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Analysis of safety aspects associated
with the plasma synthesis and handling of
   nanopowders – from design stage to
        industrial implementation

               J.W. Jurewicz, M.I. Boulos,

                  Tekna Plasma Systems Inc.
     2935 boul. Industriel, Sherbrooke, Qc, Canada J1L 2T9




                                                             1
Outline
•   Presentation of Tekna Advanced Materials
•   Risk Management Process
•   Design Considerations
•   Plasma Processing Units
•   Building Infrastructure
•   Safety Barriers System
•   Conclusion




                                               2
Tekna Advanced Materials Inc.
• The mission of Tekna Advanced Materials Inc. (TAM) is to
  develop and commercially manufacture high added value
  advanced materials using thermal plasma technology.

• There is an increasing demand for powders at the micron,
  sub-micron and nano-sized (< 100 nm) level for a wide range
  of applications varying from microelectronic, to the
  biomedical and the cosmetic industry.

• Intensive research effort is dedicated to the assessment of
  the potential hazard that nano-sized materials can have on
  human health. These materials have to be handled with
  utmost care and well defined procedures in order to minimize
  the chances of human exposure.
                                                             3
Tekna Advanced Materials Inc.
This paper explains the approach undertaken by Tekna
  engineers to design, built and run a viable operation for the
  commercial production of advanced materials including
  nanostructered materials and powders.




                                                                  4
Outline
• Presentation of Tekna Advanced Materials

 Risk Management Process

•   Design Considerations
•   Plasma Processing Units
•   Building Infrastructure
•   Safety Barriers System
•   Conclusion




                                             5
Risk Management Process [1]




[1] “Risk management – Principles and guidelines on implementation”, IEC/ISO 31000:2009 –
    CAN/CSA-IEC/ISO 31000-10 (2010)                                                         6
Accident Sequence[2]

                           ←                THE ACCIDENT SEQUENCE                                 →
Normal condition             Initial phase       Concluding phase              Injury phase
                       ▲                     ▲                        ▲
               Lack of control          Loss of control         Energy/Toxicity exposure




[2] Sklet S., “Safety barriers: Definition, classification and performance”, J. Loss Prevention
    in the Process Industries, 19, pp. 494-506 (2006)
                                                                                                  7
Accident Sequence & Principle of Barriers [2]

                           ←                THE ACCIDENT SEQUENCE                                 →
Normal condition             Initial phase       Concluding phase              Injury phase
                       ▲                     ▲                        ▲
               Lack of control          Loss of control         Energy/Toxicity exposure
                PREVENT                                            PROTECT
     PREVENT                               CONTROL                              MITIGATE
AVOID      PREVENT                         CONTROL                              PROTECT
         Barriers ⇒ generic functions of process safety management




[2] Sklet S., “Safety barriers: Definition, classification and performance”, J. Loss Prevention
    in the Process Industries, 19, pp. 494-506 (2006)
                                                                                                  8
Principle of Barriers[2]
• Safety barriers are physical and/or non-physical means
  planned to prevent, control, or mitigate undesired events or
  accidents




 [2] Sklet S., “Safety barriers: Definition, classification and performance”, J. Loss Prevention
     in the Process Industries, 19, pp. 494-506 (2006)
                                                                                                   9
Process Safety Management [2]


       Risk

                      1
                                                              Acceptation
                                                             of residual risk
 Risk identification
                                 Identification
and its characteristics /
                                        and
      parameters
                                   imposition
                       2          of barrier to        Is barrier
                                    reduce the    4   efficiency
  Identification of                  frequency        acceptable
                            3                                       YES
 possible system’s                  and/or the             ?
    failure and its             consequence of
   characteristics                    a failure              NO

                                                                           10
Nano-Materials (NM) Risk Assessment
                     Uncertainty*
  .....On the whole, a consensus is beginning to emerge,

      risk assessment for chemical should be appropriate for NM,

      but

      they most likely need some methodological modifications.

      Exactly what modifications are needed is not consistently
      made clear, and how long it will take to make these
      modifications is not often stated......


* K.H. Grieger et all., “Redefining risk research priorities for nanomaterials”, J. Nanopart. Res., Vol.
    12, 2, pp. 383-392 (2010)                                                                        11
Process Safety Management [2]


       Risk

                      1

 Risk identification
and its characteristics /
      parameters




                                            12
Nano-Materials (NM) Risk Assessment
                     Uncertainty*
  Concerning Risk Assessment:

  .....However, how long will this [Risk Assessment] process take
      especially given the diversity of NM and applications ?

      A recent analysis estimates that testing existing nanoparticles
      in the USA alone will

      cost between $249 million and 1,18 billion and

      take 34-53 years for completion.

* K.H. Grieger et all., “Redefining risk research priorities for nanomaterials”, J. Nanopart. Res., Vol.
    12, 2, pp. 383-392 (2010)                                                                        13
Nano-Materials (NM) Risk Assessment
                      Uncertainty
  ..... In some cases, the precautionary principle has been
      invoked to support decisions in the absence of full scientific
      certainty......[*]

  Conclusions[**]
  ……Presently, quantitative health hazard and exposure data
    are not available for most nanomaterials. Therefore, health
    risk evaluation for the workplace currently relies to a great
    degree on professional judgments for hazard identification,
    potential exposures and the application of appropriate safety
    measures
* K.H. Grieger et all., “Redefining risk research priorities for nanomaterials”, J. Nanopart. Res., Vol. 12, 2, pp.
    383-392 (2010)
**ISO/TR 12885, “Nanotechnologies – Health and safety practices in occupational settings relevant to
    nanotechnologies”, pp. 1-79 (2008)                                                                              14
Outline
• Presentation of Tekna Advanced Materials
• Risk Management Process

 Design Considerations
   – Hazards’ parameters
   – Hazard evaluation by control banding
   – Efficiency of risk management strategies

•   Plasma Processing Units
•   Building Infrastructure
•   Safety Barriers System
•   Conclusion
                                                15
Design Considerations
The nano-particles are characterized (among others) by their
  very high specific surface area which is the origin of their
  high reactivity leading to both pyrophoric properties for
  combustible materials and/or to toxicity to humans.

The pyrophoric properties may be attenuated by:
   – Passivation process - formation of a controlled thickness
     oxide layer over the particle surface;
   – Encapsulation process – formation of thin layer of
     secondary material (like carbon or polymer) over an entire
     surface of particle;
   – On-line wet collection of nano-powder in an inert liquid;

                                                                 16
Design Considerations
The toxicity parameters include the dose (effective, toxic and
  lethal) and the time of exposition.

The risk management program should aim at both minimizing
  the dose and shortening time and/or frequency of
  exposition.

The possible ways to minimize the dose are (among others):
   – handling the nano-particles in tightly closed
     environment (as long as possible) and
   – use the local ventilation for the case where the products
     have to be handled in open atmosphere.

                                                                 17
Design Considerations – Hazard Evaluation
S.Y.Paik et all.[3] considers two categories of hazard evaluation:
  severity and probability of exposure to nanomaterials.

As the severity is mainly material dependant, this parameter
  was treated as generic without particular identification during
  the initial stage of project.

The probability of exposure is strongly process design
  dependant and as such was the principal guiding parameter
  during the conception stage of the entire operation.

[3] Paik S.Y., D.M. Zalk, P. Swuste, “Application of a Pilot Control Banding Tool for Risk Level
    Assessment and Control of Nanoparticle Exposure”, Ann. Occup. Hyg., Vol. 52, No 6, pp.
    419-428 (2008)
                                                                                                   18
Design Considerations – Hazard Evaluation
                      Probability of Exposure [3]
       Parameter                            Points
 Estimated amount of      > 100    11-100     0-10                 Unknown

  nanomaterial [mg]         25      12,5      6,25                 18,75
                           High    Medium     Low       None       Unknown
 Dustiness / Mistiness
                            30       15        7,5        0         22,5
Number of employee with    > 15    11-15      6-10       1-5
   similar exposure         15       10         5         0
                           Daily   Weekly    Monthly   Less than   Unknown
                                                        monthly
 Frequency of operation
                            15       10         5         0        11,25
                           >4h      1-4 h   30-60 min < 30 min     Unknown
  Duration of operation
                            15       10         5         0        11,25




                                                                           19
Design Considerations – Hazard Evaluation
                      Probability of Exposure [3]
       Parameter                              Points
 Estimated amount of       > 100   11-100        0-10                 Unknown

  nanomaterial [mg]         25      12,5         6,25                 18,75
                           High    Medium        Low        None      Unknown
 Dustiness / Mistiness
                            30       15           7,5        0         22,5
Number of employee with    > 15    11-15         6-10        1-5
   similar exposure         15       10            5         0
                           Daily   Weekly      Monthly    Less than   Unknown
                                                           monthly
 Frequency of operation
                            15       10            5         0        11,25
                           >4h      1-4 h     30-60 min < 30 min      Unknown
  Duration of operation
                            15       10            5         0        11,25


        Material Pending                    Values aimed at during design
                                                                              20
Efficiency of Risk Management Strategies                                                  [4]




[4] C. Ostiguy, B. Roberge, L. Ménard, C. Endo, “ Best Practices Guide to Synthetic Nanoparticle
    Risk Management”, Studies and Research Projects, Report R-599, IRSST (2009)                21
Design Considerations
All above mentioned risk management strategies were
   analysed in the light of existing hazard management
   approach as offered by Tekna Plasma Systems Inc. in
   commercial plasma processing units.

It was decided to apply bottom-up design method to build up
   the commercial production facility by adding additional layers
   of protection / prevention to already existing ones.

At the same time, the economic aspects and processing costs
   reduction have been addressed as well.


                                                                22
Processing Costs Reduction Strategies




                                        23
Outline
• Presentation of Tekna Advanced Materials
• Risk Management Process
• Design Considerations

 Plasma Processing Units
   – Spheroidization Unit
   – Nanopowders Synthesis Unit

• Building Infrastructure
• Safety Barriers System
• Conclusion

                                             24
Plasma Processing Unit – Spheroidization
Some of the typical characteristics of Tekna’s commercial
           induction plasma processing unit
                         •   Continuous operation 24/5-7 including
                             raw material feeding, product cooling &
                             withdrawal - the latter ones are done
                             pneumatically under controlled
                             processing atmosphere;

                         •   All plasma processing operations are
                             automated (including plasma ignition)
                             through in-house conceived computer
                             programme with up to 5 levels of
                             alarms (if required by process safety);

                         •   Deflagration containment design.
                                                                   25
Nano-Powders Synthesis
                                        1 Plasma Torch
               4 Pneumatic
 5 Glove Box   Transfer Unit
                                       2 Plasma Reactor




                                              3 Filter




                               Continuous liner packing
                               to replace the glove box
                                                          26
Outline
• Presentation of Tekna Advanced Materials
• Design Considerations
• Plasma Processing Units

 Building Infrastructure
   o Cooling Water System
   o Washing / Rinsing Water System
   o Ventilation System

• Safety Barriers System
• Conclusion

                                             27
Cooling Water System
• Total power to be dissipated – 2,5 MW

• Dissipation method :
  space (building) heating
  during cold season prior to
  water evaporation in cooling
  tower;

• Cooling water exit temperature
  is kept constant by controlling
  fan speed through a frequency
  drive;

                                          28
Cooling Water System – Impurities Control
Suspended and/or dissolved solids control:

• Cooling water origin:
   – Primary water intake – rain water / melted snow collected
     in 28 m3 water tank from the roof of an entire building - (no
     dissolved solids – weak charge of suspended solids)
   – Secondary water intake – city water originating from
     Memphremagog lake (weak charge of dissolved solids, no
     suspended solids)

• Solid particles collected from dust laden outside air by
  cooling water - the water tank design allows them to
  sediment at bottom collection well
                                                                29
Cooling Water System – Impurities Control
Suspended and/or dissolved solids control:

• Biological charge growth is controlled by
  intensive (> 40000 µWs/cm2) UV irradiation of
  cooling water in closed loop circuit




                                                  30
Cooling Water System – Impurities Control
Suspended and/or dissolved solids control:
Leak of materials from plasma processing system – no
  possibility due to mechanical isolation of primary DI water
  loop from cooling water loop through stainless heat
  exchanger – water quality (resistivity) is monitored




                                                                31
Cooling Water System – Impurities Control
 Cooling water is free of corrosion prevention chemicals (the
  entire cooling system is either of polymer or stainless steel
  origin) allowing to dispose the excess of rain water into
  environment without manmade contaminants.

 The solids collected from outside air as sediments at the
  bottom collection well are evacuated periodically




                                                                  32
Washing / Rinsing Water System
Among procedures to minimize the exposition to nano-sized
  particulates, the wet collection/cleaning of reactor’s
  interiors as well as possible spills is strongly recommended.
The production halls are equipped (among others) with gray
  and deionized (DI) water distribution systems.

• The gray water serves as washing fluid for all plasma
  processing interiors during their periodic cleaning or when
  changing the treated materials; the powder laden water is
  then evacuated through sub-floor conduits to one of the
  collecting tanks where it is left for solids decantation and
  subsequent treatment; similarly, in the case of materials spill
  on the floor, the leftovers are washed down by city water and
  evacuated to the same collecting tank;
                                                                  33
Washing/Rinsing Water System
• The DI water serves as final rinsing water as well as safety
  shower water – for such application the water has to be kept
  lukewarm.

  This water is constantly treated by UV radiation to prevent
  bacterial growth - similarly to the cooling water circuit.




                                                                34
Local Ventilation System
Designing Considerations :

•Design according to the standard ANSI/AIHA Z9.2 – 2006 –
«Fundamentals Governing the Design and Operation of Local
Exhaust Ventilation Systems»

•Exhausted air leaving premises has to be cleaned to HEPA
standard (99,97 % of arrestance) through progressive retention
of particles through a sequence of filters with increasing
arrestance to avoid rapid clogging of a final filter




                                                             35
Local Ventilation System




         MERV = Minimum Efficiency Reporting
                      Value                    36
Plasma Processing Hall – Spheroidization
                                  Pre-Filter
                               & Primary Filter

                                 HEPA Filter




                                                  37
Ventilation System
• Pre-filter and primary filter are housed in one box and are fed
  from 2 exhaust arms;
• Each final filter (HEPA) collects spent air from 2-3 primary
  filters;
• Both primary and final filters’ pressure losses are monitored
  locally (gauge) and remotely (control room) – an operator is
  aware of the actual pressure loss value and a visual and
  audio alarms are set as well;
• The exhaust fan (located over the roof) is driven by a
  frequency controlled drive allowing to maintain constant air
  evacuation rate in spite of increasing pressure losses in the
  chain of filters – in the case of an emergency, the evacuation
  rate increases automatically to its maximal value.
                                                               38
Outline
•   Presentation of Tekna Advanced Materials
•   Risk Management Process
•   Design Considerations
•   Plasma Processing Units
•   Building Infrastructure

 Safety Barriers System
   – Example: Flammability hazard
   – Example: Nanoparticles spill hazard

• Conclusion

                                               39
Safety Barriers System - Examples
• Hazard – Flammability of processing gases/products:
   – Hydrogen in-situ production rate follows its consumption –
     no stocking
   – PLC activated vacuum/pressure inerting of processing
     vessels including air lock charged with powdered raw
     material and feeder hoper for each charging operation;
   – Monitoring of residual oxygen concentration in processing
     vessels;
   – Controlled passivation of pyrophoric products;
   – Stocking of pyrophoric products under inert atmosphere;
   – Equipment designed to withstand deflagration;
   – Process off gas (already saturated with inerting water
     vapour) is exhausted to outside through the flash arrestor;
                                                              40
Safety Barriers System – Nano-Particles Leak




                                          41
Safety Barriers System
• Air lock exit from production hall      ⇒

• Personal Protection Equipment ⇓




                             Motorized air blower
                             unit equipped with
                             splash protected gas,
                             vapour & particulates
                             (HEPA class) filtering
                             unit
                                                      42
Outline
•   Presentation of Tekna Advanced Materials
•   Risk Management Process
•   Design Considerations
•   Plasma Processing Units
•   Building Infrastructure
•   Safety Barriers System

 Conclusion




                                               43
Conclusion (1)
The bottom-up design approach from Tekna built standard
  thermal plasma processing units to entire production facility
  allowed to address and successfully resolve all major safety
  and economic issues involved with the production of
  advanced nano-sized materials by:

 Conceiving multiple – level barriers against Nano-Particle
  spill hazard;
 Minimizing the frequency of exposure to hazardous materials
  through (among others) high level of process automation
  including final products packaging and separate production
  halls for higher hazard level materials;


                                                                  44
Conclusion (2)
• Establishing and implementing the adequate operational
  procedures;
• Cooling water cost reduction by recovery of rain / snow;
• Space heating by spent heat from plasma processing units;
• Minimizing the waste disposal costs through in-house
  recycling procedures and elimination of water conditioning
  chemicals (replaced by UV radiation);
• On-site, consumption regulated, production of hydrogen;
• Recycling (after conditioning) the major part of consumed
  gas;
• Optimizing the production rate of each product according to
  its specifics.

                                                                45
Acknowledgments

                            Institute de recherche
Tekna Plasma Systems Inc.   Robert Sauvé en santé et
                            en sécurité du travail

 •   Loïc Brochu            • Claude Ostiguy
 •   Jean-Pierre Crête
 •   Nicolas Dignard
 •   David Héraud
 •   François Hudon




                                                       46
Tekna Plasma Systems      Tekna Advanced Materials




                       THANK YOU
                                                     47

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Jerzy Jurewicz & Boulos_Analysis of safety aspects associated with the plasma synthesis and handling of nanopowders – from design stage to industrial implementation

  • 1. Analysis of safety aspects associated with the plasma synthesis and handling of nanopowders – from design stage to industrial implementation J.W. Jurewicz, M.I. Boulos, Tekna Plasma Systems Inc. 2935 boul. Industriel, Sherbrooke, Qc, Canada J1L 2T9 1
  • 2. Outline • Presentation of Tekna Advanced Materials • Risk Management Process • Design Considerations • Plasma Processing Units • Building Infrastructure • Safety Barriers System • Conclusion 2
  • 3. Tekna Advanced Materials Inc. • The mission of Tekna Advanced Materials Inc. (TAM) is to develop and commercially manufacture high added value advanced materials using thermal plasma technology. • There is an increasing demand for powders at the micron, sub-micron and nano-sized (< 100 nm) level for a wide range of applications varying from microelectronic, to the biomedical and the cosmetic industry. • Intensive research effort is dedicated to the assessment of the potential hazard that nano-sized materials can have on human health. These materials have to be handled with utmost care and well defined procedures in order to minimize the chances of human exposure. 3
  • 4. Tekna Advanced Materials Inc. This paper explains the approach undertaken by Tekna engineers to design, built and run a viable operation for the commercial production of advanced materials including nanostructered materials and powders. 4
  • 5. Outline • Presentation of Tekna Advanced Materials  Risk Management Process • Design Considerations • Plasma Processing Units • Building Infrastructure • Safety Barriers System • Conclusion 5
  • 6. Risk Management Process [1] [1] “Risk management – Principles and guidelines on implementation”, IEC/ISO 31000:2009 – CAN/CSA-IEC/ISO 31000-10 (2010) 6
  • 7. Accident Sequence[2] ← THE ACCIDENT SEQUENCE → Normal condition Initial phase Concluding phase Injury phase ▲ ▲ ▲ Lack of control Loss of control Energy/Toxicity exposure [2] Sklet S., “Safety barriers: Definition, classification and performance”, J. Loss Prevention in the Process Industries, 19, pp. 494-506 (2006) 7
  • 8. Accident Sequence & Principle of Barriers [2] ← THE ACCIDENT SEQUENCE → Normal condition Initial phase Concluding phase Injury phase ▲ ▲ ▲ Lack of control Loss of control Energy/Toxicity exposure PREVENT PROTECT PREVENT CONTROL MITIGATE AVOID PREVENT CONTROL PROTECT Barriers ⇒ generic functions of process safety management [2] Sklet S., “Safety barriers: Definition, classification and performance”, J. Loss Prevention in the Process Industries, 19, pp. 494-506 (2006) 8
  • 9. Principle of Barriers[2] • Safety barriers are physical and/or non-physical means planned to prevent, control, or mitigate undesired events or accidents [2] Sklet S., “Safety barriers: Definition, classification and performance”, J. Loss Prevention in the Process Industries, 19, pp. 494-506 (2006) 9
  • 10. Process Safety Management [2] Risk 1 Acceptation of residual risk Risk identification Identification and its characteristics / and parameters imposition 2 of barrier to Is barrier reduce the 4 efficiency Identification of frequency acceptable 3 YES possible system’s and/or the ? failure and its consequence of characteristics a failure NO 10
  • 11. Nano-Materials (NM) Risk Assessment Uncertainty* .....On the whole, a consensus is beginning to emerge, risk assessment for chemical should be appropriate for NM, but they most likely need some methodological modifications. Exactly what modifications are needed is not consistently made clear, and how long it will take to make these modifications is not often stated...... * K.H. Grieger et all., “Redefining risk research priorities for nanomaterials”, J. Nanopart. Res., Vol. 12, 2, pp. 383-392 (2010) 11
  • 12. Process Safety Management [2] Risk 1 Risk identification and its characteristics / parameters 12
  • 13. Nano-Materials (NM) Risk Assessment Uncertainty* Concerning Risk Assessment: .....However, how long will this [Risk Assessment] process take especially given the diversity of NM and applications ? A recent analysis estimates that testing existing nanoparticles in the USA alone will cost between $249 million and 1,18 billion and take 34-53 years for completion. * K.H. Grieger et all., “Redefining risk research priorities for nanomaterials”, J. Nanopart. Res., Vol. 12, 2, pp. 383-392 (2010) 13
  • 14. Nano-Materials (NM) Risk Assessment Uncertainty ..... In some cases, the precautionary principle has been invoked to support decisions in the absence of full scientific certainty......[*] Conclusions[**] ……Presently, quantitative health hazard and exposure data are not available for most nanomaterials. Therefore, health risk evaluation for the workplace currently relies to a great degree on professional judgments for hazard identification, potential exposures and the application of appropriate safety measures * K.H. Grieger et all., “Redefining risk research priorities for nanomaterials”, J. Nanopart. Res., Vol. 12, 2, pp. 383-392 (2010) **ISO/TR 12885, “Nanotechnologies – Health and safety practices in occupational settings relevant to nanotechnologies”, pp. 1-79 (2008) 14
  • 15. Outline • Presentation of Tekna Advanced Materials • Risk Management Process  Design Considerations – Hazards’ parameters – Hazard evaluation by control banding – Efficiency of risk management strategies • Plasma Processing Units • Building Infrastructure • Safety Barriers System • Conclusion 15
  • 16. Design Considerations The nano-particles are characterized (among others) by their very high specific surface area which is the origin of their high reactivity leading to both pyrophoric properties for combustible materials and/or to toxicity to humans. The pyrophoric properties may be attenuated by: – Passivation process - formation of a controlled thickness oxide layer over the particle surface; – Encapsulation process – formation of thin layer of secondary material (like carbon or polymer) over an entire surface of particle; – On-line wet collection of nano-powder in an inert liquid; 16
  • 17. Design Considerations The toxicity parameters include the dose (effective, toxic and lethal) and the time of exposition. The risk management program should aim at both minimizing the dose and shortening time and/or frequency of exposition. The possible ways to minimize the dose are (among others): – handling the nano-particles in tightly closed environment (as long as possible) and – use the local ventilation for the case where the products have to be handled in open atmosphere. 17
  • 18. Design Considerations – Hazard Evaluation S.Y.Paik et all.[3] considers two categories of hazard evaluation: severity and probability of exposure to nanomaterials. As the severity is mainly material dependant, this parameter was treated as generic without particular identification during the initial stage of project. The probability of exposure is strongly process design dependant and as such was the principal guiding parameter during the conception stage of the entire operation. [3] Paik S.Y., D.M. Zalk, P. Swuste, “Application of a Pilot Control Banding Tool for Risk Level Assessment and Control of Nanoparticle Exposure”, Ann. Occup. Hyg., Vol. 52, No 6, pp. 419-428 (2008) 18
  • 19. Design Considerations – Hazard Evaluation Probability of Exposure [3] Parameter Points Estimated amount of > 100 11-100 0-10 Unknown nanomaterial [mg] 25 12,5 6,25 18,75 High Medium Low None Unknown Dustiness / Mistiness 30 15 7,5 0 22,5 Number of employee with > 15 11-15 6-10 1-5 similar exposure 15 10 5 0 Daily Weekly Monthly Less than Unknown monthly Frequency of operation 15 10 5 0 11,25 >4h 1-4 h 30-60 min < 30 min Unknown Duration of operation 15 10 5 0 11,25 19
  • 20. Design Considerations – Hazard Evaluation Probability of Exposure [3] Parameter Points Estimated amount of > 100 11-100 0-10 Unknown nanomaterial [mg] 25 12,5 6,25 18,75 High Medium Low None Unknown Dustiness / Mistiness 30 15 7,5 0 22,5 Number of employee with > 15 11-15 6-10 1-5 similar exposure 15 10 5 0 Daily Weekly Monthly Less than Unknown monthly Frequency of operation 15 10 5 0 11,25 >4h 1-4 h 30-60 min < 30 min Unknown Duration of operation 15 10 5 0 11,25 Material Pending Values aimed at during design 20
  • 21. Efficiency of Risk Management Strategies [4] [4] C. Ostiguy, B. Roberge, L. Ménard, C. Endo, “ Best Practices Guide to Synthetic Nanoparticle Risk Management”, Studies and Research Projects, Report R-599, IRSST (2009) 21
  • 22. Design Considerations All above mentioned risk management strategies were analysed in the light of existing hazard management approach as offered by Tekna Plasma Systems Inc. in commercial plasma processing units. It was decided to apply bottom-up design method to build up the commercial production facility by adding additional layers of protection / prevention to already existing ones. At the same time, the economic aspects and processing costs reduction have been addressed as well. 22
  • 23. Processing Costs Reduction Strategies 23
  • 24. Outline • Presentation of Tekna Advanced Materials • Risk Management Process • Design Considerations  Plasma Processing Units – Spheroidization Unit – Nanopowders Synthesis Unit • Building Infrastructure • Safety Barriers System • Conclusion 24
  • 25. Plasma Processing Unit – Spheroidization Some of the typical characteristics of Tekna’s commercial induction plasma processing unit • Continuous operation 24/5-7 including raw material feeding, product cooling & withdrawal - the latter ones are done pneumatically under controlled processing atmosphere; • All plasma processing operations are automated (including plasma ignition) through in-house conceived computer programme with up to 5 levels of alarms (if required by process safety); • Deflagration containment design. 25
  • 26. Nano-Powders Synthesis 1 Plasma Torch 4 Pneumatic 5 Glove Box Transfer Unit 2 Plasma Reactor 3 Filter Continuous liner packing to replace the glove box 26
  • 27. Outline • Presentation of Tekna Advanced Materials • Design Considerations • Plasma Processing Units  Building Infrastructure o Cooling Water System o Washing / Rinsing Water System o Ventilation System • Safety Barriers System • Conclusion 27
  • 28. Cooling Water System • Total power to be dissipated – 2,5 MW • Dissipation method : space (building) heating during cold season prior to water evaporation in cooling tower; • Cooling water exit temperature is kept constant by controlling fan speed through a frequency drive; 28
  • 29. Cooling Water System – Impurities Control Suspended and/or dissolved solids control: • Cooling water origin: – Primary water intake – rain water / melted snow collected in 28 m3 water tank from the roof of an entire building - (no dissolved solids – weak charge of suspended solids) – Secondary water intake – city water originating from Memphremagog lake (weak charge of dissolved solids, no suspended solids) • Solid particles collected from dust laden outside air by cooling water - the water tank design allows them to sediment at bottom collection well 29
  • 30. Cooling Water System – Impurities Control Suspended and/or dissolved solids control: • Biological charge growth is controlled by intensive (> 40000 µWs/cm2) UV irradiation of cooling water in closed loop circuit 30
  • 31. Cooling Water System – Impurities Control Suspended and/or dissolved solids control: Leak of materials from plasma processing system – no possibility due to mechanical isolation of primary DI water loop from cooling water loop through stainless heat exchanger – water quality (resistivity) is monitored 31
  • 32. Cooling Water System – Impurities Control  Cooling water is free of corrosion prevention chemicals (the entire cooling system is either of polymer or stainless steel origin) allowing to dispose the excess of rain water into environment without manmade contaminants.  The solids collected from outside air as sediments at the bottom collection well are evacuated periodically 32
  • 33. Washing / Rinsing Water System Among procedures to minimize the exposition to nano-sized particulates, the wet collection/cleaning of reactor’s interiors as well as possible spills is strongly recommended. The production halls are equipped (among others) with gray and deionized (DI) water distribution systems. • The gray water serves as washing fluid for all plasma processing interiors during their periodic cleaning or when changing the treated materials; the powder laden water is then evacuated through sub-floor conduits to one of the collecting tanks where it is left for solids decantation and subsequent treatment; similarly, in the case of materials spill on the floor, the leftovers are washed down by city water and evacuated to the same collecting tank; 33
  • 34. Washing/Rinsing Water System • The DI water serves as final rinsing water as well as safety shower water – for such application the water has to be kept lukewarm. This water is constantly treated by UV radiation to prevent bacterial growth - similarly to the cooling water circuit. 34
  • 35. Local Ventilation System Designing Considerations : •Design according to the standard ANSI/AIHA Z9.2 – 2006 – «Fundamentals Governing the Design and Operation of Local Exhaust Ventilation Systems» •Exhausted air leaving premises has to be cleaned to HEPA standard (99,97 % of arrestance) through progressive retention of particles through a sequence of filters with increasing arrestance to avoid rapid clogging of a final filter 35
  • 36. Local Ventilation System MERV = Minimum Efficiency Reporting Value 36
  • 37. Plasma Processing Hall – Spheroidization Pre-Filter & Primary Filter HEPA Filter 37
  • 38. Ventilation System • Pre-filter and primary filter are housed in one box and are fed from 2 exhaust arms; • Each final filter (HEPA) collects spent air from 2-3 primary filters; • Both primary and final filters’ pressure losses are monitored locally (gauge) and remotely (control room) – an operator is aware of the actual pressure loss value and a visual and audio alarms are set as well; • The exhaust fan (located over the roof) is driven by a frequency controlled drive allowing to maintain constant air evacuation rate in spite of increasing pressure losses in the chain of filters – in the case of an emergency, the evacuation rate increases automatically to its maximal value. 38
  • 39. Outline • Presentation of Tekna Advanced Materials • Risk Management Process • Design Considerations • Plasma Processing Units • Building Infrastructure  Safety Barriers System – Example: Flammability hazard – Example: Nanoparticles spill hazard • Conclusion 39
  • 40. Safety Barriers System - Examples • Hazard – Flammability of processing gases/products: – Hydrogen in-situ production rate follows its consumption – no stocking – PLC activated vacuum/pressure inerting of processing vessels including air lock charged with powdered raw material and feeder hoper for each charging operation; – Monitoring of residual oxygen concentration in processing vessels; – Controlled passivation of pyrophoric products; – Stocking of pyrophoric products under inert atmosphere; – Equipment designed to withstand deflagration; – Process off gas (already saturated with inerting water vapour) is exhausted to outside through the flash arrestor; 40
  • 41. Safety Barriers System – Nano-Particles Leak 41
  • 42. Safety Barriers System • Air lock exit from production hall ⇒ • Personal Protection Equipment ⇓ Motorized air blower unit equipped with splash protected gas, vapour & particulates (HEPA class) filtering unit 42
  • 43. Outline • Presentation of Tekna Advanced Materials • Risk Management Process • Design Considerations • Plasma Processing Units • Building Infrastructure • Safety Barriers System  Conclusion 43
  • 44. Conclusion (1) The bottom-up design approach from Tekna built standard thermal plasma processing units to entire production facility allowed to address and successfully resolve all major safety and economic issues involved with the production of advanced nano-sized materials by:  Conceiving multiple – level barriers against Nano-Particle spill hazard;  Minimizing the frequency of exposure to hazardous materials through (among others) high level of process automation including final products packaging and separate production halls for higher hazard level materials; 44
  • 45. Conclusion (2) • Establishing and implementing the adequate operational procedures; • Cooling water cost reduction by recovery of rain / snow; • Space heating by spent heat from plasma processing units; • Minimizing the waste disposal costs through in-house recycling procedures and elimination of water conditioning chemicals (replaced by UV radiation); • On-site, consumption regulated, production of hydrogen; • Recycling (after conditioning) the major part of consumed gas; • Optimizing the production rate of each product according to its specifics. 45
  • 46. Acknowledgments Institute de recherche Tekna Plasma Systems Inc. Robert Sauvé en santé et en sécurité du travail • Loïc Brochu • Claude Ostiguy • Jean-Pierre Crête • Nicolas Dignard • David Héraud • François Hudon 46
  • 47. Tekna Plasma Systems Tekna Advanced Materials THANK YOU 47