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 Status
Claims 1-17 were filed on 07/06/2023. No preliminary amendments of the claims were submitted.
Claims 1-17 are currently pending and under examination.
Priority
The instant application claims domestic benefit to U.S. provisional application no. 63,389,174 filed on 07/14/2022 and U.S. provisional application no. 63,415,457 filed on 10/12/2022. Applicant’s claim for the benefit of a prior-filed application under 35 U.S.C. 119(e) is acknowledged.
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 1-8, and 10-12 are rejected under 35 U.S.C. 103 as being unpatentable over Peng et al. (WO2021080645 A1, published on 04/29/2021, found in PTO-892) in view of Knapp et al. (WO2008024508 A1, published on 02/28/2008, found in PTO-892) in view of Dubois et al. (WO2021043989 A1, published on 03/11/2021, found in PTO-892)
Peng et al. teaches HFO-1234ze compositions and processes for producing and using the compositions. The fluorocarbon industry has been working to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) (see lines 14-22 of page 1). In addition to ozone depleting concerns, global warming is another environmental concern in many of these applications. Thus, there is a need for compositions that meet both low ozone depletion standards as well as having low global warming potentials. Certain hydrofluoroolefin compositions are believed to meet both goals. Thus, there is also a need for economical manufacturing processes that provide these compositions (see lines 23-27 of page 1). The disclosure includes a method of producing a mixture of a fluoropropene of formula CF3CH=CHF and a fluoropropene of formula CF3CF=CH2, comprising contacting a mixture of 1,1,1,3,3-pentafluoropropane (HFC-245fa) and Z-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)) in the gas phase with a catalyst to form a mixture comprising HFO-1234ze(Z), E-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 2,3,3,3-tetrafluoropropene, and optionally unreacted HFC-245fa (see lines 26-30 of page 2 and lines 1-3 of page 3). In a certain embodiment, HFO-1234ze(E) and HFO-1234yf may be separated from the HFO-1234ze(Z), hydrogen fluoride, and any unreacted HFC-245fa, which are then recycled back to the reactor with additional HFC-245fa (see lines 21-22 of page 11). One embodiment of the invention relates to any combination of the foregoing wherein said hydrogen fluoride produced in the first step is separated and recovered (see lines 21-22 of page 5). Hydrogen fluoride may be removed by scrubbing, by passing the reactor effluent through a solution of aqueous caustic, or hydrogen fluoride may be removed by distillation (see lines 22-24 of page 11). One embodiment of the invention relates to any combination of the foregoing wherein the mixture includes 0.1 to 0.5 mol% 2,3,3,3-tetrafluoropropene (see lines 25-26 of page 5). In one embodiment, the reaction vessel can be held at a temperature of between 200 °C and 375 °C (see line 5 of page 11). The reaction pressure can be subatmospheric, atmospheric, or superatmospheric. In one embodiment, the reaction is conducted at a pressure of from 14 psig to about 100 psig (see lines 9-10 of page 11). In an example provided in the specification of Peng et al., the contact time of the reactants in the reactor was 45 seconds (see line 22 on page 18).
The teachings of Peng et al. differ from that of the instantly claimed invention in that Peng et al. does not teach a process for producing HFO-1234ze(E) comprising reacting a feed stream additionally comprising CFC-113, and forming a first product stream additionally comprising CFC-113, do not teach distillation of the unreacted HFC-245fa and CFC-113 to produce an overhead recycle stream and a bottoms stream, the recycle stream comprising unreacted HFC-245fa and a first amount of CFC-113, and the bottoms stream comprising a second amount CFC-113 greater than the first amount. As recited in instant claim 2, Peng et al. does not teach wherein the distillation apparatus is conducted at a pressure above 17 psia. As recited in instant claim 12, Peng et al. does not teach wherein the distillation apparatus is operated at least one of the following conditions: (i) a temperature of about 10°C to 105°C and (ii) a pressure of about -15 to 150 psia.
Knapp et al teaches an azeotropic distillation for separating fluoroolefin from mixtures of HF and fluoroolefin may be carried out using an entrainer compound (see lines 9-11 of page 32). The chemical manufacture of fluoroolefins may produce mixtures of the desired fluoroolefins and hydrogen fluoride (HF). The separation of fluoroolefins and HF is not always easily accomplished. Existing methods of distillation and decantation are very often ineffective for separation of these compounds. Aqueous scrubbing may be effective, but requires the use of large amounts of scrubbing solutions and produces excessive waste as well as wet product that must then be dried. Therefore, there is a need for new methods of separating HF from fluoroolefins (see lines 15-22 of page 1). The term "entrainer" is used herein to describe any compound that would be effective in separation of fluoroolefins from mixtures comprising HF and fluoroolefin in an azeotropic distillation process. Included as useful entrainers are compounds that form azeotropes with one or more of the components of a mixture, including fluoroolefins, HF, and possible hydrofluorocarbons for which the boiling point of at least one of such azeotropes is lower than the boiling point of the fluoroolefin/HF azeotrope. Entrainers may be selected from the group consisting of hydrocarbons, chlorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, perfluorocarbons, fluoroethers, HFPO, SF6, chlorine, hexafluoroacetone, and mixtures thereof (see lines 27-32 of page 24 and lines 1-7 of page 25). Chlorofluorocarbon (CFC) entrainers comprise compounds with carbon, chlorine and fluorine. Representative CFCs include but are not limited to a Markush grouping which includes 1, 1,2-trichloro-1,2,2-trifluoroethane (CFC-113) (see lines 20-25 of page 25). The process for separating a fluoroolefin from a first composition comprising HF and fluoroolefin comprises contacting said first composition with an entrainer to form a second composition. The contacting may occur in a first distillation column, or the second composition may be formed by mixing the components prior to feeding to a distillation column in a premixing step (see lines 6-11 on page 33). In an embodiment is provided a process for separating HF from a mixture comprising HFC-1234ze, HF, and at least one of HFC-245fa or HFC-245eb. The process comprises:
a. adding an entrainer to the mixture comprising HFC-1234ze, HF, and at least one of HFC-245fa or HFC-245eb thus forming a second mixture;
b. distilling said second mixture in a first distillation step to form a first distillate composition comprising HF and entrainer and a first bottoms composition comprising HFC-1234ze and at least one
of HFC-245fa or HFC-245eb;
c. condensing said first distillate composition to form two liquid phases, being (i) an entrainer-rich phase and (ii) an HF-rich phase; and
d. recycling the entrainer-rich phase back to the first distillation step (see lines 19-32 of page 47). The operating variables for the first distillation column will depend strongly on the entrainer being used in the separation process. In general, the first distillation column may operate at pressures from about 14.7 psia (101 kPa) to about 500 psia (3448 kPa) with a top temperature of from about -50 ° C to about 100 ° C and a bottom temperature of from about -30 ° C to about 200 ° C.
Dubois et al. teaches Hydrofluorocarbons (HFCs) and in particular hydrofluoroolefins (HFOs), such as 2,3,3,3-tetrafluoro-propene (HF0-1234yf) are compounds known for their properties as refrigerants and heat transfer fluids, fire extinguishers, propellants, foaming agents, blowing agents, gaseous dielectrics, polymerization media or monomers, carrier fluids, abrasives, drying agents and power generation unit fluids. Most hydrofluoroolefin manufacturing processes involve a fluorination and/or dehydrohalogenation reaction. This type of reaction is carried out in the gas phase and generates impurities which must therefore be eliminated to obtain the desired compound in a degree of purity sufficient for the intended applications. It is desirable to produce hydrofluoroolefins with a low impurity content (see paragraphs 0005-0010). Dubois et al. teaches a method for purifying a composition comprising a hydrohalocarbon B, comprising the steps of:
i) supplying a composition Al comprising a hydrohalocarbon B and at least one impurity C different from said hydrohalocarbon B,
ii) compressing said composition Al, and optionally cooling it, so as to obtain said hydrohalocarbon B in liquid form to form a liquid stream A2 comprising said hydrohalocarbon B,
iii) distilling said stream A2 obtained in step ii) to form and recover a stream A3 comprising said hydrohalocarbon B, characterized in that step iii) is carried out in a pressure distillation device comprising one or more rotating packed bed(s) (see paragraph 0013).
Preferably, said composition A1 comprises a hydrohalocarbon B selected from group B1; and at least one impurity C selected from group C1 (See paragraph 0073). In another embodiment, said composition A1 comprises a hydrohalocarbide B selected from a Markush group consisting of 1,3,3,3-tetrafluoropropene and at least one impurity C selected from a Markush group consisting of 2,3,3,3-tetrafluoropropene (HFO-1234yf) (see paragraph 0076 and 0078). In particular, said A1 composition includes less than 78% in weight of said at least one impurity C on the basis of the total weight of said composition (see paragraph 0079). According to a preferred embodiment, said hydrohalocarbon B is selected from a Markush group B1 consisting of various hydrohalocarbons including 1,1,1,3,3-pentafluoropropane (HFC-245fa) and 1,3,3,3-tetrafluoropropene (HFO-1234ze) (see paragraphs 0018 and 0019). According to a preferred embodiment, said at least one impurity C is selected from group C1 consisting of a Markush group of hydrohalocarbons including trichlorotrifluoroethane (CFC-113), 1,1,1,3,3-pentafluoropropane (HFC-245fa), and 2,3,3,3-tetrafluoropropene (HFO-1234yf) (see paragraphs 0023, 0028, and 0035). Preferably in step ii), said composition A1 is compressed under a pressure of 2 to 200 absolute bars (29 to 2900 psi) (see paragraph 0081). The implementation of step iii) makes it possible to purify said stream A2 in order to obtain a stream A3 which comprises said hydrohalocarbon B and in which the content of said at least one impurity C is reduced compared to the content of said impurity in said stream A2. In particular, said A3 stream may be free of said at least one impurity C (see paragraph 0096). Preferably, the content of said at least one (of said) impurity(ies) C in said stream A3 is less than the content of said at least one (of said) impurity(ies) C in said stream A2. More specifically, said A3 stream is free from said at least one (of said) impurity(ies) C. The term "free" used here corresponds to a content of less than 0.5%, advantageously less than 0.1%, preferably less than 0.01%, more preferably less than 0.001 %, in particular less than 0.0001 % by weight on the basis of the total weight of said stream (see paragraph 101). After purification, the hydrohalocarbon B thus recovered can be used in the production process of other hydrofluorocarbon compounds or be used in applications such as blowing agents for the preparation of polyurethane or polystyrene foam, refrigerant compositions, heat transfer compositions. The said impurity(ies) recovered in the A4 stream can also be used in processes for preparing hydrofluorocarbon compounds or in refrigerant compositions or heat transfer compositions (see paragraph 0107). The implementation of step iii) also makes it possible to recover a stream A4 comprising at least some, preferably all, of said at least one impurity C present in said stream A2 (see paragraph 0088). In particular, said A4 stream comprises at least 98% by weight of said at least one impurity C (see paragraph 0106).
It would have been obvious to combine the teachings of Peng et al., Knapp et al., and Dubois et al. before the effective filing date of the claimed invention by including CFC-113 with the compounds of the feed stream during the production of HFO-1234ze(E) as taught by Knapp et al., separating HFO-1234ze(E) from HFC-245fa and CFC-113 as taught by Dubois et al. by choosing HFO-1234ze as hydrohalocarbon B in the Markush group given in Dubois et al., choosing CFC-113 and HFC-245fa as impurity C in the Markush group given by Dubois et al., distilling the mixture of HFC-245fa and CFC-113, as taught by Dubois et al., to produce an overhead recycle stream and a bottoms stream, the recycle stream comprising unreacted HFC-245fa (molecular weight (MW) = 134.05 g/mol, the lighter of the two compounds) and a first amount of CFC-113 (MW = 187.375 g/mol, the heavier impurity), and the bottoms stream (heavier impurities) comprising a second amount CFC-113 greater than the first amount, having CFC-113 present in a product stream, and recycling CFC-113 back to the feed stream. As required by instant claims 2 and 12 and taught by Dubois et al., the distillation process occurs at pressures from 2 to 200 absolute bars. As required by instant claims 3 and 5 and taught by Dubois et al., the stream containing primarily HFC-245fa (the recycle stream) is also taught to have less than 0.5% of the CFC-113 impurity after distillation. As required by instant claim 4 and taught by Dubois et al., the A1 composition comprising HFC-245fa and CFC-113 would include less than 78% by weight CFC-113 and would be distilled. As required by instant claims 6 and 7 and taught by Knapp et al., the mixture comprising HFO-1234ze, HFC-245fa, CFC-113 additionally contains HF and is conveyed to a separation device (distillation or scrubbing solution) to remove HF. As required by instant claim 8 and taught by Dubois et al., the first product stream containing HFO-1234ze and a light impurity such as HFO-1234yf would be distilled by selecting HFO-1234ze and HFO-1234yf as the components of composition A1 and distilling the composition. As required by instant claim 10 and taught by Dubois et al., the purification would reduce the level of light impurities, such as HFO-1234yf, in the composition or product stream to less than 0.5%. As required by instant claim 11 and taught by Peng et al., the reaction vessel can be held at a temperature of between 200 °C and 375 °C. It would have been prima facie obvious for one of ordinary skill in the art to combine the reaction process as taught by Peng et al. with the entrainer as taught by Knapp et al., and the distillation processes as taught by Dubois et al. to produce HFO-1234ze(E) with fewer impurities such as CFC-113 because, as taught by Dubois et al., it is desirable to produce hydrofluoroolefins with a low impurity content sufficient for intended applications. One of ordinary skill in the art would have a reasonable expectation of success because all references aim to optimize the process of producing hydrofluorocarbons.
Claim 9 is rejected under 35 U.S.C. 103 as being unpatentable over Peng et al. (WO2021080645 A1, published on 04/29/2021, found in PTO-892) in view of Knapp et al. (WO2008024508 A1, published on 02/28/2008, found in PTO-892) in view of Dubois et al. (WO2021043989 A1, Published on 03/11/2021, found in PTO-892) as applied to claims 1-8 and 10-12 above, and further in view of Low et al. (WO2021043989 A1, published on 01/16/2013, found in PTO-892.
The combined teachings of Peng et al., Knapp et al., and Dubois et al. were discussed above.
The combined teachings of Peng et al., Knapp et al., and Dubois et al. differ from that of the instantly claimed invention in that the combined teachings of Peng et al., Knapp et al., and Dubois et al. do not teach a product stream conveyed to a separation device to remove the light impurities and the separation device comprises at least one of a batch or continuous fractional distillation column, spinning band distillation equipment, a wiped film evaporator, and combinations of the foregoing.
Low et al. teaches processes for purifying tetrafluoropropene, particularly 1,3,3,3-tetrafluoropropene (HFO-1234ze) and 2,3,3,3-tetrafluoropropene (see lines 3-4 of page 1). (Hydro)fluoroalkenes are increasingly being considered as working fluids in applications such as refrigeration, heat pumping, foam blowing, fire extinguishers/retardants, propellants and solvency (e.g. plasma cleaning and etching). The processes used to make (hydro)fluoroalkenes can lead to the generation of toxic and/or otherwise undesirable by-products. The presence of small quantities of impurities may not be detrimental to the bulk physical properties of the (hydro)fluoroalkene product and for some applications their removal is unnecessary. However, some applications require very low levels of impurities and/or the presence (or absence) of certain physical properties (see lines 15-25 of Page 1). TFMA and R-1234 may be separated from a mixture comprising those components using techniques such as distillative separation, adsorption and/or membrane separation. The distillative separation of TFMA from R-1234, particularly R-1234ze, more particularly R-1234ze(E) may be performed at a range of pressures, e.g. from about 1 to about 20 bar. Continuous or semi-continuous fractional distillation of TFMA from R-1234ze(E) may be effective in allowing separation of TFMA from R-1234ze(E) (see lines 13-18 of Page 2).
It would have been obvious to combine the combined teachings of Peng et al., Knapp et al., and Dubois et al. with the teachings of Low et al. before the effective filing date of the claimed invention by using continuous fractional distillation as a separation technique for purification of a product stream in the production of HFO-1234ze(E). It would have been prima facie obvious for one of ordinary skill in the art to purify the HFO-1234ze(E) produced using continuous fractional distillation as a separation technique because, as taught by Low et al., some applications of hydrofluoroolefins require very low levels of impurities and/or the presence (or absence) of certain physical properties. One of ordinary skill in the art would have a reasonable expectation of success because all references aim towards the optimization of hydrofluoroolefin purification.
Claims 13-15 are rejected under 35 U.S.C. 103 as being unpatentable over Dubois et al. (WO2021043989 A1, published on 03/11/2021, found in PTO-892) in view of Knapp et al. (WO2008024508 A1, published on 02/28/2008, found in PTO-892).
The teachings of Dubois et al. were discussed above.
The teachings of Dubois et al. differ from that of the instantly claimed invention in that Dubois et al. does not teach the separation device comprises at least one of zeolites, liquid extractants, azeotropic distillation apparatuses, mineral oil, and combinations of the foregoing.
The teachings of Knapp et al. were discussed above.
It would have been obvious to combine Dubois et al. with Knapp et al. before the effective filing date of the claimed invention by using an azeotropic distillation apparatus to remove CFC-113 from an HFC-245fa feed stream. It would have been prima facie obvious for one of ordinary skill in the art to purify the hydrofluoroolefin produced by azeotropic distillation because it is desirable to produce hydrofluoroolefins with a low impurity content sufficient for intended applications as taught by Dubois et al. One of ordinary skill in the art would have a reasonable expectation of success because both references aim towards the optimization of hydrofluoroolefin purification.
Claims 16 and 17 are rejected under 35 U.S.C. 103 as being unpatentable over Dubois et al. (WO2021043989 A1, published on 03/11/2021, found in PTO-892) in view of Dong et al. (NPL, published in 2017, found in PTO-892).
The teachings of Dubois et al. were discussed above.
The teachings of Dubois et al. differ from that of the instantly claimed invention in that Dubois et al. does not teach wherein the composition consisting of HFC-245fa and CFC-113 is azeotropic or azeotropic-like.
Dong et al. teaches the framework of converting low-grade thermal energy into electricity, organic Rankine cycle (ORC) is proposed as a promising method due to its high efficiency and reliability, small size, and low emission. ORC has the same principle as steam Rankine cycle while uses organic substance with low boiling point as working fluid. Since pure fluid has the isothermal property during evaporation and condensation processes, the temperature profiles between pure working fluid and non-isothermal heat transfer medium cannot match mutually, which causes a large entropy generation in the corresponding process and consequently poor thermal performance. For this matter, both supercritical ORC and zeotropic ORC (the cycle using zeotropic mixtures as working fluid) are proposed to partially overcome this limitation. The selection of working fluid is very important for an ORC (see Introduction section). The performance of four pure refrigerants and their zeotropic mixtures as working fluids for low grade ORC through pinch analysis method. Dong et al. observes a 0.66-17.96% increase in cycle efficiency by using mixtures instead of their pure constituents. Among them, the cycle with R245fa/R113 (0.32/0.68) shows an efficiency of 10.73%, compared with 9.10% for R245fa (representing a relative increase of 17.96%) (see Results and Discussion section).
It would have been obvious to combine the teachings of Dubois et al. with Dong et al. before the effective filing date of the claimed invention by recognizing the composition comprising about 3.5 wt.% of CFC-113 and about 96.5 wt.% of HFC-245fa is an azeotrope or azeotrope-like. It would have been prima facie obvious for one of ordinary skill in the art to recognize the mixture of CFC-113 and HFC-245fa obtained in the purification process as taught by Dubois et al. would be an azeotrope or azeotrope-like due to the teachings of the same mixture in different weight percentages being an efficient working fluid (zeotropic mixture) for an organic Rankine cycle as taught by Dong et al. One of ordinary skill in the art would have a reasonable expectation of success because both references aim to improve thermodynamic industrial processes.
Conclusion
No claim is found allowable.
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/KRISTEN W BRADY/
Examiner, Art Unit 1692
/SCARLETT Y GOON/Supervisory Patent Examiner, Art Unit 1693