PROCESS FOR CONVERTING A BIOMASS MATERIAL
A process for converting a biomass material comprising a) pyrolyzing a biomass material to produce a biomass-derived pyrolysis product; b) providing a petroleum-derived hydrocarbon composition having a C7-asphaltenes content of equal to or more than 0.2 wt %, based on the total weight of the petroleum-derived hydrocarbon composition, which petroleum-derived hydrocarbon composition has a total acid number of equal to or more than 0.5 mg KOH/g and/or a density at 15.5° C. of equal to or more than 0.8 grams/ml and/or a viscosity at 37.8° C. of equal to or more than 500 centiStokes (cSt); c) mixing at least part of the biomass-derived pyrolysis product and at least part of the petroleum-derived hydrocarbon composition to produce a hydrocarbon-containing mixture; and d) dewatering the hydrocarbon-containing mixture to produce a dewatered hydrocarbon-containing mixture.
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This non-provisional application claims the benefit of U.S. Provisional No. 61/818,678, filed May 2, 2013, the disclosures of which are incorporated herein by reference.
TECHNICAL FIELDThe present invention relates to a process for preparing a hydrocarbon-containing mixture, more specifically a hydrocarbon-containing mixture that is suitable for processing and/or transporting. In addition the present invention relates to a process for preparing one or more fuel components and/or one or more chemical components.
BACKGROUNDDue to a diminishing supply of easily accessible sweet crude oil, other hydrocarbon resources are becoming increasingly important as a feedstock for processes for the production of liquid and gaseous fuels and or chemicals. One alternative to easily accessible sweet crude oil are so-called disadvantaged crudes and/or unconventional petroleum deposits.
Crude hydrocarbon compositions that have one or more unsuitable properties that do not allow them to be economically transported, or processed using conventional facilities, are commonly referred to as “disadvantaged crudes”. Disadvantaged crudes or derivatives thereof can include acidic components that contribute to the total acid number (“TAN”) of the crude feed; they can have a high viscosity, contain a high level of asphaltenes and/or have a high density. Disadvantaged crudes or derivatives thereof with a relatively high viscosity and/or a relatively high density and/or a relatively high level of asphaltenes and/or a relatively high level of TAN tend to be difficult and/or expensive to transport and/or process using conventional facilities.
The term “unconventional petroleum deposits” is used for petroleum deposits that are explored by other than conventional methods. Such petroleum deposits include for example bituminous sands (also sometimes referred to as oil sands or tar sands) and oil shales. These petroleum deposits may for example be explored or produced via steam assisted gravity drainage (SAGD) or mining, providing mixtures of sand, water and unconventional oil. Also the unconventional oil from these mixtures can have a relatively high viscosity and/or a relatively high density and/or a relatively high level of asphaltenes and/or a high content of TAN and tend to be difficult and/or expensive to transport and/or process using conventional facilities.
Disadvantaged crudes and/or unconventional oils may therefore sometimes be diluted with a diluent, such as for example naphtha or a condensate, before transporting and/or processing, in order to make them transportable and/or fit for processing. The use of such a diluent is disadvantageous from an economic point of view, and it would be an advancement in the art to be able to reduce the amount of diluent needed or to eliminate the use of a diluent.
Further, disadvantaged crudes and/or unconventional oils with a relatively high TAN may contribute to corrosion of metal components during transporting and/or processing of the disadvantaged crudes or unconventional oils. Corrosion-resistant metals may be used in transportation equipment and/or processing equipment. However, the use of corrosion-resistant metal often involves significant expense, and thus, the use of corrosion-resistant metal in existing equipment may not be desirable. Another method to inhibit corrosion may involve addition of corrosion inhibitors to disadvantaged crudes before transporting and/or processing of the disadvantaged crudes and/or unconventional oils. The use of corrosion inhibitors may however, negatively affect equipment used to process the crudes and/or the quality of products produced from the crudes.
Further disadvantaged crudes may exhibit instability during processing in conventional facilities. Such instability may result in undesired phase separation of components during transport and/or processing.
It would be an advancement in the art to find an economically attractive process for converting such a disadvantaged crude and/or unconventional oils into a product that is less corrosive and/or is more easy to transport and/or process.
Another alternative to easily accessible sweet crude oil are so-called renewable hydrocarbon resources. One of these renewable hydrocarbon resources is a so-called pyrolysis oil. Such a pyrolysis oil may suitably be produced by the pyrolysis of biomass comprising a lignocellulosic material. The pyrolysis product, produced by pyrolysis of a biomass comprising a lignocellulosic material may comprise hydrocarbons, oxygenated compounds, organic acids and phenolics, insoluble lignin and water. The water content may amount to 25-30 wt % or even more. The presence of water and oxygenated compounds in the pyrolysis oil is disadvantageous for the caloric value of the pyrolysis oil. Water may be removed by evaporation. The removal of water from the pyrolysis oil via evaporation, however, has been found to lead to the formation of a highly viscous, tar-like material and/or insolubles that may be difficult to transport and/or process.
It would be an advancement in the art to find an economically attractive process for converting such a dewatered pyrolysis oil into a product that is less corrosive and/or is more easy to transport and/or process.
SUMMARYIt has now unexpectedly been found that the above disadvantaged crudes and/or unconventional oils and the above pyrolysis oil can be converted into a hydrocarbon-mixture that can more easily or more economically be transported and/or processed by dewatering them together.
Accordingly, some embodiments described herein provide a process comprising a) pyrolyzing a biomass material to produce a biomass-derived pyrolysis product; b) providing a petroleum-derived hydrocarbon composition having a C7-asphaltenes content of equal to or more than 0.2 wt %, based on the total weight of the petroleum-derived hydrocarbon composition, which petroleum-derived hydrocarbon composition has a total acid number of equal to or more than 0.5 mg KOH/g and/or a density at 15.5° C. of equal to or more than 0.8 grams/ml and/or a viscosity at 37.8° C. of equal to or more than 500 centiStokes (cSt); c) mixing at least part of the biomass-derived pyrolysis product and at least part of the petroleum-derived hydrocarbon composition to produce a hydrocarbon-containing mixture; and d) dewatering the hydrocarbon-containing mixture to produce a dewatered hydrocarbon-containing mixture.
It has been surprisingly found that the above dewatered hydrocarbon-containing mixture is stable. The dewatered hydrocarbon-containing mixture may further be more easily and/or more economically be transported and/or processed.
The dewatered hydrocarbon-containing mixture obtained in step d) may conveniently be converted via one or more hydrocarbon conversion processes into one or more fuel components and/or one or more chemical components.
In some embodiments, the petroleum-derived hydrocarbon composition that has a Total acid number of equal to or more than 1.0 mg KOH/g. In some embodiments, the petroleum-derived hydrocarbon composition contains hydrocarbon compounds and water. In some embodiments, the petroleum-derived hydrocarbon composition is obtained or derived from a so-called unconventional petroleum deposit. In some embodiments, the petroleum-derived hydrocarbon composition is obtained or derived from bituminous sands.
Some embodiments provide a process comprising a) pyrolyzing a biomass material to produce a biomass-derived water-containing pyrolysis product; b) providing a petroleum-derived hydrocarbon composition containing water, having a C7-asphaltenes content of equal to or more than 0.2 wt %, based on the total weight of the petroleum-derived hydrocarbon composition, which petroleum-derived hydrocarbon composition has a total acid number of equal to or more than 0.5 mg KOH/g and/or a density at 15.5° C. of equal to or more than 0.8 grams/ml and/or a viscosity at 37.8° C. of equal to or more than 500 centiStokes (cSt); c) mixing the at least part of the biomass-derived water-containing pyrolysis product and at least part of the petroleum-derived hydrocarbon composition containing water to produce a hydrocarbon-containing mixture; and d) dewatering the hydrocarbon-containing mixture to produce a dewatered hydrocarbon-containing mixture.
In some embodiments, the process further comprises removing the water contained in the petroleum-derived hydrocarbon composition to produce a petroleum-derived hydrocarbon composition comprising less than 0.1 wt % water;
In some embodiments, the process further comprises removing a first part of the water contained in the petroleum-derived hydrocarbon composition by means of phase separation to produce a petroleum-derived hydrocarbon composition comprising residual water; where step c) comprises mixing at least part of the biomass-derived water-containing pyrolysis product and at least part of the petroleum-derived hydrocarbon composition containing residual water to produce a hydrocarbon-containing mixture; and where step d) comprises dewatering the hydrocarbon-containing mixture by evaporation and/or phase separation of residual water to produce a dewatered hydrocarbon-containing mixture.
In some embodiments, step d) further comprises converting the dewatered hydrocarbon-containing mixture in one or more hydrocarbon upgrading processes to produce an upgraded dewatered hydrocarbon-containing mixture.
In some embodiments, the hydrocarbon upgrading process comprises contacting the dewatered hydrocarbon-containing mixture with hydrogen in the presence of a catalyst to produce an upgraded dewatered hydrocarbon-containing mixture.
Some embodiments provide a process for producing one or more fuel components and/or one or more chemical components comprising: a) pyrolyzing a biomass material to produce a biomass-derived pyrolysis product containing water; b) providing a petroleum-derived hydrocarbon composition having a total acid number of at least 0.5 mg KOH/g and a C7-asphaltenes content of equal to or more than 0.2 wt %, based on the total weight of the petroleum-derived hydrocarbon composition; c) mixing at least part of the biomass-derived pyrolysis product and at least part of the petroleum-derived hydrocarbon composition to produce a hydrocarbon-containing mixture containing water; d) dewatering the hydrocarbon-containing mixture obtained in step c) to produce a dewatered hydrocarbon-containing mixture; optionally upgrading the dewatered hydrocarbon-containing mixture in one or more hydrocarbon upgrading processes; and e) converting the dewatered hydrocarbon-containing mixture via one or more hydrocarbon conversion processes into one or more fuel components and/or one or more chemical components.
In some embodiments, step e) comprises converting the dewatered hydrocarbon-containing mixture in one or more hydrocarbon conversion processes, and separating the product of the hydrocarbon conversion process into one or more hydrocarbon product fractions. In some embodiments, the one or more hydrocarbon conversion processes comprise a fluid catalytic cracking process, thermal cracking process and/or hydrocracking process.
In some embodiments, the process further comprises combining the one or more hydrocarbon product fractions with one or more additives to produce one or more fuel components and/or one or more chemical components.
Other advantages and features of embodiments of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
Some embodiments of the invention have been illustrated by the following non-limiting figures:
In step a) of an exemplary process according to some embodiments of the invention, a biomass material is pyrolyzed to produce a biomass-derived pyrolysis product.
By biomass material is herein understood a composition of matter of biological origin as opposed to a composition of matter obtained or derived from petroleum, natural gas or coal. Without wishing to be bound by any kind of theory it is believed that such biomass material may contain carbon-14 isotope in an abundance of about 0.0000000001%, based on total moles of carbon.
The biomass material may suitably comprise animal fat, tallow and/or solid biomass material. Preferably the biomass material is a solid biomass material. More preferably the biomass material is material containing cellulose and/or lignocellulose. Such a material containing “cellulose” respectively “lignocellulose” is herein also referred to as a “cellulosic”, respectively “lignocellulosic” material. By a cellulosic material is herein understood a material containing cellulose and optionally also lignin and/or hemicellulose. By a lignocellulosic material is herein understood a material containing cellulose and lignin and optionally hemicellulose.
Examples of biomass materials include aquatic plants and algae, agricultural waste and/or forestry waste and/or paper waste and/or plant material obtained from domestic waste. Examples of cellulosic or lignocellulosic material include for example agricultural wastes such as corn stover, soybean stover, corn cobs, rice straw, rice hulls, oat hulls, corn fibre, cereal straws such as wheat, barley, rye and oat straw; grasses; forestry products and/or forestry residues such as wood and wood-related materials such as sawdust and bark; waste paper; sugar processing residues such as bagasse and beet pulp; or mixtures thereof.
More preferably the solid biomass material comprises or consists of a cellulosic or lignocellulosic material selected from the group consisting of wood, sawdust, bark, straw, hay, grasses, bagasse, corn stover and/or mixtures thereof. The wood may include soft wood and/or hard wood.
When the biomass material is a solid biomass material such as for example a lignocellulosic material, it may suitably be washed, steam exploded, dried, roasted, torrefied and/or reduced in particle size before being pyrolyzed in step a). In addition, if the biomass material is a cellulosic or lignocellulosic material it may preferably be demineralized before being pyrolyzed in step a). During such a demineralization amongst others chloride may be removed.
In step a) the biomass material is pyrolyzed to produce a biomass-derived pyrolysis product. By pyrolysis or pyrolyzing is herein understood the decomposition of the biomass material, in the presence or in the essential absence of a catalyst, at a temperature of equal to or more than 380° C.
Preferably pyrolysis is carried out in an oxygen-poor, preferably an oxygen-free, atmosphere. By an oxygen-poor atmosphere is understood an atmosphere containing equal to or less than 10 vol. % oxygen, preferably equal to or less than 5 vol. % oxygen and more preferably equal to or less than 1 vol. % oxygen. By an oxygen-free atmosphere is understood an atmosphere where oxygen is essentially absent. More preferably pyrolysis is carried out in an atmosphere containing equal to or less than 2 vol. % oxygen, more preferably equal to or less than 0.5 vol. % oxygen, even more preferably equal to or less than 0.1 vol. % oxygen and most preferably equal to or less than 0.05 vol. % oxygen. In a most preferred embodiment pyrolysis is carried out in the essential absence of oxygen.
The biomass material is preferably pyrolyzed at a pyrolysis temperature of equal to or more than 400° C., more preferably equal to or more than 450° C., even more preferably equal to or more than 500° C. and most preferably equal to or more than 550° C. The pyrolysis temperature is further preferably equal to or less than 800° C., more preferably equal to or less than 700° C. and most preferably equal to or less than 650° C.
The pyrolysis pressure may vary widely. For practical purposes a pressure in the range from 0.01 to 0.5 MPa (MegaPascal), more preferably in the range from 0.1 to 0.2 MPa is preferred. Most preferred is an atmospheric pressure (about 0.1 MPa).
In one embodiment, the pyrolysis does not include an externally added catalyst. In another embodiment the pyrolysis is a so-called catalytic pyrolysis wherein a catalyst is used. Examples of suitable catalysts in such a catalytic pyrolysis include mesoporous zeolites. By a mesoporous zeolite is herein preferably understood a zeolite containing pores with a pore diameter in the range from 2-50 nanometer, in line with IUPAC notation (see for example Rouquerol et al. (1994). “Recommendations for the characterization of porous solids (Technical Report)” Pure & Appl. Chem 66 (8): 1739-1758). Especially preferred catalysts for such a catalytic pyrolysis include ZSM-5 type zeolites, such as for example Zeolyst 5524G and 8014 and Albemarle UPV-2.
In certain embodiments, chemicals may be employed for a pretreatment of the biomass material, or catalysts may be added to the pyrolysis mixture, cf. for example, H Wang cs., “Effect of acid, alkali, and steam explosion pretreatment on characteristics of bio-oil produced from pinewood”, Energy Fuels (2011) 25, p. 3758-3764.
In a preferred pyrolysis process, generally referred to as a flash pyrolysis process, the biomass is rapidly heated (for example within 3 seconds) in the essential absence of oxygen to a temperature in the range of from 400° C. to 600° C. and kept at that temperature for a short period of time (for example equal to or less than 3 seconds). Such flash pyrolysis processes are known, for example from A. Oasmaa et al, “Fast pyrolysis of Forestry Residue 1. Effect of extractives on phase separation of pyrolysis liquids”, Energy & Fuels, volume 17, number 1, 2003, pages 1-12; and A. Oasmaa et al, Fast pyrolysis bio-oils from wood and agricultural residues, Energy & Fuels, 2010, vol. 24, pages 1380-1388; U.S. Pat. No. 4,876,108; U.S. Pat. No. 5,961,786; and U.S. Pat. No. 5,395,455.
In another preferred pyrolysis process a solid heating medium is used, such as for example silica or sand. The solid heating medium may for example be a fluidized solid heating medium provided in for example a fluidized bed or a riser reactor. In such a pyrolysis process the biomass material may be fluidized within the fluidized solid heating medium and subsequently the biomass material may be pyrolysed with the heat provided by such fluidized solid heating medium. Hereafter any residual coke formed on the solid heating medium may be burned off to regenerate the solid heating medium. The coke that is burned off may conveniently supply the heat needed to preheat the solid heating medium.
The pyrolyzing in step a) may be carried out in any type of pyrolysis reactor know to the person skilled in the art to be suitable for such pyrolysis process. In a special embodiment the pyrolysis reactor comprises a so-called screw reactor, wherein the biomass material is continuously conveyed through the heated reactor by means of a screw. Such a reactor is sometimes also referred to as an “Auger” reactor.
During such pyrolysis of the biomass material a biomass-derived pyrolysis product is produced. The biomass-derived pyrolysis product referred to in this invention will contain water. The biomass-derived pyrolysis product may for example contain gas, solids (char), one or more oily phase(s), and water. Optionally part of the water may be present as a separate aqueous phase, whereas another part of the water may be contained within one or more oily phase(s) in a dispersed and/or emulsified form.
Step a) preferably further comprises separating one or more oily phase(s) containing water from the biomass-derived pyrolysis product. Such one or more oily phase(s) containing water are herein also referred to as pyrolysis oil or biomass-derived pyrolysis oil. The pyrolysis oil or biomass-derived pyrolysis oil of some embodiments will still contain water, for example in a dispersed and/or emulsified form.
In a preferred embodiment the biomass-derived pyrolysis oil is separated from any other components (for example, gas, solids or any aqueous phase) of the biomass-derived pyrolysis product. The biomass-derived pyrolysis oil can be separated from the biomass-derived pyrolysis product by any method known by the skilled person to be suitable for that purpose. This includes conventional methods such as filtration, centrifugation, cyclone separation, extraction, membrane separation and/or phase separation. Preferably such a separation is carried out at a temperature of equal to or less than 100° C. and a pressure of about 0.1 MegaPascal. Preferably the biomass-derived pyrolysis product is separated in a liquid/solid separation, gas/liquid separation and/or a gas/liquid/solid separation to separate liquid biomass-derived pyrolysis product from the remainder of the biomass-derived pyrolysis product.
In a suitable embodiment, any biomass-derived pyrolysis product (also referred to as pyrolysis product vapours) or a part thereof may be at least partly condensed, for example by cooling the biomass-derived pyrolysis product. As a result of such condensation a condensed liquid, any residual vapours and optionally solids (such as for example any solid heating medium) may be obtained. The condensation can be carried out in any manner known to be suitable therefore by the person skilled in the art. For example by means of heat-exchangers. Preferably a condensation is carried out by cooling the biomass-derived pyrolysis product or part thereof with pyrolysis oil, suitably in one or more condensers, preferably in a counter-current arrangement. Any condensed vapours of the biomass-derived pyrolysis product may suitably be captured in such countercurrently flowing pyrolysis oil. The so-obtained liquid biomass-derived pyrolysis product may contain entrained solids, such as for example the solid heating medium, that may suitably be removed by filtration thereafter. The obtained liquid biomass-derived pyrolysis product preferably may consist mostly or wholly of biomass-derived pyrolysis oil. Conveniently at least part of the liquid biomass-derived pyrolysis product, preferably consisting of biomass-derived pyrolysis oil, obtained after filtration is used to condense the biomass-derived pyrolysis product gas or part thereof.
In one embodiment the part of the biomass-derived pyrolysis product that is liquid, may comprise one or more oily phase(s) and optionally an aqueous phase. In another, preferred embodiment, however, the part of the biomass-derived pyrolysis product that is liquid may also consist of one or more oily phase(s) comprising dispersed and/or emulsified water therein.
The oily phase(s) are herein referred to as pyrolysis oil or biomass-derived pyrolysis oil. In the process of the invention, if any aqueous phase is present in the liquid biomass-derived pyrolysis product, such aqueous phase may or may not be separated from the one or more oily phases. If separated, the aqueous phase may be separated from the biomass-derived pyrolysis oil in for example a water/oil phase separation step. However, even after such a water/oil phase separation step, considerable amounts of emulsified or dispersed water may still remain within the oily phase.
The biomass-derived pyrolysis oil in the process of the invention may include for example carbohydrates, olefins, paraffins, oxygenates and residual water. By an oxygenate is herein understood a compound containing carbon, hydrogen and oxygen. The oxygenates may for example include aldehydes, carboxylic acids, ethers, esters, alkanols, phenols and ketones.
The biomass-derived pyrolysis oil, or mixture of biomass-derived pyrolysis oil and aqueous phase may suitably comprise water in an amount equal to or more than 0.1 wt %, preferably equal to or more than 1 wt %, more preferably equal to or more than 2 wt %, even more preferably equal to or more than 5 wt %, still more preferably equal to or more than 10 wt % and most preferably equal to or more than 15 wt % water and preferably equal to or less than 55 wt %, more preferably equal to or less than 45 wt %, and still more preferably equal to or less than 35 wt %, still more preferably equal to or less than 30 wt %, most preferably equal to or less than 25 wt %, based on the total weight of the biomass-derived pyrolysis oil, respectively the total weight of biomass-derived pyrolysis oil and aqueous phase. In practice, the biomass-derived pyrolysis oil or mixture of biomass-derived pyrolysis oil and aqueous phase may suitable comprise in the range from 1 to 55 wt %, more suitably in the range from 10 to 45 wt %, most suitably in the range from 15 to 35 wt %, based on the total weight of the biomass-derived pyrolysis oil, respectively the total weight of biomass-derived pyrolysis oil and aqueous phase.
Preferably, the Total Acid Number of the biomass-derived pyrolysis oil may be at most 250 mg KOH/g, more preferably in the range of from 1 mg KOH/g to 200 mg KOH/g, even more preferably in the range of from 5 mg KOH/g to 150 mg KOH/g, most preferably in the range of from 10 mg KOH/g to 100 mg KOH/g. As used herein, water content is as measured by ASTM E203 and Total acid number is as measured by using ASTM D664.
In addition, step a) may comprise demineralizing the biomass-derived pyrolysis product or part thereof (such as the biomass-derived pyrolysis oil), for example before forwarding to step c). During such a demineralization amongst others chloride may be removed. In a preferred embodiment, step a) may therefore further comprise the removal of minerals such as chloride from the biomass material before pyrolyzing and/or the removal of minerals such as chloride from the biomass-derived pyrolysis product after pyrolyzing.
The biomass-derived pyrolysis product obtained in step a) or part thereof may be forwarded directly or indirectly to step c). Preferably a biomass-derived pyrolysis oil is forwarded directly or indirectly to step c). For example the biomass-derived pyrolysis product or part thereof (such as the biomass-derived pyrolysis oil) may first be stored for a period “t” before forwarding. Such a period “t” may preferably lie in the range from 1 hour to 1 month.
In step b) a petroleum-derived hydrocarbon composition is provided having a C7-asphaltenes content of equal to or more than 0.2 wt %, based on the total weight of the petroleum-derived hydrocarbon composition, which petroleum-derived hydrocarbon composition has a total acid number of equal to or more than 0.5 mg KOH/g and/or a density at 15.5° C. of equal to or more than 0.8 grams/ml and/or a viscosity at 37.8° C. of equal to or more than 500 centiStokes (cSt).
The petroleum-derived hydrocarbon composition as mentioned in step b) may preferably be a so-called extra heavy oil. The petroleum-derived hydrocarbon composition may comprise one or more hydrocarbon compounds and preferably comprises two or more hydrocarbon compounds. By a hydrocarbon compound is herein understood a compound containing hydrogen and carbon. Such hydrocarbon compound may further contain heteroatoms such as oxygen, sulphur and/or nitrogen. The petroleum-derived hydrocarbon composition may also comprise hydrocarbon compounds consisting of only hydrogen and carbon.
The petroleum-derived hydrocarbon composition is preferably a petroleum-derived hydrocarbon composition that has a Total Acid Number (TAN) of equal to or more than 1.0 mg KOH/g, more preferably equal to or more than 2.0 mg KOH/g, even more preferably equal to or more than 3.0 mg KOH/g, still more preferably equal to or more than 5.0 mg KOH/g. It is, however, also possible for the petroleum-derived hydrocarbon composition to have a TAN of equal to or more than 7.0 mg KOH/gram. The TAN of the petroleum-derived hydrocarbon composition is preferably equal to or less than 100 mg KOH/g, more preferably equal to or less than 50 mg KOH/g and most preferably equal to or less than 10 mg KOH/g.
The petroleum-derived hydrocarbon composition preferably has a C7-asphaltene content of equal to or more than 0.5 wt %. More preferably, the C7-asphaltenes content of the petroleum-derived hydrocarbon composition may be equal to or more than 0.7 wt %, still more preferably equal to or more than 2.0 wt %, even more preferably in the range of from 0.8 to 30 wt %, still even more preferably in the range of from 2.0 wt % to 30 wt %, based on the total weight of the petroleum-derived hydrocarbon composition. Most preferably the C7-asphaltenes content is in the range of from 0.9 to 15 wt % or in the range of from 2.0 to 15 wt % based on the total weight of the petroleum-derived hydrocarbon composition. As used herein, asphaltenes content or C7-asphaltenes content is as determined by IP143, using n-heptane as a solvent.
The petroleum-derived hydrocarbon composition may have a kinematic viscosity at 37.8° C. as determined using ASTM Method D445 of equal to or more than 500 centistokes; preferably of equal to or more than 1000 centistokes; more preferably of equal to or more than 4000 centistokes; even more preferably of equal to or more than 5000 centistokes and most preferably of equal to or more than 8000 centistokes. In some embodiments the petroleum-derived hydrocarbon composition may have a kinematic viscosity at 37.8° C. as determined using ASTM Method D445 of equal to or less than 40000 centistokes. The petroleum-derived hydrocarbon composition can even have a kinematic viscosity at 100° C. of equal to or more than 5 centistokes, possibly even equal to or more than 50 centistokes, equal to or more than 100 or even equal to or more than 200 centistokes. In a preferred embodiment the petroleum-derived hydrocarbon composition has a kinematic viscosity at 100° C. of equal to or less than 3000 centistokes.
The petroleum-derived hydrocarbon composition preferably has a density at 15.5° C. of equal to or more than 0.9 grams/ml; more preferably equal to or more than 1.0 grams/ml. In some embodiments the petroleum-derived hydrocarbon composition may have a density of equal to or less than 1.3 grams/ml.
Preferably equal to or more than 10 wt %, more preferably equal to or more than 20 wt % and most preferably equal to or more than 30 wt % of the total petroleum-derived hydrocarbon composition has a boiling point equal to or higher than 95° C., more preferably equal to or higher than 200° C., even more preferably equal to or higher than 300° C. and most preferably equal to or more than 400° C. Suitable the petroleum-derived hydrocarbon composition has an initial atmospheric boiling point of equal to or more than 130° C. Preferably, the initial atmospheric boiling point of the petroleum-derived hydrocarbon composition is equal to or more than 150° C., more preferably equal to or more than 180° C. In preferred embodiments, the atmospheric boiling point range of the petroleum-derived hydrocarbon composition may be from 220° C. to 800° C., more preferably from 300° C. to 700° C.
In preferred embodiments, the hydrogen to carbon weight ratio (H/C ratio) of the petroleum-derived hydrocarbon composition may be at most 0.15 w/w, more preferably in the range of from 0.1 to 0.14 w/w, even more preferably in the range of from 0.11 to 0.13 w/w.
As used herein, boiling point is the atmospheric boiling point, unless indicated otherwise, with the atmospheric boiling point being the boiling point as determined at a pressure of 100 kiloPascal (i.e. 0.1 MegaPascal). As used herein, initial boiling point and boiling point range of the high boiling hydrocarbon mixtures are as determined by ASTM D2887. As used herein, pressure is absolute pressure. As used herein, H/C ratio is as determined by ASTM D5291. As used herein, asphaltenes content or C7-asphaltenes content is as determined by IP143, using n-heptane as a solvent.
In a preferred embodiment the petroleum-derived hydrocarbon composition is a so-called crude, also sometimes referred to as crude oil. By a crude is herein understood a petroleum-derived hydrocarbon composition that has not been processed yet. For example, by a crude may be understood a petroleum-derived hydrocarbon composition that has not been distilled and/or fractionally distilled in a treatment facility to produce multiple components with specific boiling range distributions (for example, naphtha, distillates, VGO, and/or lubricating oils).
The petroleum-derived hydrocarbon may for example be a whole crude, topped crude, desalted crude, desalted topped crude or combinations thereof. “Topped” refers to a rude that has been treated such that at least some of the components that have a low boiling point (for example a boiling point below 35° C. at 0.101 MPa) have been removed.
Preferably the petroleum-derived hydrocarbon composition is a disadvantaged crude or is derived from a disadvantaged crude. Examples of disadvantaged crudes include, but are not limited to, crudes from of the following regions of the world: U.S. Gulf Coast and southern California, Canada Tar sands, Brazilian Santos and Campos basins, Egyptian Gulf of Suez, Chad, United Kingdom North Sea, Angola Offshore, Chinese Bohai Bay, Venezuelan Zulia, Malaysia, and Indonesia Sumatra.
In another preferred embodiment the petroleum-derived hydrocarbon composition may be obtained from or derived from a so-called unconventional petroleum deposit. For example the petroleum-derived hydrocarbon composition may comprise an unconventional oil or a derivative thereof. In such case the petroleum-derived hydrocarbon composition may comprise or consist of bitumen. More preferably the petroleum-derived hydrocarbon composition may be obtained from or derived from so-called bituminous sands, also referred to as oil sands or tar sands.
In one embodiment, the petroleum-derived hydrocarbon composition can be a petroleum derived hydrocarbon composition containing hydrocarbon compounds and water. For example the petroleum-derived hydrocarbon composition may comprise equal to or more than 0.5 wt % water, equal to or more than 1.0 wt % water or even equal to or more than 5.0 wt % water, based on the total weight of such petroleum-derived hydrocarbon composition.
It is also possible for the petroleum-derived hydrocarbon composition to contain hydrocarbon compounds, water and sand. The petroleum-derived hydrocarbon composition may for example contain in the range from 0.1 to 99.9 wt % hydrocarbon compounds and in the range from 0.1 to 99.9 wt % sand and/or water, based on the total weight of the petroleum-derived hydrocarbon composition. For example, the petroleum-derived hydrocarbon composition may comprise bitumen, which bitumen may for example be supplied as a mixture of bitumen, water and sand. Such a mixture of bitumen, water and sand may for example contain in the range from 5 wt % to 50 wt %, preferably in the range from 5 wt % to 30 wt % of bitumen; and for example in the range from 50 wt % to 95 wt %, preferably in the range from 70 wt % to 95 wt % of mud, based on the total weight of the mixture. The mud may consist of water and sand, and may contain in the range of 5 wt % to 50 wt %, preferably in the range from 10 wt % to 30 wt % of water; and for example in the range from 50 wt % to 95 wt %, preferably in the range from 70 wt % to 90 wt % of sand, based on the total weight of the mud.
In one preferred embodiment the petroleum-derived hydrocarbon composition may have been provided with the help of a so-called steam assisted gravidity drainage (SAGD). In such an embodiment the petroleum-derived hydrocarbon composition may preferably comprise equal to or more than 33.3 wt % hydrocarbon compounds, more preferably equal to or more than 60 wt % hydrocarbon compounds and still more preferably equal to or more than 80 wt % hydrocarbon compounds, based on the total weight of the petroleum-derived hydrocarbon composition. In practice such a petroleum-derived hydrocarbon composition may comprise equal to or less than 99 wt % hydrocarbon compounds, based on the total weight of the petroleum-derived hydrocarbon composition. In such an embodiment the petroleum-derived hydrocarbon composition may further comprise equal to or less than 33.3 wt % water, more preferably equal to or less than 10 wt % water and most preferably equal to or less than 5 wt % water, based on the total weight of the petroleum-derived hydrocarbon composition. In practice such a petroleum-derived hydrocarbon composition may comprise equal to or more than 0.5 wt % water, based on the total weight of the petroleum-derived hydrocarbon composition. In such an embodiment the petroleum-derived hydrocarbon composition may further comprise equal to or less than 33.3 wt % sand, more preferably equal to or less than 10 wt % sand and most preferably equal to or less than 5 wt % sand, based on the total weight of the petroleum-derived hydrocarbon composition. In practice such a petroleum-derived hydrocarbon composition may comprise equal to or more than 0.5 wt % sand, based on the total weight of the petroleum-derived hydrocarbon composition.
In step c) at least part of the biomass-derived pyrolysis product containing water and at least part of the petroleum-derived hydrocarbon composition are mixed to produce a hydrocarbon-containing mixture containing water.
Preferably the “at least part of the biomass-derived pyrolysis product” is a biomass-derived pyrolysis oil as described herein above. As explained above, such biomass-derived pyrolysis oil still contains water.
The mixture of at least part of the biomass-derived pyrolysis product (for example the biomass-derived pyrolysis oil) and at least part of the petroleum-derived hydrocarbon composition can be produced in any manner known to the skilled person in the art. The part or whole of the biomass-derived pyrolysis product may be added to part or whole of the petroleum-derived hydrocarbon composition, or the petroleum-derived hydrocarbon composition may be added to part or whole of the pyrolysis product, or streams of for example the pyrolysis product or part thereof and the petroleum-derived hydrocarbon composition may be brought together, for example by in-line blending or within a static mixer. Preferably the part or whole of the pyrolysis product and the part or whole of the petroleum-derived hydrocarbon composition may be mixed, for example by means of a mixer or via one or more baffles, preferably in an in-line mixer or static mixer.
Preferably, such biomass-derived pyrolysis oil and the part or whole of the petroleum-derived hydrocarbon composition may be mixed in a weight ratio of biomass-derived pyrolysis oil to petroleum-derived hydrocarbon composition (grams biomass-derived pyrolysis oil/grams petroleum-derived hydrocarbon composition) of at least 0.5/99.5, more preferably at least 1/99, still more preferably at least 2/98, and even still more preferably at least 5/95, respectively. Preferably, the biomass-derived pyrolysis oil and the petroleum-derived hydrocarbon composition may be mixed in a weight ratio of biomass-derived pyrolysis oil to petroleum-derived hydrocarbon composition (grams biomass-derived pyrolysis oil/grams petroleum-derived hydrocarbon composition) of at most 75/25, more preferably at most 70/30, even more preferably at most 60/40, and most preferably at most 50/50 respectively. In an especially preferred embodiment the petroleum-derived hydrocarbon composition may be mixed in a weight ratio of biomass-derived pyrolysis oil to petroleum-derived hydrocarbon composition (grams biomass-derived pyrolysis oil/grams petroleum-derived hydrocarbon composition) in the range from 1/99 to 30/70, more preferably in the range from 5/95 to 25/75, most preferably in the range from 10/90 to 20/80.
Step c) results in a hydrocarbon-containing mixture being produced. This hydrocarbon-containing mixture produced in step c) will still contain water, for example in a dispersed or emulsified form.
In step d) of the process according to the present invention the hydrocarbon-containing mixture is dewatered to produce a dewatered hydrocarbon-containing mixture. Dewatering can be carried out in any manner known by the person skilled in the art to be suitable for the removal of water from a hydrocarbon-containing mixture. Dewatering of the hydrocarbon-containing mixture may for example be carried out by evaporating of the water; membrane separation; phase separation; absorption or adsorption of the water; and/or any combination thereof. The dewatering may be carried out in a continuous operation or as a batch operation.
Preferably the hydrocarbon-containing mixture is dewatered by means of evaporation. Evaporation of the water, and optionally any volatile acids, from the hydrocarbon-containing mixture may for example be achieved by flashing or distillation of the hydrocarbon-containing mixture. In another example the water may be evaporated from the hydrocarbon-containing mixture in one or more wipe-film evaporators connected in series.
In a preferred embodiment water, and optionally any volatile acids, are evaporated from the hydrocarbon-containing mixture by flashing of such hydrocarbon-containing mixture. The flashing may for example be carried out by feeding a hydrocarbon-containing mixture under a pressure for example in the range from 200 to 1000 KiloPascal (KPa) into a flash vessel operated at a pressure for example in the range from 0.1 to 50 KPa at for example a temperature in the range from 90 to 150° C.
In another embodiment a distillation apparatus having a separation column may be selected to evaporate the water. Preferably, the distillation apparatus and the conditions of operating the distillation apparatus are selected such that water is evaporated and condensed as a water rich distillate fraction, and higher boiling hydrocarbon compounds (for example hydrocarbon compounds boiling at a temperature of equal to or more than 100° C., preferably at a temperature of equal to or more than 130° C., more preferably at a temperature of equal to or more than 150° C. and most preferably at a temperature of equal to or more than 180° C. at a pressure of 0.1 MegaPascal) remains in the bottom, yielding a bottom fraction which is rich in such higher boiling hydrocarbon compounds.
Preferably the bottom temperature is selected such that the bottom fraction is sufficiently low in viscosity, and the rate of evaporation of water is sufficiently high at the prevailing pressure and remains sufficiently high at instances that the water content of the bottom fraction is low. Suitably, a bottom temperature in the range of from 50° C. to 200° C. may be selected, more suitable in the range of from 80° C. to 150° C. The pressure may suitably be selected in the range of from 0.01 kPa to 500 kPa, more suitably in the range of from 0.1 kPa to 120 kPa, preferably in the range of from 0.2 kPa to 60 kPa and more preferably in the range of from 0.2 kPa to 10 kPa (kiloPascal). Although the higher boiling hydrocarbon compounds have been defined hereinbefore by its atmospheric boiling point (i.e. at a pressure of 0.1 MegaPascal, the skilled person will appreciate that the atmospheric boiling point is specified such that a distillation apparatus can be operated at a pressure other than atmospheric pressure (i.e. 0.1 MegaPascal) while water is evaporated and condensed as a water rich distillate fraction, and higher boiling hydrocarbon compounds remain in the bottom, yielding a bottom fraction which is rich in the higher boiling hydrocarbon compounds. Such bottom fraction can suitable be used as a dewatered hydrocarbon-containing mixture, in the next steps of the process according to this invention.
In step d) preferably equal to or more than 1 wt % of the total weight of water in the hydrocarbon-containing mixture is removed, more preferably equal to or more than 10 wt %, even more preferably equal to or more than 50 wt %, still more preferably equal to or more than 70 wt % and most preferably equal to or more than 90 wt % of the total weight of water in the hydrocarbon-containing mixture is removed. Suitably equal to or less than 100 wt % of the total weight of water in the hydrocarbon-containing mixture can be removed.
Dewatering of the hydrocarbon-containing mixture may preferably be effected to the extent that a dewatered hydrocarbon-containing mixture is obtained. Such dewatered hydrocarbon-containing mixture may have a water content of at most 5 wt %, more preferably at most 2 wt %, preferably at most 1 wt %, based on the total weight of the dewatered hydrocarbon-containing mixture. In the normal practice of this invention the water content of the dewatered hydrocarbon-containing mixture obtained may be at least 0.001 wt %, or at least 0.01 wt %, based on the total weight of the dewatered hydrocarbon-containing mixture.
Some embodiments of the process according to the invention may especially be advantageous when transporting or processing a so-called unconventional oil obtained from an unconventional petroleum deposit. As mentioned above, such unconventional oil may sometimes be diluted with a diluent, such as for example naphtha, before transporting and/or processing.
In
In one embodiment, the process according to this invention can advantageously comprise: a) pyrolyzing a biomass material to produce a biomass-derived water-containing pyrolysis product; b) providing a petroleum-derived hydrocarbon composition containing water, having a C7-asphaltenes content of equal to or more than 0.2 wt %, based on the total weight of the petroleum-derived hydrocarbon composition, which petroleum-derived hydrocarbon composition has a total acid number of equal to or more than 0.5 mg KOH/g and/or a density at 15.5° C. of equal to or more than 0.8 grams/ml and/or a viscosity at 37.8° C. of equal to or more than 500 centiStokes (cSt); c) mixing at least part of the biomass-derived water-containing pyrolysis product and at least part of the petroleum-derived hydrocarbon composition containing water to produce a hydrocarbon-containing mixture; and d) dewatering the hydrocarbon-containing mixture to produce a dewatered hydrocarbon-containing mixture.
Preferences and advantages as described hereinabove also apply to this embodiment. Most preferably the petroleum-derived hydrocarbon composition for this embodiment contains bitumen, water and sand. The process according to this embodiment advantageously allows one to remove water contained in the water-containing pyrolysis product and water contained in the petroleum-derived hydrocarbon composition simultaneously. This may advantageously allow a reduction in hardware and/or operating units. In addition the process according to this embodiment could advantageously allow one to remove part of the acids from both the pyrolysis oil as well as from the petroleum-derived hydrocarbon composition.
The dewatering may suitably be carried out in one or more steps. Preferably the hydrocarbon-containing mixture may be dewatered by separating an aqueous phase in a phase separation in a first step optionally followed by removing any remaining or residual water by means of evaporation in a second step. The phase separation may suitably further include a gas/liquid, solids/liquid and/or gas/solids/liquid phase separation to remove any solids and/or gases that may be contained in the petroleum-derived hydrocarbon composition.
An example of such an embodiment is illustrated by
In a second embodiment, the process according to the invention may comprise a) pyrolyzing a biomass material to produce a biomass-derived water-containing pyrolysis product; b) providing a petroleum-derived hydrocarbon composition containing water, having a C7-asphaltenes content of equal to or more than 0.2 wt %, based on the total weight of the petroleum-derived hydrocarbon composition, which petroleum-derived hydrocarbon composition has a total acid number of equal to or more than 0.5 mg KOH/g and/or a density at 15.5° C. of equal to or more than 0.8 grams/ml and/or a viscosity at 37.8° C. of equal to or more than 500 centiStokes (cSt); and removing the water contained in the petroleum-derived hydrocarbon composition to produce a petroleum-derived hydrocarbon composition comprising less than 0.1 wt % water; c) mixing at least part of the biomass-derived water-containing pyrolysis product and at least part of the petroleum-derived hydrocarbon composition to produce a hydrocarbon-containing mixture; and d) dewatering the hydrocarbon-containing mixture by evaporation of water to produce a dewatered hydrocarbon-containing mixture.
Preferences and advantages as described hereinabove also apply to this embodiment. Most preferably the petroleum-derived hydrocarbon composition for this embodiment contains bitumen, water and sand. An example of such an embodiment is illustrated by
In a most preferred third embodiment, where the petroleum-derived hydrocarbon composition is a petroleum derived hydrocarbon composition containing hydrocarbon compounds and water, the process according to the invention may comprise: a) pyrolyzing a biomass material to produce a biomass-derived water-containing pyrolysis product; b) providing a petroleum-derived hydrocarbon composition containing water, having a C7-asphaltenes content of equal to or more than 0.2 wt %, based on the total weight of the petroleum-derived hydrocarbon composition, which petroleum-derived hydrocarbon composition has a total acid number of equal to or more than 0.5 mg KOH/g and/or a density at 15.5° C. of equal to or more than 0.8 grams/ml and/or a viscosity at 37.8° C. of equal to or more than 500 centiStokes (cSt); and removing a first part of the water contained in the petroleum-derived hydrocarbon composition by means of phase separation to produce a petroleum-derived hydrocarbon composition comprising residual water; c) mixing at least part of the biomass-derived water-containing pyrolysis product and at least part of the petroleum-derived hydrocarbon composition containing residual water to produce a hydrocarbon-containing mixture; d) dewatering the hydrocarbon-containing mixture by evaporation and/or phase separation of residual water to produce a dewatered hydrocarbon-containing mixture.
Preferences and advantages as described hereinabove also apply to this embodiment. Most preferably the petroleum derived hydrocarbon composition in step b) of this third embodiment comprises bitumeninous sand (i.e. bitumen, sand and water) and a diluent such as naphtha. This embodiment has further been illustrated in
In
The process according to the invention may also be especially be advantageous when transporting or processing a so-called disadvantaged crude. Such a disadvantaged crude may sometimes be diluted with a diluent, such as for example a condensate, before transporting and/or processing.
In
Subsequently the obtained hydrocarbon-containing mixture may be forwarded to a flasher or distillation vessel (314), where a water-containing fraction (318) and a dewatered hydrocarbon-containing mixture (320) can be separated. The flasher or distillation vessel (314) may conveniently be located at the SAGD production location or at a refinery. The dewatered hydrocarbon-containing mixture obtained in step d) may suitably be more easy and/or more economic to process and/or transport.
The transportability and/or processibility of the dewatered hydrocarbon-containing mixture may even be further improved by upgrading the dewatered hydrocarbon-containing mixture in one or more hydrocarbon upgrading processes. In a preferred embodiment step d) therefore further comprises converting the dewatered hydrocarbon-containing mixture in one or more hydrocarbon upgrading processes to produce an upgraded dewatered hydrocarbon-containing mixture.
Such one or more hydrocarbon upgrading processes preferably comprise contacting the dewatered hydrocarbon-containing mixture with hydrogen in the presence of a catalyst to produce an upgraded dewatered hydrocarbon-containing mixture. Such a catalyst is preferably a hydrotreatment catalyst as described in more detail below. Preferably the one or more hydrocarbon upgrading processes may be carried out at a temperature in the range from 250 to 550° C. and a hydrogen partial pressure in the range from 1.0 to 10.0 MPa. The hydrocarbon upgrading process may suitably be carried out in a fixed bed or in a moving bed, such as an ebullated bed or riser reactor. One example of such a hydrocarbon upgrading process is the so-called LC-FINER process (LC-Finer is a trademark).
In
Some embodiments also provide a process for producing one or more fuel components and/or one or more chemical components comprising: a) pyrolyzing a biomass material to produce a biomass-derived pyrolysis product; b) providing a petroleum-derived hydrocarbon composition having a C7-asphaltenes content of equal to or more than 0.2 wt %, based on the total weight of the petroleum-derived hydrocarbon composition, which petroleum-derived hydrocarbon composition has a total acid number of equal to or more than 0.5 mg KOH/g and/or a density at 15.5° C. of equal to or more than 0.8 grams/ml and/or a viscosity at 37.8° C. of equal to or more than 500 centiStokes (cSt); c) mixing at least part of the biomass-derived pyrolysis product and at least part of the petroleum-derived hydrocarbon composition to produce a hydrocarbon-containing mixture; d) dewatering the hydrocarbon-containing mixture to produce a dewatered hydrocarbon-containing mixture and optionally upgrading the dewatered hydrocarbon-containing mixture in one or more hydrocarbon upgrading processes; and e) converting the, optionally upgraded, dewatered hydrocarbon-containing mixture via one or more hydrocarbon conversion processes into one or more fuel components and/or one or more chemical components.
Preferences for steps a, b, c and d, are as described above. Before being forwarded to any next steps, such as one or more hydrocarbon conversion processes, the dewatered hydrocarbon-containing mixture or upgraded dewatered hydrocarbon-containing mixture obtained in step d) or part thereof may first be stored for a period “t” before forwarding. Such a period “t” may preferably lie in the range from 1 hour to 1 month.
Step e) may for example include a fluid catalytic cracking process, a hydrocracking process, a thermal cracking process, a hydro-isomerization process, a hydro-desulphurization process or any combination thereof.
In
In a preferred embodiment step e) comprises a hydrotreatment of the dewatered hydrocarbon-containing mixture. Such hydrotreatment may for example comprise a hydrogenation, hydrodeoxygenation, hydrocracking, hydroisomerization or any combination thereof. In a preferred embodiment, step e) comprises a hydrocracking step, wherein the dewatered hydrocarbon-containing mixture is contacted with hydrogen in one or more moving bed reactors comprising a catalyst at a temperature in the range from 350 to 500° C. to produce a reaction product comprising one or more cracked products.
The catalyst is preferably a hydrotreatment catalyst comprising one or more metals of group VIII of the periodic table and/or one or more metals metal of group VIB of the periodic table. For example the catalyst may comprise a metal selected from the group comprising nickel, palladium, molybdenum, tungsten, platinum, cobalt, rhenium and/or ruthenium. Most preferably the catalyst is a nickel/tungsten comprising catalyst, a nickel/molybdenum comprising catalyst, cobalt/tungsten comprising catalyst or cobalt/molybdenum comprising catalyst. Suitably the above mentioned metals may be present in an alloy or oxide form.
Preferably the catalyst further comprises a support, which may be used to carry the metal or metals. Such a catalyst comprising one or more metals on a support is herein also referred to as heterogeneous catalyst. Examples of suitable supports include alumina, silica, silica-alumina, zirconia, titania, and/or mixtures thereof. The support may comprise a zeolite, but preferably comprises amorphous alumina, silica or silica-alumina.
Most preferably the catalyst comprises one or more oxides of molybdenum, cobalt, nickel and/or tungsten on a carrier comprising amorphous alumina, silica or silica-alumina.
The catalyst may be prepared in any manner known to be suitable by the person skilled in the art. In a preferred embodiment, the catalyst is a so-called extruded catalyst, prepared by extrusion of its components.
In a preferred embodiment the catalyst is a sulfided catalyst. The catalyst may be sulfided in-situ or ex-situ. In a preferred embodiment the catalyst is sulfided in-situ or its sulfidation is maintained in-situ by contacting it with a stream of hydrogen that comprises hydrogensulfide, for example a stream of hydrogen that contains in the range from 0.1 to 10 wt % hydrogensulfide based on the total weight of the stream of hydrogen.
In addition to a heterogeneous catalyst or instead of a heterogeneous catalyst, also a colloidal or dispersed catalyst may be used. Conveniently such a colloidal or dispersed catalyst may be formed in-situ by mixing one or more catalyst precursors in the feed in such a manner that a colloidal or dispersed catalyst is formed within the one or more moving bed reactors.
If step e) comprises a hydrocracking step, a fluid catalytic cracking step and/or a thermal catalytic cracking step a reaction product is produced comprising one or more cracked products. By a cracked product is herein understood a product comprising one or more compounds obtained by cracking of one or more larger compounds.
In a preferred embodiment the reaction product or part thereof is subsequently fractionated to produce one or more product fractions. For example a product fraction boiling in the gasoline range (for example from about 35° C. to about 210° C.); a product fraction boiling in the diesel range (for example from about 210° C. to about 370° C.); a product fraction boiling in the vacuum gas oil range (for example from about 370° C. to about 540° C.); and a short residue product fraction (for example boiling above 540° C.).
In
The, optionally hydrotreated or hydroisomerized, product fraction(s) may be used as biofuel and/or biochemical component(s). In a preferred embodiment the, optionally hydrotreated or hydroisomerized, one or more product fractions produced in the fractionation can be blended as a biofuel component and/or a biochemical component with one or more other components to produce a biofuel and/or a biochemical. By a biofuel respectively a biochemical is herein understood a fuel or a chemical that is at least party derived from a renewable energy source.
Examples of one or more other components with which the, optionally hydrotreated or hydroisomerized, one or more product fractions may be blended include anti-oxidants, corrosion inhibitors, ashless detergents, dehazers, dyes, lubricity improvers and/or mineral fuel components, but also conventional petroleum derived gasoline, diesel and/or kerosene fractions.
Some embodiments can further be illustrated by the following non-limiting examples.
Examples 1 and 2A pyrolysis oil originating from pine forest residue and having a water content of about 22 wt %, obtained from Technical Research Centre of Finland (VTT), was combined and mixed with a homogeneous Peace River bitumen, a bituminous sand obtained from Athabasca, Canada. The Peace River bitumen had a Total Acid Number of about 4-5 mg KOH/g and a C7-asphaltene content of about 10.9 wt %. The resultant mixture was placed in a round-bottom flask of a standard laboratory rotary evaporator. After attaching the flask to the rotary evaporator, an oil bath was placed around the flask and heated to 110° C., while the flask was allowed to rotate. The pressure inside the rotary evaporator was carefully lowered to less than 0.5 kPa (<5 millibar), i.e. such that sudden boiling of the mixture was prevented. A water fraction was distilled off during a period of 1 hours. Table I specifies the intake of materials and the water content of the de-watered hydrocarbon-containing mixture obtained.
The dewatered mixtures were checked visibly on stability and on solids visible to the eye.
Therefore, embodiments of the present invention are well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered, combined, substituted, or modified and all such variations are considered within the scope and spirit of the present invention. The invention illustratively disclosed herein suitably may be practiced in the absence of any element that is not specifically disclosed herein and/or any optional element disclosed herein. While compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components and steps. All numbers and ranges disclosed above may vary by some amount whether accompanied by the term “about” or not. In particular, the phrase “from about a to about b” is equivalent to the phrase “from approximately a to b,” or a similar form thereof. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee. Moreover, the indefinite articles “a” or “an,” as used in the claims, are defined herein to mean one or more than one of the element that it introduces. If there is any conflict in the usages of a word or term in this specification and one or more patent or other documents that may be incorporated herein by reference, the definitions that are consistent with this specification should be adopted.
Claims
1. A process comprising:
- a) pyrolyzing a biomass material to produce a biomass-derived pyrolysis product;
- b) providing a petroleum-derived hydrocarbon composition having a C7-asphaltenes content of equal to or more than 0.2 wt %, based on the total weight of the petroleum-derived hydrocarbon composition, which petroleum-derived hydrocarbon composition has a total acid number of equal to or more than 0.5 mg KOH/g and/or a density at 15.5° C. of equal to or more than 0.8 grams/ml and/or a viscosity at 37.8° C. of equal to or more than 500 centiStokes (cSt);
- c) mixing at least part of the biomass-derived pyrolysis product and at least part of the petroleum-derived hydrocarbon composition to produce a hydrocarbon-containing mixture; and
- d) dewatering the hydrocarbon-containing mixture to produce a dewatered hydrocarbon-containing mixture.
2. The process of claim 1, wherein the petroleum-derived hydrocarbon composition that has a Total acid number of equal to or more than 1.0 mg KOH/g.
3. The process of claim 1, wherein the petroleum-derived hydrocarbon composition contains hydrocarbon compounds and water.
4. The process of claim 1, wherein the petroleum-derived hydrocarbon composition is obtained or derived from a so-called unconventional petroleum deposit.
5. The process of claim 1, wherein the petroleum-derived hydrocarbon composition is obtained or derived from bituminous sands.
6. A process comprising:
- a) pyrolyzing a biomass material to produce a biomass-derived water-containing pyrolysis product;
- b) providing a petroleum-derived hydrocarbon composition containing water, having a C7-asphaltenes content of equal to or more than 0.2 wt %, based on the total weight of the petroleum-derived hydrocarbon composition, which petroleum-derived hydrocarbon composition has a total acid number of equal to or more than 0.5 mg KOH/g and/or a density at 15.5° C. of equal to or more than 0.8 grams/ml and/or a viscosity at 37.8° C. of equal to or more than 500 centiStokes (cSt);
- c) mixing the at least part of the biomass-derived water-containing pyrolysis product and at least part of the petroleum-derived hydrocarbon composition containing water to produce a hydrocarbon-containing mixture; and
- d) dewatering the hydrocarbon-containing mixture to produce a dewatered hydrocarbon-containing mixture.
7. The process of claim 6 further comprising
- removing the water contained in the petroleum-derived hydrocarbon composition to produce a petroleum-derived hydrocarbon composition comprising less than 0.1 wt % water;
8. The process of claim 6 further comprising
- removing a first part of the water contained in the petroleum-derived hydrocarbon composition by means of phase separation to produce a petroleum-derived hydrocarbon composition comprising residual water;
- wherein step c) comprises mixing at least part of the biomass-derived water-containing pyrolysis product and at least part of the petroleum-derived hydrocarbon composition containing residual water to produce a hydrocarbon-containing mixture; and
- wherein step d) comprises dewatering the hydrocarbon-containing mixture by evaporation and/or phase separation of residual water to produce a dewatered hydrocarbon-containing mixture.
9. The process of claim 1, wherein step d) further comprises converting the dewatered hydrocarbon-containing mixture in one or more hydrocarbon upgrading processes to produce an upgraded dewatered hydrocarbon-containing mixture.
10. The process of claim 9, wherein the hydrocarbon upgrading process comprises contacting the dewatered hydrocarbon-containing mixture with hydrogen in the presence of a catalyst to produce an upgraded dewatered hydrocarbon-containing mixture.
11. A process for producing one or more fuel components and/or one or more chemical components comprising
- a) pyrolyzing a biomass material to produce a biomass-derived pyrolysis product containing water;
- b) providing a petroleum-derived hydrocarbon composition having a total acid number of at least 0.5 mg KOH/g and a C7-asphaltenes content of equal to or more than 0.2 wt %, based on the total weight of the petroleum-derived hydrocarbon composition;
- c) mixing at least part of the biomass-derived pyrolysis product and at least part of the petroleum-derived hydrocarbon composition to produce a hydrocarbon-containing mixture containing water;
- d) dewatering the hydrocarbon-containing mixture obtained in step c) to produce a dewatered hydrocarbon-containing mixture; optionally upgrading the dewatered hydrocarbon-containing mixture in one or more hydrocarbon upgrading processes; and
- e) converting the dewatered hydrocarbon-containing mixture via one or more hydrocarbon conversion processes into one or more fuel components and/or one or more chemical components.
12. The process of claim 11, wherein step e) comprises converting the dewatered hydrocarbon-containing mixture in one or more hydrocarbon conversion processes, and separating the product of the hydrocarbon conversion process into one or more hydrocarbon product fractions.
13. The process of claim 12, wherein the one or more hydrocarbon conversion processes comprise a fluid catalytic cracking process, thermal cracking process and/or hydrocracking process.
14. The process of claim 12, further comprising combining the one or more hydrocarbon product fractions with one or more additives to produce one or more fuel components and/or one or more chemical components.
Type: Application
Filed: Apr 30, 2014
Publication Date: Nov 6, 2014
Applicant: SHELL OIL COMPANY (Houston, TX)
Inventors: Johannes Pieter HAAN (Amsterdam), Carolus Matthias Anna Maria MESTERS (Sugar Land, TX), Ivo Johannes DIJS (Amsterdam), Arjen NIEUWHOF (Amsterdam)
Application Number: 14/265,428
International Classification: C10G 1/00 (20060101); C10L 1/10 (20060101); C10G 1/04 (20060101);
