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CARBON DIOXIDE STRIPPING: -Fundamentals -Computer Design Model CARBON DIOXIDE STRIPPING: -Fundamentals -Computer Design Model Brian J. Vinci Barnaby J. Watten Steven T. Summerfelt Michael B. Timmons Raul H. Piedrahita Recirculating Aquaculture Systems Short Course The title of this presentation is “Carbon Dioxide Stripping: Fundamentals and Computer Design Model”. This material is a compilation of a few years of work and has had multiple contributors including Steven Summerfelt, Raul Piedrahita of UC Davis, Mike Timmons, and Barnaby Watten of the USGS. OVERVIEW •CO2 Production •CO2 Toxicity • Carbonate System • Gas Transfer • Stripping Options Recirculating Aquaculture Systems Short Course In this presentation I will cover some of the basics of carbon dioxide in aquaculture, starting with CO2 production and CO2 toxicity. Then I will cover the carbonate system and how CO2 acts as a component of the carbonate system. I will also discuss some basics of gas transfer and the stripping of CO2 from aquaculture waters. After getting through those concepts we will start on a few of the CO2 stripping options commonly used in aquaculture. OVERVIEW • Basic Design Parameters • Design Example – Two Methods • Facility Considerations • Computer Design Model • Model Results Recirculating Aquaculture Systems Short Course For each of the CO2 stripping options I will cover some of the basic design parameters that you need to think about when considering each option. After the CO2 stripping options we’ll go through a design example for sizing a stripping tower and we’ll use two methods of calculation for the same example and compare the methods. I will also discuss some of the facility considerations concerning CO2 that are very important in indoor aquaculture operations. We will then start in on the computer model that is available for the design of CO2 control in intensive aquaculture operations and cover some model simulation results. CO2 PRODUCTION • Molar basis –1 mole of CO2 is produced for every 1 mole O2 consumed • Mass basis – 1.38 g of CO2 is produced for every 1 g O2 consumed Recirculating Aquaculture Systems Short Course Production – on a molar basis 1 mole of carbon dioxide is produced for every mole of oxygen consumed by fish. Converting to a mass basis this results in 1.38 grams of carbon dioxide being produced for every 1 gram of oxygen consumed by fish. What’s important here is that carbon dioxide is produced by the fish at a greater rate than oxygen is consumed. CO2 TOXICITY • Bohr Effect – Elevated CO2 levels decrease the ability of hemoglobin to transport oxygen • Root Effect – Elevated CO2 levels decrease the maximum oxygen binding capacity of the blood Recirculating Aquaculture Systems Short Course Toxicity – carbon dioxide is attributed to the Bohr and Root effects. The Bohr Effect is that elevated CO2 levels decrease the ability of a fish’s hemoglobin to transport oxygen. The Root Effect is that elevated CO2 levels decrease the maximum oxygen binding capacity of a fish’s blood. Both effects indicate that high levels of CO2 result in compromised fish respiration. CO2 TOXICITY • Safe levels depend on species, developmental stage, and water quality: Concentration Fish Health (mg/L) Effect Reference Operational level Timmons, 60 for Tilapia unpublished data Operational level Piedrahita, 60 for Striped Bass unpublished data Safe level for 9–30 Trout Heinen et al., 1996 Recirculating Aquaculture Systems Short Course The safe or accepted level of carbon dioxide in water depend upon fish species, the developmental stage of the fish, and the water quality. For tilapia, Mike Timmons has data that suggest that 60 mg/L CO2 is a safe operational level. For striped bass, Raul Piedrahita has data that suggest that 60 mg/L is also a safe operational level. In the case of trout, Heinen and others have reported that safe levels are much lower, from 9 to 30 mg/L. CARBONATE SYSTEM •CO2 = Carbon Dioxide •H2CO3 = Carbonic Acid – •HCO3 = Bicarbonate = •CO3 = Carbonate Recirculating Aquaculture Systems Short Course Whenever talking about dissolved carbon dioxide it is important to note that it is part of an aqueous chemical system known as the carbonate system or carbonate carbon system. The carbonate system includes all species that have inorganic carbon. There are four such species: carbon dioxide (CO2), carbonic acid (H2CO3), - = bicarbonate ion (HCO3 ), and carbonate ion (CO3 ). CARBONATE SYSTEM CO2 + H2O ⇔ H2CO3 K0 [H2CO3*] = [CO2] + [H2CO3] – + H2CO3* ⇔ HCO3 + H K1 – = + HCO3 ⇔ CO3 + H K2 Recirculating Aquaculture Systems Short Course The carbonate system relates the different carbonate carbon species through a series of acid/base reactions. The first reaction is the hydration of aqueous carbon dioxide into carbonic acid. The equilibrium constant for this reaction is denoted here as KO. Because it is very difficult to determine the difference between dissolved carbon dioxide and carbonic acid, the two species are often “lumped” together into the functional species H2CO3*. H2CO3* is simply known as dissolved CO2. The second reaction is the acid/base reaction where carbon dioxide, H2CO3*, dissociates into - + bicarbonate ion, HCO3 , and a hydrogen ion, H . The equilibrium constant for this reaction is denoted here as K1. The third reaction is the acid/base reaction where = + bicarbonate dissociates into carbonate ion, CO3 , and a hydrogen ion, H . The equilibrium constant for this reaction is denoted here as K2. CARBONATE SYSTEM • Total Carbonate Carbon (mol/L) – = CT = [H2CO3*] + [HCO3 ] + [CO3 ] • Alkalinity (eqv/L) – = – + Alk = [HCO3 ] + 2[CO3 ] + [OH ] – [H ] Recirculating Aquaculture Systems Short Course The carbonate system also has two important definitions: total carbonate carbon and alkalinity. The total carbonate carbon is the sum of all the inorganic carbon in the water expressed as moles of carbon per liter. Total carbonate carbon or CT is the - = sum of carbon dioxide (H2CO3*), plus bicarbonate (HCO3 ), plus carbonate (CO3 ), all individually expressed in moles per liter. The alkalinity of water is also known as the acid neutralizing capacity and is expressed in equivalents per liter. Alkalinity - = or Alk is the sum of bicarbonate (HCO3 ), plus twice the carbonate (CO3 ), plus hydroxyl ion (OH-), minus hydrogen ion (H+). Alkalinity is also commonly expressed in mg CaCO3 per liter through the use of an equivalents conversion. CARBONATE SYSTEM 70 Alkalinity 60 100 mg/L 50 CO2 40 (mg/L) 30 20 10 0 6.5 7.0 7.5 8.0 8.5 pH Recirculating Aquaculture Systems Short Course Just to give an example of how all this chemistry works together is this graph of dissolved carbon dioxide versus pH for a water with an alkalinity of 100 mg CaCO3 per liter. At lower pHs a larger proportion of the total carbonate carbon exists as CO2. But as the pH is increased less and less carbonate carbon exists as CO2, but shifts to bicarbonate. This is shown in the plot where at a pH of 6.5 the dissolved CO2 is approximately 70 mg/L, at a pH of 7.0 the dissolved CO2 is approximately 20 mg/L and at a pH of 8.0 the dissolved CO2 is approximately 3.0 mg/L. Please take note that this is for an alkalinity of 100 mg CaCO3/L. The same graph at a different alkalinity would have a similar shape but different values of CO2 at increasing pHs. GAS TRANSFER • Air is contacted with water and dissolved gases approach equilibrium with the atmospheric partial pressures air CO2 O2 water air air N2 Recirculating Aquaculture Systems Short Course To shift gears a little lets move on to gas transfer. As air is contacted with water the dissolved gases approach equilibrium with atmospheric partial pressures. In this figure we’re trying to show that in a typical aquaculture water with low dissolved oxygen and high dissolved carbon dioxide and nitrogen that as water is exposed to atmospheric air the tendency to approach equilibrium will transfer oxygen in and carbon dioxide and nitrogen out of the water. GAS TRANSFER • Driving force for CO2 transfer out of water is the concentration gradient: DF = Bulk _ Saturation Concentration Concentration Recirculating Aquaculture Systems Short Course With this concept in mind, the driving force for CO2 transfer out of water is the concentration gradient between the bulk dissolved CO2 concentration and the saturation dissolved CO2 concentration. Whenever possible you want to maximize this driving force and this can be accomplished by manipulating the saturation concentration with gas phase partial pressures. In the case of CO2 you want to minimize the gas phase partial pressure for CO2 removal. GAS TRANSFER • Dissolved Gas Solubility at 15oC: Mole Saturation Mole Saturation Fraction (mg/L) Fraction (mg/L) CO2 1 1,993 0.00035 0.69 N2 1210.7816.4 O2 1480.2110.1 Ar 1 66 0.0093 0.62 Recirculating Aquaculture Systems Short Course In a review of dissolved gas solubility, you can see the saturation concentration of the following gases in water. First, under pure environments of each gas we have the saturation concentrations. Then, at standard atmospheric conditions we have the saturation concentrations. The important point here is that CO2 is much more soluble in water than nitrogen, oxygen, or argon. STRIPPING OPTIONS • Stripping Tower Influent water Water Distribution Effluent Air Water Breakup Influent Air Effluent water Recirculating Aquaculture Systems Short Course One of the most common ways to strip carbon dioxide out of the water is with a stripping tower. Here influent water from the culture tank with high CO2 enters at the top of a tower and is distributed for uniform loading. The tower internals may have water breakup of some sort like plastic packing. As the water passes through the tower air is blown through the tower and it exits having picked up CO2 from the water. STRIPPING OPTIONS • Stripping Tower Design Parameters: Low Range High Range Water Drip Plate Spray Nozzles Distribution Hydraulic 2 2 10 kg/m s 30 kg/m s Loading Water Splash Random Breakup Screens Packing Tower Height 0.5 m 2 m Volumetric G:L 1 20 Recirculating Aquaculture Systems Short Course Some of the basic parameters important in designing stripping towers are water distribution, hydraulic loading, water breakup, tower or packing height, and volumetric gas to liquid flowrate ratio.
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