CN109870561B - Method for detecting high-density or low-density polyethylene reclaimed material - Google Patents
Method for detecting high-density or low-density polyethylene reclaimed material Download PDFInfo
- Publication number
- CN109870561B CN109870561B CN201711272882.7A CN201711272882A CN109870561B CN 109870561 B CN109870561 B CN 109870561B CN 201711272882 A CN201711272882 A CN 201711272882A CN 109870561 B CN109870561 B CN 109870561B
- Authority
- CN
- China
- Prior art keywords
- sample
- density polyethylene
- low
- density
- reclaimed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229920001903 high density polyethylene Polymers 0.000 title claims abstract description 44
- 239000004700 high-density polyethylene Substances 0.000 title claims abstract description 44
- 229920001684 low density polyethylene Polymers 0.000 title claims abstract description 37
- 239000004702 low-density polyethylene Substances 0.000 title claims abstract description 37
- 238000004458 analytical method Methods 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 238000003988 headspace gas chromatography Methods 0.000 claims abstract description 22
- 238000001514 detection method Methods 0.000 claims abstract description 15
- 239000004698 Polyethylene Substances 0.000 claims abstract description 11
- 238000012360 testing method Methods 0.000 claims description 25
- -1 polyethylene Polymers 0.000 claims description 9
- 230000000087 stabilizing effect Effects 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002329 infrared spectrum Methods 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 238000009826 distribution Methods 0.000 abstract description 11
- 229910052736 halogen Inorganic materials 0.000 abstract description 7
- 150000002367 halogens Chemical class 0.000 abstract description 7
- 238000002411 thermogravimetry Methods 0.000 abstract description 3
- 239000008187 granular material Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000029087 digestion Effects 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000000184 acid digestion Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000004836 empirical method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Sampling And Sample Adjustment (AREA)
- Investigating Or Analyzing Materials Using Thermal Means (AREA)
Abstract
The invention discloses a method for detecting high-density or low-density polyethylene reclaimed materials, which comprises the following steps: (1) Taking a sample, and judging the sample to be high-density polyethylene or low-density polyethylene; (2) And detecting the sample by adopting at least one method of headspace gas chromatography, element distribution analysis, halogen distribution analysis, thermogravimetric analysis and electron microscope analysis, and judging the sample as high-density polyethylene reclaimed material or low-density polyethylene reclaimed material if at least one method is adopted for detection. The detection method of PE reclaimed materials can accurately distinguish reclaimed materials from raw materials, is simple and convenient to operate, does not need excessive pretreatment, and has strong selectivity and simple and easy implementation.
Description
Technical Field
The invention relates to a method for detecting recycled materials, in particular to a method for detecting high-density or low-density polyethylene recycled materials.
Background
Because of the limited petroleum resources, the resource conservation requirements are slowly extended to the heart, and therefore, the widespread use of reclaimed materials has become an unblockable trend. While reclaimed materials do not have the same overall performance and attributes as virgin materials, some materials do not require as good a performance and if made with virgin materials, much of the performance is wasted. For recycled materials, only certain aspects of the performance are needed to manufacture corresponding products.
However, not all areas are suitable for use with regrind. In the current market, there are phenomena that merchants are charged with time or with good charge in order to reduce the cost. Then we need to identify whether the material is recycled by means of practical tests. From the existing identification methods, some empirical methods can distinguish regenerated materials through appearance, combustion and other methods, but most of the methods are empirical and lack accurate theoretical basis.
There are several methods of identifying plastic regrind. Patent CN201110397857.8 discloses a method for detecting regenerated polyester fiber, which needs to use a catalyst to catalyze and degrade materials, and damages the integrity of the materials; patent CN201510711491.5 discloses a method for detecting polystyrene reclaimed materials, which uses DSC test only to identify the reclaimed styrene, but the glass transition temperature may also be affected by the structure of PS itself, so that erroneous judgment may be caused; therefore, the discrimination of the reclaimed material is performed by only one method, and the reliability thereof is relatively limited.
The identification of PE reclaimed materials is always a difficult problem, and no related patent literature exists at present.
Disclosure of Invention
Based on this, the object of the present invention is to overcome the above-mentioned drawbacks of the prior art and to provide a method for detecting high-density or low-density polyethylene reworked material, which is simple and accurate.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a method for detecting high-density or low-density polyethylene reworked material comprises the following steps:
(1) Taking a sample, and judging the sample to be high-density polyethylene or low-density polyethylene;
(2) Detecting the sample by at least one method of headspace gas chromatography, element distribution analysis, halogen distribution analysis, thermal weightlessness analysis and electron microscope analysis;
When the headspace gas chromatography method is adopted for detection, when the sample is high-density polyethylene, setting the peak area of the chromatogram at the position with the time of 7-8min as a, setting the peak area of the chromatogram at the position with the time of 10-11min as b, setting the peak area of the chromatogram at the position with the time of 12-13min as c, and if the value of b/a is less than 1 and the value of c/a is less than 0.7, taking the sample as a high-density polyethylene raw material, otherwise, taking the sample as high-density polyethylene reclaimed material; when the sample is low-density polyethylene, if the total area of the chromatogram is more than 1 and the ratio of the peak area at the position on the chromatogram for 3.5-6.5min to the peak area of the full chromatogram is not less than 50%, the sample is a low-density polyethylene raw material, otherwise, the sample is a low-density polyethylene reclaimed material;
when the element distribution analysis method is adopted for detection, if more than 10 elements are contained in the sample, the sample is high-density polyethylene reclaimed material or low-density polyethylene reclaimed material, otherwise, the sample is high-density polyethylene raw material or low-density polyethylene raw material;
When the halogen distribution analysis method is adopted for detection, if the total halogen content in the sample exceeds 1000mg/kg, the sample is high-density polyethylene reclaimed material or low-density polyethylene reclaimed material, otherwise, the sample is high-density polyethylene raw material or low-density polyethylene raw material;
When the thermal weight loss analysis method is adopted for detection, if the residual weight rate of the sample is less than 10%, the sample is a high-density polyethylene raw material or a low-density polyethylene raw material, otherwise, the sample is a high-density polyethylene reclaimed material or a low-density polyethylene reclaimed material;
When the electron microscope analysis method is adopted for detection, if the surface of the sample is smooth, the sample is a high-density polyethylene raw material or a low-density polyethylene raw material; if the surface of the sample has scratches and pollution, the sample is high-density polyethylene reworked material or low-density polyethylene reworked material;
if at least one of the above methods is used for the detection, at least one method determines that the sample is a high density polyethylene reclaimed material or a low density polyethylene reclaimed material, and then determines that the sample is a high density polyethylene reclaimed material or a low density polyethylene reclaimed material.
In addition, it is noted that the present invention selects the above methods for experiments, if one or more methods are verified as reclaimed materials, the reclaimed materials can be determined, and the methods have no priority relationship, and can be selected according to specific laboratory conditions.
The method for detecting the element distribution analysis can be carried out by ICP, the method for detecting the halogen distribution analysis can be carried out by ion chromatography, but the method is not limited to the ICP, and the method can be used as long as the method can be used for analyzing the elements of the sample.
Preferably, in the step (1), if the sample is not determined to be a polyethylene material, the sample is subjected to infrared spectrum test analysis to confirm the material type of the sample; if the sample is determined to be a polyethylene material, but the sample is not determined to be a high density polyethylene or a low density polyethylene, the melting point of the sample is measured and the sample is identified as a high density polyethylene or a low density polyethylene.
More preferably, the melting point of the sample is measured by DSC method, which is referred to standard GB/T19466.3-2004.
The specific method for infrared spectrum testing provided by the invention comprises the following steps: cutting the sample into granules with the diameter of 3mm multiplied by 3mm, wrapping the granules with a polytetrafluoroethylene film, and hot-pressing the granules into a semitransparent wafer sample at the temperature of 200 ℃ and the pressure of 3 kN; putting the wafer sample into an infrared absorption instrument, and measuring the infrared absorption of the wafer sample within the wave number range of 400-4000 cm -1; the resolution is 4cm -1, and the scanning times are 32 times; test environment requirements: the relative humidity is below 75%, the dew is not formed, the ambient temperature is 15-30 ℃, and the temperature is kept constant.
The invention uses infrared spectrum test, through detecting different functional groups, through comparing with standard spectrograms, it is confirmed whether the material type of the sample is PE, DSC can be used to measure the melting point of the sample, the melting point of HDPE is above 130 ℃ and the melting point of LDPE is below 125 ℃, but the invention is not limited thereto. That is, the sample in the detection method of the present invention may be a known high-density or low-density polyethylene material or may be an unknown one, but the detection method is not limited to the above method, and may be any other method capable of identifying a high-density or low-density polyethylene material in the art.
Preferably, in the headspace gas chromatography in the step (2), when the sample is high-density polyethylene, the number of times of passing the sample is determined based on the value of b/a and the value of c/a, and the service time of the sample is evaluated based on the peak areas of the main characteristic peak and the chromatographic peaks other than the solvent peak.
The above-mentioned judging standard is obtained by the inventor through a great deal of creative labor exploration, the number of times of passing the machine is the processing number of times of the reclaimed material in the use process, and the like, and the raw material and the virgin material can be better judged through comprehensive detection analysis of the number of times of passing the machine and the use time.
Preferably, in the step (2), the conditions for performing headspace gas chromatography on the sample are: stabilizing the sample at 110-130deg.C for 250-330min, loading into capillary chromatographic column, stabilizing at 30-60deg.C for 1-10min, heating to 150-250deg.C at 10-15K/min, and stabilizing at final temperature for 1-10min.
The type of column in the present invention is recommended as J & W122-7021 30m x 250um x0.25um.
Preferably, elemental distribution analysis of the sample is performed using an ICP test under the following conditions: sample treatment using acid digestion: and heating the sulfuric acid and the sample at 400-600 ℃ for 30-50min for digestion, adding hydrogen peroxide after the digestion is completed, and performing on-machine test after the digestion solution is subjected to constant volume by deionized water.
Preferably, the analysis of the halogen distribution in the sample is performed using ion chromatography, the pretreatment steps of which are: and (3) burning the sample by using an oxygen bomb, and then, carrying out constant volume on the absorption liquid and then carrying out ion chromatographic analysis.
Preferably, the halogen distribution analysis method is referred to standard EN14582.
Preferably, the thermogravimetric analysis method is in reference to standard ISO 11358-1:2014. The thermal weight loss analysis is mainly aimed at searching the filling materials in the reclaimed materials, and can give reference to the identification of the reclaimed materials in trend, and the thermal weight loss test method comprises the following steps: a small sample was taken, warmed to 700 ℃ at a constant rate, and its mass change was recorded and analyzed for its residual weight.
When the surface of the sample was observed by electron microscopy, it was found that the surface smoothness of the raw material was high, and even with protrusions, it was smooth. On the surface of the reclaimed material, there are marks for scratches, dust, and the like caused by use. It should be noted here that the area of interest is the surface of the material and not the location where the material is cut.
Compared with the prior art, the invention has the beneficial effects that:
The detection method of PE reclaimed materials can accurately distinguish reclaimed materials from raw materials, is simple and convenient to operate, does not need excessive pretreatment, has strong selectivity, is simple and easy to operate, and breaks through in the field of PE reclaimed material detection.
Drawings
FIG. 1 is a method diagram of a method for detecting a high density or low density polyethylene reclaimed material according to the present invention;
FIG. 2 shows the peak appearance of sample 1 in example 1 in the headspace gas chromatography according to the present invention;
FIG. 3 shows the peak appearance of sample 2 in example 1 in the headspace gas chromatography according to the present invention;
FIG. 4 shows the peak appearance of sample 3 in example 1 in the headspace gas chromatography according to the present invention;
FIG. 5 shows the peak appearance of sample 4 in example 1 in the headspace gas chromatography according to the present invention;
FIG. 6 shows the peak appearance of sample 5 in example 1 in the headspace gas chromatography according to the present invention;
FIG. 7 shows the peak appearance of sample 6 in example 1 in the headspace gas chromatography according to the present invention;
FIG. 8 shows the peak appearance of sample 7 in example 1 in the headspace gas chromatography according to the present invention;
FIG. 9 shows the peak appearance of sample 8 in example 1 in the headspace gas chromatography according to the present invention;
FIG. 10 is a scanning electron microscope image of sample 1 in example 2 of the present invention;
FIG. 11 is a scanning electron microscope image of sample 2 in example 2 of the present invention;
FIG. 12 is a scanning electron microscope image of sample 3 in example 2 of the present invention;
FIG. 13 is a scanning electron microscope image of sample 4 in example 2 of the present invention;
FIG. 14 is a graph showing the area ratio data of characteristic peaks of samples No.1 to No. 5 in example 3 of the present invention.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
Example 1
The detection method of the high-density or low-density polyethylene reclaimed material provided by the invention is used for detecting 8 unknown sample materials, namely samples 1 to 8, and comprises the following steps:
(1) Infrared test
Cutting the sample into granules with the diameter of 3mm multiplied by 3mm, wrapping the granules with a polytetrafluoroethylene film, and hot-pressing the granules into a semitransparent wafer sample at the temperature of 200 ℃ and the pressure of 3 kN; putting the wafer sample into an infrared absorption instrument, and measuring the infrared absorption of the wafer sample within the wave number range of 400-4000 cm -1; the resolution is 4cm -1, and the scanning times are 32 times; test environment requirements: the relative humidity is below 75%, dew is not formed, the ambient temperature is 23 ℃, and the temperature is kept constant. Analysis was performed using a fourier infrared analyzer, and it was confirmed that the components were PE.
(2) DSC test
10.5Mg of the sample is taken out in an aluminum crucible, pressed and then enters DSC for testing, and the testing method is referred to the standard GB/T19466.3-2004. DSC measured the melting point of 134 ℃, 135 ℃, 134 ℃, 135 ℃ and 134 ℃ respectively, and judged that the materials are HDPE materials.
(3) ICP analysis
The conditions for ICP testing were: and (3) treating the sample by using an acid digestion method, heating 10ml of sulfuric acid and 0.5g of the sample at 500 ℃ for 30min for digestion, adding less than 10ml of hydrogen peroxide after the digestion is completed, and performing on-machine test after the digestion solution is subjected to volume fixation by deionized water. The ICP data are shown below, and the data in Table 1 are the concentrations of the respective ions in mg/kg.
Table 1 ICP analytical data
As can be seen from the data in table 1, samples 4 to 8 contained ten or more elements at the same time, and therefore samples 4 to 8 were judged to be HDPE reclaimed materials, whereas samples 1 to 3 were judged to be HDPE raw materials, and the types of elements in samples 1 to 3 were not in conformity with the above-mentioned rules.
(4) Headspace gas chromatography
Taking 1.2g of each sample in a 12mL sample bottle, stabilizing for 300min at 120 ℃, then entering a capillary chromatographic column, stabilizing for 4min at 50 ℃, then heating to 200 ℃ at a rate of 15K/min, stabilizing for 2min at the final temperature of 200 ℃, and analyzing the obtained data with a carrier gas flow of 20 mL/min.
Comparing the peak emergence condition (figures 2-4) of the three raw material HDPE judged in the step (3) with a plurality of characteristic peaks of the peak emergence condition (figures 5-9) of the five regenerated material HDPE, and further verifying the test result in the step (3) according to the ratio of the characteristic peak areas and the number of the impurity peaks. Carrying out area integration on each peak of the headspace gas chromatography, and dividing the area of the b peak by the area of the a peak to obtain a b/a characteristic value; and dividing the area of the peak c by the area of the peak a to obtain a c/a characteristic value. If the b/a value is greater than 1 and the c/a value is greater than 0.7, the regenerated material is judged, and if not satisfied, the raw material is judged. In this example, the characteristic values of the respective samples are shown in table 2 below:
TABLE 2 characterization values for each sample
| Sample 1 | Sample 2 | Sample 3 | Sample 4 | Sample 5 | Sample 6 | Sample 7 | Sample 8 | |
| b/a | 0.363726 | 0.635218 | 0.404433 | 1.113946 | 1.797281 | 2.224026 | 1.751964 | 2.147003 |
| c/a | 0.136259 | 0.249621 | 0.132432 | 1.295493 | 1.192107 | 5.795929 | 6.547886 | 1.797445 |
As can be seen from the data in Table 2, samples 4 to 8 were judged to be regrind if the b/a value was greater than 1 and the c/a value was greater than 0.7, whereas samples 1 to 3 were not in conformity with the above-mentioned rule, and were judged to be raw materials, which were consistent with the identification result in step (3), and the rationality of the identification method in step (3) was further verified.
Example 2
The method for detecting the high-density or low-density polyethylene reclaimed materials provided by the invention is used for detecting 4 samples, and comprises the following steps:
(1) Infrared test
Cutting the sample into granules with the diameter of 3mm multiplied by 3mm, wrapping the granules with a polytetrafluoroethylene film, and hot-pressing the granules into a semitransparent wafer sample at the temperature of 200 ℃ and the pressure of 3 kN; putting the wafer sample into an infrared absorption instrument, and measuring the infrared absorption of the wafer sample within the wave number range of 400-4000 cm -1; the resolution is 4cm -1, and the scanning times are 32 times; test environment requirements: the relative humidity is below 75%, dew is not formed, the ambient temperature is 23 ℃, and the temperature is kept constant. Analysis was performed using a fourier infrared analyzer, and it was confirmed that the components were PE.
(2) DSC test
Samples of 10.5mg were placed in an aluminum crucible, pressed and tested by DSC, with reference to standard GB/T19466.3-2004. DSC measured the melting point at 134 deg.C, and judged to be HDPE material.
(3) Electron microscope data: raw material data
One sample is taken and a plane is cut. Fixing the plane downwards on the conductive adhesive to ensure that the highest point of the sample is approximately parallel to the conductive adhesive, and the height is below 10 mm; the height difference of the upper surface of the sample is smaller than 1mm, metal spraying is carried out for 40s, and the upper surface of the sample is observed by SEM. SEM images are shown in fig. 10 to 13, wherein fig. 10 is a scanning electron microscope view of sample 1, and fig. 11 to 13 are scanning electron microscope views of samples 2 to 4.
From the structure of the plastic surface of fig. 11 to 13 we can clearly distinguish scratches and contamination of the material after use, thus deciding the samples represented by fig. 11 to 13 as reclaimed materials; in the sample 1 in fig. 10, although there were a small number of protrusions, the smoothness of the surface was much better, and therefore, it was judged as a raw material.
(4) Thermogravimetric analysis
And (3) obtaining a sample 1 serving as a raw material and samples 2 to 4 serving as regenerated materials through the test analysis in the step (3).
The method for testing the thermal weight loss comprises the following steps: taking a small amount of samples, heating to 700 ℃ at a constant rate, recording the mass change of the samples, and analyzing the residual weight mass of the samples; and (3) respectively carrying out thermal weight loss analysis on the samples 1 to 4, and testing the residual weight of the samples to obtain the residual weight rate of less than 10% in the sample 1, wherein the residual weight rates of 27%, 41% and 19% in the TGA (tgA) in the samples 2 to 4 are respectively measured, so that the rationality of the thermal weight loss analysis method is further verified.
Example 3
Since the environment and thermal history of the actual recycled material itself are very complex, in order to simplify the process, this example simulates the continuous recycling of the recycled material by continuously repeating the process (the extruder is used to heat the material, and each actual recycling of the recycled material must be performed), and observing the change of the material during the continuous recycling by the headspace gas chromatography test, as shown in fig. 14, the abscissa of fig. 14 represents samples 1 to 5, and the ordinate represents: and carrying out headspace gas chromatography test on samples 1-5, and calculating the area ratio of the characteristic peaks.
The treatment process of the specific samples 1 to 5 is as follows: the raw material (sample No. 1) is repeatedly processed once to obtain sample No. 2, repeatedly processed once to obtain sample No. 3, repeatedly processed once to obtain sample No. 4, and repeatedly processed once to obtain sample No. 5.
As can be seen from fig. 14, the area ratio of the characteristic peaks tends to increase with the number of repeated processes (from sample No. 1 to sample No. 5), which indicates that: the area ratio of the characteristic peaks of the regenerated material is high, while the area ratio of the characteristic peaks of the raw material is low. Although the present example cannot specifically verify the basis of the determination in the headspace gas chromatography according to the present invention, the trend simulated in the present example is consistent with the trend in the headspace gas chromatography according to the present invention.
Although the magnitude of the simulated regeneration characteristic change used herein is not as pronounced as the actual regeneration due to differences in actual service conditions, the gradient change may also support the criteria of the present invention.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (1)
1. The method for detecting the high-density or low-density polyethylene reclaimed material is characterized by comprising the following steps of:
(1) Taking a sample, and judging the sample to be high-density polyethylene or low-density polyethylene; if the sample is uncertain whether the sample is made of polyethylene material, carrying out infrared spectrum test analysis on the sample, and confirming the material type of the sample; if the sample is determined to be a polyethylene material, but the sample is not determined to be high-density polyethylene or low-density polyethylene, measuring the melting point of the sample, and identifying the sample as high-density polyethylene or low-density polyethylene;
(2) Detecting the sample by headspace gas chromatography;
When the headspace gas chromatography method is adopted for detection, when the sample is high-density polyethylene, setting the peak area of the chromatogram at the position with the time of 7-8min as a, setting the peak area of the chromatogram at the position with the time of 10-11min as b, setting the peak area of the chromatogram at the position with the time of 12-13min as c, and if the value of b/a is less than 1 and the value of c/a is less than 0.7, taking the sample as a high-density polyethylene raw material, otherwise, taking the sample as high-density polyethylene reclaimed material; when the sample is low-density polyethylene, if the total area of the chromatogram is more than 1 and the ratio of the peak area at the position on the chromatogram for 3.5-6.5min to the peak area of the full chromatogram is not less than 50%, the sample is a low-density polyethylene raw material, otherwise, the sample is a low-density polyethylene reclaimed material;
In the step (2), the conditions of the headspace gas chromatography are as follows: stabilizing the sample at 110-130deg.C for 250-330min, introducing into capillary chromatographic column, stabilizing at 30-60deg.C for 1-10min, heating to 150-250deg.C at 10-15K/min, and stabilizing at final temperature for 1-10min; the chromatographic column is of the type J & W122-7021 30m x 250um x0.25um.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711272882.7A CN109870561B (en) | 2017-12-04 | 2017-12-04 | Method for detecting high-density or low-density polyethylene reclaimed material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711272882.7A CN109870561B (en) | 2017-12-04 | 2017-12-04 | Method for detecting high-density or low-density polyethylene reclaimed material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109870561A CN109870561A (en) | 2019-06-11 |
| CN109870561B true CN109870561B (en) | 2024-05-14 |
Family
ID=66915290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711272882.7A Active CN109870561B (en) | 2017-12-04 | 2017-12-04 | Method for detecting high-density or low-density polyethylene reclaimed material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109870561B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114764099A (en) * | 2021-05-07 | 2022-07-19 | 上海睿聚环保科技有限公司 | Evaluation system for evaluating quality of regenerated plastic at multiple angles |
| CN115616205B (en) * | 2022-12-21 | 2023-03-21 | 国高材高分子材料产业创新中心有限公司 | Method and system for identifying high impact polystyrene reclaimed material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001310160A (en) * | 2000-05-01 | 2001-11-06 | Sony Corp | Apparatus for discriminating plastic and method for discriminating plastic |
| CN102175637A (en) * | 2010-12-30 | 2011-09-07 | 中国药品生物制品检定所 | Method for detecting plastics |
| CN102520082A (en) * | 2011-12-01 | 2012-06-27 | 湖南省湘维有限公司 | Method for determining volatile components in polyvinyl alcohol in full-evaporation headspace gas chromatography |
| CN102585361A (en) * | 2012-01-06 | 2012-07-18 | 中山大学 | Method for regenerating polypropylene reclaimed material |
| CN106769986A (en) * | 2017-01-11 | 2017-05-31 | 天津市建筑材料产品质量监督检测中心 | The discriminating of recycling plastics and quantitative detecting method in a kind of plastic pipe |
-
2017
- 2017-12-04 CN CN201711272882.7A patent/CN109870561B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001310160A (en) * | 2000-05-01 | 2001-11-06 | Sony Corp | Apparatus for discriminating plastic and method for discriminating plastic |
| CN102175637A (en) * | 2010-12-30 | 2011-09-07 | 中国药品生物制品检定所 | Method for detecting plastics |
| CN102520082A (en) * | 2011-12-01 | 2012-06-27 | 湖南省湘维有限公司 | Method for determining volatile components in polyvinyl alcohol in full-evaporation headspace gas chromatography |
| CN102585361A (en) * | 2012-01-06 | 2012-07-18 | 中山大学 | Method for regenerating polypropylene reclaimed material |
| CN106769986A (en) * | 2017-01-11 | 2017-05-31 | 天津市建筑材料产品质量监督检测中心 | The discriminating of recycling plastics and quantitative detecting method in a kind of plastic pipe |
Non-Patent Citations (12)
| Title |
|---|
| "再生塑料的识别研究";谢桂兰;《中国博士学位论文全文数据库 工程科技Ⅱ辑》;20130115(第1期);摘要，第82页3.3聚乙烯（高密度或低密度聚乙烯）再生料与新料的元素差异，第83页图67 * |
| 低密度聚乙烯再生料改性基础研究;赵雪艳;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20140215(第2期);第21页2.3.4差示扫描量热分析 * |
| 再生聚乙烯回掺量对无卤阻燃保温泡沫材料性能的影响;廖坤添;许绿丝;李嘉桐;;功能材料;20130430(第08期);全文 * |
| 刘能盛等.基于热分析技术对聚氯乙烯再生料的热稳定性研究.《塑料科技》.2015,(第02期), * |
| 国家技术监督局.聚苯乙烯和丙烯腈一丁二烯-苯乙烯树脂中残留苯乙烯单体的测定 气相色谱法.《GB/T16867—1997》.1997, * |
| 张庆飞等.红外光谱法对PE食品包装膜中再生料的快速鉴别.《现代食品》.2016,(第10期), * |
| 王美华 ; 丛林凤 ; .食品包装用聚乙烯树脂再生料鉴别技术研究.包装工程.2009,(第04期),全文. * |
| 王美华等.食品包装用聚乙烯树脂再生料鉴别技术研究.《包装工程》.2009,(第04期), * |
| 谢桂兰."再生塑料的识别研究".《中国博士学位论文全文数据库 工程科技Ⅱ辑》.2013,(第1期), * |
| 贾春晓等.定性分析.《现代仪器分析技术及其在食品中的应用》.2005, * |
| 赵雪艳.低密度聚乙烯再生料改性基础研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2014,(第2期), * |
| 食品包装用聚乙烯树脂再生料鉴别技术研究;王美华;丛林凤;;包装工程;20090415(第04期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109870561A (en) | 2019-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Akoueson et al. | Identification and quantification of plastic additives using pyrolysis-GC/MS: A review | |
| CN109870561B (en) | Method for detecting high-density or low-density polyethylene reclaimed material | |
| CN108918724B (en) | Method for detecting characteristic odor of polyurethane synthetic leather | |
| CN113686805A (en) | Oil product characteristic fingerprint spectrum, establishing method and application in cigarette oil spot identification | |
| CN112331281B (en) | High polymer material service life prediction method based on environmental big data and machine learning | |
| CN109870560A (en) | A kind of discrimination method of polypropene recycled materials | |
| CN109115908B (en) | Hierarchical clustering extraction feature-based cheddar cheese identity distinguishing and identifying method | |
| CN102449469A (en) | Method for quantifying red phosphorus in resin | |
| CN103969557A (en) | GIS insulation state diagnosis method based on gas component analysis | |
| CN116087135B (en) | Evaluation test method for performance of inner layer adhesive of aluminum plastic film | |
| CN111413324A (en) | Raman spectrum detection method for trace crude oil in naphtha by using fluorescence background | |
| CN109900849A (en) | The determination method and system of organic additive degradation effect in a kind of gel phase | |
| CN106442798B (en) | A kind of accurate measuring method of humic-acid kind organic matter high-temperature decomposition product | |
| CN217638892U (en) | Device for detecting non-methane total hydrocarbons in ambient air | |
| CN113916865A (en) | Online Raman measurement method for gas retention performance of hollow microspheres | |
| CN109870559A (en) | A kind of discrimination method of ABS plastic reworked material | |
| CN107402191A (en) | A kind of oil product of gasoline quality determining method for evading disturbing factor | |
| CN113311076A (en) | Method for rapidly distinguishing different varieties of rice based on aldehyde compounds | |
| CN110715985A (en) | Method for judging frying oil quality by combining gas phase fingerprint spectrum with partial least square method | |
| CN112649384B (en) | Method for measuring content of calcium stearate in polymer resin | |
| CN113237971B (en) | Wine production area identification method and identification system thereof | |
| CN114460200B (en) | Method for identifying weight gain of silk floss methacrylamide grafted polymer | |
| CN109030640B (en) | Qualitative screening method of hexabromocyclododecane in polymer material of electronic and electrical products | |
| Jayawardene et al. | Accessing Biobanks to Obtain Human Biomonitoring Data | |
| Milczarek et al. | Way to distinguish car paint traces based on epoxy primer layers analysis by pyrolysis-gas chromatography-mass spectrometry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |