Decarbonising hydrogen and syngas production
Electrified steam methane reforming by eREACT™: Emissions-free syngas manufacturing
Peter Mølgaard Mortensen; Kim Aasberg-Petersen; Yassir Ghiyati, Topsoe A/S
Topsoe’s eREACT™ is the electrified evolution of the world’s most common syngas-production method, steam-methane reforming (SMR). Bridging existing syngas manufacturing with renewable electricity allows for an emissions free chemical plant, built on the existing principles of the syngas platform, allowing leverage of existing hydrocarbon infrastructure or integration with other carbon feedstocks such as biogenic carbon or captured CO2. While SMR typically generates needed heat through combustion of natural gas – which results in CO2 emissions – eREACT™ facilitates the same reaction without the associated environmental impact. The reaction heat for eREACT™ is generated directly by (renewable) electricity, thereby eliminating the flue gas altogether. With decreasing cost of renewable electricity, this technology empowers even existing industrial complexes to electrify syngas production in a cost-effective manner.
Recuperative reforming – A key element for blue syngas production
Jan-Jaap Riegman, Technip Energies; Stefan Gebert, Clariant; Ermanno Filippi, Casale
The Enhanced Annular Reforming Tube for Hydrogen (EARTH®) for hydrogen/ syngas production and the Technip Parallel Reformer (TPR®) are two technologies for Blue H2 that ultilise high-grade heat to minimise the energy input required for reforming. EARTH® technology is a novel recuperative reforming process. Recent successful installations and start-ups of EARTH applications in large European refineries highlight the benefits of the technology. The TPR® is a well referenced recuperative reformer where high grade heat is utilized to drive reforming reaction in parallel to main reforming section.
While traditional steam methane reforming technologies degrade high-grade process heat to generate high-pressure steam, recuperative reforming offers the possibility to utilize high-value heat to produce additional hydrogen/syngas, and/or to save energy (and operating cost) by reducing the firing duty of the reformer. The tradeoff between steam generation and energy savings may be easily optimized to meet the desired outcome.
The paper will explain the EARTH® and TPR® technology’s benefits for syngas production and will showcase some recent experiences of these technologies in hydrogen plants. Additionally, it will present a flow scheme based on an ammonia plant including the impact on the Secondary Reformer and the total energy balance. The paper will finally highlight how EARTH and TPR together with Casale’s proprietary ammonia technology can directly contribute to >30% CO2 emission reduction that can further be enhanced by synergistic design modifications in the rest of the plant leading to significantly lower emissions compared to conventional scheme using steam for driven machinery.
Low carbon hydrogen: A climate silver bullet
Elena Petriaeva; Bernhard Geis, BASF
BASF's OASE® white is a proven amine scrubbing technology for deep CO2 removal from syngas, achieving a targeted process gas CO2 capture rate of up to 99.97 mass%. For flue gas carbon capture, OASE® blue technology was developed specifically as an optimized post-combustion capture technology with low energy consumption, low solvent losses and an exceptionally flexible operating range. Combining the two technologies, OASE® blue for flue gas CO2 emissions capture and OASE® white for process gas CO2 emissions capture, the lowest CO2 footprint overall is possible. The paper also investigates potential process options to convert grey to blue hydrogen facilities, including discussion of several specific projects utilising CO2 capture.
Blue hydrogen production: Achieving minimum carbon footprint and minimum operating cost, comparing SMR and ATR
Menica Antonelli; Stefano Carenza; Giulio Galdieri; Stefania Taraschi; Alessandro Buonomini, KT – Kinetics Technology SpA
A blue hydrogen production unit enables the reduction of CO2 emissions by removing part of the produced carbon dioxide. The carbon dioxide is produced in the reactors, as by-product of the hydrogen production, and in the Steam Methane Reformer (SMR), as product of the combustion. The CO2 removal can be performed either in the pre-combustion section and in the post-combustion section of the plant. Reduction of the carbon footprint is achieved by both reducing the CO2 production and maximizing the CO2 capture.
The selection of the most optimized configuration for a blue hydrogen production unit is not uniquely identified and it depends on several parameters. This paper will review a case study of a blue hydrogen production unit to select the optimized plant configuration. A particular focus will be given on plant CO2 footprint target and on related OPEX, with the case study illustrating the sensitivity analysis when comparing two technical solutions. The case study refers to a blue hydrogen production unit with 120.000 Nm3/h capacity: one plant configuration is based on Primary Reformer (SMR) only and the other is based on Primary Reformer (SMR) followed by Secondary Reformer (ATR).
Reducing the carbon footprint of ammonia and methanol production
The best of low carbon hydrogen technologies for ammonia
Martin Gorny; Sophia Schmidt; Sayan Dasgupta, Air Liquide Engineering & Construction
This presentation will identify the process steps with the highest impact on CO2 intensity of ammonia, and different technology options for these will be discussed. Based on the discussed rationale, a comprehensive and optimized technology chain for low carbon ammonia production will be presented. The suitability of Air Liquide E&C’s oxygen-blown ATR, which, to date, has predominantly been used in methanol production will be presented. Due to its inherent advantages for carbon capture, availability of all CO2 at high pressure, its relevance for low carbon syngas production is increasing. The ATR for syngas production can be coupled with two CO2 capture technologies: CryocapTM H2, a referenced cryogenic CO2 separation technology, which is suitable whenever abundant electricity is available or high CO2 purity is required; Alternatively, RecticapTM, the RectisolTM tailored for CO2 capture only. This syngas preparation can then be coupled with any ammonia synthesis technology to deliver an energy and cost efficient low carbon ammonia product.
Blue NH3 with HISORP CC: An adsorptive CO2 removal process
Thomas Ried, Linde
Linde has developed a new CO2 removal process called HISORP CC, which is based on pressure swing adsorption (PSA) technology. CO2 is a strong adsorbing compound on most commercially available adsorbent materials and can effectively be separated from other compounds like H2, N2, CO or CH4. The PSA offers a simple and very robust process unit without the usage of chemicals. Unlike absorptive CO2 removal processes, like amine-based washing units, no steam is required for the adsorbent regeneration. As no extra steam production is required, no additional CO2 is emitted. CO2 purities between 90 and even above 99.9 Vol-% can be achieved, following the requirements of utilization.
According to the Linde Ammonia Concept, the syngas for the NH3 synthesis is generated by pure H2 and N2. The H2 can be produced by all different production technologies, such as steam reforming, partial oxidation (POX), by autothermal reforming (ATR), and also by electrolysis. The N2 is provided by an air separation unit (ASU). In order to produce blue NH3, CO2 from the fossil-based production process needs to be separated and sequestrated. If the ASU runs on green power, no extra CO2 removal related to N2 production is required. For all conventional H2 production methods except for electrolysis, CO2 is emitted by firing carbon containing fuels. Depending on the H2 production process set-up, carbon capture rates even above 95% are feasible applying HISORP CC. HISORP CC can be applied at three different positions in the H2 production process: In the syngas, after the CO shift; in the H2-PSA tail gas; or, in the flue gas
The presentation will focus on the general HISORP CC concept. Additionally, the pros and cons for the different positions of the CO2 removal in the H2 production route will be discussed. Moreover, typical carbon capture rates of the different HISORP CC options will be presented.
Reducing CO2 footprint and increasing ammonia production via injection of green hydrogen into existing ammonia plants
Frederick Kessler; Bernd Mielke; Klaus Noelker, thyssenkrupp Industrial Solutions AG
The possibilities to reduce the CO2 emission of existing ammonia plants are very limited if the plant already has a relatively good energy efficiency. One option is the replacement of a part of the natural gas feed by green hydrogen, that means, hydrogen coming from electrolysis of water, using electricity from renewable sources. Besides the effect of a specific reduction of CO2 emission of ammonia production, the additional hydrogen can also serve for a capacity increase.
Fertiglobe has implemented such capacity increase measures based primarily on the addition of Green Hydrogen to its three ammonia plants at its fertilizer production complex at EFC in Ain Sokhna, Egypt. The future overall goal of transforming the existing gray ammonia plants into truly hybrid (green / gray) ammonia plants by further capacity increase coupled with the reduction of natural gas usage will continue on the same path that was already started during the initial phases of the project.
This paper will describe the measures that were taken in order to achieve the initial introduction of the green Hydrogen into the ammonia plant, as well as measures that are still planned in order to further increase the capacities of the ammonia plants, while simultaneously reducing their carbon footprint. Challenges and lessons learned from the retrofit, particularly in respect to the change of flow rates, temperatures and compositions in the reformer area will be shared.
Barents blue ammonia project: A landmark towards sustainability
Massimiliano Sala; Andrea Zambianco; Bjørgulf Haukelidsæter Eidesen, Saipem
Horisont Energi has an ambitious plan to develop a large-scale blue ammonia complex in Finnmark, Norway exploiting the favorable combination of abundant feedstock gas, cold climate conditions which allow higher process efficiency, and proximity to offshore CO2 storage. Saipem’s consolidated background in the execution of ammonia projects worldwide is supporting Horisont Energi’s vision with project tailor made solutions.
This article describes the main Barents Blue Ammonia Project features such as 99% carbon capture rate target, high degree of modularization, winterization, infrastructure for ammonia and CO2 management and provision for future expansion.
How optimal integration of SOEC electrolysis and Topsoe ammonia technology can significantly impact plant economics
Christian Wix, Topsoe A/S
One of the inherent challenges of power to X plants, including green ammonia, running on renewable energy sources is managing significant load variations.
This paper will cover how the electrolysis section will handle load variations in the renewable energy input. It will also cover how to effectively operate the ammonia loop at various loads and with rapid changes in the load. These areas are both very important for the CAPEX and OPEX for a new green ammonia plant.
This paper will highlight some of the challenges in designing and operating a green ammonia plant optimally. It will also illustrate some of the solutions as to how to optimally integrate the ammonia plant and the SOEC electrolysis, and how to operate optimally with large load variations.
Blue ammonia for lower CO2 emissions
Klaus Noelker, thyssenkrupp Industrial Solutions AG
Reforming-based ammonia production has two places of CO2 emission: The CO2 removal from the process gas and (with a smaller quantity) the reformer flue gas. The major part of the CO2 comes sequestration-ready since the CO2 has to be removed from the process gas anyway. Instead of venting it to the atmosphere, the additional effort for CCS is just the compression for export. This unit can also be added to any existing ammonia plant, thus lowering its CO2 emission by about two thirds already.
However, further reduction is possible by also treating or lowering the flue gas from the primary reformer or – in case of an autothermal reformer (ATR) plant – from the fired heater. Several technologies, suitable for new plants and as a revamp, exist for such CO2 removal.
For an ATR plant, reduction of the CO2 emission by more than 90% can be achieved also without the costly installation of a CO2 recovery unit. Uhde presents a process which replaces this costly post-combustion method by a pre-combustion technology, which is usage of hydrogen-rich gas from the process as heater fuel.
Tangible solutions to face the challenge and implement a sustainable transition: Casale technologies for emission reduction in existing plants and newbuilds
Francesco Baratto, Casale SA
This paper will present the suite of Casale products for emission reduction via retrofit of existing plants. Solutions for both blue and green newbuilds will be explored. Tchnologies and solutions are described step by step, considering the different project context and the relevant impact on the economics. It will demonstrate how emission reduction is not necessarily an additional cost for plant owners; conversely, it can be turned into a profitable investment in the wider decarbonisation journey.
TrueBlue Methanol™ - A low carbon emission methanol production process
Dan Barnett, BD Energy Systems LLC
BD Energy Systems LLC introduces TrueBlue Methanol™, an innovative low carbon emission methanol production process that utilises proven techniques to achieve greater than 90% reduction in the emission of CO2 from the stack of the Steam Methane Reformer [SMR] furnace while producing methanol with an overall energy consumption that is competitive with even the newest operating SMR-based methanol plants.
The TrueBlue™ process can be implemented not only on grassroot and relocated methanol plants but as an upgrade to existing methanol plants for any natural gas fed process configuration.
This process delivers a product CO2 stream using an amine-based CO2 removal system placed upstream of the methanol synthesis reactor. Doing so reduces the consumption of hydrogen in the methanol synthesis process, resulting in greater hydrogen availability for SMR fuel. The use of a pressure-swing-adsorption [PSA] unit on the methanol synthesis loop purge stream recovers hydrogen from that stream for use as SMR fuel, and recompression of the carbon containing PSA tail
gas allows recycle of most of that tail gas to the SMR feed. This recycle results in more complete conversion of incoming feed to synthesis gas and effectively reduces SMR stack gas CO2 emissions to a very low level.
New developments in renewable energy technology
KBR Ammonia Cracking Technology: A roadmap from renewable energy source to green hydrogen supply where it is needed the most
Henrik Larsen; Elena Stylianou, KBR
Green hydrogen is earmarked as the renewable fuel of the future while green ammonia offers a flexible, high energy density solution for storage and distribution, utilizing existing and reliable infrastructure. The advent of ammonia cracking technology, dissociating green ammonia back into green hydrogen, completes the missing link in the roadmap to sustainability, enabling the production of green ammonia where the renewable energy is abundant with the ability to supply green hydrogen in locations with high demand but low availability of natural resources to produce it.
KBR has successfully developed a competitive ammonia cracking technology, high efficiency and able to meet stringent environmental requirements on carbon emissions, targeting moderate to very large-scale capacity green hydrogen production.
This paper presents the KBR technology roadmap from renewable energy to green hydrogen supply where it is needed most, highlighting the process steps, the efficiency achieved, while completing the ammonia to hydrogen value chain without emitting any CO2.
Syngas processing in waste-to-renewable energy technology with reduction of CO2 footprint
Zbigniew Urban, Siemens Process Systems Engineering Ltd.
The processing of organic material from growing landfills of domestic and other types of waste is important because it can significantly reduce CO2 emissions and secretion of chemical toxins whilst contributing to meeting current demands for renewable energy.
This presentation considers the integration of three disruptive technologies aiming to achieve these objectives while allowing the production of automotive grade hydrogen and/or zero sulphur jet fuels within a very low CO2 footprint:
- Pure, high temperature pyrolysis of waste material with no partial combustion
- Fischer-Tropsch synthesis with 80% single-pass conversion of carbon monoxide and 80+% of hydrogen
- Plasma torch for decomposing methane and light hydrocarbons to hydrogen and carbon black or for conversion of CO2 and hydrogen to syngas.
The above are combined with standard, established gas processing components including the UOP Benfield process, catalytic methanation of CO2, and high- and low-temperature Water Gas Shift reactors.
The three new technologies have been studied individually in experiments at pilot or demonstration scale. Based on these experimental data, a simulation study of the integrated plant has been carried out, the results of which will be shared.
Effective reduction of nitrogen oxide and ammonia emissions by utilising environmentally compliant technologies
Tomohiro Otani; Shinya Fukuzawa; So Akimoto; Masahiro Hayashi; Ryota Shimura, Mitsubishi Heavy Industries Engineering, Ltd
Husen Saidov, Navoiyazot JSC
This paper will demonstrate how Mitsubishi Heavy Industries Engineering, Ltd. (MHIENG), utilized a distinct set of emission-mitigating technologies to reduce NOx and ammonia emission level in Uzbekiztan Navoiy Fertilizer (UNF) Plant.
MHIENG applied the Selective Catalytic Reduction (SCR) technology by Haldor Topsoe A/S (HTAS) for Primary Reformer, Non-Catalytic Reduction of NOx contents for Auxiliary Boiler and Acid Scrubbing System for ammonia reduction in Granulation Plant. The combination of these systems to reduce environmental impact is not commonly found among fertilizer plants.
To guarantee the effectiveness of the installed technologies, their performance was evaluated. By installing the SCR type-DeNOx system in the reformer, NOx emission was reduced to less than the expected Vendor’s design limit of 25 mg/Nm3 (at 3.0 vol% O2, as dry NO2). Emission reduction ratio of about 80% was achieved. Likewise, for Auxiliary Boiler, adequate NOx reduction up to less than 40 mg/Nm3 was achievable using low NOx burner with simultaneous steam injection and Flue Gas Recirculation (FGR). This was equivalent to 80% reduction when compared to a blank case - without steam injection and FGR.
For the Urea Granulation Plant, ammonia emissions were reduced to less than 20 mg/Nm3, achieved using the Acid Scrubbing system. This was below Vendor design figure of 50 mg/Nm3. The 20 mg/Nm3 result, being compliant with IFC ammonia emission standard of 50 mg/Nm3 could clear the strict standards of foreign countries such as United States of America. Moreover, dust emission was also tested to be only 15 mg/Nm3 versus the design point of 50 mg/Nm3.
The combination of SCR DeNOx Unit, non-catalytic NOx reduction method and Acid Scrubbing system as applied by MHIENG in UNF Project are proven to effectively reduce nitrogen oxide and ammonia gas emissions respectively way beyond the standard criteria.
Asset integrity and process safety
Pressure equipment failures on ammonia and nitric acid plants from stress relaxation cracking
David Keen, Becht
Equipment operating at elevated temperatures in ammonia and nitric acid plants can be susceptible to a damage mechanism termed ‘stress relaxation cracking’ (SRC). This paper outlines:
• An overview of actual case studies where SRC failures have occurred leading to plant downtime and potentially putting plant personnel’s safety at risk.
• A summary of key contributing factors which lead to equipment failures from SRC.
• What preventative controls need to be put into place during the design and construction stage to prevent SRC from occurring.
• What do we need to do to ensure this potentially serious damage mechanism is always included in our design & risk analysis processes?
• How the potential for SRC can be recognised during an RBI assessment and what inspections need to be put into place as failure preventative controls.
• How to repair equipment which has suffered a failure due to SRC.
Stress relaxation cracking requires the presence of high stresses either residual and/or applied, and therefore is more likely, but not limited, to occur in thicker sections and higher strength (creep) materials. SRC occurs at elevated temperatures when creep ductility is insufficient to accommodate the strains required for the relief of applied or residual stress(es). Several case studies will be shared.
Creep Life Assessment of Non-Standard Materials: Reformer Tubes and Outlet Manifolds
Charles Thomas; Tim Hill; Alice Young, Quest Integrity
Methods used to assess the fitness for service and remaining life of high temperature components are well established and embodied in codes such as API 579 “Fitness for Service”. These approaches assume that the relationship between applied stress, temperature and time in service remains constant over the life of the equipment while accounting for some material property scatter from batch to batch. There are a number of materials however for which this appears to be not the case.
The stability of material creep properties will depend upon the metallurgical details of how any given material develops its creep resistance. For many materials this does not change significantly. But for a few key materials such as those used for reformer tubes and outlet manifolds, this is not the case. At the same time as creep damage accumulates, the creep strength of the material deteriorates or ages in service due to long term exposure to high temperature. This is in effect an extremely elongated heat treatment.
This paper describes how this process influences the strength of the materials used to manufacture reformer tubes and outlet manifolds and how the continuously changing creep properties can be incorporated into modified methodologies to provide reliable estimates of remaining life. Such methodologies provide confidence that the extremely large capital cost associated with tube and manifold replacement can be confidently deferred or enacted at the right time.
Optimising the production of nitric acid
Start me up – improved activation can improve gauze performance
Thomas Ithell, Johnson Matthey
The start-up of a nitric acid plant can have a significant influence on the performance of the ammonia oxidation gauze catalyst over the duration of the campaign. A successful light off will ensure the rapid restructuring of the gauze surface to maximise conversion efficiency early in the process, whilst avoiding the formation of an ammonium nitrate or creating an explosive atmosphere.
This paper ‘Start-up 101 paper’ reviews a range of start-up learnings and the parameters, including rate of ammonia addition to the process, controls and monitoring of the gauze during start-up, and sources of contamination, and discusses the impact these variables can have of gauze performance and plant safety including review of how offering includes products that can offer the following features - enhanced light off, reduced rhodium oxide formation and lower OPEX costs.
Optimization of ammonia oxidation by CFD modelling and experiments. Role of mass transfer on product selectivity
Artur Wiser, Umicore
After 100 years the Ostwald process is still the most common way for the industrial manufacturing of nitric acid. The process is divided into three steps, the first step is the catalytic combustion of ammonia with air towards nitrogen monoxide, with the by-products being N2 and N2O.
As catalyst, mainly Pt-alloy gauzes are applied with different compositions and structures. Although the process is well known, and highly optimised, knowledge of the influencing factors and kinetic details under realistic conditions is limited due to the harsh conditions (up to 1000 °C, corrosive atmosphere) and the mass transport limitation of the reaction.
This paper will demonstrate how a very established but very complex chemical process like Ostwald process can be improved using new modelling and experimental techniques. The main focus will be the investigation of product selectivity (NO, N2 and N2O) on different process conditions tin a lab scale reactor and using CFD-simulation. Based on this knowledge, new optimized gauze structures are design and tested in the industrial environment. The newly developed and optimized catalytic gauzes for ammonia oxidation can significantly increase the efficiency of the process, by reducing NH3 consumption, and reducing N2O emissions, yielding improvement in production economics.
Optimized FTC Flex Gauze Packs For Catalysis Of Ammonia Oxidation
Oliver Henkes, Heraeus Deutschland GmbH & Co
For nitric acid production, each catalyst gauze design has to be tailored to the operating conditions of a specific plant and to the market requirements perceived by the customer. The most important cost factors which are influenced by the market development are the NH3 prices, precious metals costs and nitrous oxide emission prices in certain regional areas.
This paper will introduce the latest development of the Heraeus FTC Flex concept, which takes into account not only plant operation conditions but also cost factors arising from market conditions to provide the gauze design with the best economic benefit for nitric acid plants. Considering the catalyst reaction kinetics, the gas flow dynamics, and the changes of catalyst micro-surfaces during the operating time, the catalyst CFD simulation software enables to find the best alloy composition and the best 3D geometric structure of each gauze type located at the different positions from top to bottom of a catalyst gauze pack.
Heraeus FTC Flex gauze packs offer the possibility to reduce N2O emissions by primary abatement. The primary N2O abatement with the catalytic gauze pack is fully customizable, making it suitable for both full and partial loads. By using Heraeus FTC Flex gauze packs in combination with Heraeus iron oxide-based secondary catalyst, average nitrous oxide emissions in the tail gas of medium pressure plants of less than 50 ppmv can be achieved. This catalyst combination is used successfully in many nitric acid plants worldwide.
The new development FTC Flex gauze packs takes into account plant operating conditions and cost factors of market conditions to provide the gauze design with the best economic benefit for nitric acid plants. FTC Flex gauzes in combination with secondary catalyst help to achieve continuous improvements for the benefit of Heraeus customers.
Predicting precious metal recoveries from nitric acid plant cleaning
David Kelly, PGM Technologies
Gle Park, KBR
For nitric acid producers, estimating precious metal recoveries from heat train components and tanks is just as predictable as estimating precious metal losses from the installed catalyst pack. Many items factor into these estimates such as temperature exchange, location of the vessel in the heat train, surface area of an exchanger, etc. KBR and PGM Technologies are now working together to provide customers performance based guarantees for precious metal recoveries. This paper will go into the logic and technical expertise used to determine recovery estimates for cleaning entire facilities, individual heat exchangers and tanks. The paper will also address different cleaning methods and their predicted outcomes.
Latest Improvements in the Uhde EnviNOx® Process for N2O abatement
Alexander Sasonow; Meinhard Schwefer; Daniel Birke, thyssenkrupp Industrial Solutions
The EnviNOx® process, developed in the mid-2000s has been successfully installed in more than 30 HNO3 plants around the world. The process was originally intended solely for the abatement of N2O and NOx in the tail gas of HNO3 production plants, with the N2O reduction being achieved either through catalytic decomposition or selective catalytic reduction with hydrocarbons. The EnviNOx® system toolbox comprised, for example, alongside the commonly known EnviNOx® variants 1 and 2 (NOx reduction combined with N2O decomposition or reduction using hydrocarbons), a plain DeNOx variant and a plain DeN2O® variant.
Driven by increased demand and special customer requirements, the EnviNOx® toolbox has been systematically expanded in recent years. For example, the use of NH3 as a reducing agent for N2O as an alternative to fossil hydrocarbons, or the coupling of the tertiary EnviNOx® process with catalysts for the secondary decomposition of N2O in the process gas of HNO3 production plants. The progress and developments achieved are presented and explained, by way of example, based on recent successful installations of selected commercial EnviNOx® plants.