DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Election/Restrictions
Applicant's election with traverse of Species 2 and Subspecies B in the reply filed on March 12th. 2026 is acknowledged. The traversal is on the grounds that “it implies the chemical and thermal parameter claims are species-specific. Claims 3, 7-9, and 14-18 are directed to the chemical composition and molar proportions of the "first cycle gas." These chemical requirements are independent of the hardware configuration (the number of phase separators). Similarly, Claims 10, 19, and 20 are directed to system-level thermal targets and purification steps that apply regardless of the specific hardware embodiment elected”. The Examiner agrees claims 3, 7-10, and 14-20 are generic.
However, the requirement is still deemed proper and is therefore made FINAL.
Claim Objections
Claims 1-20 are objected to because of the following informalities:
Claim 1, lines 9-10: “a first set of the heat exchanger(s)” should read “a first set of the plurality of heat exchangers”
Claim 1, lines 13-14: “a second set of the heat exchanger(s)” should read “a second set of the plurality of heat exchangers”
Claim 1, lines 17-18: “a third set of the heat exchanger(s)” should read “a third set of the plurality of heat exchangers”
Claim 1, line 36: “the first set of the heat exchangers” should read “the first set of the plurality of heat exchangers”
Claim 1, line 45: “the first set of the heat exchangers” should read “the first set of the plurality of heat exchangers”
Claim 2, line 2: “a refrigeration cycle” should read “the closed refrigeration cycle”
Claim 4, line 5: “one of the compressors” should read “one of the at least two centrifugal compressors”
Claim 4, line 8: “the compressors” should read “the at least two centrifugal compressors”
Claim 5, lines 4-5: “a first initial temperature” should read “the first initial temperature”
Claim 5, line 5: “a second temperature” should read “the second temperature”
Claim 5, lines 5-6: “the first set of the heat exchanger(s)” should read “the first set of the plurality of heat exchangers”
Claim 5, line 8: “the second set of the heat exchangers” should read “the second set of the plurality of heat exchangers”
Claim 5, line 10: “a third set of the heat exchangers” should read “the third set of the plurality of heat exchangers”
Claim 5, line 17: “a two-phase fluid” should read “the two-phase fluid”
Claim 5, line 18: “a first phase separator” should read “the first phase separator”
Claim 5, line 19: “a gas” should read “the gas”
Claim 5, line 20: “a liquid” should read “the liquid”
Claim 5, lines 22-23: “a second phase separator” should read “the second phase separator”
Claim 5, line 25: “the first set of the heat exchangers” should read “the first set of the plurality of heat exchangers”
Claim 5, line 27: “a third phase separator” should read “the third phase separator”
Claim 5, lines 33-34: “the first set of the heat exchangers” should read “the first set of the plurality of heat exchangers”
Claim 5, lines 34-35: “the centrifugal compressor” should read “the centrifugal compressor”
Claim 9, line 2: “light component(s)” should read “of the at least one light component”
Claim 9, lines 2-3: “medium component(s)” should read “of the at least one medium component”
Claim 9, line 3: “heavy component(s)” should read “of the at least one heavy component”
Claim 12, line 4: “at least one compressor” should read “at least one compressor of the at least two compressors”
Claim 12, line 4: “the two compressors” should read “the at least two compressors”
Claim 13, line 3: “a first of the turbines” should read “a first of the at least two expansion turbines”
Claim 13, lines 4-5: “a second of the turbines” should read “a second of the at least two expansion turbines”
Claim 15, line 2: “41% C3H8,,” should read “41% C3H8,”
Claim 18, line 3: “of 3%; 37%, 32%, 13% and 14%” should read “of 3%, 37%, 32%, 13% and 14%””
Claim 19, line 3: “these two pre-cooling portions” should read “the first pre-cooling device and the second pre-cooling device”
Claim 20, line 3: “these two pre-cooling portions” should read “the second pre-cooling device and the cooling system”
Claims 2-5 are also objected to by virtue of their dependency on claim 1.
Claims 6-8, 10-11, 14-20 are also objected to by virtue of their dependency on claim 5.
Claim 9 is also objected to by virtue of its dependency on claim 8.
Claims 12-13 are also objected to by virtue of their dependency on claim 11.
Appropriate correction is required.
Claim Interpretation
The following is a quotation of 35 U.S.C. 112(f):
(f) Element in Claim for a Combination. – An element in a claim for a combination may be expressed as a means or step for performing a specified function without the recital of structure, material, or acts in support thereof, and such claim shall be construed to cover the corresponding structure, material, or acts described in the specification and equivalents thereof.
The following is a quotation of pre-AIA 35 U.S.C. 112, sixth paragraph:
An element in a claim for a combination may be expressed as a means or step for performing a specified function without the recital of structure, material, or acts in support thereof, and such claim shall be construed to cover the corresponding structure, material, or acts described in the specification and equivalents thereof.
The claims in this application are given their broadest reasonable interpretation using the plain meaning of the claim language in light of the specification as it would be understood by one of ordinary skill in the art. The broadest reasonable interpretation of a claim element (also commonly referred to as a claim limitation) is limited by the description in the specification when 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, is invoked.
As explained in MPEP § 2181, subsection I, claim limitations that meet the following three-prong test will be interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph:
(A) the claim limitation uses the term “means” or “step” or a term used as a substitute for “means” that is a generic placeholder (also called a nonce term or a non-structural term having no specific structural meaning) for performing the claimed function;
(B) the term “means” or “step” or the generic placeholder is modified by functional language, typically, but not always linked by the transition word “for” (e.g., “means for”) or another linking word or phrase, such as “configured to” or “so that”; and
(C) the term “means” or “step” or the generic placeholder is not modified by sufficient structure, material, or acts for performing the claimed function.
Use of the word “means” (or “step”) in a claim with functional language creates a rebuttable presumption that the claim limitation is to be treated in accordance with 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph. The presumption that the claim limitation is interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, is rebutted when the claim limitation recites sufficient structure, material, or acts to entirely perform the recited function.
Absence of the word “means” (or “step”) in a claim creates a rebuttable presumption that the claim limitation is not to be treated in accordance with 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph. The presumption that the claim limitation is not interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, is rebutted when the claim limitation recites function without reciting sufficient structure, material or acts to entirely perform the recited function.
Claim limitations in this application that use the word “means” (or “step”) are being interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, except as otherwise indicated in an Office action. Conversely, claim limitations in this application that do not use the word “means” (or “step”) are not being interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, except as otherwise indicated in an Office action.
This application includes one or more claim limitations that do not use the word “means,” but are nonetheless being interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, because the claim limitation(s) uses a generic placeholder that is coupled with functional language without reciting sufficient structure to perform the recited function and the generic placeholder is not preceded by a structural modifier. Such claim limitation(s) is/are:
Claim 1, lines 5-6 recite, “at least one liquefied hydrogen collection member” which draws corresponding structure to the following recitation of the present disclosure, “The hydrogen collection member 30 may comprise, for example, at least one cryogenic storage unit (Paragraph 60 of PGPUB US 2024/0393041)”, or equivalents thereof.
Claim 1, line 29 recites, “a cooling member” which draws corresponding structure to the following recitation of the present disclosure, “a cooling member 180 for the compressed first cycle gas (for example, a heat exchanger cooled by a heat transfer fluid such as water, for example) (Paragraph 66 of PGPUB US 2024/0393041)”, or equivalents thereof.
Claim 1, line 32 recites, “a pair of second compression members” which draws corresponding structure to the following recitation of the present disclosure, “second respective compression members 38, 58 (a compressor 38 and a pump 58) (Paragraph 66 of US PGPUB 2024/0393041)”, or equivalents thereof.
Claim 1, line 39 recites, “a first expansion member” which draws corresponding structure to the following recitation of the present disclosure, “a first expansion member 78 such as a valve (Paragraph 71 of US PGPUB 2024/0393041)”, or equivalents thereof.
Claim 2, line 4 recites, “an expansion member” which draws corresponding structure to the following recitation of the present disclosure, “a first expansion member 78 such as a valve (Paragraph 71 of US PGPUB 2024/0393041)”, or equivalents thereof.
Because this/these claim limitation(s) is/are being interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, it/they is/are being interpreted to cover the corresponding structure described in the specification as performing the claimed function, and equivalents thereof.
If applicant does not intend to have this/these limitation(s) interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, applicant may: (1) amend the claim limitation(s) to avoid it/them being interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph (e.g., by reciting sufficient structure to perform the claimed function); or (2) present a sufficient showing that the claim limitation(s) recite(s) sufficient structure to perform the claimed function so as to avoid it/them being interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 1-20 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
A broad range or limitation together with a narrow range or limitation that falls within the broad range or limitation (in the same claim) may be considered indefinite if the resulting claim does not clearly set forth the metes and bounds of the patent protection desired. See MPEP § 2173.05(c). In the present instance, claim 1 recites the broad recitation “which is below the first initial temperature”, and the claim also recites “and is between 120 K and 163 K” which is the narrower statement of the range/limitation. The claim(s) are considered indefinite because there is a question or doubt as to whether the feature introduced by such narrower language is (a) merely exemplary of the remainder of the claim, and therefore not required, or (b) a required feature of the claims. For purposes of examination, the Examiner will interpret the narrower language as (a) merely exemplary of the remainder of the claim, and therefore not required.
A broad range or limitation together with a narrow range or limitation that falls within the broad range or limitation (in the same claim) may be considered indefinite if the resulting claim does not clearly set forth the metes and bounds of the patent protection desired. See MPEP § 2173.05(c). In the present instance, claim 1 recites the broad recitation “which is below the second temperature”, and the claim also recites “and is between 103 K and 80 K” which is the narrower statement of the range/limitation. The claim(s) are considered indefinite because there is a question or doubt as to whether the feature introduced by such narrower language is (a) merely exemplary of the remainder of the claim, and therefore not required, or (b) a required feature of the claims. For purposes of examination, the Examiner will interpret the narrower language as (a) merely exemplary of the remainder of the claim, and therefore not required.
Claim 1, line 27 recites, “wherein the second refrigeration cycle of the first pre-cooling device comprises” which is unclear to the Examiner as line 23 of claim 1 attributes a closed refrigeration cycle to the first pre-cooling device. For purposes of examination, the Examiner will interpret the claim to read “wherein the closed refrigeration cycle of the first pre-cooling device comprises”. The Examiner recommends amending the claim as interpreted herein.
Claim 1, line 34 recite, “the two-phase fluid” which is unclear to the Examiner as to how the two-phase fluid of line 34 relates to the two-phase fluid of line 30 produced by the cooling member. For purposes of examination, the Examiner will interpret the claim to read “a two-phase fluid produced by the pair of second compression members”. The Examiner recommends amending the claim as interpreted herein.
Claim 2 recites the limitation "the refrigerator" in lines 1-2. There is insufficient antecedent basis for this limitation in the claim. The Examiner recommends changing "the refrigerator" in lines 1-2 of claim 2 to “a refrigerator”.
Claim 4 recites the limitation "the refrigerator" in lines 1-2. There is insufficient antecedent basis for this limitation in the claim. The Examiner recommends changing "the refrigerator" in lines 1-2 of claim 2 to “a refrigerator”.
Claim 4, lines 3-5 recite, “at least one expansion turbine of the second cycle gas coupled to a rotating shaft which is preferably also coupled to one of the compressors” which is unclear the Examiner if the recitation of “preferably also coupled to one of the compressors” is a required limitation of the claims or optional. For purposes of examination, the Examiner will interpret “preferably also coupled to one of the compressors” to be an optional limitation of the claims and therefore not required. The Examiner recommends making amendments to clarify whether or not the rotating shaft of the at least one expansion turbine is required to be coupled to one of the compressors.
Claim 5, line 5 recites, “a second temperature of 163 K or below” which is unclear to the Examiner as the range for the second temperature of claim 1 from which claim 5 depends is said to be between 120 K and 163 K, therefore the recitation of line 5 does not further limit the claim, but broaden the claim. For purposes of Examination, the Examiner will interpret the second temperature of claim 5 to have the same required temperature range of the second temperature of claim 1. The Examiner recommends amending the claim to have the same or a lesser temperature range than the second temperature of claim 1.
Claim 5, lines 7-8 recites, “the third temperature of 103 K or below” which is unclear to the Examiner as the range for the second temperature of claim 1 from which claim 5 depends is said to be between 103 K and 80 K, therefore the recitation of lines 7-8 does not further limit the claim, but broaden the claim. For purposes of examination, the Examiner will interpret the third temperature of claim 5 to have the same required temperature range of the third temperature of claim 1. The Examiner recommends amending the claim to have the same or a lesser temperature range than the third temperature of claim 1.
Claim 5 recites the limitation "the temperature below the critical temperature" in line 11. There is insufficient antecedent basis for this limitation in the claim. The Examiner recommends changing "the temperature below the critical temperature" in line 11 to “the fourth temperature below the critical temperature”. For purposes of examination, the Examiner will interpret the claim as recommended herein.
Claim 5, lines 19-20 recite, “compressing a gas from the first phase separator in a second centrifugal compressor, and pressurizing a liquid from the first phase separator” which is unclear to the Examiner as to how the second centrifugal compressor of claim 5 relates to the pair of second compression members configured to compress a gas and liquid from the first phase separator of claim 1 from which claim 5 depends. For purposes of examination, the Examiner will interpret the claim to read “compressing a gas from the first phase separator in a second centrifugal compressor of the pair of second compression members, and pressurizing a liquid from the first phase separator”. The Examiner recommends amending the claim to read as interpreted herein.
Claim 10, lines 3-7 recite, “at which the hydrogen flow is sent to an adsorption purification unit operating at a cryogenic temperature, and then, if necessary, to a catalytic conversion unit for converting ortho hydrogen to para hydrogen, in order to produce a hydrogen flow having a para hydrogen content of between 30% and 55% before being re-cooled” which is unclear to the Examiner as to when it would or would not be “necessary” to send the flow to a catalytic conversion unit for converting ortho hydrogen to para hydrogen. For purposes of examination, the Examiner will interpret “and then, if necessary, to a catalytic conversion unit for converting ortho hydrogen to para hydrogen” to be an optional recitation of the claims and therefore not required.
Claim 11, lines 6-7 recite, “at least one expansion turbine” which is unclear to the Examiner as to how the at least one expansion turbine relates to the at least one valve or turbine of claim 11. For purposes of examination, the Examiner will interpret the at least one expansion turbine and the turbine of claim 11 to be the same components. The Examiner recommends making clarifying amendments to clarify the relation between the turbine and the at least one expansion turbine.
Claim 11, lines 6-7 recite, “at least one expansion turbine providing mechanical work if necessary for driving at least one compressor” which is unclear to the Examiner as to when it would or would not be “necessary” for the at least one expansion turbine to provide mechanical work for driving at least one compressor. For purposes of examination, the Examiner will interpret “at least one expansion turbine providing mechanical work if necessary for driving at least one compressor” to be an optional recitation of the claims and therefore not required.
A broad range or limitation together with a narrow range or limitation that falls within the broad range or limitation (in the same claim) may be considered indefinite if the resulting claim does not clearly set forth the metes and bounds of the patent protection desired. See MPEP § 2173.05(c). In the present instance, claim 16 recites the broad recitation “wherein the first cycle gas consists of a mixture of four components from among: CH4 and/or N2, C2H6 and/or C3H8, C5H10”, and the claim also recites “expressed in moles as 49% CH4, 11 % C2H6, 31 % C3H8 and 9% C5H10” which is the narrower statement of the range/limitation. The claim(s) are considered indefinite because there is a question or doubt as to whether the feature introduced by such narrower language is (a) merely exemplary of the remainder of the claim, and therefore not required, or (b) a required feature of the claims. For purposes of examination, the Examiner will interpret the narrower language as (a) merely exemplary of the remainder of the claim, and therefore not required.
Claim 18, lines 3 recites, “of 3%; 37%, 32%, 13% and 14%” which Is unclear to the Examiner as these percentages only add up to 99%. For purposes of examination, the Examiner will interpret the claim to allow for any of these percentages to be 1% higher than claimed. The Examiner recommends amending the claim to ensure the percentages add up to 100%.
Claims 2-5 are also rejected by virtue of their dependency on claim 1.
Claims 6-8, 10-11, 14-20 are also rejected by virtue of their dependency on claim 5.
Claim 9 is also rejected by virtue of its dependency on claim 8.
Claims 12-13 are also rejected by virtue of their dependency on claim 11.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
Claims 1-2, 4-7, 10-12, and 19-20 are rejected under 35 U.S.C. 103 as being unpatentable over Grenier (US Patent No. 5,579,655) in view of Watanabe et al. (US 20190063824), hereinafter Watanabe and Ducote, Jr. et al. (US 20230366620), hereinafter Ducote.
Regarding claim 1, Grenier discloses an installation for the liquefaction of hydrogen, the installation (Fig. 1; Col. 2, lines 13-21, FIG. 1 represents schematically a portion of a hydrogen liquefaction apparatus according to the invention. There is shown in the drawing the diagram of a hydrogen liquefaction installation, except its coldest portion, which is conventional and in which the precooled cycle hydrogen is cooled, liquefied and expanded to produce the cold necessary for the liquefaction of the treated hydrogen or "process hydrogen") comprising:
a supply circuit for supplying hydrogen to be cooled, having an upstream end designed to be connected to a source of gaseous hydrogen under pressure at a first initial temperature and (Fig. 1, conduits 26-29; Col. 2, lines 37-42, Hydrogen to be liquefied arrives under 20 bars pressure via a conduit 26, is precooled in passages 27 of exchanger 3 to about -178° C., and is further cooled to about -192° C. in the passages 28 of the exchanger 4, from which it issues via conduit 29 to be sent to the cold portion of the installation; Further, the teachings of the hydrogen arriving imply the upstream in is designed to be connected to a source of gaseous hydrogen under pressure since it has been held in considering the disclosure of a reference, it is proper to take into account not only specific teachings of the reference but also the inferences which one skilled in the art would reasonably be expected to draw therefrom (MPEP 2144.01));
a plurality of heat exchangers arranged in series in heat exchange with the supply circuit (Fig. 1, heat exchangers 3 and 4; Col. 2, lines 37-42, Hydrogen to be liquefied arrives under 20 bars pressure via a conduit 26, is precooled in passages 27 of exchanger 3 to about -178° C., and is further cooled to about -192° C. in the passages 28 of the exchanger 4, from which it issues via conduit 29 to be sent to the cold portion of the installation);
a first pre-cooling device in heat exchange with a first set of the heat exchanger(s), the first pre-cooling device being configured to reduce the temperature of the hydrogen from the first initial temperature to a second temperature, which is below the first initial temperature, and is between 120 K and 163 K (See annotated Fig. 1 of Grenier below, first pre-cooling device A is in heat exchange with exchanger 3; Col. 2, lines 37-39, Hydrogen to be liquefied arrives under 20 bars pressure via a conduit 26, is precooled in passages 27 of exchanger 3 to about -178° C; Further, the first pre-cooling device of Grenier has the same structure as the claimed first pre-cooling device and is capable of functioning in the manner claimed; As best understood, see 112(b) rejections above);
a second pre-cooling device in heat exchange with a second set of the heat exchangers, the second pre-cooling device being configured to reduce the temperature of the hydrogen from the second temperature to a third temperature, which is below the second temperature, and is between 103 K and 80 K (See annotated Fig. 1 of Grenier below, second pre-cooling device B is in heat exchanger with exchangers 3 and 4; Col. 2, lines 39-42, further cooled to about -192° C. in the passages 28 of the exchanger 4, from which it issues via conduit 29 to be sent to the cold portion of the installation; Further, the second pre-cooling device of Grenier has the same structure as the claimed second pre-cooling device and is capable of functioning in the manner claimed; As best understood, see 112(b) rejections above),
wherein the second pre-cooling device comprises a second refrigeration cycle for a second cycle gas consisting of nitrogen (See annotated Fig. 1 of Grenier below, second pre-cooling device B includes compressor 2, refrigerator 16, fan 8, expansion turbine 9, separator 13, expansion valves 24-25 and connecting passages 33-37; Col. 2, lines 23-24, a nitrogen cycle compressor 2, also of the centrifugal or axial type),
wherein the first pre-cooling device comprises a closed refrigeration cycle for a first cycle gas comprising at least three components including at least one first component that is more volatile than at least one second component, the at least one second component being more volatile than at least one third component (See annotated Fig. 1 of Grenier below, first pre-cooling device A includes, compressor 1, refrigerators 14-15, separators 10-12, column 5, expansion valves 18-23 and connecting passages 38-48, Col. 3, lines 6-11, The first stage of compressor 1 is supplied under about 1 bar with the following mixture: H2=66.8%, C2H6=14.2%, C3H8=11.5%, C5H12=7.5 %),
wherein the second refrigeration cycle of the first pre-cooling device comprises:
a first centrifugal compressor for the first cycle gas (Fig. 1, compressor 1; Col. 2, lines 22-23, There will thus be seen on the drawing a hydrogen cycle compressor 1, of the centrifugal or axial type);
a cooling member for the compressed first cycle gas configured to produce a two-phase fluid (Fig. 1, refrigerator 15; Col. 3, lines 36-38, The high pressure mixture from the last stage of compressor 1 is brought to the vicinity of ambient temperature in 15 and introduced into the separator 11; Further, the refrigerator 15 of Grenier has the same structure as the claimed cooling member and is capable of functioning in the manner claimed);
a first phase separator configured to separate the two-phase fluid (Fig. 1, separator 11, passage 43; Col. 3, lines 39-49, The liquid phase collected in this latter is subcooled to about -45° C. and divided into two fractions. The first fraction, after expansion to about 6 bars in 19, is vaporized in the passages 39 and then reunited with the mixture from the expansion valve 18. The other fraction, after expansion to about 1 bar in 20, is vaporized and reheated in the passages 41 of exchanger 3, then returned to the intake of the first stage of the compressor 1 via a conduit 42. The vapor phase from separator 11 is cooled to about -120° C., while being partially liquified in passages 43 of exchanger 3, then introduced into the separator 12; Further, the separator 11 of Grenier has the same structure as the claimed first phase separator and is capable of functioning in the manner claimed);
a second phase separator configured to separate the two-phase fluid produced by the pair of second compression members (Fig. 1, separator 12; Col. 3, lines 49-62, The liquid phase collected in this latter is in its tum divided into two fractions which, after expansion respectively to about 6 bars and about 1 bar in 21 and 22, vaporizes in passages 39 and 41 respectively, then is reunited with the previously mentioned fractions introduced into the passages at higher temperature levels. The vapor phase from separator 12, constituted of hydrogen containing about 1 part per million of propane and 0.3% ethane, is reintroduced into the exchanger 3, cooled to the cold end of this exchanger in passages 44 of the latter, then introduced into the base of column 5, which is supplied at its head, via a conduit 45, with subcooled liquid propane from the reserve of makeup propane of the hydrogen cycle; Further, the separator 12 of Grenier has the same structure as the claimed second phase separator and is capable of functioning in the manner claimed);
a first duct in heat exchange with the first set of the heat exchangers and configured to cool and partially condense gas produced by the second phase separator and to transfer this partially condensed gas to a third phase separator (Fig. 1, passage 44, column 5; The vapor phase from separator 12, constituted of hydrogen containing about 1 part per million of propane and 0.3% ethane, is reintroduced into the exchanger 3, cooled to the cold end of this exchanger in passages 44 of the latter, then introduced into the base of column 5, which is supplied at its head, via a conduit 45, with subcooled liquid propane from the reserve of makeup propane of the hydrogen cycle; Further, the passage 44 of Grenier has the same structure as the claimed first duct and is capable of functioning in the manner claimed);
a first expansion member configured to expand a liquid produced by the second phase separator (Fig. 1, expansion valves 21-22; Col. 3, lines 49-55, The liquid phase collected in this latter is in its tum divided into two fractions which, after expansion respectively to about 6 bars and about 1 bar in 21 and 22, vaporizes in passages 39 and 41 respectively, then is reunited with the previously mentioned fractions introduced into the passages at higher temperature levels; Further, the expansion valves 21-22 of Grenier has the same structure as the claimed first expansion member and are capable of functioning in the manner claimed); and
a return passage configured to transfer fluid from the phase separators through the first set of heat exchangers and into an inlet of the first centrifugal compressor (Fig. 1, passages 39 and 41; Col. 32-35, vaporized under this pressure in the warm portion of passages 39 of exchanger 3, and returned via a conduit 40 to the intake of said first intermediate stage of compressor 1; Col. 4, lines 11-14, for reheating the cycle hydrogen returning from this cold portion, these passages being connected to the cold end of the passages 39 and 41 of the exchanger 3; Further, the return passages 39 and 41 of Grenier has the same structure as the claimed return passage and is capable of functioning in the manner claimed).
However, Grenier does not disclose the supply circuit to have a downstream end designed to be connected to at least one liquefied hydrogen collection member,
each of the first pre-cooling cycle and the second pre-cooling cycle to be in heat exchange with separate sets of heat exchangers, and
a cooling system in heat exchange with a third set of the heat exchangers, the cooling system being configured to reduce the temperature of the hydrogen from the third temperature to a fourth temperature below the critical temperature of the hydrogen.
Watanabe teaches the supply circuit to have a downstream end designed to be connected to at least one liquefied hydrogen collection member (Fig. 1, raw material hydrogen 10, liquefied hydrogen tank 18),
multiple pre-cooling cycles in heat exchange with separate sets of heat exchangers (Fig. 5 of Watanabe depicts nitrogen refrigerant loop 30, mixed refrigerant loop 50, and propane refrigerant loop 60 to each be in heat exchanger with different sets of plate heat exchanger 13; Pg. 6, paragraph 106, The hydrogen liquefaction step in Example 1 is schematically illustrated in FIG. 5. In the hydrogen liquefaction step, the hydrogen gas is precooled through a refrigeration cycle using nitrogen as a refrigerant (nitrogen refrigerant loop), a refrigeration cycle using a mixed refrigerant (mixed refrigerant loop), and a refrigeration cycle using propane as a refrigerant (propane refrigerant loop), and the hydrogen is then cooled through a refrigeration cycle using hydrogen as a refrigerant (hydrogen refrigerant loop) to provide liquefied hydrogen), and
a cooling system in heat exchange with a third set of the heat exchangers, the cooling system being configured to reduce the temperature of the hydrogen from the third temperature to a fourth temperature below the critical temperature of the hydrogen (Fig. 5, hydrogen refrigerant loop 40, plate heat exchangers 13; Pg. 6, paragraph 112, The hydrogen refrigerant loop 40 is the same as in the step used in Comparative Example 1 illustrated in FIG. 4; Pg. 5, paragraphs 97 and 99, Specifically, raw material hydrogen 10 for the hydrogen liquefaction step is increased in pressure with a raw material hydrogen compressor 11 and cooled with a cooler 12, and is then fed to a plate heat exchanger 13 and subjected to heat exchange with a nitrogen refrigerant and a hydrogen refrigerant. Next, the raw material hydrogen 10 is expanded through an expansion valve 14, and is separated in a flash drum 15 into liquefied hydrogen 16 and a hydrogen gas 17. The liquefied hydrogen 16 is stored in a liquefied hydrogen tank 18… In a hydrogen refrigerant loop 40, a hydrogen refrigerant 41 is compressed with a low-pressure hydrogen refrigerant compressor 42 and cooled with a cooler 43, and is then compressed with a high-pressure hydrogen refrigerant compressor 44 and cooled with a cooler 45. Next, the hydrogen refrigerant 41 is fed to the plate heat exchanger 13 (and subjected to heat exchange with the nitrogen refrigerant, the hydrogen gas 17 derived from the raw material hydrogen and capable of being utilized as cold heat, the boil off gas 19 from the liquefied hydrogen tank 18, and a hydrogen refrigerant after passing through hydrogen refrigerant expansion turbines 46 and 47 and a flash drum 49), and then, part of the hydrogen refrigerant is reduced in temperature/liquefied with the hydrogen refrigerant expansion turbines 46 and 47. The rest of the hydrogen refrigerant is separated into liquefied hydrogen and a hydrogen gas in the flash drum 49 after expanded through an expansion valve 48, and the liquefied hydrogen and the hydrogen gas are each fed to the plate heat exchanger 13 again and subjected to heat exchange with the raw material hydrogen; Further, the teachings of the raw gas hydrogen being liquified prior to storage in liquefied hydrogen tank 18 at least implies the temperature is reduced to a fourth temperature below the critical temperature of the hydrogen since it has been held in considering the disclosure of a reference, it is proper to take into account not only specific teachings of the reference but also the inferences which one skilled in the art would reasonably be expected to draw therefrom (MPEP 2144.01); Further, the hydrogen refrigerant loop 40 of Watanabe has the same structure as the claimed cooling system and is capable of functioning in the manner claimed).
Grenier fails to teach the supply circuit to have a downstream end designed to be connected to at least one liquefied hydrogen collection member, each of the first pre-cooling cycle and the second pre-cooling cycle to be in heat exchange with separate sets of heat exchangers, and a cooling system in heat exchange with a third set of the heat exchangers, the cooling system being configured to reduce the temperature of the hydrogen from the third temperature to a fourth temperature below the critical temperature of the hydrogen, however Watanabe teaches that it is a known method in the art of hydrogen liquefaction to include the supply circuit to have a downstream end designed to be connected to at least one liquefied hydrogen collection member, multiple pre-cooling cycles in heat exchange with separate sets of heat exchangers; and a cooling system in heat exchange with a third set of the heat exchangers, the cooling system being configured to reduce the temperature of the hydrogen from the third temperature to a fourth temperature below the critical temperature of the hydrogen. This is strong evidence that modifying Grenier as claimed would produce predictable results (i.e. liquefying and storing gaseous hydrogen). Accordingly, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to Grenier as modified by Watanabe and arrive at the claimed invention since all claimed elements were known in the art and one having ordinary skill in the art could have combined the elements as claimed by known methods with no changes in their respective functions and the combination would have yielded the predictable result of liquefying and storing gaseous hydrogen.
Further, Grenier as modified does not disclose a pair of second compression members configured to compress a gas and liquid from the first phase separator; and
a fourth phase separator configured to recover the liquid produced by the second phase separator and expanded by the first expansion member and to be additionally supplied with a liquid produced by the third phase separator.
Ducote teaches a pair of second compression members configured to compress a gas and liquid from a phase separator (Fig. 1, mixing vessel 13, second mixed gas compressor 14, mixing vessel pump 49, second mixture 123, accumulated liquid 175; Pg. 3, paragraph 33, second mixture 123 exits the mixing vessel 13 and is compressed in a second mixed gas compressor 14 and cooled in a second compressor aftercooler 15 to form a second intermediate-pressure mixture 124 that is fed to a first phase separator or interstage separation device 16 designed to remove any small amount of liquid that might form; Pg. 4, paragraph 35, An accumulated liquid 175 from the mixing vessel 13 can be pressurized using a mixing vessel pump 49 to from a pressurized accumulated liquid 176 and mixed with the first liquid 160 or the second liquid 162); and
a phase separator configured to recover the liquid produced by the other phase separator and expanded by expansion members and to be additionally supplied with a liquid produced by the additional phase separators (Fig. 1, low-press gas mixture vessel 24, interstage separation device 16, high-pressure accumulator 19; Pg. 4, paragraphs 34-35, A first liquid 160 exits the bottom of the interstage separation device 16 and can be drained through a first phase separator valve 41 to form a low-pressure first liquid 161. A second liquid 162 that contains primarily the high molecular weight component(s) in the original mixture exits the bottom of the high-pressure accumulator 19 and can be drained through a second phase separator valve 42 to form a low-pressure second liquid 163 and mixed with the low-pressure first liquid 161 to form a low-pressure mixed liquid 164. The low-pressure mixed liquid 164 can be distributed among four different streams, a mixing vessel recycle stream 170, a mixing vessel refrigeration feed 166, a low-pressure gas mixture vessel refrigeration feed 167, and a low-pressure gas mixture vessel recycle stream 172. The mixing vessel recycle stream 170 is expanded through a mixing vessel valve 43 to form a low-pressure mixing vessel recycle stream 171 that is returned to the mixing vessel 13. The mixing vessel refrigeration feed 166 is expanded through a mixing vessel refrigeration expansion device 45, such as a valve, to form a cooled mixing vessel refrigerant 169 that provides cooling to the pre-cooling heat exchanger 1 and returns to the mixing vessel 13. A portion of the cooled mixing vessel refrigerant 174 can be sent through the pre-cooling heat exchanger 1 as a separate stream so that it exits the pre-cooling heat exchanger 1 as a two-phase stream. This can decrease the temperature difference in the heat exchanger and improve efficiency. The low-pressure gas mixture vessel refrigeration feed 167 is expanded through a low-pressure mixture vessel refrigeration expansion device 46, such as a valve, to form a cooled low-pressure gas mixture vessel refrigerant 168 that provides cooling to the pre-cooling heat exchanger 1 and returns to a low-pressure gas mixture vessel 24. The low-pressure gas mixture vessel recycle stream 172 is expanded through a low-pressure gas mixture vessel valve 44 to form a reduced pressure gas mixture vessel recycle stream 173 that returns to the low-pressure gas mixture vessel 24).
Grenier as modified fails to teach a pair of second compression members configured to compress a gas and liquid from the first phase separator; and a fourth phase separator configured to recover the liquid produced by the second phase separator and expanded by the first expansion member and to be additionally supplied with a liquid produced by the third phase separator, however Ducote teaches that it is a known method in the art of hydrogen liquefaction to include a pair of second compression members configured to compress a gas and liquid from a phase separator; and a phase separator configured to recover the liquid produced by the other phase separator and expanded by expansion members and to be additionally supplied with a liquid produced by the additional phase separators. This is strong evidence that modifying Grenier as modified as claimed would produce predictable results (i.e. reducing the power required for the supplemental refrigerant precooling cycle by leveraging the supplemental refrigeration duty provided by the higher molecular weight components (Ducote, Pg. 3, paragraph 28)). Accordingly, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to modify Grenier as modified by Ducote and arrive at the claimed invention since all claimed elements were known in the art and one having ordinary skill in the art could have combined the elements as claimed by known methods with no changes in their respective functions and the combination would have yielded the predictable result of reducing the power required for the supplemental refrigerant precooling cycle by leveraging the supplemental refrigeration duty provided by the higher molecular weight components (Ducote, Pg. 3, paragraph 28).
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Regarding claim 2, Grenier as modified discloses the installation according to Claim 1 (see the combination of references used in the rejection of claim 1 above).
However, Grenier as modified does not disclose wherein the refrigerator having a refrigeration cycle of the first pre-cooling device comprises a fifth phase separator, configured to receive the gas produced by the third phase separator of the refrigerator and expanded in an expansion member of the refrigerator of the first pre-cooling device.
Ducote teaches wherein the refrigerator having the refrigeration cycle of the first pre-cooling device comprises an additional phase separator, configured to receive the gas produced by an upstream phase separator of the refrigerator and expanded in an expansion member of the refrigerator of the first pre-cooling device (Fig. 2, refrigerant separator 65, expansion valve 64; Pg. 5-6, paragraph 46, The third cold heat exchanger refrigerant feed 231 is fed to the third cold heat exchanger 57 and exits as a third hydrogen refrigerant 232 that is fed to a hydrogen refrigerant expansion valve 64 to form a two-phase hydrogen refrigerant 233 that is separated in a refrigerant separator 65. A liquid refrigerant 237 is removed from the bottom of the separator and provides cooling in the fourth cold heat exchanger 59 where it is at least partially vaporized and returned to the refrigerant separator as a second two-phase refrigerant 238. A cold hydrogen refrigerant vapor 234 is removed from the top of the refrigerant separator 65, mixed with the second hydrogen expander product 228 to form a cold refrigerant feed 229 and fed to the third cold heat exchanger 57, exiting as a second cold refrigerant feed 235, the second cold heat exchanger 55, exiting as a third cold refrigerant feed 236, and the first cold heat exchanger 53 where it is warmed to provide cooling for the hydrogen feed).
Grenier as modified fails to teach wherein the refrigerator having a refrigeration cycle of the first pre-cooling device comprises a fifth phase separator, configured to receive the gas produced by the third phase separator of the refrigerator and expanded in an expansion member of the refrigerator of the first pre-cooling device, however Ducote teaches that it is a known method in the art of hydrogen liquefaction to include wherein the refrigerator having the refrigeration cycle of the first pre-cooling device comprises an additional phase separator, configured to receive the gas produced by an upstream phase separator of the refrigerator and expanded in an expansion member of the refrigerator of the first pre-cooling device. This is strong evidence that modifying Grenier as modified as claimed would produce predictable results (i.e. reducing the power required for the supplemental refrigerant precooling cycle by leveraging the supplemental refrigeration duty provided by the higher molecular weight components (Ducote, Pg. 3, paragraph 28)). Accordingly, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to modify Grenier as modified by Ducote and arrive at the claimed invention since all claimed elements were known in the art and one having ordinary skill in the art could have combined the elements as claimed by known methods with no changes in their respective functions and the combination would have yielded the predictable result of reducing the power required for the supplemental refrigerant precooling cycle by leveraging the supplemental refrigeration duty provided by the higher molecular weight components (Ducote, Pg. 3, paragraph 28).
Regarding claim 4, Grenier as modified discloses the installation according to Claim 1 (see the combination of references used in the rejection of claim 1 above), wherein the refrigerator of the second pre-cooling device comprises, arranged in a cycle circuit, at least two centrifugal compressors in series, configured to compress the second cycle gas, at least one expansion turbine of the second cycle gas coupled to a rotating shaft which is preferably also coupled to one of the compressors, the cycle circuit further comprising a thermosiphon device comprising a phase separator reservoir configured to receive at least one flow of the second cycle gas expanded by the at least one expansion turbine and to return cycle gas to the compressors (See annotated Fig. 1 of Grenier below, second pre-cooling device B includes compressor 2, refrigerator 16, fan 8, expansion turbine 9, separator 13, expansion valves 24-25 and connecting passages 33-37; Col. 2-3, lines 49-67 and 1-4, High pressure nitrogen, leaving at 30 bars from the last stage of compressor 2, is brought in 16 to about ambient temperature, further compressed to 50 bars in 8, brought in 17 to the vicinity of ambient temperature, and introduced into the warm end of the exchanger 3, in passages 31 of this latter. At an intermediate temperature, of the order of -120° C., a portion of this high pressure nitrogen leaves the 9. exchanger and is expanded to 5 bars in the turbine The rest of the high-pressure nitrogen continues its cooling, is liquefied and subcooled until the cold end of exchanger 3, then is expanded to 5 bars in 24 and introduced into the separator 13. The nitrogen from the turbine 9 is sent to the separator 13, whose vapor phase is reheated from the cold end to the warm end of exchanger 3 in passages 32, then returned via a conduit 33 to the intake of an intermediate stage of compressor 2. The liquid phase collected in the separator 13 is subcooled in passages 34 of exchanger 4, expanded to about atmospheric pressure in 25, vaporized in passages 35 of the same exchanger, then reheated from the cold end to the warm end of exchanger 3 in passages 36 before being sent via a conduit 37 to the intake of the first stage of compressor 2; As best understood, see 112(b) rejections above).
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Regarding claim 5, Grenier as modified discloses a method for the liquefaction of hydrogen (Grenier, Fig. 1; Col. 2, lines 13-21, FIG. 1 represents schematically a portion of a hydrogen liquefaction apparatus according to the invention. There is shown in the drawing the diagram of a hydrogen liquefaction installation, except its coldest portion, which is conventional and in which the precooled cycle hydrogen is cooled, liquefied and expanded to produce the cold necessary for the liquefaction of the treated hydrogen or "process hydrogen"), the method comprising the following steps:
providing the installation according to Claim 1 (see the combination of references used in the rejection of claim 1 above);
cooling a flow of hydrogen, having a pressure of at least 20 bars abs and a first initial temperature, to a second temperature of 163 K or below in the first set of heat exchanger(s) (Grenier, Fig. 1, conduits 26-29; Col. 2, lines 37-39, Hydrogen to be liquefied arrives under 20 bars pressure via a conduit 26, is precooled in passages 27 of exchanger 3 to about -178° C);
cooling the hydrogen flow from the second temperature to the third temperature of 103 K or below, in the second set of heat exchangers (Grenier, Col. 2, lines 39-42, further cooled to about -192° C. in the passages 28 of the exchanger 4, from which it issues via conduit 29 to be sent to the cold portion of the installation; Further, the second pre-cooling device of Grenier has the same structure as the claimed second pre-cooling device and is capable of functioning in the manner claimed; As best understood, see 112(b) rejections above);
cooling the hydrogen flow from the third temperature to a temperature below the critical temperature of hydrogen in a third set of heat exchangers, and liquefying the hydrogen flow cooled to the temperature below the critical temperature in order to obtain a flow of liquid hydrogen (Watanabe, Fig. 5, hydrogen refrigerant loop 40, plate heat exchangers 13; Pg. 6, paragraph 112, The hydrogen refrigerant loop 40 is the same as in the step used in Comparative Example 1 illustrated in FIG. 4; Pg. 5, paragraphs 97 and 99, Specifically, raw material hydrogen 10 for the hydrogen liquefaction step is increased in pressure with a raw material hydrogen compressor 11 and cooled with a cooler 12, and is then fed to a plate heat exchanger 13 and subjected to heat exchange with a nitrogen refrigerant and a hydrogen refrigerant. Next, the raw material hydrogen 10 is expanded through an expansion valve 14, and is separated in a flash drum 15 into liquefied hydrogen 16 and a hydrogen gas 17. The liquefied hydrogen 16 is stored in a liquefied hydrogen tank 18… In a hydrogen refrigerant loop 40, a hydrogen refrigerant 41 is compressed with a low-pressure hydrogen refrigerant compressor 42 and cooled with a cooler 43, and is then compressed with a high-pressure hydrogen refrigerant compressor 44 and cooled with a cooler 45. Next, the hydrogen refrigerant 41 is fed to the plate heat exchanger 13 (and subjected to heat exchange with the nitrogen refrigerant, the hydrogen gas 17 derived from the raw material hydrogen and capable of being utilized as cold heat, the boil off gas 19 from the liquefied hydrogen tank 18, and a hydrogen refrigerant after passing through hydrogen refrigerant expansion turbines 46 and 47 and a flash drum 49), and then, part of the hydrogen refrigerant is reduced in temperature/liquefied with the hydrogen refrigerant expansion turbines 46 and 47. The rest of the hydrogen refrigerant is separated into liquefied hydrogen and a hydrogen gas in the flash drum 49 after expanded through an expansion valve 48, and the liquefied hydrogen and the hydrogen gas are each fed to the plate heat exchanger 13 again and subjected to heat exchange with the raw material hydrogen; Further, the teachings of the raw gas hydrogen being liquified prior to storage in liquefied hydrogen tank 18 at least implies the temperature is reduced to a fourth temperature below the critical temperature of the hydrogen since it has been held in considering the disclosure of a reference, it is proper to take into account not only specific teachings of the reference but also the inferences which one skilled in the art would reasonably be expected to draw therefrom (MPEP 2144.01)),
wherein the closed refrigeration cycle of the first pre-cooling device comprises the steps of:
compressing the first cycle gas from a pressure of between 1.1 bara and 10 bara to a pressure of between 7 and 30 bara (Grenier, Col. 3, lines 6-7 and 25-26, The first stage of compressor 1 is supplied under about 1 bar with the following mixture… This mixture is withdrawn at 20 bars from the output of a second intermediate stage of the compressor 1);
cooling the first cycle gas to form a two-phase fluid (Grenier, Col. 3, lines 36-38, The high pressure mixture from the last stage of compressor 1 is brought to the vicinity of ambient temperature in 15 and introduced into the separator 11);
separating the two-phase fluid in a first phase separator (Grenier, Fig. 1, separator 11; Col. 36-49, The high pressure mixture from the last stage of compressor 1 is brought to the vicinity of ambient temperature in 15 and introduced into the separator 11. The liquid phase collected in this latter is subcooled to about -45° C. and divided into two fractions. The first fraction, after expansion to about 6 bars in 19, is vaporized in the passages 39 and then reunited with the mixture from the expansion valve 18. The other fraction, after expansion to about 1 bar in 20, is vaporized and reheated in the passages 41 of exchanger 3, then returned to the intake of the first stage of the compressor 1 via a conduit 42. The vapor phase from separator 11 is cooled to about -120° C., while being partially liquified in passages 43 of exchanger 3, then introduced into the separator 12);
compressing a gas from the first phase separator in a second centrifugal compressor, and pressurizing a liquid from the first phase separator to a pressure of between 25 bara and 70 bara (Ducote, Fig. 1, mixing vessel 13, second mixed gas compressor 14, mixing vessel pump 49, second mixture 123, accumulated liquid 175; Pg. 3, paragraph 33, second mixture 123 exits the mixing vessel 13 and is compressed in a second mixed gas compressor 14 and cooled in a second compressor aftercooler 15 to form a second intermediate-pressure mixture 124 that is fed to a first phase separator or interstage separation device 16 designed to remove any small amount of liquid that might form; Pg. 4, paragraph 35, An accumulated liquid 175 from the mixing vessel 13 can be pressurized using a mixing vessel pump 49 to from a pressurized accumulated liquid 176 and mixed with the first liquid 160 or the second liquid 162; Further, Greiner as modified teaches the claimed invention except for pressurizing the liquid pressure of between 25 bara and 70 bara. It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to include pressurizing the liquid pressure of between 25 bara and 70 bara, since it has been held that where the general conditions of a claim are disclosed in the prior art, discovering the optimum or workable ranges [or optimum value] involves only routine skill in the art. In re Aller, 105 USPQ 233. MPEP 2144.05-II-A. Moreover, since applicants have not disclosed that these modifications solve any stated problem or are for any particular purpose and it appears that the device would perform equally well with either designs, these modifications are a matter of design choice. Absent a teaching as to criticality of pressurizing the liquid pressure of between 25 bara and 70 bara, this particular arrangement is deemed to have been known by those skilled in the art since the instant specification and evidence of record fail to attribute any significance (novel or unexpected results) to a particular arrangement. In re Kuhle, 526 F.2d 553,555,188 USPQ 7, 9 (CCPA 1975). MPEP 2144.05.);
sending the compressed gas and the pressurized liquid to a second phase separator, and separation of the compressed gas and the pressurized liquid in the second phase separator to form a second gas and a second liquid (Grenier, Fig. 1, separator 12, passages 39, 41, and 44; Col. 3, lines 49-62, The liquid phase collected in this latter is in its tum divided into two fractions which, after expansion respectively to about 6 bars and about 1 bar in 21 and 22, vaporizes in passages 39 and 41 respectively, then is reunited with the previously mentioned fractions introduced into the passages at higher temperature levels. The vapor phase from separator 12, constituted of hydrogen containing about 1 part per million of propane and 0.3% ethane, is reintroduced into the exchanger 3, cooled to the cold end of this exchanger in passages 44 of the latter, then introduced into the base of column 5, which is supplied at its head, via a conduit 45, with subcooled liquid propane from the reserve of makeup propane of the hydrogen cycle);
cooling of the second gas in the first set of heat exchangers to at least the second temperature, in order to condense the second gas partially (Grenier, Fig. 1, passage 44; The vapor phase from separator 12, constituted of hydrogen containing about 1 part per million of propane and 0.3% ethane, is reintroduced into the exchanger 3, cooled to the cold end of this exchanger in passages 44 of the latter, then introduced into the base of column 5, which is supplied at its head, via a conduit 45, with subcooled liquid propane from the reserve of makeup propane of the hydrogen cycle);
sending the partially condensed gas to a third phase separator to form a third gas and a third liquid (Grenier, Fig. 1, column 5, passage 46; Col. 3-4, lines 66-67 and 1-9, The liquid at the base of column 5, constituted of ethane and propane and traces of hydrogen, is expanded to about 1 bar in 23, then introduced into the passages 41, near the cold end of these passages. This liquid represents a small fraction, for example of the order of less than 1 %, of the flow of the cycle mixture. The vapor at the head of column 5, constituted by hydrogen containing typically less than 5 ppm (parts per million) of hydrocarbons, is subjected to final purification by adsorption in 6, then is cooled in passages 46 of exchanger 4 and sent to the cold portion of the installation);
cooling and expanding the second liquid via a valve or a turbine to form an expanded fluid (Grenier, Fig. 1, expansion valves 21-22; Col. 3, lines 49-55, The liquid phase collected in this latter is in its tum divided into two fractions which, after expansion respectively to about 6 bars and about 1 bar in 21 and 22, vaporizes in passages 39 and 41 respectively, then is reunited with the previously mentioned fractions introduced into the passages at higher temperature levels); and
introducing the expanded fluid and the third liquid from the third phase separator to the fourth phase separator (Watanabe, Fig. 1, low-press gas mixture vessel 24, interstage separation device 16, high-pressure accumulator 19; Pg. 4, paragraphs 34-35, A first liquid 160 exits the bottom of the interstage separation device 16 and can be drained through a first phase separator valve 41 to form a low-pressure first liquid 161. A second liquid 162 that contains primarily the high molecular weight component(s) in the original mixture exits the bottom of the high-pressure accumulator 19 and can be drained through a second phase separator valve 42 to form a low-pressure second liquid 163 and mixed with the low-pressure first liquid 161 to form a low-pressure mixed liquid 164. The low-pressure mixed liquid 164 can be distributed among four different streams, a mixing vessel recycle stream 170, a mixing vessel refrigeration feed 166, a low-pressure gas mixture vessel refrigeration feed 167, and a low-pressure gas mixture vessel recycle stream 172. The mixing vessel recycle stream 170 is expanded through a mixing vessel valve 43 to form a low-pressure mixing vessel recycle stream 171 that is returned to the mixing vessel 13. The mixing vessel refrigeration feed 166 is expanded through a mixing vessel refrigeration expansion device 45, such as a valve, to form a cooled mixing vessel refrigerant 169 that provides cooling to the pre-cooling heat exchanger 1 and returns to the mixing vessel 13. A portion of the cooled mixing vessel refrigerant 174 can be sent through the pre-cooling heat exchanger 1 as a separate stream so that it exits the pre-cooling heat exchanger 1 as a two-phase stream. This can decrease the temperature difference in the heat exchanger and improve efficiency. The low-pressure gas mixture vessel refrigeration feed 167 is expanded through a low-pressure mixture vessel refrigeration expansion device 46, such as a valve, to form a cooled low-pressure gas mixture vessel refrigerant 168 that provides cooling to the pre-cooling heat exchanger 1 and returns to a low-pressure gas mixture vessel 24. The low-pressure gas mixture vessel recycle stream 172 is expanded through a low-pressure gas mixture vessel valve 44 to form a reduced pressure gas mixture vessel recycle stream 173 that returns to the low-pressure gas mixture vessel 24); and
withdrawing a fluid from the fourth phase separator and heating the fluid in the first set of heat exchangers before returning the fluid to the inlet of the centrifugal compressor as part of the first cycle gas (Grenier, Fig. 1, passages 39 and 41; Col. 32-35, vaporized under this pressure in the warm portion of passages 39 of exchanger 3, and returned via a conduit 40 to the intake of said first intermediate stage of compressor 1; Col. 4, lines 11-14, for reheating the cycle hydrogen returning from this cold portion, these passages being connected to the cold end of the passages 39 and 41 of the exchanger 3). Further, the limitations of claim 5 are the result of the modification of references used in the rejection of claim 1 above.
Regarding claim 6, Grenier as modified discloses the method according to Claim 5 (see the combination of references used in the rejection of claim 5 above), wherein the installation uses a fifth phase separator to receive the third gas produced by the third phase separator following expansion in a second valve or a second turbine (Ducote, Fig. 2, refrigerant separator 65, expansion valve 64; Pg. 5-6, paragraph 46, The third cold heat exchanger refrigerant feed 231 is fed to the third cold heat exchanger 57 and exits as a third hydrogen refrigerant 232 that is fed to a hydrogen refrigerant expansion valve 64 to form a two-phase hydrogen refrigerant 233 that is separated in a refrigerant separator 65. A liquid refrigerant 237 is removed from the bottom of the separator and provides cooling in the fourth cold heat exchanger 59 where it is at least partially vaporized and returned to the refrigerant separator as a second two-phase refrigerant 238. A cold hydrogen refrigerant vapor 234 is removed from the top of the refrigerant separator 65, mixed with the second hydrogen expander product 228 to form a cold refrigerant feed 229 and fed to the third cold heat exchanger 57, exiting as a second cold refrigerant feed 235, the second cold heat exchanger 55, exiting as a third cold refrigerant feed 236, and the first cold heat exchanger 53 where it is warmed to provide cooling for the hydrogen feed). Further, the limitations of claim 6 are the result of the modification of references used in the rejection of claim 5 above.
Regarding claim 7, Grenier as modified discloses the method according to Claim 5 (see the combination of references used in the rejection of claim 5 above), wherein the first cycle gas comprises a mixture of three to six components chosen from among nitrogen, methane, ethane or ethylene, propane or propene, butane or butene, and pentane (Grenier, Col. 3, lines 6-11, The first stage of compressor 1 is supplied under about 1 bar with the following mixture: H2=66.8%, C2H6=14.2%, C3H8=11.5%, C5H12=7.5 %).
Regarding claim 10, Grenier as modified discloses the method according to Claim 5 (see the combination of references used in the rejection of claim 5 above), wherein the cooling of the hydrogen flow from the second temperature to the third temperature comprises a cooling of the hydrogen flow to an intermediate temperature of between 113 K and 153 K (Grenier, Col. 2, lines 37-42, Hydrogen to be liquefied arrives under 20 bars pressure via a conduit 26, is precooled in passages 27 of exchanger 3 to about -178° C., and is further cooled to about -192° C. in the passages 28 of the exchanger 4, from which it issues via conduit 29 to be sent to the cold portion of the installation; Further, cooling the gaseous hydrogen to -178° C (which is approx. 95 K) at least implies at some point the hydrogen will pass through an intermediate temperature 113 K and 153 K since it has been held in considering the disclosure of a reference, it is proper to take into account not only specific teachings of the reference but also the inferences which one skilled in the art would reasonably be expected to draw therefrom (MPEP 2144.01)).
However, Grenier as modified does not explicitly disclose the hydrogen flow is sent to an adsorption purification unit operating at a cryogenic temperature, and then, if necessary, to a catalytic conversion unit for converting ortho hydrogen to para hydrogen, in order to produce a hydrogen flow having a para hydrogen content of between 30% and 55% before being re-cooled.
Ducote teaches the hydrogen flow is sent to an adsorption purification unit operating at a cryogenic temperature, and then, if necessary, to a catalytic conversion unit for converting ortho hydrogen to para hydrogen, in order to produce a hydrogen flow having a para hydrogen content of between 30% and 55% before being re-cooled (Fig. 2, adsorption-based cryogenic purifier 51, catalyst passages 52, 54, 56, 58; Pg. 3, paragraph 30, The pre-cooled hydrogen feed 102 is sent to an adsorption-based cryogenic purifier (51, shown in FIG. 2); Pg. 5, paragraph 42-43, The pre-cooled hydrogen feed 102 from FIG. 1 enters a hydrogen feed purifier 51, similar to the second refrigerant purifier in FIG. 1. The hydrogen feed purifier removes any impurities in the hydrogen feed before the stream is cooled further. These impurities generally consist of primarily nitrogen and argon and other trace components that could freeze in the lower-temperature heat exchangers. A purified hydrogen feed 201 exits the hydrogen feed purifier 51 and enters a first cold heat exchanger 53, where it is cooled and a portion of the ortho hydrogen is converted to para hydrogen over a conversion catalyst located in a first cold heat exchanger catalyst passage 52, to produce a second purified hydrogen feed 202. The second purified hydrogen feed 202 exits the first cold heat exchanger 53 and enters a second cold heat exchanger 55, where a portion of the ortho hydrogen is converted to para hydrogen over a conversion catalyst located in a second cold heat exchanger catalyst passage 54, to produce a third purified hydrogen feed 203. The third purified hydrogen feed 203 exits the second cold heat exchanger 55 and enters a third cold heat exchanger 57, where a portion of the ortho hydrogen is converted to para hydrogen over a conversion catalyst located in a third cold heat exchanger catalyst passage 56, to produce a fourth purified hydrogen feed 204. The fourth purified hydrogen feed 204 exits the third cold heat exchanger 57 and enters a fourth cold heat exchanger 59, where a portion of the ortho hydrogen is converted to para hydrogen over a conversion catalyst located in a fourth cold heat exchanger catalyst passage 58, to produce a fifth purified hydrogen feed 205; Further, Grenier as modified teaches the claimed invention except for the hydrogen flow having a para hydrogen content of between 30% and 55% before being re-cooled. It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to include for the hydrogen flow having a para hydrogen content of between 30% and 55% before being re-cooled, since it has been held that where the general conditions of a claim are disclosed in the prior art, discovering the optimum or workable ranges [or optimum value] involves only routine skill in the art. In re Aller, 105 USPQ 233. MPEP 2144.05-II-A. Moreover, since applicants have not disclosed that these modifications solve any stated problem or are for any particular purpose and it appears that the device would perform equally well with either designs, these modifications are a matter of design choice. Absent a teaching as to criticality of for the hydrogen flow having a para hydrogen content of between 30% and 55% before being re-cooled, this particular arrangement is deemed to have been known by those skilled in the art since the instant specification and evidence of record fail to attribute any significance (novel or unexpected results) to a particular arrangement. In re Kuhle, 526 F.2d 553,555,188 USPQ 7, 9 (CCPA 1975). MPEP 2144.05; As best understood, see 112(b) rejections above).
Grenier as modified fails to teach the hydrogen flow is sent to an adsorption purification unit operating at a cryogenic temperature, and then, if necessary, to a catalytic conversion unit for converting ortho hydrogen to para hydrogen, in order to produce a hydrogen flow having a para hydrogen content of between 30% and 55% before being re-cooled, however Ducote teaches that it is a known method in the art of hydrogen liquefaction to include the hydrogen flow is sent to an adsorption purification unit operating at a cryogenic temperature, and then, if necessary, to a catalytic conversion unit for converting ortho hydrogen to para hydrogen, in order to produce a hydrogen flow having a para hydrogen content of between 30% and 55% before being re-cooled. This is strong evidence that modifying Grenier as modified as claimed would produce predictable results (i.e. ensuring efficient liquefaction of the pre-cooled hydrogen to improve overall system efficiencies). Accordingly, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to modify Grenier as modified by Ducote and arrive at the claimed invention since all claimed elements were known in the art and one having ordinary skill in the art could have combined the elements as claimed by known methods with no changes in their respective functions and the combination would have yielded the predictable result of ensuring efficient liquefaction of the pre-cooled hydrogen to improve overall system efficiencies.
Regarding claim 11, Grenier as modified discloses the method according to Claim 5 (see the combination of references used in the rejection of claim 5 above), wherein the method comprises producing of pre-cooling power by the second pre-cooling device with the following steps: centrifugal compression of the second cycle gas in at least two compressors arranged in series, from an inlet pressure of between 1 and 5 bara to a pressure of between 10 and 50 bara, and expansion of the compressed second cycle gas at a temperature of between 173 K and 128 K in at least one valve or turbine to a pressure of between 1.1 and 2 bara, at least one expansion turbine providing mechanical work if necessary for driving at least one compressor (See annotated Fig. 1 of Grenier below, second pre-cooling device B includes compressor 2, refrigerator 16, fan 8, expansion turbine 9, separator 13, expansion valves 24-25 and connecting passages 33-37; Col. 2, lines 30-32, a turbo-compressor group 7 comprising a fan 8 and an expansion turbine 9 whose rotors are keyed on the same shaft; Col. 2-3, lines 49-67 and 1-4, High pressure nitrogen, leaving at 30 bars from the last stage of compressor 2, is brought in 16 to about ambient temperature, further compressed to 50 bars in 8, brought in 17 to the vicinity of ambient temperature, and introduced into the warm end of the exchanger 3, in passages 31 of this latter. At an intermediate temperature, of the order of -120° C., a portion of this high pressure nitrogen leaves the 9. exchanger and is expanded to 5 bars in the turbine The rest of the high-pressure nitrogen continues its cooling, is liquefied and subcooled until the cold end of exchanger 3, then is expanded to 5 bars in 24 and introduced into the separator 13. The nitrogen from the turbine 9 is sent to the separator 13, whose vapor phase is reheated from the cold end to the warm end of exchanger 3 in passages 32, then returned via a conduit 33 to the intake of an intermediate stage of compressor 2. The liquid phase collected in the separator 13 is subcooled in passages 34 of exchanger 4, expanded to about atmospheric pressure in 25, vaporized in passages 35 of the same exchanger, then reheated from the cold end to the warm end of exchanger 3 in passages 36 before being sent via a conduit 37 to the intake of the first stage of compressor 2; Grenier as modified teaches the claimed invention except for a pressure of between 1.1 and 2 bara. It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to include a pressure of between 1.1 and 2 bara, since it has been held that where the general conditions of a claim are disclosed in the prior art, discovering the optimum or workable ranges [or optimum value] involves only routine skill in the art. In re Aller, 105 USPQ 233. MPEP 2144.05-II-A. Moreover, since applicants have not disclosed that these modifications solve any stated problem or are for any particular purpose and it appears that the device would perform equally well with either designs, these modifications are a matter of design choice. Absent a teaching as to criticality of a pressure of between 1.1 and 2 bara, this particular arrangement is deemed to have been known by those skilled in the art since the instant specification and evidence of record fail to attribute any significance (novel or unexpected results) to a particular arrangement. In re Kuhle, 526 F.2d 553,555,188 USPQ 7, 9 (CCPA 1975). MPEP 2144.05; As best understood, see 112(b) rejections above).
Regarding claim 12, Grenier as modified discloses the method according to Claim 11 (see the combination of references used in the rejection of claim 11 above), wherein the production of precooling power by the second pre-cooling device comprises a transfer of the expanded second cycle gas to a phase separator reservoir of a thermosiphon device and a return of the second cycle gas from the reservoir to an intake of the two compressors (Grenier, Col. 2-3, lines 66-67 and 1-4, The liquid phase collected in the separator 13 is subcooled in passages 34 of exchanger 4, expanded to about atmospheric pressure in 25, vaporized in passages 35 of the same exchanger, then reheated from the cold end to the warm end of exchanger 3 in passages 36 before being sent via a conduit 37 to the intake of the first stage of compressor 2).
Regarding claim 19, Grenier as modified discloses the method according to Claim 5 (see the combination of references used in the rejection of claim 5 above), wherein a cut-off temperature between the first pre-cooling device and the second pre-cooling device, which is the temperature of the hydrogen flow between these two pre-cooling portions, is between 148 K and 123 K (Grenier, Col. 2, lines 37-42, Hydrogen to be liquefied arrives under 20 bars pressure via a conduit 26, is precooled in passages 27 of exchanger 3 to about -178° C., and is further cooled to about -192° C. in the passages 28 of the exchanger 4, from which it issues via conduit 29 to be sent to the cold portion of the installation; Further, Grenier as modified teaches the claimed invention except for wherein a cut-off temperature between the first pre-cooling device and the second pre-cooling device, which is the temperature of the hydrogen flow between these two pre-cooling portions, is between 148 K and 123 K. It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to include wherein a cut-off temperature between the first pre-cooling device and the second pre-cooling device, which is the temperature of the hydrogen flow between these two pre-cooling portions, is between 148 K and 123 K, since it has been held that where the general conditions of a claim are disclosed in the prior art, discovering the optimum or workable ranges [or optimum value] involves only routine skill in the art. In re Aller, 105 USPQ 233. MPEP 2144.05-II-A. Moreover, since applicants have not disclosed that these modifications solve any stated problem or are for any particular purpose and it appears that the device would perform equally well with either designs, these modifications are a matter of design choice. Absent a teaching as to criticality of wherein a cut-off temperature between the first pre-cooling device and the second pre-cooling device, which is the temperature of the hydrogen flow between these two pre-cooling portions, is between 148 K and 123 K, this particular arrangement is deemed to have been known by those skilled in the art since the instant specification and evidence of record fail to attribute any significance (novel or unexpected results) to a particular arrangement. In re Kuhle, 526 F.2d 553,555,188 USPQ 7, 9 (CCPA 1975). MPEP 2144.05).
Regarding claim 20, Grenier as modified discloses the method according to Claim 5 (see the combination of references used in the rejection of claim 5 above), wherein a cut-off temperature between the second pre-cooling device and the cooling system, which is the temperature of the hydrogen flow between these two pre-cooling portions, is between 93 K and 73 K (Grenier, Col. 2, lines 37-42, Hydrogen to be liquefied arrives under 20 bars pressure via a conduit 26, is precooled in passages 27 of exchanger 3 to about -178° C., and is further cooled to about -192° C. in the passages 28 of the exchanger 4, from which it issues via conduit 29 to be sent to the cold portion of the installation).
Claims 3, 8-9, 16 are rejected under 35 U.S.C. 103 as being unpatentable over Grenier as modified by Watanabe and Ducote as applied to claims 1 and 5 above, respectively, and further in view of Cardella et al. (WO 2017072018), hereinafter Cardella.
Regarding claim 3, Grenier as modified discloses the installation according to Claim 1 (see the combination of references used in the rejection of claim 1 above).
However, Grenier as modified does not disclose wherein the first cycle gas consists of a mixture of three to six components chosen from among nitrogen, methane, ethane or ethylene, propane or propene, butane or butene, and pentane.
Cardella teaches wherein the first cycle gas consists of a mixture of three to six components chosen from among nitrogen, methane, ethane or ethylene, propane or propene, butane or butene, and pentane (Pg. 31, lines 20-25, A preferred mixture composition for a precooling temperature in the range of 90 K to 100 K consists of 23 mol. % nitrogen, 29 mol. % methane, 24 mol. % ethane and 0.24 mol. % isobutane. Ethylene may replace the ethane component for precooling temperature above 100 K. For precooling temperatures between 90 K and 100 K, iso butane may be replaced by 1-butene, isopentane, propane or propylene (due to lower melting points)).
Grenier as modified fails to teach wherein the first cycle gas consists of a mixture of three to six components chosen from among nitrogen, methane, ethane or ethylene, propane or propene, butane or butene, and pentane, however Cardella teaches that it is a known method in the art of hydrogen liquefaction to include wherein the first cycle gas consists of a mixture of three to six components chosen from among nitrogen, methane, ethane or ethylene, propane or propene, butane or butene, and pentane. This is strong evidence that modifying Grenier as modified as claimed would produce predictable results (i.e. efficiently achieving low temperature precooling with a refrigerant mixture optimized specifically for hydrogen liquefaction (Cardella, Pg. 31, lines 16-17)). Accordingly, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to modify Grenier as modified by Cardella and arrive at the claimed invention since all claimed elements were known in the art and one having ordinary skill in the art could have combined the elements as claimed by known methods with no changes in their respective functions and the combination would have yielded the predictable result of efficiently achieving low temperature precooling with a refrigerant mixture optimized specifically for hydrogen liquefaction (Cardella, Pg. 31, lines 16-17).
Regarding claim 8, Grenier as modified discloses the method according to Claim 5 (see the combination of references used in the rejection of claim 5 above).
However, Grenier as modified does not disclose wherein the first cycle gas comprises a mixture composed of at least one light component chosen from the group of: nitrogen and methane, at least one medium component chosen from the group of: ethane, ethylene, propane, propene, butane, butene, and at least one heavy component which is pentane, or butane if the medium component is chosen from the group of: ethane, ethylene, propane, and propene.
Cardella teaches wherein the first cycle gas comprises a mixture composed of at least one light component chosen from the group of: nitrogen and methane, at least one medium component chosen from the group of: ethane, ethylene, propane, propene, butane, butene, and at least one heavy component which is pentane, or butane if the medium component is chosen from the group of: ethane, ethylene, propane, and propene (Pg. 31, lines 20-25, A preferred mixture composition for a precooling temperature in the range of 90 K to 100 K consists of 23 mol. % nitrogen, 29 mol. % methane, 24 mol. % ethane and 0.24 mol. % isobutane. Ethylene may replace the ethane component for precooling temperature above 100 K. For precooling temperatures between 90 K and 100 K, iso butane may be replaced by 1-butene, isopentane, propane or propylene (due to lower melting points)).
Grenier as modified fails to teach wherein the first cycle gas comprises a mixture composed of at least one light component chosen from the group of: nitrogen and methane, at least one medium component chosen from the group of: ethane, ethylene, propane, propene, butane, butene, and at least one heavy component which is pentane, or butane if the medium component is chosen from the group of: ethane, ethylene, propane, and propene, however Cardella teaches that it is a known method in the art of hydrogen liquefaction to include wherein the first cycle gas comprises a mixture composed of at least one light component chosen from the group of: nitrogen and methane, at least one medium component chosen from the group of: ethane, ethylene, propane, propene, butane, butene, and at least one heavy component which is pentane, or butane if the medium component is chosen from the group of: ethane, ethylene, propane, and propene. This is strong evidence that modifying Grenier as modified as claimed would produce predictable results (i.e. efficiently achieving low temperature precooling with a refrigerant mixture optimized specifically for hydrogen liquefaction (Cardella, Pg. 31, lines 16-17)). Accordingly, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to modify Grenier as modified by Cardella and arrive at the claimed invention since all claimed elements were known in the art and one having ordinary skill in the art could have combined the elements as claimed by known methods with no changes in their respective functions and the combination would have yielded the predictable result of efficiently achieving low temperature precooling with a refrigerant mixture optimized specifically for hydrogen liquefaction (Cardella, Pg. 31, lines 16-17).
Regarding claim 9, Grenier as modified discloses the method according to Claim 8 (see the combination of references used in the rejection of claim 8 above), wherein the first cycle gas comprises, m moles, between 10% and 50% light component(s), between 30% and 70% medium component(s) and 10% and 35% heavy component(s), the total being equal to 100% (Cardella, Pg. 31, lines 20-25, A preferred mixture composition for a precooling temperature in the range of 90 K to 100 K consists of 23 mol. % nitrogen, 29 mol. % methane, 24 mol. % ethane and 0.24 mol. % isobutane. Ethylene may replace the ethane component for precooling temperature above 100 K. For precooling temperatures between 90 K and 100 K, iso butane may be replaced by 1-butene, isopentane, propane or propylene (due to lower melting points); Grenier as modified teaches the claimed invention except for wherein the first cycle gas comprises, m moles, between 10% and 50% light component(s), between 30% and 70% medium component(s) and 10% and 35% heavy component(s), the total being equal to 100%. It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to include wherein the first cycle gas comprises, m moles, between 10% and 50% light component(s), between 30% and 70% medium component(s) and 10% and 35% heavy component(s), the total being equal to 100%, since it has been held that where the general conditions of a claim are disclosed in the prior art, discovering the optimum or workable ranges [or optimum value] involves only routine skill in the art. In re Aller, 105 USPQ 233. MPEP 2144.05-II-A. Moreover, since applicants have not disclosed that these modifications solve any stated problem or are for any particular purpose and it appears that the device would perform equally well with either designs, these modifications are a matter of design choice. Absent a teaching as to criticality of wherein the first cycle gas comprises, m moles, between 10% and 50% light component(s), between 30% and 70% medium component(s) and 10% and 35% heavy component(s), the total being equal to 100%, this particular arrangement is deemed to have been known by those skilled in the art since the instant specification and evidence of record fail to attribute any significance (novel or unexpected results) to a particular arrangement. In re Kuhle, 526 F.2d 553,555,188 USPQ 7, 9 (CCPA 1975). MPEP 2144.05.).
Regarding claim 16, Grenier as modified discloses the method according to Claim 5 (see the combination of references used in the rejection of claim 5 above).
However, Grenier as modified does not disclose wherein the first cycle gas consists of a mixture of four components from among: CH4 and/or N2, C2H6 and/or C3H8, C5H10, expressed in moles as 49% CH4, 11 % C2H6, 31 % C3H8 and 9% C5H10.
Cardella teaches wherein the first cycle gas consists of a mixture of four components from among: CH4, N2, C2H6 and C3H8 (Pg. 31, lines 20-25, A preferred mixture composition for a precooling temperature in the range of 90 K to 100 K consists of 23 mol. % nitrogen, 29 mol. % methane, 24 mol. % ethane and 0.24 mol. % isobutane. Ethylene may replace the ethane component for precooling temperature above 100 K. For precooling temperatures between 90 K and 100 K, iso butane may be replaced by 1-butene, isopentane, propane or propylene (due to lower melting points); As best understood, see 112(b) rejections above).
Grenier as modified fails to teach wherein the first cycle gas consists of a mixture of four components from among: CH4 and/or N2, C2H6 and/or C3H8, C5H10, however Cardella teaches that it is a known method in the art of hydrogen liquefaction to include wherein the first cycle gas consists of a mixture of four components from among: CH4 and/or N2, C2H6 and/or C3H8, C5H10. This is strong evidence that modifying Grenier as modified as claimed would produce predictable results (i.e. efficiently achieving low temperature precooling with a refrigerant mixture optimized specifically for hydrogen liquefaction (Cardella, Pg. 31, lines 16-17)). Accordingly, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to modify Grenier as modified by Cardella and arrive at the claimed invention since all claimed elements were known in the art and one having ordinary skill in the art could have combined the elements as claimed by known methods with no changes in their respective functions and the combination would have yielded the predictable result of efficiently achieving low temperature precooling with a refrigerant mixture optimized specifically for hydrogen liquefaction (Cardella, Pg. 31, lines 16-17).
Claim 13 is rejected under 35 U.S.C. 103 as being unpatentable over Grenier as modified by Watanabe and Ducote as applied to claims 11 above, and further in view of Kim et al. (WO 2024106678), hereinafter Kim.
Regarding claim 13, Grenier as modified discloses the method according to Claim 11 (see the combination of references used in the rejection of claim 11 above).
However, Grenier as modified does not disclose wherein the expansion of the compressed second cycle gas to a pressure of between 1.1 and 2 bara is carried out in two expansion turbines in series, a pressure of the second cycle gas entering a first of the turbines being between 15 and 50 bara, a temperature of the second cycle gas entering a second of the turbines being between 143 K and 103 K.
Kim teaches wherein the expansion of the compressed cycle gas to a pressure of between 1.1 and 2 bara is carried out in two expansion turbines in series, a pressure of the cycle gas entering a first of the turbines being between 15 and 50 bara, a temperature of the second cycle gas entering a second of the turbines being between 143 K and 103 K (Fig. 2, HEP2, HEP3; Pg. 9, In addition, the hydrogen refrigerant closed circulation unit may further include at least one hydrogen refrigerant expander among a second hydrogen refrigerant expander (HEP2) and a third hydrogen refrigerant expander (HEP3). For example, the second hydrogen refrigerant expander (HEP2) and the third hydrogen refrigerant expander (HEP3) may each be expansion turbines, but the present invention is not limited thereto. The second hydrogen refrigerant expander (HEP2) and the third hydrogen refrigerant expander (HEP3) each expand some of the hydrogen refrigerant discharged from the third heat exchanger (HX3) after being supplied to the third heat exchanger (HX3) for additional cooling. It can be configured to do so; Further, Grenier as modified teaches the claimed invention except for a pressure of the second cycle gas entering a first of the turbines being between 15 and 50 bara, a temperature of the second cycle gas entering a second of the turbines being between 143 K and 103 K. It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to include a pressure of the second cycle gas entering a first of the turbines being between 15 and 50 bara, a temperature of the second cycle gas entering a second of the turbines being between 143 K and 103 K, since it has been held that where the general conditions of a claim are disclosed in the prior art, discovering the optimum or workable ranges [or optimum value] involves only routine skill in the art. In re Aller, 105 USPQ 233. MPEP 2144.05-II-A. Moreover, since applicants have not disclosed that these modifications solve any stated problem or are for any particular purpose and it appears that the device would perform equally well with either designs, these modifications are a matter of design choice. Absent a teaching as to criticality of a pressure of the second cycle gas entering a first of the turbines being between 15 and 50 bara, a temperature of the second cycle gas entering a second of the turbines being between 143 K and 103 K, this particular arrangement is deemed to have been known by those skilled in the art since the instant specification and evidence of record fail to attribute any significance (novel or unexpected results) to a particular arrangement. In re Kuhle, 526 F.2d 553,555,188 USPQ 7, 9 (CCPA 1975). MPEP 2144.05.).
Grenier as modified fails to teach wherein the expansion of the compressed second cycle gas to a pressure of between 1.1 and 2 bara is carried out in two expansion turbines in series, a pressure of the second cycle gas entering a first of the turbines being between 15 and 50 bara, a temperature of the second cycle gas entering a second of the turbines being between 143 K and 103 K, however Kim teaches that it is a known method in the art of hydrogen liquefaction to include wherein the expansion of the compressed cycle gas to a pressure of between 1.1 and 2 bara is carried out in two expansion turbines in series, a pressure of the cycle gas entering a first of the turbines being between 15 and 50 bara, a temperature of the second cycle gas entering a second of the turbines being between 143 K and 103 K. This is strong evidence that modifying Grenier as modified as claimed would produce predictable results (i.e. ensuring sufficient cooling capacity is supplied to the heat exchangers to improve overall system efficiencies). Accordingly, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to modify Grenier as modified by Kim and arrive at the claimed invention since all claimed elements were known in the art and one having ordinary skill in the art could have combined the elements as claimed by known methods with no changes in their respective functions and the combination would have yielded the predictable result of ensuring sufficient cooling capacity is supplied to the heat exchangers to improve overall system efficiencies.
Claims 14-15 are rejected under 35 U.S.C. 103 as being unpatentable over Grenier as modified by Watanabe and Ducote as applied to claims 5 above, and further in view of Kojima et al. (WO 2024090504), hereinafter Kojima.
Regarding claim 14, Grenier as modified discloses the method according to Claim 5 (see the combination of references used in the rejection of claim 5 above).
However, Grenier as modified does not disclose wherein the first cycle gas consists of a mixture of three components: CH4, C2H6 or C3H8, C5H10.
Kojima teaches a refrigerant mixture consisting of three components: CH4, C2H6 or C3H8, C5H10 (Pg. 15, The hydrocarbon refrigerant may be one or more selected from the group consisting of methane, ethane, ethylene, propane (R290), cyclopropane, propylene, n-butane, isobutane (R600a), 2-methylbutane, n-pentane, neopentane, cyclopentane, and normal hexane).
Grenier as modified fails to teach wherein the first cycle gas consists of a mixture of three components: CH4, C2H6 or C3H8, C5H10, however Kojima teaches that it is a known method in the art of hydrocarbon refrigerant mixtures to include a refrigerant mixture consisting of three components: CH4, C2H6 or C3H8, C5H10. This is strong evidence that modifying Grenier as modified as claimed would produce predictable results (i.e. a low boiling point refrigerant (Kojima, Pg. 15)). Accordingly, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to modify Grenier as modified by Kojima and arrive at the claimed invention since all claimed elements were known in the art and one having ordinary skill in the art could have combined the elements as claimed by known methods with no changes in their respective functions and the combination would have yielded the predictable result of a low boiling point refrigerant (Kojima, Pg. 15).
Regarding claim 15, Grenier as modified discloses the method according to Claim 5 (see the combination of references used in the rejection of claim 5 above).
However, Grenier as modified does not disclose wherein the first cycle gas consists of, expressed in moles, 53% CH4, 41% C3H8, 6% C5H10.
Kojima teaches a refrigerant mixture consisting of, expressed in moles, 53% CH4, 41% C3H8, 6% C5H10 (Pg. 15, The hydrocarbon refrigerant may be one or more selected from the group consisting of methane, ethane, ethylene, propane (R290), cyclopropane, propylene, n-butane, isobutane (R600a), 2-methylbutane, n-pentane, neopentane, cyclopentane, and normal hexane; Further, Grenier as modified teaches the claimed invention except for optimum mole percentages for each component (53% CH4, 41% C3H8, 6% C5H10). It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to include optimum mole percentages for each component (53% CH4, 41% C3H8, 6% C5H10), since it has been held that where the general conditions of a claim are disclosed in the prior art, discovering the optimum or workable ranges [or optimum value] involves only routine skill in the art. In re Aller, 105 USPQ 233. MPEP 2144.05-II-A. Moreover, since applicants have not disclosed that these modifications solve any stated problem or are for any particular purpose and it appears that the device would perform equally well with either designs, these modifications are a matter of design choice. Absent a teaching as to criticality of optimum mole percentages for each component (53% CH4, 41% C3H8, 6% C5H10), this particular arrangement is deemed to have been known by those skilled in the art since the instant specification and evidence of record fail to attribute any significance (novel or unexpected results) to a particular arrangement. In re Kuhle, 526 F.2d 553,555,188 USPQ 7, 9 (CCPA 1975). MPEP 2144.05.).
Grenier as modified fails to teach wherein the first cycle gas consists of, expressed in moles, 53% CH4, 41% C3H8, 6% C5H10, however Kojima teaches that it is a known method in the art of hydrocarbon refrigerant mixtures to include a refrigerant mixture consisting of, expressed in moles, 53% CH4, 41% C3H8, 6% C5H10. This is strong evidence that modifying Grenier as modified as claimed would produce predictable results (i.e. a low boiling point refrigerant (Kojima, Pg. 15)). Accordingly, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to modify Grenier as modified by Kojima and arrive at the claimed invention since all claimed elements were known in the art and one having ordinary skill in the art could have combined the elements as claimed by known methods with no changes in their respective functions and the combination would have yielded the predictable result of a low boiling point refrigerant (Kojima, Pg. 15).
Claim 17 is rejected under 35 U.S.C. 103 as being unpatentable over Grenier as modified by Watanabe and Ducote as applied to claims 5 above, and further in view of Ducote, Jr. et al. (US 20140260415), hereinafter Ducote ‘415.
Regarding claim 17, Grenier as modified discloses the method according to Claim 5 (see the combination of references used in the rejection of claim 5 above).
However, Grenier as modified does not disclose wherein the first cycle gas consists of a mixture of CH4, C2H4, C3H8 and C5H12, in respective proportions in moles of 24%, 39%, 22%, and 15%, or in respective proportions in moles of 6%, 33%, 26%, 35%.
Ducote ‘415 teaches wherein the first cycle gas consists of a mixture of CH4, C2H4, C3H8 and C5H12, in respective proportions in moles of 24%, 39%, 22%, and 15%, or in respective proportions in moles of 6%, 33%, 26%, 35% (Pg. 4, paragraph 47, thermally contacting a feed fluid and a circulating mixed refrigerant in the heat exchanger of claim 1, to obtain a cooled product fluid, the circulating mixed refrigerant comprising two or more C1-C5 hydrocarbons, and optionally N2; Pg. 9. Claim 23, wherein the mixed refrigerant includes two or more of methane, ethane, ethylene, propane, propylene, butane, N-butane, isobutane, butylenes, N-pentane, isopentane, and a combination thereof; Further, Grenier as modified teaches the claimed invention except for in respective proportions in moles of 24%, 39%, 22%, and 15%, or in respective proportions in moles of 6%, 33%, 26%, 35%. It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to include in respective proportions in moles of 24%, 39%, 22%, and 15%, or in respective proportions in moles of 6%, 33%, 26%, 35%, since it has been held that where the general conditions of a claim are disclosed in the prior art, discovering the optimum or workable ranges [or optimum value] involves only routine skill in the art. In re Aller, 105 USPQ 233. MPEP 2144.05-II-A. Moreover, since applicants have not disclosed that these modifications solve any stated problem or are for any particular purpose and it appears that the device would perform equally well with either designs, these modifications are a matter of design choice. Absent a teaching as to criticality of in respective proportions in moles of 24%, 39%, 22%, and 15%, or in respective proportions in moles of 6%, 33%, 26%, 35%, this particular arrangement is deemed to have been known by those skilled in the art since the instant specification and evidence of record fail to attribute any significance (novel or unexpected results) to a particular arrangement. In re Kuhle, 526 F.2d 553,555,188 USPQ 7, 9 (CCPA 1975). MPEP 2144.05).
Grenier as modified fails to teach wherein the first cycle gas consists of a mixture of CH4, C2H4, C3H8 and C5H12, in respective proportions in moles of 24%, 39%, 22%, and 15%, or in respective proportions in moles of 6%, 33%, 26%, 35%, however Ducote ‘415 teaches that it is a known method in the art of hydrocarbon refrigerant mixtures for gas liquefaction to include wherein the first cycle gas consists of a mixture of CH4, C2H4, C3H8 and C5H12, in respective proportions in moles of 24%, 39%, 22%, and 15%, or in respective proportions in moles of 6%, 33%, 26%, 35%. This is strong evidence that modifying Grenier as modified as claimed would produce predictable results (i.e. ensuring sufficient cooling capacity to efficiently achieve liquefaction to improve overall system efficiencies). Accordingly, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to modify Grenier as modified by Ducote ‘415 and arrive at the claimed invention since all claimed elements were known in the art and one having ordinary skill in the art could have combined the elements as claimed by known methods with no changes in their respective functions and the combination would have yielded the predictable result of ensuring sufficient cooling capacity to efficiently achieve liquefaction to improve overall system efficiencies.
Claim 18 is rejected under 35 U.S.C. 103 as being unpatentable over Grenier as modified by Watanabe and Ducote as applied to claims 5 above, and further in view of Yang et al. (CN 203454604), hereinafter Yang.
Regarding claim 18, Grenier as modified discloses the method according to Claim 5 (see the combination of references used in the rejection of claim 5 above).
However, Grenier as modified does not disclose wherein the first cycle gas consists of a mixture of five components: N2; CH4, C2H6; C3H8; C5H10, in respective proportions in moles of 3%; 37%, 32%, 13% and 14% or in respective proportions in moles of 3%, 31 %, 34%, 18%, 14%, or in respective proportions in moles of 3%, 33%, 37%, 13%, and 14%.
Yang teaches wherein the first cycle gas consists of a mixture of five components: N2; CH4, C2H6; C3H8; C5H10, in respective proportions in moles of 3%; 37%, 32%, 13% and 14% or in respective proportions in moles of 3%, 31 %, 34%, 18%, 14%, or in respective proportions in moles of 3%, 33%, 37%, 13%, and 14% (Pg. 9, paragraph 2, a mixed refrigerant comprising N2, CH4, C2H6, C3H8 and 1-C5H10; Further, Grenier as modified teaches the claimed invention except for in respective proportions in moles of 3%; 37%, 32%, 13% and 14% or in respective proportions in moles of 3%, 31 %, 34%, 18%, 14%, or in respective proportions in moles of 3%, 33%, 37%, 13%, and 14%. It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to include in respective proportions in moles of 3%; 37%, 32%, 13% and 14% or in respective proportions in moles of 3%, 31 %, 34%, 18%, 14%, or in respective proportions in moles of 3%, 33%, 37%, 13%, and 14%, since it has been held that where the general conditions of a claim are disclosed in the prior art, discovering the optimum or workable ranges [or optimum value] involves only routine skill in the art. In re Aller, 105 USPQ 233. MPEP 2144.05-II-A. Moreover, since applicants have not disclosed that these modifications solve any stated problem or are for any particular purpose and it appears that the device would perform equally well with either designs, these modifications are a matter of design choice. Absent a teaching as to criticality of in respective proportions in moles of 3%; 37%, 32%, 13% and 14% or in respective proportions in moles of 3%, 31 %, 34%, 18%, 14%, or in respective proportions in moles of 3%, 33%, 37%, 13%, and 14%, this particular arrangement is deemed to have been known by those skilled in the art since the instant specification and evidence of record fail to attribute any significance (novel or unexpected results) to a particular arrangement. In re Kuhle, 526 F.2d 553,555,188 USPQ 7, 9 (CCPA 1975). MPEP 2144.05).
Grenier as modified fails to teach wherein the first cycle gas consists of a mixture of five components: N2; CH4, C2H6; C3H8; C5H10, in respective proportions in moles of 3%; 37%, 32%, 13% and 14% or in respective proportions in moles of 3%, 31 %, 34%, 18%, 14%, or in respective proportions in moles of 3%, 33%, 37%, 13%, and 14%, however Yang teaches that it is a known method in the art of hydrocarbon refrigerant mixtures for gas liquefaction to include wherein the first cycle gas consists of a mixture of five components: N2; CH4, C2H6; C3H8; C5H10, in respective proportions in moles of 3%; 37%, 32%, 13% and 14% or in respective proportions in moles of 3%, 31 %, 34%, 18%, 14%, or in respective proportions in moles of 3%, 33%, 37%, 13%, and 14%. This is strong evidence that modifying Grenier as modified as claimed would produce predictable results (i.e. ensuring sufficient cooling capacity to efficiently achieve liquefaction to improve overall system efficiencies). Accordingly, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to modify Grenier as modified by Yang and arrive at the claimed invention since all claimed elements were known in the art and one having ordinary skill in the art could have combined the elements as claimed by known methods with no changes in their respective functions and the combination would have yielded the predictable result of ensuring sufficient cooling capacity to efficiently achieve liquefaction to improve overall system efficiencies.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Sleiti et al. (US 20250290691) discloses similar refrigerant compositions for hydrogen liquefaction.
Knoche (US 20240377127) discloses a similar installation for the liquefaction of hydrogen.
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/DEVON MOORE/Examiner, Art Unit 3763 April 30th, 2026
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