CN109870561A - A kind of detection method of high density or low density polyethylene (LDPE) reworked material - Google Patents
A kind of detection method of high density or low density polyethylene (LDPE) reworked material Download PDFInfo
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- CN109870561A CN109870561A CN201711272882.7A CN201711272882A CN109870561A CN 109870561 A CN109870561 A CN 109870561A CN 201711272882 A CN201711272882 A CN 201711272882A CN 109870561 A CN109870561 A CN 109870561A
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- 239000000463 material Substances 0.000 title claims abstract description 112
- 229920001684 low density polyethylene Polymers 0.000 title claims abstract description 100
- 239000004702 low-density polyethylene Substances 0.000 title claims abstract description 100
- 229920001903 high density polyethylene Polymers 0.000 title claims abstract description 80
- 239000004700 high-density polyethylene Substances 0.000 title claims abstract description 80
- 238000001514 detection method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000004458 analytical method Methods 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 238000003988 headspace gas chromatography Methods 0.000 claims abstract description 22
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 12
- 150000002367 halogens Chemical class 0.000 claims abstract description 12
- 239000004698 Polyethylene Substances 0.000 claims abstract description 10
- 238000002203 pretreatment Methods 0.000 claims abstract description 4
- 238000012360 testing method Methods 0.000 claims description 18
- -1 otherwise Substances 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004255 ion exchange chromatography Methods 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 238000010998 test method Methods 0.000 claims description 6
- 238000002329 infrared spectrum Methods 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000029087 digestion Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000184 acid digestion Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000012958 reprocessing Methods 0.000 description 3
- 239000004793 Polystyrene Substances 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
- 230000008901 benefit Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000012850 discrimination method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004836 empirical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
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- 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 kind of high density or the detection method of low density polyethylene (LDPE) reworked material, include the following steps: that (1) takes sample, determines the sample for high density polyethylene (HDPE) or low density polyethylene (LDPE)；(2) sample is detected using at least one of head space gas chromatography, element distribution analysis, halogen distributional analysis, thermogravimetic analysis (TGA), electron microscope analysis method, when being detected according to above-mentioned at least one method, at least a kind of method determines that sample is high density polyethylene (HDPE) reworked material or low density polyethylene (LDPE) reworked material, then determines sample for high density polyethylene (HDPE) reworked material or low density polyethylene (LDPE) reworked material.The detection method of PE reworked material of the present invention, can accurately distinguish reworked material and raw material, and it is easy to operate, without carrying out excessive pre-treatment, and analysis method alternative is strong, simple and easy.
Description
Technical field
The present invention relates to a kind of detection method of reworked material, especially a kind of high density or low density polyethylene (LDPE) reworked material
Detection method.
Background technique
Due to the finiteness of petroleum resources, the requirement to economize on resources is slowly rooted in the hearts of the people, and therefore, reworked material is widely used
At irresistible trend.Although reworked material is all not so good as virgin material in overall performance and attribute, some materials do not need that
Good performance just wastes many performances if all manufactured with virgin material.And for reworked material, we only need to process certain
The performance of a little aspects can produce corresponding product.
However, not all field is suitable for using reworked material.Currently on the market, there are businessmans in order to reduce cost
And it adulterates or the phenomenon to fill well time.So, whether we just need to be again to material by the means of actual test
Raw material are identified.From the point of view of current existing discrimination method, there are some empirical methods can be by the side such as appearance, burning
Method distinguishes reworked material, but these methods be mostly it is empirical, lack accurate theoretical foundation.
There are some methods for identifying recycled plastics polymers at present.Patent CN201110397857.8 discloses a kind of detection regeneration
The method of polyester fiber, this method need to use catalyst degradable material, destroy the integrality of material；Patent
CN201510711491.5 discloses a kind of method for detecting polystyrene reworked material, and this method is only identified with DSC test
Regenerated phenylethene, but glass transition temperature may also be subjected to the structure influence of PS itself, it is possible that causing to judge by accident；Therefore,
The identification of reworked material is only carried out with a kind of method, reliability is relatively too limited.
The identification of PE reworked material is always a problem, and there is presently no relevant patent documents.
Summary of the invention
Based on this, a kind of high density or low is provided it is an object of the invention to overcome in place of above-mentioned the deficiencies in the prior art
The detection method of density polyethylene reworked material, the method are simple, accurate.
To achieve the above object, the technical solution used in the present invention are as follows: a kind of high density or low density polyethylene (LDPE) regeneration
The detection method of material, includes the following steps:
(1) sample is taken, determines the sample for high density polyethylene (HDPE) or low density polyethylene (LDPE)；
(2) sample is used into head space gas chromatography, element distribution analysis, halogen distributional analysis, thermogravimetic analysis (TGA), electricity
At least one of mirror analysis method is detected；
When being detected using head space gas chromatography method, when sample is high density polyethylene (HDPE), by the time in chromatogram
It is set as a for the peak area at 7-8min, the time in chromatogram is set as b for the peak area at 10-11min, when by chromatogram
Between for 12-13min place peak area be set as c, if the value of b/a is less than 1 and the value of c/a is less than 0.7, sample for high density gather
Ethylene raw material, otherwise, sample are high density polyethylene (HDPE) reworked material；When sample is low density polyethylene (LDPE), if the total face of chromatogram
Product is greater than the ratio that the time on 1 and chromatogram is the peak area and full spectrogram peak area at 3.5-6.5min and is not less than 50%, then
Sample is low density polyethylene (LDPE) raw material, and otherwise, sample is low density polyethylene (LDPE) reworked material；
When being detected using element distribution analysis method, if element is 10 kinds or more in sample, sample is high-density polyethylene
Alkene reworked material or low density polyethylene (LDPE) reworked material, otherwise, sample are high density polyethylene (HDPE) raw material or low density polyethylene (LDPE) former material
Material；
When being detected using halogen distributional analysis method, if in sample, total halogen content is more than 1000mg/kg, then sample is
High density polyethylene (HDPE) reworked material or low density polyethylene (LDPE) reworked material, otherwise, sample are high density polyethylene (HDPE) raw material or low-density
Polyethylene raw material；
When being detected using thermogravimetic analysis (TGA) method, if the residual heavy rate of sample, less than 10%, sample is high density polyethylene (HDPE)
Raw material or low density polyethylene (LDPE) raw material, otherwise, sample are high density polyethylene (HDPE) reworked material or low density polyethylene (LDPE) reworked material；
When being detected using electron microscope analysis method, if sample surfaces are smooth, sample is high density polyethylene (HDPE) raw material or low
Density polyethylene raw material；If sample surfaces have scratch and pollution, sample is that high density polyethylene (HDPE) reworked material or low-density are poly-
Ethylene reworked material；
When being detected according to above-mentioned at least one method, at least a kind of method determines that sample is high density polyethylene (HDPE)
Reworked material or low density polyethylene (LDPE) reworked material then determine that sample regenerates for high density polyethylene (HDPE) reworked material or low density polyethylene (LDPE)
Material.
Furthermore it is noted that the present invention selects above method to test, if there is one or more of method validations
For reworked material, it can be determined as reworked material, there is no dominance relation between each method, can be selected according to specific experiment room condition
It takes.
The detection method of element distribution analysis can take ICP to carry out in the present invention, the detection method of halogen distributional analysis
Ion chromatography can be used, but it is not limited to this, as long as the method for being able to achieve the analysis to sample element can use,
Why the present invention analyzes the element in sample, is because the reprocessing of reworked material and reusing that number is more, this must
So will cause and affect using in process to the distribution of its element, it is above-mentioned about Elemental redistribution to reworked material
Judgment basis is inventor by a large amount of creative works exploration gained.
Preferably, in the step (1), if whether it is polythene material that sample is uncertain, sample is taken to carry out infrared spectroscopy
Test analysis, the material category of confirmatory sample；If sample is determined as polythene material, but sample does not know as high-density polyethylene
Alkene or low density polyethylene (LDPE) measure the fusing point of sample, and identifying sample is high density polyethylene (HDPE) or low density polyethylene (LDPE).
It is highly preferred that the fusing point of the sample is tested using DSC method, test method reference standard GB/T
19466.3-2004。
Examination of infrared spectrum of the present invention method particularly includes: sample is cut into the pellet of 3mm × 3mm, and with poly-
Tetrafluoroethylene is wrapped up, and carries out being hot pressed into translucent wafer sample under 200 DEG C, the pressure of 3kN；Wafer sample is packed into
Infrared absorption instrument measures its 400~4000cm-1The infrared absorption of wave-number range；Resolution ratio is 4cm-1, scanning times 32 times；It surveys
Examination environmental requirement: for relative humidity 75% hereinafter, not condensing, environment temperature is 15 DEG C~30 DEG C, keeps temperature constant.
The present invention utilizes examination of infrared spectrum, by detecting different functional groups, by being compared with standard spectrogram, really
Whether the material category for recognizing sample is PE, and the fusing point of dsc measurement sample can be used, and judges that it is molten from the position of DSC melting peak
Point, HDPE fusing point is at 130 DEG C or more, and the fusing point of LDPE is at 125 DEG C hereinafter, still not limited to this.In other words, the present invention examines
Sample in survey method can be known high density or low-density polyethylene material, be also possible to it is unknown, but by upper
It states the available high density of identification or low-density polyethylene material, the measuring method is also not limited to the above method, it can also
Think that this field can identify the other methods of high density or low-density polyethylene material.
Preferably, in the head space gas chromatography in the step (2), when sample is high density polyethylene (HDPE), with b/a
Value, the value of c/a be according to determine sample cross machine number, with the peak area of the chromatographic peak other than principal character peak, solvent peak
That judges sample uses the time.
Above-mentioned criterion is inventor by a large amount of creative works exploration gained, and crossing machine number that is to say reworked material
Processing times etc. in use, by can preferably comment to crossing machine number and being analyzed using the comprehensive detection of time
Sentence raw material and primary material, because it is less to cross machine number generally without reprocessing for raw material, and reworked material generally passes through very much
It is more to cross machine number for secondary reprocessing.
Preferably, in the step (2), the sample carries out the condition of head space gas chromatography are as follows: by sample 110
Enter capillary chromatographic column after stablizing 250-330min at DEG C -130 DEG C, then in 30-60 DEG C of stable 1-10min, then with 10-
The rate of 15K/min is warming up to 150-250 DEG C, at the final temperature stable 1-10min.
Chromatographic column type in the present invention is recommended as J&W 122-7021 30m x 250um x0.25um.
Preferably, the element distribution analysis for carrying out sample, the condition of the ICP test are as follows: disappear using acid are tested using ICP
Solution carries out sample treatment: sulfuric acid and sample being heated to 30-50min at 400-600 DEG C and cleared up, is added after the completion of resolution
Then hydrogen peroxide will carry out examination with computer after digestion solution deionized water constant volume.
Preferably, the halogen distributional analysis in sample, the pre-treatment of the ion chromatography sample are carried out using ion chromatography
Step are as follows: after sample Oxygen Bomb Combustion, constant volume is carried out to absorbing liquid, then carries out ion chromatography.
Preferably, the halogen distributional analysis method reference standard EN14582.
Preferably, the thermogravimetic analysis (TGA) method reference standard ISO 11358-1:2014.Thermogravimetic analysis (TGA) mainly for
Filler material in reworked material is retrieved, and can provide reference, the test method of thermal weight loss to the identification of reworked material in trend
Are as follows: a small amount of sample is taken, is warming up to 700 DEG C with constant rate of speed, and record its mass change, analyzes its residual heavy amount.
When Electronic Speculum observes sample surfaces, discovery raw material surface flatness is higher, also more smooth even if there is protrusion.
And on reworked material surface, have scratch caused by using, the marking that dust etc. uses.It is noted here that the position of concern
It is the surface of material rather than the position cut out of material.
Compared with the existing technology, the invention has the benefit that
The detection method of PE reworked material of the present invention, can accurately distinguish reworked material and raw material, and easy to operate,
Without carrying out excessive pre-treatment, and analysis method is alternative strong, simple and easy, PE reworked material detection field
It breaks through.
Detailed description of the invention
Fig. 1 is a kind of method figure of the detection method of high density of the present invention or low density polyethylene (LDPE) reworked material；
Fig. 2 is the appearance situation of the sample 1 in embodiment 1 in head space gas chromatography of the present invention；
Fig. 3 is the appearance situation of the sample 2 in embodiment 1 in head space gas chromatography of the present invention；
Fig. 4 is the appearance situation of the sample 3 in embodiment 1 in head space gas chromatography of the present invention；
Fig. 5 is the appearance situation of the sample 4 in embodiment 1 in head space gas chromatography of the present invention；
Fig. 6 is the appearance situation of the sample 5 in embodiment 1 in head space gas chromatography of the present invention；
Fig. 7 is the appearance situation of the sample 6 in embodiment 1 in head space gas chromatography of the present invention；
Fig. 8 is the appearance situation of the sample 7 in embodiment 1 in head space gas chromatography of the present invention；
Fig. 9 is the appearance situation of the sample 8 in embodiment 1 in head space gas chromatography of the present invention；
Figure 10 is a kind of scanning electron microscope (SEM) photograph of sample 1 in the embodiment of the present invention 2；
Figure 11 is a kind of scanning electron microscope (SEM) photograph of sample 2 in the embodiment of the present invention 2；
Figure 12 is a kind of scanning electron microscope (SEM) photograph of sample 3 in the embodiment of the present invention 2；
Figure 13 is a kind of scanning electron microscope (SEM) photograph of sample 4 in the embodiment of the present invention 2；
Figure 14 is the area ratio datagram of the characteristic peak of 1~No. 5 sample in the embodiment of the present invention 3.
Specific embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with the drawings and specific embodiments pair
The present invention is described further.
Embodiment 1
The detection method of high density of the present invention or low density polyethylene (LDPE) reworked material, the present embodiment is to 8 unknown samples
Material is detected, respectively sample 1~8, the detection method are as follows:
(1) infrared test
Sample is cut into the pellet of 3mm × 3mm, and is wrapped up with polytetrafluoroethylene film, in 200 DEG C, the pressure of 3kN
Under carry out being hot pressed into translucent wafer sample；Wafer sample is packed into infrared absorption instrument, measures its 400~4000cm-1Wave number model
The infrared absorption enclosed；Resolution ratio is 4cm-1, scanning times 32 times；Test environmental requirement: relative humidity is 75% hereinafter, not tying
Dew, environment temperature are 23 DEG C, keep temperature constant.It is analyzed using Fourier's infrared spectrum analyser, confirms that its ingredient is PE.
(2) DSC is tested
It takes sample 10.5mg in aluminum cup, is tested after suppressing sample into DSC, test method reference standard
GB/T 19466.3-2004.It is respectively 134 DEG C, 134 DEG C, 134 DEG C, 135 DEG C, 134 DEG C, 134 DEG C, 135 that DSC, which measures its fusing point,
DEG C, 134 DEG C, determine that it is HDPE material.
(3) icp analysis
The condition of ICP test are as follows: handle sample using Acid digestion method, 10ml sulfuric acid and 0.5g sample are added at 500 DEG C
Hot 30min is cleared up, and the hydrogen peroxide for being less than 10ml is added after the completion of resolution, then that digestion solution is laggard with deionized water constant volume
Row examination with computer.The following are ICP data, and as shown in table 1, the data in table are the corresponding concentration of each ion, and concentration unit is
mg/kg。
1 icp analysis data of table
It can be seen that in sample 4~8 while measuring from the data in table 1 and contain ten kinds and the above element in sample, because
This, judgement sample 4~8 is HDPE reworked material, and the element species in sample 1~3 do not meet above-mentioned rule, therefore, determines sample
Product 1~3 are HDPE raw material.
(4) head space gas chromatography
It takes each 1.2g of each sample in 12ml sample bottle, stablizes 300min at 120 DEG C, enter capillary chromatography later
Then column is warming up to 200 DEG C in 50 DEG C of stable 4min with the rate of 15K/min, stablize 2min at 200 DEG C of final temperature, carries
Throughput is 20mL/min, is analyzed obtained data.
Appearance situation (attached drawing 2~4) to the three kinds of raw material HDPE determined in step (3) and five kinds of reworked material HDPE's
Several characteristic peaks of appearance situation (attached drawing 5~9) are compared, according to the quantity of the ratio between characteristic peak area and miscellaneous peak, further
Test result in step (3) is verified.The each peak of headspace gas chromatography is subjected to area integral, and with the area at the peak b
Divided by the area at the peak a, b/a characteristic value is obtained；And c/a characteristic value is obtained divided by the area at the peak a with the area at the peak c.If b/a
Value is greater than 1 and c/a value and is greater than 0.7, then is determined as reworked material, raw material are determined as if being unsatisfactory for.In this embodiment, respectively
The characteristic value of a sample see the table below shown in 2:
Each characteristic value of each sample of table 2
| 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 |
It can be seen that b/a value in sample 4~8 from the data in table 2 and be greater than 1 and c/a value greater than 0.7, then determine that it is again
Raw material, and above-mentioned rule is not met in sample 1~3, determining that it is raw material, this is consistent with the qualification result in step (3),
Also the reasonability of identification method in step (3) is further demonstrated.
Embodiment 2
The detection method of high density of the present invention or low density polyethylene (LDPE) reworked material, the present embodiment carry out 4 samples
Detection, the method are as follows:
(1) infrared test
Sample is cut into the pellet of 3mm × 3mm, and is wrapped up with polytetrafluoroethylene film, in 200 DEG C, the pressure of 3kN
Under carry out being hot pressed into translucent wafer sample；Wafer sample is packed into infrared absorption instrument, measures its 400~4000cm-1Wave number model
The infrared absorption enclosed；Resolution ratio is 4cm-1, scanning times 32 times；Test environmental requirement: relative humidity is 75% hereinafter, not tying
Dew, environment temperature are 23 DEG C, keep temperature constant.It is analyzed using Fourier's infrared spectrum analyser, confirms that its ingredient is PE.
(2) DSC is tested
It takes in sample 10.5mg and aluminum cup, is tested after suppressing sample into DSC, test method reference standard
GB/T 19466.3-2004.It is respectively 134 DEG C, 134 DEG C, 134 DEG C, 134 DEG C that DSC, which measures its fusing point, determines that it is HDPE material
Material.
(3) electron microscopic data: raw material data
One, sample is taken, and a plane will be determined.This plane is downwardly fixed on conducting resinl, it is ensured that sample highest point
It is substantially parallel with conducting resinl, it is highly 10mm or less；Sample upper level gap is less than 1mm, carries out metal spraying 40s, uses SEM
Observe sample upper surface.SEM schemes as shown in attached drawing 10~13, and wherein Figure 10 is the scanning electron microscopic observation figure of sample 1, Figure 11~13
For the scanning electron microscopic observation figure of sample 2~4.
Scratch caused by we can be clear resolved materials after usage from the structure of the frosting of Figure 11~13
And pollution, therefore, it is determined that the sample that represents of Figure 11~13 is reworked material；Although and also have a small amount of protrusion in the sample 1 in Figure 10,
But the excellent many of the smooth degree on its surface, therefore, it is determined that it is raw material.
(4) thermogravimetic analysis (TGA)
By the test analysis in step (3), derived sample 1 is raw material, and sample 2~4 is reworked material.
The test method of thermal weight loss are as follows: a small amount of sample is taken, is warming up to 700 DEG C with constant rate of speed, and record its mass change,
Analyze its residual heavy amount；Thermogravimetic analysis (TGA) is carried out respectively to sample 1~4, to its it is residual it is heavy test, test obtain in sample 1
Residual heavy rate less than 10%, and the TGA in sample 2~4 measure its it is residual it is heavy be respectively 27%, 41%, 19%, this further verify
The reasonability of thermogravimetic analysis (TGA) method of the present invention.
Embodiment 3
Due to the use environment and thermal history of real regeneration material itself be it is extremely complex, in order to simplify this process, this
Embodiment (carries out hot-working to material with extruder, each regeneration of real reworked material is also all necessary with continuous repetition processing
By this process) to simulate the constantly regenerating of reworked material, and material is observed constantly again by headspace gas chromatography test
Variation during life, as shown in Fig. 14, abscissa represents 1~No. 5 sample in attached drawing 14, and ordinate represents: to 1~No. 5
Sample carries out headspace gas chromatography test, the area ratio of the characteristic peak calculated.
The treatment process of specific sample 1~5 is as follows: raw material (No. 1 sample) repeated to process once, obtains No. 2 samples,
It repeats processing and once obtains No. 3 samples, repeat processing and once obtain No. 4 samples, repeat processing and once obtain No. 5 samples
Product.
From attached drawing 14 as can be seen that with the variation (from No. 1 sample to No. 5 samples) for repeating processing times, characteristic peak
Area ratio have raised trend, this explanation: the area ratio of the characteristic peak of reworked material is high, and the area ratio of the characteristic peak of raw material
It is low.Although the present embodiment cannot specifically verify judgment basis in head space gas chromatography of the present invention, this reality
It is consistent with the trend in head space gas chromatography of the present invention for applying example and simulating this trend come.
Although the amplitude of simulation reworked material characteristic value variation used herein above is not due to the difference for actually using operating condition
There is real reworked material obvious, but its change of gradient still can support criterion of the invention.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (8)
1. the detection method of a kind of high density or low density polyethylene (LDPE) reworked material, which comprises the steps of:
(1) sample is taken, determines the sample for high density polyethylene (HDPE) or low density polyethylene (LDPE)；
(2) by sample using head space gas chromatography, element distribution analysis, halogen distributional analysis, thermogravimetic analysis (TGA), Electronic Speculum point
At least one of analysis method is detected；
It is 7- by the time in chromatogram when sample is high density polyethylene (HDPE) when being detected using head space gas chromatography method
Peak area at 8min is set as a, and the time in chromatogram is set as b for the peak area at 10-11min, is by the time in chromatogram
Peak area at 12-13min is set as c, if the value of b/a is less than 1 and the value of c/a is less than 0.7, sample is high density polyethylene (HDPE)
Raw material, otherwise, sample are high density polyethylene (HDPE) reworked material；When sample is low density polyethylene (LDPE), if the chromatogram gross area is big
It is not less than 50% in the time on 1 and chromatogram for the ratio of peak area and full spectrogram peak area at 3.5-6.5min, then sample
For low density polyethylene (LDPE) raw material, otherwise, sample is low density polyethylene (LDPE) reworked material；
Using element distribution analysis method detect when, if in sample element be 10 kinds or more, sample be high density polyethylene (HDPE) again
Raw material or low density polyethylene (LDPE) reworked material, otherwise, sample are high density polyethylene (HDPE) raw material or low density polyethylene (LDPE) raw material；
When being detected using halogen distributional analysis method, if in sample, total halogen content is more than 1000mg/kg, then sample is highly dense
Recycled polyethylene or low density polyethylene (LDPE) reworked material are spent, otherwise, sample is high density polyethylene (HDPE) raw material or low density polyethylene
Alkene raw material；
When being detected using thermogravimetic analysis (TGA) method, if the residual heavy rate of sample, less than 10%, sample is high density polyethylene (HDPE) former material
Material or low density polyethylene (LDPE) raw material, otherwise, sample are high density polyethylene (HDPE) reworked material or low density polyethylene (LDPE) reworked material；
When being detected using electron microscope analysis method, if sample surfaces are smooth, sample is high density polyethylene (HDPE) raw material or low-density
Polyethylene raw material；If sample surfaces have scratch and pollution, sample is high density polyethylene (HDPE) reworked material or low density polyethylene (LDPE)
Reworked material；
When being detected according to above-mentioned at least one method, at least a kind of method determines sample for high density polyethylene (HDPE) regeneration
Material or low density polyethylene (LDPE) reworked material, then determine sample for high density polyethylene (HDPE) reworked material or low density polyethylene (LDPE) reworked material.
2. the detection method of high density as described in claim 1 or low density polyethylene (LDPE) reworked material, which is characterized in that the step
In (1), if whether it is polythene material that sample is uncertain, sample is taken to carry out examination of infrared spectrum analysis, the material of confirmatory sample suddenly
Expect type；If sample is determined as polythene material, but sample does not know as high density polyethylene (HDPE) or low density polyethylene (LDPE), measurement
The fusing point of sample, identifying sample is high density polyethylene (HDPE) or low density polyethylene (LDPE).
3. the detection method of high density as claimed in claim 2 or low density polyethylene (LDPE) reworked material, which is characterized in that the sample
The fusing point of product is tested using DSC method, test method reference standard GB/T19466.3-2004.
4. the detection method of high density as described in claim 1 or low density polyethylene (LDPE) reworked material, which is characterized in that the step
Suddenly in (2), the condition of the head space gas chromatography are as follows: it is laggard that sample is stablized to 250-330min at 110 DEG C -130 DEG C
Enter capillary chromatographic column, then in 30-60 DEG C of stable 1-10min, be then warming up to 150-250 DEG C with the rate of 10-15K/min,
Stable 1-10min at the final temperature.
5. the detection method of high density as described in claim 1 or low density polyethylene (LDPE) reworked material, which is characterized in that use
ICP test carries out the element distribution analysis of sample, the condition of the ICP test are as follows: carry out sample treatment using Acid digestion method: will
Sulfuric acid and sample heat 30-50min at 400-600 DEG C and are cleared up, and hydrogen peroxide are added after the completion of resolution, then by digestion solution
With carrying out examination with computer after deionized water constant volume.
6. the detection method of high density as described in claim 1 or low density polyethylene (LDPE) reworked material, which is characterized in that use from
Sub- chromatography carries out the halogen distributional analysis in sample, the pre-treatment step of the ion chromatography sample are as follows: fire sample with oxygen bomb
After burning, constant volume is carried out to absorbing liquid, then carries out ion chromatography.
7. the detection method of high density as described in claim 1 or low density polyethylene (LDPE) reworked material, which is characterized in that the halogen
Plain distributional analysis method reference standard EN14582.
8. the detection method of high density as described in claim 1 or low density polyethylene (LDPE) reworked material, which is characterized in that the heat
Zero-g aircraft method reference standard ISO 11358-1:2014.
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