = n * M 平均 ;

[0127] S6. Calculate the content ω of the sulfur-containing compound in the asphalt based on the mass m0 of the asphalt and the mass m of the sulfur-containing compound gas, and obtain ω = m / m0 = 35.24 μg / g.

[0128] Comparative Example 1

[0129] In this comparative example, the temperature of the heating thermostat 3 in Examples 1-5 was adjusted to 140 °C, and the sulfur-containing compound was detected. The results are shown in Table 6 below.

[0130] Table 6 Comparative Example

[0131]

[0132] According to this comparative example, when the heating temperature of the asphalt is lower than 150 °C set in the present invention, the sulfur-containing compound in the asphalt cannot volatilize to form gas, and thus cannot be detected by the method of the present invention.

[0133] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A device for determining the content of volatile sulfur compounds in asphalt, characterized in that, include: An inert gas storage tank (1), used for storing inert gas; A gas flow controller (2) for controlling the flow rate of the inert gas introduced into the heating thermostat (3); A heating thermostat (3) is used to receive the inert gas and heat the asphalt under the protection of the inert gas to volatilize the sulfur compound gas in the asphalt; A glass fiber filter device (4) for filtering out solid particles in the sulfur compound-containing gas; A liquid trap (5) for filtering out liquid and heavy vapor in the sulfur compound-containing gas; A hydrogen sulfide analyzer (6), used for receiving the sulfur compound gas treated by the liquid trap (5) and measuring the concentration of hydrogen sulfide; A gas chromatograph (7) is used to receive the sulfur-containing compound gas after being treated by the liquid trap (5) and perform chromatographic analysis on it to obtain the relative content of each component in the sulfur-containing compound gas; The host computer (8) is used to receive the hydrogen sulfide concentration measured by the hydrogen sulfide analyzer (6) and perform integration processing to obtain the amount of substance of the sulfur-containing compound gas; to correct the amount of substance of the sulfur-containing compound gas to obtain the corrected amount of substance of the sulfur-containing compound gas; and to calculate the average relative molecular mass of the sulfur-containing compound gas based on the relative content and relative molecular mass of the amount of substance of each component in the sulfur-containing compound gas. Used to calculate the mass of the sulfur-containing compound gas according to the corrected amount of the sulfur-containing compound gas and the average relative molecular mass of the sulfur-containing compound gas; It is used to calculate the content of sulfur-containing compounds in asphalt based on the mass of asphalt and the mass of sulfur-containing compound gas.

2. The measuring device for the content of volatile sulfur compounds in asphalt according to claim 1, characterized in that, The inert gas is nitrogen, argon or a mixture of nitrogen and argon.

3. The measuring device for the content of volatile sulfur compounds in asphalt according to claim 1, characterized in that, A heat transfer medium is added into the heating thermostat (3).

4. A method for determining the content of volatile sulfur-containing compounds in asphalt, characterized in that, The method is implemented by using a device for determining the content of volatile sulfur compounds in asphalt as claimed in any one of claims 1 to 3, and comprises the following steps: Step S1: Under inert gas protection conditions, a heating thermostat (3) is used to heat the asphalt of mass m0 to a certain temperature, and the volatilized sulfur compound gas is processed by a glass fiber filter device (4) and a liquid trap (5) in turn and then enters a hydrogen sulfide analyzer (6) and a gas chromatograph (7) respectively; Step S2: the upper computer (8) reads the reading of the hydrogen sulfide analyzer (6) and performs integration processing to obtain the amount n' of the sulfur compound gas, and the amount n' of the sulfur compound gas is corrected by using the correction coefficient k to obtain the corrected amount n=k*n' of the sulfur compound gas; Step S3: Use a gas chromatograph (7) to perform chromatographic analysis on the sulfur-containing compound gas to obtain the relative molar content a of each component in the sulfur-containing compound gas i , and upload it to the host computer (8); Step S4: Calculate the average relative molecular mass \(M\) of the sulfur-containing compound gas based on the relative molar content \(a\) of each component in the sulfur-containing compound gas i and the relative molecular mass \(M\) i to obtain the average relative molecular mass \(M\) of the sulfur-containing compound gas 平均 ; Step S5: According to the corrected amount of substance n of the sulfur-containing compound gas and the average relative molecular mass M of the sulfur-containing compound gas 平均 Calculate the mass m of the sulfur-containing compound gas as m = n * M 平均 ; Step S6: Calculate the content of sulfur-containing compounds in the asphalt ω=m / m0 based on the mass m0 of the asphalt and the mass m of the sulfur-containing compound gas.

5. The method for determining the content of volatile sulfur compounds in asphalt according to claim 4, characterized in that, In step S1, the inert gas protection conditions are as follows: First, purge with inert gas, then use a small flow of inert gas to maintain the temperature under slightly positive pressure conditions, and finally use a certain flow rate of inert gas to remove the sulfur compound gas.

6. The method for determining the content of volatile sulfur compounds in asphalt according to claim 4, characterized in that, In step S1, the flow rate of the inert gas is 80 ml / min-120 ml / min.

7. The method for determining the content of volatile sulfur compounds in asphalt according to claim 4, characterized in that, In step S1, the asphalt is heated to 150°C-200°C using the heating thermostat (3).

8. The method for determining the content of volatile sulfur compounds in asphalt according to claim 4, characterized in that, In step S2, the correction coefficient k = 1 / (1 - a 硫醇 / 2), where a 硫醇 is the relative molar content of mercaptan substances in the sulfur compound gas.

9. The method for determining the content of volatile sulfur-containing compounds in asphalt according to claim 4, characterized in that, In step S4, the average relative molecular mass M of the sulfur-containing compound gas 平均 = a1M1 + a2M2 +... + a i M i , where a1, a2, …, a i are the relative molar contents of components 1, 2, …, i in the sulfur-containing compound gas, and M1, M2, …, M i are the relative molecular masses of components 1, 2, …, i in the sulfur-containing compound gas.

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