Report 2016:05. Avfall Sverige's Devlopment Project Energy Recovery ISSN Method Comparison for Dioxin Sampling SRM-AMESA

Transcription

1 Report 2016:05 Avfall Sverige's Devlopment Project Energy Recovery ISSN Method Comparison for Dioxin Sampling SRM-AMESA

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3 FOREWORD On behalf of Avfall Sverige, Miljömätarna has made comparative measurements of dioxins with respect to the permanently installed, semi-continuous system, Amesa. The assignment was conducted using a modified standard method, SS-EN Magnus Andersson was the administrator for Miljömätarna and Mats Gustafsson for Sakab. The project was financed by Avfall Sverige's Development Project Energy Recovery, Sakab and Miljömätarna i Linköping. Malmö February 2016 Ulf Kullh Chairman Avfall Sveriges Development Project Energy Recovery Weine Wiqvist CEO Avfall Sverige

4 CONTENTS 1 Summary Administrative details The assignment 2 Departures from standards/measurement methods The operations Description of the measurement location 3 2 Results of the measurements Comparison between SRM and Amesa Proportion in Ampoule Comparison between SRM Ampoule 1+2 and Amesa 6 3 Comments on Departures Viewpoints regarding the sampling 7 4 Conclusions 8 5 For continued discussions 9 6 Graphs Sample Sample Sample Sample Set-up measurement Equipment SRM 18 8 Appendices 19

5 1 SUMMARY Miljömätarna i Linköping AB has conducted a Method Comparison of Dioxin Sampling SRM - Amesa on behalf of Avfall Sverige at SAKAB's plant in Norrtorp, Kumla The purpose of the measurements was to investigate whether it is possible to carry out dioxin sampling for a longer period of time using the Standard Reference Method (SRM) than the standard currently permits. By prolonging the sampling time to 1 week and, simultaneously, changing sample in the plant's existing semi-continuous sampling system, a comparison between the measurement methods can be evaluated. The prolonged SRM is intended to be used when incineration plants receive investigation requirements regarding dioxins during permit applications or when longer sampling periods need to be conducted with short set-up times in the case of operating problems, disruptions or test runs with new types of waste. The SRM equipment with prolonged sampling could be a good option for linking together the simultaneous taking of more samplings in different cleaning steps in the plant find out where formation or memory effects of dioxins or furans are created or exist. By extracting a dioxin sample in one week instead of 8 hr, the result will better reflect the normal operating conditions for waste incineration because more, small, waste-related spikes are included in the analysis. A small disruption during an 8 hr sample may show elevated levels and may not be a reliable reference for determining a plant's total emission of dioxins for the year. If the SRM equipment is used to measure two week-long-samples/year, more comprehensive data for dioxins and furans is obtained compared to the two 8 hr samples that are stipulated in the standard. The difference is from approx. 0.2 % to approx. 5 % of the incineration plant's operating time/year, which gives a substantially more representative basis for determining the total emissions and verifying the control condition of 0.1ng/m3 without any large cost increase. The method is significantly more cost-effective as well as easier to install and set-up, which reduces the changeover time for sampling by several weeks compared to the rental of semi-continuous sampling equipment, which requires more regarding transport, installation and commissioning. Semi-continuous sampling equipment is normally hired out for at least three months. Figure 1. Results of the measurements 1

6 1.1 Administrative details Table 1 Details about the Company and the plant CLIENT Principal AVFALL SVERIGE Postal address - Contact person Mats Gustafsson, SAKAB Telephone number Fax number Corporate registration number PLANT Site name Plant number Property designation Code according to the Ordinance on Environmental Assessment (SFS 2013:251) Supervisory authority SAKAB, Shared duct for WTE1 and WTE2 The County Administrative Board 1.2 The assignment The emission measurements included the following parameters: Table 2 Controlled parameters PARAMETER SAMPLE TIME THE RESULT IS USED FOR PCDD Approx. 1 week Comparison with SAKAB's Amesa O 2 Check of leakage on the PCCD sampling Sampling was conducted in accordance with current international and national standards, for which Miljömätarna AB is accredited. Departures from standards/measurement methods The assignment was performed with the following departures from the measurement methods: Table 3 Departures from standards/measurement methods MEASUREMENT POINT PARAMETER STANDARD/MEASUREMENT METHOD DEPARTURE Shared duct Dioxins SS-EN 1948:1 No traverse of the measurement plane done during the sampling. Sampling without filter. Probe unheated. Stipulated time limit of 6-8 hours exceeded. Field blank not extracted according to standard Isokinetic sampling not carried out. 1.3 The operations AVFALL SVERIGE is a Swedish trade association for waste management and recycling. 2

7 SAKAB is today a part of the Finnish EKOKEM Group, whose business idea is to be a comprehensive supplier of environmental and waste management by offering; material recycling and energy recovery, final storage, soil remediation and environmental construction services in Scandinavia. Shared duct for WTE1 and WTE2 WTE1 is a rotary furnace for the high temperature incineration of hazardous waste. WTE2 is a grate-fired boiler After the boilers, the flue gases are cleaned in a separate semi-dry flue gas treatment plant using milk of lime for each boiler and a shared scrubber before the flue gases are led out into a 60 m high chimney. 1.4 Description of the measurement location Table 4 Measurement plane DESCRIPTION REQUIREMENTS IN STANDARD COMMENTS The duct's shape - Circular diameter 180 cm Undisturbed straight section prior to measurement plane Undisturbed straight section after the measurement plane > 5 hydraulic diameters > 5 hydraulic diameters > 2 hydraulic diameters > 2 hydraulic diameters Number of sampling ports - 7 Design of the sampling ports - 3" internal pipe thread The option to traverse the duct cross-section according to, inter alia, SS EN Number of points for traversing in the measurement plane shall be done Can be done with approx. 45 displacement - 16 Access - Inbuilt stairs to measurement plane. For mapping max 2.5 m probe. Protection measures - OK Cooling water - Available by measurement plane. Electricity - 16 A 400 V Compressed air - Available by measurement plane. Space by measurement plane - Good 3

8 2 RESULTS OF THE MEASUREMENTS 2.1 Comparison between SRM and Amesa In the table below, the results from the comparison between the systems are presented. SRM is calculated based on Ampoule 1, i.e. only the sample ampoule. Table 5 The result of the comparison between SRM and Amesa SAMPLE SRM AMESA DIFFERENCE Sample 1 PCDD (ng/m 3 at 11% O 2 ) % O 2 level, dry (vol-%) Sample 2 PCDD (ng/m 3 at 11% O 2 ) % O 2 level, dry (vol-%) Sample 3 PCDD (ng/m 3 at 11% O 2 ) % O 2 level, dry (vol-%) Sample 4 PCDD (ng/m 3 at 11% O 2 ) % O 2 level, dry (vol-%) Figure 2 Graphic summary of the table above. 4

9 2.2 Proportion in Ampoule 2 In the table below, the proportion in the second ampoule for the series is presented. The ampoules are linked in series, where Ampoule 2 is a control for "bleed-through" in Ampoule 1. In the comparison, Upper Bound was used, this gives the largest "bleed-through" i.e. our worst case. Table 6 SAMPLE SAMPLE AMPOULE 1 CONTROL AMPOULE 2 Sample 1 PCDD (ng tot) % PROPORTION IN AMPOULE 2 OF TOTAL Sample 2 PCDD (ng tot) % Sample 3 PCDD (ng tot) % Sample 4 PCDD (ng tot) % Figure 3 Graphic summary of the table above. 5

10 2.3 Comparison between SRM Ampoule 1+2 and Amesa In order to give a more equivalent volume of the ampoules' granulate, an example is given of adding together ampoule 1 and 2 in the sampling and comparing against the Amesa sampling. The analysis result (Upper Bound) has been summed for ampoule 1 and 2 and compared with Amesas's result. Table 7 The result of the comparison between SRM (Ampoule 1+2) and Amesa SAMPLE SRM AMESA DIFFERENCE Sample 1 PCDD (ng/m 3 at 11% O 2 ) % Sample 2 PCDD (ng/m 3 at 11% O 2 ) % Sample 3 PCDD (ng/m 3 at 11% O 2 ) % Sample 4 PCDD (ng/m 3 at 11% O 2 ) % Figure 4 Graphic summary of the table above. 6

11 3 COMMENTS ON DEPARTURES The departures that were made from standard were made to ensure minimum work while taking the samples. This was in order to minimise costs but also to better resemble permanent equipment. Departure: No traverse of the measurement plane done during the sampling. Explanation: Requires a lot of time increased cost. Semi-continuous equipment measuring in one point. Due to both of these, SRM also measured in one point. Departure: Sampling without filter. Explanation: Plants that incinerate waste have good control of dust levels exiting the plant and these are usually under 1 mg/m3n. Filters also need to be kept warm and there is a large risk that this heating could fail over a longer period of time. If there is dust, it is guessed that the largest part will stick in the ampoule and, in this way, will even so be included in the analysis. There is no filter in the semi-continuous equipment. Departure: Probe unheated. Explanation: The probe's heating, like the filter heating, could fail during longer sampling times. Nor is the semi-continuous equipment's probe heated. The probe tube is rinsed according to standard and applied to the sample. Departure: Stipulated time limit of 6-8 hours exceeded. Explanation: The starting point for the assignment was to exceed this. Departure: Field blank not extracted according to standard. Explanation: The field blank for each sample was placed in series with the same to control any "bleedthrough". There are no field blanks associated with the semi-continuous equipment. Departure: Isokinetic sampling not carried out. Explanation: A fixed sample gas flow was chosen to facilitate sampling during a long period of time. 3.1 Viewpoints regarding the sampling The sampling was stable and functional. We see a small variation in the temperature of the XAD-2 ampoule over the weeks and days. This variation is due to the outdoor temperature and the long water pipe for the cooling water. 7

12 4 CONCLUSIONS The opinion of Avfall Sverige, Sakab AB and Miljömätarna is that the sampling of dioxins and furans over approx. 1 week's time is completely feasible and these measurements demonstrate a good comparison with the permanent semi-continuous system. During the sampling weeks, the incineration in the waste plants was normal with varying operating conditions and waste flows. When a malfunction occurred in one of the plants during the first sample, a clearly higher level of dioxins were generated and already by sample number two, the levels were lower and dropped slowly in subsequent weeks, when the plants were at 100 % normal waste operation. Our assessment is that a better and more reliable value for determining dioxins has been sampled since a long period of time of approx. 1 week includes more normal variations in operation. The differences between the semi-continuous sampling system and prolonged SRM are also significantly less than the analysis uncertainty of 35 %, which laboratories give on dioxin/furan analyses. The samples were taken simultaneously with two completely separate systems and the analyses were sent to two different laboratories for analysis and the difference between the analyses, depending on comparison with the first ampoule or both ampoules in SRM, vary according to the table below. Table 8 SAMPLE AMESA SRM AMPOULE 1 SRM AMPOULE 1+2 DIFFERENCE % % % % ng/m 3 at 11% O 2 8

13 5 FOR CONTINUED DISCUSSIONS To investigate the conditions under which it is possible to conduct the measurements, it could be an idea to make measurements during longer test periods and/or higher levels. The levels were highest during the first week of sampling, when a two-day stop in operations in the rotating furnace, with start and stop periods, was included in the sample. The production during the next three weeks was stable with 100 % availability for both of the incineration plants. Assuming that the dioxin levels from the incineration were constant during the last three weeks, the declining level could indicate a storage or "memory effect" for dioxins in the treatment plant, which were released over a longer period of time. In week two, there was a bleed-through of dioxin to ampoule 2. Possible causes for this could be that the XAD-2 granulate in ampoule 1 may have been heterogeneously packed so the gas stream did not pass uniformly through the ampoule. In which case, this could happen on other occasions during dioxin sampling but has not been detected before since there is only one ampoule in the sampling system. 9

14 6 GRAPHS 6.1 Sample 1 Figure 5 Oxygen concentration SAKAB vs after sampling XAD-2, sample 1 Figure 6 Temperature XAD-2 while taking sample 1 10

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16 6.2 Sample 2 Figure 8 Oxygen concentration SAKAB vs after sampling XAD-2, sample 2 Figure 9 Temperature XAD-2 while taking sample 2 12

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18 6.3 Sample 3 Figure 11 Oxygen concentration SAKAB vs after sampling XAD-2, sample 3 Figure 12 Temperature XAD-2 while taking sample 3 14

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20 6.4 Sample 4 Figure 14 Figure 15 16

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22 7 SET-UP MEASUREMENT EQUIPMENT SRM GLASS COOLER XAD-2 AMPOULE 1, COOLED XAD-2 AMPOULE 2, COOLED CONDENSATE SEPARATION H 2 O GAS PUMP MOISTURE TRAP GAS SAMPLER O 2 INSTRUMENT 18

23 8 APPENDICES Appendix 1 Appendix 2 Primary data PCDD/PCDF Analyses 19

24 Sample no. 1:1 1:2 Unit Date 07/05/ /05/ Time 07/05/ :45-15/05/ :30 Barometric pressure: kpa Gas sampler temperature: C Extracted gas volume m 3 ntg Quantity PCDD/F I-TEQ LB ng/sample Quantity PCDD/F I-TEQ UB ng/sample O 2 concentration vol-% ntg Concentration PCDD/F-equ. I-TEQ(LB) ng/m 3 ntg Concentration PCDD/F-equ. I-TEQ(UB) ng/m 3 ntg Concentration PCDD/F-equ. I-TEQ(LB) ng/m 3 ntg 11% O 2 Concentration PCDD/F-equ. I-TEQ(UB) ng/m 3 ntg 11% O 2 Measuring uncertainty (UB) ± ng/m 3 ntg 11% O 2 Sample no. 2:1 2:2 Unit Date 07/05/ /05/ Time 15/05/ :10-22/05/ :30 Barometric pressure: kpa Gas sampler temperature: C Extracted gas volume m 3 ntg Quantity PCDD/F I-TEQ LB ng/sample Quantity PCDD/F I-TEQ UB ng/sample O 2 concentration vol-% ntg Concentration PCDD/F-equ. I-TEQ(LB) ng/m 3 ntg Concentration PCDD/F-equ. I-TEQ(UB) ng/m 3 ntg Concentration PCDD/F-equ. I-TEQ(LB) ng/m 3 ntg 11% O 2 Concentration PCDD/F-equ. I-TEQ(UB) ng/m 3 ntg 11% O 2 Measuring uncertainty (UB) ± ng/m 3 ntg 11% O 2 20

25 Sample no. 3:1 3:2 Unit Date 22/05/ /05/ Time 22/05/ :15-28/05/ :30 Barometric pressure: kpa Gas sampler temperature: C Extracted gas volume m 3 ntg Quantity PCDD/F I-TEQ LB ng/sample Quantity PCDD/F I-TEQ UB ng/sample O 2 concentration vol-% ntg Concentration PCDD/F-equ. I-TEQ(LB) ng/m 3 ntg Concentration PCDD/F-equ. I-TEQ(UB) ng/m 3 ntg Concentration PCDD/F-equ. I-TEQ(LB) ng/m 3 ntg 11% O 2 Concentration PCDD/F-equ. I-TEQ(UB) ng/m 3 ntg 11% O 2 Measuring uncertainty (UB) ± ng/m 3 ntg 11% O 2 Sample no. 4:1 4:2 Unit Date 04/06/ /05/ /06 Time 28/05/ :20-04/06/ :00 Barometric pressure: kpa Gas sampler temperature: C Extracted gas volume m 3 ntg Quantity PCDD/F I-TEQ LB ng/sample Quantity PCDD/F I-TEQ UB ng/sample O 2 concentration vol-% ntg Concentration PCDD/F-equ. I-TEQ(LB) ng/m 3 ntg Concentration PCDD/F-equ. I-TEQ(UB) ng/m 3 ntg Concentration PCDD/F-equ. I-TEQ(LB) ng/m 3 ntg 11% O 2 Concentration PCDD/F-equ. I-TEQ(UB) ng/m 3 ntg 11% O 2 Measuring uncertainty (UB) ± ng/m 3 ntg 11% O 2 21

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59 REPORTS FROM AVFALL SVERIGE :01 Trends for waste plants with landfill. Statistics :02 Follow-up of techniques for increasing concentration of plant nutrients in biofertilizers 2016:03 Collection of food waste in multi-occupancy buildings. Good examples from municipals and public housing firms 2016:04 Critical evaluation of methods for hazard classification of waste's ecotoxic properties (HP14) 2016:05 Method Comparison of Dioxin Sampling SRM-AMESA

60 Avfall Sverige is the expert organisation within waste management and recycling. It is the members of Avfall Sverige who ensure that waste is managed and recycled in all the municipalities in Sweden. We do this on behalf of society: environmentally safe, sustainably and in the long-term. Our vision is "There is no waste". We act to prevent waste from arising and for more to be reused. The municipalities and their companies are that motor and guarantee for this change. Avfall Sverige Development 2016:05 ISSN Avfall Sverige AB Address Telephone Fax Home page Prostgatan 2, Malmö +46 (0) (0)