• 专利附录
  • 专利说明
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    • 专利摘要:
    The invention relates to a method for determining the content of plastics (microplastics) in water or wastewater samples under defined and controllable laboratory conditions. In order to enable a precise determination of the plastic content, the determination is carried out by determining at least the mass balance and one of the following material balances: the carbon balance, the hydrogen balance, the oxygen balance, the sulfur balance, and the nitrogen balance.
    公开号:AT519548A4
    申请号:T50072/2017
    申请日:2017-01-31
    公开日:2018-08-15
    发明作者:Helmut Rechberger Dr；Ing Oliver Cencic Dipl；Johann Fellner Dr；Ole Mallow Dr；Ing Stefan Spacek Dipl；Therese Schwarzböck MSc
    申请人:Univ Wien Tech；
    IPC主号:
    专利说明:

    Summary
    The invention relates to a method for determining the content of plastics (microplastics) in water or wastewater samples under defined and controllable
    Laboratory conditions.
    To enable an exact determination of the plastic content, the determination is made by determining at least the mass balance and one of the following material balances: the carbon balance, the hydrogen balance, the oxygen balance, the
    Sulfur balance, and the nitrogen balance.
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    Procedure for determining the plastic content in water and waste water samples
    The invention relates to a method for determining the content of plastics in water and wastewater samples (e.g. suspended matter samples from rivers, or suspended matter samples from the effluent from sewage treatment plants or industrial waste water), the solids of which mostly consist of an unknown mixture of biomass, inert and plastics, according to the Preamble of claim 1.
    Plastics are one of the most important materials in our economies. With an annual per capita consumption of almost 100 kg within the European Union, they represent the most important material of our time in terms of mass of mineral building materials, steel and wood (cellulose).
    The same applies to the waste generated. Within the EU, almost 50 kg / person of plastic waste is generated each year, with a large part already being recycled or thermally recycled (recycling quota for 2011 of almost 70%). Nevertheless, recent studies show that even economies with high environmental standards (Austria, Germany) emit significant amounts of plastic particles diffusely in water. Of particular importance here are microplastic particles (size 1 pm - 5 mm), which either arise from larger fragments due to environmental influences or are entered directly. Although there is awareness of environmental pollution on both the producer and the consumer side, there is still a lack of practical and cost-effective quantification methods.
    The following methods have generally been used to determine the plastic or microplastic content in water samples:
    Detection using a light microscope
    Detection using Fourier transform infrared spectroscopy (FT-IR) and Raman spectroscopy (conventional and using microscopy).
    All of these methods are based on the counting of particles and, when using spectroscopic methods, also on the identification of the type of plastic. at
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    Smaller particles in the range of less than 100 pm require an increased technical and personal effort, since only small sections of the sample can be scanned with an appropriately equipped (IR or Raman) microscope and the number of particles identified must be extrapolated to the total sample , Another problem with light microscopy is that it is very difficult to distinguish between natural particles and plastic particles, especially with smaller particles (Lenz, et al. 2015). Recent studies speak in this context of Lehler rates of almost 70% for particles with a diameter smaller than 50 pm (Hidalgo-ruz, et al. 2012).
    Another method of separating plastic particles based on their, in this case chemical, properties is a selective dissolving method. Here, chemicals with an oxidative effect are added, which ideally oxidize the biogenic part of the sample to CO2, but do not attack the plastic part. The literature describes methods with sulfuric acid (H2SO4), nitric acid (HNO3), hydrogen peroxide (H2O2) or even alkaline variants with concentrated alkalis such as sodium hydroxide (NaOH) and potassium hydroxide (KOH) (Liebmann 2015, van Dijk and Steketee 2002, van Dijk and de Boer 2005). The disadvantage of these methods is the different stability of the different types of polymer against the chemicals used. Aged particles or polycondensation products (such as polyesters and polyamides), which are mainly used in the textile industry, are only partially stable against strongly oxidative acids.
    The radiocarbon method ( 14 C method) can be used as a further method for analyzing the plastic content in a sample, which is used scientifically mainly for the age dating of fossil finds. The method is based on the isotope ratio of the two carbon isotopes 14 C and 12 C, the most common natural isotope being 12 C. 14 C is formed in the atmosphere and is found in photosynthesis in a specific percentage in living organisms and biomater. In the case of old samples or biomaterial no longer involved in the exchange, however, the 14 C content steadily decreases corresponding to the half-life of 5730 ± 40 years. Accordingly, plastics made from fossil oil no longer contain 14 C and therefore have a 14 C / 12 C ratio of zero (poppy,
    3.25
    -3 et al. 2008). This method is currently used to determine the ratio of biogenic / fossil parts in alternative fuels, whereby the facts should also be technically and theoretically applicable to water samples, but the application would face the same problems as exist for waste (see Fellner and Rechberger 2009).
    In all of the methods mentioned, the application is therefore either associated with high uncertainties or with high costs, often both, and there is a need for a method which is reliable with simple and inexpensive application.
    According to the invention, these objectives are achieved by a method which has the features specified in the characterizing part of claim 1.
    Ultimately, this method is based on the different chemical composition of biomass and plastics. While the content of carbon and oxygen (in percent by weight) is approximately similar in biogenic materials, the content of carbon dominates in most plastics. Similar differences are also noticeable for hydrogen.
    Specifically, the method of determination developed is based on the following flowchart, whereby the order of individual steps can be changed, as explained below:
    I) A representative sample is taken from the water sample (suspended matter sample)
    Π) The sample material is dried to constant weight (preferably at 105 ° C)
    III) Then the grain size of the material by different grinding or. Cutting process reduced. The required grain size, to which the material has to be shredded, is primarily determined by the analysis weight of the elemental analyzer (see point VI).
    IV) Depending on the type of sample, a selective oxidation (e.g. using hydrogen4 / 25) can optionally be carried out in addition to or before the grain size reduction
    -4peroxide) biodegradable substances. This preparation step is particularly recommended if the biomass contained in the sample has a very heterogeneous composition and, on the one hand, the treatment leaves a more homogeneous biomass (with regard to its C, Η, O, S and N content) and, on the other hand, it is ensured that the plastic particles contained are not be oxidized. After this step, the sample must be dried to constant weight (preferably at 105 ° C) and the oxidized biomass mBiomasse_oxidiert determined by weighing.
    V) The ash content or loss on ignition is determined on part of the comminuted or oxidatively pretreated sample material (in general, the sample is annealed at temperatures above 500 ° C. until no more weight can be found).
    VI) With the help of an elemental analyzer the content of C, H, Ο, N and S or C, Η, O and N or C, H and O or H and O or C and O or C and H of the (dry) sample material (suspended matter sample) and the residue on ignition were determined.
    VII) The proportion of biogenic or fossil materials in the fuel or secondary raw material to be investigated is determined using the equations listed below.
    mass balance
    The sum of the mass fractions of water- and ash-free biomass m biomass and plastics m KST is 1.
    ^ Biomass h KST 1
    Carbon equation:
    The sum of the organic carbon of biogenic materials and the plastics contained (TOC biomass * m biomass or TOC KST * m KSr ) corresponds to the total organic carbon content of the dry water sample TOC sample (e.g. suspended matter), where m biomass and m KST are the mass fractions of water and
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    -5 Represent ashless biomass and plastics in the samples that need to be determined.
    Areas for the organic carbon content of biomass in water or of plastics in water (TOC biomass or TOC KST ) can be derived from separate analyzes or from literature references.
    TOC Biomass * OT Biomass b TOC KBT * KST ~ TOHProbe - ~ TCp robe ~ Tasche * ^ -Asche
    Oxygen equation:
    The sum of the organic oxygen of biogenic materials and the plastics contained (TOO biomass * m biomass or T00 KST * m KST ) corresponds to the total organic oxygen content of the dry water sample TOO sample (e.g. suspended matter), where m biomass and m KST are the mass fractions of water and represent ash-free biomass and plastics in the samples that need to be determined.
    Areas for the organic oxygen content of biomass in water or of plastics in water (TOO biomass or TOO KST ) can be derived from separate analyzes or from literature references.
    TOO Biomass * TTT-Biomass b ΤΟΟχςψ * KST TOOp robe - - TO Probe - TO Asche * rnAsche
    What substance equation:
    The sum of the organic hydrogen of biogenic materials and the plastics contained (TOH biomass * m biomass or T0H KST * m KST ) corresponds to the total organic hydrogen content of the dry water sample TOH sample (e.g. suspended matter), where m biomass and m KST are the mass fractions of water and represent ash-free biomass and plastics in the samples that need to be determined.
    6.25
    -6Ranges for the organic hydrogen content of biomass in water or plastics in water (TOH biomass or TOH KST ) can be derived from separate analyzes or from literature references.
    TOH Biomass * WT-Biomass + * W-KST TOHp robe ~ THprobe ~ T ^ Asche * ^ Asche
    Sulfur equation:
    The sum of the organic sulfur of biogenic materials and the plastics contained (TOS Biomass * m Biomass or T0S KST * m KST ) corresponds to the total organic sulfur content of the dry water sample TOS Probe (e.g. suspended matter), where wi biomass and m KST are the mass fractions of water and represent ash-free biomass and plastics in the samples that need to be determined.
    Areas for the organic sulfur content of biomass in water or plastics in water (TOS Biomass or TOS KST ) can be derived from separate analyzes or from literature references.
    TOS Biomass * TTT-Biomass Ή T ^^ KST * W-KST ~ TOSp robe - ~ TSprobe ~ T ^ Asche * mAsche
    Nitrogen equation:
    The sum of the organic nitrogen of biogenic materials and the plastics contained (TON biomass * m biomass or T0N KST * m KST ) corresponds to the total organic nitrogen content of the dry water sample TON sample (e.g. suspended matter), with wi biomass and m KST the mass fraction of water and represent ash-free biomass and plastics in the samples that need to be determined.
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    -Ί Areas for the organic nitrogen content of biomass in water or plastics in water (TON biomass or TON KST ) can be derived from separate analyzes or from literature references.
    TON biomass * WT biomass T TON kbt * KST TONp robe - TNp robe - TN ash * WT ash
    The mass balance and three material balances carbon, hydrogen and oxygen are preferably used for the evaluations. However, cases are conceivable where the sulfur and / or the nitrogen balance should also be included, or only the mass balance and a mass balance (carbon, oxygen, or hydrogen equation) are sufficient for a reliable determination.
    In addition to the substance equations listed, the following constraints in the form of equations must be taken into account in the calculation:
    For biomass it can be assumed that the total of TOC, TOH, TOO, TON and TOS contents is approximately 1000 g / kg (based on water- and ash-free biogenic substance), while for plastics, depending on the proportion of chlorinated fluorinated plastics and thus the fluorine or chlorine content) a slightly lower value than 1000 g / kg can be assumed.
    TOC Biomass + TOO B i omasse + TOH Biomass + TON Biomass + TOS B i omasse 1000
    TOC KST + TOO KST + TOH KST + TON KST + TOS kst ~ 975 + 25
    Likewise, the sum of the TOC, TOH, TOO, TON and TOS contents of the ash-free organic substance in the water sample must be approximately 1000 g / kg, again depending on the proportion of chlorinated or fluorinated plastics can be assumed as 1000 g / kg.
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    -8TC Probe + TO Probe + TH Probe + TN Probe + TS, 'Probe' m-Asche - (TCAsche + T0 A
    Mathematical solution of the equations
    Merging the presented equations leads to a system of equations consisting of several equations with 2 unknowns (mass fractions of biogenic or
    fossil water- and ash-free materials ( biomass or not KST ). In the event that at least 3 balance equations (e.g. mass, carbon and hydrogen balance) are used, this is an over-determined system, the solution of which must be determined using a non-linear compensation calculation (Narasimhan et al, 2000). The application of the nonlinear compensation calculation is based on the
    The fact that the coefficients of the unknowns and the results of the laboratory analyzes are given by means (most probable values) and areas of uncertainty, and that the propagation of the errors must be taken into account for the end result, as shown in the following overview 1:
    Overview 1
    Mass balance kojtens Obviously: .if; g
    SiMersioffgie / chung
    Wassersioffgteifihijng
    Siicksioffgleiebunff
    Scbivafelgiaichi / ng
    Condiifons 1 ίίί:;:; ··: ;;:;:. · «, + I ΟΟ ^ Τ '
    ΤΟΟ ^, ^ '/ TOOjy ^', · + 'S f' 7ίί <; · Ί
    T0S 8fcf , ass / + I ÖSkst '* Töö ^ llllllllüoüüüüi
    A TÖN ^ 'S' s Stet *
    TOC ^ »^ · * roH f . ^ W · io ^. TO ". roc>< : fTQ! -i xS v ^ TOO. ,, - t -> TON. ,, T * fOS s ;
    9.25
    -9 Calculation of the plastic content in the water sample (suspended matter sample):
    From the ascertained mass fractions of the water- and ash-free biomass and plastics (m biomass or m KST ), the plastic content KST content (given in g plastic per g dry sample) can be obtained with knowledge / estimation of a corresponding inorganic additive proportion oi additive in the plastics determine in the drawn sample:
    In the event that no oxidative pretreatment has been selected:
    cm _ m Ksr * (1 - m Asc / ie )
    Salary ~ _
    -L ™ additive
    In the event that the sample has been pretreated with oxidizing agent to oxidize easily degradable biogenic substances:
    i7cm _ m Ksr * (1 - m ash). ίΛ _ λ λοϊ content ~ -i ™ * 11 'OlBiomasse oxidized)
    - ^ additive
    The formula given applies in the event that the proportion of inorganic (inert) present in the samples is not changed in mass by pretreatment with an oxidizing agent. In the event of a significant increase or decrease in the proportion of inert material (can be determined by analyzing the ash content before and after treatment with an oxidizing agent and taking into account the change in mass of the overall sample due to the oxidation of biogenic substances), the formula for calculating the plastic content of the KST content must be adjusted accordingly adapt.
    Chemical composition of water and ash-free biomass or plastics in the samples
    For the determination of the organic carbon, hydrogen, oxygen, sulfur and nitrogen content of biomass and plastics
    TOC Biomass , TOO B i omasse , TOH Biomass , TON Biomass , TOS B i omasse ,
    TOC KST , TOO kst , TOH kst , TON kst , TOS kst
    a) Information from the literature is used (compositions of plastic mixtures or biomass in different types of water), or
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    -10b) Sorting (clean separation into biogenic and fossil materials) with subsequent ignition residue determination and elemental analyzes (C, Η, Ο, N, and S content of the dried sample material and the ignition residue) of the biogenic or fossil materials are carried out.
    The following values were used for the application example described below (industrial wastewater with only contamination by polyolefins) (see Table 1 and Table 2), "Stabw." Always stands for "standard deviation" in the following.
    Table 1 Elementary composition of biogenic and fossil materials (for industrial waste water with only contamination by polyolefins) in the event that no oxidative pretreatment is chosen
    unit Average ΙΪΙ ^ ΒΟΒΒΙ !! Ι® ΤΠΓ 1 biomass 487 30 TOH biomass74 7 TOO biomass380 35 TDg 1 ° biomass [G / kg 10 8th TON biomass water and 49 35 TOC KST ashlessly] 856 4 TOH kst142 1 TOO kst0 0.5 t os KST1 0.4 SOUND KST1 1
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    - 11 Table 2 Elemental composition of biogenic and fossil materials (for industrial waste water with only contamination by polyolefins) in case an oxidative pretreatment is chosen
    unit Average ΤΠΓ 1 biomass [G / kgwater andashlessly] 473 2 TOH biomass 60 0.5 TOO biomass 449 14 της 1 0 biomass 5 3 TON biomass 13 8th TOC KST 856 4 TOH kst 142 2 TOO kst 0 0.5 t os KST 1 0.4 SOUND KST 1 1
    A comparison of the elementary levels for biomass with and without oxidative pretreatment (values from Table 1 and Table 2) shows that the oxidative pretreatment significantly reduces the standard deviation of the elementary levels and thus leads to the fact that the biomass matrix contained in the samples with regard to their carbon content,
    Hydrogen, oxygen, sulfur and nitrogen are more narrowly defined (i.e. have a significantly lower standard deviation of the elementary composition).
    APPLICATION EXAMPLE:
    Characterization of suspended matter from industrial wastewater that is only contaminated with 15 polyolefins.
    In the specific application example, a total of 11 suspended matter samples from industrial waste water were analyzed for their plastic content, with 8 samples without oxidative pretreatment (without step IV) and 3 samples with oxidative pretreatment (including step
    IV) were analyzed. Specifically, these 3 samples were mixed with H2O2 (30%, p.a.) and the mass loss due to oxidation processes was determined after seven days.
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    - 12 The remaining residue (now exclusively inert material, plastic, biomass that is difficult to oxidize) was ground using an ultracentrifugal mill to a grain size of <0.2 mm, dried and analyzed accordingly.
    The amount of sample material available varied between 100 and 200 g dry matter per sample. In the laboratory, the samples were dried to constant weight at 105 ° C in the first step. The samples were then prepared and analyzed in accordance with the steps outlined on pages 3 and 4.
    analyzes
    The sample material obtained was divided, a part of which was used to determine the loss on ignition or the ash content (DIN EN 15935: 2012-11). The second part of the ground sample was analyzed for the C, Η, Ο, N, and S content using a CHNSO elemental analyzer. Analogously, the glow residue on the C,
    Η, Ο, N, and S content analyzed. Multiple determinations were carried out both for the loss on ignition and for the elementary analyzes.
    In addition, samples were pretreated with H2O2 over a week to remove easily oxidizable biogenic substances (in the present case algae)
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    -13 ash content and loss of ignition
    The ash content and loss on ignition of the samples taken are summarized in Table 3.
    Table 3 Ash content and loss on ignition of the samples
    Rehearse-number description Ash content *mesh Loss on ignition * (l - rn ^ sc / ie ) mass percentTrockensubst related to num (TS) a) MW Stabw. MW Stabw. 1 Suspended matter from industrial waste water 31.1% 0.1% 68.9% 0.1% 2 Suspended matter from industrial waste water 49.0% 0.1% 51.0% 0.1% 3 Suspended matter from industrial waste water 31.0% 0.1% 69.0% 0.1% 4 Suspended matter from industrial waste water 60.2% 0.1% 39.8% 0.1% 5 Suspended matter from industrial waste water 17.7% 0.1% 82.3% 0.1% 6 Suspended matter from industrial waste water 50.9% 0.1% 49.1% 0.1% 7 Suspended matter from industrial waste water 65.0% 0.1% 35.0% 0.1% 8th Suspended matter from industrial waste water 24.0% 0.1% 76.0% 0.1% 9 # Suspended matter from industrial waste water 73.8% 0.1% 26.2% 0.1% 10 # Suspended matter from industrial waste water 83.0% 0.1% 17.0% 0.1% 11 # Suspended matter from industrial waste water 34.0% 0.1% 66.0% 0.1%
    * Triplicate determinations were performed # Sample 9 for the ash content or loss on ignition, 10 and 11 were analyzed by H 2 O 2 a> pretreated In the case of Samples 9 to 11 (pre-treatment with H 2 O 2) refers to the ash break in the 10 dry substance of the pretreated sample (of the solid treatment residue)
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    - 14 Total TC, -Η, -Ο, -N and -S contents
    The total C, Η, Ο, N and S contents of the samples taken are summarized in Table 4.
    Table 4 TC, TH, TO, TS and TN contents *
    sample number sample name TC contentrespectively. TH contentrespectively.THprobe TO content or TO sample TS content or TS sample TN-contentrespectively.TN sample [g / kg TS] a) MW Stabw MW Stabw MW Stabw MW Stabw MW Stabw 1 Suspended matterindustrial wastewater 429.4 2.2 62.4 0.3 217.0 0.5 8.8 5.3 53.08 5.31 2 Suspended matterindustrial wastewater 329.0 1.7 47.5 0.2 188.0 0.5 7.0 4.2 36.87 3.69 3 Suspended matterindustrial wastewater 438.6 2.2 64.9 0.3 205.0 0.5 7.6 4.5 49.02 4.90 4 Suspended matterindustrial wastewater 258 1.3 36.3 0.2 172.0 0.5 5.6 3.3 26.0 2.60 5 Suspended matterindustrial wastewater 526 2.6 79.6 0.4 214.0 0.5 8.6 5.1 58.1 5.81 6 Suspended matterindustrial wastewater 317 1.6 45.0 0.2 188.6 0.5 7.0 4.2 36.9 3.69 7 Suspended matterindustrial wastewater 257 1.6 35.0 0.2 200.0 0.5 5.2 3.1 21.0 2.10 8th Suspended matterindustrial wastewater 470 1.6 71.1 0.2 230.0 0.5 8.3 5.0 62.0 6.20 9 * Suspended matterindustrial wastewater 212.8 1.1 32.4 0.2 100.3 0.7 2.6 1.3 1.32 0.9 10 * Suspended matterindustrial wastewater 154 0.8 19.5 0.1 154.0 1.1 2.2 1.1 1.2 0.8 11 * Suspended matterindustrial wastewater 491 2.5 80.8 0.4 119.0 0.8 3.0 1.5 3.7 2.4
    * Five-fold determinations were carried out # Samples 9, 10 and 11 were pretreated with H2O2 a> In the case of samples 9 to 11 (pretreatment with H2O2), the total contents of C, H, O, S 10 and N refer to the dry matter of the pretreated sample (des solid treatment residue)
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    -15 content of TIC, -Η, -Ο, -N and -S in the ignition residue of the samples
    The C, Η, Ο, N and S contents of the ashes of the samples are summarized in Table 5.
    Table 5 TIC, TIH, TIO, TIS and TIN levels *
    sample number sample name TIC content or TC ash TIH contentrespectively.TCAsche TIO content or T0 ash TIS content or TS ash TIN contentrespectively.TCAsche g / kg ash] a) MW Stabw MW Stabw MW Stabw MW Stabw MW Stabw 1 Suspended matterindustrial wastewater 31.8 0.2 1.23 0.01 99.4 0.5 4.2 2.53 3.4 2.0 2 Suspended matterindustrial wastewater 25.9 0.1 1.05 0.01 99.4 0.5 4.4 2.62 2.4 1.4 3 Suspended matterindustrial wastewater 30.1 0.2 0.82 0.00 99.4 0.5 3.4 2.03 1.6 1.0 4 Suspended matterindustrial wastewater 25.9 0.1 0.8 0.0 99.4 0.5 2.3 1.37 1.0 0.6 5 Suspended matterindustrial wastewater 24.8 0.1 1.2 0.0 99.4 0.5 5.6 3.34 4.7 2.8 6 Suspended matterindustrial wastewater 29.1 0.2 0.7 0.0 99.4 0.5 2.5 1.51 1.0 0.6 7 Suspended matterindustrial wastewater 52.0 0.2 1.1 0.0 150.0 0.5 2.3 1.38 1.0 0.6 8th Suspended matterindustrial wastewater 31.7 0.2 1 0.0 99.4 0.5 4 2.40 6 3.6 9 * Suspended matterindustrial wastewater 26.5 0.1 0.9 0.04 87 0.4 0.8 0.4 0.8 0.5 10 * Suspended matterindustrial wastewater 51.5 0.3 0.8 0.04 157 0.8 0.6 0.3 0.7 0.4 11 * Suspended matterindustrial wastewater 31.3 0.2 2.1 0.10 115 0.6 1.3 0.7 0.9 0.5
    * There were triplicate determinations performed # Sample 9, 10 and 11 were analyzed by H 2 O 2 a> pretreated In the case of Samples 9 to 11 (pre-treatment with H 2 O 2) refers to the ash grip on the
    Dry substance of the pretreated sample (the solid treatment residue)
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    -16Resultate
    Proportion of plastics in the samples
    The proportions of biogenic or fossil materials were calculated based on the described method. The results are summarized in the following Table 6 and FIG. 1.
    Table 6 Mass fraction of biogenic or fossil materials (water and ash free)
    sample number sample name fossil mass fraction m KST Part oxidized by H 2 O 2 Plastic content in the samples b) KST Ge h a t i Mass percent based on water- and ash-free organic substance a) mass percentbased on thedry matter [g / 100g TS] MW Stabw MW Stabw MW Stabw 1 Suspended matterindustrial wastewater 27.5% 4.0% - - 19.9 2.9 2 Suspended matterindustrial wastewater 28.7% 4.0% - - 15.4 2.1 3 Suspended matterindustrial wastewater 31.9% 3.8% - - 23.2 2.8 4 Suspended matterindustrial wastewater 26.3% 4.1% - - 11.0 1.7 5 Suspended matterindustrial wastewater 35.5% 3.6% - - 30.8 3.1 6 Suspended matterindustrial wastewater 26.8% 4.1% - - 13.8 2.1 7 Suspended matterindustrial wastewater 27.7% 4.1% - - 10.2 1.5 8th Suspended matterindustrial wastewater 28.8% 3.9% - - 23.0 3.2 9 * Suspended matterindustrial wastewater 70.9% 0.6% 34% 0.7% 12.9 0.3 10 * Suspended matterindustrial wastewater 61.3% 1.0% 19% 0.4% 8.9 0.2 11 * Suspended matterindustrial wastewater 72.5% 0.5% 56% 1.1% 22.2 0.7
    # Samples 9, 10 and 11 were pretreated with H 2 O 2
    In the case of samples 9 to 11 (pretreatment with H 2 O 2 ), the fossil mass fraction 10 m KST refers to the water- and ash-free substance of the solid treatment residue b ) According to information from the emitter of the industrial waste water and own analyzes of larger plastic particles, an inorganic additive content m Additive estimated from 0.05 + 0.02 g / g plastic
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    - 17 Fig. 1 shows the content of plastics (including inorganic additives) and mass fractions of fossil, biogenic and inert materials (plastic content without inorganic additives, biomass content and ash content). It shows in detail
    Plastic contents in suspended matter samples filtered from industrial waste water (in addition to the plastic contents including the inorganic additive content, the contents of biogenic materials, inert materials and plastics excluding inorganic additives are also shown), whereby samples 9 to 11 were pretreated with H2O2, thereby reducing the uncertainty of the result (standard deviation of the plastic content) in
    Comparison to the analyzed samples 1 to 8 (without H2O2 pretreatment) could be reduced - A more detailed description of the individual samples can be found in Tables 3 to 6
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    -18 literature
    DIN EN 15935: 2012-11, sludge, treated bio-waste, soil and waste Determination of loss on ignition; German version EN 15935: 2012
    Fellner, J., and H. Rechberger. "Abundance of 14C in biomass fractions of wastes and 5 solid recovered fuels." Waste Management, 2009: 1498-1503.
    Hidalgo-ruz, Valeria, Lars Gutow, Richard C. Thompson, and Martin Thiel. "Microplastics in the Marine Environment: A Review of the Methods Used for Identification and Quantification." Environmental Science & Technology, 2012.
    Lenz, Robin, Kristina Enders, Colin A. Stedmon, David Μ. A. MacKenzie, and Torkel 10 Gissel Nielsen. "A critical assessment of visual identification of marine microplastic using Raman spectroscopy for analysis improvement." Marine
    Pollution Bulletin 100 (2015): 82-91.
    Liebmann, Bettina. MICROPLASTICS IN THE ENVIRONMENT - Occurrence, evidence and need for action. Vienna: Umweltbundesamt GmbH, 2015.
    Mohn, J „et al. "Determination of biogenic and fossil CO2 emitted by waste incineration based on 14CO2 and mass balances." Bioresour Technol., 2008: 6471-6479.
    Narasimhan, S. Jordache C. 2000. Data Reconciliation & Gross Error Detection. Gulf Publishing Company, Houston, Texas.
    van Dijk, E. A „and J. J. Steketee. "Feasibility study of three methods for determining the 20 biomass fraction in secondary fuels." Tech, rep., 2002.
    van Dijk, E. A „and R. C. de Boer. "Pre-normative research on SRF." Tech, rep., 2005.
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    -19 Formula symbols used ^ • Biomass_Oxidiert ^ Biomass m KST ^ • Ash
    TOC
    Biomass toc kst
    TOC sample
    Oxidizable biomass fraction of the anhydrous total amount of the sample [kg oxidized biomass / kg dry matter of the sample]
    Mass fraction of the water- and ash-free biogenic substance (based on the total water- and ash-free organic substance of the sample or the solid residue of the sample remaining after the pretreatment) [kg water- and ash-free biogenic substance / kg water- and ash-free organic substance]
    Mass fraction of water-free and ash-free plastics (based on the total water-free and ash-free organic substance of the samples or the solid residue of the sample remaining after pretreatment) [kg water-free and ash-free biogenic substance / kg water-free and ash-free organic substance] ash content (based on dry substance 1 ) [kg As che / kg TS], determined by means of an annealing test Organic carbon content of the biogenic substance [g C / kg water and ash-free organic substance] Organic carbon content of the plastic portion [g C / kg water and ash-free organic Substance] Organic carbon content of the sample [g C / kg water and ash-free organic substance] 1 In the case of pretreatment with H2O2, the ash content refers to the dry sample mass remaining after the pretreatment
    20/25
    TCprobe Total carbon content of the sample (organic and inorganic) [g C / kg TS] 2 TCAsche Carbon content of the ash (inorganic) [g C / kgAsh] TOO biomass Organic oxygen content of the biogenic substance[g O / kg water- and ash-free organic substance] too kst Organic oxygen content of the plastic part[g O / kg water- and ash-free organic substance] TOO rehearsal Organic oxygen content of the sample[g O / kg water- and ash-free organic substance] TO sample Total sample oxygen content (organic andinorganic) [g O / kg TS] TOAsche Ashes oxygen content (inorganic)[g O / kg ash] TOH biomass Organic hydrogen content of the biogenic substance[g H / kg water and ash-free organic substance] toh kst Organic hydrogen content of the plastic part[g H / kg water and ash-free organic substance] TOH sample Organic hydrogen content of the sample[g H / kg water and ash-free organic substance] THp robe Total sample hydrogen content (organicand inorganic) [g H / kg TS] THAsche Hydrogen content of the ash (inorganic)[g H / kg ash] TO 9 1 ° biomass Organic sulfur content of the biogenic substance[g S / kg water and ash-free organic substance] tos kst Organic sulfur content of the plastic part[g S / kg water and ash-free organic substance] TOS sample Organic sulfur content of the sample[g S / kg water and ash-free organic substance]
    2 In the case of pretreatment with H 2 O 2 , the contents of TC, TH, TO, TS and TN in the sample refer to the dry sample mass remaining after the pretreatment
    21/25
    -21 TSp robe
    27 4sc / ie
    TON biomass
    SOUND KST
    TONE sample
    TN sample
    T ^ ash ^ additive
    KST Gehatt
    Abbreviations 14 C method
    FT-IR
    H 2 O 2
    TS
    Stabw
    Total sulfur content of the sample (organic and inorganic) [g S / kg TS]
    Ash sulfur content (inorganic) [g S / kg ash]
    Organic nitrogen content of the biogenic substance lg N / kg water-free and ash-free organic substance] Organic nitrogen content of the plastic part lg N / kg water-free and ash-free organic substance] Organic nitrogen content of the sample lg N / kg water-free and ash-free organic substance] Total nitrogen content of the sample (organic and inorganic) [gN / kg TS]
    Nitrogen content of the ash (inorganic) lg N / kg ash]
    Mass fraction of the inorganic additive fraction lg inorganic additives / g plastic incl. Inorganic.
    additives]
    Plastic content (incl. Inorganic additives) of the sample] g plastic / g dry sample 3 ]
    Radiocarbon
    Fourier Transform Infrared Spectroscopy
    W a ter peroxide
    dry matter
    Standard deviation 3 The sample mass also refers to the original sample, ie in the case of pretreatment with an oxidizing agent. on the dry sample before pretreatment
    22/25
    权利要求:
    Claims (10)
    [1]
    claims
    1.Procedure for determining the plastic content in the suspended matter (filterable or undissolved portion) of water and waste water samples, characterized in that the portions are determined by determining at least two of the following balances: the mass balance, the carbon balance, the hydrogen balance, the Oxygen balance, nitrogen balance, and sulfur balance.
    [2]
    2. The method according to claim 1, characterized in that the determination of the shares is carried out by determining at least three balance sheets.
    [3]
    3. The method according to claim 2, characterized in that the determination of the shares is carried out by determining at least four balance sheets.
    [4]
    4. The method according to claim 3, characterized in that the determination of the shares is carried out by determining five balance sheets.
    [5]
    5. The method according to claim 4, characterized in that the determination of the shares is carried out by determining six balance sheets.
    [6]
    6. The method according to any one of claims 1 to 5, characterized in that the suspended matter to be analyzed is analyzed for the contents of carbon, hydrogen, oxygen, sulfur and nitrogen and that these contents are used in the respective balance sheets.
    [7]
    7. The method according to claim 6, characterized in that the analysis takes place in the laboratory in batch operation under precisely defined conditions.
    [8]
    8. The method according to any one of claims 1 to 6, characterized in that the suspended matter to be analyzed is processed, for example by oxidation, so that the remaining biomass matrix is narrowly defined with regard to its content of carbon, hydrogen, oxygen, sulfur and nitrogen.
    [9]
    9. The method according to any one of claims 1 to 7, characterized in that the shares are determined by means of a compensation calculation.
    [10]
    10. The method according to claim 1 to 8, characterized in that the proportions are determined by means of Monte Carlo simulation.
    23/25
    Plastic content of the samples (mW, inorganic plastic additive [g / 100 g dry sample material]
    sample
    Plastic content including anorg. additives
    Composition of the samples (content of biomass, inert and plastics - without inorganic additives) [mass%]
    Marriage to marriage
    1, Processes for fatigue of the synthetic substance content in the suspended matter (ahEhrierharer or undissolved portion) of water and Äbwssssrprohea thereby
    3 records, that the determination of the shares by the determination of the kdassenbiianz and. at least one of the following balance sheets takes place: the Koulensioff balance sheet, the Arfssersfeffbiianz, the Sannestoffbilana, the StfekstoffbilanZ: and the sulfur sulfide.
    2, Method according to claim I. characterized in that the determination of
    10 shares; of which at least three balance sheets are determined
    3. The method according to claim 2, characterized in that the determination: of the shares is carried out by determining at least four balance sheets,
    4. The method of claim 3 characterized in that the shares are determined by determining five balance sheets,
    $ 1. 5, Method according to claim 4 ,. characterized, that the determination of the
    Shares by determining six balance sheets,
    6. The method according to any one of claims 1 to 5, characterized in that the visual substance to be analyzed is analyzed for the contents of carbon, hydrogen, oxygen, sulfur and nitrogen and that these contents are called the respective
    20 balance sheets are used
    7. Method according to claim e characterized in that the analysis in the Lahor in batch mode under precisely defined. Conditions takes place.
    8, Method according to one of claims 1 to 6, characterized in that the suspended matter to be analyzed is prepared for example by oxidation,
    25 that the remaining bioams matrix in terms of its carbon content
    Hydrogen oxygen sulfur and nitrogen is narrowly defined,
    9, Method according to one of claims f to 7, characterized in that the proportions are determined by means of adjustment stretching.
    i o. Method according to claim I to 8, characterized in that the shares are determined by means of 30 Monte Carlo simulation.
    25/25 [LAST CLAIMS)
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    同族专利:
    公开号 | 公开日
    WO2018140995A1|2018-08-09|
    AT519548B1|2018-08-15|
    DE112018000603A5|2020-01-23|
    引用文献:
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    WO2000075569A1|1999-06-04|2000-12-14|Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno|System for determining process parameters relating to thermal processes such as, for instance, waste incineration|
    EP1715339B1|2005-03-30|2012-12-26|Technische Universität Wien|Method for determining the proportion of biogenic and fossil energy carriers and of biogenic and fossil carbon dioxide emissions in the operation of combustion systems|
    EP2270492B1|2009-07-03|2014-08-20|Technische Universität Wien|Determining the biogenic and fossil carbon content, as well as the share of mass and energy, of fuels and recycling materials|
    FR3042870A1|2016-05-20|2017-04-28|Cabinet Merlin|METHOD FOR TIME DETERMINATION AND MONITORING OF BIOGENIC AND FOSSIL MASS CONTENT OF HETEROGENEOUS FUEL FROM CARBON ANALYSIS 14 POST-COMBUSTION OF COMBUSTION GAS CO2.|
    CN110244016B|2019-07-16|2020-06-05|中国矿业大学|Method and device for measuring degradation rate of organic pollutants|
    CN111257275B|2020-02-17|2021-05-14|中国科学院生态环境研究中心|Method for quantitatively determining total amount of micro-nano plastic in water environment based on total organic carbon|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA50072/2017A|AT519548B1|2017-01-31|2017-01-31|Method for determining the plastic content in water and wastewater samples|ATA50072/2017A| AT519548B1|2017-01-31|2017-01-31|Method for determining the plastic content in water and wastewater samples|
    PCT/AT2018/060029| WO2018140995A1|2017-01-31|2018-01-31|Method for determining the plastic content in water samples and in waste water samples|
    DE112018000603.4T| DE112018000603A5|2017-01-31|2018-01-31|Procedure for determining the plastic content in water and wastewater samples|
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