CN112630343A - Method for testing, tracing and rectifying hydrocarbon pollutants of automobile tire - Google Patents
Method for testing, tracing and rectifying hydrocarbon pollutants of automobile tire Download PDFInfo
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- 238000004458 analytical method Methods 0.000 claims description 6
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8631—Peaks
- G01N30/8634—Peak quality criteria
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Abstract
The invention provides a method for testing and tracing and rectifying hydrocarbon pollutants of an automobile tire, which comprises the following steps of S1: cleaning and equipment confirmation before testing; s2: hot dipping test; s3: carrying out normal-temperature sample soaking in a closed chamber, and setting the closed chamber to be in a maximum ventilation state; s4: carrying out a day and night ventilation test; s5: calculating the results of day and night ventilation and hot dipping stages in various evaporative pollutant emission tests described according to the test procedures, and analyzing carbides to determine the substance information of the hydrocarbons. The invention relates to a method for testing, tracing and rectifying hydrocarbon pollutants of an automobile tire, which is a high-efficiency method for testing the hydrocarbon pollutants of the tire based on the national emission standard, improves the testing efficiency by nearly 50 percent, analyzes and traces the source of main hydrocarbon pollutants by sampling, determines the types of the main hydrocarbon pollutants, provides accurate directional data for adjusting the formula of the tire, and essentially solves the problem of reducing the hydrocarbon pollutants of the tire.
Description
Technical Field
The invention belongs to the field of automobile tire inspection and chemical analysis, and particularly relates to a method for testing and tracing and rectifying hydrocarbon pollutants of an automobile tire.
Background
At present, the influence of pollutants generated by automobiles on the atmospheric environment is more and more prominent and serious, and according to research, the emission of Volatile Organic Compounds (VOC) causes 20% -30% of PM2.5 and 47% of haze in China, and one of the main sources of the emission of VOC is the hydrocarbon emission of automobiles. The automobile keeping quantity in China is large, about 110 ten thousand tons of hydrocarbon emission can be generated every year, the automobile is concentrated in urban areas, 7% -12% of PM2.5 and 15% -20% of haze are directly caused, and the influence on the environment is obvious.
The hydrocarbon emission of automobiles has attracted attention, and before GB18352.6-2016, "limit of light vehicle pollutant emission and measurement method for automobile (sixth stage of china)" (hereinafter, referred to as "national emission standard"), the united states is the world with the highest emission control index and the most stringent emission regulations, and the reduction rate of the U.S. regulations on the hydrocarbon emission of automobiles reaches 80%, and the improvement of the quality of the ambient air is significant. In 2016, 12 months, the national environmental protection department releases national six-emission standards, compared with the standards in the fifth stage, the new standards greatly tighten the hydrocarbon emission control requirements, the original 2 g/test is reduced to 0.70 g/test of the national six-emission standards, the standard limit value is tightened by 65%, and the control requirements are improved by at least 80% by considering the strict degree of the test method. The automobile industry in China needs to quickly form a reduction route and a control strategy for the emission of hydrocarbon pollutants of automobiles so as to meet the standard requirements.
Sources of hydrocarbon emissions from automobiles are automotive fuel and non-fuel related components. The non-fuel parts include parts, semi-finished products and materials which are on the vehicle and are not in contact with fuel. These parts, semi-finished products and materials are mostly non-metallic materials, such as plastics, foamed, rubber materials, and parts or semi-finished products produced from plastics, foamed, rubber materials. The influence of hydrocarbon emission generated by non-fuel oil components on the hydrocarbon emission of the whole vehicle is quite remarkable, and researches show that the hydrocarbon emission of the non-fuel oil components can account for about 30-50% of the whole vehicle. It is therefore necessary to measure and manage hydrocarbon emissions from non-fuel components. The domestic automobile industry mainly focuses on the hydrocarbon emission generated by fuel before the national six standards, the research on a non-fuel part hydrocarbon emission system is deficient, and the research experience is basically zero.
The patent group provides an evaporative pollutant emission test method of non-fuel parts based on research, and draws a draft T/CSAE 121-2019 'emission test method of evaporative pollutants of non-fuel related vehicle parts and materials', the test method prescribes hot dipping for 1h, a day-night cycle for 48h, and sampling is carried out during the period, and the total mass of the hydrocarbon pollutants of the sample is the hydrocarbon emission mass in the hot dipping test and the hydrocarbon emission mass in the day-night ventilation test (the larger value in the 1 st 24h day-night cycle and the 2 nd 24h day-night cycle).
In the research process of hydrocarbon pollutants of non-fuel components, the hydrocarbon pollutant emission level of tires is not negligible, the hydrocarbon pollutant emission of the whole vehicle is greatly contributed, and important reduction and control are needed. The existing reduction scheme mainly comprises high-temperature baking, tire formula adjustment and a vulcanization process. The baking scheme of the tire is easy to set, the temperature and the baking time are not adjusted, but baking is used as a post-treatment method, the method is a 'fake' method which treats symptoms and causes no root causes, the emission of hydrocarbon pollutants can be accelerated, the production cost is increased, the baked hydrocarbon pollutants still enter the environment, the influence on the environment is not changed essentially, and the performance and the service life of the rubber product can be influenced by high-temperature baking. Therefore, the reduction of the hydrocarbon emission of the tire should be started from the adjustment of the tire formula and the vulcanization process, but the blind adjustment of the tire formula and the process not only has a large workload, but also cannot ensure the hydrocarbon emission effect after the adjustment.
Disclosure of Invention
In view of the above, the invention aims to provide a method for testing and tracing and modifying hydrocarbon pollutants of an automobile tire, so as to form an efficient method for testing the hydrocarbon pollutants of the tire based on the national emission standard, the testing efficiency of the testing method is improved by nearly 50%, the types of main hydrocarbon pollutants are determined by analyzing and tracing the main hydrocarbon pollutants through sampling, accurate directional data are provided for adjusting a tire formula, and the problem of reducing the hydrocarbon pollutants of the tire is solved essentially.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
testing of a vehicle tyre for hydrocarbon contaminants:
1. pre-test cleaning and equipment validation
(1) Checking the sealing performance and other functions of the closed chamber;
(2) all surfaces in contact with the volatile organic components in the closed chamber are cleaned. The specific cleaning method is as follows: removing residual particles and impurities generated in the last test by using a mechanical cleaning method (such as an industrial dust collector), then aging the box body by using high-temperature baking, opening a mixing fan of a closed chamber, cleaning the closed chamber for a plurality of minutes until the background total hydrocarbon concentration is reduced to below 1ppm at the hot dipping temperature and is kept stable (at least 30min), and baking and cleaning related accessories such as sealing rings.
(3) The closed cell background concentration was monitored and recorded after cleaning and before the test began.
(4) Before the test is started, the tires are unpacked and placed in a standard environment of GB/T2918 for one week for testing, and the storage mode is carried out according to the following requirements: the test tire was not contacted by other objects on each side (not including the side in contact with the frame); pretreatment environmental pollutant background concentration value: TVOC is less than or equal to 0.2mg/m 3; after the pretreatment is finished, the tire is put into a closed chamber within 60min to start the test.
2. Hot dip test
(1) The initial temperature of the closed chamber is set to be 38 +/-2 ℃;
(2) the method is characterized in that a test sample tire is transferred into a closed chamber after being mounted with a matched metal hub, and when a sample to be tested is placed, the best air circulation effect is ensured, and the sample piece cannot shift in the whole test process. Immediately sealing the closed chamber after the sample piece is placed in the closed chamber;
(3) the door of the closed chamber was closed and sealed and hot dipping was initiated for 60min + -0.5 min. The initial conditions of the hot dip test were measured and recorded, including: concentration C of hydrocarbonsHC,iTemperature TiAtmospheric pressure Pi. These data will be used to calculate hydrocarbon pollutant emission values;
(4) 12min before 60min +/-0.5 min, connecting a gas collecting device at a sampling port of the closed chamber, taking 2min for pumping residual gas in the distribution pipe, connecting a TENAX sampling pipe for sampling, and collecting hydrocarbon pollutant gas, wherein sampling parameters are shown in a table 6;
(5) near the end of the 60min + -0.5 min hot dip test period, the final hydrocarbon concentration C of the hot dip test is recordedHC,fTemperature TfAtmospheric pressure Pf. These data will be used to calculate evaporative pollutant emissions values 8.
3. Soaking sample at normal temperature
And (3) carrying out normal-temperature sample leaching in a closed chamber, setting the closed chamber to be in a maximum ventilation state, and reducing the temperature of the closed chamber to 20 +/-2 ℃ within 20 min. The above state is kept until the concentration of the hydrocarbon pollutants is stable, and the process is about 1-2 h.
4. Diurnal ventilation test
(1) The test samples should be cycled through the ambient temperature variations specified in table 1 in a closed chamber with the maximum deviation at any time in the temperature variation cycle being within ± 1 ℃. The average value of the temperature deviation from the specified profile should not exceed 1 c, calculated as the absolute value of the deviation per measurement. Ambient temperature is measured at least once per minute. The temperature cycle is started from the time point when T starts to 0.
(2) At tstart 0, an initial reading of the hydrocarbon concentration C is recordedHC,iTemperature TiAnd atmospheric pressure Pi。
(3) Within 12min of starting the test, connecting a gas collecting device at a sampling port of a closed chamber, taking 2min when extracting residual gas in a distribution pipe, connecting a TENAX sampling pipe for sampling, and collecting hydrocarbon pollutant gas for 10min, wherein sampling parameters are shown in a table 2;
(4) 11min before the test is finished, connecting a gas collecting device at a sampling port of a closed chamber, extracting residual gas in a distribution pipe, connecting a TENAX sampling pipe, consuming 1min, collecting hydrocarbon pollutants for 10min, wherein the sampling parameters are shown in a table 2;
(5) at the end of the test, when T is 24h, the hydrocarbon concentration CH is recordedC,24Temperature T24And atmospheric pressure P24. These data will be used for calculations;
TABLE 1 closed-chamber calibration and day and night ventilation discharge test day and night environment temperature change table
TABLE 2 acquisition parameters
5. Computing
According to the results of day and night ventilation and hot dipping stages in various evaporative pollutant emission tests described in the test procedures, hydrocarbon calculation is carried out. The hydrocarbon concentration, initial and final readings of the temperature and pressure within the enclosure, and the net volume of the enclosure are used to calculate the evaporative contaminant emissions for each stage.
The following formula is used:
hot dip test
Diurnal ventilation test
In the formula:
MHC-hydrocarbon mass, g;
H/C-hydrogen to carbon ratio;
MHC, out-mass g of hydrocarbons discharged from the volumetric closed chamber during hot dip or diurnal ventilation tests with the volumetric closed chamber;
MHC, into-mass g of hydrocarbons entering the constant volume closed chamber when hot dipping or day and night ventilation test is carried out by the constant volume closed chamber;
CHC-hydrocarbon concentration in ppm (by volume) C in the closed chamber1Equivalent weight;
v is the net volume of the closed chamber after sample volume correction;
t-the ambient temperature in the closed room, K;
p-atmospheric pressure, kPa;
k——1.2×(12+H/C)；
i — subscript, initial reading;
f-subscript, end reading;
HS — hot dip;
24-subscript, 24 hour reading;
for the loss of the day and night ventilation test, the H/C is 2.33;
for hot dip losses, 2.20H/C was taken.
6. Overall results of the test
The total emission mass of the hydrocarbon evaporation pollutants of the sample is measured as follows:
Mgeneral assembly＝MDI+MHS
In the formula:
Mgeneral assembly-total hydrocarbon mass emitted by sample evaporation contaminants, g;
MDI-mass of hydrocarbon emissions at 24h day-night ventilation test, g;
MHS-mass of hydrocarbons emitted during hot dip test, g.
7. Carbon hydrogen pollutant tracing and reforming scheme
(1) Performing gas chromatography mass spectrometry on TANAX collected in a hot dipping test and a day-night ventilation test to determine the substance information of hydrocarbons, wherein the analysis conditions of equipment are as follows:
analysis conditions were as follows: thermal desorption: blowing the Tenax pipe for 1min at a flow rate of 20 mL/min; desorption temperature: desorption time at 280 ℃: 8 min; (ii) a Desorption gas flow: 40 mL/min; cold trap temperature: -10 ℃; cold trap heating temperature: heating at 300 deg.C for 3 min; the split ratio is as follows: 62:1. Mass spectrum: solvent excision time: 3 min; ion source temperature: 230 ℃; detector temperature: 150 ℃; the scanning mode is as follows: full scan 30-550 amu; electron bombardment energy: 70 Ev. Gas chromatography: carrier gas: 1 helium gas; column flow mL/min; a chromatographic column: agilent 122 and 5562DB-5MS (60m × 0.25mm × 0.25 um); temperature rising procedure: keeping at 40 deg.C for 10min, heating to 120 deg.C at 5 deg.C/min, heating to 280 deg.C at 10 deg.C/min, and keeping for 8 min.
(2) And carrying out full-spectrum qualitative analysis to obtain a substance list of the hydrocarbon pollutants, and sequencing the substance list according to the peak area from large to small, wherein the more the peak area is reached, the more the substance is considered to be, so that the main hydrocarbon pollutants are screened out.
(3) And (3) comparing main hydrocarbon pollutants in a hot dipping stage and a day and night ventilation stage, selecting several substances with the highest quantity, and comparing the occurrence tracks and content changes of the several main hydrocarbon pollutants through a plurality of tests.
(4) The properties and the application of the main hydrocarbon pollutants are known, the generation reasons of the main hydrocarbon pollutants are judged by combining rubber formula components and base materials, and the formula and the process are adjusted in a targeted manner, so that the generation of the main hydrocarbon pollutants is reduced from the source.
Compared with the prior art, the method for testing, tracing and rectifying the hydrocarbon pollutants of the automobile tire has the following advantages:
the invention relates to a method for testing and tracing and rectifying hydrocarbon pollutants of an automobile tire, which has the advantages of forming a testing method for the emission of the hydrocarbon pollutants of the tire and a tire reduction and rectification strategy, shortening the testing time by about half, providing an important basis for the reduction and control of the hydrocarbon pollutants of other key parts for vehicles including the tire, reducing the industry rectification cost, providing an important content for forming a comprehensive scheme for reducing the emission of the hydrocarbon pollutants of the automobile, accelerating the green development of the automobile industry, and helping the relevant automobile production enterprises to better fulfill the social responsibility of protecting the atmospheric environment.
Drawings
FIG. 1 illustrates a method of placing a tire into an enclosed chamber;
FIG. 2 is a graph of hydrocarbon emissions for the 1 st and 2 nd diurnal cycles;
FIG. 3 shows the results of the 1 st and 2 nd diurnal cycles for the final hydrocarbon emissions test.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and accompanying drawings, and the general technical process is shown in table 3.
Table 3 hydrocarbon pollutant emission test procedure for tire components
The test was carried out using 4 tires of the same lot from a certain tire factory, which were tire 1, tire 2, tire 3 and tire 4. The baking time of 4 tire samples of the same batch of a certain brand for different baking pretreatment is 0h, 4h, 12h and 24h respectively, so that different hydrocarbon pollutant emission levels can be obtained, and the four samples are sample 1, sample 2, sample 3 and sample 4.
Example 1
1. Pre-test cleaning and equipment validation
(1) Checking the sealing performance and other functions of the closed chamber; a tire 1 is used.
(2) All surfaces in contact with the volatile organic components in the closed chamber are cleaned. The specific cleaning method is as follows: removing residual particles and impurities generated in the last test by using a mechanical cleaning method (such as an industrial dust collector), then aging the box body by using high-temperature baking, opening a mixing fan of a closed chamber, cleaning the closed chamber for a plurality of minutes until the background total hydrocarbon concentration is reduced to below 1ppm at the hot dipping temperature and is kept stable (at least 30min), and baking and cleaning related accessories such as sealing rings.
(3) The closed cell background concentration was monitored and recorded after cleaning and before the test began.
(4) Before the test is started, the tires are unpacked and placed in a standard environment of GB/T2918 for one week for testing, and the storage mode is carried out according to the following requirements: the test tire was not contacted by other objects on each side (not including the side in contact with the frame); pretreatment environmental pollutant background concentration value: TVOC is less than or equal to 0.2mg/m 3; after the pretreatment is finished, the tire is put into a closed chamber within 60min to start the test.
2. Hot dip test
(1) The initial temperature of the closed chamber is set at 38 ℃;
(2) the method is characterized in that a test sample tire is transferred into a closed chamber after being mounted with a matched metal hub, and when a sample to be tested is placed, the best air circulation effect is ensured, and the sample piece cannot shift in the whole test process. Immediately sealing the closed chamber after the sample piece is placed in the closed chamber;
(3) the door of the closed chamber was closed and sealed and a 60min hot dip was initiated. The initial conditions of the hot dip test were measured and recorded, including: concentration C of hydrocarbonsHC,iTemperature TiAtmospheric pressure Pi. These data will be used to calculate hydrocarbon pollutant emission values;
(4) connecting a gas collecting device at a sampling port of the closed chamber 12min before 60min, taking 2min when extracting residual gas in the distribution pipe, connecting a TENAX sampling pipe for sampling, and collecting hydrocarbon pollutant gas, wherein sampling parameters are shown in a table 6;
(5) near the end of the 60min hot dip test period, the final hydrocarbon concentration CH of the hot dip test is recordedC,fTemperature TfAtmospheric pressure Pf. These data will be used to calculate evaporative pollutant emissions values 8.
3. Soaking sample at normal temperature
And (3) carrying out normal-temperature sample leaching in a closed chamber, setting the closed chamber to be in a maximum ventilation state, and reducing the temperature of the closed chamber to 20 +/-2 ℃ within 20 min.
The above state is maintained until the concentration of hydrocarbon pollutants is stable, and the process is about 1 h.
4. Diurnal ventilation test
(1) The test samples should be cycled through the ambient temperature variations specified in table 1 in a closed chamber with the maximum deviation at any time in the temperature variation cycle being within ± 1 ℃. The average value of the temperature deviation from the specified profile should not exceed 1 c, calculated as the absolute value of the deviation per measurement. Ambient temperature is measured at least once per minute. The temperature cycle is started from the time point when T starts to 0.
(2) At tstart 0, an initial reading of the hydrocarbon concentration C is recordedHC,iTemperature TiAnd atmospheric pressure Pi。
(3) Within 12min of starting the test, connecting a gas collecting device at a sampling port of a closed chamber, taking 2min when extracting residual gas in a distribution pipe, connecting a TENAX sampling pipe for sampling, and collecting hydrocarbon pollutant gas for 10min, wherein sampling parameters are shown in a table 2;
(4) 11min before the test is finished, connecting a gas collecting device at a sampling port of a closed chamber, extracting residual gas in a distribution pipe, connecting a TENAX sampling pipe, consuming 1min, collecting hydrocarbon pollutants for 10min, wherein the sampling parameters are shown in a table 2;
(5) at the end of the test, when T is 24h, the hydrocarbon concentration CHC,24, the temperature T24 and the atmospheric pressure P24 are recorded.
Comparative example 1
The same batch of tyres 11 was used as in example 1, with a difference from example 1 in the test method of 2 diurnal cycles (48 h).
Example 2
The same test method as in example 1 was conducted except that the tire 2 was used.
Comparative example 2
The same test method as in comparative example 1 was used except that the same batch of tires 22 as in example 2 was used.
Example 3
The same test method as in example 1 was conducted except that the tire 3 was used.
Comparative example 3
The same test method as in comparative example 1 was used except that the same batch of tire 33 as in example 3 was used.
Example 4
The same test method as in example 1 was conducted except that the tire 4 was used.
Comparative example 4
The same test method as in comparative example 1 was used except that the same batch of tire 44 as in example 4 was used.
The requirement of the day and night environment temperature change time of the hydrocarbon emission test of the known non-fuel oil parts is 48h, namely 2 day and night cycles, and the hydrocarbon emission value of the larger day and night cycle in the 2 day and night cycles is selected as the test result. Comparing the hydrocarbon emission test values of 2 diurnal emissions for a plurality of tire samples, see fig. 2, 98% of the samples, the emission test value for the 1 st diurnal cycle is greater than the emission test value for the 2 nd diurnal emission; for the remaining 2% of the samples, the emission values of the 1 st and 2 nd day and night cycles are different by less than 20%, and for the tire samples, the emission values of the hydrocarbon pollutants of the day and night cycles can be obtained only by carrying out the emission test of the 1 st day and night cycle. Therefore, the tire testing method proposed by the patent requires 24h of day and night environment temperature change time, namely 1 day and night cycle.
The test method of the embodiment is represented by 24h in the figure, the test method of the comparative example of 2 day-night cycles is represented by 48h, and the numerical values in the figure show that the test result of 24h has no deviation (less than 5%) with the test result of 48h basically, so that the test method of 24h specified in the patent can represent the test method of 48h well, the test time can be reduced by nearly 50% by using the test method, and the test efficiency of the carbon-hydrogen pollutant emission of the tire is greatly improved.
Example 5
The same test method as in example 1 was used except that the baking pretreatment baking time was 0h, and sample 1 was used.
Example 6
The same test method as in example 1 was used except that the baking pretreatment baking time was 4 hours, and sample 2 was used.
Example 7
The same test method as in example 1 was used, except that the baking pretreatment baking time was 12 hours, and that sample 3 was used.
Example 8
The same test method as in example 1 was used except that the baking pretreatment baking time was 24 hours, and sample 4 was used. The baking pretreatment protocol is shown in table 4.
TABLE 4 baking pretreatment protocol
The pretreated tire samples were subjected to hydrocarbon pollutant emission tests, and the test results are shown in table 5.
TABLE 5 carbon and Hydrogen emissions from tires at different baking pretreatment times
The total hydrocarbon emission of the (single) tires which are not subjected to the baking pretreatment is 0.01718g, the total hydrocarbon emission of the tires is gradually reduced along with the increase of the baking pretreatment time, and the total hydrocarbon emission of the tires is reduced to 0.00787g after being baked for 24h, so that the hydrocarbon emission is reduced by 54%. But the trend of the total hydrocarbon emission of the tires is reduced along with further extension of the baking time. It can be seen that the baking method has limited effectiveness in reducing hydrocarbon emissions, too high baking temperature and too long baking time will affect the performance of the tire, and other ways are needed to better reduce the hydrocarbon pollutant emissions from forums.
The hydrocarbon pollutants in the hydrocarbon pollutant testing process are collected and analyzed according to the steps described in the patent, and the main hydrocarbon pollutants and content sequences of four tire samples with different hydrocarbon pollutant emission levels are obtained, and are shown in tables 6-8.
TABLE 6 main pollutants and concentration ratios of unbaked tires
TABLE 7 main pollutants and concentration ratios for 4h baked tires
TABLE 8 main pollutants and concentration ratios for 12h baked tires
TABLE 9 main pollutants and concentration ratios for 24h baked tires
The method mainly comprises the following steps of determining the hydrocarbon pollutants: the main hydrocarbon pollutants are methyl isobutyl ketone, tert-butylamine, xylene, ethylbenzene and the like, and the methyl isobutyl ketone and the tert-butylamine can be removed in a large amount by baking, but the xylene and the ethylbenzene substances must be further reduced by formula adjustment.
Tracing and rectifying the direction of main hydrocarbon pollutants: from the analysis of the properties and sources of main hydrocarbon pollutants, the use of organic solvents such as methyl isobutyl ketone, xylene and the like should be reduced as much as possible in the rubber synthesis process, and styrene with smaller ethylbenzene residue should be selected as a raw material.
After the correction, the brand properly adjusts the raw materials and the formula of the tire according to the correction direction, the corrected tire sample A is obtained by keeping other process conditions unchanged, meanwhile, the tire B with the original formula is also produced, and the tires A and B are only different in formula. The two tires were subjected to a hydrocarbon pollutant test, and the total hydrocarbon pollutant emissions A were 0.005g and B was 0.021 g. The hydrocarbon pollutants of the tire after the formula adjustment are reduced by 76 percent compared with the tire with the original formula, the reduction amplitude is obvious, and the effect is greater than that of the baking method.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A test of hydrocarbon contamination of automobile tires, characterized by: the method comprises the following steps:
s1: cleaning and equipment confirmation before testing;
s2: hot dipping test;
s3: carrying out a normal temperature sample soaking test;
s4: carrying out a day and night ventilation test;
s5: the hydrocarbon calculation is performed according to the results of the diurnal ventilation and hot dip phases.
2. A test of hydrocarbon contamination of automobile tires, characterized by: the method comprises the following steps:
s1: cleaning and equipment confirmation before the test, monitoring and recording the background concentration of the closed chamber before the test starts after cleaning, removing the package of the tire before the test starts, and testing;
s2: hot dipping test; mounting a test sample tire on a metal hub, transferring the test sample tire into a closed chamber, ensuring that a sample piece cannot shift in the whole test process, and sealing the closed chamber; measuring and recording the initial condition of the hot dipping test, connecting a gas acquisition device, and recording data when the test is finished;
s3: carrying out normal-temperature sample soaking in a closed chamber, and setting the closed chamber to be in a maximum air exchange state;
s4: day and night ventilation test: the test sample is circulated in a closed chamber according to certain temperature change, the environmental temperature is measured at least once every minute, relevant data are recorded, sampling is carried out, hydrocarbon pollutants are collected, and the data are recorded at the end of the test;
s5: the hydrocarbon concentration, initial and final readings of the temperature and pressure within the enclosure, and the net volume of the enclosure are used to calculate the evaporative contaminant emissions for each stage. And calculating the total mass of the emission of the evaporated pollutants of the sample hydrocarbon.
3. A test for hydrocarbon contamination of a vehicle tyre according to claim 1 or 2, characterized in that: the cleaning and equipment confirmation in S1 is: the leakproofness and other functions to the sealed chamber are examined, all surfaces that contact with volatile organic component in the sealed chamber are cleaned, the test after cleaning is carried out before beginning to monitor and record sealed chamber background concentration, wherein all surfaces that contact with volatile organic component in the sealed chamber are cleaned and are specifically: removing residual particles and impurities generated in the last test by adopting a mechanical cleaning method, then carrying out aging treatment on the box body by adopting high-temperature baking, opening a mixing fan of a closed chamber, cleaning the closed chamber for a plurality of minutes until the concentration of background total hydrocarbons is reduced to below 1ppm at the hot dipping temperature, keeping the stability for at least 30min, and baking and cleaning related accessories.
4. A test for hydrocarbon contamination of a vehicle tyre according to claim 1 or 2, characterized in that: in the step S1, the tyre is unpacked and placed for a week for testing according to the standard environment in GB/T2918, and the storage mode is carried out according to the following requirements: not in contact with other objects; the storage mode is that the background concentration value of the environmental pollutants is pretreated according to the requirement: TVOC is less than or equal to 0.2mg/m 3; after the pretreatment is finished, the tire is put into a closed chamber within 60min to start the test.
5. A test for hydrocarbon contamination of a vehicle tyre according to claim 1 or 2, characterized in that: the hot dipping time in S2 is 60min + -0.5 min, and the initial condition in S2 is the concentration C of hydrocarbonsHC,iTemperature TiAtmospheric pressure PiThese data will be used to calculate hydrocarbon pollutant emission values, sampled at S2 for 12min before 60min + -0.5 min of the dip sample.
6. A test for hydrocarbon contamination of a vehicle tyre according to claim 1 or 2, characterized in that: and in the S3, the temperature of the closed chamber is reduced to 20 +/-2 ℃ within 20min, the state is maintained until the concentration of the hydrocarbon pollutants is stable, and the time of the process is 1-2 h.
7. A test for hydrocarbon contamination of a vehicle tyre according to claim 1 or 2, characterized in that: the maximum deviation at any time in the variation cycle in S4 is within + -1 deg.C, the temperature deviation from the specified variation curve should not exceed 1 deg.C, calculated as the absolute value of the deviation of each measurement, and the recorded data includes the hydrocarbon concentration C of the recorded initial readingHC,iTemperature TiAnd atmospheric pressure PiThe sampling comprises the following steps: in 12min of beginning experiment, connect gaseous collection system at the sample connection of sealed chamber, take out residual gas in the piping and consume time 2min, connect TENAX sampling pipe and sample, gather hydrocarbon pollutant gas 10min, gather hydrocarbon pollutant and include as follows: connecting a gas collection device at a sampling port of the closed chamber, pumping residual gas in the distribution pipe to connect a TENAX sampling pipe, consuming 1min, collecting hydrocarbon pollutants for 10min, wherein the collected data comprises hydrocarbon concentration CHC，iTemperature T24And atmospheric pressure P24。
8. A test for hydrocarbon contamination of a vehicle tyre according to claim 1 or 2, characterized in that: the formula of the hot dipping test in the S5 is as follows:
the formula of the diurnal ventilation test is as follows:
in the formula:
MHC-hydrocarbon mass, g;
H/C-hydrogen to carbon ratio;
MHC, outBy usingWhen the constant volume closed chamber is used for carrying out hot dipping or day and night ventilation test, the mass g of hydrocarbon discharged from the constant volume closed chamber;
MHC, into-mass g of hydrocarbons entering the constant volume closed chamber when hot dipping or day and night ventilation test is carried out by the constant volume closed chamber;
CHC-hydrocarbon concentration in ppm (by volume) C in the closed chamber1Equivalent weight;
v is the net volume of the closed chamber after sample volume correction;
t-the ambient temperature in the closed room, K;
p-atmospheric pressure, kPa;
k——1.2×(12+H/C)；
i — subscript, initial reading;
f-subscript, end reading;
HS — hot dip;
24-subscript, 24 hour reading;
for the loss of the day and night ventilation test, the H/C is 2.33;
for hot dip losses, 2.20H/C was taken.
9. A vehicle tyre for testing for hydrocarbon contaminants according to claim 1 or 2, wherein: the total emission mass of the sample hydrocarbon evaporation pollutants in the S5 is measured as follows:
Mgeneral assembly＝MDI+MHS
In the formula:
Mgeneral assembly-total hydrocarbon mass emitted by sample evaporation contaminants, g;
MDI-mass of hydrocarbon emissions at 24h day-night ventilation test, g;
MHS-mass of hydrocarbons emitted during hot dip test, g.
10. The traceability and rehabilitation program of hydrocarbon contaminants as claimed in claim 1, wherein: the tracing and reforming scheme of the hydrocarbon pollutants comprises the following steps:
(1) performing gas chromatography mass spectrometry on TANAX collected in a hot dipping test and a day-night ventilation test to determine the substance information of hydrocarbons, wherein the analysis conditions of equipment are as follows:
analysis conditions were as follows: thermal desorption: blowing the Tenax pipe for 1min at a flow rate of 20 mL/min; desorption temperature: desorption time at 280 ℃: 8 min; desorption gas flow: 40 mL/min; cold trap temperature: -10 ℃; cold trap heating temperature: heating at 300 deg.C for 3 min; the split ratio is as follows: 62:1, mass spectrum: solvent excision time: 3 min; ion source temperature: 230 ℃; detector temperature: 150 ℃; the scanning mode is as follows: full scan 30-550 amu; electron bombardment energy: 70Ev, gas chromatography: carrier gas: helium gas; column flow mL/min; a chromatographic column: agilent 122 and 5562DB-5MS (60m × 0.25mm × 0.25 um); temperature rising procedure: keeping the temperature at 40 ℃ for 10min, heating to 120 ℃ at the speed of 5 ℃/min, heating to 280 ℃ at the speed of 10 ℃/min, and keeping the temperature for 8 min;
(2) performing full-spectrum qualitative analysis to obtain a substance list of the hydrocarbon pollutants, and sequencing the substance list according to peak areas from large to small, wherein the more the peak area is reached, the more the substance is considered to be, so as to screen out the main hydrocarbon pollutants;
(3) comparing main hydrocarbon pollutants in a hot dipping stage and a day and night ventilation stage, selecting several substances with the highest quantity, carrying out multiple tests, and comparing the occurrence tracks and content changes of the several main hydrocarbon pollutants;
(4) the properties and the application of the main hydrocarbon pollutants are known, the generation reasons of the main hydrocarbon pollutants are judged by combining rubber formula components and base materials, and the formula and the process are adjusted in a targeted manner, so that the generation of the main hydrocarbon pollutants is reduced from the source.
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