COD Reduction in Pharma Waste

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I am handling a pharmaceutical wastewater treatment plant which uses activated sludge treatment followed by MBR.

The wastewater has COD ranging from 200 to 300 gpm on average and it needs to be reduced to < 30 mg/l - 100 mg/l.

I am screening various AOP' s (advanced oxidation process) and other BAT's (best available technologies) for reducing the COD from the waste water.

I am investigating some alternative options such as:

  1. Ozone/Perozone
  2. UV Peroxide
  3. Activated Carbon
  4. Resins
  5. RO
  6. Ultrasonic
  7. AOP followed by a fluidized  bed reactor ( FBR)
  8. Wet Air Oxidation

Are there any other methods that are worth screening or does someone have experience with similar (pharmaceutical) wastewater and COD removal to very low levels? 

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27 Answers

  1. hi Andrew,  with pharma , the main difficulties are usually dealing with polyphenols and high big levels of amines. 

    1 Comment

  2. I am not sure what is happening to my responses. I have tried deleting and re-posting to no success.

    Please email me at andrew@waterandoilsolutions.com.au and I can email you the response. I believe I can help with troubleshooting the problem. My company specialises in MBR processes and removal of complex synthetic chemicals from wastewater.

  3. My experience with MBR processes is that treated effluent is typically

  5. Any specific solution will be dependent on the flow and COD composition remaining after first stage biological process . I  would suggest you to check for the composition of COD at first so that you can estimate whether it is biodegradable or not. 

  6. BIOLOGICAL TREATMENT IS GOOD FOR REDUCES COD BOD ETC.

     

    ANY QUIRE CONTACT: abdulgaffar557.agMohummadrashid@gmail Siddiqui 

    REGARDS,

    ABDUL GAFFAR - SENIOR CHEMIST.

  8. @ what you need to optimise your current ETP to optimum levels.If you are able to give me inlet/outlet values for BOD/COD it will make able to provide some suggestions now I working for one of pharma giant as consultant for ETP upgradation as capacity has increased. 

     

  9. We are developing a next-generation plasma water treatment system (fourth state of matter, ionized gas) that generates UV in addition hydroxyl radicals and other reactive species. We have had success in treatability tests with pharmaceutical wastewater. Please contact me if you'd like more info about it.

  11. Hi Asher,  Along with the AOP treatment, quick COD monitoring will be important to determine efficiency and also are you meeting the final limits. We are involved in a similar project in Europe to reduce hard COD in water intensive industries.  Using peroxide AOP or O3 which can product peroxide, will lead to false high COD results when measuring with the dichromate method. Our project discovered H2O2 is a positive interference to the CODCr method.  We have a green chemistry method that generates the COD results in 15min.  It is available as on-line and lab units.  Send me an email rmenegotto@mantech-inc.com if you would like additional information.  Robert  

  12. You should really consider the 'hybrid' treatment processes  of combining adsorption with AOP processes along with enhanced biological treatment, once the recalcitrant COD is made more biodegradable. Since they already have MBR it may be that this can be done as a "side-stream"?

    Once approach that I see great future opportunities is nano-bubbles to provide very efficient AOP with O2 and/or ozone (see NABAS technolgy). They provide lots of OH- free-radicals very efficiently. feel free to contact me for further support (Farid Turan at MBR Solutions Ltd. UK).

  14. Another important factor which you should consider is wether your effluent is BIO-DEGRADABLE. If yes then you can use aerobic treatment as well. In order to determine that you need to calclulate the ratio COD/BOD5. If this number is around 1,5 then most of your effluent is bio-degradable. If it's over 3 then most of your effluent is not, so you need to apply oxidation methods.

    2 Comments

    1. Hi Eros, thank you for the comment. Can you give me an example of this set of microbes please ? The degradation of ammonia is a real pain, especially when it's in inorganic form.

      Also remember that pharmaceutical waste might contain some traces of materials that could kill some microbes ??????

    2. hi George,   the right microbe set can degrade what was not traditionally considered biodegradable.  high levels of ammonia and benzene and phenolates are easily degraded.    cheers

  16. Resins on natural Zeoliths and inverse osmosis if no > 5m3/h or only this fitration and after Ozone treatment to 240nM  Ray

  17. Asher, 

    take a look at this video.  its pharma waste and it went from cod 50,000 to under 30.

     

    https://www.youtube.com/watch?v=Al7UHDb6zoU

     

    it uses only 2 kw per hour.  uses very little energy.

    you do not need any chemicals to treat it.  they cut their operating cost by over 95%.

    This plant tolls for GSK.  Its open for any one to go see.

     

    no sludge to waste too and no odor.

    no need to buy enzyme, microbes or any fancy AOP.

     

    thanks

     

    1 Comment

  18. hello Hasher we can use BDD quite effectively

    what volume/ flow are you looking at

    we can offer direct oxidation or use other technic like adoption destruction on AC we will certainly be lower then 30mg/l.

    You can contact me directly gerald.busca@quazarconsulting.co.uk

    2 Comments

    1. Hi Asher, if you give me your starting COD levels we can give you an idea of size and costs our technology would be. either as a pre-treatment or to polish your final effluent down to 30ppm. we offer BDD and BDD + adsorption.

      gerald

    2. Gerald my flows are in the range of 200-300 gpm (average to peak)

      2 Comment replies

      2. OK Asher that was in your question 300gpm ~60m3/hr and what is the starting COD? We can do a quick calculation for you. It would definitely be possible to achieve the levels you are looking at but we need to assess if it is viable. Just give me your starting COD for now and we can carry on the conversation. Regards

  19. As per my experience and understanding, MBR would not have been required in this case, simple activated sludge system then having Pressure Sand Filter+GAC Filter and done.

    MBR is an expensive solution for such less pollution.

    1 Comment

  20. Dear Asher,

    Achieving of Results from COD 300ppm to 30 - 100 ppm is normally an easy job which could be achieved by simple Activated sludge Treatment without any other addition. However you are using MBR which is quite expensive in this regards can achieve it easily no need to worry about any other process you mentioned. 50ppm is very easy to achieve.

     

    In addition if you wish to polish extra the treated wastewater, simply have a GAC Filter, which will remove odor and any color and will bring down the COD may be up to 20ppm.

     

    We have successful installations in Pharmaceuticals as well Food & Beverages and got very good good results with Simply Activated Sludge Treatment where the Inlet COD was 400 - 500ppm.

  21. Dear Asher:

    Do you mean 200 - 300 grams COD per cubic metre? In addition I would like to ask you the following questions:

    How much is it the wastewater daily volume the plant treats?

    Area available for the treatment plant?

    Thanking you in advance,

    Eduardo

    1 Comment

    1. I mean 200-300 gpm (gallons per minute), Area is limited but not sufficient for all AOP's being screened (if built to scale).

  22. Hi Asher, Arvia combines the advantages of adsorption and advanced oxidation with its Organics Destruction Cell. It could provide the reduction you need in a single step. The ODC has recently treated some pharmaceutical wastewater for polishing COD. The client also had some particular pharmaceutical compounds they needed to show 80% removal of, so we have been able to tackle this as well. Please get in touch if you'd like to learn more about it. I would certainly be interested to discuss your wastewater problem in more detail.

    2 Comments

    2. would like to know more about the technology

  23. We have our own technology which is called OFR and we manage to reduce the COD to less than 30 mg/l. Our reactors produces Hydroxel Radicals that oxidize the contaminant under normal temperature and pressure. We don't use chemicals in our process. we treated waste water with COD exceeding 1800 mg/l  

    1 Comment

  24. You might also want to consider UV with titanium dioxide, or electrolytic oxidation (see http://www.arviatechnology.com/).  (Please note: I have no link to Arvia and this should not be interpreted as an endorsement, but it is an interesting technology!)

    The best method for your application will be dependent on the nature of the pharmaceutical effluent, the volume and (importantly!) the variability of the effluent. One method may work for one compound, but if the upstream factory begins production of a different pharmaceutical, removal may be very different! Look at typical constituents in the effluent after biological treatment and how much needs to be removed. Methods like RO, AC and resins are unlikely to be economical for large quantities, unless there's a high value to recycling water via RO. For large quantities, you'll probably want to focus on oxidation methods and ozone is NOT the "only guaranteed method"!

  25. The only guaranteed method to reduce COD by at least 90% is OZON. Ozon has no residual effect (usually) but any excess ozon must be destructed or the treated wastewater must be stored for a certain period of time (max 24 hrs) so the ozon will revert to molecular oxygene. The whole process can be monitored by measuring either the ORP or the residual ozone.

  26. If you allpy an ozonation unit downstream of the biological unit and recycle back the ozonate effluent you may get substantial removal. See

    Valeria Mezzanotte , Roberto Canziani , Elisabetta Sardi & Lorenzo Spada (2005) Removal of Pesticides by a Combined Ozonation/Attached Biomass Process Sequence, Ozone: Science & Engineering, 27:4, 327-331, DOI: 10.1080/01919510591008362

    Keisuke Ikehata , Naeimeh Jodeiri Naghashkar & Mohamed Gamal El-Din (2006) Degradation of Aqueous Pharmaceuticals by Ozonation and Advanced Oxidation Processes: A Review, Ozone: Science & Engineering, 28:6, 353-414, DOI: 10.1080/01919510600985937

    Best regards

    Roberto Canziani

  27. You havent considered any anaerobic digestion technology.

    Primarily, I feel that incorporation of a pre-aeration anaerobic digester can significantly help you in achieving the desired norms. The RO and other membrane technologies again result in high end reject wastewaters, the disposal of which is again an issue.

    Anaerobic phase can help in reduction of the organic load without any significant electrical energy addition. Also, the reduction efficiency of this reactor can reduce the load on the further units, as well as, provide a source of fuel gas, which can be used for gas generation. The organic load you have is high, so gas generation will be significant as well. The calculation is

    {(FLOW*ORG.LOAD [COD]) / 1000} x 0.5 x 0.45

    Here, 0.5 is the percentage of COD Reduction (50%), 0.45 is methane content of this gas (45%)

    Further, thumb rule suggests that 12000 m3 of methane generates 1MW electricity.

    1 Comment

    1. Thanks Sagar, there isn't any room to change the upstream processes (already existing) and hence the search into AOP's.