WO2009103088A1 - System and method for introducing an additive to a coking process for improving the yields and properties of desired products - Google Patents
System and method for introducing an additive to a coking process for improving the yields and properties of desired products Download PDFInfo
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- WO2009103088A1 WO2009103088A1 PCT/US2009/034335 US2009034335W WO2009103088A1 WO 2009103088 A1 WO2009103088 A1 WO 2009103088A1 US 2009034335 W US2009034335 W US 2009034335W WO 2009103088 A1 WO2009103088 A1 WO 2009103088A1
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- Prior art keywords
- coking
- coke
- catalyst
- additive
- coker
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
- C10B55/02—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials
- C10B55/04—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials
- C10B55/08—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form
- C10B55/10—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form according to the "fluidised bed" technique
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/005—Coking (in order to produce liquid products mainly)
Definitions
- This invention relates generally to the field of thermal coking processes, and more specifically to modifications of petroleum refining thermal coking processes to improve the product yields and/or the characteristics of the products of the coking process.
- Exemplary embodiments of the invention also relate generally to the production of various types of petroleum coke with unique characteristics for fuel, anode, electrode, or other specialty carbon products and markets.
- Thermal coking processes have been developed since the 1930s to help crude oil refineries process the "bottom of the barrel.”
- modern thermal coking processes employ high-severity, thermal decomposition (or “cracking") to maximize the conversion of very heavy, low-value residuum feeds to lower boiling hydrocarbon products of higher value.
- Feedstocks for these coking processes normally consist of refinery process streams which cannot economically be further distilled, catalytically cracked, or otherwise processed to make fuel-grade blend streams.
- these materials are not suitable for catalytic operations because of catalyst fouling and/or deactivation by ash and metals.
- Common coking feedstocks include atmospheric distillation residuum, vacuum distillation residuum, catalytic cracker residual oils, hydrocracker residual oils, and residual oils from other refinery units.
- the petroleum coke is considered a by-product that is tolerated in the interest of more complete conversion of refinery residues to lighter hydrocarbon compounds, referred to as 'cracked liquids' throughout this discussion.
- These cracked liquids range from pentanes to complex hydrocarbons with boiling ranges typically between 350 and 950 degrees F.
- the 'cracked liquids' and other products move from the coking vessel to the fractionator in vapor form.
- the heavier cracked liquids e.g. gas oils
- FCCUs Fluid Catalytic Cracking Units
- coker feedstocks are often modified to alleviate safety issues associated with shot coke production or 'hot spots' or steam 'blowouts' in cutting coke out of the coking vessel.
- decanted slurry oil, heavy cycle oil, and/or light cycle oil from the FCCU are added to the coker feed to increase sponge coke morphology (i.e. reduce shot coke production). This increase in sponge coke is usually sufficient to alleviate the safety problems associated with shot coke (e.g. roll out of drum, plugged drain pipes, etc.).
- the increase in sponge coke can provide sufficient porosity to allow better cooling efficiency of the quench to avoid 'hot spots' and steam 'blowouts' due to local areas of coke that are not cooled sufficiently before coke cutting.
- the addition of these materials to coker feed reduces coking process capacities.
- these 'heavy tail' components are primarily polycyclic aromatic hydrocarbons (or PAHs) that have a high propensity to coke and contain much of the remaining, undesirable contaminants of sulfur, nitrogen, and metals.
- PAHs polycyclic aromatic hydrocarbons
- these undesirable contaminants of the 'heavy tail' components can significantly increase contaminants in downstream product pools, consume capacities of refinery ammonia recovery / sulfur plants, and increase emissions of sulfur oxides and nitrous oxides from the FCCU regenerator.
- these problematic 'heavy tail' components of coker gas oils can significantly deactivate cracking catalysts by increasing coke on catalyst, poisoning of catalysts, and/or blockage or occupation of active catalyst sites.
- 4,394,250 describes a delayed coking process in which small amounts of cracking catalyst and hydrogen are added to the hydrocarbon feedstock before it is charged to the coking drum to increase distillate yield and reduce coke make.
- the catalyst settles out in the coke and does not affect the utility of the coke.
- U.S. Pat. No. 4,358,366 describes a delayed coking process in which small amounts of hydrogen and a hydrogen transfer catalyst, a hydrogenation catalyst, and/or a hydrocracking catalyst are added to a coker feed consisting of shale oil material and a petroleum residuum to enhance yields of liquid product.
- This known art adds catalyst to the coker feed, which has substantially different chemical and physical characteristics than the reactants of the present invention.
- the coker feed of the known art is typically comprised of very heavy aromatics (e.g. asphaltenes, resins, etc.) that have theoretical boiling points greater than 1000 oF.
- the primary reactants exposed to the catalysts of the known art are heavy aromatics with a much higher propensity to coke (vs. crack), particularly with the exposure to high vanadium and nickel content in the coker feed.
- mineral matter in the coker feed tends to act as a seeding agent that further promotes coking.
- Calcium, sodium, and iron compounds/particles in the coker feed have been known to increase coking, particularly in the coker feed heater.
- the primary reactants of the known art are a very viscous liquid (some parts semi-solid) at the inlet to the coker feed heater.
- the temperature of the multi-phase material at the inlet to the drum is typically between 900 oF and 950 oF.
- exemplary embodiments of the present invention may (1 ) improve a quantity of a coker product or the overall yield distributions of coker products, (2) improve a quality or a property of one or more of the coker products, (3) improve operation, maintenance, throughput capacity, efficiency, and/or processing alternatives of the coking process (4) improve the operation, maintenance, throughput capacity, efficiency, and/or processing alternatives for other refinery processing units, and/or (5) provide additional catalytic cracking capacity for a crude oil refinery or upgrading system.
- An exemplary embodiment of the present invention can increase or decrease the yield of the various types of coking process products (e.g. cracked liquids, coke, and/or gases).
- An exemplary embodiment of the present invention can effectively use the catalytic additive (by design) to effect an increase or decrease in the various types of desired coking process products, including but not limited to, naphtha, light gas oil, heavy gas oil, liquid petroleum gases (e.g. propanes & butanes), olefin gases, fuel gas, hydrogen, and coke.
- the catalytic additive can be designed to convert the chemical compounds in the coking process feed or products (intermediate and final) of the thermal cracking and thermal coking reactions of the traditional coking process into other types of chemical compounds or desired products.
- the catalyst characteristics can be modified to perform desired reactions.
- the catalytic additive added to the coking process can convert chemical compounds from the thermal decomposition of the coking process feed (that would normally form coke in the coking process) into cracked liquids or gas products.
- the catalytic additive can effectively be used to reduce excess cracking of hydrocarbon vapors (commonly referred to as Vapor overcracking' in the art) by quenching or catalytically altering such cracking reactions, that convert valuable 'cracked liquids' to less valuable gases (ethanes and lower) that are typically used as fuel (e.g. refinery fuel gas).
- Another exemplary embodiment of the present invention can improve the quality of various products of the coking process.
- thermally altered components of the feed to the coking process can be catalytically converted by the catalytic additive added to the coking process into cracked liquids and gas products.
- Alternatives of this exemplary embodiment can use catalysts that are designed for higher selectivity and reactivity toward certain process streams of the coking process to the coking process or products of the thermal cracking and thermal coking of the traditional coking process.
- the quality of gas oils can be effectively improved by the catalytic additive of exemplary embodiments of the present invention by (1 ) catalytically cracking various gas oil components to increase lighter cracked liquids or gases and/or (2) catalytically coking them.
- exemplary embodiments of the present invention may be used to significantly improve the quality of the petroleum coke.
- An exemplary embodiment of the present invention may also be used to enhance the quality of the petroleum coke by selective catalytic coking of any components of the feed to the coking process and/or chemical intermediates formed in the coking process. This embodiment of the catalytic coking may be done in a manner that improves the quality of the pet coke for anode, electrode, fuel, or specialty carbon markets.
- An exemplary embodiment can also increase sponge coke morphology to avoid safety issues associated with shot coke production and 'hot spots' and steam 'blowouts' during coke cutting. In many cases, this can be done by catalytically cracking and/or coking heavy aromatics (e.g. asphaltenes and their derivatives) that otherwise fill and block cooling channels in the coke. Typically, this can be done without using valuable capacity to add slurry oil or other additives to the coker feed to achieve these objectives. Furthermore, an exemplary embodiment of the present invention can reduce shot coke in a manner that may improve coke quality sufficiently to allow sales in the anode coke market.
- heavy aromatics e.g. asphaltenes and their derivatives
- a catalytic additive may be added to the coking process in a manner that changes the coking process in a positive manner that can improve operation and/or maintenance.
- a catalytic additive can reduce the chemical compounds that have a high propensity to coke in the coking process heater, vapor line to the fractionator, and other coking process components and reduce operational problems and maintenance issues.
- a catalytic additive can be added to the coking process in a manner that achieves a reduction of pet coke, gas production, and/or coker recycle that can all help to increase the throughput capacity of the coking process.
- a catalytic additive can also be effectively used to provide other means to debottleneck the coking process.
- An exemplary embodiment of the present invention may also provide a superior means to increase coking process capacity without sacrificing the quality and quantity of desirable coker products, such as coker gas oil quality. In many cases, the increase in coking capacity also leads to an increase in refinery throughput capacity in refineries where the coking process is the refinery bottleneck.
- Other exemplary embodiments of the present invention can increase the efficiency of the coking process.
- a catalytic additive may effectively (1 ) increase valuable products without additional process severity, (2) decrease required recycle and associated heater fuel per barrel of feed processed, and/or (3) decrease vapor loading to the fractionator, which all increase coking process efficiency.
- additional exemplary embodiments of the present invention may be used to provide processing alternatives in the coking process, including but not limited to, changing (1 ) coking process feed quality, (2) gas oil quantity and/or quality, (3) coke quantity and/or quality, and/or (4) quantity and/or quality of gas production.
- Other exemplary embodiments of the present invention improve the operation, maintenance, throughput capacity, efficiency, and/or processing alternatives for other refinery processing units.
- the catalytic additive added to the coking process may be used to improve these by improving the quantity and/or quality of the coking process products that are further processed in downstream refinery processing units.
- improving the quality of gas oils can increase the efficiency and improve the operation, maintenance, and throughput capacity of the downstream fluid catalytic cracking unit (FCCU), and/or provide the opportunity to process some of these gas oil components in a hydrocracking process.
- Decreasing the quantity of these gas oils can also provide the opportunity to decrease the process severity of the FCCU and/or provide processing alternatives for other types of FCCU feeds.
- An exemplary embodiment of the present invention may also allow crude slate flexibility for refineries that want to increase the proportion of heavy, sour crudes without sacrificing coke quality, particularly with refineries that currently produce anode grade coke.
- Another exemplary embodiment of the present invention improves the quality of the coke in a manner that improves the operation and efficiency of downstream calcining facilities.
- other exemplary embodiments of the present invention can provide additional catalytic cracking capacity for a crude oil refinery (or upgrading systems for shale oil, tar sands, etc.) by achieving cracking of feed derivativesin the coking process beyond the thermal cracking that normally occurs.
- the additional catalytic cracking in the coking process may be sufficient to provide an economic alternative to adding downstream cracking capacity (e.g. fluid catalytic cracking unit or hydrocracker) and/or the addition of feed pretreatment for downstream catalytic cracking.
- the present invention has many exemplary embodiments that can occur somewhat independently, depending on several factors, including the quality and quantity of the catalytic additive. In many cases, however, the exemplary embodiments will overlap and occur concurrently, but to different degrees. As such, an exemplary embodiment of the present invention provides the opportunity to develop catalytic additive(s) to address the specific needs of a particular refinery. That is, the catalytic additive(s) can be specifically designed to improve the yield distribution to the products that are most valuable to that refinery's process scheme and crude slate opportunities. This approach may simply involve catalytic cracking to produce greater yields of cracked liquids or may involve more sophisticated catalytic additive to be selective in desired types of cracked liquids.
- an additional catalytic additive could be added to produce more of the desired products at that particular facility (e.g. propylene for local plastics plant) or selectively convert particular types of chemical species from the feed to the coking process or intermediate chemical species in the coking process from other chemical reactions.
- intermediate products' or intermediate chemical species' shall refer to chemical species, including coking process products, in the coking process caused by thermal cracking, thermal coking, and various other chemical reactions with the coking process feed components.
- the process optimization model in each refinery could be used as an effective tool in determining what catalytic additives would be preferable and worth pursuing (e.g. cost effectiveness and return on investment). All of the exemplary embodiments of the present invention potentially improve the overall refinery profitability. Further objects and advantages of this invention will become apparent from consideration of the drawings and ensuing descriptions.
- Exemplary embodiments of the present invention provide improvements of coking processes which introduce an additive to a coking process to convert intermediate hydrocarbon compounds of the coking process and improve the quality and/or value of the products of the coking process.
- the basic technology contemplated in U.S. Provisional Application No. 60/866,345 uses this additive (often containing catalyst) to crack or coke high boiling point compounds (e.g. heavy coker gas oils).
- 'conversion includes cracking these high boiling point compounds to lighter hydrocarbons,' including 'naphtha, gas oil, gasoline, kerosene, jet fuel, diesel fuel, & heating oil.
- Various other exemplary embodiments are discussed, including the use of the additive (with or without catalyst) as a quenching agent to reduce vapor overcracking reactions.
- Much discussion is devoted to what is considered one of the best modes of operation for the present invention, which uses the additive (with catalyst) to selectively convert the highest boiling point materials in the product vapors of the coking process to minimize the coker recycle and/or significantly improve the quality of the heavy coker gas oil.
- this exemplary embodiment of the present invention potentially provides the greatest upgrade in value for the coking process: (1 ) increasing liquid yields, while decreasing coke yields, (2) minimizing coker recycle, (3) improving quality of coker gas oil and/or petroleum coke, (3) reducing 'vapor overcracking' and associated loss of liquids to lower value gases, (4) reducing 'hotspots' and/or 'blowouts' & associated safety issues and costs, (5) increasing coker capacity and potentially refinery capacity, (6) increasing crude slate flexibility, and/or (7) improving operation & maintenance of the coking process and downstream processing units.
- further improvements of the basic technology include the use of a broader spectrum of catalysts (and their improvements) to affect a greater breadth of chemical reactions and their potential utility in the coking process.
- the additive package used in exemplary embodiments of the present invention offers substantial flexibility in providing beneficial conversion of various intermediate hydrocarbons of the coking process.
- an improvement to the present invention is claimed relative to the use of (1 ) hydrogen to enhance the catalytic reactions and (2) net heat input to the coking process through heating the additive (e.g. catalyst) or hydrogen.
- another improvement of the basic technology employs additional catalyst improvements to provide a more comprehensive approach to optimize the benefits at each coking process application.
- a catalytic additive can be introduced into traditional coking processes to modify the quantity or yield of a coking process product and/or modify certain characteristics or properties of coking process products. Minor changes in coking process operating conditions can enhance the effectiveness of these catalytic additive packages.
- the change in the products of the coking process is dependent on (but not limited to) (1 ) the quality and quantity of the catalytic additive package, (2) the existing design and operating conditions of the particular coking process, (3) the types and degree of changes in the coking process operating conditions, and (4) the coking process feed characteristics.
- Figure 1 shows an example of the present invention in its simplest form.
- This basic process flow diagram shows a heated, mixing tank (an exemplary means of mixing and temperature regulation) where components of the present invention's additive can be blended: catalyst(s), seeding agent(s), excess reactant(s), carrier fluid(s), and/or quenching agent(s).
- the mixed additive is then added to a generic coking process via a properly sized pump (an exemplary means of pressurized injection) and piping, preferably with a properly sized atomizing injection nozzle.
- Figure 2 shows a basic process flow diagram of the traditional, delayed coking technology of the known art.
- Figure 3 shows the integration of an example of an additive injection system of the present invention into the delayed coking process.
- the actual additive injection system may vary from refinery to refinery, particularly in retrofit applications.
- the injection points can be through injection nozzles at one or more points on the side walls above the vapor / liquid interface (also above the coking interface) in the coking vessel.
- the injection of the additive can take place at various places: any point above the vapor/liquid interface of the coking vessel, a coking process feed, a coking process recycle, a coking process heater feed, a coking process heater outlet stream, a coking vessel inlet stream, a coking vessel vapor line, a coking process fractionator, or any combination thereof.
- FIG. 4 shows a basic process flow diagram of the traditional, fluid coking technology of the known art. Flexicoking is essentially the same process with an additional gasifier vessel for the gasification of the by-product pet coke.
- Figure 5 shows the integration of an example of an additive injection system of the present invention into the fluid coking and flexicoking processes.
- the additive can be injected into the coking vessel above the level where the product vapors separate from the liquid and coke particles (i.e. coking interface in this case) or other injection points (i.e. said various points in a coking process) which may include (but should not be limited to) the fluid coking process feed, the fluid coking process heavy oil recycle to feed, the fluid coking process recycle of carbon particles, the fluid coking process heater feed, a coking process heater outlet stream, the fluid coking process coking vessel inlet stream, the coking vessel vapor line, the coking process fractionator, or any combination thereof.
- the actual additive injection system may vary from refinery to refinery, particularly in retrofit applications
- Figure 1 provides a visual description of the present invention in its simplest form.
- This basic process flow diagram shows a heated, mixing tank (210) (as an exemplary means of mixing and means of controlling temperature) where components of the present invention's additive can be blended: catalyst(s) (220), seeding agent(s) (222), excess reactant(s) (224), carrier fluid(s) (226), and/or quenching agent(s) (228).
- catalyst(s) (220
- seeding agent(s) 222
- excess reactant(s) 224
- carrier fluid(s) 226
- quenching agent(s) quenching agent
- the mixed additive (230) is then injected into a generic coking process (240) via properly sized pump(s) (250) (as an exemplary means of pressurized injection) and piping, preferably with properly sized atomizing injection nozzle(s) (260).
- the pump is controlled by a flow meter (270) with a feedback control system relative to the specified set point for additive flow rate.
- the primary purpose of this process is to consistently achieve the desired additive mixture of components of the present invention and evenly distribute this additive to introduce said catalyst additive at the desired point or points in the coking process.
- the system should be designed to (1 ) handle the process requirements at the point(s) of injection and (2) prevent entrainment of the additive's heavier components (e.g. catalyst) into downstream equipment.
- the additive in an exemplary embodiment of the present invention may be a combination of components that have specific functions in achieving the utility of the respective exemplary embodiment.
- the additive is not just a catalyst in all applications of the present invention, though it can be in many of them. In some applications (e.g. quenching vapor overcracking), there may be no catalyst at all in the additive.
- the term 'catalytic additive' does not apply in all embodiments, but could in many embodiments.
- the following discussion provides further breadth of the possible additive components, their utility, and potential combinations.
- Said catalytic additive package consists of (1 ) catalyst(s), (2) seeding agent(s), (3) excess reactant(s), (4) quenching agent(s), (5) carrier fluid(s), or (6) any combination thereof.
- the optimal design of said catalytic additive package can vary considerably from refinery to refinery due to differences including, but not limited to, coking process feed blend characteristics, process design & operating conditions, coker operating problems, refinery process scheme & processing objectives, downstream processing of the heavy coker gas oil and other coking process products, and/or the pet coke market & specifications.
- Catalvst(s) In general, the catalyst consists of any chemical element(s) or chemical compound(s) that reduce the energy of activation for the desired reaction for coker feed, intermediate chemical species of the coking process, and/or other process streams of the coking process.
- the catalyst can be designed to preferably favor certain cracking reactions and/or provide selectivity for the cracking of specific types of hydrocarbon reactants or products in the coking process (e.g. feed, intermediate and/or vapor products).
- the catalyst may be designed to preferably favor certain coking reactions and/or provide selectivity for the coking of specific types of hydrocarbon reactants or products, including specifications for coke morphology, quality & quantity of volatile combustible materials (VCMs), concentrations of contaminants (e.g. sulfur, nitrogen, and metals), or combinations thereof.
- VCMs volatile combustible materials
- the catalyst may be designed to selectively convert any heavy components (i.e. liquid, semi-liquid, or solid) of the coking process feed that tend to cause "hot spots" in the coke and 'blowouts' in decoking operations.
- the catalyst may be designed to preferentially coke via an exothermic, asphaltene polymerization reaction mechanism (vs. endothermic, free-radical coking mechanism).
- the temperature of coke drum can increase, and potentially increase the level of thermal and/or catalytic cracking or coking.
- catalyst may be formulated to enhance any one or more types of chemical reactions including but not limited to, cracking reactions, coking reactions, pyrolysis reactions, hydrogenation reactions, hydrogenolysis reactions, hydrolysis reactions, addition reactions, dehydrogenation reactions, condensation reactions, polymerization reactions, aromatization reactions, oligomerization reactions, isomerization reactions, or any combination thereof. These reactions may occur in the vapor phase, liquid phase, and/or solid phase.
- exemplary embodiments of the present invention describe a variety of methods to introduce a variety of catalytic additives (either alone or in combination) into a coking process to enhance a variety of chemical reactions.
- the present invention anticipates the potential use of wide variety of catalysts, including various catalyst substrates and treatments.
- exemplary embodiments of the catalyst of this invention may include chemical compounds that are not traditional catalysts, yet provide sufficient catalytic effects whether solid, liquid, or gaseous in nature.
- the presence of certain sodium and calcium compounds can increase undesirable coking in coking process heaters.
- similar sodium or calcium compounds e.g.
- liquid may be used in an exemplary embodiment of the present invention to enhance coking reactions near the point of injection of a catalytic additive with these compounds.
- a catalytic additive with these compounds.
- the development of various catalysts, totally new or based on existing catalysts, is anticipated for exemplary embodiments of the present invention.
- a variety of combinations of basic components of an FCC catalyst may allow a broad range of capabilities, including but not limited to (1 ) high cracking activity for cracking a variety of hydrocarbons in the coking process (2) high coking activity for exemplary embodiments of this invention for improving coke quality, and/or (3) the optimal combination of various catalyst components and treatments for other applications.
- the basic components and associated treatments of FCC catalysts include, but are not limited to (1 ) zeolite synthesis and processing, (2) active matrix synthesis, (3) clay processing, and (4) binder synthesis.
- the zeolite component is a synthetic (man-made) crystalline aluminosilicate.
- the second basic component is an active matrix; typically a synthetic amorphous aluminosilicate.
- This catalyst component is very porous and has a higher concentration of mesopores (30 to 500 angstroms) and macropores (> 500 angstroms).
- This basic catalyst component has higher accessibility for larger molecules in the coking process and has greater bottoms cracking capability.
- Certain types of clay are used as sinks for heat and sodium, and provides mechanical strength of the catalyst, but have limited effects on catalytic activity.
- the binder holds the catalyst components together.
- alumina polymers can further increase catalyst activity and aid in bottoms cracking.
- the key to providing the optimal catalyst for various exemplary embodiments of the present invention in various coking process applications can be finding the right combination of catalyst components and treatments.
- the optimal ratio of zeolite to active matrix i.e. Z/M in the art
- physical and catalytic characteristics of this type of catalyst may be designed to perform the desired functions of the catalyst in the catalytic additive, described throughout the description of this invention.
- the present invention should not be limited to this type of catalyst due to the many catalyst alternatives, now and in the future.
- catalyst substrates that promote a large concentration of acid sites are generally preferred, but not required.
- concentrations of acid sites can be too high for the desired reactions (e.g. excessive hydrogen transfer activity).
- several types of treatments and selection of catalyst components in FCC catalysts preferably reduce Si/AI ratios to reduce the concentration of acid sites for desired reactions (e.g. production of olefins vs. parafins).
- catalyst substrates of a different nature may be preferred, including non-acid catalyst sites.
- a catalyst may be in liquid or gaseous form.
- the porosity characteristics of solid catalysts of the present invention would need to be designed for the desired reactions in the coking process.
- the larger the molecular size of the reactants or products the greater pore size required to mitigate diffusion resistance becoming a limiting factor in the reaction kinetics.
- asphaltene molecules with molecular weights of 3000 to 48,000 can have molecular diameters of 50 to 300 Angstroms.
- Acceptable diffusion levels require at least 3 times the molecular diameter: 150 to 900 Angstroms, which is in the upper end of the mesopores range (i.e. 20 to 500 Angstroms) and the lower end of the macro pore range (i.e. > 500 Angstroms).
- catalysts for these large molecules may preferably have a range of pore size distributions, including the need for a high matrix activity with a distribution of macropores with lower activity to control coke and gas make, and/or mesopores with higher activity.
- traditional FCCU catalysts with an average diameter of 70 microns can have substantial proportions of micropores (zeolites component) with very high activity for predominantly lower boiling point feedstocks with lower molecular size.
- zeolites micropores
- the catalyst would preferably allow the large, aromatic molecules easy access to the acid sites.
- zeolites have very high acidic activity, but have pore size of approximately 9 angstroms, which are inaccessible to large hydrocarbon molecules.
- the exemplary embodiments of solid catalysts in the present invention is preferably sized between 10 and 600 microns, (most preferably between 40 and 300 microns) small enough for catalyst fluidization and prevention of injector pluggage, but sufficiently large (e.g. > 50 microns) to avoid entrainment in the vapors exiting the coking vessel (e.g. coke drum of the delayed coking process).
- the catalyst and reactants e.g. heavy aromatics
- the settling time to the vapor/liquid interface can provide valuable residence time in cracking the various feed components or cracked liquids vapor products (e.g. gas oils) of the coking process, prior to reaching the vapor/liquid interface.
- equilibrium favors maximum aromatics cracking at low temperatures (e.g. 600 to 900 degrees Fahrenheit) preferably 700 to 850 degrees Fahrenheit with long residence times.
- the catalyst can continue promoting catalytic cracking reactions of the liquids/vapors flowing through the coke, even after it becomes part of the porous coke. If the catalyst and the coke have sufficient porosity, the residence time for cracking potential hydrocarbon reactants (e.g.
- the catalyst may be preferably be designed to be effective with liquid phase reactants, vapor phase reactants, and/or both.
- Sizing a solid catalyst for exemplary embodiments of the present invention to promote fluidization (e.g. 40 to >100 microns) for the catalyst in the coking vessel can further enhance the residence time of the catalyst in the vapor zone.
- this may not be desirable in many coking processes due to excessive gas production from cracking valuable cracked liquid products to gas.
- cyclones similar to those in a fluid catalytic cracker (i.e. FCC) or other particle separation equipment could be used in the coking vessel (e.g. coke drum) to control entrainment of catalyst particles in the gas vapors to the fractionation tower, and keep catalyst particles and silica out of the product vapors and fractionator.
- An exemplary embodiment would include a solid catalyst in the catalytic additive for the fluid coking or flexicoking coking processes, where coke particles up to 600 microns remain fluidized in the coking vessel.
- Catalyst substrates can be composed of various porous, natural or man-made materials, including (but should not be limited to) alumina, silica, zeolite, active matrix, activated carbon, crushed coke, calcium compounds, iron compounds, or any combinations thereof. These substrates can be treated or processed to achieve the desired catalytic and physical properties for exemplary embodiments of the present invention. These substrates can also be impregnated or activated with other chemical elements or compounds that enhance catalyst activity, selectivity, other catalyst properties, or combinations thereof.
- These chemical elements or compounds may include (but should not be limited to) nickel, iron, vanadium, iron sulfide, nickel sulfide, cobalt, calcium, magnesium, molybdenum, sodium, associated compounds, or combinations thereof.
- the catalyst may likely include nickel, since nickel strongly enhances coking in the absence of significant hydrogen partial pressures.
- increased levels of porosity, particularly mesoporosity can be beneficial in allowing better access by larger molecules to the active sites of the catalyst.
- the catalyst in the additive can improve cracking of the coking process feed components and cracked liquids/product vapors (e.g.
- the catalyst normally ends up in the coke. It is anticipated that various catalysts will be designed for the purposes above, particularly catalysts to achieve greater cracking of components of the feed, cracked liquids, and/or product vapors of the coking process to more valuable products. In these cases, a preferred catalyst formulation would initially crack feed components to maximize valuable, lighter products (e.g. cracked liquids), but ultimately promote the cracking or coking of other heavy aromatics to alleviate pitch materials (with a very high propensity to coke vs. crack) in the coke that cause 'hot spots.' However, with certain chemical characteristics of these materials and properly designed catalysts, substantial catalytic conversion of these materials to cracked liquids could be accomplished (e.g. > 50 Wt. %).
- catalysts can be selected from a group consisting of new catalyst, FCCU equilibrium catalyst, spent catalyst, regenerated catalyst, multifunctional catalysts, bimodal catalysts, pulverized catalyst, classified catalyst, impregnated catalyst, treated catalyst, or any combination thereof.
- coke specifications for fuel grade coke typically have few restrictions on metals, but low cost can be the key issue.
- FCCU catalysts or spent, pulverized, and classified hydrocracker catalysts may be preferred.
- new, low cost catalysts designed for these purposes or new catalyst enhancers that can be mixed with spent or regenerated catalysts may be most preferred.
- coke specifications for anode grade coke often have strict limits for sulfur and certain metals, such as iron, silicon, and vanadium. In these applications, cost is not as critical.
- new catalysts preferably made with alumina or activated carbon to prevent metals contamination
- Alumina or activated carbon (or crushed coke) impregnated with nickel may be most preferred for applications, where selective coking is desirable.
- the amount of catalyst used will vary for each application, depending on various factors, including (1 ) the catalyst's characteristics (e.g. activity, selectivity conversion, efficiency, and porosity), (2) coke specifications and (3) catalyst cost. In many applications, the quantity of catalyst will be less than 15 weight percent of the coker feed. Most preferably, the quantity of catalyst would be between 0.1 weight percent of the coker feed input to 7.0 weight percent of the coker feed input. Above these levels, the costs will tend to increase significantly, with diminishing benefits per weight of catalyst added. In some cases, the catalytic additive may not include a traditional catalyst at all, but still have desired effect(s) of the catalytic additive package.
- the catalytic additive(s) can be added at various points in a coking process, including but not limited to an injection into the vapors exiting the coking vessel (e.g. above the vapor/liquid interface or foam layer in the coke drum during the coking cycle of the delayed coking process) by various means, including pressurized injection with or without carrier fluid(s): hydrocarbon (s), oil(s), inorganic liquids, water, steam, nitrogen, or combinations thereof.
- the means of pressurizing the catalytic additive include (but should not be limited to) a pump or compressed fluids as part of the catalytic additive or separately as a driving force only (e.g.
- the compressed fluid in mixing tank to push through lines and through injector') the compressed fluid may include (but should not be limited to) nitrogen, hydrogen, fuel gas, water, hydrocarbon liquid/vapor, air, and/or oxygen. Air and/or oxygen would be the least desirable driving fluid due to potential injection into coking process, causing dangerous fire or explosion potential.
- Injectors' will refer to various devices to conduct the catalytic additive to the injection point for the introduction of said catalytic additive into the coking process of exemplary embodiments of the present invention. Acceptable 'injectors' would include (but should not be limited to) fluid atomizers, nitrogen assist atomizers, atomization systems, injector systems, lances, and/or simply pipe.
- an injector system may be as sophisticated as a modified drill stem that is retracted through the upper drum flange to keep catalytic additive injection above the rising coke mass above the foam layer.
- Other injection points (i.e. said various points in a coking process) to add the catalytic additive may include (but not limited to) a coking process feed line, a coking process vapor line, a coking process fractionator, a coking process feed pump, a coking process heater, or any combination thereof.
- process streams where the catalytic additive can be injected into include (but should not be limited to), a coking process feed, a coking process recycle, a coking process heater feed, a coking process heater outlet stream, a coking vessel inlet stream, a coking vessel vapors, a coking process fractionator bottoms, or any combination thereof.
- addition of catalyst alone can be undesirable. That is, injection of a catalyst without excess reactant(s), quenching agent(s), and/or carrier oil, can actually increase undesirable reactions (e.g. vapor overcracking) and cause negative economic impacts.
- the addition of catalyst only may be desirable. For example, heating the catalyst to high temperatures (e.g. 800 to 1200 oF) may be desirable to add net heat to the coking process and improve catalytic reactions.
- seeding agent consists of any chemical element(s) or chemical compound(s) that enhances catalytic cracking or catalytic coking, particularly the formation of coke by providing a surface for the coking reactions and/or the development of coke crystalline structure (e.g. coke morphology) to take place.
- the seeding agent can be a liquid droplet, a semi-solid, solid particle, or a combination thereof.
- the seeding agent can be the catalyst itself or a separate entity.
- Compounds of sodium, calcium, iron, and carbon particles e.g. crushed coke or activated carbon
- These and other chemical elements or compounds can be included in the catalytic additive to enhance cracking or coke development from feed components or chemical intermediates in the coking process.
- the amount of seeding agent(s) used will vary for each application, depending on various factors, including (but not limited to) the amount of catalyst, catalyst characteristics (e.g. activity, selectivity conversion, efficiency, and porosity), coke specifications, and cost.
- catalyst characteristics e.g. activity, selectivity conversion, efficiency, and porosity
- coke specifications e.g. activity, selectivity conversion, efficiency, and porosity
- cost e.g. activity, selectivity conversion, efficiency, and porosity
- coke specifications e.g. activity, selectivity conversion, efficiency, and porosity
- cost e.g. activity, selectivity conversion, efficiency, and porosity
- catalytic cracking will be more desirable than catalytic coking.
- seeding agents that enhance catalytic coking may be minimized or not included at all, and the catalyst will be the only seeding agent.
- little or no catalyst may be desirable in the additive.
- the amount of seeding agent will be less than 15 weight percent of the coker feed.
- the quantity of seeding agent would be between 0.1 weight percent of the coker feed input to 7.0 weight percent of the coker feed input. In many cases, the amount of seeding agent is preferably less than 3.0 weight percent of the coker feed.
- this seeding agent can be added to various points in the coking process by various means, including (but not limited to) pressurized injection with or without carrier fluid(s): hydrocarbon (s), oil(s), inorganic liquids, water, steam, nitrogen, or combinations thereof.
- the excess reactant consists of any chemical element(s) or chemical compound(s) that react with feed components, intermediate chemical species, and/or product vapors of the coking process to provide the desired reactions and reaction products.
- the excess reactant can be a gas, a liquid, a semi-solid, solid particle or a combination thereof.
- the excess reactants of choice are chemically reactive compounds.
- Various types of excess reactants can be used for this purpose.
- the excess reactant would contain very high concentrations of chemical elements or chemical compounds that react directly with a desired feed component, intermediate chemical species, cracked liquids, and/or vapor products of the coking process in the vapor phase, liquid phase, solid phase, or any combination thereof.
- Excess reactants would include, but should not be limited to, slurry oils, gas oils, extract from aromatic extraction units (e.g. phenol extraction unit in lube oil refineries), coker feed, bitumen, other aromatic oils, crushed coke, activated carbon, or combinations thereof.
- These excess reactants can be further processed (e.g. distillation) to increase the concentration of desired excess reactants components (e.g.
- the injection of hydrogen or other reactive gas may be desirable to enhance the catalyst's effectiveness. This is particularly true for situations where additional yields of cracked liquids would occur from mild hydrotreating, hydrocracking, hydroprocessing, or any combination thereof.
- An exemplary embodiment of the present invention with hydrogen injection would include high pressure coking vessels, such as needle cokers with pressures in excess of 80 psig.
- the amount of excess reactant used will vary for each application, depending on various factors, including (but not limited to) the amount of catalyst, catalyst characteristics (e.g. activity, selectivity conversion, efficiency, and porosity), coke specifications, and cost.
- the quantity of excess reactant will be sufficient to provide more than enough moles of reactant to achieve the desired conversion of feed components, intermediate chemical species, cracked liquids, and/or vapor products in a coking process.
- the molar ratio of excess reactant to targeted component(s) of the coking process would be in excess of that determined by one skilled in the art. However, in some cases, little or no excess reactant can be desirable in the additive.
- the amount of excess reactant will be less than 15 weight percent of the coker feed. Most preferably, the quantity of excess reactant would be between 0.1 weight percent of the coker feed input to 7.0 weight percent of the coking process feed input. As described, this excess reactant can be added to various points in the coking process by various means, including (but not limited to) pressurized injection with or without carrier fluid(s): gas oils hydrocarbon(s), oil(s), inorganic liquids, water, steam, nitrogen, or combinations thereof.
- carrier Fluid(s) gas oils hydrocarbon(s), oil(s), inorganic liquids, water, steam, nitrogen, or combinations thereof.
- Carrier Flu id (s) In general, a carrier fluid consists of any fluid that makes the catalytic additive easier to inject into the coking process.
- the carrier can be a liquid, gas, hydrocarbon vapor, or any combination thereof.
- the carrier will be a fluid available at the coking process, such as gas oils or lighter liquid process streams, such as kerosene.
- gas oil at the coking process is the preferable carrier fluid.
- carriers would include, but should not be limited to, FCCU slurry oils, decanted FCCU slurry oils, FCCU cycle oils, gas oils, other hydrocarbon(s), other oil(s), inorganic liquids, water, steam, nitrogen, hydrogen, or combinations thereof.
- the amount of carrier fluid(s) used will vary for each application, depending on various factors, including (but not limited to) the amount of catalyst, characteristics (e.g. activity, selectivity conversion, efficiency, and porosity), coke specifications, and cost.
- the quantity of carrier fluid(s) will be sufficient to improve the ability to pressurize the additive for addition via pump or otherwise. In many cases, the amount of carrier will be less than 15 weight percent of the coker feed. Most preferably, the quantity of carrier fluid(s) would be between 0.1 weight percent of the coker feed input to 7.0 weight percent of the coker feed input. As described, this carrier fluid can help with addition of the catalytic additive into various points of the coking process by various means, including (but not limited to) pressurized injection.
- Quenching Aaent(s) In general, a quenching agent consists of any fluid that has a net effect of further reducing the temperature of various points in a coking process.
- the quenching agent(s) can be a liquid, gas, hydrocarbon vapor, or any combination thereof.
- Many refinery coking processes use a quench in the vapors downstream of the coking vessel (e.g. coke drum). In some cases, this quench can be moved forward into the coking vessel. In many cases, a commensurate reduction of the downstream quench can be desirable to maintain the same overall heat balance in the coking process. In many cases, gas oil available at the coking process will be the preferred quench agent.
- quenching agents would include, but should not be limited to, gas oils, FCCU slurry oils, FCCU cycle oils, other hydrocarbon(s), other oil(s), inorganic liquids, water, steam, nitrogen, or combinations thereof.
- the quenching agent(s) may be added either with the catalytic additive and/or separately, which may be desirable to enhance the catalyst's effectiveness.
- the amount of quench used will vary for each application, depending on various factors, including (but not limited to) the temperature of the coking process, the desired temperature of the coking process, and the quenching effect of the additive without quench, and/or characteristics and costs of available quench options.
- the catalytic additive components can be added to the coking process in combination or separately. In many applications, a blended additive would combine any one or all of the 5 components to the degree determined to be desirable in each application.
- the catalytic additive components would be blended by a means of mixing, preferably to a homogeneous consistency, and heated to the desired temperature (e.g. heated, mixing tank) by a means of temperature regulation. For example, the desired temperature (e.g. >150 degrees F) of the mixture may need to be increased to maintain a level of viscosity for proper pumping characteristics and fluid nozzle atomization characteristics. In addition, heating the catalyst to a temperature (e.g.
- the catalyst may be heated and added to a coking process in a separate delivery system from the rest of the additive.
- the heated catalyst may be the only component of the additive.
- the additive at the desired temperature and pressure, would then be pressurized (e.g. via pump) and added (e.g. via injection nozzle) to a coking process at the desired point.
- insulated piping will be desirable to keep the additive at the desired temperature.
- injection nozzles can be desirable in many cases to evenly distribute the additive across the cross sectional profile of the coking process (e.g. coking vessel).
- the injection nozzles would also be designed to provide the proper droplet size (e.g. 50 to 600 microns) to prevent entrainment of undesirable components into other components of the coking process. Typically, these injection nozzles would be aimed countercurrent to the flow of coking process. The injection velocity should be sufficient to penetrate the process flow and avoid undesirable entrainment into the coking process streams. However, the injection nozzles design and metallurgy must take into account the potential for plugging and erosion from the solids (e.g. catalyst) in the catalytic additive package, since the sizing of such solids must be sufficient to avoid entrainment into undesirable components of the coking process (e.g. product vapor stream).
- the solids e.g. catalyst
- the catalytic additive(s) can be added at various points in a coking process, including but not limited to an injection into the vapors in the coking vessel (e.g. above the vapor/liquid interface or foam layer in the coke drum during the coking cycle of the delayed coking process) by various means, including pressurized injection with or without carrier fluid(s): hydrocarbon(s), oil(s), inorganic liquids, water, steam, nitrogen, or combinations thereof.
- the means of pressurizing the catalytic additive include (but should not be limited to) a pump or compressed fluids as part of the catalytic additive or separately as a driving force only (e.g.
- the compressed fluid in mixing tank to push through lines and through injector') the compressed fluid may include (but should not be limited to) nitrogen, hydrogen, fuel gas, water, hydrocarbon liquid/vapor, air, and/or oxygen. Air and oxygen would be the least desirable driving fluid due to potential injection into coking process, causing dangerous fire or explosion potential.
- injectors' refer to various devices to conduct the catalytic additive to the injection point for the introduction of said catalytic additive into the coking process of exemplary embodiments of the present invention. Acceptable injectors' would include (but should not be limited to) fluid atomizers, nitrogen assist atomizers, atomization systems, injector systems, lances, and/or simply pipe.
- an injector system may be as sophisticated as a modified drill stem that is retracted through the upper drum flange to keep catalytic additive injection above the rising coke mass above the foam layer.
- Other injection points (i.e. said various points in a coking process) to add the catalytic additive may include (but not limited to) a coking process feed line, a coking process vapor line, a coking process fractionator, a coking process feed pump, a coking process heater, or any combination thereof.
- catalytic additive package for exemplary embodiments of the present invention may also include anti-foam solution that is used by many refiners to avoid foamovers.
- antifoam solutions are high density chemicals that typically contain siloxanes to help break up the foam at the vapor/liquid interface (or foam layer) by its affect on the surface tension of the bubbles.
- the additive package of the present invention may provide some of the same characteristics as the antifoam solution; significantly reducing the need for separate antifoam.
- the existing antifoam system may no longer be necessary in the long-term, but can be modified for commercial trials and/or implementation of the present invention. It should be noted that not all coking vessels have a foam layer (depending on feed character and operating conditions). Thus, vapor/liquid interface will be often used, though 'foam layer' is synonymous in most delayed cokers.
- Said catalytic additive is believed to catalytically convert any feed components, intermediate chemical species, cracked liquids, or vapor products of the coking process by (1 ) providing a catalyst to reduce the activation energy of the desired chemical reactions, and/or (2) providing an excess reactant and appropriate reaction conditions to promote the desired chemical reactions in a vapor phase, liquid phase, solid phase, semi-solid phase, or any combination thereof. That is, said catalytic additive with a catalyst that has sufficient activity (e.g.
- Said catalyst can be a solid, a liquid, and/or a gas and be homogeneous or heterogeneous in nature. As such said catalyst can react with a reactant(s) of the coking process in the gas phase, liquid phase, solid phase, or any combination thereof.
- the reactants can diffuse to the catalysts' active sites, (2) the reactants react to form the desired products, byproducts, or any combination thereof, and (3) the products and/or byproducts diffuse from the catalyst's active sites.
- the catalytic additive is injected into the product vapors in the coking vessel above the coking mass, the localized quench effect of the catalytic additive can cause the highest boiling point components (e.g. heavy aromatics) in the vapors to condense on the catalyst and/or seeding agent, and cause selective exposure of the said highest boiling point components to the catalysts' active sites.
- the temperature of the product vapors in the coking vessel can range from 750 to 875 degrees Fahrenheit.
- the additive settling time and the time at or below the vapor/liquid interface i.e. in the foam layer, liquid layer and coke layer
- FCCU catalytic cracking units
- the additive's active sites in many applications would repetitively crack hydrocarbons, prior to and after reaching the vapor/liquid interface (or foam layer), liquid layer, or coke layer, before cracking and/or coking additional hydrocarbon components and being integrated into the petroleum coke.
- This invention should not be limited by this theory of operation.
- both the injection of this type of said catalytic additive package and the selective cracking and coking of various feed components, intermediate chemical species, cracked liquids, and/or vapor products are contrary to conventional wisdom and current trends in the petroleum coking processes.
- Enhancement of Additive Effectiveness It has also been discovered that minor changes in coking process operating conditions can enhance the effectiveness of the catalytic additive package.
- the changes in coker operating conditions include, but should not be limited to, (1 ) reducing the coking vessel outlet temperature, (2) increasing the coking vessel outlet pressure, (3) reducing the coking feed heater outlet temperature, or (4) any combination thereof.
- the first two operational changes represent additional means to condense the highest boiling point materials in the product vapors to increase their residence time in the coking vessel.
- the additive package is already lowering the temperature of the product vapors by its quenching effect and the intentional inclusion of a quenching agent in the additive package to increase this quenching effect. This quench effect reduces vapor overcracking reactions, as well as increases condensation of the highest boiling point materials in the product vapors.
- coking units have a substantial quench of the product vapors in the vapor line between the coking vessel and the fractionator to prevent coking of these lines.
- a commensurate reduction in the downstream vapor quenching is often desirable to maintain the same overall heat balance in the coking process unit.
- the coking unit is not pressure (compressor) limited, slightly increasing the coking vessel pressure can be preferable in many cases due to less vapor loading (caused by the quenching effect) to the fractionator and its associated problems.
- slight reductions of the feed heater outlet temperature may be desirable, in some cases, to optimize the use of the additive in an exemplary embodiment of the present invention.
- reduction of the cracking of heavy aromatics and asphaltenes to the 'heavy tail' components of the coking process gas oils can reduce the amount of additive required to remove the 'heavy tail' and improve its effectiveness in changing coke morphology from shot coke to sponge coke crystalline structure.
- other operational changes in the coking process can be desirable to improve the effectiveness of an exemplary embodiment of the present invention.
- the optimal combination of methods and embodiments will vary significantly. That is, site-specific, design and operational parameters of the particular coking process and refinery must be properly considered. These factors include (but should not be limited to) coker design, coker feedstocks, and effects of other refinery operations. With the present invention, one skilled in the art can readily determine the optimal combination of methods and embodiments presented herein, and apply them accordingly to site-specific, design and operational parameters of the particular coking process and refinery.
- Exemplary embodiments of the present invention generally introduce a catalytic additive into the coking vessel of the coking process at or above the vapor/liquid interface or, alternatively, at or above the coking interface (i.e. the coke / liquid interface).
- the primary reactants exposed to the catalyst in exemplary embodiments of the present invention are (1 ) the vapor products resulting from the thermal cracking and thermal coking of the coker feed and (2) essentially coker feed derivatives (also from thermal cracking and thermal coking of the feed) in the liquid, emulsion, and foam layers (below the vapor / liquid interface), after the catalyst has settled there.
- the primary catalytic reactants in exemplary embodiments of the present invention have substantially different chemical and physical characteristics than the reactants of the known art, wherein catalyst is added to the coker feed of the coking process.
- mineral matter in the coker feed tends to act as a seeding agent that further promotes coking.
- Calcium, sodium, and iron compounds/particles in the coker feed have been known to increase coking, particularly in the coker feed heater.
- the catalyst may act as a seeding agent, as well.
- the primary reactants of the known art are a very viscous liquid (some parts semi-solid) at the inlet to the coker feed heater. Throughout the heater and into the coke drums the feed becomes primarily hot liquid, some solids (from feed minerals and coking), and vapors (e.g. from coker feed cracking).
- the temperature of the multi-phase material at the inlet to the drum is typically between 900 and 950 degrees Fahrenheit.
- the catalyst reactants in an exemplary embodiment of the present invention are primarily derivatives (or partially cracked portions) of the coker feed. That is, the reactants that are exposed to the catalyst additive in exemplary embodiments of the present invention are mostly the products of the thermal cracking and thermal coking of the coker feed.
- the catalyst additive of the exemplary embodiments of the present invention have very limited exposure to coking process feed components, when the catalyst settles to the liquids above the coking interface (e.g. coke/liquid interface) and becomes part of the solid coke. Even here, most of the coker feed has been converted to smaller compounds with lower propensity to coke (vs. coking process feed).
- reactants exposed to the catalyst additive of the present invention are substantially more likely to crack than the components of the coker feed that are exposed to catalysts introduced into the coking process feed in the known art.
- the product vapors at or above the vapor/liquid interface in the coking vessel comprise various derivatives of the coker feed components, that are thermally cracked upstream of this point in the coking vessel. In the known art, these product vapors continue to thermally crack until they exit the coking vessel, where they are typically quenched in the vapor line to stop coking and cracking reactions.
- these product vapors are normally classified by boiling point range into the following groups: gas (less than 90 degrees Fahrenheit), light naphtha (roughly 90 to 190 degrees Fahrenheit), heavy naphtha (roughly 190 to 330 degrees Fahrenheit), Light Coker Gas Oil - LCGO (roughly 330 to 610 degrees Fahrenheit), Heavy Coker Gas Oil - HCGO (roughly 610 to 800 degrees Fahrenheit), and coker recycle (greater than roughly 800 degrees Fahrenheit).
- gas less than 90 degrees Fahrenheit
- light naphtha roughly 90 to 190 degrees Fahrenheit
- heavy naphtha roughly 190 to 330 degrees Fahrenheit
- Light Coker Gas Oil - LCGO roughly 330 to 610 degrees Fahrenheit
- Heavy Coker Gas Oil - HCGO roughly 610 to 800 degrees Fahrenheit
- coker recycle greater than roughly 800 degrees Fahrenheit.
- the vapor products in the coking vessel can be thought of as having the same boiling point classifications at any point in time
- the vapor products are recognized to have higher proportions of heavier products than what comes from the fractionator due to further thermal cracking in the vapors prior to the vapor line quench and the fractionator. In other words, the further upstream from the fractionator, the higher the proportions of heavier products.
- the solids, liquids, and vapors comprise mostly chemical compounds of converted coker feed components.
- the catalyst in an exemplary embodiment of the present invention settles into the foam and liquid layers, it may be exposed to these solids, liquids and vapors. In many cases, the solid portions represent coke from thermal coking of the coker feed components.
- the liquid and some semi-solid portions in these layers may contain components of the coker feed, but many of the liquids are likely derivatives (or cracked) components of the coker feed at this point, particularly toward the end of the coking cycle.
- the vapors emerging from the coking interface are essentially cracked coker feed components, derivatives of the heavier saturates, aromatics, resins, and asphaltenes in the coking process feed that have theoretical boiling points greater than 1050 degrees Fahrenheit.
- the catalyst of exemplary embodiments of the present invention can still facilitate cracking and coking reactions, even as the catalyst becomes part of the coke layer.
- the catalyst is still exposed primarily to derivatives of the coker feed: coke and vapor / liquids passing through the coke layer.
- the catalyst in exemplary embodiments of the present invention can still facilitate cracking and coking reactions (inherent aspects of the present invention). Even at these levels, the overall exposure of the catalyst to coker feed components with a higher propensity to coke is limited.
- the product classifications have broader classification of low boiling point, middle boiling point, and high boiling point materials or products.
- the classification of low boiling point products comprises the chemical compounds that are in the gas phase at ambient temperatures and pressures, including methane, ethane, propanes, butanes, and the corresponding olefins. These compounds typically have boiling points less than roughly 90 degrees Fahrenheit, and are commonly referred to C4- in the industry, referring to the number of carbon atoms in each molecule.
- the middle boiling point products are typically liquids at ambient temperatures and pressures, and boiling points between roughly 90 and 610 degrees Fahrenheit.
- middle boiling point products including middle distillates
- further processing e.g. hydrotreating, reforming, isomerization
- high boiling point materials are considered to be refinery process streams with boiling point ranges greater than the middle distillates.
- process streams normally require further processing (e.g. hydrocracker or fluid catalytic cracking unit) to lower their boiling point range before they can be blended into liquid transportation fuels.
- these materials have boiling points greater than the highest end point of the middle distillates; typically the end point of light gas oils or approximately 610 degrees Fahrenheit.
- Coker Gas Oil would be classified as 'high boiling point materials' in the product vapors in the coking vessel.
- some exemplary embodiments of the present invention can use the catalytic additive in to quench the vapor products and condense the 'highest boiling point' materials in the product vapors. By condensing these highest boiling point materials, exemplary embodiments of the present invention can essentially create an 'internal recycle' that increases the residence time of the heaviest components of the coker recycle and/or part of the HCGO.
- this 'internal recycle' may also be used to provide intimate contact with the catalyst and make it more selective and efficient, thereby lowering catalyst requirements and costs.
- the catalyst must be designed to crack effectively with these very large molecules in the liquid phase, until the catalyst settles to a level in the coking vessel where these highest boiling point materials revaporize due to the higher temperatures or other local sources of heat (e.g. release of heat from condensation of adjacent molecules).
- the quantity of internal recycle' depends on various factors, including (1 ) the coking vessel outlet temperature of the known art, (2) the quantity of catalytic additive and its associated quenching effect, and (3) the quality and quantity of coker recycle and Heavy Coker Gas Oil.
- catalytic cracking of the highest boiling point materials in the product vapors of the coking vessel may allow one skilled in the known art to reduce the quantity of traditional coker recycle (i.e.
- the primary catalytic reactants of the present invention are primarily vapors, condensed liquids of the highest boiling point vapors, and liquids, semi-solids and solids at the coking interface (after the catalyst settles to the vapor/liquid interface and below).
- the temperature of the primary reactants is typically ⁇ 875 oF, which is normally more conducive to aromatic cracking (vs. coking) with high residence time and reaction equilibrium, favoring these lower temperatures.
- the primary catalytic reactants of exemplary embodiments of the present invention are substantially different from the primary catalytic reactants of the known art and much less conducive to coking.
- the chemical and physical characteristics of the catalyst reactants are vastly different for an exemplary embodiment of the present invention, when compared to the chemical characteristics of the catalytic reactants of the known art. That is, the catalyst additive of an exemplary embodiment of the present invention is typically added to the coking vessel downstream of the primary cracking and coking zones of the coking process.
- the primary reactants are derivatives of the coker feed after extensive cracking and coking of the coker feed: coker recycle, heavy coker gas oil (HCGO), light coker gas oil (LCGO), naphtha, and various gases with less than 5 carbon atoms per molecule.
- the highest boiling point materials e.g.
- the primary reactants exposed to the catalyst of an exemplary embodiment of the present invention are substantially smaller molecules that are more conducive to cracking (vs. coking) than the known art.
- the primary catalytic reactants of an exemplary embodiment of the present invention are substantially different and much less conducive to coking than the primary catalytic reactants of the known art.
- the physical and chemical characteristics of the primary reactants in the present invention are more similar to those in a fluid catalytic cracking unit (FCCU). That is, a typical FCCU further processes the HCGO generated by the coking process.
- the FCCU is typically used to convert (catalytically crack) the high boiling point materials (e.g. greater than roughly 610 degrees Fahrenheit) of the HCGO in a similar operating environment with low pressure, limited hydrogen, and slightly higher temperatures.
- the substantially longer residence time for the catalyst in exemplary embodiments of the present invention is advantageous in achieving efficient use of the catalyst with reaction kinetics that may more closely approach equilibrium values.
- Differentiation Over Fluid Catalytic Cracking Process The known art of fluid catalytic cracking in the refining industry is very different from the introduction of a catalytic additive in the coking vessel of a coking process in exemplary embodiments of the present invention.
- the fluid catalytic cracking (FCC) process typically introduces high boiling point hydrocarbon feed(s) into fluidized catalyst particles in a specially designed reactor (e.g. combinations of feed-riser and dense-bed reactors).
- the high boiling point feeds typically include heavy atmospheric gas oil, vacuum gas oil, and/or heavy coker gas oil (HCGO).
- the catalyst sufficiently lowers the activation energy of cracking reactions to preferably promote the catalytic cracking of these high boiling point materials to lower boiling point hydrocarbon products, including gasoline and middle distillates.
- FCC catalysts typically increase some coking reactions, as well.
- the FCC process also produces coke that remains on the catalyst and rapidly lowers its activity. Consequently, the catalyst is circulated to a regeneration vessel, where the coke is burned off of the catalyst to regenerate catalyst activity to acceptable levels.
- the reaction conditions of the FCC reactor are also substantially different from the vapor zone of the coking vessel.
- the catalytic reactants in both processes typically include heavy coker gas oil, but the vapor products in the coking vessel of the coking process also include higher boiling point compounds in the coker recycle component and lower boiling point compounds in the components of light coker gas oil, naphtha, and gases.
- the FCC reactor pressure e.g. 8-12 psig
- the coking vessel e.g. 12-25 psig
- the FCC reactor temperature e.g. 900 to 1000 degrees Fahrenheit
- the coking vessel e.g. 800 to 900 degrees Fahrenheit
- the residence time of catalyst exposure to the reactants is substantially different: FCC typically measured in seconds, where the catalyst in the coking vessel can conceivably continue to catalyze reactions for minutes to hours, depending on various factors including fluidization in the coking vessel product vapors. Though they both have low partial pressures of hydrogen, the much higher residence time and lower temperatures can favor substantially more cracking of aromatic compounds in the coking vessel.
- the catalytic cracking in the coking vessel in the exemplary embodiments of the present invention is substantially differentiated over the known art of fluid catalytic cracking.
- Various types of FCC catalyst e.g. equilibrium, fresh, etc.
- the catalytic cracking and coking reactions of certain reactants e.g. HCGO
- the basic reactor design and reaction conditions are substantially different.
- Refinery computer optimization models can be used to establish the utility of various exemplary embodiments of the present invention. Most refineries currently use refinery optimization models (e.g.
- the optimization model typically contains individual models for each refinery process in its refinery process scheme to assess the optimal operation to best utilize its capabilities and capacity.
- These refinery models typically estimate values of various process streams, including the feed and products of a coking process.
- the value of the internal recycle' in some exemplary embodiments of the present invention of a coking process can be valued based on its effects on process capacity and associated products. These values are typically generated in a dollars per barrel basis (i.e. $/Bbl.), but can be readily converted to cents per pound (c/Lb.), as well.
- the relative rankings (lowest to highest value in c/Lb) of the coker process streams are as follows: coke (lowest), recycle, feed, refinery fuel gas, HCGO, LCGO, Naphtha, LPGs, and gaseous olefins (highest).
- coke lowest
- recycle recycle
- refinery fuel gas HCGO, LCGO, Naphtha, LPGs
- gaseous olefins highest.
- the HCGO, LCGO, and naphtha values are comparable and actually can have different relative rankings from refinery to refinery, due to differences in refinery process scheme and refinery crude blend.
- the FCC capacity and/or capacities of downstream processing units for LCGO and naphtha can have effects on their relative values.
- Boiling Point Olefins Another exemplary embodiment of the present invention is the use of the olefin production from newly developed and/or existing types of catalysts to increase the production of light olefins (e.g. ethylene, propylenes, butylenes, pentenes) for alkylation process unit feed, the production of oxygenates, and petrochemical feedstocks, such as plastics manufacture.
- light olefins e.g. ethylene, propylenes, butylenes, pentenes
- oxygenates e.g. ethylene, propylenes, butylenes, pentenes
- petrochemical feedstocks such as plastics manufacture.
- LPG liquid petroleum gas
- the injection of a catalytic additive in the coking process would be used to optimize the olefin production with existing types of acid catalysts (including but not limited to traditional Fluid Catalytic Cracking Unit (FCCU) catalysts in traditional oil refineries).
- FCCU Fluid Catalytic Cracking Unit
- a low activity catalyst can be used to provide sufficient acid density for cracking, but maintain a lower hydrogen activity level to preferentially produce olefins over parafins.
- new catalysts could also be developed to enhance (or maximize) the quantity of olefins produced in the gas production of the coking process for a given feed or injection level of the catalytic additive.
- This exemplary embodiment of the present invention is an improvement over the present invention described in the priority document. That is, this exemplary embodiment of the present invention would represent a new benefit (with results not expected in the coking process) from an existing catalyst already described previously, and not necessarily require the development or use of a new catalyst formulation. However, the development of a new catalyst formulation for this specific function may provide even greater utility, particularly in applications where incremental olefins would justify the appropriate separation equipment. This exemplary embodiment of the present invention would be more useful in refineries that are geared for higher production of petrochemical feedstocks.
- the flow rate of the additive of the present invention may be proportional to the flow rate of the coking process feed (e.g. 1.5 wt. %) and can be adjusted accordingly as the coking process feed flow rate changes.
- the additive package is designed to promote the desired reactions with the coker feed, intermediate chemical species, cracked liquids, vapor products, and/or other process streams in the coking process. This is primarily achieved by the choice of catalyst.
- the catalyst(s)' substrate and impregnated materials, activity, selectivity, conversion, efficiency, and/or porosity characteristics will determine the types of reactants (e.g. gas oils) and products (e.g. Naphtha and fuel gas) from the catalytic cracking in the coking process.
- reactants e.g. gas oils
- products e.g. Naphtha and fuel gas
- cracking catalysts that are traditionally used for cracking in fluid catalytic cracking units (e.g.
- Fluid Catalytic Cracking Unit can be very effective in an application to crack various hydrocarbon molecules into lighter 'cracked liquids'.
- residua cracking catalysts have a higher degree of mesoporosity and other characteristics that allow the large molecules of the high boiling point components to have better access to and from the catalyst's active cracking sites.
- the other components of the additive package can influence cracking reactions over coking reactions, as well.
- various catalysts will be designed for the purposes above, particularly catalysts to achieve greater selective cracking of the coker feed, intermediate chemical species, cracked liquids, vapor products, and/or other coker process streams.
- These lower boiling point hydrocarbon process streams include naphtha, gas oils, gasoline, kerosene, jet fuel, diesel fuel, heating oil, liquid petroleum gases, and fuel gas.
- this catalytic additive selectively cracks the heavier components of the coker feed or intermediate chemical species to produce additional cracked liquids, while reducing coke production, and/or quenching cracking reactions in the vapor to reduce gas production.
- This pilot-scale system was used to generate data to demonstrate the benefits of the present invention over the known art. That is, the injection of the catalyst additive into the coking vessel of the present invention and the addition of catalyst to the coker feed of the known art were compared to a common baseline with no catalyst.
- FIG. 2 is a basic process flow diagram for the traditional delayed coking process of the known art. Delayed coking is a semi-continuous process with parallel coking drums that alternate between coking and decoking cycles.
- An exemplary embodiment of the present invention integrates one or more additive injection system(s) into the delayed coking process equipment. The operation with an exemplary embodiment of the present invention is similar, as discussed below, but significantly different.
- delayed coking is an endothermic reaction with the furnace supplying the necessary heat to complete the cracking and coking reactions in the coke drum. The exact mechanism of delayed coking is so complex that it is not possible to determine all the various chemical reactions that occur, but three distinct steps take place:
- coker feedstock is heated and transferred to the coke drum until full.
- Hot residua feed 10 (most often the vacuum tower bottoms) is introduced into the bottom of a coker fractionator 12, where it combines with condensed recycle.
- This mixture 14 is pumped through a coker heater 16, where the desired coking temperature (normally between 900 degrees F and 950 degrees F) is achieved, causing partial vaporization and mild cracking.
- Steam or boiler feed water 18 is often injected into the heater tubes to prevent the coking of feed in the furnace.
- the heater outlet temperature is controlled by a temperature gauge 20 that sends a signal to a control valve 22 to regulate the amount of fuel 24 to the heater.
- a vapor-liquid mixture 26 exits the heater, and a control valve 27 diverts it to a coking drum 28. Sufficient residence time is provided in the coking drum to allow thermal cracking and coking reactions to proceed to completion. By design, the coking reactions are "delayed” until the heater charge reaches the coke drums. In this manner, the vapor-liquid mixture is thermally cracked in the drum to produce lighter hydrocarbons, which vaporize and exit the coke drum.
- the drum vapor line temperature 29 i.e. temperature of the vapors leaving the coke drum
- Quenching media e.g. Gas Oil
- Petroleum coke and some residuals e.g.
- the contents of the coking drum are cooled down, remaining volatile hydrocarbons are removed, the coke is drilled from the drum, and the coking drum is prepared for the next coking cycle. Cooling the coke normally occurs in three distinct stages. In the first stage, the coke is cooled and stripped by steam or other stripping media 30 to economically maximize the removal of recoverable hydrocarbons entrained or otherwise remaining in the coke.
- water or other cooling media 32 is injected to reduce the drum temperature while avoiding thermal shock to the coke drum. Vaporized water from this cooling media further promotes the removal of additional vaporizable hydrocarbons.
- the drum is quenched by water or other quenching media 34 to rapidly lower the drum temperatures to conditions favorable for safe coke removal. After the quenching is complete, the bottom and top heads of the drum are removed. The petroleum coke 36 is then cut, typically by a hydraulic water jet, and removed from the drum. After coke removal, the drumheads are replaced, the drum is preheated, and otherwise readied for the next coking cycle.
- FIG. 3 shows the traditional delayed coking system of Figure 2 with the addition of an example of the present invention.
- This simplified example shows the addition of a heated, mixing tank (210) (an exemplary means of mixing and a means of temperature regulation) where components of the present invention's additive can be blended: catalyst(s) (220), seeding agent(s) (222), excess reactant(s) (224), carrier fluid(s) (226), and/or quenching agent(s) (228).
- the mixed additive (230) is then injected into the one or more points in the delayed coking process via properly sized pump(s) (250) (an exemplary means of pressurized injection) and piping, preferably with properly sized injection nozzle(s) (260).
- the pump is controlled by a flow meter (270) with a feedback control system relative to the specified set point for additive flow rate.
- Said one or more points in the delayed coking process would include (but should not be limited to) a hot residua feed 10, the bottom of a coker fractionator 12, condensed recycle, feed/recycle mixture 14, a coker heater 16, a vapor-liquid mixture 26 which exits the heater, and any combination thereof.
- the catalytic additive can be added to a coking vessel at or above where the feed enters said coking vessel.
- the catalytic additive can be injected into a coker feed line, a coker vapor line, a coker fractionator, a coker feed pump, a coker heater, or any combination thereof.
- the catalytic additive can be introduced before a coking cycle, during a coking cycle, after a coking cycle, or any combination thereof.
- the target operating conditions are normally established by linear programming (LP) models that optimize the particular refinery's operations.
- LP models typically use empirical data generated by a series of coker pilot plant studies.
- each pilot plant study is designed to simulate the particular refinery's coker design.
- Appropriate operating conditions are determined for a particular feedstock blend and particular product specifications set by the downstream processing requirements.
- the series of pilot plant studies are typically designed to produce empirical data for operating conditions with variations in feedstock blends and liquid product specification requirements. Consequently, the coker designs and target operating conditions vary significantly among refineries.
- the primary independent variables are feed quality, heater outlet temperature, coke drum pressure, and fractionator hat temperature.
- the primary dependent variables are the recycle ratio, the coking cycle time and the drum vapor line temperature. The following target control ranges are normally maintained during the coking cycle for these primary operating conditions:
- Heater outlet temperatures in range of about 900 degrees F to about 950 degrees F
- Coke drum pressure in the range of about 15 psig to 100 psig: typically 15-25 psig,
- Recycle Ratio in the range of 0-100%; typically 10-20%
- Coking cycle time in the range of about 12 to 24 hours; typically 15-20 hours
- cracked liquids refers to hydrocarbon vapor products of the coking process that have 5 or more carbon atoms. They typically have boiling ranges between 97 and 870 degrees F, and are liquids at standard conditions. Most of these hydrocarbon products are valuable transportation fuel blending components or feedstocks for further refinery processing. Consequently, cracked liquids are normally the primary objective of the coking process. [0097] Over the past ten years, some refineries have switched coker operating conditions to maximize (or increase) the coker throughput, instead of maximum efficiency of feedstock conversion to cracked liquids.
- refineries Due to processing heavier crude blends, refineries often reach a limit in coking throughput that limits (or bottlenecks) the refinery throughput. In order to eliminate this bottleneck, refiners often change the coker operating conditions to maximize (or increase) coker throughput in one of three ways:
- drum pressure e.g. 15 to 20 psig.
- the reduction in recycle is often accomplished by a reduction in coke drum pressure and an increase in the heavy gas oil end point (i.e. highest boiling point of gas oil).
- the gas oil end point is controlled by refluxing the trays between the gas oil drawoff and the feed tray in the fractionator with partially cooled gas oil.
- This operational mode increases the total liquids and maintains the efficiency of feedstock conversion to cracked liquids (i.e. per barrel of feed basis).
- the increase in liquids is primarily highest boiling point components (i.e. 'heavy tail') that are undesirable in downstream process units.
- An exemplary embodiment of the present invention provides the opportunity to (1 ) increase coker throughput (regardless of the coker section that is limiting), (2) increase liquid yields, (3) reduce coke yield, (4) reduce gas production, and/or (5) substantially reduce highest boiling point components in either recycle, heavy gas oil, or both. In this manner, each application of the present invention may determine which process is preferable to reduce the undesirable, highest boiling point components.
- an exemplary embodiment of the present invention provides the opportunity to develop catalytic additive(s) to address the specific needs of the particular refinery. That is, the catalytic additive(s) can be specifically designed to improve the qualities or yield distribution of the products that are most valuable to that refinery's process scheme and crude slate opportunities. This approach may simply involve catalytic cracking to produce greater yields of cracked liquids or may involve more sophisticated catalytic additive to be selective in what types of cracked liquids predominate. Similarly, an additional catalytic additive could be added to produce more of the desired products at that particular facility (e.g. propylene for local plastics plant). In this approach, the process optimization model in each refinery could be used as an effective tool in determining what catalytic additives would be preferable and worth pursuing (e.g. cost effectiveness and return on investment).
- the process optimization model in each refinery could be used as an effective tool in determining what catalytic additives would be preferable and worth pursuing (e.g. cost effectiveness and return on investment).
- an exemplary embodiment of the present invention can achieve one or more of the following: (1 ) improved coker gas oil quality, (2) improved coke quality and market value, (3) less gas production, (4) less coke production, (5) increased coker and refinery capacities, (6) increased use of cheaper, lower quality crudes and/or coker feeds, (7) increased efficiency and run time of downstream cracking units, (8) decreased operation & maintenance cost of coker and downstream cracking units, (9) reduced incidents of 'hotspots' in pet coke drum cutting, and/or (10) reduced catalyst make-up and emissions in downstream cracking units.
- Example 1 In fuel grade coke applications, the delayed coking feedstocks are often residuals derived from heavy, sour crude, which contain higher levels of sulfur and metals. As such, the sulfur and metals (e.g. vanadium and nickel) are concentrated in the pet coke, making it usable only in the fuel markets. Typically, the heavier, sour crudes tend to cause higher asphaltene content in the coking process feed. Consequently, the undesirable 'heavy tail' components (e.g. PAHs) are more prominent and present greater problems in downstream catalytic units (e.g. cracking). In addition, the higher asphaltene content (e.g. > 15 wt. %) often causes a shot coke crystalline structure, which can cause coke cutting 'hot spots' and difficulties in fuel pulverization.
- the sulfur and metals e.g. vanadium and nickel
- an exemplary embodiment of the present invention further provides the selective cracking and coking of the 'heavy tail' components (e.g. PAHs) in coker gas oil of the traditional delayed coking process.
- Gas oil end points may be selectively reduced from over 1050 degrees of Fahrenheit to 1000 degrees of Fahrenheit or less (e.g. preferably ⁇ 950 degrees of Fahrenheit)
- additional heavy components of the heavy coker gas oil and the coker recycle can be selectively cracked or coked. This improves coker gas oil quality/value and the performance of downstream cracking operations.
- the selective cracking of PAHs and quench (thermal & chemical) of the vapor overcracking improves the value of the product yields and increases the 'cracked liquids' yields.
- the reduction of heavy components that have a high propensity to coke reduces the buildup of coke in the vapor lines and allows the reduction of recycle and heater coking.
- the heavy gas oil quality can deteriorate due to excessive cracking of heavier components that would otherwise form coke. Sufficient cracked liquids from these heavier components can still cause a net increase in the heavy gas oil endpoint. However, sufficient reduction in coke production can be still worth an increase in gas oil endpoint or an increase in recycle to reduce gas oil endpoint.
- the delayed coker is coke drum limited, which allows additional recycle without limiting capacity.
- This additional recycle may allow the refinery to maintain or improve gas oil endpoint through sufficient recycle.
- the coker throughput capacity (and refinery throughput capacity) may increase due to less coke production in a drum limited coker, while gaining additional profitability of increased cracked liquids.
- an exemplary embodiment of the present invention may also be effectively used to alleviate problems with 'hot spots' in the coke drums of traditional delayed coking. That is, the heavy liquids that remain in the pet coke, block coke quenching channels, and cause the 'hot spots' during the decoking cycle (e.g. coke cutting) are encouraged to further crack (preferable) or coke by the catalyst and excess reactants in the additive package.
- a properly designed catalytic additive package e.g. catalyst & excess reactants
- catalyst(s) and excess reactant(s) for this purpose can include, but should not be limited to, FCCU catalysts, hydrocracker catalysts, activated carbon, crushed coke, FCCU slurry oil, FCCU cycle oils, and coker heavy gas oil.
- catalyst(s) in the additive package has greater number of options, since the composition of the catalyst (e.g. metals) is less of an issue in fuel grade pet coke specifications (e.g. vs. anode).
- the catalyst can contain substrates and exotic metals to preferentially and selectively crack (vs. coke) various coker feed components, intermediate chemical species, and gas oil components, including the undesirable, heavy hydrocarbons (e.g. PAHs).
- catalyst(s) and excess reactant(s) for this purpose may include, but should not be limited to, FCCU catalysts, hydrocracker catalysts, iron, activated carbon, crushed coke, FCCU slurry oil, and coker heavy gas oil.
- the most cost effective catalyst(s) may include spent or regenerated catalysts from downstream units (e.g. FCCU, hydrocracker, and hydrotreater) that have been sized and injected in a manner to prevent entrainment in coking process product vapors to the fractionator.
- downstream units e.g. FCCU, hydrocracker, and hydrotreater
- the nickel content of hydrocracker or FCCU spent catalyst may be very effective in selectively coking the undesirable, heavy components (e.g. PAHs) of coker gas oil.
- PAHs undesirable, heavy components
- the equilibrium catalyst is often regenerated prior to disposal and could be used in an exemplary embodiment of the present invention to crack feed components, intermediate chemical species, cracked liquids, vapor products, or other coking process streams, particularly if the FCCU catalyst is designed to handle residua in the FCCU feed. If the equilibrium catalyst does not provide sufficient cracking catalyst activity, it could be blended with a new catalyst (e.g. catalyst enhancer) to achieve the desired activity while maintaining acceptable catalyst costs. Finally, certain new catalysts may be cost effective, as well. [00107] When applied to greater degrees, an exemplary embodiment of the present invention can also be used to improve the coke quality while improving the value of coke product yields and improved operations and maintenance of the coker and downstream units.
- a new catalyst e.g. catalyst enhancer
- the Hardgrove Grindability Index (HGI) of the coke can be increased to improve pulverization characteristics and market value. HGI values of greater than 50 (preferably 55 to 80) are possible.
- the heating value can be increased by up to 10% and the Volatile Materials (VM with theoretical boiling points > 950 degrees Fahrenheit but ⁇ 1780 degrees Fahrenheit) from 12 to 25 wt.% (preferably 13 to 18 wt.%) of the fuel grade coke can also be increased to improve the fuel quality. In this manner, increasing the quality and/or quantity of catalytic additive(s) may incrementally improve return on investment according to the particular refinery's LP model.
- the present invention may also provide incremental catalytic cracking capacity for a crude oil refinery or upgrading system (e.g. shale oil, tar sands, bitumen, etc.). That is, additional catalytic cracking in some coking process applications can provide a cost-effective alternative to adding or debottlenecking downstream cracking units.
- cyclones similar to those used in FCCUs could be retrofitted in the top of the coke drum to avoid entrainment of catalyst in the product vapors.
- an exemplary embodiment of the present invention may provide additional utility for various types of anode grade facilities: (1 ) refineries that currently produce anode coke, but want to add opportunity crudes to their crude blends to reduce crude costs and (2) refineries that produce pet coke with sufficiently low sulfur and metals, but shot coke content is too high for anode coke specifications.
- an exemplary embodiment of the present invention can be used to reduce shot coke content to acceptable levels, even with the presence of significant asphaltenes (e.g. > 15 wt. %) in the coker feed.
- refineries that currently produce anode quality coke can potentially add significant levels of heavy, sour opportunity crudes (e.g. > 5 wt. %) without causing shot coke content higher than anode coke specifications. That is, an exemplary embodiment of the present invention can be used to convert feed components, intermediate chemical species, cracked liquids, and/or product vapors in a manner that preferably produces sponge coke crystalline structure (coke morphology) rather than shot coke crystalline structure.
- these refineries can reduce crude costs without sacrificing anode quality coke and its associated higher values.
- refineries that currently produce shot coke content above anode coke specifications can reduce shot coke content to acceptable levels in many cases. That is, the present invention converts feed components, intermediate chemical species, cracked liquids, and/or product vapors in a manner that preferably produces sponge coke crystalline structure (coke morphology) rather than shot coke crystalline structure.
- these refineries can increase the value of its petroleum coke while maintaining or improving coker product yields and coker operation and maintenance.
- the additive package In both anode coke cases, the additive package must be designed to minimize any increases in the coke concentrations with respect to sulfur, nitrogen, and metals that would add impurities to the aluminum production process. Thus, the selection of catalyst(s) is less flexible for these cases and would likely include alumina or carbon based (e.g. activated carbon or crushed coke) catalyst substrates. In both anode coke cases, the additive package must be designed to minimize the increase in VCMs and/or preferably produce additional VCMs with theoretical boiling points greater than 1250 degrees Fahrenheit. Thus, catalyst(s) and excess reactants for this additive package would be selected to promote the preferential production of sponge coke with higher molecular weights in the coking vessel.
- VCMs greater than 1250 degrees Fahrenheit may be desirable to (1 ) provide volatilization downstream of the upheat zone in the coke calciner and (2) cause recoking of these volatile materials in the internal pores of the calcined coke to increase coke density.
- the resulting calcined coke will preferably have a substantially greater vibrated bulk density and require less pitch binder to be adsorbed in the coke pores to produce acceptable anodes for aluminum production facilities.
- any coke produced by an exemplary embodiment of the present invention will preferably not contain any VCMs. That is, any further coke produced will all have theoretical boiling points greater than 1780 degrees Fahrenheit, as determined by the ASTM test method for VCMs.
- Example 3 In addition to the previously described benefits for all delayed coking systems, an exemplary embodiment of the present invention may provide additional utility for various types of needle coke facilities.
- the coking process uses special coker feeds that preferably have high aromatic content, but very low asphaltene content. These types of coker feeds are necessary to achieve the desired needle coke crystalline structure.
- These delayed coker operations have higher than normal heater outlet temperatures and recycle rates.
- these coking processes may maintain needle coke crystalline structure with higher concentrations of asphaltenes and lower concentrations of aromatics in the coker feed.
- An exemplary embodiment of the present invention may also reduce the recycle rate required to produce the needle coke crystalline structure with acceptable quality for electrodes, potentially increasing the coker capacity and improving coker operations and maintenance. In this manner, an exemplary embodiment of the present invention could decrease coker feed costs, while potentially increasing needle coke production and profitability.
- an exemplary embodiment of the present invention may provide additional utility for various types of delayed coker facilities that produce specialty carbon products.
- Some delayed coker systems have the potential to produce petroleum coke for certain specialty carbon products, but do not due to economic and/or safety concerns.
- These specialty carbon products include (but should not be limited to) graphite products, electrodes, and steel production additives.
- An exemplary embodiment of the present invention allows improving the coke quality for these applications, while addressing safety concerns and improving economic viability.
- certain graphite product production processes require a petroleum coke feed that has higher VCM content and preferably sponge coke crystalline structure.
- An exemplary embodiment of the present invention can be optimized to safely and economically produce the pet coke meeting the unique specifications for these applications.
- the quality of the VCMs may be adjusted to optimize the graphite production process and/or decrease process input costs.
- the present invention may also provide significant improvements in other coking technologies, including the fluid coking and flexicoking processes.
- the Flexicoking process is essentially the fluid coking process with the addition of a gasifier vessel for gasification of the petroleum coke.
- a detailed description of how an exemplary embodiment of the present invention is integrated into the fluid coking and flexicoking processes is followed by discussions of its operation in the fluid coking and flexicoking processes and alternative exemplary embodiments relative to its use in these types of coking processes.
- Figure 4 shows a basic process flow diagram for a traditional, fluid coking process.
- the flexicoking process equipment is essentially the same, but has an additional vessel for the gasification of the product coke 178 (remaining 75 to 85% of the coke that is not burned in the Burner 164).
- Fluid coking is a continuous coking process that uses fluidized solids to further increase the conversion of coking feedstocks to cracked liquids, and reduce the volatile content of the product coke. Fluid coking uses two major vessels, a reactor 158 and a burner 164.
- the coking feedstock blend 150 is typically preheated to about 600 to 700 degrees F, combined with the recycle 156 from the scrubber section 152, where vapors from the reactor are scrubbed to remove coke fines.
- the scrubbed product vapors 154 are sent to conventional fractionation and light ends recovery (similar to the fractionation section of the delayed coker).
- the feed and recycle mixture is sprayed into the reactor 158 onto a fluidized bed of hot, fine coke particles. The mixture vaporizes and cracks, forming a coke film (.about 0.5 urn) on the particle surfaces.
- ground product coke must be added to these hot coke particles to maintain a particle size distribution that is suitable for fluidization.
- the remaining product coke 178 must be removed from the system to keep the solids inventory constant. It contains most of the feedstock metals, and part of the sulfur and nitrogen.
- Coke is withdrawn from the burner and fed into the quench elutriator 174 where product coke (larger coke particles) 178 are removed and cooled with water 176.
- a mixture 180 of steam, residual combustion gases, and entrained coke fines are recycled back to the burner.
- this process flow diagram shows the traditional Flexicoking system of Figure 4 with the addition of an example of the present invention.
- This simplified example shows the addition of a heated, mixing tank (210) (as an exemplary means of mixing and means of controlling temperature) where components of the present invention's additive can be blended: catalyst(s) (220), seeding agent(s) (222), excess reactant(s) (224), carrier fluid(s) (226), and/or quenching agent(s) (228).
- catalyst(s) (220) seeding agent(s) (222), excess reactant(s) (224), carrier fluid(s) (226), and/or quenching agent(s) (228).
- the additive package is comprised of only one or two of these components, the need for a heated, mixing tank or other means of mixing and temperature control can be reduced or eliminated.
- the mixed additive (230) is then injected into one or more points in the flexicoking and fluid coking systems via properly sized pump(s) (250) (as an exemplary means of pressurized injection) and piping, preferably with properly sized injection nozzle(s) (260).
- the pump is controlled by a flow meter (270) with a feedback control system relative to the specified set point for additive flow rate.
- Said one or more points in the flexicoking and fluid coking may include, but should not be limited to, coking process feed blend 150, coking process reactor vessel (e.g.
- coking Vessel 158, coking process burner 164, coking process recycle 156, coking process scrubber system 152, scrubbed product vapors 154, recirculated hot coke 170, or any combination thereof.
- the target operating conditions in a traditional fluid coker depend on the composition of the coker feedstocks, other refinery operations, and the particular coker's design.
- the desired coker products also depend greatly on the product specifications required by other process operations in the particular refinery. That is, downstream processing of the coker liquid products typically upgrades them to transportation fuel components.
- the target operating conditions are normally established by linear programming (LP) models that optimize the particular refinery's operations. These LP models typically use empirical data generated by a series of coker pilot plant studies. In turn, each pilot plant study is designed to simulate the particular coker design, and determine appropriate operating conditions for a particular coker feedstock blend and particular product specifications for the downstream processing requirements.
- LP linear programming
- the series of pilot plant studies are typically designed to produce empirical data for operating conditions with variations in feedstock blends and liquid product specification requirements. Consequently, the fluid coker designs and target operating conditions vary significantly among refineries.
- various operational variables are monitored and controlled to achieve the desired fluid coker operation.
- the primary operational variables that affect coke product quality in the fluid coker are the reactor temperature, reactor residence time, and reactor pressure.
- the reactor temperature is controlled by regulating (1 ) the temperature and quantity of coke recirculated from the burner to the reactor and (2) the feed temperature, to a limited extent.
- the temperature of the recirculated coke fines is controlled by the burner temperature.
- the burner temperature is controlled by the air rate to the burner.
- the reactor residence time i.e.
- the reactor residence time is controlled by regulating the flow and levels of fluidized coke particles in the reactor and burner.
- the reactor pressure normally floats on the gas compressor suction with commensurate pressure drop of the intermediate components.
- the burner pressure is set by the unit pressure balance required for proper coke circulation. It is normally controlled at a fixed differential pressure relative to the reactor. The following target control ranges are normally maintained in the fluid coker for these primary operating variables:
- Reactor temperatures in the range of about 950 degrees F to about 1050 degrees F
- Reactor residence time in the range of 15-30 seconds
- Burner Temperature typically 100-200 degrees F above the reactor temperature
- an exemplary embodiment of the present invention provides the opportunity to develop catalytic additive(s) to address the specific needs of the particular refinery. That is, the catalytic additive(s) can be specifically designed to improve the yield distribution to the products that are most valuable to that refinery's process scheme and crude slate opportunities. This approach may simply involve catalytic cracking to produce greater yields of cracked liquids or may involve more sophisticated catalytic additive to be selective in what types of cracked liquids predominate. Similarly, an additional catalytic additive could be added to produce more of the desired products at that particular facility (e.g. propylene for local plastics plant). In this approach, the process optimization model in each refinery could be used as an effective tool in determining what catalytic additives would be preferable and worth pursuing (e.g. cost effectiveness and return on investment).
- the process optimization model in each refinery could be used as an effective tool in determining what catalytic additives would be preferable and worth pursuing (e.g. cost effectiveness and return on investment).
- an exemplary embodiment of the present invention can achieve one or more of the following: (1 ) improved coker gas oil quality, (2) improved coke quality and market value, (3) less gas production, (4) less coke production, (5) increased coker and refinery capacities, (6) increased use of cheaper, lower quality crudes and/or coker feeds, (7) increased efficiency and run time of downstream cracking units, (8) decreased operation & maintenance cost of coker and downstream cracking units, and (10) reduced catalyst make-up and emissions in downstream cracking units.
- Example 5 In the fluid coking and flexicoking processes, the coke formation mechanism and coke morphology are substantially different from the delayed coking process.
- Injection of a properly designed catalytic additive into the coking vessel would provide a fluidized cracking catalyst that would catalytically increase cracking of the coker feed and reduce the amount of coke production.
- a catalytic additive primarily quenching agent
- An exemplary embodiment of the present invention would still tend to push the pet coke toward sponge coke morphology, but would have less impact on the resulting coke (compared to the delayed coking process). Also, an exemplary embodiment of the present invention would have less impact on the quantity and quality of the additional VCMs in the pet coke.
- the catalyst of the additive of the present invention can be sized properly (100 to 600 microns) to promote the fluidization of the catalyst to increase the residence time of the catalyst in this system and reduce the amount of catalyst that would be needed for the same level of conversion.
- This novel coking process modification provides the following advantages over traditional coking processes and recent improvements: (1 ) Increased cracked liquids, (2) less coke production, (3) less gas production, (4) improved coker gas oil quality, (2) improved coke quality and market value, (5) increased coker and refinery capacities, (6) increased use of cheaper, lower quality crudes and/or coker feeds, (7) increased efficiency and run time of downstream cracking units, (8) decreased operation & maintenance cost of coker and downstream cracking units, (10) reduced catalyst makeup and emissions in downstream cracking units, and/or (1 1 ) incremental catalytic cracking capacity for a crude oil refinery or upgrading system.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2736613A CA2736613A1 (en) | 2008-02-14 | 2009-02-17 | System and method for introducing an additive to a coking process for improving the yields and properties of desired products |
BRPI0907874-6A BRPI0907874A2 (en) | 2008-02-14 | 2009-02-17 | System and method for introducing an additive to a coking process to improve desired product yields and properties |
EP09709937.8A EP2254968A4 (en) | 2008-02-14 | 2009-02-17 | System and method for introducing an additive to a coking process for improving the yields and properties of desired products |
MX2010008908A MX2010008908A (en) | 2008-02-14 | 2009-02-17 | System and method for introducing an additive to a coking process for improving the yields and properties of desired products. |
JP2010546958A JP5743552B2 (en) | 2008-02-14 | 2009-02-17 | Systems and methods for introducing additives into the coking process to improve the yield and properties of the desired product |
CN200980112963.8A CN102007201A (en) | 2008-02-14 | 2009-02-17 | System and method for introducing an additive to a coking process for improving the yields and properties of desired products |
Applications Claiming Priority (6)
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US2878508P | 2008-02-14 | 2008-02-14 | |
US61/028,785 | 2008-02-14 | ||
US37718809A | 2009-02-11 | 2009-02-11 | |
US12/377,188 | 2009-02-11 | ||
US12/371,909 | 2009-02-16 | ||
US12/371,909 US8372264B2 (en) | 2006-11-17 | 2009-02-16 | System and method for introducing an additive into a coking process to improve quality and yields of coker products |
Publications (1)
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WO2009103088A1 true WO2009103088A1 (en) | 2009-08-20 |
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PCT/US2009/034335 WO2009103088A1 (en) | 2008-02-14 | 2009-02-17 | System and method for introducing an additive to a coking process for improving the yields and properties of desired products |
Country Status (5)
Country | Link |
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EP (1) | EP2254968A4 (en) |
JP (3) | JP5743552B2 (en) |
CN (1) | CN102007201A (en) |
CA (1) | CA2736613A1 (en) |
WO (1) | WO2009103088A1 (en) |
Cited By (8)
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WO2015021225A1 (en) * | 2013-08-09 | 2015-02-12 | Albemarle Corporation | Delayed coking process using steamed additive |
US8968553B2 (en) | 2006-11-17 | 2015-03-03 | Roger G. Etter | Catalytic cracking of undesirable components in a coking process |
US9011672B2 (en) | 2006-11-17 | 2015-04-21 | Roger G. Etter | System and method of introducing an additive with a unique catalyst to a coking process |
US9150796B2 (en) | 2006-11-17 | 2015-10-06 | Roger G. Etter | Addition of a modified vapor line reactor process to a coking process |
WO2016024244A1 (en) * | 2014-08-14 | 2016-02-18 | Reliance Industries Limited | A process for reduction of coke formation during hydrocarbon production |
US9475992B2 (en) | 1999-08-20 | 2016-10-25 | Roger G. Etter | Production and use of a premium fuel grade petroleum coke |
EP2956528A4 (en) * | 2013-02-12 | 2017-01-18 | Roger G. Etter | Enhanced catalytic reactions in a coking process to improve process operation and economics |
US10113122B2 (en) | 2015-08-31 | 2018-10-30 | University Of New Brunswick | Process for upgrading heavy hydrocarbon liquids |
Families Citing this family (4)
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CN106554796B (en) * | 2015-09-25 | 2019-06-11 | 中国石油天然气股份有限公司 | A kind of catalytic coking process improving liquid product yield |
CN109420524B (en) * | 2017-08-22 | 2021-07-02 | 中国石油天然气股份有限公司 | Coking additive for improving product yield and preparation method thereof |
JP7093207B2 (en) * | 2018-03-27 | 2022-06-29 | コスモ石油株式会社 | Method for Quantifying Silicon Element in Heavy Nafsa and Method for Producing Heavy Nafsa |
CN110618667B (en) * | 2019-09-27 | 2021-02-23 | 南京大学 | Intelligent chemical system based on process effect selection |
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- 2009-02-17 EP EP09709937.8A patent/EP2254968A4/en not_active Withdrawn
- 2009-02-17 CN CN200980112963.8A patent/CN102007201A/en active Pending
- 2009-02-17 WO PCT/US2009/034335 patent/WO2009103088A1/en active Application Filing
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Publication number | Priority date | Publication date | Assignee | Title |
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US9475992B2 (en) | 1999-08-20 | 2016-10-25 | Roger G. Etter | Production and use of a premium fuel grade petroleum coke |
US8968553B2 (en) | 2006-11-17 | 2015-03-03 | Roger G. Etter | Catalytic cracking of undesirable components in a coking process |
US9011672B2 (en) | 2006-11-17 | 2015-04-21 | Roger G. Etter | System and method of introducing an additive with a unique catalyst to a coking process |
US9150796B2 (en) | 2006-11-17 | 2015-10-06 | Roger G. Etter | Addition of a modified vapor line reactor process to a coking process |
US9187701B2 (en) | 2006-11-17 | 2015-11-17 | Roger G. Etter | Reactions with undesirable components in a coking process |
EP2956528A4 (en) * | 2013-02-12 | 2017-01-18 | Roger G. Etter | Enhanced catalytic reactions in a coking process to improve process operation and economics |
WO2015021225A1 (en) * | 2013-08-09 | 2015-02-12 | Albemarle Corporation | Delayed coking process using steamed additive |
WO2016024244A1 (en) * | 2014-08-14 | 2016-02-18 | Reliance Industries Limited | A process for reduction of coke formation during hydrocarbon production |
US10113122B2 (en) | 2015-08-31 | 2018-10-30 | University Of New Brunswick | Process for upgrading heavy hydrocarbon liquids |
Also Published As
Publication number | Publication date |
---|---|
JP2015165029A (en) | 2015-09-17 |
EP2254968A4 (en) | 2015-02-18 |
JP5743552B2 (en) | 2015-07-01 |
JP2011512446A (en) | 2011-04-21 |
CN102007201A (en) | 2011-04-06 |
EP2254968A1 (en) | 2010-12-01 |
CA2736613A1 (en) | 2009-08-20 |
JP2017020040A (en) | 2017-01-26 |
JP6030701B2 (en) | 2016-11-24 |
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