KALNES, Tom N. (Uop Llc, 25 East Algonquin RoadP. O. Box 501, Des Plaines Illinois, 60017-5017, US)
1. A process for producing a renewable hydrocarbon fuel, comprising:
A) providing a feed comprising a lignocellulosic material to a pyrolysis zone to produce a stream comprising a pyrolysis oil;
B) providing the pyrolysis oil stream to a refining zone producing a refined stream;
C) providing at least a portion of the refined stream to a reforming zone producing a stream comprising hydrogen;
D) providing at least a portion of the hydrogen stream to the refining zone; and
E) recovering the renewable hydrocarbon fuel from the refined stream.
2. The process according to claim 1, wherein the lignocellulosic material comprises at least one of cellulose, hemicellulose, and lignin.
3. The process according to claim 1 or 2, wherein the renewable hydrocarbon fuel has lifecycle greenhouse gas emissions of no more than 40 g C02 equivalent/MJ.
4. The process according to claim 1, 2, or 3, wherein the reforming zone comprises a steam reforming zone.
5. The process according to claim 1, 2, 3, or 4, further comprising providing the refined stream to a separation zone to obtain the renewable hydrocarbon fuel and a fuel gas stream comprising one or more of CO, C02, CH4, C2H6, C3¾, C4Hi0, H2, and H2S.
6. The process according to claim 5, wherein the separation zone comprises one or more flash drums.
7. The process according to claim 5, further comprising passing the fuel gas stream to a conditioning zone.
8. The process according to claim 7, wherein the conditioning zone comprises a scrubber.
9. The process according to claim 8, further comprising passing the scrubbed fuel gas stream to the steam reforming zone.
10. The process according to one of the proceeding claims, further comprising pretreating the renewable feed prior to entering the pyrolysis zone.
A RENEWABLE HYDROCARBON FUEL
STATEMENT OF PRIORITY
 This application claims priority to U.S. Application No. 12/969,335 which was filed on December 15, 2010, the contents of which are hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
 This invention generally relates to a process for producing a renewable hydrocarbon fuel.
DESCRIPTION OF THE RELATED ART
 Generally, concerns over fossil fuel greenhouse gas emissions have led to an increasing emphasis on renewable energy sources. Wood and other forms of biomass including agricultural and forestry residues are examples of some types of biomass feedstocks being considered for the production of liquid fuels.
 Pyrolysis may be used for obtaining liquid fuels from these biomass feedstocks. Generally, pyrolysis refers to thermal decomposition in the substantial absence of oxygen or in the presence of significantly less oxygen than required for complete combustion. In addition to the desired liquid product, other streams, such as char ash, and non-condensible gases may be obtained as less desirable byproducts. However, significantly improved yields of primary, non-equilibrium liquids and gases, such as valuable chemicals, chemical intermediates, petrochemicals, and fuels, may be obtained from carbonaceous feedstocks through fast pyrolysis.
 When producing transportation fuels by combination of pyrolysis and hydrogen refining, a very significant quantity of hydrogen can be required to produce a fully deoxygenated biofuel meeting ASTM standards for use as either blend stocks or drop-in replacements for petroleum gasoline, kerosene, and diesel fuel. If this hydrogen is supplied by reforming a fossil fuel, the greenhouse gas (may be abbreviated hereinafter "GHG") footprint for the biofuel can suffer because the fossil fuel can have a relatively high carbon footprint. As a consequence, it would be difficult to produce a biofuel meeting regulatory requirements with a reduced GHG emission. SUMMARY OF THE INVENTION
 One exemplary embodiment can be a process for producing a renewable hydrocarbon fuel. The process can include providing a feed including a lignocellulosic material to a pyrolysis zone to produce a stream including a pyrolysis oil, providing the pyrolysis oil stream to a refining zone producing a refined stream, providing at least a portion of the refined stream to a reforming zone producing a stream including hydrogen, providing at least a portion of the hydrogen stream to the refining zone, and recovering the renewable hydrocarbon fuel from the refined stream.
 Another exemplary embodiment may be a process for producing a renewable hydrocarbon fuel while minimizing fossil fuel derived carbon dioxide emissions. The process can include providing a lignocellulosic material to a pretreating zone to obtain a pretreated feed, providing the pretreated feed to a pyrolysis zone to produce a stream including a pyrolysis oil, providing the pyrolysis oil stream to a refining zone producing a refined stream, providing the refined stream to a separation zone to obtain a stream including a fuel gas and a stream including one or more hydrocarbons, providing the fuel gas stream to a conditioning zone to obtain a conditioned stream, providing the conditioned stream to a reforming zone to obtain a stream including hydrogen, and providing the hydrogen stream to the refining zone.
 A further exemplary embodiment can be a process for producing a renewable hydrocarbon fuel while minimizing fossil-derived carbon dioxide emissions. Generally, the process includes grinding a lignocellulosic material in a pretreating zone to obtain a pretreated feed, heating the pretreated feed in a pyrolysis zone to produce a stream including a pyrolysis oil, hydrotreating the pyrolysis oil in a refining zone to produce a refined stream, separating the refined stream to obtain a stream including a fuel gas and a stream including one or more hydrocarbons, scrubbing the fuel gas stream, reforming the fuel gas stream to obtain a stream including hydrogen, and providing the hydrogen stream to the refining zone.
 The embodiments disclosed herein can use a renewable feed, particularly a lignocellulosic material that can be utilized in a pyrolysis process that generates multiple liquid streams. At least one of the liquid streams, such as an aqueous stream rich in water, can be provided to an aqueous phase reforming zone to reform the stream as well as generate hydrogen that can be recycled to a refining zone. In addition, another stream can be provided to a steam reforming zone for reforming as well as generating hydrogen that can be recycled to the refining zone. As a result, the life cycle GHG emissions from refining can be minimized allowing the production of a biofuel that can meet either local and/or federal regulatory requirements.
 As used herein, the term "stream" can include various hydrocarbon molecules, such as straight-chain, branched, or cyclic alkanes, alkenes, alkadienes, and alkynes, and other substances, such as gases, e.g., hydrogen, carbon oxides, or inorganic impurities, such as alkali metals, and sulfur and nitrogen compounds. The stream can also include aromatic and non-aromatic hydrocarbons. Moreover, the hydrocarbon molecules may be abbreviated CI, C2, C3...Cn where "n" represents the number of carbon atoms in the one or more hydrocarbon molecules. Furthermore, a superscript "+" or "-" may be used with an abbreviated one or more hydrocarbons notation, e.g., C3 + or C3 ~ , which is inclusive of the abbreviated one or more hydrocarbons. As an example, the abbreviation "C3 " means one or more hydrocarbon molecules of three carbon atoms and/or more.
 As used herein, the term "zone" can refer to an area including one or more equipment items and/or one or more sub-zones. Equipment items can include one or more reactors or reactor vessels, heaters, exchangers, pipes, pumps, compressors, and controllers. Additionally, an equipment item, such as a reactor, dryer, or vessel, can further include one or more zones or sub-zones.
 As used herein, the term "rich" can mean an amount of at least generally 50%, and preferably 70%, by mole, of a compound or class of compounds in a stream.
 As used herein, the term "substantially" can mean an amount of at least generally 80%), preferably 90%>, and optimally 99%, by mole, of a compound or class of compounds in a stream.
 As depicted, process flow lines in the figures can be referred to interchangeably as, e.g., lines, pipes, feeds, products, effluents, portions, parts, or streams.
 As used herein, the term "pyrolysis oil," may refer to an oil obtained directly from pyrolysis or having undergone treatment such as filtration to remove solids and/or ion exchange to remove soluble metals, prior to hydroprocessing.
 As used herein, the term "vapor" can mean a gas or a dispersion that may include or consist of one or more hydrocarbons and/or water.  As used herein, the term "overhead stream" can mean a stream withdrawn at or near a top of a column, typically a flash drum or distillation column.
 As used herein, the term "bottom stream" can mean a stream withdrawn at or near a bottom of a column, typically a flash drum or distillation column.
 As used herein, the terms "alkane" and "paraffin" may be used interchangeably.
 As used herein, the terms "alkene" and "olefin" may be used interchangeably, and may include one or more olefins and diolefms.
 As used herein, the term "renewable hydrocarbon fuel" may be any fuel at least partially derived from sources other than a fossil fuel. A renewable hydrocarbon fuel can include renewable naphtha and renewable diesel, and having a distillation range as defined by, e.g., ASTM Test Method D86 or D2887.
 As used herein, the term "fossil fuel" can mean any fuel derived from animal or vegetable sources in past geologic ages buried in the earth. Exemplary fossil fuels may include petroleum, natural gas, coal, and lignite.
 As used herein, a lifecycle greenhouse gas emission value can be based on carbon dioxide equivalents, as measured according to guidelines set forth by the Intergovernmental Panel on Climate Change (IPCC) and the U.S. Federal Government. Lifecycle assessment values of emissions in terms of carbon dioxide equivalents, from raw material cultivation (in the case of plant materials) or raw material extraction (in the case of fossil fuels) through fuel combustion, can be calculated using SimaPro 7.1 software and IPCC GWP 100a
methodologies and provide in units of grams of carbon dioxide equivalent per mega joule (herein may be abbreviated "g C0 2 equivalent/MJ").
BRIEF DESCRIPTION OF THE DRAWING
 FIG. 1 is a schematic depiction of an exemplary biofuel production facility.
 Referring to FIG. 1, a biofuel production facility 10 can include a pretreating zone 100, a pyro lysis zone 140, a refining zone 180, a separation zone 200, a conditioning zone 220, a reforming zone 240, a fractionation zone 260, and another reforming zone 280.
 Generally, the biofuel production facility 10 can receive a feed 50 including one or more carbonaceous feedstocks that are classified as renewable. Typically, the feed 50 can be any biomass material or mixture of biomass materials having lignocellulosic material, including a hardwood, a softwood, a hardwood or softwood bark, or logging residues. The feed 50 may also include energy crops, agricultural residues, or other types of plant wastes or plant-derived wastes. Specific exemplary plant materials may include corn fiber, corn stover, and sugar cane bagasse, in addition to "on-purpose" energy crops such as switchgrass, miscanthus, and algae. Generally, short rotation forestry products, as energy crops, include alder, ash, southern beech, birch, eucalyptus, poplar, willow, paper mulberry, Australian blackwood, sycamore, and varieties of paulownia elongate. Other examples of suitable biomass can include organic waste materials, such as waste paper and construction, demolition, and municipal wastes. In general, the feed 50 may include any biomass including lignocellulosic material. Because the lignocellulosic biomass may be composed of the same building blocks, namely cellulose, hemicellulose, and lignin, pyrolysis conditions can be relatively similar for processing varying feeds.
 The feed 50 can be provided to a pretreating zone 100. The pretreating zone 100 can utilize any suitable process for reducing the feed 50 to a suitable material for being processed by the pyrolysis zone 140. The pretreating process can include at least one of sizing, magnetic separation, drying, and grinding. Such pretreating processes are disclosed in, e.g., US 2010/0140136 Al .
 Afterwards, a pretreated feed 120 can be provided to the pyrolysis zone 140. The pyrolysis zone 140 can operate under any suitable conditions, such as a temperature of 300 - 600° C and a residence time of 0.1 - 5 seconds. Exemplary pyrolysis zones and operating conditions are disclosed in, e.g., US 5,792,340 and US 2009/0239279 Al . The pyrolysis zone 140 can include any suitable pyrolysis reactor, such as a fluidized-bed reactor, a transport reactor, a cyclonic ablative reactor, or a vacuum pyrolysis reactor.
 The pyrolysis zone 140 can provide a solid byproduct stream 144, an aqueous byproduct stream 148 rich in water, a gas byproduct stream 152, and a pyrolysis oil stream 160. The aqueous byproduct stream 148 can optionally be provided to another reforming zone 280, which can be an aqueous phase reforming zone, such as disclosed in, e.g., US 6,964,758 B2. Typically, the reaction is conducted in a condensed liquid phase over a metal catalyst impregnated on a water-compatible support. The reaction can be conducted at any suitable temperature and pressure.  The reforming zone 280 can process the aqueous byproduct stream 148 to produce one or more hydrocarbons as a stream 282 as well as a hydrogen stream 284. Optionally, the hydrogen stream 284 can be recycled to the refining zone 180, as hereinafter described.
Usually, the hydrogen generated from the aqueous byproduct stream 148 can supplement or even provide the quantities of hydrogen required by the refining zone 180.
 The pyro lysis zone 140 can produce the pyro lysis oil stream 160. Typically, the pyro lysis oil stream 160 includes a mixture of water, organic compounds having lower water solubility, and other oxygenated hydrocarbons having higher water solubility, e.g., aldehydes, ketones, alcohols, and phenolics.
 Fast pyro lysis can involve rapid heat transfer to the pretreated feed 120, which can be maintained at a relatively high temperature for a very short time. The temperature of the primary pyrolysis products may then be rapidly reduced before achieving chemical equilibrium. The fast cooling can prevent the valuable reaction intermediates, formed by depolymerization and fragmentation of the biomass building blocks, namely cellulose, hemicellulose, and lignin, from degrading to lesser value final products.
 The pyrolysis oil stream 160 can be acidic with a pH of less than 4.0. Generally, the water molecules are split during pyrolysis and held separately in other compounds within the complex pyrolysis liquid. Thus, the "water" in pyrolysis oil may not separate from the organic fraction of the pyrolysis oil as a phase as in standard petroleum-derived fuels.
Generally, the pyrolysis oil stream 160 contains 30 - 35%, by weight, of oxygen in the form of organic oxygenates such as hydroxyaldehydes, hydroxyketones, sugars, carboxylic acids, and phenolic oligomers as well as dissolved water. For this reason, although a pourable and transportable liquid fuel, usually the pyrolysis oil, has only 55 - 60%> of the energy content of crude oil-based fuel oils. Generally, representative values of the energy content are in the range from 19.0 - 25.0 MJ/liter.
 Properties of a pyrolysis oil can include a heating value of 15 - 21 MJ/kg, a pour point of -12 - -33° C, no cloud point observed until -21° C, a carbon residue of 17 - 23%>, by weight, based on the weight of the pyrolysis oil, and a flash point of 40 - 100° C. As such, the pyrolysis oil may not auto-ignite in a diesel engine, and the cetane number can be significantly less than ASTM requirements for use in transportation vehicle service, e.g., less than 25.  While the exact composition of the pyrolysis oil usually depends on the feed 50 and processing conditions, a typical composition is as follows:
(%, By Weight)
Water 20 - 28
Suspended solids and 22 - 36
Hydroxyacetaldehyde 8 - 12
Levoglucosan 3 - 8
Acetic acid 4 - 8
Acetol 3 - 6
Cellubiosan 1 - 2
Glyoxal 1 - 2
Formaldehyde 3 - 4
Formic Acid 3 - 6
 The pyro lysis oil stream 160 can be combined with a portion of a recycle stream 270 as hereinafter described, to form a combined stream 164 to the refining zone 180.
Generally, the refining zone 180 hydrogenates and deoxygenates the pyrolysis oil stream 160.
 Often, the raw pyrolysis product is corrosive and exhibits chemical instability due to the presence of highly unsaturated compounds such as olefins and alkenylaromatics.
Hydroprocessing of this pyrolysis oil stream 160 in the refining zone 180 can reduce its oxygen content and increase its stability, thereby rendering a refined product more suitable for blending in fuels, such as gasoline or diesel. Refining involves contacting the pyrolysis oil with hydrogen and in the presence of a suitable catalyst, generally under conditions sufficient to convert a large proportion of the organic oxygen in the raw pyrolysis oil to carbon monoxide, carbon dioxide, and water that are easily removed.
 The catalyst may be present in the form of a fixed bed of particles, including a catalytically active metal disposed on a support, with suitable metals and supports being described below. Otherwise, the catalyst either supported or otherwise unsupported, in the form of fine particles of a compound containing the catalytically active metal, may be used in an ebullated bed or a back-mixed multi-phase bed, such as in the case of a slurry reactor. Homogeneous systems operating with catalysts soluble in the reactants and products may also be used. Catalytic refining conditions can vary depending on the quality of the refined pyrolysis oil desired, with higher severity operations directionally resulting in greater conversion of organic oxygenates and other undesirable compounds, e.g., reactive olefins and diolefins by hydrogenation.
 Typically, refining conditions include an average catalyst bed temperature from 40 - 540° C, preferably 280 - 430° C, and a hydrogen partial pressure from 0.7 - 21 MPa or 2.8 - 21 MPa, preferably 0.7 - 14 MPa or 5 - 14 MPa. A typical range of liquid hourly space velocity (herein may be abbreviated "LHSV") for hydroprocessing may be 0.1 - 10 h 1 , preferably 0.3 - 3 hr \ Generally, a sufficient quantity of hydrogen is provided to convert organic oxygenates to hydrocarbons and water. The refining zone 180 can receive hydrogen from the reforming zone 240 and the another reforming zone 280 via, respectively, the stream 252 and the stream 284.
 Suitable refining catalysts include those having at least one Group VIII (IUPAC 8- 10) metal, such as iron, cobalt, and nickel and at least one Group VI (IUPAC 6) metal, such as molybdenum and tungsten, on a high surface area support material such as a refractory inorganic oxide, e.g., silica, alumina, titania, and/or zirconia support or a carbon support.
Preferably, the catalyst includes at least one of cobalt, molybdenum, nickel, tungsten, platinum, palladium, ruthenium, rhodium, osmium, and iridium.
 Typically, the Group VIII metal is present in the catalyst in an amount ranging from 2 - 20%, by weight, and preferably 4 - 12%, by weight, based on the volatile-free catalyst weight. Usually, the Group VI metal is present in an amount ranging from 1 - 25%, by weight, and preferably 2 - 25%, by weight, also based on the volatile-free catalyst weight.
A volatile-free catalyst sample may be obtained by subjecting the catalyst to drying at 200 - 350° C under an inert gas purge or vacuum for a period of time, e.g., 2 hours, to drive water and other volatile components from the catalyst.
 Other suitable refining catalysts include zeolitic catalysts, as well as noble metal catalysts where the noble metal is selected from palladium and platinum. More than one type of refining catalyst may be utilized in the same or different reaction vessel. Other suitable refining zones and operating conditions for hydrogenating, hydrotreating, and/or isomerizing are disclosed in, e.g., US 2009/0287029 Al .  After refining, the resulting oil has an oxygen content that is generally reduced from 90 - 99.9%, relative to the oxygen content of the pyrolysis oil. Typically, the heating value, on a mass basis, of the refined pyrolysis oil is simultaneously increased, usually by a factor of 1.5 - 3, compared to that of unrefined pyrolysis oil.
 The refining zone 180 can provide a refined stream 184 to a separation zone 200. Typically, any separation device can be utilized, such as one or more flash drums. In one exemplary embodiment, a series of high, medium, and optionally low pressure flash drums can be utilized to remove gaseous components that can be combined as a fuel gas stream 210 and a stream 214 including one or more hydrocarbons. Therefore, the fuel gas stream 210 can include one or more of CO, C0 2 , CH 4 , C 2 H 6 , C3¾, C4H10, H 2 , and H 2 S. Usually, a high pressure flash drum can operate at 5 - 21 MPa, a medium pressure flash drum can operate at 3 - 14 MPa, and a low pressure flash drum can operate at 1 - 7 MPa.
 The fuel gas stream 210 can be provided to a conditioning zone 220. Typically, the conditioning zone 220 can include one or more scrubbers, such as an amine scrubber. The fuel gas stream 210 can include one or more gases, such as one or more C1-C4 hydrocarbons, typically alkanes, carbon monoxide, carbon dioxide, and hydrogen. The conditioning zone can include one or more scrubbers to remove hydrogen sulfide, carbon dioxide, and optionally ammonia. Usually, the conditioning zone 220 can include a water wash column. An exemplary conditioning zone is disclosed in, e.g., US 2009/0287029 Al . After scrubbing, the conditioning zone 220 may optionally also contain one or more vessels for conducting a water shift reaction to convert the carbon monoxide and water to carbon dioxide and hydrogen.
 The conditioned stream 230, optionally combined with a make-up fuel gas stream 234, can form a combined stream 238 and be provided to a reforming zone 240. Typically, the reforming zone 240 is a steam reforming zone, as disclosed in, e.g., US 2009/0287029 Al, which may provide hydrogen to the refining zone 180. Usually, a hydrocarbon and steam mixture is catalytically reacted at high temperature to form hydrogen and the carbon oxides, such as carbon monoxide and carbon dioxide. Because the reforming reaction is strongly endothermic, heat is typically supplied by a furnace to the reactant mixture.
 One exemplary steam reforming process is autothermal reforming, also called catalytic partial oxidation, which may supply heat by the partial internal combustion of a feed with oxygen or air. Generally, exit temperatures may range from 500 - 950° C and pressures may be up to 6 MPa.
 The steam reforming product may be recycled to any of the reaction zones to provide at least hydrogen to the reaction zone. Optionally, the hydrogen may be separated from the carbon oxides generated in the steam reforming reaction, and the separated hydrogen may be recycled to the refining zone 180.
 Generally, the reforming zone 240 can not only reform the fuel gas stream to provide components that may optionally be used in fuel, but can also provide power and steam as indicated by the line 248. In addition, a hydrogen stream 252 can be obtained that may optionally pass through a compressor and be provided back to the refining zone 180. Optionally, the hydrogen stream 252 can be purified in a pressure swing absorber prior to being provided to the refining zone 180. As such, the reforming zone 240 can not only provide hydrogen, but also power to the biofuel production facility 10. As such, this recycling of components can minimize the greenhouse gas emissions of any subsequent renewable hydrocarbon fuel produced.
 The one or more hydrocarbons in the stream 214 from the separation zone 200 can be provided to a fractionation zone 260. The fractionation zone 260 can produce a fuel gas stream 262; a first renewable hydrocarbon fuel stream 264, typically a renewable naphtha or gasoline; a second renewable hydrocarbon fuel stream 266, typically a renewable diesel; and a bottom stream 268. Typically, the naphtha or gasoline has an initial boiling point temperature characteristic of C5 hydrocarbons, for example from 30 - 40° C and a distillation end point temperature generally of 130 - 220° C, and typically 130 - 160° C. The boiling point range of naphtha or gasoline may be 20 - 180° C, preferably 50 - 150° C. The renewable diesel can have boiling point characteristics similar to petroleum fuel and may have a range of 120 - 380° C, preferably 150 - 350° C. These boiling point temperatures, which are also characteristic of petroleum derived gasoline and diesel, may be measured according to ASTM D86. In one exemplary embodiment, the fuel gas stream 262 can include one or more C4 ~ hydrocarbons. Optionally, at least a portion of these biomass-derived C4 ~ hydrocarbons can be provided to the reforming zone 240 to generate at least a portion of the hydrogen for the refining zone 180.
 The bottom stream 268 can include one or more heavier hydrocarbons, such as one or more C9 + hydrocarbons, which can be recycled to at least one of the refining zone 180 as a portion 270 or to the pyro lysis zone 140 as another portion 274. The recycle to the pyro lysis zone 140 can be provided to the reactor outlet as a more thermally stable quench oil for cooling the hot pyrolysis vapor leaving the pyrolysis reactor. Quenching the hot vapor can quickly stop the thermal reactions and prevent polymerization and the associated formation of high molecular weight oxygenated hydrocarbons. When the bottom stream 268 is recycled to the refining zone 180, the temperature rise can be favorably buffered. In addition, the concentration of reactive species entering the refining zone 180 is diluted with a more thermally stable and hydrogen rich bottom stream 268 so as to minimize undesirable side reactions that can lead to high coke formations. In addition, removing the bottom stream 268 from the fractionation zone 260 can not only provide the recycle streams 270 and 274, but a portion of this heavier hydrocarbon can be taken as a product stream 278.
 The embodiments disclosed herein can provide a process utilizing a renewable hydrogen stream to reduce carbon emissions. In one estimate, utilizing such a renewable feed in a pyrolysis process can reduce lifecycle greenhouse gas emissions of 80% or more for producing a renewable hydrocarbon or transportation fuel, usually renewable gasoline, as compared to a petroleum derived transportation fuel.
 Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
 In the foregoing, all temperatures are set forth in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.
 From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.
Next Patent: HEAT GENERATING SYSTEM FOR ENHANCING OIL RECOVERY