DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claim Rejections - 35 USC § 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.
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 1-20 are rejected under 35 U.S.C. 103 as being unpatentable over Quignard et al., US Patent Application Publication No. 2011/0167713 (hereinafter referred to as Quignard) in view of Abhari et al., US Patent Application Publication No. 2012/0238791 (hereinafter referred to as Abhari).
Regarding claims 1-20, Quignard discloses in paragraph 0001, for direct hydroliquefaction of biomass selected from algae, lignocellulosic biomass and/or of one or more constituents of lignocellulosic biomass selected from the group comprising cellulose, hemicellulose and/or lignin for producing fuel bases. More particularly, the invention relates to a process comprising two successive hydroconversion stages using ebullating bed (slurry reactor) technology under high hydrogen pressure.
Quignard discloses in paragraph 0046, the biomass feed can be selected from algae, lignocellulosic biomass and/or of one or more constituents of lignocellulosic biomass selected from the group comprising cellulose, hemicellulose and/or lignin.
Quignard discloses in paragraph 0047, "Lignocellulosic biomass" means feeds rich in cellulose and/or hemicellulose and/or lignin. Only one of the constituents of this lignocellulosic biomass can be extracted for hydroliquefaction. This extract or the other remaining fraction can also constitute a feed usable in the invention, in particular lignin. Quignard discloses in paragraph 0048, the lignocellulosic raw material can consist of wood or of vegetable waste. Other non-limiting examples of lignocellulosic biomass material are agricultural residues (straw etc.), forestry residues (products from first clearing), forestry products, dedicated crops (short- rotation coppice), residues from the food and agriculture industry, household organic waste, waste from woodworking establishments, scrap timber from construction, and paper, recycled or not.
Quignard discloses in paragraph 0055, the lignocellulosic biomass can also be processed with feeds obtained from other renewable sources, for example oils and fats of vegetable or animal origin, or mixtures of said feeds, containing triglycerides and/or free fatty acids and/or esters. The vegetable oils can advantageously be raw or refined, partly or completely, and are obtained from the following plants: colza, sunflower, soya, palm, cabbage palm, olive, coconut, jatropha, this list not being limitative. Oils from algae or fish are also relevant. The oils can also be produced from genetically modified organisms. Animal fats are advantageously selected from lard or fats composed of residues from the food industry or from the catering trader. All products or mixtures of products resulting from the thermochemical conversion of biomass, for example charcoal or pyrolysis oil, are also feeds that can be used.
Quignard discloses in paragraph 0088, hydroliquefaction (Hydroconversion): First Stage, the liquefaction of biomass is carried out by a catalytic process of hydroconversion in at least two stages using reactors of the ebullating bed (slurry reactor) type connected in series directly.
Quignard discloses in paragraph 0093, the suspension is then introduced at the bottom of the first hydroconversion reactor containing an ebullating bed (slurry reactor) operating with ascending flow of liquid and gas and containing at least one hydroconversion catalyst. The hydrogen necessary for operation can be supplied by make-up hydrogen and/or by hydrogen recycled from the process and/or from another nearby refining process.
Quignard discloses in paragraph 0094, the manner of operation of the ebullating bed (slurry) catalytic reactor, including recycling of the liquids from the reactor upwards through the agitated catalyst bed, is generally well known. Ebullating bed technologies use supported catalysts, generally in the form of extrudates the diameter of which is generally of the order of 1 mm or less than 1 mm. The catalysts remain inside the reactors and are not discharged with the products. The catalytic activity can be kept constant by in-line replacement of catalyst. Therefore, it is not necessary to stop the unit in order to replace spent catalyst, nor to increase the reaction temperatures in the course of the cycle in order to compensate for deactivation. Moreover, by working under constant operating conditions it is possible to obtain yields and product qualities that remain constant throughout the cycle. Also, because the catalyst is constantly agitated by considerable recycling of liquid, the pressure loss in the reactor remains low and constant, and the exothermic effects of the reaction are quickly averaged over the catalyst bed, which is therefore almost isothermal and does not require injection of quenches.
Quignard discloses in paragraph 0098, hydroliquefaction (Hydroconversion): Second Stage, at least a proportion of the effluent originating from the first hydroconversion stage is then injected into a second hydroconversion reactor containing an ebullating bed catalyst and operating with ascending flow of liquid and gas and containing at least one hydroconversion catalyst. The effluent is mixed with additional hydrogen, which can be make-up hydrogen and/or hydrogen recycled from the liquefaction process and/or from another nearby refining process.
Quignard discloses in paragraph 0101, the operating conditions, for a given catalyst and feed, are adjusted depending on the total conversion desired.
Quignard discloses in paragraph 0102, the effluent obtained at the end of the first hydroconversion stage is subjected to separation of the light fraction and at least a proportion, preferably all, of the residual effluent is treated in the second hydroconversion stage. This separation is advantageously carried out in an inter-stage separator. This separation avoids overcracking of the light fraction in stage (2). It also makes it possible to reduce capital expenditure for the reactor in stage (2) (less feed to be treated, less catalyst etc.) or to supply an external feed to the reactor in stage (2) or to increase the residence time in the reactor in stage (2). The hydrogen thus separated from the light fraction can be recycled to the process after purification. So as to improve the separation of the light fraction, the bottom product of the inter- stage separator containing predominantly the heavy fraction and optionally a proportion of the light fraction, can be treated in a stage of vacuum distillation or liquid/liquid extraction or high- pressure stripping with hydrogen, for example.
Quignard discloses in paragraph 0103, although the process for hydroliquefaction in two hydroconversion stages according to the invention produces high yields of fuel bases, a third ebullating bed hydroconversion reactor operating at a higher temperature than the second reactor can be envisaged for certain feeds of biomass or of biomass/co-feed mixture. The possibility of inter-stage separation of gaseous effluents applies similarly upstream of this third reactor.
Quignard discloses in paragraph 0104, in the two stages of hydroliquefaction, it is possible to use any conventional catalyst for hydrotreating and/or hydroconversion of feeds of high molecular weight, in particular a granular catalyst comprising, on an amorphous support, at least one metal or metal compound having a hydrodehydrogenating function.
Quignard discloses in paragraph 0105, this catalyst is advantageously a catalyst comprising at least one group VIII metal, selected from the group comprising Ni, Pd, Pt, Co, Rh and/or Ru, preferably nickel and/or cobalt, most often in combination with at least one group VIB metal, preferably molybdenum and/or tungsten. For example, a catalyst will be used comprising from 0.5 to 10 wt. % of nickel and preferably from 1 to 5 wt. % of nickel (expressed as nickel oxide NiO) and from 1 to 30 wt. % of molybdenum, preferably from 5 to 20 wt. % of molybdenum (expressed as molybdenum oxide MoO₃) on an amorphous mineral support. This support will be selected for example from the group comprising alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of these minerals. Advantageously, said support contains other doping compounds, in particular oxides selected from the group comprising boron oxide, zirconia, ceria, titanium dioxide, phosphoric anhydride and a mixture of these oxides. An alumina support is used most often, and very often an alumina support doped with phosphorus and optionally with boron. The concentration of phosphoric anhydride P₂O₅ is usually comprised between 0 or 0.1% and approximately 10 wt%.
Quignard discloses in paragraph 0108, prior to injection of the feed, the catalysts used in the process according to the present invention are preferably subjected to a treatment of sulphidation for transforming, at least partly, the metallic species to sulphide before bringing them into contact with the feed to be treated. This treatment of activation by sulphidation is well known to a person skilled in the art and can be carried out by any method already described in the literature either in situ, i.e. in the reactor, or ex situ.
Quignard discloses in paragraph 0040, slurry reactor hydroconversion techniques of course use a dispersed catalyst in the form of very small particles, the size of which is of a few tens of microns or less (generally 0.001 to 100 µm). The catalysts or their precursors are injected at the entry to the reactors, with the feed to be converted.
Quignard discloses in paragraph 0113, for the purpose of producing fuel bases (naphtha, kerosene and/or diesel), the effluent obtained at the end of the second hydroconversion stage preferably undergoes a separation stage, for separating a gaseous phase, an aqueous phase, at least one light fraction of liquid hydrocarbons of the naphtha, kerosene and/or diesel type, a vacuum gas oil fraction, a vacuum residue fraction and a solid fraction, which can be in the vacuum residue.
Quignard discloses in paragraphs 0114-0115, the effluent from the second
hydroconversion stage is advantageously treated according to the following optional stages: the effluent obtained from the process according to the invention undergoes at least one separation stage and preferably a stage of gas/liquid separation and of separation of the aqueous phase and of at least one liquid hydrocarbon base, said stages being optional, and applicable in any order relative to one another. The separation stage can advantageously be implemented by any method known to a person skilled in the art, for example by combining one or more high and/or low
pressure separators, and/or stages of high and/or low pressure distillation and/or stripping, and/or stages of liquid/liquid extraction, and/or stages of solid/liquid separation and/or stages of centrifugation.
Quignard further discloses in paragraph 0117, advantageously, the effluent originating from stage (2) first undergoes a stage of gas/liquid separation. Preferably, the effluent from the second reactor is separated in a high-pressure high-temperature (HPHT) separator, from which a vapour phase and a liquid phase are recovered.
Quignard discloses in paragraph 0135, the effluent treated in reactor (30) is sent by line (38) to a high-pressure high-temperature (HPHT) separator (40) from which a vapour phase (41) and a liquid phase (44) are recovered. The vapour phase (41) is sent, optionally mixed with vapour phase (71) originating from the optional inter-stage separator (70) between the two reactors, generally via an exchanger (not shown) or an air cooler for cooling (not shown) to a high-pressure low-temperature (HPLT) separator (72) from which a vapour phase (73) containing gases (H₂, H2S, NH₃, H₂O, CO₂, CO, C1-C4 hydrocarbons, etc.), an aqueous phase (75) containing predominantly water and oxygen-containing compounds, in particular phenols, and a liquid phase (74), are recovered.
Quignard discloses in paragraph 0122, the gases extracted from the HPLT separator undergo a purification treatment to recover the hydrogen and recycle it to the hydroconversion reactors. The same applies to the gaseous effluents originating from the optional units for further processing, for example hydrotreating and/or hydrocracking of hydrocarbon cuts. The gaseous phase received from the inter-stage separator can also be added.
Quignard discloses in paragraph 0130, thus, in the process according to the invention, the degrees of conversion in hydroliquefaction of the starting biomass obtained for the two stages of hydroconversion are of the order of 80 to 99.5%. The yield of upgradeable gases and liquids, the fraction C3 -450° C., is greater than 30%.
It is to be noted, Quignard discloses adding the catalyst to the hydroconversion reactors but fails to further disclose backmixing in the reactor through a gas sparger in order to the flow of gas bubbles.
However, it is known in the art to add a gas sparger to a hydroconversion reactor in order for the flow of gas bubbles, as taught by Abhari.
Abhari discloses in paragraph 0039, a plurality of reactors are employed to divide the hydrogenation/hydrogenolysis load over two or more reactors. Those skilled in the art will recognize that the reactors-in-series configuration is used in back-mixed reactor systems to achieve higher conversion at same or lower total reactor volume.
Abhari discloses in paragraph 0040, biological feedstock 201 is pressurized to the reactor system pressure in pump 202. The reactor system pressures are in the same range previously specified herein. The reactor system further contains catalyst of type and size specified in the detailed description of the invention. The pressurized feed 203 is optionally heated in heater 240. The preheated feed 203A enters the first stage reactor 204 wherein partial conversion occurs in the catalyst slurry phase. Hydrogen-rich gas 205 is introduced into slurry bubble column reactor 204 through a sparger device (not shown) at the rates previously specified herein. Abhari further discloses in paragraph 0033, a heated hydrogen-rich gas 105A is dispersed through a sparger 119. The sparger may be of various configurations including but not limited to a ring-type sparger with multiple orifices, a sintered metal plate or sintered metal distributing pipe(s) or co-fed with the biological feedstock via a simple pipe distributor. In some embodiments the catalyst is dispersed in the slurry phase by mechanical agitation. The gas flow through the reactor 104 produces a uniform catalyst slurry 106. Alternatively, a side arm/downcomer (not shown) can also be deployed to recirculate de-gassed slurry to the reactor 104 which also aids catalyst distribution in the reactor 104.
Therefore, it would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to add the sparger of Abhari to the slurry reactor (hydroconversion reactor) of Quignard. The motivation to do so is to use a gas sparger in order for the flow of gas bubbles in the reactor.
Double Patenting
The nonstatutory double patenting rejection is based on a judicially created doctrine grounded in public policy (a policy reflected in the statute) so as to prevent the unjustified or improper timewise extension of the “right to exclude” granted by a patent and to prevent possible harassment by multiple assignees. A nonstatutory double patenting rejection is appropriate where the claims at issue are not identical, but at least one examined application claim is not patentably distinct from the reference claim(s) because the examined application claim is either anticipated by, or would have been obvious over, the reference claim(s). See, e.g., In re Berg, 140 F.3d 1428, 46 USPQ2d 1226 (Fed. Cir. 1998); In re Goodman, 11 F.3d 1046, 29 USPQ2d 2010 (Fed. Cir. 1993); In re Longi, 759 F.2d 887, 225 USPQ 645 (Fed. Cir. 1985); In re Van Ornum, 686 F.2d 937, 214 USPQ 761 (CCPA 1982); In re Vogel, 422 F.2d 438, 164 USPQ 619 (CCPA 1970); and In re Thorington, 418 F.2d 528, 163 USPQ 644 (CCPA 1969).
A timely filed terminal disclaimer in compliance with 37 CFR 1.321(c) or 1.321(d) may be used to overcome an actual or provisional rejection based on a nonstatutory double patenting ground provided the reference application or patent either is shown to be commonly owned with this application, or claims an invention made as a result of activities undertaken within the scope of a joint research agreement. A terminal disclaimer must be signed in compliance with 37 CFR 1.321(b).
The USPTO internet Web site contains terminal disclaimer forms which may be used. Please visit http://www.uspto.gov/forms/. The filing date of the application will determine what form should be used. A web-based eTerminal Disclaimer may be filled out completely online using web-screens. An eTerminal Disclaimer that meets all requirements is auto-processed and approved immediately upon submission. For more information about eTerminal Disclaimers, refer to http://www.uspto.gov/patents/process/file/efs/guidance/eTD-info-I.jsp.
Claims 1-20 are rejected on the ground of nonstatutory obviousness-type double patenting as being unpatentable over claims 1-20 co-pending of application No. 18/667,035. Although the conflicting claims are not identical, they are not patentably distinct from each other.
The co-pending '035 application discloses the same limitations as does the instant application and would therefore be obvious in light of the disclosures discussed above and incorporated herein by reference.
A timely filed terminal disclaimer in compliance with 37 CFR 1.321(c) or 1.321(d) may be used to overcome an actual or provisional rejection based on a nonstatutory double patenting ground provided the reference application or patent either is shown to be commonly owned with this application, or claims an invention made as a result of activities undertaken within the scope of a joint research agreement. A terminal disclaimer must be signed in compliance with 37 CFR 1.321(b).
The USPTO internet Web site contains terminal disclaimer forms which may be used. Please visit http://www.uspto.gov/forms/. The filing date of the application will determine what form should be used. A web-based eTerminal Disclaimer may be filled out completely online using web-screens. An eTerminal Disclaimer that meets all requirements is auto-processed and approved immediately upon submission. For more information about eTerminal Disclaimers, refer to http://www.uspto.gov/patents/process/file/efs/guidance/eTD-info-I.jsp.
Double Patenting II
Claims 1-20 are rejected on the ground of nonstatutory obviousness-type double patenting as being unpatentable over claims 1-20 co-pending of application No. 18/667,043. Although the conflicting claims are not identical, they are not patentably distinct from each other.
The co-pending '043 application discloses the same limitations as does the instant application and would therefore be obvious in light of the disclosures discussed above and incorporated herein by reference.
A timely filed terminal disclaimer in compliance with 37 CFR 1.321(c) or 1.321(d) may be used to overcome an actual or provisional rejection based on a nonstatutory double patenting ground provided the reference application or patent either is shown to be commonly owned with this application, or claims an invention made as a result of activities undertaken within the scope of a joint research agreement. A terminal disclaimer must be signed in compliance with 37 CFR 1.321(b).
The USPTO internet Web site contains terminal disclaimer forms which may be used. Please visit http://www.uspto.gov/forms/. The filing date of the application will determine what form should be used. A web-based eTerminal Disclaimer may be filled out completely online using web-screens. An eTerminal Disclaimer that meets all requirements is auto-processed and approved immediately upon submission. For more information about eTerminal Disclaimers, refer to http://www.uspto.gov/patents/process/file/efs/guidance/eTD-info-I.jsp.
Conclusion
8. There were unused X references from the ISR report. The examiner is of the position that the prior art cited adequately reads on the claims as instantly recited.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to VISHAL V VASISTH whose telephone number is (571)270-3716. The examiner can normally be reached M-F 9:00-4:30 and 7:00-10:00p.
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/VISHAL V VASISTH/Primary Examiner, Art Unit 1771