CO2 Recovery: Improved Performance with a Newly Developed System

Ulrich Buchhauser1, Jadran Vrabec2, Martin Faulstich1, Roland Meyer-Pittroff3

1) 2)

Instititute of Resource and Energy Technology, TU Mnchen, Freising Institute of Thermodynamics and Thermal Process Engineering, University of Stuttgart 3) CPW Competence Pool Weihenstephan, TU Mnchen, Freising 10 ABSTRACT State of the art CO2 recovery systems gain up to 2 - 2.5 kg CO2/hl cooled wort (CW) out of about 4.2 kg CO2/hL CW released during fermentation. The system presented in this article enables breweries to recover up to 3.5 kg CO2/hl CW. To increase the amount of collected CO2 it was necessary to begin recovery earlier than like usual 24 h after fermentation start. The input purity of CO2 decreases thereby from 99.5 % to 95 %. Based on a theoretical approach on Equation of State (EOS) of the ternary mixture CO2 + O2 + N2 a recovery system was developed with a fluidizing temperature of the fermentation CO2 of 223 K to separate the additional amount of O2. To reach this cooling temperature a second cooling stage with CO2 as cooling agent was added to the existing cooling device of the brewery. The installed device reaches an output purity of the CO2 of 99.998 % with an O2 concentration of 5 mg/kg. KEYWORDS Carbon Dioxide, CO2, CO2 Recovery, Equation of State, Two staged cooling device

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Introduction
30 Carbon dioxide (CO2) is one of the most naturally occurring chemical compounds. The use of CO2 in beverage production is widespread. Its high purity, plus its origin from biological processes, along with its ease of use make CO2 very suitable for the use in the food industry. There it is used for example as an additive in the production of beer. Increased consumer awareness of product shelf life and product staling has resulted in increased use of CO2 for oxygen-free processing. For beer producers who want to assure beer stability and a one-year shelf-life, their production procedures will require the use of large amounts of CO2. CO2 recovery from fermenters in breweries has been widespread since the early 1970s. The basic CO2 recovery procedure has not changed much since these times. What has changed is how the separation of the permanent gases (oxygen and nitrogen) differs between the actual recovery systems. Current CO2 recovery systems are based on a well-known and published design (4, 9), shown in Figure 1. In this system CO2 is drawn off the storage tank and flows through a counter-flow water washer where water-soluble compounds are dissolved. Next, the compressors increase the pressure up to the water condensation level and separate any remaining water from the gas. The next step is to dry and purify the gas. Depending on the gas quality, the order of drier and purifier may vary. Most of the permanent gases, oxygen and nitrogen, are separated in the condenser following a purification step after which the condensed gas is stored. Inefficient separation of the permanent gases is the main drawback with this traditional CO2 recovery system.

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Dryer Washer Compressors Foam separator CO2 Gas storage

Figure 1. The standard method for CO2 recovery. 50 Only about 50 % of the released CO2 from fermentation can be recovered by means of this type system due to the difficulty of separating the initially high concentrations of Nitrogen and Oxygen. Therefore, CO2 recovery normally begins 24 hours after the start of fermentation to assure that the incoming fermentation gas has a minimum CO2 concentration of 99.5 Vol.-%. This is the reason why most of the newly installed recovery systems use a rectification column for separating the permanent gases. Herein the dried CO2 gas gets liquefied and afterwards cleaned CO2 is led in counter flow to boil out the permanent gases (Figure 2). The rectification enables users to recover about 60 % of the released CO2 (7, 10). 60

Condenser

Purifier

Blow off pipe Condenser Rectification coloumn

CO2 from dryer

Figure 2. CO2 rectification.

Storage tank

The paper details the results of research work relative to a new CO2 recovery system which enables recovering of up to 83 % of released CO2. Part I gives an overview about the thermodynamic principles on which the new system is based upon. The thermodynamic

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simulation was the background for the planning of the plant. The result of the planning is explained in Part II. After the plant was working properly, several studies were made relative to the impact of different plant components on the purity of the recovered CO2. These studies are shown in Part III.

Materials and Methods

All used methods were developed during the theoretical and practical work. The theoretical basics of the fluidizing developed by Vrabec (11) based on the Peng-Robinson EOS (see Part I). The recovery system based on these findings was developed in a co-operation between Krones AG, Neutraubling, DEU and the Chair for Energy and Environmental Technologies of the Food Industry, TU Mnchen, Freising, DEU. A prototype of the device was installed at Flensburger Brauerei Emil Petersen GmbH & Co. KG, Flensburg, DEU (see Part II). The analyses were made with a special GC/MS system developed by Hrtl (8) based upon systems of JAS, Joint Analytical Systems GmbH, Moers, DEU. The system is a coupling between an Agilent Technologies 6890N Gas Chromatograph (GC) and an Agilent Technologies 5973N Mass Selective Detector (MSD). In addition a Helium-Ionization-Detector (HID) produced by Valco Instruments Co. Inc., Houston, TX was integrated into the system (8).

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Discussion
Part I: Principles of the New System called Cold Condensing. 90 This system was developed cooperatively between the Chair of Energy and Environmental Technologies of the Food Industry at the Technische University of Munich at Weihenstephan, Krones AG and the Institute of Thermodynamics and Thermal Process Engineering of the University of Stuttgart (ITT, Stuttgart, DEU). The system is based on the fact that the solubility of the permanent gases decreases with the decreasing temperature of the condensed CO2. In the case of liquefying the CO2 at temperatures below 223 K and pressures between 0.7 and 2.0 MPa, the solubility decreases and the permanent gases volatilize from the liquid phase. For this process no experimental data about the ternary mixture of O2+N2+CO2 can be found in the literature. Data only exist about the three binary systems (i.e O2 + CO2, N2 + CO2 and O2 + N2) (1, 2, 5, 12). Figure 3 shows the concentration of oxygen and nitrogen in binary mixture with liquid CO2 at 232 K (12).

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Figure 3. Concentration of O2 and N2 in binary mixture with CO2 at 232 K (12). Therefore a new model was developed based on the Peng-Robinson EOS. This correlates the binary experimental data and describes the ternary data well, except at high pressures approaching the critical region. A recent molecular model from the ITT is verified by simulation against binary and ternary experimental data. On the basis of this model, the Henry constants of N2 and O2 in CO2 are calculated by molecular simulation. A Henry model is developed that can be used reliably in the very CO2-rich region (11). Figure 4 shows the maximum oxygen concentration after condensing depending on pressure and temperature. At 0.7 MPa and 223 K only 15 mg/kg of the oxygen remains by equation in the liquid phase. So its easily possible to purify the CO2 up to a concentration of maximum 5 mg/kg oxygen.
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110

60

Concentration of O2 in liquid CO2 [mg/kg] [mg/kg]

50 2 MPa 40 1.5 MPa 30 1 MPa 20 0.7 MPa 10

0 223 K 233 K 243 K

Temperature

Figure 4. Concentration of O2 in liquid CO2 depending on temperature and pressure (11). 120

Part II: Function of the New System Based on the results above, an optimized system for the purification of fermentation CO2 was developed. As in the rectification system, only the last step of the purification process was changed. The first parts (washer, compressor, dryer, cleaner and purifier) were kept from the basic system. It was only necessary to achieve the low condensing temperatures and to separate the different phases. The first installation was made in a German brewery to check the theoretical figures shown above. 130 The low temperatures could not be achieved by utilizing the brewerys central cooling plant, which works with NH3 and boiling temperatures between 263 and 269 K. To assure a good handling without needing too much additional energy, a two-stage cooling-cascade was planned. The original central cooling plant was utilized for the high temperature stage and a second cooling stage (low temperature stage) with a condensing temperature of 263 K was installed. With this system we could achieve condensing temperatures of the fermentation gas between 223 K and 233 K. The working agent in the second stage is CO2. Compared to NH3 it has a higher vapor pressure range (8 20 bar) at the prevalent temperatures and it is non-toxic. So the newly developed recovery system and a two-staged cooling stage, as shown in Figure 5, were installed in the brewery. A two-stage cooling stage has the advantage that it can be shut down during nonproduction periods to save energy.

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Buffer Dryer Washer

Blow Out Compressors Condenser Purifier Storage

Recovery System

Purification Tank Low Temperature Stage

High Temperature Stage

Condenser

Reservoir Compressor

Cooling Plant

Evaporator

Condenser Separator

Compressors

Figure 5. Components of the installed system. In the recovery systems condenser, the gaseous CO2 will be liquefied and slightly sub cooled. Afterwards the CO2 flows to the additional purification tank. This tank enables the separation of the phases. There are three heaters installed which heat up the fluid. This causes a boiling of the liquid phase and an escape of the permanent gases. The gaseous phase (enriched with O2 and N2) is blown out, and the liquid phase flows into the storage tank. So the purified CO2 reaches the quality of technical grade CO2 (3). Part III: Influences on the Purity of the Recovered CO2 The first part of the project was to install a plant, which produces CO2 with a purity of about 99.998 vol.%. The system was installed in a German brewery, which produces mainly one kind of beer with an original wort gravity of 12.8 % and a fermentability of about 85 %.

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During the first experiments it was possible to recover nearly 80% of the released CO2. The separation of the permanent gases in the purification tank worked so well, that the recovery process could be started 16 h after the start of fermentation. Even CO2 with a purity of about 93 vol.% was purified up to an oxygen concentration of 7 mg/kg. Table 1 compares the amounts of recovered CO2 of the different systems. Table 1. Specifications of different recovery systems. _____________________________________________________________________________ System Input Output Amount Purity (%) purity (%) _____________________________________________________________________________ Basic System 99.5 99.998 <2.5 kg/hL cooled wort* Split System 99.5 99.998 <2.5 kg/hL cooled wort* Rectification 95. 99.997 2.5 - 2.8 kg/hL cooled wort* Cold Condensing 95. 99.998 3.0-3.5 kg/hL cooled wort _____________________________________________________________________________ * Literature values After achieving these results, the influences of the different components on the purification processes were surveyed.

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180 Start of the Recovery Fermentation tanks are pre-filled with CO2. To decrease the losses of CO2 the atmosphere is not completely blown out of the tanks. Therefore the remaining CO2 is strongly polluted with oxygen and nitrogen. After a certain period it is pure enough to get recovered. Figure 6 shows the purity of the tanks CO2 throughout the fermentation process.

Figure 6: Purity of fermentation gas. (6)

Molar Fraction of CO2

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The earlier the recovery starts the more CO2 can be recovered. By means of the cold condensing system working at a condensing temperature of 221 K, it is possible to start the recovery after 16 hours. The impact of the time of recovery start on the purity of the liquefied CO2 is shown in Figure 7. Oxygen Concentration [mg/kg] 9 8 7 6 5 4 3 2 1 0 24 h 20 h 18 h Start of Recovery 16 h

Figure 7. Impact of the recovery start on the purity of CO2 at a condensing temperature of 221 K. The impact of the recovery start on the output purity of the CO2 is not very strong. However, the results show clearly that the new system purifies the CO2 even at a recovery start 16 hours after the beginning of the fermentation up to the demanded oxygen concentration 5 mg/kg. Many breweries in Germany and Europe use the so-called Coca-Cola-Standard which demands a maximum O2 concentration in purified CO2 of 30 mg/kg. As the condensing at 221 K needs a lot of energy, the impact of the recovery start was also tested at a condensing temperature of 231 K (Figure 8).
90 80 70 60 50 40 30 20 10 0 24 h 20 h 18 h 16 h Start of Recovery

200

Figure 8. Impact of the recovery start on the CO2 purity at a condensing temperature of 231 K.

Oxygen Concentration [mg/kg]

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The higher temperature increases the impact on the quality of the gas and the limit of 5 mg/kg can only be reached with starting 24 hours after the beginning of fermentation. With a condensing temperature of 231 K it is also possible to increase the boiling temperature of the central cooling plant to the normally used temperature of 269 K. Here the breweries must decide for themselves what their focus is on, energy or purity. Another result is that the recovery start determines the amount of CO2 that gets recovered. When the recovery starts 16 hours after the beginning of fermentation, up to 3.5 kg/he CW can be recovered (Figure 9).
3,6 3,4 Amount of CO2 [kg/hl] 3,2 3 2,8 2,6 2,4 2,2 2 24 h 20 h 18 h 16 h Recovery Start after Fermentation Begin

Figure 9. Amount of recovered CO2 depending on the recovery start time. 220 Condensing Temperature As the calculations showed, the condensing temperature is the main aspect of the new system. During the following experiments the condensing pressure was fixed to 1.0 MPa. These results are shown in Figure 10.

Recovery Start after 18 h Recovery Start after 20 h Recovery Start after 24 h Oxygen Concentration [mg/kg] 60 50 40 30 20 10 0 233 229 Fluidising Temperature [K] Figure 10: Impact of the Condensing Temperature on the CO2-Purity 230 The comparison of the theoretical data (Figure 4) with the results of these experiments (Figure 10) shows that the theoretical calculations were near to reality. An oxygen concentration of maximal 20 mg/kg was calculated for the equilibrium state while the experiments with the heaters of the purification tank result in concentrations of about 8 mg/kg. So, the thesis that a decreasing temperature improves the purification of the fermentation CO2 is proven. We have seen that with a condensing temperature of 225 K, the demanded O2 concentration of 5 mg/kg can be reached. Also, as seen below, the additional purification during the experiments is the result of the installed purification tank. Heating of the Purification Tank The second innovation is the installation of a purification tank. The tank is positioned directly behind the condenser to minimize the radiation losses. In this tank, the temperature is raised to boiling temperature and the permanent gases are boiled out. Three heaters are installed in the tank (Figure 11). 225

240

Blow Out Fluidized CO 2

Purified CO 2

Figure 11. Function of the purification tank.

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Depending on the heating power of the implemented heaters, an improvement of up to 85 mass.-% of the O2 separation can be realized (Figure 12). The heating-system has three stages: 1. Without heating 2. Process-oriented heating 3. Full-load. Process-oriented heating means that one heating section is running permanently, one heating section is switched on together with the recovery plant and the third one starts when both compressors of the recovery plant are running.
24 h Oxygen Concentration [mg/kg] 120 100 80 60 40 20 0 Without heating Process-oriented heating Full load heating 20 h 18 h 16h

260 Figure 12. Impact of the purification tank heating.

The effect of the heaters is obvious. It is impossible to gain CO2 with sufficient quality as long as the heaters are shut off. On the other hand the full-load heating does not significantly improve the purity. Too much energy is wasted without adequate success. Only slight improvements can be reached. Intensity of the Blow-Out from the Purification Tank The last experiment investigated the effect of the intensity of the blow-out from the purification tank. The Blow-Out system has three operating modes like the heating system: 1. No Blow-Out 2. Process oriented Blow-Out 3. Full Blow-Out Process-oriented means, that one of three end pipes of the blow-out line opens when the low temperature cooling system starts. The second opens with the second cooling compressor starting and the third opens when the recovery system pressure exceeds 1.6 MPa. Full blow-out means that all three end pipes are open. 280 Figure 13 shows that between the process-oriented and the full blow-out, no significant effect on the purification of the CO2 exists, but the full blow-out leads to an increased CO2 loss.

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120 Oxygen Concentration [mg/kg] 100 80 60 40 20 0 No Blow-Out Process oriented Blow-Out Full Blow-Out 20h 18h

Figure 13. Impact of the purification tank blow-out.

Conclusion
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The new developed cool condensing system for CO2 recovery produces a higher amount of CO2 with the same quality as the state-of-the-art system with rectification column. The production costs per ton of collected CO2 were calculated throughout the experiments and compared to the production costs with a rectification column. Depending on the focus of the brewery it is possible to run the system different ways to reach the needed quality at acceptable costs.

300 REFERENCES 1 Arai, Y., Kaminishi G.-I., Saito, S. (1971). The Experimental Determination of the p-V-Tx-Relations for the Carbon dioxide-Nitrogen and the Carbon dioxide-Methane Systems. J. Chem. Eng. Japan 4: 113-122. Barnett F. Dodge, A. (1927). An Investigation of the Coexisting Liquid and Vapor Phases of Solutions of Oxygen and Nitrogen. J. Am. Chem. Soc.: 591 - 610. Buchhauser, U., Meyer-Pittroff, R. (2007). Novel Procedure for the Recovery of CO2 Emerging at the Alcoholic Fermentation. In: Proc. Congr. Eur. Brew. Conv., Venice 31, EBC electr. publ. Collins, T., Bandy, J. (2000). CO2 Generation and Harvesting. Tech. Quart. Master Brew. Assoc. Am. 37(2): 255-260. Fredeslund, A. (1970). Gas-Liquid Equilibrium of the Oxygen-Carbon Dioxide System. J. Chem. Eng. Data 15: 17-22. Groer, A. (2006). Thermodynamische Modellierung der Rckgewinnung von GrungsCO2 und Kostenreduzierung des Prozesses durch Einsatz des Kltemittels CO2. Lehrstuhl fr Energie- und Umwelttechnik der Lebensmittelindustrie, TU Mnchen, Freising. Harder, S. D. (1997). An Update on CO2 Recovery Systems and Quality in the Brewing Industry. Tech. Quart. Master Brew. Assoc. Am. 34(4): 235-239. Hrtl, M. (2007). Entwicklung und Inbetriebnahme von Spurenanalytik zur Qualittsbestimmung von Grungskohlendioxid im Hinblick auf die Optimierung bestehender Rckgewinnungsanlagen. Lehrstuhl fr Energie- und Umwelttechnik der Lebensmittelindustrie, TU Mnchen, Freising. Martin, E. G. (1970). A Carbon Dioxide System Design. Tech. Quart. Master Brew. Assoc. Am. 7(1): 21-28. Selz, P. (1991). The Removal of Oxygen from Liquid CO2. Tech. Quart. Master Brew. Assoc. Am. 28: 38-40.

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Vrabec, J. (2004). Thermodynamic Models for Vapor-Liquid Equilibria of the ternary mixture Nitrogen+Oxygen+Carbon Dioxide from -55 to -20 C. In: Einsatz von CO2 als Kltemittel bei der CO2-Verflssigung : Abschlussbericht ber ein Entwicklungsprojekt. pp. 51 - 90. U. Buchhauser, ed. Deutsche Bundesstiftung Umwelt, Osnabrck. Zenner, G., Dana, L. (1963). Liquid-Vapor equilibrium compositions of Carbon DioxideOxygen-Nitrogen mixtures. Chemical Engineering Progress Symposium Series.

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