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 .
Election/Restriction
REQUIREMENT FOR UNITY OF INVENTION
As provided in 37 CFR 1.475(a), a national stage application shall relate to one invention only or to a group of inventions so linked as to form a single general inventive concept (“requirement of unity of invention”). Where a group of inventions is claimed in a national stage application, the requirement of unity of invention shall be fulfilled only when there is a technical relationship among those inventions involving one or more of the same or corresponding special technical features. The expression “special technical features” shall mean those technical features that define a contribution which each of the claimed inventions, considered as a whole, makes over the prior art.
The determination whether a group of inventions is so linked as to form a single general inventive concept shall be made without regard to whether the inventions are claimed in separate claims or as alternatives within a single claim. See 37 CFR 1.475(e).
When Claims Are Directed to Multiple Categories of Inventions:
As provided in 37 CFR 1.475 (b), a national stage application containing claims to different categories of invention will be considered to have unity of invention if the claims are drawn only to one of the following combinations of categories:
(1) A product and a process specially adapted for the manufacture of said product; or
(2) A product and a process of use of said product; or
(3) A product, a process specially adapted for the manufacture of the said product, and a use of the said product; or
(4) A process and an apparatus or means specifically designed for carrying out the said process; or
(5) A product, a process specially adapted for the manufacture of the said product, and an apparatus or means specifically designed for carrying out the said process.
Otherwise, unity of invention might not be present. See 37 CFR 1.475 (c).
Restriction is required under 35 U.S.C. 121 and 372.
This application contains the following inventions or groups of inventions which are not so linked as to form a single general inventive concept under PCT Rule 13.1.
In accordance with 37 CFR 1.499, applicant is required, in reply to this action, to elect a single invention to which the claims must be restricted.
Group I, claims 1-17, drawn to a method for production of butadiene.
Group II, claim(s) 18-20, drawn to a plant for the production of butadiene.
The groups of inventions listed above do not relate to a single general inventive concept under PCT Rule 13.1 because, under PCT Rule 13.2, they lack the same or corresponding special technical features for the following reasons:
Groups I and II lack unity of invention. The technical feature is:
An apparatus comprising:
i) a reactor having at least one zone for producing 1,3-butadiene;
ii) a means for feeding a feed comprising ethanol and acetaldehyde; and
iii) a means for regenerating the catalyst, which further comprises:
a means for feeding inert gas into the reactor, a means for feeding a flow comprising oxygen, and a means for heating the inert gas and oxygen before entering the reactor.
Even though the inventions of these groups require the technical feature, this technical feature is not a special technical feature as it does not make a contribution over the prior art in view of Drobyshev et al. (WO 2020/126920).
US 2022/0048833 is used as the English language version of WO 2020/126920 herein, and all citations are directed thereto.
Drobyshev teaches an apparatus (Figure 2 and corresponding description [0075]) comprising a reactor R1 for producing butadiene, the reactor R1 comprising a catalyst zone and a means for feeding ethanol and acetaldehyde 1. Drobyshev further teaches regenerating the catalyst in the reactor, where inert gas AA1 is passed through loop L1 (means for feeding inert gas), oxygen containing gas AO2 is passed through loop L2 (means for feeding oxygen flow), and both are passed through heater F1 (means for heating) before regenerating the catalyst in reactor R1. Thus, Drobyshev teaches the technical feature of the apparatus, the apparatus is not a special technical feature, and restriction is proper.
During a telephone conversation with Xiaoxiang Liu on 15 June 2025 a provisional election was made without traverse to prosecute the invention of Group I, claims 1-17. Affirmation of this election must be made by applicant in replying to this Office action. Claims 18-20 are withdrawn from further consideration by the examiner, 37 CFR 1.142(b), as being drawn to a non-elected invention.
Applicant is reminded that upon the cancelation of claims to a non-elected invention, the inventorship must be corrected in compliance with 37 CFR 1.48(a) if one or more of the currently named inventors is no longer an inventor of at least one claim remaining in the application. A request to correct inventorship under 37 CFR 1.48(a) must be accompanied by an application data sheet in accordance with 37 CFR 1.76 that identifies each inventor by his or her legal name and by the processing fee required under 37 CFR 1.17(i).
Claim Objections
Claims 1, 5, 7, and 8 are objected to because of the following informalities:
With regard to claim 1, the claim recites in step a) “at least one adiabatic reaction zone, the adiabatic reaction zone comprising…” The second recitation should be “the at least one adiabatic reaction zone comprising…” for antecedent basis purposes.
Also with regard to claim 1, steps b)i. to b)iv. and additionally the last wherein clause at the end of claim 1 each recites “the supported catalyst”. This should be “the spent supported catalyst” in each case for antecedent basis purposes.
With regard to claim 5, the claim recites in line 2 “the molar ratio” and in line 3 “the range”. This should be “a molar ratio” and “a range” for antecedent basis purposes.
With regard to claim 7, the claim recites “the time” in line 2. This should be “a time” for antecedent basis purposes.
With regard to claim 8, the claim recites “the total time” in line 1. This should be “a total time” for antecedent basis purposes.
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 2-9 and 13-17 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 claims 2-9 and 13-17, each claim recites the terms “preferably”, “more preferably”, “most preferably”, and/or “in particular”. These phrases render the claims indefinite because it is unclear whether the limitations following the phrase are part of the claimed invention. See MPEP § 2173.05(d).
Also with regard to claim 4, the claim also recites “(and optionally ethanol)” in line 2. The use of parentheses is improper and indefinite, because it is unclear whether the limitations inside the parentheses are required or optional.
Also with regard to claim 6, the claim also recites “(and preferably the entire effluent)” in line 6. The use of parentheses is improper and indefinite, because it is unclear whether the limitations inside the parentheses are required or optional.
Also with regard to claim 17, the claim also recites “(bulk)” in step x). The use of parentheses is improper and indefinite, because it is unclear whether the limitations inside the parentheses are required or optional.
For purposes of examination, the claims will be interpreted as reciting only the following limitations:
Claim 2: wherein the supported catalyst comprises one or more of tantalum, zirconium, niobium, hafnium, titanium, and tin.
Claim 3: wherein, in reaction stage a), the 1,3-butadiene producing reactor includes a first adiabatic reaction zone comprising a supported catalyst and producing 1,3-butadiene and a second adiabatic reaction zone comprising a supported catalyst and producing 1,3-butadiene.
Claim 4: wherein, in reaction stage a), an additional feed comprising acetaldehyde is fed into the reactor after the first adiabatic reaction zone comprising a supported catalyst and producing 1,3-butadiene.
Claim 5: wherein, in reaction stage a), the additional feed further comprises ethanol, and the molar ratio of ethanol to acetaldehyde in the additional feed is in the range of from 0.1 to 5.
Claim 6: wherein, in reaction stage a), a first 1,3-butadiene producing reactor having at least a first adiabatic reaction zone comprising a supported catalyst and producing 1,3-butadiene, and a second 1,3- butadiene producing reactor having at least a second adiabatic reaction zone comprising a supported catalyst and producing 1,3-butadiene are connected in series, and at least part of the effluent from the first 1,3-butadiene producing reactor is fed to the second 1,3-butadiene producing reactor.
Claim 7: wherein regeneration stage b) is carried out for a time period in a range of from 1/6 to 1/2 of the time period for which reaction stage a) is carried out.
Claim 8: wherein the total time period of regeneration stage b) is less than 80 h.
Claim 9. wherein, in regeneration stage b), the gas flow in stripping step i. comprises steam.
Claim 13: wherein, in regeneration stage b), the heated gas flow, at the end of stripping step i., contacts the supported catalyst at a temperature of 400 °C or less.
Claim 14: wherein, in regeneration stage b), the heated gas flow, at the end of first combustion step ii., contacts the supported catalyst at a temperature of 400 °C or less.
Claim 15: wherein, in regeneration stage b), the heated gas flow, at the end of second combustion step iii., contacts the supported catalyst at a temperature of 550 °C or less.
Claim 16: wherein, in regeneration stage b), the heated gas flow, at the end of stripping step iv., contacts the supported catalyst at a temperature of 450 °C or less.
Claim 17: A process for the production of 1,3-butadiene from ethanol with catalyst regeneration comprising x) producing acetaldehyde from ethanol in an acetaldehyde producing reactor having a reaction zone, the reaction zone of the acetaldehyde producing reactor comprising a supported or unsupported catalyst, and y) producing 1,3-butadiene with catalyst regeneration according to the process of claim 1.
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 1-8 and 12-17 are rejected under 35 U.S.C. 103 as being unpatentable over Drobyshev et al. (WO 2020/126920) in view of Song (US 2017/0342009).
US 2022/0048833 is used as the English language version of WO 2020/126920 herein, and all citations are directed thereto.
With regard to claims 1 and 2, Drobyshev teaches a method for producing butadiene from ethanol (paragraph [0001]) comprising the following steps:
a) reacting a mixture of ethanol and acetaldehyde in a reaction zone comprising n fixed bed reactors comprising a catalyst which is preferably tantalum, where n is 4 or a multiple thereof, to produce 1,3-butadiene (paragraphs [0035]). Drobyshev further teaches that the catalyst is a supported catalyst comprising tantalum (instant claim 2) (paragraph [0053]).
b) regenerating the catalyst in a regeneration step comprising the following phases (paragraph [0036]):
i) a stripping phase comprising a temperature of 300-400°C and contacting the supported catalyst with a flow of inert gas (paragraph [0037]). This is identical to the range of 300-400°C of step b)i. of instant claim 1. Drobyshev only teaches the presence of inert gas in the stripping phase i), where the inert gas can be only nitrogen. Therefore, because Drobyshev teaches a similar stripping step b)i. at the same temperature and comprising the same inert gas, and further because Drobyshev is silent regarding any oxygen content in the inert gas stream for stripping step b)i., one of ordinary skill in the art would reasonably conclude that the inert gas stream of Drobyshev comprises no oxygen, which is within the range of 200 vppm or less oxygen as claimed.
ii) a first combustion phase comprising a temperature of 300-450°C and contacting with a stream having inert gas and an oxygen content of 0.1 to 1 vol% (paragraph [0038]). These overlap the ranges of 350-400°C and 0.2 to 8 vol% of step b)ii. of instant claim 1, rendering the ranges prima facie obvious.
iii) a second combustion phase comprising a temperature of 390-550°C and contacting with a stream having inert gas and an oxygen content of 4 to 8 vol% (paragraph [0039]). This overlaps the range of 400-550°C, rendering the range prima facie obvious, and is within the range of 0.2 to 8 vol% of step b)iii. of instant claim 1.
iv) a stripping step having a temperature of 550-300°C and contacting with a flow of inert gas (paragraph [0040]). This is identical to the range of 550-300°C of step b)iv. of instant claim 1. Drobyshev only teaches the presence of inert gas in the stripping phase iv), where the inert gas can be only nitrogen (paragraph [0040]). Therefore, because Drobyshev teaches a similar stripping step b)iv. at the same temperature and comprising the same inert gas, and further because Drobyshev is silent regarding any oxygen content in the inert gas stream for stripping step b)iv., one of ordinary skill in the art would reasonably conclude that the inert gas stream of Drobyshev comprises no oxygen, which is within the range of 200 vppm or less oxygen as claimed.
Drobyshev also teaches that the gas flows to the regeneration steps L1, L2, and L3 are heated in a heater F1 before passing to the reactor R1 when it is in the regeneration phase (paragraph [0075] and Figure 2).
Drobyshev fails to teach that the reactors for step a) are adiabatic reactors.
Song teaches a method of producing 1,3-butadiene from a ketone (Abstract). Song teaches that using an adiabatic reactor obviates using a heat transfer medium, thus providing an economic and efficient conversion process for the endothermic reaction (paragraphs [0014], [0016]). Thus, Song teaches that it is known to convert oxygenates by an endothermic reaction to 1,3-butadiene using an adiabatic reactor.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use adiabatic reactors in the process of Drobyshev, because Drobyshev teaches conversion of ethanol to 1,3-butadiene (paragraph [0001]) and Song teaches that adiabatic reactors allow for economic and efficient conversion of oxygenates to butadiene by endothermic reactions (paragraph [0016]).
With regard to claim 3, Drobyshev in view of Song teaches the n adiabatic reactors, where n is 4 or a multiple of 4, and where the reactors function in parallel (paragraph [0057]). Thus, Drobyshev in view of Song teaches the first and second adiabatic reaction zones each comprising a catalyst and producing 1,3-butadiene, as claimed.
With regard to claim 4, Drobyshev teaches that each of the reactors for conversion of ethanol/acetaldehyde to butadiene are also fed with a supply of acetaldehyde (paragraph [0056]) and that the reactors are functioning in sequence (paragraph [0057]). Thus, Drobyshev teaches feeding acetaldehyde to the reactor after the first adiabatic reactor comprising the catalyst for producing butadiene, as claimed.
With regard to claim 5, Drobyshev teaches that the additional feed also comprises ethanol, such that the mole ratio of ethanol to acetaldehyde is 1 to 5 (paragraph [0056]), which is within the range of 0.1 to 5 of instant claim 5.
With regard to claim 6, Drobyshev teaches that there are n reactors, where n is 4 or a multiple of 4, and the reactors are functioning in sequence (paragraph [0057]). Thus, Drobyshev teaches at least a first and second reactor connected in series, where at least part of the effluent from the first reactor is fed to the second reactor.
With regard to claim 7, Drobyshev teaches that the regeneration stage is carried out for a total time equal to half the catalytic cycle time (time period for which the butadiene reaction is carried out) (paragraph [0036]) which is within the range of 1/6 to ½ of instant claim 7.
With regard to claim 8, Drobyshev teaches that the catalytic cycle time is 1 to 20 days (paragraph [0053]). As such, the regeneration stage is carried out for 12 to 240 hours, which overlaps the range of less than 80 hours of instant claim 8, rendering the range prima facie obvious.
With regard to claim 12, Drobyshev does not specifically teach the combustion iii is carried out until there is no local temperature maximum in the reactor. However, one of ordinary skill in the art would understand that a local temperature maximum indicates that there is catalyst still containing coke. Thus, the absence of the local temperature maximum indicates the absence of coke on the catalyst, and that the combustion reaction is substantially complete. Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to carry out combustion step iii until there is no local temperature maximum, as one of ordinary skill in the art is aware this is an indication the combustion is substantially complete, and stopping the combustion when it is complete saves energy and oxygen gas,
With regard to claim 13, Drobyshev teaches the method above, where the stripping step i. takes place at a temperature of 300-400°C and the inert gas is heated before entering the zone (paragraph [0075]).
Drobyshev does not explicitly teach that the heated gas flow at the end of the stripping step contacts the catalyst at a temperature of 400°C or less.
However, because one of ordinary skill in the art knows that regeneration is endothermic and because Drobyshev teaches a maximum temperature of the stripping step i. of 400°C, one of ordinary skill in the art would reasonably expect the temperature of the inert stream to be less than 400°C at the end of the stripping step i., as claimed.
With regard to claim 14, Drobyshev teaches the method above, where the combustion step ii. takes place at a temperature of 300-450°C (paragraph [0038]) and the oxygen gas is heated before entering the zone (paragraph [0075]).
Drobyshev does not explicitly teach that the heated gas flow at the end of the combustion step ii. contacts the catalyst at a temperature of 400°C or less.
However, because one of ordinary skill in the art knows that regeneration is endothermic and because Drobyshev teaches a maximum temperature of the combustion step is 450°C, one of ordinary skill in the art would reasonably expect the temperature of the oxygen stream to be less than 450°C at the end of the combustion step ii., as claimed, which overlaps the range of 400°C or less of instant claim 14, rendering the range prima facie obvious.
With regard to claim 15, Drobyshev teaches the method above, where the combustion step iii. takes place at a temperature of 390-550°C (paragraph [0039]) and the oxygen gas is heated before entering the zone (paragraph [0075]).
Drobyshev does not explicitly teach that the heated gas flow at the end of the combustion step iii. contacts the catalyst at a temperature of 550°C or less.
However, because one of ordinary skill in the art knows that regeneration is endothermic and because Drobyshev teaches a maximum temperature of the combustion step is 550°C, one of ordinary skill in the art would reasonably expect the temperature of the oxygen stream to be less than 550°C at the end of the combustion step iii., as claimed
With regard to claim 16, Drobyshev teaches the method above, where the stripping step iv. takes place at a temperature of 550-300°C on a temperature decrease and then maintained at a temperature of 300-370°C (paragraph [0067]). This is within the range of 450°C or less of instant claim 16.
With regard to claim 17, Drobyshev teaches the process above (instant claim 17 step y). Drobyshev further teaches that the reaction process also comprises a step of converting ethanol into an ethanol/acetaldehyde mixture over a catalyst (Ca) which is on a matrix (support) (instant claim 17 step x) (paragraph [0046]).
Claims 9 and 10 are rejected under 35 U.S.C. 103 as being unpatentable over Drobyshev et al. (WO 2020/126920) in view of Song (US 2017/0342009) as applied to claim 1 above, and further in view of Heckelsberg (US 3,586,731).
With regard to claim 9, Drobyshev teaches regeneration comprising the stripping step i. with a stream comprising an inert gas (paragraph [0037]).
Drobyshev does not teach that steam can be used in the stripping step i.
Heckelsberg teaches a reaction comprising a tantalum catalyst on a support to produce olefins (Abstract). Heckelsberg further teaches that during regeneration, steam can be added to control the regeneration temperature during the regeneration which comprises flushing with an inert gas and then contacting with an oxygen gas for combustion (column 5, lines 1-11). While Heckelsberg does not teach the same reaction as Drobyshev, Heckelsberg teaches a similar catalyst comprising tantalum on a support and a similar regeneration with inert gas and combustion steps. Thus, one of ordinary skill in the art would reasonably conclude that the regeneration of Heckelsberg is related art to the regeneration of Drobyshev.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to add steam to the stripping step as taught by Heckelsberg, because Drobyshev and Heckelsberg each teach regeneration of a tantalum catalyst on a support with inert gas and oxygen containing gas, and Heckelsberg teaches that adding the steam allows for controlling the regeneration temperature (column 5, lines 10-11).
With regard to claim 10, Drobyshev teaches regeneration comprising the combustion step ii. with a stream comprising an inert gas and oxygen (paragraph [0038]).
Drobyshev does not teach that steam can be used in the combustion step ii.
Heckelsberg teaches a reaction comprising a tantalum catalyst on a support to produce olefins (Abstract). Heckelsberg further teaches that during regeneration, steam can be added to control the regeneration temperature during the regeneration which comprises flushing with an inert gas and then contacting with an oxygen gas for combustion (column 5, lines 1-11). While Heckelsberg does not teach the same reaction as Drobyshev, Heckelsberg teaches a similar catalyst comprising tantalum on a support and a similar regeneration with inert gas and combustion steps. Thus, one of ordinary skill in the art would reasonably conclude that the regeneration of Heckelsberg is related art to the regeneration of Drobyshev.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to add steam to the combustion step ii. as taught by Heckelsberg, because Drobyshev and Heckelsberg each teach regeneration of a tantalum catalyst on a support with inert gas and oxygen containing gas, and Heckelsberg teaches that adding the steam allows for controlling the regeneration temperature (column 5, lines 10-11).
Drobyshev in view of Heckelsberg does not specifically teach that the amount of steam added may be decreased during the combustion step ii such that the end of the combustion step ii contains no steam. However, because Drobyshev in view of Heckelsberg teaches that the steam is for the purpose of controlling the regeneration temperature, the addition rate of steam is a result-effective variable, and can be optimized. Therefore, it would have been obvious to one having ordinary skill in the art to have determined the optimum rate decreasing the steam such that there is no steam at the end of combustion step ii. as claimed, because it has been held that discovering an optimum value of a result effective variable involves only routine skill in the art. See MPEP 2144.05(II).
Claim 11 is rejected under 35 U.S.C. 103 as being unpatentable over Drobyshev et al. (WO 2020/126920) in view of Song (US 2017/0342009) and Heckelsberg (US 3,586,731) as applied to claim 9 above, and further in view of Huppke (US 2,279,198).
With regard to claim 11, Drobyshev in view of Heckelsberg teaches the process above, where the oxygen content in the first combustion stage ii is 0.1 to 1 vol% (paragraph [0038]).
Drobyshev in view of Heckelsberg does not teach that the oxygen content is initially less than 1 vol% and then increased to 1 to 6 vol%.
Huppke teaches a tantalum supported catalyst (page 1, second column, lines 23-31) for conversion of hydrocarbons (page 1, first column, lines 1-5). Huppke further teaches that during regeneration, gradually increasing the proportion of oxygen introduced into the inert gas stream avoids sudden access of oxygen to the spent catalyst, which has the danger of building up harmfully high temperatures by rapid combustion (page 3, second column, lines 67-75). Thus, Huppke teaches that the amount of oxygen added over time is a result-effective variable, and can be optimized. While Huppke does not teach the same reaction as Drobyshev, Huppke teaches a similar catalyst comprising tantalum on a support and a similar regeneration with inert gas and oxygen steps. Thus, one of ordinary skill in the art would reasonably conclude that the regeneration of Huppke is related art to the regeneration of Drobyshev.
Therefore, it would have been obvious to one having ordinary skill in the art to have determined the optimum rate adding the oxygen such that there is less than 1 vol% at the beginning of step ii. and 1-6 vol% at the end of step ii, because it has been held that discovering an optimum value of a result effective variable involves only routine skill in the art. See MPEP 2144.05(II).
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