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 .
Claim Rejections - 35 USC § 102
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
Claims 1-4, 6-13 are rejected under 35 U.S.C. 102(a)(1) as being clearly anticipated by Nair et al(2013/0313193).
Nair et al teaches a porous membrane comprising: a first Zeolitic Imidazolate Fragments (ZIFs) part formed on a surface of a porous support(para 0066 stating “a dip coating technique is used to disperse these nanoparticles on the surfaces of microporous hollow fibers of the porous polymer”, para 0074 stating “the fibers were dip-coated into a 4g/L ZIF-90/methanol suspension and air-dried for about 30 minutes before secondary growth. This resulted in a dense layer of ZIF-90 seed crystals being deposited on the fiber surface of nm thickness”); and a second ZIFs part embedded in the porous support, wherein the second ZIFs part is formed in a state in which it penetrates from an interface between the first ZIFs part and the second ZIFs part to a predetermined depth(“ para 0034 stating “growing larger MOF crystals on the dip coated porous polymer at less than about 100 C in a growth solution to make a MOF-membrane-polymer”, para 0037 stating “the MOF can be any MOF, but in some embodiments a ZIF is preferred, such as ZIF 1-12, ZIF 80, ZIF 90 and the like” , para 0077 stating “highly intergrown ,polycrystalline membranes were obtained that covered the entire fiber face with no visible gaps, pinholes, or cracks, … , membrane thicknesses were approximately 4-5 microns, but thickness can be controlled by increasing or decreasing crystal growth time, and/or temperature, as desired”; examiner also noting a statement in Nair et al that a seeded fiber was added(added equating to immersed) to a growth solution equates to a second ZIF parts penetrating from an interface between the first ZIFs part and the second ZIFs part to a predetermined depth).
Examiner respectfully submits the limitations “and wherein the first ZIFs part and the second ZIFs part are formed by: immersing the porous support in a zinc salt solution for 1 to 12 hours to pre-adsorb a Zn precursor on the surface and inside of the porous support; drying the porous support having the Zn precursor pre-adsorbed thereon in a vacuum oven at a temperature of 30 to 200° C. for 1 to 24 hours to immobilize the Zn precursor; and reacting the porous support having the Zn precursor immobilized thereon with an imidazole or imidazole derivative solution” represent a process of making the claimed “porous membrane” product, wherein examiner respectfully submits “If the product in the product-by-process claim is the same as or obvious from a product of the prior art, the claim is unpatentable even though the prior product was made by a different process” (MPEP 2113 I).
With regards to claim 2, Nair et al further teaches wherein the first ZIFs portion has a thickness of 0.1 to 10 micrometers(noting dip coating with a thickness of 0.1 to 10 micrometers), and the second ZIFs portion is formed by penetrating from an interface between the first ZIFs portion and the second ZIFs portion to a depth of 10 to 500 micrometers(noting a membrane thickness of 4-5 microns, however adjusting crystal growth time and/or temperature provides a depth of second ZIFs portion of 10 to 500 micrometers).
With regards to claim 3, Nair et al further teaches wherein the first ZIFs portion and the second ZIFs portion are formed by pre-depositing and immobilizing a Zn precursor on the surface and inside of the porous support using a zinc salt solution of a first concentration, and then reacting the porous support on which the Zn precursor has been pre-deposited and immobilized with an imidazole or imidazole derivative solution(Examiner noting the limitations of claim 3 are directed to process limitations, and noting that Nair et al teaches the same Zn precursor and imidazole carboxylate aldehyde solution, therefore the porous membrane of Nair et al is expected to provide first ZIFs and second ZIFs formed by the claimed process of claim 3).
With regards to claim 4, Nair et al further teaches wherein the first concentration is in a range of 0.27 M to 0.58 M(examiner noting the concentration does not further limit the structural elements of the claimed porous membrane, therefore the porous membrane of Nair et al is expected to provide a concentration in the claimed range).
With regards to claim 6, Nair et al further teaches wherein the reaction with the imidazole or imidazole derivative solution is performed such that the porous support having the Zn precursor pre-deposited and immobilized thereon is immersed in the imidazole or imidazole derivative solution and then reacted at 50 to 200° C. for 1 to 72 hours to form crystals of the Zn precursor and the imidazole on the surface and inside of the porous support(Examiner noting the limitations of claim 6 are directed to process limitations, and noting that Nair et al teaches the same Zn precursor and imidazole carboxylate aldehyde solution, therefore the porous membrane of Nair et al is expected to provide the claimed amount of first ZIFs part and second ZIFs part).
With regards to claim 7, Nair et al further teaches wherein the zinc salt is at least one selected from the group consisting of zinc nitrate, zinc acetate, zinc chloride, zinc sulfate, zinc bromide, and zinc iodide(para 0039 stating zinc (II) nitrate).
With regards to claim 8, Nair et al further teaches wherein the imidazole or imidazole derivative is at least one selected from the group consisting of benzimidazole, 2-methylimidazole, 4-methylimidazole, 2-methylbenzimidazole, 2-nitroimidazole, 5-nitrobenzimidazole, and 5- chlorobenzimidazole(para 0039 stating imidazole carboxyaldehyde).
With regards to claim 9, Nair et al further teaches wherein the zinc salt solution or the imidazole or imidazole derivative solution is dissolved in at least one solvent selected from the group consisting of methanol, ethanol, propanol, iso-propanol, tert-butanol, n-butanol, methoxyethanol, ethoxyethanol, dimethylacetamide, dimethylformamide, n-methyl-2-pyrrolidone (NMP), formic acid, nitromethane, acetic acid, and distilled water(para 0039 stating methanol).
With regards to claim 10, Nair et al further teaches wherein the surface of the porous support may be polished a predetermined number of times, and even when the surface of the porous support is polished 20 to 100 times, a H₂/CO₂ separation coefficient of 3.1 to 3.8 at 200° C is exhibited.
With regards to claim 11, Nair et al further teaches wherein the separation performance is maintained at 300 to 360° C. for 36 to 168 hours (examiner noting the separation performance does not further limit the structural elements of the claimed porous membrane, therefore the porous membrane of Nair et al is expected to provide a separation performance as recited in claim 11).
With regards to claim 12, Nair et al further teaches a method of separating hydrogen from a mixed gas or a syngas of H2 and CO2 using the porous separation membrane of claim 1(para 0033 stating “the mixture of gases can include C02 plus at least one gas selected from the group consisting of H2 …”).
With regards to claim 13, Nair et al further teaches which is carried out at a temperature of 100 to 500° C.
Allowable Subject Matter
Claims 14-16 and 18-23 are allowed.
The following is a statement of reasons for the indication of allowable subject matter:
Amended claim 14 includes limitations from claim 17 which were indicated as allowable in the previous office action.
Response to Arguments
Applicant's arguments filed 6-27-2026 have been fully considered but they are not persuasive.
Applicant argues the specific manufacturing process steps explicitly recited in claim 1 impart distinct structural characteristics to the resulting porous membrane that are not present in Nair.
Examiner respectfully submits that for a product by process claim as in amended claim 1, the claimed structural elements of the product have to be consistent in scope with the specific process steps claimed, wherein determination of patentability of a product by process claim is based on the product itself. Examiner respectfully submits that Nair et al teaches the unamended structure of the claimed porous membrane product, as specifically delineated in the rejection of the current office action and the previous non final rejection. Examiner respectfully submits that the claimed product of claim 1 was not amended to impart distinct structural characteristics to overcome the porous membrane of Nair.
Applicant argues this pre-deposition and drying process ensures high dispersion of the Zn precursor and induces the formation of a continuous separation layer on the support, enabling the formation of a dense film inside the support with ZIF-8 particles densely formed to a depth of about 80 µm. This deep, interlocking membrane construction physically blocks the pores inside the porous support, creating a unique structure that provides unprecedented thermal and long- term stability at high temperatures. In contrast, Nair discloses a simple dip-coating technique where fibers are dip-coated into a ZIF-90/methanol suspension and air-dried for about 30 minutes, resulting in a dense layer of seed crystals deposited on the fiber surface with a thickness of only nm to 4-5 microns. Nair does not teach or suggest forcibly impregnating and immobilizing a precursor deep within the support through the claimed long-duration immersion and vacuum drying process. As a result, Nair's membrane lacks the deeply embedded, dense interlocking ZIFs structure inside the support that is imparted by the process steps of claim 1.
Examiner respectfully submits claim 1 does not require several distinct structural characteristics argued by Applicant, specifically ZIF-8 particles densely formed to a depth of about 80 µm, and a deep, interlocking membrane construction physically blocks the pores inside the porous support, creating a unique structure that provides unprecedented thermal and long- term stability at high temperatures. Examiner notes page 10 of the specification stating “As a result, it is likely that a continuous ZIF-8 layer has formed on the upper surface, more preferably at the interface with the particles of the porous support, and has reached a penetration depth (thickness) of approximately 80 µm. Therefore, this enables effective blocking and high dispersion of the support pores by the ZIF-8 particles”. Therefore limitations to ZIF-8 particles formed to a depth of about 80 µm within the porous support, the limitations incorporated into the product of claim 1, would seem to represent a distinct structural difference over a layer of seed crystals deposited on the fiber surface with a thickness of 4-5 microns.
Examiner also notes page 30 of the specification stating “instead of forming an existing well-intergrown separation layer or membrane on top of the porous support, embedding, more precisely plugging, the ZIF-8 particles inside the support was strategically effective to minimize the aforementioned thermally induced ZIF-8 structural damage while maintaining the integrity of the original ZIF-8.”. Examiner notes page 32 of the specification stating “the unique interlocking microstructure of the particles that blocks through the pores of the ZIF-8-A1₂O₃ disk improved the thermal stability of the Z_Zna membrane to a significant thickness of about 80 um. A major differentiator from the prior art is that the Z_Zna membrane formed a dense pore blocking structure of ZIF-8 particles at a thick penetration depth (about 80 µm).”. Therefore limitations to ZIF-8 particles blocking pores within the porous support , the limitations incorporated into the product of claim 1, would seem to represent a distinct structural difference over a second ZIFs part embedded in a porous support of Nair et al, but wherein Nair et al does not seem to teach ZIF-8 particles blocking pores within the porous support.
Applicant argues “the ambient air-drying in Nair, see e.g., para. 0074: ‘air-dried for about 30 minutes,’ serves only to remove the coating solvent from the outer surface, not to immobilize a Zn precursor within the pores of the support. The absence of this step in Nair is precisely what the Office Action recognized in finding claim 17 allowable.
Examiner respectfully submits that claim 14 is directed to a manufacturing method of a porous membrane, wherein the process limitations of claim 17 are analyzed differently from a product by process claim of claim 1, wherein the limitations of claim 17 represent specific process limitations which differentiate a claimed process of manufacturing a porous membrane over a process of manufacturing a porous membrane as taught by Nair et al. As noted in the previous response with regards to amended claim 1, patentability of the product of a product by process claim does not depend on the specific process claimed.
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ROBERT A HOPKINS whose telephone number is (571)272-1159. The examiner can normally be reached Mon-Thurs 6am-4pm.
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/ROBERT A HOPKINS/Primary Examiner, Art Unit 1776
July 16, 2026
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