The present invention relates to a process and an apparatus for the recovery of boil-off gas from liquefaction of hydrogen. Liquefied hydrogen is generally transferred through a loading bay to supply one or more hydrogen transport trucks for the transportation of liquid hydrogen.
The hydrogen transport truck filling duration (or Boil Off Gas (BOG) recovery capacity is today limited by the flexibility of the overall hydrogen liquefaction system (including the hydrogen production system) that requires the speeds of hydrogen transport truck depressurization and filling (or the amount of recoverable BOG) have to be limited, because the flow of BOG sent back to any BOG recovery system needs to match the ramp-up and ramp-down speeds of the complete system in order to maximise the recovery rate.
It is known from US2013/291585 to recycle BOG in a helium liquefier, the point to which the BOG is recycled being chosen purely as a function of the temperature and purity of the BOG.
It has been found more reliable to base the decision on whether to recycle the BOG of a hydrogen liquefier either to the feed stream or to the hydrogen refrigeration cycle, based on measurements of the pressure of the BOG. In particular, liquid stratification phenomena in the truck can mean that there is not a direct relation between the temperature and pressure of the BOG from the truck.
According to certain embodiments of the invention, the recovery of the BOG can be maximized by using those H2 molecules in any one of three different ways:
For such a configuration, separating the BOG depending on its pressure level and designing the compression trains capacities in consistency with the hydrogen transport truck operations is the key. The process control philosophy of the whole system is based on the adaptability of H2 feedstock load “following” the BOG generation.
In certain embodiments, the invention allows the duration of the hydrogen transport truck filling sequence to be reduced (or the volume of recovered BOG to be maximized) by controlling the feed flow rate (at the inlet of the hydrogen liquefaction system) with the BOG flow rate (by turning down the production capacity of hydrogen generation unit (or Feed flow rate) simultaneously with the recovery of BOG).
According to an object of the invention, there is provided a hydrogen boil-off gas recovery method, comprising liquefying hydrogen by cooling a hydrogen feed stream at a first pressure in a first cryogenic cold box, further cooling the hydrogen in a second cryogenic cold box, using the hydrogen refrigeration cycle to refrigerate the second cryogenic cold box, liquefying the hydrogen in the second cryogenic cold box or downstream thereof, providing liquefied hydrogen to a storage or a loading bay containing at least one hydrogen transport truck, sending boil-off gas from at least one hydrogen transport truck in the loading bay to which liquefied hydrogen has been provided to an indirect heat exchanger outside the first and second cryogenic cold boxes in order to warm the boil-off gas, measuring the pressure of the boil-off gas and if the boil-off gas stream from at least one hydrogen transport truck is below a previously determined pressure, at least part of the boil off gas stream is warmed in a first heater and mixed with a hydrogen refrigeration cycle stream and if the boil-off gas stream from at least one hydrogen transport truck is above a previously determined pressure, at least part of the boil off gas stream from at least one hydrogen transport truck is warmed in the first heater or in a second heater and mixed with a hydrogen feed stream upstream of the first cryogenic cold box.
According to further optional features:
According to another aspect of the invention, there is provided a hydrogen liquefier and boil-off gas recovery apparatus, comprising a liquefier for liquefying hydrogen comprising a first cryogenic cold box for cooling a hydrogen feed stream at a first pressure and a second cryogenic cold box for further cooling the hydrogen so as to liquefy the hydrogen in the second cryogenic cold box or downstream thereof, a loading bay containing at least one hydrogen transport truck, means for providing liquefied hydrogen to a storage or a loading bay containing at least one hydrogen transport truck, a hydrogen refrigeration cycle used to provide refrigeration for the second cryogenic cold box, means for detecting the pressure of a boil-off gas stream from at least one hydrogen transport truck, first and second heaters outside the first and second cryogenic cold boxes, means for sending the boil-off gas stream from at least one hydrogen transport truck to the first heater if, preferably only if, the detected pressure is below a previously determined pressure, means for sending the boil-off stream warmed in the first heater to be mixed with the hydrogen refrigeration cycle and means for sending the boil-off gas stream from at least one hydrogen transport truck to the second heater if, preferably only if, the detected pressure is above a previously determined pressure and means for sending the boil-off stream warmed In the first heater to be mixed with a hydrogen feed stream upstream of the first cryogenic cold box.
Preferably the liquefier comprises means for detecting the temperature of a boil-off gas stream from at least one hydrogen transport truck, means for sending the boil-off gas stream from at least one hydrogen transport truck to the hydrogen refrigeration cycle without being heated if the detected temperature is below a previously determined temperature and if the detected pressure is also below a previously determined pressure.
The liquefier may comprise an additional first cryogenic cold box for cooling a hydrogen feed stream at a first pressure and an additional second cryogenic cold box (20K CB) for further cooling the hydrogen so as to liquefy the hydrogen in the second additional cryogenic cold box or downstream thereof, means for providing liquefied hydrogen from the second additional cryogenic cold box or downstream thereof to the storage or the loading bay containing at least one hydrogen transport truck, an additional hydrogen refrigeration cycle used to provide refrigeration for the second cryogenic cold box, means for sending the boil-off stream warmed in the first heater to be mixed with the additional hydrogen refrigeration cycle and means for sending the boil-off stream warmed In the first heater to be mixed with a hydrogen feed stream upstream of the first additional cryogenic cold box.
This process allows also to mutualize the flexibility of all compressors and hydrogen generation system by separating the BOG depending on its pressure level in order to route it to different tie-in points with different inlet pressures to maximize the flexibility of the integrated liquefaction system and speed up the filling sequence of the hydrogen transport trucks or increase the recovery of BOG. Temperature conditions may be taken into account but preferably only when the BOG is sufficiently cold to be sent to the hydrogen refrigeration cycle without any heating step.
Hydrogen liquefaction is an expensive process and BOG recovery of vaporized hydrogen molecules is extremely valuable, especially when the gaseous hydrogen is produced at a high cost, for example by electrolysis. BOG generation generally occurs through the liquefier cold end flash, LH2 piping, LH2 storage, during the hydrogen transport truck loading process and afterwards during the delivery of the liquid hydrogen.
The invention will be understood better from reading the following description and from studying the accompanying figures. These figures are given only by way of illustration and do not in any way limit the invention.
There are different ways to recover the BOG from those different areas of the plant (liquefier, storage and loading).
The hydrogen (1) can be generated by a steam methane reformer (SMR) or electrolysis or any other known means, indicated on the figure as H2 Generation. Hydrogen (1) can also come from an industrial complex off-gas or from a pipeline. Once free of any components that may freeze in the downstream cold box, it enters the liquefier.
In
Once liquefied within or downstream the 20K cold box, the liquid hydrogen is stored, typically in vacuum insulated storage bullet tank(s) LH2 STORAGE or a sphere depending on the capacity. Downstream of the storage LH2 STORAGE is the loading area LOADING BAYS which includes multiple loading bays and sometimes transfer pumps. In the loading bay, at least one truck is present, to be filled or having been filled with liquefied hydrogen. The term ‘loading bay’ is thus a convenient manner of referring to the at least one hydrogen transport truck present therein.
In
This has the advantage of recycling the boil-off BOG1 without affecting the liquefier operation. Also, another advantage is that the BOG flow does not affect the rated flow of the Feed gas Compressor train(s) capacity since the H2 generation unit can be turned down by the same amount to ensure that the feed gas compressor FEED COMP always sees a constant flowrate. Generally, however, the Feed Gas Compressor FEED COMP may be located even farther from the loading bay from which the BOG originates than the LP compressor LP H2 COMP. The distance between the loading area and the Feed compressor may be a concern as regards the maximum allowable pressure drop as the return BOG pressure may be extremely low (1 to 2 bara).
This invention focuses on the BOG generation and recovery from the loading area. The BOG generated in the loading area presents many challenges:
The BOG amount when the hydrogen transport truck returns to the loading bay depends on the logistics chain, delivery method, distance to customers, number of customers delivered, billing method etc.
BOG generation can be diverse and includes the following:
Valorizing all the type of BOG using the process according to
Managing the BOG only with the solution of
BOG recovery with such schemes is typically limited to ˜70%.
It is important to note that when the BOG is recycled to the liquefier, the feed gas flowrate is reduced by the same amount. Hence, BOG recovery is even more valuable when the H2 generation comes at a high OPEX cost as in the case of electrolysis.
One embodiment of the proposed invention as shown in
Thus
As shown in
Only in the case where the temperature is below a predetermined value and the pressure is also below the predetermined value, for example if the pressure is less than 2 bars and the temperature around −200° C., the low pressure boil-off gas is routed to the 20K Cold Box.
The advantages of the process are as follows:
It will be appreciated that the liquefaction process may be producing liquid hydrogen to be sent to a storage tank or to a hydrogen transport truck whilst BOG is recovered from the storage tank and/or the hydrogen transport truck being filled and/or another hydrogen transport truck, e.g. a truck returning to the facility after delivering liquid hydrogen but still containing BOG.
It is possible to use a purity detection for the BOG coming from the loading bay however any BOG below a predetermined purity level will be discarded upstream of the detectors TI, PI and the choice of destination for the BOG is not dependent on its purity.
The BOG systems for both trains are connected. The benefit of the invention when there are multiple liquefaction trains is that the BOG recovery is quasi-independent of whether or not one liquefaction train is shut down. A single loading bay is fed from the two liquefaction trains.
When the loading bay containing at least one truck produces a boil-off gas whose pressure and/or temperature is detected such that if the pressure and/or the temperature is below a predetermined value, at least one inlet valve to at least one low pressure circuit is opened and an inlet valve to a high pressure circuit is closed.
Thus the low pressure boil-off gas at, for example, less than 2 bars, is sent via the low pressure circuit to the low pressure heater and thence to the hydrogen refrigeration circuits of the two liquefaction trains. If the pressure is above a predetermined value, at least one inlet valve to at least one low pressure circuit is closed and an inlet valve to a high pressure circuit is opened. Thus the higher pressure boil-off gas at, for example, between 2 and 10 bars, is sent via the higher pressure circuit to the hydrogen feed stream which feeds both liquefier trains, preferably being compressed in the five parallel compressors GH2 COMP.
In the case of peak BOG flow, for example during depressurization of a truck, a BOG compressor is added in order to recycle the extra BOG flow to the hydrogen liquefaction system feed inlet by increasing the pressure of the extra BOG flow up to the suction pressure of the feed process (typically in the above scheme, up to the suction of the feed compressor FEED COMP). For this a dedicated boil-off compressor BOG COMP is used.
While the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the appended claims. The present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed. Furthermore, if there is language referring to order, such as first and second, it should be understood in an exemplary sense and not in a limiting sense. For example, it can be recognized by those skilled in the art that certain steps can be combined into a single step.
The singular forms “a”, “an” and “the” include plural referents, unless the context clearly dictates otherwise.
“Comprising” in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing (i.e., anything else may be additionally included and remain within the scope of “comprising”). “Comprising” as used herein may be replaced by the more limited transitional terms “consisting essentially of” and “consisting of” unless otherwise indicated herein.
“Providing” in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actor in the absence of express language in the claim to the contrary.
Optional or optionally means that the subsequently described event or circumstances may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur.
Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range.
All references identified herein are each hereby incorporated by reference into this application in their entireties, as well as for the specific information for which each is cited.
Number | Date | Country | Kind |
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EP 21217744.8 | Dec 2021 | EP | regional |
This application is a § 371 of International PCT Application PCT/EP2022/076501, filed Sep. 23, 2022, which claims the benefit of: EP21217744.8, filed Dec. 24, 2021, U.S. Ser. No. 17/743,839, filed May 13, 2022, and U.S. Provisional Application 63/248,185, filed Sep. 24, 2021, all of which are herein incorporated by reference in their entireties.
Filing Document | Filing Date | Country | Kind |
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PCT/EP2022/076501 | 9/24/2021 | WO |
Number | Date | Country | |
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63248185 | Sep 2021 | US |