Methods for large-scale hydrogen liquefaction systems.

Abstract

A method and apparatus for hydrogen liquefaction is provided that may include pre-cooling a hydrogen feed stream in a pre-cooling cold box having a heat exchanger disposed therein to form a cooled hydrogen stream, the heat exchanger configured to cool the feed stream in the pre-cooling cold box by indirect heat exchange between the hydrogen feed stream and a pre-cooling refrigerant, withdrawing the cooled hydrogen stream from the pre-cooling cold box, and introducing the cooled hydrogen stream to a plurality of liquefaction cold boxes, where the cooled hydrogen stream is liquefied in the plurality of liquefaction cold boxes by indirect heat exchange against a liquefaction refrigerant to form a product hydrogen stream in each of the plurality of liquefaction cold boxes, the product hydrogen stream being in liquid or quasi-liquid form, where there are a total of M pre-cooling cold boxes and a total of N liquefaction cold boxes, where M is less than N.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63,293,080, filed December 22, 2021, which is incorporated herein by reference in its entirety.

[0002] The present invention relates generally to methods and apparatus for producing liquid hydrogen, especially in large quantities. [Background technology]

[0003] Hydrogen is an important molecule as a sustainable energy carrier. Liquefaction of hydrogen is important for its transportation and distribution to local markets.

[0004] The hydrogen liquefaction process requires refrigeration over a very wide temperature range (20 K to 300 K). It is common to use separate, dedicated refrigeration systems for the hot end (80 K to 300 K) and the cold end (20 K to 80 K) because the specific refrigeration demand varies greatly with temperature. For the high-temperature range (80 K to 300 K), reference technologies include a) a closed-loop N2 cycle, b) vaporization of LIN from an ASU, c) a mixed hydrocarbon refrigerant, and d) pre-cooling to a first temperature (250 K to 300 K) optionally using NH3 and / or water. For the low-temperature range (20 K to 80 K), reference technologies include a closed-loop H2 cycle, He cycle, and / or Ne / He cycle.

[0005] It is known in the art that the largest piece of equipment in a cold box is the heat exchanger (typically brazed aluminum). As shown in Table I, the required heat exchanger surface area (which is directly related to UA, i.e., heat transfer coefficient x area) decreases significantly at lower temperatures. As a result, a typical good engineering practice would be to design multiple modules separated by temperature level (and different insulation types), and for each temperature level, design multiple parallel trains according to the heat exchange surface area. Thus, a typical engineering product would consist of M pre-cooling cold boxes and N liquefaction cold boxes, where M > N. In the table below, MR is mixed refrigerant, N2 is nitrogen, He is helium, Ne is neon, and H2 is hydrogen.

[0006] [Table 1]

[0007] Cold-end cooling (20 K to 80 K) is achieved by turboexpansion and / or isenthalpic expansion and / or vaporization of light gases such as H2, He, and Ne. Primary cooling is achieved by turboexpansion due to its high efficiency, but this facility is capacity-limited by the low molecular weight gas expansion technology. This is typically partially offset by the use of multiple expanders in series or parallel (e.g., 2 x 50%, 3 x 33%, etc.). However, for hydrogen liquefaction facilities, the capacity constraints that are limiting for low molecular weight turbines are on the order of 10 to 30 times smaller than the capacity constraints that are limiting for other primary processing facilities.

[0008] A typical hydrogen liquefaction process may include a pre-cooling section consisting of dual N2 expanders (one hot, one cold N2 expander) and a cooling / liquefaction section consisting of H2 or He expanders. In this example, if the LH2 liquefaction capacity is designed to maximize the utilization of a single hot and cold N2 turbine frame, the resulting number of H2 or He turbine units would be on the order of 10. Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, there is a need for processes and apparatus for mechanisms that allow utilization of greater capacity of other facilities. [Means for solving the problem]

[0010] The present invention relates to an apparatus and methods and devices that meet at least one of these needs.

[0011] The hydrogen liquefaction system includes a pre-cooling zone and a cooling / liquefaction zone. The pre-cooling zone includes a plurality of pre-cooling units to cool the H2 feed stream to a first intermediate temperature, which is then cooled / liquefied in the cooling / liquefaction zone. The cooling / liquefaction zone includes N units, each receiving at least a portion of the hydrogen stream separated from the pre-cooling zone, and the number of pre-cooling units is less than N. This is surprising and in contrast to the conventional wisdom discussed above and shown in Table I.

[0012] In a first embodiment, the intermediate temperature is in the range of 70 K to 300 K, preferably in the range of 70 K to 100 K. In one embodiment, the pre-cooling zone cools the H stream with a refrigerant comprising one or more of ammonia, mixed hydrocarbon nitrogen, or other known refrigerants.

[0013] In other embodiments, the cooling / liquefaction zone cools the H2 stream with a refrigerant comprising one or more of hydrogen, helium, and neon.

[0014] In other embodiments, there is an intermediate cooling zone where the hydrogen stream is cooled to a second intermediate temperature, where the number of units in the warmer section is less than the number of units in the cooler section. Optional embodiments can include multiple cooling stages, such as (1) water, (2) NH refrigerant, (3) mixed hydrocarbon refrigerant, (4) N refrigerant, and (5) H and / or He refrigerant.

[0015] In another embodiment, at least a portion of the low pressure refrigerant stream received from the cooling / liquefaction unit is sent to a refrigerant pre-cooling unit, and at least a portion of the HP refrigerant stream is cooled against a lower pressure return refrigerant stream.

[0016] In one embodiment, a hydrogen liquefaction apparatus may include a pre-cooling cold box having a heat exchanger disposed therein configured to cool a feed stream within the pre-cooling cold box by indirect heat exchange between the feed stream and a pre-cooling refrigerant; a plurality of liquefaction cold boxes in fluid communication with the pre-cooling cold box, each liquefaction cold box including its own heat exchanger, each heat exchanger in the plurality of liquefaction cold boxes configured to liquefy the feed stream by indirect heat exchange with a liquefied refrigerant; a pre-cooling cooling system configured to provide cooling to the pre-cooling zone; and a liquefaction cooling system configured to provide liquefied refrigerant to the plurality of liquefaction cold boxes, wherein there are a total of M pre-cooling cold boxes and a total of N liquefaction cold boxes, where M is less than N.

[0017] In an optional embodiment of the device, the liquefaction cooling system includes a recycle compression system and an expansion system, the recycle compression system configured to compress the liquefied refrigerant, and the expansion system configured to expand the liquefied refrigerant; There are a total of M recycle compression systems and / or a total of N liquefaction expansion systems, The recycle compression system includes one or more recycle compressors; One or more recycle compressors are arranged in parallel and / or series; The liquefaction expansion system includes one or more liquefaction expanders, the one or more liquefaction expanders being arranged in parallel and / or in series; The liquefied refrigerant is selected from the group consisting of hydrogen, neon, helium, and combinations thereof; The liquid refrigerant includes one or more of hydrogen, neon, and helium; The pre-cooling system includes a pre-cooling cooling cycle, The pre-cooling refrigerant is selected from the group consisting of nitrogen, argon, ammonia, carbon monoxide, carbon dioxide, water, hydrocarbons, mixed hydrocarbons, fluorocarbons, and combinations thereof; The pre-cooling refrigerant comprises one or more of nitrogen, argon, ammonia, carbon monoxide, carbon dioxide, water, hydrocarbons, mixed hydrocarbons, and fluorocarbons; The liquefaction cooling system includes a single common recycle compression system, The apparatus may further include an intermediate cold box in fluid communication with the pre-cooling cold box and the plurality of liquefaction cold boxes, the intermediate cold box being disposed between the pre-cooling cold box and the plurality of liquefaction cold boxes; and / or The ratio of the total number of N liquefaction cold boxes to the total number of M pre-cooling cold boxes is 1.25 to 3.0 (1.25≦N / M≦3.0).

[0018] In another embodiment, the liquefaction apparatus includes a first refrigeration cold box configured to receive a feed stream at an initial temperature T0 and to cool the feed stream to form a cooled feed stream at a refrigeration temperature T1; a first pre-cooling draw line configured to remove the cooled feed stream from the first refrigeration cold box; means for splitting the cooled feed stream, the means being in fluid communication with the pre-cooling draw line; and a plurality of secondary cold boxes in fluid communication with the means for splitting the cooled feed stream, the secondary cold boxes receiving the cooled feed stream from the means for splitting the cooled feed stream and liquefying the cooled feed stream therein to form a cooled feed stream at a liquefaction temperature T1. L and a plurality of secondary cold boxes configured to form a liquefied stream of M, where there are a total of M first refrigeration cold boxes and a total of N secondary cold boxes, where M is less than N.

[0019] In an optional embodiment of the device, each secondary cold box includes its own heat exchanger, and each heat exchanger in the plurality of secondary cold boxes is configured to liquefy the cooling supply stream by indirect heat exchange with a liquefied refrigerant; The apparatus may further include a liquefaction refrigeration system, the liquefaction refrigeration system including a recycle compression system and an expansion system, the recycle compression system configured to compress the liquefied refrigerant, and the expansion system configured to expand the liquefied refrigerant; The apparatus may further include means for combining the liquefied refrigerant, the means for combining the liquefied refrigerant being configured to receive the liquefied refrigerant from the warm ends of each of the plurality of secondary cold boxes via the plurality of pipes, and thereafter deliver the liquefied refrigerant to the first refrigeration cold box after being combined via the first return line; the apparatus may further include a second pre-cooling withdrawal line configured to withdraw the liquefied refrigeration stream from the cold end of the first refrigeration cold box; and / or The apparatus may further include means for splitting the liquefied cooling stream, the means for splitting the liquefied cooling stream in fluid communication with the second pre-cooling draw line.

[0020] In yet another embodiment, a hydrogen liquefaction method may include pre-cooling a hydrogen feed stream in a pre-cooling cold box having a heat exchanger disposed therein to form a cooled hydrogen stream, the heat exchanger being configured to cool the feed stream in the pre-cooling cold box by indirect heat exchange between the hydrogen feed stream and a pre-cooling refrigerant; withdrawing the cooled hydrogen stream from the pre-cooling cold box; and introducing the cooled hydrogen stream to a plurality of liquefaction cold boxes, wherein the cooled hydrogen stream is liquefied in the plurality of liquefaction cold boxes by indirect heat exchange against a liquefied refrigerant to form a product hydrogen stream in each of the plurality of liquefaction cold boxes, the product hydrogen stream being in liquid or quasi-liquid form, wherein there are a total of M pre-cooling cold boxes and a total of N liquefaction cold boxes, where M is less than N.

[0021] In an optional embodiment of the method, the liquefaction cooling system includes a recycle compression system and an expansion system, the recycle compression system configured to compress the liquefied refrigerant, and the expansion system configured to expand the liquefied refrigerant; There are a total of M recycle compression systems and a total of N liquefaction expansion systems. The recycle compression system includes one or more recycle compressors; One or more recycle compressors arranged in parallel or series, The liquefaction expansion system includes one or more liquefaction expanders, the one or more liquefaction expanders being arranged in parallel or in series; The liquefied refrigerant is selected from the group consisting of hydrogen, neon, helium, and combinations thereof; The liquid refrigerant includes one or more of hydrogen, neon, and helium; The pre-cooling system includes a pre-cooling cooling cycle, the pre-cooling refrigerant is selected from the group consisting of nitrogen, argon, ammonia, carbon monoxide, carbon dioxide, water, hydrocarbons, mixed hydrocarbons, fluorocarbons, and combinations thereof; The pre-cooling refrigerant comprises one or more of nitrogen, argon, ammonia, carbon monoxide, carbon dioxide, water, hydrocarbons, mixed hydrocarbons, and fluorocarbons; The cold end refrigeration cycle includes a single common recycle compression system, The method may also include an intermediate cold box in fluid communication with the pre-cooling cold box and the plurality of liquefaction cold boxes, the intermediate cold box being disposed between the pre-cooling cold box and the plurality of liquefaction cold boxes; The temperature of the cold end of the pre-cooling cold box is in the range of 30K to 250K. The temperature at the hot end of the liquefaction zone is in the range of 30K to 150K, and / or The ratio of the total number of N liquefaction cold boxes to the total number of M pre-cooling cold boxes is 1.25 to 3.0 (1.25≦N / M≦3.0).

[0022] In another embodiment, a liquefaction method includes the steps of introducing a feed stream at an initial temperature T0 into a pre-cooling cold box and cooling the feed stream therein to form a cooled feed stream at a cooled temperature T1; withdrawing the cooled feed stream from the pre-cooling box using a first pre-cooling withdrawal line; splitting the cooled feed stream into a first cooled feed stream and a second cooled feed stream; providing a plurality of sub-cooling cold boxes, the plurality of sub-cooling cold boxes including a first sub-cooling cold box and a second sub-cooling cold box; and introducing the first cooled feed stream into the first sub-cooling cold box under conditions effective to sub-cool the first cooled feed stream to form a product temperature T1. L forming a first product stream, wherein the first product stream is in liquid or quasi-liquid form; introducing a second cooled feed stream into a second sub-cooling cold box under conditions effective to sub-cool the second cooled feed stream to form a second product stream, wherein the second product stream is in liquid or quasi-liquid form; withdrawing the first and second product streams from the first and second sub-cooling cold boxes; and combining the first and second product streams into a final product stream.

[0023] In an optional embodiment of the liquefaction method, each secondary cold box includes its own heat exchanger, and each heat exchanger in the plurality of secondary cold boxes is configured to liquefy the feed stream by indirect heat exchange with a liquefied refrigerant; The liquefaction method may also include a liquefaction refrigeration system, the liquefaction refrigeration system including a recycle compression system and an expansion system, the recycle compression system configured to compress the liquefied refrigerant, and the expansion system configured to expand the liquefied refrigerant; The liquefaction method may also include means for combining the liquefied refrigerant, the means for combining the liquefied refrigerant being configured to receive the liquefied refrigerant from the warm ends of each of the plurality of secondary cold boxes via a plurality of pipes, and then send the liquefied refrigerant, after being combined, to the first cooling cold box via a first return line; The liquefaction method may also include a second pre-cooling draw line configured to remove the liquefied refrigerant stream from the first refrigeration cold box; The liquefaction method may also include means for splitting the liquefied refrigerant stream, the means for splitting the liquefied refrigerant stream being in fluid communication with the second pre-cooling draw line; and / or The feed stream consists essentially of hydrogen.

[0024] The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter which form the subject of the claims of the invention. Those skilled in the art will appreciate that the conception and specific embodiments disclosed herein may be modified or readily utilized as a basis for designing other structures for carrying out the same purposes of the present invention.

[0025] Those skilled in the art should also realize that such equivalent constructions do not depart from the subject matter and scope of the invention as set forth in the appended claims. The features and believed novel features of the invention, both as to its organization and method of operation, together with other features and advantages, will be better understood from the following description when considered in connection with the accompanying drawings. It is to be expressly understood, however, that the drawings are provided for the purpose of illustration and description only and are not intended as a definition of the limits of the invention.

[0026] For a more detailed understanding of the present invention, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which: [Brief explanation of the drawings]

[0027] [Figure 1] FIG. 1 is a process flow diagram of one embodiment of the prior art. [Figure 2] FIG. 2 shows an embodiment of the prior art. [Figure 3] FIG. 3 provides an embodiment of the present invention. [Figure 4] FIG. 4 provides another embodiment of the present invention. [Figure 5]FIG. 5 provides yet another embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0028] Certain embodiments of the present invention enable reduced capital expenditures by reducing the number of pre-cooling zones in a hydrogen liquefaction system having multiple cold end liquefaction zones. In certain embodiments, a hydrogen liquefaction system may have N cold end liquefaction zones while also having fewer than N pre-cooling zones (e.g., N-1, N-2, N-3, etc.).

[0029] As shown in Figure 1, prior art hydrogen liquefaction units use two identical trains 1a, 1b that operate separately from one another. Each train includes a pre-cooling zone 10 and a liquefaction zone 5. In Figure 1, refrigeration for pre-cooling zone 10 is provided by a closed-loop refrigeration circuit 11, which is provided by compression 2, 4, 6 and expansion 5, 7 of a pre-cooled refrigerant. Refrigeration for liquefaction zone 5 is provided by a second closed-loop refrigeration circuit 13.

[0030] 2 provides a flow chart for a hydrogen liquefaction unit having five trains, each train having six main sections: hydrogen compression, nitrogen compression, pre-cooling, refrigeration, liquefaction, and storage. These same trains can all operate independently of one another (i.e., the operating conditions of each train have little or no relationship to the operating conditions of the other trains).

[0031] 3 represents one embodiment of the present invention and provides a process flow diagram illustrating how a hydrogen liquefaction unit having two liquefaction zones 20, 25 can have one pre-cooling zone 10. Refrigeration for the pre-cooling zone 10 is provided by compression 2, 4, 6 and expansion 5, 7 of a pre-cooling refrigerant configured to cool the hydrogen feed to a first intermediate temperature in the range of 70K to 300K, more preferably 70K to 100K.

[0032] In one embodiment, the pre-cooling refrigerant can be ammonia, mixed hydrocarbons, nitrogen, or any other known refrigerant.

[0033] Following the pre-cooling zone, the hydrogen feed gas is split at 17, 19 and sent to two separate liquefaction zones 20, 25 where the hydrogen is condensed at 23a, 23b, and after removing any uncondensed gas in gas-liquid separator 39, the liquid hydrogen is finally sent to hydrogen liquid storage tank 40. In certain embodiments, the hydrogen may exit the heat exchanger in quasi-liquid form. As used herein, quasi-liquid form may include a supercritical fluid, i.e., any substance at a temperature and pressure above its critical point, where there are no distinct liquid and gas phases.

[0034] In another optional embodiment, boil-off gas 42, 43 withdrawn from hydrogen liquid storage tank 40 may be reheated in one or both liquefaction zones and then combined and further reheated in pre-cooling zone 10. The heated boil-off gas may then be compressed at 50 to become recycle boil-off gas 52, which may be fed into the hydrogen feed and / or may optionally provide make-up gas for a hydrogen recycle (not shown).

[0035] A cold end refrigerant 22, also cooled in pre-cooling zone 10, is withdrawn from pre-cooling zone 10 and then split into two streams 12, 14, and the cold end refrigerant is expanded in a set of turbines (15a, 15b) preferably having different inlet temperatures to provide refrigeration energy for the two liquefaction zones. After providing this refrigeration energy, the cold end refrigerant is withdrawn from the warm end of liquefaction zones 20, 25 and further heated in pre-cooling zone 10. After being sufficiently heated, the cold end refrigerant is then compressed again 24 as part of its refrigeration cycle. As an optional embodiment, each of the expansion turbines in the set of turbines (15a, 15b) can be two or more turbines in parallel.

[0036] 4 again provides an alternative embodiment of one pre-cooling zone 10 for the hydrogen feed stream. However, in this embodiment, the cold end refrigerant is not used to provide any pre-cooling energy (e.g., the cold end refrigerant enters another heat exchanger 30 to cool a portion of the cold end refrigerant rather than re-entering the pre-cooling zone 10 for reheating). Rather, all of the pre-cooling of the hydrogen feed stream is performed by the pre-cooling refrigerant in the closed-loop refrigeration circuit 11. In this way, there is a simple set of standardized modular pre-cooling heat exchangers and cold boxes, and another set of complex custom exchangers and cold boxes. The customized complex set can include most of the project-specific complexities, such as H2 feed, purification, and pre-cooling cycles.

[0037] The cooling balance between the simple and complex heat exchanger sets is achieved by adjusting the split of the HP refrigerant flow between the simple and complex cores (as shown in the diagram) and / or isolating one of the low-pressure refrigerant return flows between the simple and complex cores. The number of simple heat exchangers / cold boxes is independent of the number of complex heat exchangers / cold boxes. Similarly, there can be a set of modular simple standard liquefaction heat exchangers / cold boxes integrated with the liquefaction refrigerant system, whereby more complex site details (H2 product subcooling and boil-off return) can be managed in separate customized heat exchangers / cold boxes.

[0038] As in Figure 3, the hydrogen feed stream is again split into two, 17 and 19, and then further cooled and liquefied in multiple (two in this embodiment) liquefaction zones 20 and 25. In Figure 4, the cold end refrigerant is split into two streams 31 and 33, with one stream 31 first cooled in pre-cooling zone 10 and the second stream 33 cooled in second heat exchanger 30. This second heat exchanger does not involve cooling of the hydrogen feed stream, thereby allowing for more flexibility in the cooling temperature within this second heat exchanger. For example, this portion of cold end refrigerant 33 can be cooled to a lower temperature than the cold end refrigerant 31 in the pre-cooling zone. In other words, the cold end temperature of the second heat exchanger can be different from the cold end temperature of the pre-cooling zone.

[0039] Following the first cooling, the two cold end refrigerant streams can be mixed together before being split into two and sent to two separate liquefaction zones. By coupling the two cold end refrigerant streams together, the two streams used to liquefy hydrogen in the liquefaction zones will have substantially similar temperatures, allowing the same train to be used, resulting in significant reductions in engineering and manufacturing costs and thereby complexity. Thus, according to the embodiment shown in Figure 4, the temperature of the cold end refrigerant can be changed prior to its introduction into the hydrogen liquefaction unit, offering the advantage that the temperature is not directly tied to the hydrogen feed gas being liquefied and may offer modular (standardized package) options for portions of the pre-cooling cooling system.

[0040] Although Figure 4 does not show boil-off gas recycle, one skilled in the art will recognize that the boil-off gas recycle shown in Figure 3 may also be used in the embodiment shown in Figure 4. Thus, the absence of this element in Figure 4 should not be construed as limiting.

[0041] Figure 5 provides a process flow diagram according to one embodiment of the present invention. As can be seen, this embodiment includes five trains for the liquefaction unit. Therefore, in this embodiment, N=5. However, only one train for pre-cooling is required. This means that the illustrated embodiment includes four fewer pre-cooling systems than prior art embodiments. Therefore, embodiments of the present invention can produce the same amount of liquid hydrogen as prior art methods while requiring less capital investment to do so.

[0042] While the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions, and alterations can be made herein without departing from the subject matter and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the processes, machines, manufacture, compositions of matter, means, methods, and steps described herein. As will be readily apparent to those skilled in the art from this disclosure, any existing or later-developed processes, machines, manufacture, compositions of matter, means, methods, or steps that perform substantially the same function or achieve substantially the same results as the corresponding embodiments described herein can be utilized in accordance with the present invention. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

[0043] The present invention may suitably comprise, consist of, or consist essentially of elements disclosed herein, or may be practiced without elements not disclosed. Furthermore, when there is language indicating a sequence, such as first or second, this should be interpreted in an illustrative sense, not a limiting sense. For example, one skilled in the art will recognize that certain steps can be combined into one step or the order can be reversed.

[0044] Unless the context clearly requires otherwise, the singular forms "a", "an", "per se" and "the" include the plural forms.

[0045] The term "comprising" in the claims is an open-ended transitional phrase indicating a non-exclusive listing of the claim elements specified thereafter (i.e., other elements may additionally be included and are within the scope of the "comprising"). As used herein, "comprising" may be replaced with more restrictive transitional phrases such as "consisting essentially of" and "consisting of," unless otherwise stated herein.

[0046] "Providing" in the claims is defined to mean furnishing, supplying, providing, or preparing something. It is understood that steps may be performed by any actor, absent express language to the contrary in the claims, the scope is stated, and other embodiments flow therefrom.

[0047] Optionally or optionally means that the subsequently described event or circumstance may or may not occur. The description includes instances in which the event or circumstance occurs and instances in which it does not occur.

[0048] Ranges may be expressed herein as from about a particular value and / or to about another particular value, including all combinations within that range.

[0049] All references set forth herein are hereby incorporated by reference in their entirety and individually for the specific information for which each is cited.

Claims

1. A method for liquefying hydrogen, comprising: pre-cooling the hydrogen feed stream to form a cooled hydrogen stream in one or more pre-cooling cold boxes comprising a pre-cooling zone, the pre-cooling cold boxes having a heat exchanger disposed therein, the heat exchanger configured to cool the hydrogen feed stream within the one or more pre-cooling cold boxes by indirect heat exchange between the hydrogen feed stream and a pre-cooling refrigerant; withdrawing the cooled hydrogen stream from the one or more pre-cooling cold boxes; introducing the cooled hydrogen stream into a plurality of liquefaction cold boxes constituting a liquefaction zone, wherein the cooled hydrogen stream is liquefied in the plurality of liquefaction cold boxes by indirect heat exchange against a liquefied refrigerant to form a product hydrogen stream in each of the plurality of liquefaction cold boxes, the product hydrogen stream being in liquid or quasi-liquid form; Including, there are M total pre-cooling cold boxes and N total liquefaction cold boxes, where M is less than N; the liquefied refrigerant is supplied by a liquefaction refrigeration system, the liquefaction refrigeration system including a recycle compression system and a liquefaction expansion system, the recycle compression system configured to compress the liquefied refrigerant, and the liquefaction expansion system configured to expand the liquefied refrigerant; the liquefaction expansion system includes one or more liquefaction expanders, the one or more liquefaction expanders being arranged in parallel or in series; the temperature of the cold end of the one or more pre-cooled cold boxes is in the range of 30 K to 250 K; the temperature at the hot end of the liquefaction zone is in the range of 30 K to 150 K; The hydrogen liquefaction method, wherein the liquefied refrigerant comprises one or more of hydrogen, neon, and helium.

2. 10. The method of claim 1, wherein there are M total recycle compression systems and N total liquefaction expansion systems. The hydrogen liquefaction method according to claim 1.

3. 10. The method of claim 1, wherein the recycle compression system comprises one or more recycle compressors arranged in parallel or in series.

4. 2. The hydrogen liquefaction method according to claim 1, wherein the pre-cooling refrigerant is supplied by a pre-cooling refrigeration cycle.

5. 10. The method of claim 1, wherein the pre-cooling refrigerant comprises one or more of nitrogen, argon, ammonia, carbon monoxide, carbon dioxide, water, hydrocarbons, mixed hydrocarbons, and fluorocarbons.

6. A hydrogen liquefaction method as described in claim 1, wherein the liquefaction cooling system includes a single common recycle compression system.

7. 2. The hydrogen liquefaction method of claim 1, further comprising an intermediate cold box in fluid communication with the one or more pre-cooling cold boxes and the plurality of liquefaction cold boxes, the intermediate cold box being disposed between the one or more pre-cooling cold boxes and the plurality of liquefaction cold boxes.

8. 2. The hydrogen liquefaction method according to claim 1, wherein the ratio of the total number of N liquefaction cold boxes to the total number of M pre-cooling cold boxes is 1.25 to 3.0 (1.25≦N / M≦3.0).

9. A hydrogen liquefaction apparatus comprising: one or more pre-cooling cold boxes constituting a pre-cooling zone, the one or more pre-cooling cold boxes having heat exchangers disposed therein configured to cool a feed stream within the one or more pre-cooling cold boxes by indirect heat exchange between the feed stream and a pre-cooling refrigerant; a plurality of liquefaction cold boxes in fluid communication with the one or more pre-cooling cold boxes, each liquefaction cold box including its own heat exchanger, each heat exchanger in the plurality of liquefaction cold boxes configured to liquefy the feed stream by indirect heat exchange with a liquefied refrigerant; a pre-cooling cooling system configured to provide cooling to the pre-cooling zone; a liquefaction cooling system configured to provide the liquefied refrigerant to the plurality of liquefaction cold boxes; Including, there are M total pre-cooling cold boxes and N total liquefaction cold boxes, where M is less than N; The liquefaction refrigeration system includes a recycle compression system and a liquefaction expansion system, the recycle compression system configured to compress the liquefied refrigerant, and the liquefaction expansion system configured to expand the liquefied refrigerant.

10. 10. The hydrogen liquefaction apparatus of claim 9, wherein there are a total of M recycle compression systems and / or a total of N liquefaction expansion systems.

11. 10. The hydrogen liquefaction apparatus of claim 9, wherein the recycle compression system includes one or more recycle compressors.

12. 12. The hydrogen liquefaction apparatus of claim 11, wherein the one or more recycle compressors are arranged in parallel and / or in series.

13. A hydrogen liquefaction apparatus as described in claim 9, wherein the liquefaction expansion system includes one or more liquefaction expanders, the one or more liquefaction expanders being arranged in parallel and / or series.

14. 10. The hydrogen liquefaction apparatus of claim 9, wherein the liquefied refrigerant is selected from the group consisting of hydrogen, neon, helium, and combinations thereof.

15. 10. The hydrogen liquefaction apparatus of claim 9, wherein the liquefied refrigerant comprises one or more of hydrogen, neon, and helium.

16. The hydrogen liquefaction apparatus of claim 9 , wherein the pre-cooling refrigeration system includes a pre-cooling refrigeration cycle.

17. 10. The hydrogen liquefaction apparatus of claim 9, wherein the pre-cooling refrigerant is selected from the group consisting of nitrogen, argon, ammonia, carbon monoxide, carbon dioxide, water, hydrocarbons, mixed hydrocarbons, fluorocarbons, and combinations thereof.

18. 10. The hydrogen liquefaction apparatus of claim 9, wherein the pre-cooling refrigerant comprises one or more of nitrogen, argon, ammonia, carbon monoxide, carbon dioxide, water, hydrocarbons, mixed hydrocarbons, and fluorocarbons.

19. 10. The hydrogen liquefaction apparatus of claim 9, wherein the liquefaction cooling system includes a single common recycle compression system.

20. 10. The hydrogen liquefaction apparatus of claim 9, further comprising an intermediate cold box in fluid communication with the one or more pre-cooling cold boxes and the plurality of liquefaction cold boxes, the intermediate cold box being disposed between the one or more pre-cooling cold boxes and the plurality of liquefaction cold boxes.

21. 10. The hydrogen liquefaction apparatus according to claim 9, wherein the ratio of the total N liquefaction cold boxes to the total M pre-cooling cold boxes is 1.25 to 3.0 (1.25≦N / M≦3.0).

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