CO2 applications. for drinking water production, process water treatment and waste water treatment

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1 CO2 applications for drinking water production, process water treatment and waste water treatment Dr. Dr. Hermans Hermans

2 Carbon dioxide in water is -a natural food additive, non poisonous -a weak acid -partly dissociated to bicarbonate HCO - 3 and carbonate CO 2-3 -highly soluble: at 10 o C and 1 bar (a) solubility amounts to 2330 mg/l These properties make it useful for water treatment

3 Waste water portfolio Main applications: Carbon dioxide Neutralisation of industrial waste water Emulsion separation Oxygen Waste water transport without septic conditions Flexible capacity increase of biological waste water treatment Cracking of persistent COD with Ozone Oxygenation of surface waters

4 Example power plant Neutralization of waste water with CO 2 - Savings and salt consent level met Alkaline waste water originates from hydraulic ash handling. Process water for ash handling is a closed system in principle, but waste water discharge is required to maintain the water level in the buffer pond. Before discharge, waste water is neutralized with CO 2 Savings: Hydrochloric acid replaced by CO 2 Salt consent level: salting up with 2800 mg/l chloride is avoided. Balti power plant in Narva (EE), operated by AS Narva Elektrijaamad

5 Aspects in the decision for CO 2 Average alkalinity of 79 mmol/l requires significant acid dose - Avoid salting up with chloride or sulphate - Avoid discharge fee for chloride or sulphate Acid chosen Consent level [mg/l] Increase in sulphate [mg/l] Increase in chloride [mg/l] Sulfuric acid H 2 SO Hydrochloric acid HCl Carbon dioxide CO 2 3 scenarios for waste water neutralization: only CO 2 avoids salting up

6 Aspects in the decision for CO 2 - CO 2 is economic in consumption - No investment for hydrochloric acid storage - No corrosion of surrounding hardware 3 2,5 37 % kg acid/ kg NaOH 2 1,5 1 ph >10.5 ph = % 96 % [100 %] 0,5 0 CO 2 H 2 SO 4 HCl Acid consumption for neutralization: Reduced consumption reduces operating costs

7 Aspects in the decision for CO 2 Avoid problems with ph control associated with hydrochloric acid Phase I CO 2 Phase II Phase III mineral acid ph discharge limits 2 OH _ + CO 2 CO 3 2 _ + H 2 O CO 3 2 _ + CO 2 + H 2 O 2 HCO 3 _ CO 2 consumption Neutralization curves of mineral acid and CO 2 : With the weak acid CO 2 overacidification cannot occur

8 Aspects in the decision for CO 2 Proven process technology for rated capacity 2000 kg CO 2 /h ph control QC Neutra- Box CO 2 - storage tank *Liquid CO 2 injection Liquid CO 2 injection in side stream for high rate neutralization

9 Neutralisation of alkaline waste water with CO 2 Advantages safe and simple ph control, overdosing not possible inert gas with no corrosion of surrounding plant no impact on salt content storage and handling simple and safe low investment costs, stable price Messer offers a custom made package consisting of engineering, hardware and supply ph mineral acid CO 2 discharge limits CO 2 consumption

10 Process water treatment with CO 2 Mechanisms based on specific CO 2 - properties - Acid used for ph control in alkaline and neutral range, e.g. hypochlorite disinfection, pulp washing, sticky reduction; - Acid used for LSI control to prevent calcium scaling, stabilize dissolved calcium in the neutral range e.g. cooling water systems, R.O. feed, vacuum pumps - Supply of carbonate ions for precipitation reactions, e.g. scrubber water treatment, brine purification; often replaces soda-ash - High solubility in water, e.g. special cleaning treatments

11 ph and LSI control with CO 2 in open, recirculating cooling systems Advantages: -Easy and safe ph-control -Maintains alkalinity -CO 2 is not an hazardous good -Environmentally safe, not corrosive -Reduced salinity in blow down Economics: -CO 2 -consumption is usually higher than mineral acid consumption -Reduced consumptions of make-up water, scale inhibitor and/or biocides -Economic in several cases

12 Precipitation with CO 2 Example - Steel plant Wet scrubber process water from steel plants may have high calcium uptake and become alkaline. In process water treatment step Calcium is removed by precipitation with carbonate ions (CO 32 -) Removal of calcium - : Ca 2+ + CO 3 2- CaCO 3 Carbonate (CO 3 2- ) ions are supplied by Soda- ash (Na 2 CO 3 ) or by CO 2 + OH - : Supply of carbonate : Soda-ash: Na 2 CO 3,aq 2 Na + + CO 3 2- CO 2 : CO 2,aq + 2 OH - CO H 2 O Advantages of CO 2 compared to Soda-ash: Cost savings for chemicals: kg CO 2 replaces 1 kg Soda ash Cost savings for equipment: CO 2 - injection is simpler than solid soda-ash dosing Simultaneous ph control

13 Precipitation with CO 2 Example - Brine purification in Chlor- Alkali Electrolysis Advantages no investments for storage, dosing and dissolution of soda easy logistics and handling, no dust compact dosing system high purity chemical low investment costs, low variable costs Simplified flow-sheet for chlor-alkali-electrolysis Solvic Antwerp (B) CO 2 -Injection in alkaline side stream; Messer offers a custom made package consisting of engineering, hardware and supply

14 Clean Operator or Champagnespoeling Membranes are cleaned with over-saturated carbonated water; Innovation of Vitens and WE Consult Mechanism Turbulence, due to degassing in the inter-membrane space achieves removal of organic deposits and particles. Due to its high solubility in water CO 2 achieves a large degassing volume CO 2 -supply and dissolu- tion designed by Messer Advantages for spirally wound membranes, compared to chemical cleaning -Improved cleaning results -Cleaning CO 2 -footprint reduced by 75% - Reduced shut down time (~5-10 min vs. 8 h)

15 Drinking water portfolio Main applications: Carbon dioxide ph and LSI control with CO 2 Mineralization with CO 2 and lime to increase alkalinity and hardness Oxygen Ozone treatment based on oxygen Fe/Mn/NH 4 oxidation with pure oxygen

16 LSI adjustment with CO 2 after Softening by Lime Decarbonisation CO 2 Lime or caustic soda

17 LSI adjustment with CO 2 after Softening by Lime Decarbonisation Blanketing the water surface with CO 2 -Prevents scaling after reactor outlet -prolongs run time of subsequent filters Drinking water production Spannenburg, Vitens (NL)

18 ph adjustment with carbon dioxide before coagulation - Achieves optimum ph for coagulation - Minimizes residual Al-concentration: solubility of aluminum is a function of ph - CO 2 replaces sulfuric acid. This improves ph control, improves corrosion index and avoids loss of alkalinity in ph steps. Example Etappe L Ampolla, Consorci d Aigües de Tarragona (CAT) Spain Directive 98/83/EC required new flocculent ph set-point 7.6 ph raw water Rated production 3.6 m 3 /s

19 Panel Injection into main pipe Etappe L Ampolla

20 Messer supplies: Gas supply and storage; with design and engineering Proposal on process optimization with CO 2 and/or O 2 after evaluating present situation Hardware for Injection, dissolution, dosing and control often custom-made; we work with a broad portfolio of injection technologies Trials, trial equipment, training

21 Thank you for your attention! Dr. Hermans Dr. Hermans

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