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 .
Claim Objections
Claims 1, 3, and 16-18 are objected to because of the following informalities:
Claim 1 recites in line 9 “the selective hydrogenation”. The “the” should be deleted so that the claim only recites “selective hydrogenation” for antecedent basis purposes.
Claims 3 and 16 each recite “the metals”. This recitation lacks antecedent basis in each case, and one of ordinary skill in the art is aware that the elements listed are metals. Thus, the Examiner suggests the phrase should be deleted so that each claim recites “containing molybdenum, vanadium, and niobium”.
Claims 17 and 18 each recite “the metal”. For the same reasons as claims 3 and 16 above, these claims should be amended to delete this phrase and recite “further contain tellurium.”
Appropriate corrections are required.
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 1-14 and 16-21 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.
With regard to claim 1, the claim recites in line 8 “to obtain hydrocarbon fractions (C2H4, C2H6)…” The presence of parentheses renders the claim indefinite because it is unclear whether the limitations within the parentheses are a required part of the claimed invention.
For purposes of examination, the Examiner will consider only the broader required recitation of hydrocarbon fractions.
With regard to claim 2, the claim recites “in particular an amine scrubbing”. The phrase "in particular" renders the claim indefinite because it is unclear whether the limitation(s) following the phrase are part of the claimed invention. See MPEP § 2173.05(d).
For purposes of examination, the Examiner will consider only the broader term “regenerative scrubbing”.
With regard to claim 13, the claim recites “downstream of the feed point, at least a portion of the gas mixture being processed in each case…” The phrase “the gas mixture being processed” lacks antecedent basis, as there are no previous recitations of gas mixtures in the claim. Further, the phrase “in each case” is indefinite, because downstream of the feed point, the oxidative dehydrogenation effluent “subsequent stream” has already been fed to the steam cracking effluent “treatment”. Thus, there are no longer two streams being process separately, but only one stream, and the phrase “in each case” is confusing and indefinite.
For purposes of examination, the Examiner will consider that the claim is reciting that downstream of the feed point, the combined effluents are cooled to the claimed temperature before the demethanizer step (instant Figures 1 and 2 and instant specification paragraphs [0067] and [0024]).
With regard to claim 14, the claim recites “the condensate stream is in particular subjected” and “a valuable product”. The phrase "in particular" renders the claim indefinite because it is unclear whether the limitation(s) following the phrase are part of the claimed invention. See MPEP § 2173.05(d). The term “valuable” is a relative term which renders the claim indefinite. The term “valuable” is not defined by the claim, the specification does not provide a standard for ascertaining the requisite degree, and one of ordinary skill in the art would not be reasonably apprised of the scope of the invention.
For purposes of examination, the Examiner will consider that the condensate stream is subjected to the further treatment to obtain acetic acid, and that the acetic acid is just a “product” as the term valuable is unnecessary and does not further limit the phrase.
With regard to claims 2-12 and 16-21, the claims are rejected as being dependent on a rejected base claim.
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 1-6, 8-11, and 16-21 are rejected under 35 U.S.C. 103 as being unpatentable over Mitkidis et al. (US 2019/0194091) in view of Mitkidis et al. (US 2020/0002251).
Mitkidis et al. (US 2019/0194091) will be referred to as Mitkidis A and Mitkidis et al. (US 2020/0002251) will be referred to as Mitkidis B herein.
With regard to claims 1, 9, 10, 20, and 21, Mitkidis A teaches a process for producing ethylene from ethane (paragraph [0001]), comprising the following steps (Fig. 3 and corresponding paragraphs [0125]-[0139]):
a) subjecting an ethane stream 1 (first feed stream) to steam cracking 2 to produce a product stream 3 (first product stream) (paragraph [0127]);
b) subjecting an ethane stream 28 (second feed stream) to oxidative dehydrogenation 31 to produce a product stream 32 (second product stream) (paragraph [0132]);
c) passing the product stream 3 (first product stream) to a series of steps (treatment) including selective hydrogenation 22 and demethanization 11 (paragraph [0137]);
d) subjecting the product stream 32 (second product stream) to carbon dioxide removal to produce a stream 44 (paragraph [0137]);
e) introducing the stream 44 to the process through line 45 upstream of the demethanization unit 11 (paragraph [0137]).
Mitkidis A fails to specifically teach i) subjecting the product stream 32 (second product stream) to trace removal of oxygen and acetylene, ii) the residual oxygen content and acetylene content of the subsequent stream after trace removal, or iii) introducing the subsequent stream after trace removal to the steam cracker treatment downstream of the selective hydrogenation.
With regard to trace removal i) and ii), Mitkidis A teaches that the product stream 32 comprises water, ethane, ethylene, acetylene, carbon monoxide, and carbon dioxide (paragraph [0132]) and also unconverted oxygen which is removed before combining the product stream with the steam cracker effluent (paragraph [0079]).
Mitkidis B teaches a process for oxidative dehydrogenation comprising the following steps
a) oxidative dehydrogenation of an alkane to a stream comprising alkene, unconverted alkane, water, carbon dioxide, unconverted oxygen, carbon monoxide, and an alkyne (paragraph [0027]),
b) removing unconverted oxygen, carbon monoxide, and alkyne from the stream (paragraph [0029]). When the alkane is ethane, the alkyne is acetylene (paragraph [0036]). Thus the stream of Mitkidis B is equivalent to the stream of Mitkidis A, and
c) carbon dioxide removal of the stream after oxygen removal (paragraph [0030]).
Mitkidis B further teaches that the resulting stream after oxygen and alkyne removal comprises at most 50 ppm by volume oxygen and at most 1 ppmv alkyne (acetylene) (paragraph [0066]). These are within the ranges of less than 500 vol ppm oxygen and less than 5 vol ppm acetylene of instant claim 1, at most 250 vol ppm and at most 100 vol ppm oxygen of instant claims 9 and 20, respectively, and less than 2 vol ppm acetylene of instant claim 10. The range of at most 1 ppmv alkyne also overlaps the range of less than 1 vol ppm acetylene of instant claim 21, rendering the range prima facie obvious. Mitkidis B additionally teaches that the removing step prevents conversion of the alkene and alkane in the product as much as possible, and where the process is technically advantageous, efficient, and affordable (paragraph [0012]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the oxygen and acetylene removal step of Mitkidis B as the oxygen removal step of Mitkidis A, where the step takes place before removing carbon dioxide from the ODH effluent as claimed, because each of Mitkidis A and Mitkidis B teaches a process for oxidative dehydrogenation of ethane to a product comprising ethylene, acetylene, and residual oxygen, and removing carbon dioxide from the effluent, Mitkidis A teaches removing unconverted oxygen before combining with the steam cracking effluent, and Mitkidis B teaches that the oxygen and acetylene removal step should be placed before the carbon dioxide removal step, and that the oxygen and acetylene removal step prevents conversion of the alkene and alkane in the product as much as possible, and where the process is technically advantageous, efficient, and affordable (paragraph [0012]).
With regard to the location of selective hydrogenation iii), Mitkidis A teaches that the acetylene hydrogenation unit may be placed at another position within the steam cracker configuration (paragraph [0139]) and gives some examples, such as in Figure 3, the unit can be placed between the point where streams 10 (steam cracker product) and 45 (oxidative dehydrogenation product) are combined (the feed point) and the separation unit 11 (demethanizer) (paragraph [0139]). Mitkidis A does not teach explicitly that the selective hydrogenation unit can be upstream of the point where streams 10 and 45 meet (the feed point), as claimed. However, Mitkidis B teaches the oxygen removal step, which also reduces the acetylene concentration to less than 5 vol ppm (Mitkidis B paragraph [0066]). As such, when following the combined process of Mitkidis A in view of Mitkidis B, one of ordinary skill in the art would conclude there is no need to perform the acetylene hydrogenation on the combined effluent, because the acetylene has already been reduced to less than 5 vol ppm in the oxygen removal (trace removal) step, which takes place upstream of the combining step.
Therefore, one of ordinary skill in the art would find it obvious to place the acetylene hydrogenation unit in the steam cracking effluent train before the combining of streams 10 and 45, as claimed, because Mitkidis A teaches the selective hydrogenation unit can be moved elsewhere in the process and specifically mentions upstream of the demethanizer, Mitkidis B already teaches removing acetylenes in the oxygen removal step, and because one of ordinary skill in the art would know that placing the unit upstream of the combining avoids an unnecessary and cost inefficient acetylene hydrogenation on the oxidative dehydrogenation effluent which already has had the acetylene removed.
With regard to claim 2, Mitkidis A teaches the carbon dioxide removal comprises contacting with an amine (regenerative scrubbing) (paragraph [0108]).
With regard to claims 3 and 16-18, Mitkidis A teaches that the oxidative dehydrogenation catalyst comprises molybdenum, vanadium, niobium (instant claims 3 and 16) and tellurium (instant claims 17 and 18) (paragraph [0098]).
With regard to claim 4, Mitkidis A teaches the embodiment above, which is a 1st embodiment where the unit 11 is a demethanization unit. Alternatively, Mitkidis A teaches a 2nd embodiment for Figure 3, where the unit 11 is a deethanization unit, and where the selective hydrogenation unit can be placed after combining the streams 10 and 46 and before unit 19 (paragraph [0139]), which is downstream of unit 11 as claimed.
With regard to claims 5 and 19, Mitkidis A also teaches that the demethanization unit 11 is upstream of a deethanization unit 15 (Figure 3). Thus, when the selective hydrogenation unit is placed upstream the demethanization unit 11 (paragraph [0139]), the selective hydrogenation unit is also upstream of a deethanization unit, as claimed in instant claims 5 and 19.
With regard to claim 6, Mitkidis A teaches that the stream 32 after carbon dioxide removal (subsequent stream) is introduced into a drying unit 42 before being combined with the steam cracker effluent (paragraph [0137] and Figure 3).
With regard to claim 8, Mitkidis B teaches that the catalyst for the oxygen and acetylene removal (trace removal) includes copper, manganese, zinc, nickel, platinum, palladium, rhodium, ruthenium, or combinations thereof (paragraph [0069]).
With regard to claim 11, Mitkidis A further teaches obtaining an ethane stream 26 from a C2 splitter 24, where the ethane stream 26 is recycled to the steam cracker and/or the ODH unit (paragraph [0133]).
Claim 7 is rejected under 35 U.S.C. 103 as being unpatentable over Mitkidis et al. (US 2019/0194091) in view of Mitkidis et al. (US 2020/0002251) as applied to claim 1 above, and further in view of Sun et al. (US 2010/0048972).
With regard to claim 7, Mitkidis A in view of Mitkidis B teaches the method above, comprising an acetylene hydrogenation step in unit 22 (Figure 3). Mitkidis further teaches the acetylene hydrogenation takes place in a reactor comprising a catalyst (paragraph [0053]).
Mitkidis A is silent regarding the specific catalyst used in the acetylene hydrogenation.
Sun teaches a method of purification of ethylene containing feedstock from a steam cracker (Abstract). Sun further teaches that most selective acetylene hydrogenation operations use Pd-based catalysts (paragraph [0004]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use palladium in the acetylene hydrogenation of Mitkidis A because Mitkidis A and Sun each teach acetylene hydrogenation of ethylene containing streams from steam crackers, Mitkidis A teaches a catalyst is used but is silent regarding the specifics, and Sun teaches that palladium is a typical commercial scale selective hydrogenation catalyst (paragraph [0004]).
Claim 12 is rejected under 35 U.S.C. 103 as being unpatentable over Mitkidis et al. (US 2019/0194091) in view of Mitkidis et al. (US 2020/0002251) as applied to claim 1 above, and further in view of Arnold et al. (US 2010/0256432, cited on IDS of 5/23/2025).
With regard to claim 12, Mitkidis A in view of Mitkidis B teaches the method above, where the oxygen removal is performed on the gas which is produced after condensation of the water from the ODH reactor (raw gas) (Mitkidis B paragraphs [0028]-[0029]).
Mitkidis A in view of Mitkidis B fails to teach the presence of a compression step for the oxidative dehydrogenation effluent.
Arnold teaches a method for oxidative dehydrogenation (paragraph [0002]). Arnold teaches that the process comprises passing the effluent from the ODH through a condensation unit and to an oxygen elimination reactor, followed by compression and separation of carbon dioxide (paragraph [0110]). Arnold additionally teaches that the compression results in additional water being removed from the gas (paragraph [0110]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to add a compression step downstream of the oxygen elimination (trace removal) step, as claimed, because Mitkidis A in view of Mitkidis B and Arnold each teach ODH followed by condensation and oxygen elimination on the gas from the condensation unit (raw gas), and Arnold teaches a compression step downstream of the oxygen elimination is useful to remove additional water from the effluent (paragraph [0110]).
Claim 13 is rejected under 35 U.S.C. 103 as being unpatentable over Mitkidis et al. (US 2019/0194091) in view of Mitkidis et al. (US 2020/0002251) as applied to claim 1 above, and further in view of Beauchamp et al. (US 2019/0062236).
With regard to claim 13, Mitkidis A in view of Mitkidis B teaches the method above, where the gas is cooled as it is separated (paragraph [0107]).
Mitkidis A in view of Mitkidis B fails to teach cooling at least a portion of the combined gas to temperatures below -120°C.
Beauchamp teaches a method for oxidative dehydrogenation (paragraph [0005]). Beauchamp further teaches the product is compressed, carbon dioxide is removed, and then the effluent is cooled to less than -150°C (paragraph [0055]), which is within the range of below -120°C of instant claim 13. Beauchamp further teaches that the method comprising the cooling is a sustainable and environmentally friendly process to produce ethylene (paragraph [0060]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to add the cooling to below -120°C to the process of Mitkidis A in view of Mitkidis B, because Mitkidis A in view of Mitkidis B and Beauchamp each teach oxidative dehydrogenation and separation of the effluent after cooling, and Beauchamp teaches cooling to less than -150°C (paragraph [0055]) as part of the method produces an overall method which is sustainable and environmentally friendly (paragraph [0060]).
Claims 14 is rejected under 35 U.S.C. 103 as being unpatentable over Mitkidis et al. (US 2019/0194091) in view of Mitkidis et al. (US 2020/0002251) as applied to claim 1 above, and further in view of Johnston et al. (US 2008/0132723).
With regard to claim 14, Mitkidis A in view of Mitkidis B teaches the method above, where the oxidative dehydrogenation effluent is condensed to obtain an effluent 34 comprising water and acetic acid (Mitkidis A paragraph [0132], Fig. 3).
Mitkidis A in view of Mitkidis B fails to specifically teach i) the amount of acetic acid in the condensate or ii) obtaining the acetic acid as a product.
With regard to i), Mitkidis A in view of Mitkidis B teaches oxidative dehydrogenation of the same ethane with the same catalyst comprising Mo, V, Nb, and Te (paragraph [0098]). The instant specification recites that when using the catalyst system comprising these metals, acetic acid is formed as a co-product in an amount that is typically 1 to 30 wt% (instant specification paragraph [0042]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to expect that the product of the oxidative dehydrogenation of Mitkidis A in view of Mitkidis B also comprises at least 1 wt% acetic acid in the condensate, as claimed, as the process of Mitkidis A in view of Mitkidis B uses the same catalyst and the instant specification recites that when using the catalyst, the product typically comprises the claimed amount of acetic acid, absent any evidence to the contrary.
With regard to ii), Johnston teaches a process for oxidative dehydrogenation of ethane to a product comprising ethylene and acetic acid (Abstract), followed by condensation of the water and acetic acid into a stream, and then recovering the acetic acid as product from the stream (paragraph [0028]). Johnston further teaches that acetic acid is a useful reactant for making vinyl acetate commercially (paragraph [0006]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to add the step of recovering the acetic acid from the product of Mitkidis A in view of Mitkidis B, because Mitkidis A in view of Mitkidis B and Johnston each teach oxidative dehydrogenation to produce ethylene and acetic acid and condensation of the water and acetic acid, and Johnston teaches that recovering acetic acid as product is known and useful because acetic acid is used to make vinyl acetate (paragraph [0006]).
Conclusion
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