DETAILED ACTION
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 26 May 2026 has been entered.
Claim Status
Claims 1, 10, 13, 14, 17, and 21 are amended. Claim 15 is cancelled.
The amendments to claims 1, 10, 13, 14, 17, and 21 overcome the previous claim objections and 112(a),(b), and (d) rejections.
Claims 1-14 and 16-21 are pending for examination below.
Response to Arguments
Applicant’s arguments, see Remarks, filed 28 April 2026, with respect to the rejection(s) of claim(s) 1-14 and 16-21 under USC 103 over Kuznicki in view of Ramachandran have been fully considered and are persuasive. Kuznicki in view of Ramachandran does not teach that the adsorbent is self-bound and/or subjected to low temperature annealing prior to cation exchange. Therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of newly discovered prior art in view of the amendment. Kuznicki in view of Ramachandran continues to teach the method comprising the adsorbent, and De Luca is added to teach self-binding when forming the adsorbent.
Specification
The disclosure is objected to because of the following informalities:
The instant specification in paragraph [0018] recites that the titania/silica molar ratio is about 1 to about 10. However, the instant specification also recites an inventive titanium silicate material which has a titanium to silicon molar ratio of 5:12 (0.42). The titanium to silicon and titania to silica ratios are the same because there is one mole of titanium in titania and one mole of silicon in silica. As such, the exemplified titanium silicate material does not have the described molar ratio. It is unclear if this is intentional or if perhaps the ratio in paragraph [0018] should have instead been a silica/titania ratio. Appropriate clarification is respectfully requested.
Appropriate correction is required.
Claim Objections
Claims 1, 14, and 17 are objected to because of the following informalities:
Claims 1, 14, and 17 each recite “alkene and an alkane having a same carbon content as the alkene” in the first three lines. While the specification uses “carbon content” and “carbon number” interchangeably when discussing the alkane and alkene, the phrasing of “carbon number” is more common. Thus, the claims would be more clear if the term “carbon number” replaced “carbon content” in each claim.
Appropriate corrections are required.
Claim Rejections - 35 USC § 103
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.
Claims 1-5, 7-14, 16, and 21 are rejected under 35 U.S.C. 103 as being unpatentable over Kuznicki et al. (US 6,517,611) in view of Ramachandran et al. (US 5,470,925) and De Luca et al. (IT RM2003A000456, machine translation provided herein).
With regard to claims 1 and 2, Kuznicki teaches a method comprising:
contacting a gaseous mixture comprising an olefin and a paraffin having the same carbon content as said olefin with a barium exchanged (claimed ion-exchanged with barium instant claims 1 and 2) ETS-4 titanium silicate to selectivity adsorb said olefin and size exclude said paraffin from the pores (column 14, Kuznicki claim 1); and
recovering a product stream which has a higher concentration of said olefin than said mixture (column 14, Kuznicki claim 1). Kuznicki teaches that the barium exchanged ETS-4 has a titania/silica molar ratio of 1:1 to 10:1 (0.1 to 1) (column 8, lines 63-65), which overlaps the range of about 1 to about 10 of instant claim 1, rendering the range prima facie obvious.
Kuznicki further teaches that the gaseous mixture is a product of thermal cracking, FCC, hydrocracking, or other sources (column 7, lines 25-26 and 38-41).
Kuznicki fails to teach i) that the source of the gaseous mixture is a gas from polyethylene or polypropylene production or ii) that the rectified titanium silicate is a product of (1) low temperature annealing or (2) subjecting the titanium silicate to self-binding techniques to increase an aggregate volumetric concentration.
With regard to gaseous mixture source i), Ramachandran teaches a process for production of alkene polymers (Title). Ramachandran further teaches withdrawing a gas stream comprising olefins and paraffins having the same carbon number from a polymerization process, and passing the gas stream to pressure swing or temperature swing absorption comprising an absorbent which preferentially removes alkenes from the gas mixture (column 2, lines 29-44). Thus, Ramachandran teaches that it is known to use an absorbent to preferentially absorb alkenes over alkanes in a gas mixture resulting from polymer production.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the gas comprising olefins and paraffins from polymerization of Ramachandran as the source to the absorbent of Kuznicki, because each of Kuznicki and Ramachandran teach selectively absorbing alkenes over alkanes in a gas stream comprising the mixture, Kuznicki teaches that the source can be other gas mixtures, and Ramachandran teaches that the gas resulting from polyalkene production is a known source of alkanes and alkenes which can be passed to an absorbent to absorb the alkenes (column 2, lines 29-44).
With regard to self-binding ii), De Luca teaches forming a titanium silicate molecular sieve material (page 1, last three paragraphs) obtainable from the initial reaction mixture without the need to add any type of binder (page 5, second paragraph). De Luca further teaches that the material which is self-bound can be used as an adsorbent for separations (page 2, sixth paragraph and page 6, sixth paragraph) and that the self-binding allows for avoiding the need for the calcination phase of the synthesis (page 5, second paragraph).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the self-binding techniques of De Luca to form the adsorbent of Kuznicki, because Kuznicki and De Luca each teach a titanium silicate adsorbent for separations, and De Luca teaches that forming the material with self-binding techniques avoids the need for the calcination phase of synthesis (page 5, second paragraph.
Kuznicki in view of De Luca does not explicitly teach that the self-binding techniques increase an aggregate volumetric concentration of the titanium silicate. However, De Luca teaches the same concept of self-binding and De Luca and Kuznicki teaches the same use as an adsorbent. One of ordinary skill in the art is aware that when the same amount of self-bound adsorbent is used in place of an adsorbent comprising a binder, the volumetric concentration of the adsorbent is inherently increased because there is more adsorbent present due to the absence of binder. Therefore, one of ordinary skill in the art would understand that the forming the adsorbent by self-binding as taught by De Luca would have the same effect of increasing an aggregate volumetric concentration of the titanium silicate in the adsorbing step of Kuznicki, as claimed.
With regard to claim 3, Kuznicki teaches calcining the ETS-4 at a temperature of 150-250°C and cooling (column 14, claim 4), which is within the range of about 100 to about 300°C of instant claim 3. Kuznicki further teaches the calcining adjusts the pore size to the desired size (column 9, line 50).
With regard to claims 4 and 5, Kuznicki teaches pressure swing adsorption (instant claim 5) using the ETS-4 adsorbent in a particulate bed (instant claim 4) (column 15, claim 16). One of ordinary skill in the art understands that pressure swing adsorption includes a step of reducing the pressure of the particulate bed relative to a pressure of the particulate bed during the contacting, as claimed in instant claim 5.
With regard to claim 7, Kuznicki alternatively teaches a membrane comprising the titanium silicate where the olefin passes through the pores, said olefin being obtained downstream (column 15, claim 23).
With regard to claim 8, Kuznicki teaches the feed stream to the adsorbing further comprises acetylene with the alkene and alkane, and that the product recovered from the adsorbing has a higher concentration of acetylene than the feed (column 16, claim 27).
With regard to claim 9, Ramachandran teaches that the polymerization is to make polyethylene or polypropylene (column 1, lines 13-14). Ramachandran further teaches the gas comprising the alkane and alkene used to be purged (vented) and is now being passed to the adsorber to obtain the alkenes (column 2, lines 1-5 and 30-35). Thus, Ramachandran teaches the source of the gas is a vent gas stream from polyethylene or polypropylene production, as claimed.
With regard to claims 10 and 13, Kuznicki teaches cracking gas oil (claimed thermal cracking of a hydrocarbon liquid stream) to produce the product comprising olefin and alkane which is separated with the titanium silicate (column 1, lines 14-15).
With regard to claim 11, Ramachandran teaches the gaseous mixture from the polymer production comprises ethylene and ethane (column 2, lines 31-32).
With regard to claim 12, Ramachandran teaches the gaseous mixture from the polymer production comprises propylene and propane (column 2, line 33).
With regard to claim 14, Kuznicki teaches a method comprising:
calcining ETS-4 to contract the pores to a desired smaller size (column 9, lines 49-50);
contacting a gaseous mixture comprising an olefin and a paraffin having the same carbon content as said olefin with the ETS-4 titanium silicate to selectivity adsorb said olefin
and size exclude said paraffin from the pores; and
recovering a product stream which has a higher concentration of said olefin than said mixture (column 14, claim 1). Kuznicki teaches that the barium exchanged ETS-4 has a titania/silica molar ratio of 1:1 to 1:10 (column 8, lines 63-65), which overlaps the range of about 1 to about 10 of instant claim 14, rendering the range prima facie obvious.
Kuznicki further teaches that the gaseous mixture is a product of thermal cracking, FCC, hydrocracking, or other sources (column 7, lines 25-26 and 38-41).
Kuznicki fails to teach i) that the source of the gaseous mixture is a gas from polyethylene or polypropylene production or ii) that the rectified titanium silicate is a product of subjecting the titanium silicate to self-binding techniques to increase an aggregate volumetric concentration.
With regard to gaseous mixture source i), Ramachandran teaches a process for production of alkene polymers (Title). Ramachandran further teaches withdrawing a gas stream comprising olefins and paraffins having the same carbon number from a polymerization process, and passing the gas stream to pressure swing or temperature swing absorption comprising an absorbent which preferentially removes alkenes from the gas mixture (column 2, lines 29-44). Thus, Ramachandran teaches that it is known to use an absorbent to preferentially absorb alkenes over alkanes in a gas mixture resulting from polymer production.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the gas from polymerization of Ramachandran as the source to the absorbent of Kuznicki, because each of Kuznicki and Ramachandran teach selectively absorbing alkenes over alkanes in a gas stream comprising the mixture, Kuznicki teaches that the source can be other gas mixtures, and Ramachandran teaches that the gas resulting from polyalkene production is a known source of alkanes and alkenes which can be passed to an absorbent to absorb the alkenes (column 2, lines 29-44).
With regard to self-binding ii), De Luca teaches forming a titanium silicate material obtainable from the initial reaction mixture without the need to add any type of binder (page 5, second paragraph). De Luca further teaches that the material which is self-bound can be used as an adsorbent for separations (page 2, sixth paragraph and page 6, sixth paragraph) and that the self-binding allows for avoiding the need for the calcination phase of the synthesis (page 5, second paragraph).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the self-binding techniques of De Luca to form the adsorbent of Kuznicki, because Kuznicki and De Luca each teach a titanium silicate adsorbent for separations, and De Luca teaches that forming the material with self-binding techniques avoids the need for the calcination phase of synthesis (page 5, second paragraph.
Kuznicki in view of De Luca does not explicitly teach that the self-binding techniques increase an aggregate volumetric concentration of the titanium silicate. However, De Luca teaches the same concept of self-binding and Kuznicki teaches the same use as an adsorbent for separation of olefins and paraffins in a gas mixture. Therefore, one of ordinary skill in the art would reasonably conclude that the self-binding of Kuznicki in view of De Luca would have the same effect of increasing an aggregate volumetric concentration of the titanium silicate, as claimed, absent any evidence to the contrary.
With regard to claim 16, Kuznicki teaches the pore size is 2.5 to 4 Angstroms (column 6, lines 46-47), which is identical to the range of 2.5 to 4 Angstroms of instant claim 16.
With regard to claim 21, Kuznicki teaches that ion-exchange is performed multiple times such that more than 95% of the original sodium is exchanged with the barium cation (column 12, lines 35-39 and 51-53). This is considered to be exhaustive ion exchange, as claimed, absent any evidence to the contrary.
Claim 6 is rejected under 35 U.S.C. 103 as being unpatentable over Kuznicki et al. (US 6,517,611, Kuznicki I below) as applied to claim 4 above, and further in view of Kuznicki et al. (US 2009/0187053, Kuznicki II below).
With regard to claim 6, Kuznicki I teaches the method above where the adsorption is performed with a PSA bed (column 15, claim 16).
Kuznicki I does not specifically teach pulling a vacuum or heating to increase recovery.
Kuznicki II teaches PSA adsorption for separation of ethane and ethylene with a cation exchanged ETS-10 (Abstract). Kuznicki further teaches vacuum swing adsorption (VSA) or thermal swing adsorption (TSA) can be used with the modified ETS-10 (paragraph [0089]). TSA is known in the art to mean a variant of PSA where the temperature is increased. VSA is known in the art to mean adding a vacuum to PSA to increase the desorption.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use TSA or VSA as a variant of the PSA to increase the recovering in the process of Kuznicki I, as Kuznicki I and Kuznicki II each teaches PSA with a cation exchanged ETS to separate ethylene and ethane, and Kuznicki II teaches TSA and VSA are known alternatives to use instead of base PSA to recover the olefin (paragraph [0089]).
Claims 17-20 are rejected under 35 U.S.C. 103 as being unpatentable over Kuznicki et al. (US 6,517,611) in view of Ramachandran et al. (US 5,470,925).
With regard to claims 17 and 18, Kuznicki teaches a system for separating a mixture comprising alkene and alkane comprising a membrane (claimed option b) of instant claims 17) comprising a titanium silicate which has been exchanged with barium (instant claim 18), such that the alkene passes through the pores and across the plane of the membrane to provide a downstream product having a higher concentration of alkene than the feed (column 15, claims 14 and 23).
Kuznicki further teaches that the gaseous mixture is a product of a unit for thermal cracking, FCC, hydrocracking, or other sources (column 7, lines 25-26 and 38-41).
Kuznicki does not specifically teach that the system comprises a unit for polymer production as the source of the gaseous mixture.
Ramachandran teaches production of alkene polymers (Title). Ramachandran further teaches a system comprising a unit for polymerization which produces a gas stream comprising olefins and paraffins having the same carbon number from a polymerization process, and a unit comprising an adsorbent for pressure swing or temperature swing adsorption, which preferentially removes alkenes from the gas mixture (column 2, lines 29-44). Thus, Ramachandran teaches that it is known to have a system comprising a polymer production unit and an adsorption unit for separating alkenes from alkanes.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to add the polymerization unit of Ramachandran to the system of Kuznicki, because Kuznicki and Ramachandran each teach a system comprising a source of a gaseous mixture comprising alkanes and alkenes, Kuznicki teaches that the unit can be another source not listed, and Ramachandran teaches that the polymerization unit is a known source of alkanes and alkenes which can be passed to an absorbent unit to absorb the alkenes (column 2, lines 29-44).
With regard to claim 19, Kuznicki teaches calcining the titanium silicate at a temperature of 150-250°C and cooling (column 14, claim 4), which is within the range of about 100 to about 300°C of instant claim 19.
With regard to claim 20, Kuznicki alternatively teaches a system comprising pressure swing adsorption (claimed option a) of instant claims 17 and 20) instead of the membrane (claimed option b), where the system comprising the adsorber involves a unit where the gas stream comprising alkane and alkene contacts an ETS-4 adsorbent in a particulate bed (column 15, claim 16). The ETS adsorbent is the barium exchanged ETS-4 having a titania/silica molar ratio of 1:1 to 1:10 (column 8, lines 63-65), which overlaps the range of about 1 to about 10 of option a) of instant claim 17, rendering the range prima facie obvious
While Kuznicki does not explicitly teach the presence of an inlet and at least one outlet for the particulate bed in the adsorber, one of ordinary skill in the art would understand that the particulate bed used in PSA of Kuznicki implicitly involves the feed gas entering the bed in an inlet, removing the non-adsorbed gas through an outlet, and removing the product gas during desorption through an outlet, as claimed.
While Kuznicki does not specifically teach the titanium silicate is produced by low temperature annealing or self-binding techniques as in option a) of instant claim 17, the method of making the adsorbent does not affect the structural limitations of the system comprising the adsorber because it is a material worked on and does not limit the apparatus. See MPEP 2115. Therefore, Kuznicki in view of Ramachandran continues to teach the patentable limitations of the claimed system.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Kuznicki (US 2009/0202655) teaches that a titanosilicate molecular sieve is formed by annealing the material from 75 to 400°C after cation exchange (paragraph [0045]). This overlaps the claimed temperature of 125°C to 200°C, rendering the range obvious, but is not before cation exchange as claimed. However, the selection of the order of steps is obvious absent any evidence of criticality or unexpected results (MPEP 2144.04(IV)C).
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ALYSSA L CEPLUCH whose telephone number is (571)270-5752. The examiner can normally be reached M-F, 8:30 am-5 pm, EST.
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/Alyssa L Cepluch/Examiner, Art Unit 1772
/IN SUK C BULLOCK/Supervisory Patent Examiner, Art Unit 1772
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