Neutralizing pH
I am our facility’s environmental, health and safety manager. Periodically, we have very high-pH wastewaters that cause the pH within the cyanide oxidation step to be well above our desired upper limit of 11. Our operator has requested that we add sulfuric acid into the cyanide oxidation stage whenever the pH rises above 11. I am very concerned about the release of hydrogen cyanide if something goes wrong and the system accidentally drives the pH well below 7. Are there any safer acid substitutes?
Q: I am our facility’s environmental, health and safety manager. As part of our wastewater pretreatment system, we have a single-stage, flow-through cyanide oxidation step before the wastewater mixes with the other waste streams for pH adjustment and metals removal. Our cyanide oxidation has a bleach and caustic feed controlled by ORP and pH controllers, respectively. Periodically, we have very high-pH wastewaters that cause the pH within the cyanide oxidation step to be well above our desired upper limit of 11; sometimes the incoming wastewater has pH above 12.5.
This high pH causes our ORP reading to decrease enough to add excessive amounts of bleach into the wastewater. While this bleach is more than enough to treat the cyanide, it creates problems downstream when the waste streams mix. Our operator is afraid to raise the ORP set point since it works fine during normal flow conditions.
Since the controller has the capability, and we already use concentrated sulfuric acid for the pH adjustment stage, our operator has requested that we add sulfuric acid into the cyanide oxidation stage whenever the pH rises above 11. I am very concerned about the release of hydrogen cyanide if something goes wrong and the system accidentally drives the pH well below 7.
Are there any safer acid substitutes? J.W.
A: J.W., you are not the first to express concern about using concentrated sulfuric acid in cyanide treatment; however, it has been used safely in this application for many decades. If you do decide to proceed with sulfuric acid, I would strongly recommend that you cover the reactor tank and install a small exhaust to the outside, discharging as high as possible above the roof. You will not need much flow rate, maybe 50–100 cfm, just enough to keep a slight negative pressure in the headspace between the wastewater and cover as well as enough velocity when the access door is opened.
Another consideration is the use of two pH sensors; if the difference between the two readings exceeds a preset limit, an alarm is sounded and the acid feed shut down.
Yes, there are alternatives, but they are very expensive to implement. Some people have recommended the use of saturated sodium bicarbonate (baking soda) which has a pH in the 8s, however, the massive quantities needed for a flow-through system in order to drive the pH from 12.5 to 11, and its slow reaction time at the high pH you are experiencing, makes it infeasible.
Another “safer acid” is carbonic acid, H2 CO3 , formed by dissolving carbon dioxide, CO2 , into water. In your application, the best way to dissolve CO2 into the waste stream is to pump the wastewater through a sidestream pipe, inject the carbon dioxide through a diffuser in the pipe under pressure, and recirculate the wastewater back to the treatment tank. The carbon dioxide can be supplied from 50-lb high-pressure cylinders or 250-lb low-pressure liquefied cylinders. At the high pH that you described, the carbon dioxide or carbonic acid will react quite quickly, and 1/2–3/4 lb of carbon dioxide has the same neutralizing power as 1 lb of sulfuric acid.
Another advantage of carbon dioxide is that, theoretically at least, it cannot drive the pH lower than about 5.7. Again, the disadvantage is the initial high equipment cost for the carbon dioxide storage, feed, and injection system, especially for such a small application.
Some can argue for the use of phosphoric acid, since it behaves more like a weak acid as the pH decreases, however, it still is powerful enough to drive the pH very low to generate hydrogen cyanide.
I was thinking that you could try a dilute solution of acetic acid, a weak acid, however, I am not quite sure of its reaction with bleach or sodium hypochlorite since acetic acid is an organic compound. I am afraid that some odorous byproducts could be generated, at least.
Last, you can contact your chemical supplier to inquire if they have a proprietary “safe” acid product. One of our clients uses a boiler treatment chemical for their pH adjustment acid feed because of its safety; however, this product may still be able to drive the pH very low.
In summary, the challenge here is to use an acidic material that is powerful enough to neutralize the alkalinity in the wastewater fairly efficiently and effectively, but not have the capability to dangerously lower the pH. Based on my experience, carbon dioxide is the best to meet this criteria, but is likely cost prohibitive in your application. If any reader has an additional experience to share, please e-mail me.
Related Content
NASF/AESF Foundation Research Project #122: Electrochemical Approaches to Treatment of PFAS in Plating Wastewater - 9th Quarterly Report
The NASF-AESF Foundation Research Board selected a project addressing the problem of PFAS and related chemicals in plating wastewater streams. This report covers the ninth quarter of work (January-March 2023). In this report, we describe our work on evaluating the performance of PFAS degradation by electrooxidation using surface fluorinated Ti4O7 anodes in batch mode.
Read MoreNASF/AESF Foundation Research Project #122: Electrochemical Approaches to Treatment of PFAS in Plating Wastewater - 7th Quarterly Report
The NASF-AESF Foundation Research Board has selected a project on addressing the problem of PFAS and related chemicals in plating wastewater streams, studying PFAS destruction via electrooxidation and electrocoagulation. Our last report described the results from experiments of EO with a Magnéli phase Ti4O7 anode on the degradation of eight perfluoroalkyl acids (PFAAs). In this seven quarter report, we describe work to further explore how the degradation of different PFAAs are related to their molecular structures.
Read MoreNASF/AESF Foundation Research Project #120: Electrochemical Destruction of Perfluorooctanesulfonate in Electroplating Wastewaters - April 2022-March 2023
This NASF-AESF Foundation research project report covers project work from April 2022 to March 2023 at the University of Illinois at Chicago. The overall objective of this work is to utilize a cost-effective reactive electrochemical membrane (REM) for the removal of PFAS from synthetic electroplating wastewater. Initial results for the oxidation of PFOA with three different catalysts are discussed.
Read MoreTop 5 Areas to Consider Automation of Plating Operations
Automation for finishing operations can lead to improvements in process time, repeatability and consistency of quality. Yet, processes that make sense to explore for these operational efficiencies may not always be readily apparent.
Read MoreRead Next
Education Bringing Cleaning to Machining
Debuting new speakers and cleaning technology content during this half-day workshop co-located with IMTS 2024.
Read MoreEpisode 45: An Interview with Chandler Mancuso, MacDermid Envio Solutions
Chandler Mancuso, technical director with MacDermid Envio discusses updating your wastewater treatment system and implementing materials recycling solutions to increase efficiencies, control costs and reduce environmental impact.
Read MoreA ‘Clean’ Agenda Offers Unique Presentations in Chicago
The 2024 Parts Cleaning Conference, co-located with the International Manufacturing Technology Show, includes presentations by several speakers who are new to the conference and topics that have not been covered in past editions of this event.
Read More