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Kalina cycle

The Kalina cycle is a thermodynamic power generation cycle that employs a binary working fluid consisting of ammonia and water to convert low- to medium-temperature heat sources (typically below 400°C) into electricity, achieving thermal efficiencies 15–50% higher than conventional steam Rankine cycles through better thermal matching via variable boiling and condensation temperatures during phase changes.^[1]^[2] Invented by Russian engineer Aleksandr I. Kalina in the mid-1980s, the cycle was developed as an alternative to single-component fluid cycles like the Rankine or organic Rankine cycle (ORC), particularly for waste heat recovery where traditional systems suffer from low efficiency due to mismatched temperature profiles.^[2]^[3] In operation, the ammonia-water mixture—often around 70% ammonia and 30% water—is heated in a boiler, where ammonia vaporizes preferentially owing to its lower boiling point (approximately -33°C compared to water's 100°C at standard pressure), producing a high-concentration ammonia vapor that drives a high-pressure turbine for power generation.^[4] The remaining water-rich liquid is separated via a rectifier and throttle valve, then recombined after a low-pressure turbine stage to facilitate recuperative preheating, before condensation in a cooler and repressurization by a pump to close the loop; this process enables a gliding temperature change that closely follows the heat source's profile, minimizing exergy losses.^[4]^[1] The cycle's advantages include reduced fuel consumption leading to 15–20% lower emissions of NOx, SO2, and particulates compared to Rankine systems, as well as lower capital costs of $1,100–$1,500 per kW for installations under 10 MW, making it suitable for decentralized power production.^[2]^[1] It excels in recovering waste heat from industrial processes like steelworks, cement kilns, and gas turbine exhausts, as well as in geothermal and solar thermal applications, with demonstrated efficiencies up to 25% for heat sources around 100–200°C where ORC systems might achieve only 10–15%.^[1]^[4] Key commercial deployments highlight its viability, including a 4.5 MW waste-to-energy plant in Fukuoka, Japan, operational since 1999, a 2 MW geothermal facility in Húsavík, Iceland, since 2000, and a 3.5 MW unit at the Kashima steelworks in Japan since 1999, collectively proving its reliability and scalability for global energy efficiency improvements.^[2]^[1]^[5]

Overview

Definition and Principles

The Kalina cycle is a thermodynamic cycle designed for converting low- to medium-temperature thermal energy into mechanical power, utilizing a binary working fluid mixture such as ammonia-water.^[6] This cycle operates by leveraging the properties of a zeotropic mixture, where the working fluid exhibits a composition-dependent boiling and condensation behavior over a range of temperatures rather than at a single point.^[7] The core principle of the Kalina cycle relies on the zeotropic mixture's ability to achieve better thermal matching with variable-temperature heat sources and sinks, thereby minimizing exergy losses during heat transfer processes.^[8] In contrast to single-component fluids in traditional cycles, the ammonia-water mixture allows for a temperature glide during evaporation and condensation, which reduces irreversibilities and enhances overall cycle efficiency.^[9] This variable boiling point characteristic enables more effective utilization of heat from sources like waste heat or geothermal fluids in the 100–200°C range. Operationally, the cycle involves pressurizing the mixture, heating it to produce vapor-rich phases for expansion in a turbine to generate power, followed by separation, condensation, and recombination to recycle the fluid.^[7] For low-temperature heat sources (100–200°C), the Kalina cycle typically achieves thermal efficiencies of 15–20%, representing an improvement of 10–50% over conventional Rankine cycles in comparable applications due to its superior heat recovery.^[10]^[8]^[11]

Key Advantages

The Kalina cycle offers significant efficiency improvements over the conventional Rankine cycle, particularly for low-temperature heat sources below 200°C, where it can achieve 10–50% higher thermal efficiency.^[8] This gain stems from the zeotropic properties of the ammonia-water mixture, which enable a closer temperature match between the working fluid and the heat source in the evaporator, minimizing exergy losses due to reduced temperature differences in heat exchangers.^[12] As a result, the cycle extracts more usable energy from low-grade waste heat, such as industrial exhaust or geothermal fluids, compared to steam-based systems that suffer from larger pinch points and irreversibilities. A key advantage is the cycle's operational flexibility, achieved through adjustable concentrations of the ammonia-water working fluid, allowing adaptation to fluctuating heat source temperatures without requiring major system redesigns.^[13] By varying the mixture composition—typically between 50% and 90% ammonia—the boiling and condensation processes can be tuned to match variable inlet conditions, such as seasonal changes in geothermal output or intermittent industrial waste heat, enhancing overall system responsiveness and utilization rates. The Kalina cycle also provides reduced complexity relative to gas-steam combined cycles while approaching similar efficiency levels, with reported net efficiencies up to 50% in optimized configurations for waste heat recovery.^[14] Unlike multi-stage combined setups that demand separate gas and steam turbines, the Kalina cycle integrates power generation in a single loop using a binary fluid, simplifying installation and maintenance for low- to medium-grade heat applications. Environmentally, the cycle contributes to lower greenhouse gas emissions per kilowatt-hour generated in waste heat scenarios by maximizing energy recovery from existing thermal streams, thereby reducing the need for additional fossil fuel-based power.^[15] The ammonia-water mixture is non-ozone-depleting and has a low global warming potential, avoiding the environmental drawbacks of synthetic refrigerants used in some alternative cycles.^[16] Economically, the Kalina cycle features lower capital costs for low-grade heat recovery systems, primarily due to smaller heat exchanger sizes enabled by the efficient temperature gliding of the working fluid.^[17] In industrial settings, such as cement or steel plants, payback periods can range from 3 to 5 years in optimized configurations, driven by higher power output and reduced operational expenses compared to organic Rankine cycles.^[18]

Thermodynamic Principles

Cycle Processes

The Kalina cycle is a closed-loop thermodynamic process that utilizes an ammonia-water mixture as the working fluid to convert low-grade heat into mechanical power, with key steps involving heat addition, expansion, phase separation, and recombination. The cycle's efficiency stems from the zeotropic nature of the mixture, which allows for a temperature glide during boiling and condensation, better matching the heat source and sink profiles and reducing exergy destruction. A rectifier is often incorporated to control the composition of the vapor phase by distilling the mixture prior to expansion, ensuring optimal ammonia enrichment in the vapor stream. The cycle begins with heat addition in the evaporator, where the high-pressure liquid mixture is heated and undergoes boiling over a temperature range (process 4-1 in typical numbering), transitioning from subcooled liquid to a two-phase mixture with the ammonia component vaporizing preferentially due to its higher volatility. This nonlinear boiling curve on the temperature-entropy (T-s) diagram reflects the zeotropic behavior, where the bubble point and dew point temperatures differ, enabling progressive heat absorption that minimizes irreversibilities compared to isothermal phase changes in pure fluid cycles. The resulting two-phase mixture then enters a separator, where the ammonia-rich vapor is isolated from the water-rich liquid. The ammonia-rich vapor from the separator undergoes isentropic expansion in the turbine (process 1-2), converting thermal energy into mechanical work while dropping to lower pressure; during this expansion, partial condensation may occur as the mixture enters the wet region, with the exiting stream being a vapor-liquid mixture at lower temperature and pressure. The separated water-rich liquid is throttled isenthalpically to the low pressure (process 3-4), maintaining its temperature nearly constant while reducing pressure, before it is directed to the absorber for recombination. The turbine exhaust mixture is cooled in a condenser, rejecting heat to the environment and fully condensing the ammonia-rich portion. In the absorber, the throttled water-rich liquid absorbs the condensed ammonia-rich stream from the condenser, recombining into a uniform mixture at intermediate concentration, which is then pumped back to high pressure for preheating in a recuperator before returning to the evaporator to close the loop. On the T-s diagram, the condensation process exhibits a glide similar to boiling but in reverse, with the nonlinear curves for both phases ensuring closer temperature matching to the cooling medium, further minimizing exergy losses; overall, the diagram illustrates a rounded cycle shape with reduced area under the curve for heat rejection relative to traditional Rankine cycles using pure fluids.

Working Fluid Characteristics

The primary working fluid employed in the Kalina cycle is an ammonia-water binary mixture, typically comprising 50-80% ammonia by mass fraction. This composition is selected for its advantageous thermophysical properties, including a high latent heat of vaporization and a pronounced temperature glide during evaporation and condensation, which enable superior thermal matching with variable-temperature heat sources compared to single-component fluids like water or pure ammonia.^[9]^[19] The mixture displays zeotropic behavior, characterized by non-isothermal phase changes where the bubble point and dew point differ, resulting in a temperature glide of up to several tens of degrees Celsius depending on pressure and concentration. Specifically, the saturation temperature decreases with increasing ammonia concentration at a given pressure, allowing the mixture to absorb heat more gradually and closely follow the profile of the heat source. This zeotropic nature also supports fractional distillation in the cycle's phase separator, where the vapor phase becomes enriched in ammonia (often exceeding 90% mass fraction) while the liquid remains depleted, facilitating efficient separation without additional energy input.^[9]^[19] Key thermophysical attributes of the ammonia-water mixture include an effective specific heat capacity that exceeds that of pure components in the relevant operating ranges, aiding in sensible heat transfer during preheating and desuperheating stages. The critical point varies with ammonia mass fraction, spanning from approximately 132°C and 11.3 MPa for pure ammonia to 374°C and 22.1 MPa for pure water, which permits subcritical operation across low- to medium-temperature applications (typically below 200°C) without entering the supercritical regime.^[9]^[20] While the ammonia-water mixture remains the standard due to its commercial availability and manageable handling in closed systems, alternative working fluids such as hydrocarbon zeotropic blends (e.g., propane-isobutane) or other binary pairs have been investigated for specific conditions, though they have not achieved widespread adoption owing to compatibility and performance trade-offs. Optimization of the ammonia concentration, commonly tuned to around 70% for many configurations, maximizes the cycle's approach to the Carnot efficiency limit, often reaching up to 70% relative efficiency by aligning the mixture's temperature glide with the heat source profile.^[21]

System Design

Main Components

The evaporator, often integrated with a recuperator in Kalina cycle systems, serves as the primary heat absorption component where the ammonia-water working fluid mixture is heated and partially boiled using a low-grade heat source, such as waste heat or geothermal fluids. This process occurs over a temperature range due to the zeotropic nature of the mixture, enabling better thermal matching with the heat source compared to single-component fluids. Design typically employs a counterflow heat exchanger configuration to maximize efficiency, with the recuperator section preheating the incoming lean mixture using residual heat from the turbine exhaust before it enters the main evaporation zone. The separator is a gravity-based or mechanical device positioned after the evaporator, functioning to divide the two-phase ammonia-water mixture into an ammonia-rich vapor stream, which proceeds to the turbine for work extraction, and a water-rich liquid stream, which is throttled and directed toward the absorber. This separation exploits the differing volatilities of ammonia and water, typically achieving a dryness fraction around 0.3 at the inlet, and is designed as a simple vertical vessel to minimize pressure losses while ensuring phase purity for downstream processes.^[22] The turbine, or expander, extracts mechanical work from the high-pressure, ammonia-enriched vapor exiting the separator by expanding it to lower pressure, driving a generator for power output. It is usually implemented as a single-stage unit suitable for the relatively low pressure drops in Kalina cycles, with inlet conditions often around 35-50 bar and 160°C, and designed for high isentropic efficiency to handle the wet vapor without excessive erosion. The condenser and absorber work in tandem at the cycle's low-temperature, low-pressure end to recombine the vapor and liquid phases of the working fluid. The absorber mixes the turbine exhaust vapor with the throttled water-rich liquid, facilitating ammonia absorption into the aqueous solution through cooling with an external medium like cooling water, while the condenser handles any residual vapor condensation; this combined unit often includes provisions for a desorber to strip trace ammonia from the lean solution, ensuring complete phase recombination and minimizing losses. Designs emphasize adiabatic mixing in the absorber to control temperature rise, with heat rejection via shell-and-tube exchangers.^[22] The pump, or compressor in some variants, recirculates the recombined lean ammonia-water mixture from the absorber back to the evaporator by increasing its pressure from the condenser outlet (typically 1-4 bar) to the high-side operating pressure (e.g., 35-50 bar). Due to the predominantly liquid state of the fluid, it requires relatively low power input and is designed with high isentropic efficiency, often as a centrifugal pump to handle the solution's properties without cavitation. Auxiliary components enhance overall efficiency, including the rectifier column, which purifies the ammonia-rich vapor post-separator or evaporator by fractional distillation to remove residual water, producing a higher-concentration vapor for the turbine without additional external heat; it is typically a packed or tray column operating on the sensible heat of the incoming mixture. The solution heat exchanger recovers internal heat between the strong (ammonia-rich) solution leaving the absorber and the weak (water-rich) solution returning from the separator, preheating the former to reduce evaporator duty; this is usually a counterflow plate or shell-and-tube exchanger integrated into the cycle piping.^[22]

Typical Configurations

The basic single-effect configuration of the Kalina cycle employs a closed loop comprising an evaporator, turbine, separator, condenser, and pump, where the ammonia-water mixture is heated in the evaporator, separated into vapor and liquid streams, expanded through the turbine for power generation, condensed, and pumped back to the evaporator.^[23] This layout is particularly suitable for small-scale waste heat recovery applications, such as those ranging from 50 kW to 5 MW, including industrial processes with moderate temperature sources.^[24] A common enhancement is the recuperated design, which incorporates an internal heat exchanger—often positioned between the turbine exhaust and the incoming mixture—to recover heat from the hot process stream to the cold return stream, thereby improving overall system performance by approximately 5-10%.^[25] This configuration maintains the core loop of the basic setup while adding the recuperator to minimize exergy losses, making it ideal for applications where heat source temperatures are between 100°C and 300°C, such as diesel engine exhaust.^[25] Multi-stage variants extend the basic design by incorporating series evaporators or multiple separators and mixers, allowing the cycle to accommodate broader temperature ranges in the heat source by stepwise evaporation and expansion.^[24] These setups, such as the KC12 configuration with dual recuperators and condensers, are commonly applied in geothermal power generation, where variable fluid temperatures require phased heat absorption to optimize matching with the source profile.^[25] In bottoming cycle setups, the Kalina cycle is integrated downstream of an existing Rankine cycle power plant to utilize low-grade exhaust heat, forming a combined system where the Kalina evaporator captures residual thermal energy from the Rankine condenser or stack gases.^[26] The flow arrangement typically includes 4-6 major loops: the primary Rankine steam loop (boiler-turbine-condenser-pump), the Kalina working fluid loop (evaporator-separator-turbine-condenser-pump), an absorption/mixing path for the ammonia-water blend, and interconnecting heat transfer conduits between the cycles, enabling enhanced overall plant output without major modifications to the host system.^[24] Scale adaptations of these configurations allow the Kalina cycle to fit diverse deployment needs; micro-scale systems under 100 kW, often based on the basic or recuperated layouts, support distributed generation in remote or small industrial settings like hot spring utilization.^[24] In contrast, utility-scale implementations exceeding 10 MW incorporate multi-stage or bottoming designs with multiple turbines in parallel or series to handle larger heat inputs, such as those from combined-cycle gas plants.^[27]

Performance and Efficiency

Theoretical Analysis

The thermal efficiency of the Kalina cycle is defined as \eta = \frac{W_{\text{net}}}{Q_{\text{in}}} = 1 - \frac{Q_{\text{out}}}{Q_{\text{in}}}, where W_{\text{net}} represents the net work output, calculated as the turbine work minus the pump work, and Q_{\text{in}} and Q_{\text{out}} are the heat input and rejection, respectively. This formulation derives directly from the first law of thermodynamics applied to the closed cycle, assuming steady-state conditions and negligible kinetic and potential energy changes.^[28]^[8] Exergy efficiency provides a second-law perspective, expressed as \eta_{\text{ex}} = 1 - \frac{I}{E_{\text{in}}}, where I denotes the total exergy destruction across cycle components and E_{\text{in}} is the exergy input from the heat source. This metric underscores the Kalina cycle's advantage in minimizing irreversibilities through better temperature matching between the working fluid and the heat source, resulting in lower exergy losses compared to single-component cycles.^[29]^[30] The working fluid, an ammonia-water mixture, exhibits non-ideal behavior characterized by bubble point temperature T_b = f(x_{\text{NH}_3}) and dew point temperature T_d = f(x_{\text{NH}_3}), where x_{\text{NH}_3} is the ammonia mass fraction. The temperature glide \Delta T = T_d - T_b typically ranges from 20–50°C for optimal mixtures, enabling closer thermal matching during heat addition and rejection.^[19] For low-temperature heat sources, the Kalina cycle approximates 70–80% of the Carnot efficiency, outperforming the Rankine cycle's typical 50% attainment due to the mixture's variable boiling characteristics. Accurate simulation of the cycle necessitates iterative numerical methods to handle the non-ideal vapor-liquid equilibrium of the mixture, often employing the Peng-Robinson equation of state.^[31]^[30]

Practical Considerations

The ammonia-water working fluid in the Kalina cycle is highly corrosive, particularly due to its alkaline nature (pH approximately 12.3 at ambient conditions), necessitating the use of corrosion-resistant materials such as stainless steels (e.g., 304, 316) or duplex alloys like Nitronic 60 to mitigate stress corrosion cracking and erosion-corrosion in components like turbines and heat exchangers.^[32]^[33] Impurities such as dissolved oxygen or carbon dioxide can exacerbate cracking in milder steels, while pH control through regular fluid monitoring and adjustment is essential to maintain system integrity and prevent material degradation.^[32] Safety concerns arise primarily from ammonia's toxicity, classified as a high-risk substance by standards like those from the National Fire Protection Association, requiring enclosed systems, advanced leak detection (e.g., via its pungent odor or fixed gas detectors), and strict pressure management to avoid hazards like autoignition at elevated temperatures above 651°C.^[34]^[14] Maintenance challenges include fouling in the separator due to impurities in the working fluid, which can reduce separation efficiency, alongside the need for periodic analysis of the ammonia-water mixture concentration to ensure optimal performance and prevent shifts that degrade cycle efficiency.^[33]^[35] The Kalina cycle is most scalable in the 100 kW to 50 MW power range, where its complexity is manageable for applications like geothermal or waste heat recovery, but larger installations often incorporate hybrids with other cycles (e.g., ORC) to address escalating design and operational intricacies.^[36]^[37]^[38] Economically, the Kalina cycle offers a levelized cost of energy (LCOE) approximately 5-10% lower than organic Rankine cycle (ORC) systems in geothermal contexts (e.g., 0.18 €/kWh vs. 0.22 €/kWh), driven by superior efficiency at low temperatures, though higher upfront costs stem from custom fluid handling and specialized components.^[39] Environmentally, the closed-loop design minimizes water consumption compared to open steam cycles, using negligible makeup water for the ammonia-water mixture, and lends itself to integration with CO2 capture processes by recovering waste heat to drive absorption or liquefaction units, potentially reducing emissions by 15-23%.^[33]^[40]

History and Development

Invention and Early Work

The Kalina cycle was invented by Aleksandr I. Kalina, a Russian engineer who emigrated to the United States in 1978 after holding a senior position in the Soviet Union.^[41] Kalina, born in 1933 near Odesa, Ukraine (then part of the USSR), drew on his expertise in thermodynamics to develop the cycle while working independently and later founding Exergy, Inc., to advance its commercialization.^[42]^[43] His work built on earlier binary cycle concepts from the 1970s, which aimed to enhance power generation from low-enthalpy geothermal and waste heat sources using multi-component fluids, but sought to address their limitations in efficiency and temperature matching.^[44] The core concept emerged in the late 1970s, with Kalina proposing a thermodynamic power cycle that utilized an ammonia-water mixture as the working fluid to improve heat recovery from low-temperature sources below 200°C, where traditional steam Rankine cycles perform poorly.^[35] Inspired by the variable-temperature boiling characteristics of ammonia-water mixtures in absorption refrigeration systems, the cycle allows for better thermal matching between the working fluid and heat source, reducing irreversibilities during heat transfer.^[35] This motivation addressed the inefficiencies of conventional cycles in recovering waste heat, potentially increasing overall plant efficiency by optimizing the exergy utilization of low-grade thermal energy.^[19] Kalina filed the foundational patent in 1980, which was granted as US Patent 4,346,561 in 1982, describing a system for energy generation using a multi-component working fluid with regenerative preheating. In the early 1980s, initial research focused on modeling the phase behavior and thermodynamic properties of ammonia-water mixtures for power applications, involving theoretical analyses published in engineering journals.^[35] Collaborations with academic institutions, such as those contributing to exergy-based studies, helped validate the cycle's potential through simulations of mixture compositions and heat exchanger designs.^[19] By the mid-1980s, lab-scale prototypes and bench tests confirmed the cycle's advantages, demonstrating thermal efficiency improvements of 10-20% over equivalent Rankine cycles for low-temperature heat recovery, primarily due to reduced exergy losses in the boiler and condenser.^[19] These early experiments, often using simplified configurations like the Kalina Cycle System 11 (KCS-11), highlighted gains of around 15% in second-law efficiency for sources around 100-150°C, establishing a foundation for further development without venturing into full-scale implementation.^[2]

Key Milestones

A significant early demonstration occurred in 1992 at the U.S. Department of Energy's Energy Technology Engineering Center in Canoga Park, California, where a ~3 MW prototype plant validated the cycle using nuclear waste heat, paving the way for commercial applications.^[45] The first commercial implementation of the Kalina cycle occurred in 1998 at the Kashima Steel Works of Sumitomo Metal Industries in Japan, where a 3.5 MW waste heat recovery plant was commissioned, marking the transition from experimental to operational use.^[2]^[46] This facility utilized low-grade waste heat from steel production processes, demonstrating the cycle's viability for industrial applications and achieving reliable power generation over subsequent years.^[2] Geothermal adoption advanced significantly with the 2000 commissioning of a 2 MW electric plant in Húsavík, Iceland, by Orkuveita Húsavíkur, which harnessed low-temperature brine at around 121°C to supply over 80% of the town's electricity needs with minimal environmental impact through full fluid reinjection.^[47] By 2010, the system had been expanded to a 17 MW thermal capacity, incorporating additional modules to enhance output while maintaining high efficiency in variable geothermal conditions.^[48] In Europe, a notable project commissioned in 2009 at Unterhaching, Germany, featured a 3.4 MW Kalina cycle plant integrated with geothermal resources for combined heat and power generation, operational until its 2017 shutdown due to gradual resource depletion in the aquifer.^[49] This installation highlighted the cycle's adaptability to moderate-temperature geothermal sources but also underscored challenges in long-term resource sustainability.^[50] The 2000s saw the introduction of second-generation Kalina cycle systems by Kalex LLC, founded by Alexander Kalina, focusing on enhanced low-temperature efficiency through optimized working fluid mixtures and process configurations, supported by key patents filed between 2004 and 2010.^[51] For instance, U.S. Patent 6,820,421 (granted 2004) detailed a low-temperature geothermal system improving energy conversion from sources below 150°C, while subsequent filings like U.S. Patent 6,923,000 (2005) addressed dual-pressure operations for broader applicability.^[52] These innovations achieved up to 20-30% higher efficiency compared to first-generation designs in low-grade heat scenarios.^[53] In the 2020s, advancements continued with hybrid integrations of Kalina cycles with solar thermal systems and modifications for improved efficiency in waste heat recovery, as detailed in thermodynamic studies and literature reviews published through 2025.^[54]^[55] Market analyses as of 2025 project compound annual growth rates of 8-10% for Kalina-based waste heat and geothermal systems through 2033, driven by renewable energy demands.^[55] The lapse of first-generation Kalina cycle patents around 2015, including several original filings from the 1990s, facilitated wider licensing and independent implementations by reducing barriers to technology access.^[56]

Applications

Waste Heat Recovery

The Kalina cycle is particularly suited for recovering low- to medium-grade waste heat from industrial processes, with optimal source temperatures ranging from 80°C to 250°C, including exhaust streams from steel mills, oil refineries, and cement plants.^[1]^[57] This application leverages the ammonia-water working fluid's variable boiling point to achieve superior thermal matching compared to single-component cycles, enabling the conversion of 10-20% of the available waste heat into electrical power.^[15] In such systems, the cycle typically operates as a bottoming process, either recovering heat from gas turbine exhaust or via direct flue gas exchangers, with reported thermal efficiencies reaching up to 18% for a 150°C source temperature.^[58] A notable example is the 4 MW installation at Fuji Oil's Tokyo Bay Refinery in Japan, commissioned in 2005, which utilizes waste heat from refinery operations at approximately 116°C to generate power and offset over 60 million kWh of grid electricity annually.^[59]^[57] Similar implementations, such as the 3.5 MW system at a Japanese steelworks in 1999 recovering heat from 98°C cooling water, demonstrate reductions in host process fuel consumption by 5-10% through enhanced overall energy utilization.^[1] These cases highlight the cycle's ability to integrate seamlessly into existing industrial infrastructure, producing reliable baseload power while improving site-wide efficiency. Optimization strategies for the Kalina cycle in waste heat applications include adjusting the ammonia-water mixture concentration to accommodate fluctuating heat loads, which minimizes irreversibilities and maintains performance under variable conditions.^[57] Hybrid configurations combining the Kalina cycle with organic Rankine cycles (ORC) have also been explored to broaden recovery across temperature gradients, enhancing exergy efficiency to around 68% in low-temperature steel industry streams.^[15] Benefits include short payback periods of 2-4 years due to low operational costs and electricity sales, alongside emission reductions of 1-2 tons of CO2 per MWh generated by displacing fossil fuel-based power.^[60] However, challenges arise from heat source variability, often necessitating buffer storage systems to stabilize input temperatures and ensure consistent output.^[1]

Geothermal and Renewable Energy

The Kalina cycle is well-suited for geothermal power generation from low-enthalpy resources, typically in the 60–150°C range, where it functions as a binary cycle alternative to flash steam plants by employing an ammonia-water zeotropic mixture to more closely match the temperature profile of the heat source. This configuration allows efficient extraction of energy from geothermal brines that are too cool for direct steam production, with the cycle's variable boiling point enhancing heat recovery compared to single-phase working fluids. In practice, the cycle has demonstrated superior performance over organic Rankine cycles (ORC) in handling low-grade geothermal fluids, particularly by better managing non-condensable gases that can reduce efficiency in ORC systems.^[61]^[62]^[63] A prominent example is the 2 MW Húsavík geothermal power plant in Iceland, which utilizes brine at approximately 120–124°C to produce electricity while co-generating 20 MW of thermal power for district heating, achieving an overall utilization efficiency exceeding 80% of the available exergy. The plant's integration into the local geothermal district heating system highlights the cycle's ability to maximize resource value from moderate-temperature sources, with the ammonia-water mixture enabling operation at lower pressures and temperatures than traditional cycles.^[2]^[64]^[65] In solar thermal applications, the Kalina cycle pairs effectively with parabolic trough collectors delivering heat at around 200°C, converting it to dispatchable electricity with efficiencies of 12–15% when combined with thermal storage for continuous operation. This integration leverages the cycle's adaptability to variable heat inputs, outperforming steam Rankine cycles in economic terms for mid-temperature solar fields by reducing capital costs through optimized working fluid composition.^[39]^[66] The cycle also extends to other renewables, such as ocean thermal energy conversion (OTEC), where ammonia-water variants boost Carnot efficiency by up to 50% over pure-fluid closed cycles by minimizing irreversibilities in the evaporator and condenser. In biomass cogeneration, Kalina systems recover low-grade heat from combustion processes, enhancing overall plant efficiency in decentralized setups.^[67]^[68]^[69] Scalability is a key advantage, with modular Kalina units enabling deployment in remote geothermal sites and facilitating hybrid solar-geothermal configurations that provide 24/7 baseload power by compensating for solar intermittency, as explored in recent 2025 studies on multi-generation systems combining low-enthalpy geothermal with solar power.^[70]^[71] These hybrids improve system reliability and output in variable-resource environments, with ongoing research as of 2025 focusing on integrations for desalination and hydrogen production. Environmentally, Kalina cycle applications in renewables contribute to low-carbon energy production with minimal land footprint—often less than 1 km² per MW for geothermal installations—and enhanced resource utilization in water-scarce areas through reduced cooling water needs compared to evaporative systems. By integrating with renewables, the cycle supports greenhouse gas emission reductions and sustainable development in regions with abundant but underutilized thermal resources.^[72]^[73]

Commercialization

Licensing and Patents

The Kalina cycle's intellectual property framework originated with patents filed by Alexander I. Kalina in the early 1980s, including the foundational U.S. Patent No. 4,346,561 issued in 1982 for generating energy using a zeotropic mixture as the working fluid. Additional key patents, such as U.S. Patent No. 4,548,043 granted in 1985, covered methods for energy generation and thermodynamic processes integral to the cycle's design. These first-generation patents, primarily focused on ammonia-water mixtures and basic cycle configurations, generally expired in the early 2000s, approximately 20 years after their filing dates, allowing for broader public domain access to core concepts. A second generation of Kalina cycle technology emerged in the mid-2000s, developed by Kalina through Kalex LLC, which he co-founded. This iteration introduced optimizations like reduced structural losses and enhanced efficiency for low-temperature heat sources, with patents such as U.S. Patent No. 6,923,000 issued in 2005 for dual-pressure geothermal systems. These second-generation patents, assigned to Kalex LLC, remain active and are projected to hold validity through the 2030s, protecting advanced variants including cascade and multi-stage configurations.^[74] Ownership of first-generation rights transitioned to Wasabi Energy plc and its subsidiary Global Geothermal Ltd. in the late 2000s, which acquired global licensing control over remaining active patents and the Kalina Cycle trademark.^[75] Some rights were restructured or transferred during Wasabi Energy's financial challenges in the 2010s, including administration proceedings in 2013, leading to partnerships that distributed usage in specific sectors.^[76] Following Wasabi Energy's voluntary administration in 2013, licensing rights were restructured, with Kalina Power Limited acquiring control over key patents and trademarks by the late 2010s. As of 2025, Kalina Power Ltd. (ASX: KPO) continues to license the technology globally, focusing on waste heat and geothermal applications.^[77] Kalex LLC retains exclusive control over second-generation advancements, enabling independent commercialization of improved systems without overlapping claims on expired foundational patents.^[74] Licensing has been central to the technology's dissemination, with exclusive agreements facilitating integration into industrial applications. In the 2000s, Global Geothermal Ltd. entered a partnership with Siemens AG for turbine integration in geothermal projects, exemplified by the 2009 licensing for the Unterhaching plant in Germany, which combined Kalina cycles with Siemens equipment.^[78] For Asian markets, a 2009 exclusive license was granted to Shanghai Shenge New Energy Technology Co., Ltd. (SSNE) by Global Geothermal, covering waste heat recovery and energy efficiency applications in China through 2024, with royalties tied to installed capacity.^[75] In 2011, FLSmidth secured global exclusive rights from Wasabi Energy for Kalina cycle deployment in the cement and lime industries (excluding China), including a $2 million upfront fee and ongoing royalties to support waste heat recovery systems.^[79] Following the expiration of original patents, generic implementations of first-generation Kalina cycles have proliferated in academic and research settings, enabling open experimentation with basic ammonia-water systems without licensing fees. Commercial deployments, however, typically involve royalty-based models for patented variants, with rates ranging from $35,000 to $150,000 per megawatt of installed capacity annually, equating to approximately 2-5% of plant revenue depending on operational scale.^[76]^[80] By 2025, the Kalina cycle supports dozens of licensed projects worldwide, with a growing emphasis on emerging markets like China and Southeast Asia for waste heat and geothermal applications, driven by energy efficiency mandates and technology transfer agreements.^[78]

Notable Installations

One of the earliest commercial implementations of the Kalina cycle is the Kashima Steel Works plant in Japan, commissioned in 1999 by Sumitomo Metal Industries. This 3.45 MW facility recovers waste heat from a steel revolving furnace at approximately 98°C, marking the first fully commercial application of the technology and demonstrating its viability for industrial processes. The plant has operated continuously for over 20 years with minimal downtime, producing reliable electricity from low-grade heat sources that would otherwise be wasted.^[2] The Húsavík geothermal power plant in Iceland, operational since July 2001, represents a pioneering use of the Kalina cycle for renewable energy, with a design capacity of 2 MW electric output from a 121°C geothermal brine flow of 90 kg/s. The facility achieves a thermal efficiency of approximately 10%, utilizing about 17 MW of thermal input while enabling full reinjection of the geothermal fluid and integration with district heating. As of 2025, the plant remains operational, now functioning as a hybrid system that combines Kalina cycle power generation with additional low-temperature resource utilization for enhanced overall efficiency.^[48]^[81]^[82] In Germany, the Unterhaching geothermal plant, started in 2006, generated 3.4 MW of electricity from a 123°C brine at 150 kg/s, supported by a thermal capacity of up to 70 MW for combined heat and power applications. The system demonstrated a net efficiency of around 15%, outperforming traditional organic Rankine cycles in low-temperature conditions. Operations ceased in 2017 due to depletion of the geothermal brine resource, but the installation provided valuable data on long-term performance and scalability for urban geothermal projects.^[49]^[50]^[65] The Bruchsal pilot plant in Germany, commissioned in December 2009, is a smaller-scale demonstration with 580 kW electric output integrated into a district heating network using geothermal resources. Developed by EnBW and Siemens with Energent's Euler turbine technology, it validated the Kalina cycle's effectiveness for micro-scale applications, achieving stable operation and proving the feasibility of modular systems for localized heat recovery. As of 2021, the plant continued operations, including a pilot for lithium extraction from geothermal brine.^[83]^[84] A notable example of modularity is the 50 kW EcoGen unit installed at Matsunoyama Onsen hot spring in Niigata, Japan, in December 2011 by Wasabi Energy. This compact, packaged system harnesses low-temperature hot spring fluid below 100°C to provide remote power generation, highlighting the Kalina cycle's adaptability for off-grid and small-scale renewable installations with field-tested stability over initial operations.^[85]^[86] Recent developments include hybrid enhancements at existing sites, such as at Húsavík, further integrating the Kalina cycle with advanced resource management for sustained geothermal output.

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None
### Summary of Tokyo Bay Oil Refinery Kalina Cycle
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