Patent Application
20230242395
Global interest in renewable energy and using this renewable energy to generate green hydrogen has driven the interest in converting the green hydrogen to green ammonia, as ammonia is simpler to transport over distance of hundreds or thousands of miles. Particularly, shipping liquid hydrogen is not commercially possible currently but shipping ammonia, which is in a liquid state, is currently practiced.
For use in a commercial fuel cell, the ammonia must be converted back to hydrogen according to the reaction.
This is an endothermic process, i.e., a process that requires heat, and is performed over a catalyst. This process is known as cracking. The gas produced (or “cracked gas”) is a combination of hydrogen (H2) and nitrogen (N2). Since the cracking reaction is an equilibrium reaction, there is also some residual ammonia. In most applications of crackers currently, the hydrogen + nitrogen mixture is utilised as is. However, as ammonia can be a poison to fuel cells, this stream, with ammonia suitably removed such as by scrubbing with water, can be used directly in a fuel cell. However, if the hydrogen is to be used in vehicle fueling, the nitrogen present provides a penalty to the process. The fuel to a vehicle fueling system is compressed to significant pressure — up to 900 bar. This means that the nitrogen, which is merely a diluent in the process, is also compressed, taking power, and taking storage volume and increasing anode gas purge requirement, decreasing efficiency. It is therefore beneficial where hydrogen is to be used in vehicle fueling, for the hydrogen + nitrogen to be purified.
Small scale cracking reactors, or “crackers”, typically use pressure swing adsorption (“PSA”) devices to separate the cracked gas and recover the hydrogen and generate a PSA tail gas (or offgas). However, these crackers are generally heated electrically and the PSA tail gas is typically vented to atmosphere.
As is common in hydrogen production from a steam methane reforming (SMR) reactor, a PSA can be used to purify the nitrogen + hydrogen. The cracking reaction is performed in tubes packed with catalyst which are externally heated by a furnace (see GB1142941).
GB1142941 discloses a process for making town gas from ammonia. The ammonia is cracked and the cracked gas scrubbed with water to remove residual ammonia. The purified hydrogen/nitrogen mixture is then enriched with propane and/or butane vapor to produce the town gas for distribution.
US6835360A discloses an endothermic catalytic reaction apparatus for converting hydrocarbon feedstock and methanol to useful gases, such as hydrogen and carbon monoxide. The apparatus comprises a tubular endothermic catalytic reactor in combination with a radiant combustion chamber. The resultant cracked gas is used directly in a fuel cell after passing through a gas conditioning system.
GB977830A discloses a process for cracking ammonia to produce hydrogen. In this process, the hydrogen is separated from the nitrogen by passing the cracked gas through a bed of molecular sieves which adsorbs nitrogen. The nitrogen is then driven off the bed and may be stored in a holder.
JP5330802A discloses an ammonia cracking process in which the ammonia is contacted with an ammonia decomposition catalyst at a pressure of 10 kg/cm2 (or about 9.8 bar) and a temperature of 300 to 700° C. Hydrogen is recovered from the cracked gas using a PSA device. The reference mentions that the desorbed nitrogen may be used to boost the upstream process but no details are provided.
US2007/178034A discloses a process in which a mixture of ammonia and hydrocarbon feedstock is passed through a fired steam reformer at 600° C. and 3.2 MPa (or about 32 bar) where it is converted into a synthesis gas containing about 70 vol. % hydrogen. The synthesis gas is enriched in hydrogen in a shift reaction, cooled and condensate removed. The resultant gas is fed to a PSA system to generate a purified hydrogen product having 99 vol. % hydrogen or more. The offgas from the PSA system is fed as fuel to the fired steam reformer.
CN111957270A discloses a process in which ammonia is cracked in a tubular reactor within a furnace. The cracked gas is separated by adsorption to produce hydrogen gas and a nitrogen-rich offgas. The fuel demand of the furnace appears to be satisfied using a combination of cracked gas, hydrogen product gas and/or offgas.
There is a need generally for improved processes for the production of hydrogen from ammonia and specifically for processes that are more efficient in terms of energy consumption and/or that have higher levels of hydrogen recovery and/or that reduce or eliminate the need to combust fossil fuels.
In the following discussion of embodiments of the present invention, the pressures given are absolute pressures unless otherwise stated.
According to a first aspect of the present invention, there is provided a method for producing hydrogen from ammonia, comprising:
The liquid ammonia is typically pressurized to a pressure that is greater than 1.1 bar, e.g. at least 5 bar or at least 10 bar. In some embodiments, the liquid ammonia is pressurized to a pressure in a range from about 5 bar to about 50 bar, or in a range from about 10 to about 45 bar, or in a range from about 30 bar to about 40 bar.
The liquid ammonia is typically heated to produce heated ammonia at a temperature greater than about 250° C., e.g. in a range from about 350° C. to about 800° C., or from about 400° C. to about 600° C. At the pressures in question, the liquid ammonia is typically vaporized completely to form heated ammonia vapour.
The temperature is ultimately determined by the identity of the catalyst, the operating pressure and the desired “slip”, i.e. the amount of ammonia that passes through the cracking reactor without being cracked. In this regard, the process is typically operated with no more than about 4% slip which would be the amount of slip if the cracking process were operated 5 bar and 350° C. with a close approach to equilibrium. Problems may arise with some construction materials at any appreciable pressure at temperatures above about 700° C.
The cracking reaction takes place in catalyst-filled reactor tubes that are heated by a furnace. However, in theory any heterogeneously catalysed gas reactor could potentially be used for the conversion.
There are a large number of catalysts known in the art as useful for the ammonia cracking reaction and any of these conventional catalysts may be used in this invention.
The primary fuel for the furnace typically comprises methane. The fuel may be pure methane but is more likely natural gas or biogas. In some embodiments, the primary fuel is natural gas or biogas which is supplemented with hydrogen as a secondary fuel, optionally in the form of an ammonia cracked gas. In these embodiments, liquid ammonia may be pumped and cracked to form the cracked gas which is added to the primary fuel.
The PSA device may operate a PSA cycle or a vacuum swing adsorption (VSA) cycle. A TSA device may be used in combination with the PSA device, the TSA device to remove ammonia (see US10787367) and the PSA device to remove nitrogen and produce the hydrogen product. Suitable PSA cycles include any of the cycles disclosed in US9381460, US6379431 and US8778051.
Recycling the hydrogen-rich permeate gas for further processing in the PSA device (or, for simplicity, the “PSA”) improves hydrogen recovery significantly and recovery rates may approach 100%, e.g. may be about 99%.
Like hydrogen, ammonia is a “fast gas” that readily permeates across membranes used for gas separation. Some membranes, such as those constructed of polyamide or polysulfone polymers, are more tolerant of ammonia. However, some membranes, such as those constructed of polyimide polymers, are less tolerant of ammonia. Therefore, ammonia is typically removed, or its concentration is at least reduced, upstream of the membrane separator.
Ammonia removal may be achieved in several different locations within the process. Prior to separating the PSA tail gas, ammonia may be removed from the PSA tail gas. Alternatively, prior to purifying the cracked gas, ammonia may be removed from the cracked gas. In both cases, the removed ammonia may be recovered and recycled into the ammonia supplied to the catalyst-containing reactor tubes.
Ammonia may be removed from a gas by adsorption (e.g. by TSA) or by absorption in water, e.g. by washing the gas with water in a scrubber column. The resultant ammonia-depleted gas and ammonia solution are separated so the ammonia-depleted gas can be further processed without the ammonia causing any difficulties. Ammonia can be recovered from the ammonia solution by stripping in a distillation column system. Such a process may be applied to the cracked gas prior to being supplied to the PSA unit or alternatively to the PSA tail gas prior to being supplied to the membrane separator.
In some preferred embodiments, however, ammonia is condensed out of the PSA tail gas and the condensed ammonia is fed to the ammonia feed to the cracker. In these embodiments, the process comprises:
The one or more cold fluids may comprise an external refrigerant although, in preferred embodiments, the one or more cold fluids comprise the pressurized liquid ammonia and/or the ammonia-depleted PSA tail gas for internal heat integration of the process.
The condensed ammonia may be rejected from the process but is preferably combined with the pressurized liquid ammonia.
The membrane separator may comprise only a single membrane separation unit (also referred to as a membrane stage). In these embodiments, the membrane separator does not comprise more than one membrane separation unit. In preferred embodiments, however, the membrane separator comprises a first membrane separation unit and a second membrane separation unit in series. In these embodiments, the method further comprising:
Using two membrane separation units in this way helps avoid having to use a second compressor for compressing the hydrogen being recycled to the PSA and therefore uses less power overall than involving two compressors while maintaining high hydrogen recovery rates (-99%).
The nitrogen-rich retentate gas may be expanded in a turbine to recover power prior to being vented to the atmosphere after suitable treatment to remove contaminants such as ammonia. In such embodiments, the nitrogen-rich retentate gas is typically heated by heat exchange with the one or more hot fluids prior to expansion. Alternatively, the nitrogen-rich retentate gas may be purified to produce a nitrogen product.
According to a second aspect of the present invention, there is provided apparatus for producing hydrogen from ammonia, comprising:
The furnace may be separate from the catalyst-filled reactor tubes although the furnace and the catalyst-filled reactor tubes are preferably integrated within the same unit. In preferred embodiments, a steam methane reforming (SMR) type reactor is used in which the furnace comprises a radiant section through which pass the catalyst-containing reactor tubes.
The apparatus typically comprises an ammonia removal system upstream of the membrane separator in order to protect ammonia intolerant membranes and/or to prevent ammonia from passing through the membranes with the hydrogen. The ammonia removal system may be a scrubbing column for removing the ammonia by absorption in water, or may be a TSA device for removing the ammonia by adsorption.
The ammonia removal system may be located downstream of the PSA device and so removes ammonia from the PSA tail gas. Alternatively, the ammonia removal system may be located downstream of the at least one heat exchange and upstream of the PSA device and so removes ammonia from the cracked gas.
The apparatus may also comprise an ammonia recovery system for recovering ammonia gas from the aqueous ammonia solution produced in the scrubbing column. The recovery system may comprise a stripping column (or a stripping section in a distillation column system) for recovering ammonia from the aqueous ammonia solution.
Additionally or alternatively, the apparatus may comprise a selective catalytic reduction (SCR) reactor for removing oxides of nitrogen from the flue gas to which at least part of the aqueous ammonia solution is fed to provide ammonia for the SCR reaction.
A PSA tail gas compressor is typically provided downstream of the PSA device for compressing the PSA tail gas for the membrane separator. The compressor may consist of one or more stages and cooling will take place between each stage and after the final stage. Water will typically condense out of the compressed PSA tail gas at the interstages or at the aftercooler stage. The aqueous condensate is typically removed after each cooling stage of the compressor and a small amount of ammonia will come out of the PSA tail gas with this condensate.
Additionally or alternatively, a hydrogen-rich gas compressor is typically downstream of the membrane separator for compressing the hydrogen-rich gas for the PSA device and/or for combining with the hydrogen product gas.
In some preferred embodiments, the apparatus comprises:
In these embodiments, the apparatus may comprise a conduit for supplying the condensed ammonia to the pressurized liquid ammonia.
In addition, where the membrane separator comprises a first membrane separation unit and a second separation unit in series, the apparatus may further comprise:
The apparatus typically comprises a conduit for supplying nitrogen-rich retentate gas from the membrane separator to a vent, optionally together with a turbine located downstream of the membrane separator for expanding nitrogen-rich retentate gas and recovering power. In addition, a heat exchanger may be located upstream of the turbine for heating nitrogen-rich retentate gas by heat exchange with one or more hot fluids.
Alternatively, a nitrogen purification device may be in fluid communication with the membrane separator for purifying nitrogen-rich retentate gas to produce nitrogen gas product.
A process is described herein for producing hydrogen by cracking ammonia. The process has particular application to producing so-called “green” hydrogen which is hydrogen created using renewable energy instead of fossil fuels. In this case, the ammonia is typically produced by electrolyzing water using electricity generated from renewable energy, such as wind and/or solar energy, to produce hydrogen which is then reacted catalytically with nitrogen (Haber process) to produce the ammonia which is more easily transported than hydrogen. After reaching its destination, the ammonia is then cracked to regenerate the hydrogen.
In this inventive process, the heat required for the reaction is typically provided by combustion of PSA tail gas (which usually contains some amount of residual hydrogen and ammonia) in the furnace. If the PSA tail-gas has insufficient heating value than either vaporised ammonia, a portion of the product hydrogen, or an alternative fuel may be used with the tail-gas as a trim fuel.
In practice, natural gas could be used as a trim fuel, together with the PSA tail gas, as is practiced in SMRs for hydrogen. However, with the desire to maintain the “green” or renewable credentials of the hydrogen so produced, there is an incentive to use a “renewable fuel”. This can be the cracked “renewable” ammonia, the ammonia itself, or another renewable energy source, such as biogas, or indeed electric heating whether the electricity is itself from a renewable source, in this case local to the cracking process as opposed to the renewable electricity used to generate the hydrogen which has been transported in the form of ammonia.
A reference example of the process is shown in
The pressurised liquid ammonia (line 4) is then heated, vaporised (if it is below its critical pressure) and heated further, up to a temperature of greater than 250° C. via a heat exchanger (E101) using the heat available in the cracked gas leaving the reaction tubes and the flue gas from the furnace. In the figure, the heat exchanger (E101) is shown as one heat exchanger but, in practice, it will be a series of heat exchangers in a network.
The initial heating and vaporization of the pressurized liquid ammonia may alternatively take place against an alternative heat source, such as cooling water or ambient air. Typical reaction temperatures are greater than 500° C. (see US2601221), palladium-based systems can run at 600° C. and 10 bar, whereas RenCat’s metal oxide-based system runs at less than 300° C. and 1 bar. (See https://www.ammoniaenergy.org/articles/ammonia-craking-to-high-purity-hydrogen-for-pem-fuel-cells-in-denmark/). The operating pressure of the cracker is typically an optimization of several factors. Cracking of ammonia into hydrogen and nitrogen is favored by low pressure but other factors favor higher pressure, such as power consumption (which is minimized by pumping the feed ammonia rather than compressing the product hydrogen), and the PSA size (which is smaller at higher pressure).
The hot ammonia (line 6) enters reaction tubes of a reactor (8) at the desired pressure where additional heat is provided by the furnace (10) to crack the ammonia into nitrogen and hydrogen. The resulting mixture of residual ammonia, hydrogen and nitrogen exits (line 12) the reaction tubes of the reactor (8) at the reaction temperature and pressure. The reaction products are cooled in a heat exchanger (E101) against a combination of feed ammonia (from line 4), furnace fuel (in this case pumped ammonia from line 14, pump P202 and line 16; PSA tail gas from line 18; and product hydrogen to be used as fuel in line 20) and combustion air (from line 22, fan K201 and line 24) to reduce the temperature as close as possible to that required for the inlet of a PSA device (26). Any residual heat in the cracked gas mixture (line 28) is removed in a water cooler (not shown) to achieve an inlet temperature to the PSA device (26) of in a range from about 20° C. to about 60° C., e.g. about 50° C.
The PSA product (line 30) is pure hydrogen compliant with ISO standard 14687 - Hydrogen Fuel Quality - with residual ammonia < 0.1 ppmv and nitrogen < 300 ppmv - at approximately the reaction pressure. The product hydrogen (line 30) is further compressed (not shown) for filling into tube trailers (not shown) for transport or it may be liquefied in a hydrogen liquefier (not shown) after any required compression. The PSA tail gas (line 18) or “purge gas” from the PSA device (26) is shown as being heated via the heat exchanger E101, using the cracked gas (line 12) leaving the reaction tubes of the reactor (8) or furnace flue gas (line 32), before being sent (in line 36) to the furnace as a combustion fuel. However, the PSA tail gas (line 18) may be fed directly to the furnace (10) without heating.
The resultant warmed ammonia fuel (line 34) and warmed hydrogen (line 40) are depicted as combined with the (optionally) warmed PSA tail gas (line 36) in a mixer (42) to produce a combined fuel which is fed (line 44) to the furnace (10) for combustion to generate the flue gas (line 32 and, after cooling in E101, line 48). However, it should be noted that one or more of the fuels could be fed directly to the furnace without prior mixing. The warmed air (for combustion of the fuel) is fed to the furnace (10) in line 46.
One of the aims of preferred embodiments of the present process is to maximise the amount of hydrogen generated by cracking the renewable ammonia. That means minimising the amount of hydrogen used as fuel, or ammonia if ammonia were to be used as a fuel directly. Therefore, heat integration is important so as to use the hot flue gas and cracked gas appropriately, for instance to preheat air (line 24) and ammonia (line 4) to the cracker as this reduces the amount of “fuel” to be used in the burners of the furnace (10). This leads to higher hydrogen recovery as less of the hydrogen is lost in the furnace flue gas (lines 32 & 48) as water. Therefore, steam generation, for instance, should be minimised in favour of intra-process heat integration.
The inventors are aware that stable combustion of ammonia is facilitated if hydrogen is also used as a fuel, particularly at start-up and warm-up.
Should there be a viable alternative source of renewable energy for the cracking reactions, as discussed above, one could consider recovering hydrogen from the PSA tail gas to increase the net hydrogen production from the process in addition to the hydrogen produced from the PSA. Such a process could use membranes, which have a selective layer that is readily permeable to hydrogen but relatively impermeable to nitrogen, to separate hydrogen from the nitrogen rich PSA tail gas stream (
Ammonia may need to be removed particularly but not exclusively if membranes are being used as part of the separation process since membrane material can be intolerant of high concentrations of ammonia and ammonia is a fast gas and would permeate with the hydrogen so would accumulate in the process if not removed. Ammonia may be removed for instance by a water wash or other well-known technology for ammonia removal, upstream of the membrane. Ammonia may be recovered from an aqueous ammonia solution generated in the water wash using a stripping column and the recovered ammonia could be recycled to the feed to the cracking reactor. This could theoretically increase the hydrogen recovery from the process up to 100%. Recovering ammonia from the cracked gas simplifies the hydrogen purification steps, may increase the recovery of hydrogen from the ammonia if the separated ammonia is recovered as feed, and also removes ammonia from the feed to the burners, eliminating concerns over production of NOx caused by burning ammonia.
Water may also need to be removed from the feed ammonia to prevent damage to the ammonia cracking catalyst. Typically ammonia has small quantities of water added to it to prevent stress corrosion cracking in vessels during shipping and storage. This might need to be removed. However, the water removal can be incorporated into the stripping column mentioned above. The ammonia would be evaporated at the required pressure, taking care in the design of the evaporator to ensure that the water was also carried through to the stripping column with the evaporator ammonia. This mostly vapor phase ammonia enters a mid-point of the column and pure ammonia leaves through the top of the column. The column has a partial condenser (condenses only enough liquid for the reflux) and the overhead vapor contains the feed ammonia (free of water) plus the ammonia recovered from the cracker gas stream.
It may be more energy efficient to feed the cracked gas first to a membrane to produce a hydrogen-enriched permeate stream and a nitrogen-rich retentate stream that could be vented. The hydrogen-enriched permeate can be further purified in the PSA. A second membrane could be added to the PSA tail gas stream to further boost the overall hydrogen recovery. This configuration would greatly reduce the tail-gas compressor size.
The use of a membrane separator to increase hydrogen recovery allows the nitrogen to be vented from the process without passing through the combustion section of the process. In processes where the nitrogen stream is at pressure, it would be beneficial to expand the nitrogen to atmospheric pressure before venting to recover power through an expansion turbine. It would increase the amount of power recovered if the pressurized nitrogen were to be heated before expansion using heat available in the flue gas or cracked gas stream.
A renewable fuel source (line 50) is warmed in the heat exchange (E101) and fed (line 52) to the furnace (10) for combustion to heat the catalyst-filled tubes of the cracking reactor (8).
The cooled cracked gas (line 28) is combined with compressed hydrogen-rich permeate gas (line 62) to form a combined gas which is fed (line 64) to the PSA device (26). The combined gas is separated to form the hydrogen product (line 30). The tail gas (line 54) from the PSA is compressed in a first compressor (K301) and the compressed gas is fed (line 56) to a membrane separation unit (M301) to produce an enriched hydrogen permeate stream (line 58) and a nitrogen-rich retentate stream (line 60). The membrane separation unit can consist of multiple membrane devices arranged in parallel or series as determined by the feed flow and desired hydrogen recovery. The permeate stream is compressed in a second compressor (K302) to form the compressed hydrogen-rich gas (line 62) which is recycled (line 64) to the PSA (26) with the cooled cracked gas (line 28) to increase overall rate of recovery of hydrogen.
Assuming the purity of the hydrogen produced by the membrane is sufficiently high, part (line 68) of the hydrogen permeate gas may be combined after compression with the hydrogen product (line 30), with the remainder being recycled (line 64) to the PSA with the cooled cracked gas (line 28). Combining part of the hydrogen permeate gas with the hydrogen product in this way would reduce the required size of the PSA and the power of K301 and K302.
Alternatively, all of the compressed hydrogen-rich permeate gas (line 62) may be combined with the hydrogen product (line 30) with none being recycled to the PSA (26).
However, ammonia can also be condensed out of the compressed PSA off gas stream using the cold feed ammonia - that is shown in
In
Ammonia usually passes through the membrane with recycled hydrogen so the low temperature separator is a way of removing and recycling ammonia to the feed stream. This process also produces a purge stream (line 60) that may be around 98% nitrogen. Should this stream contain residual ammonia, then it would need to be treated before it can be vented. However, the purge stream is at pressure and could be purified to produce a product nitrogen stream.
Overall, the process depicted in
In
The power requirement in
The present invention is not to be limited in scope by the specific aspects or embodiments disclosed in the examples which are intended as illustrations of a few aspects of the invention and any embodiments that are functionally equivalent are within the scope of this invention. Various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art and are intended to fall within the scope of the appended claims.
The invention will now be illustrated with reference to the following Invention Examples and by comparison with the following Reference Examples. For the purposes of the simulations, both the Invention Examples and the Reference Examples assume an equilibrium for the cracking reaction at 11 bar and 500° C.
The process depicted in
In this Reference Example, hydrogen recovery from the ammonia is 77.18% with the PSA recovery at 83.5%. The total power of the ammonia feed pump (P201), the ammonia fuel pump (P202) and the air fan (K201) is about 1.36 kW.
The process depicted in
In this Reference Example, hydrogen recovery from the ammonia is 77.05% with the PSA recovery at 79.4%. The total power of the ammonia feed pump (P201) and the air fan (K201) is about 1.37 kW.
The process depicted in
In this Invention Example, hydrogen recovery from the ammonia is 98.95%. In addition, the total compression power requirement (PSA off gas compressor and membrane compressor) is about 60.59 kW.
The process depicted in
In this Invention Example, hydrogen recovery from the ammonia is 98.95%. In addition, the total compression power requirement (PSA off gas compressor alone) is about 56.54 kW.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2021/038007 | 6/18/2021 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 63040707 | Jun 2020 | US |
