EP1751253B1 - Delayed coking process for the production of substantially fre-flowing coke from a deeper cut of vacuum resid - Google Patents
Delayed coking process for the production of substantially fre-flowing coke from a deeper cut of vacuum resid Download PDFInfo
- Publication number
- EP1751253B1 EP1751253B1 EP05748076.6A EP05748076A EP1751253B1 EP 1751253 B1 EP1751253 B1 EP 1751253B1 EP 05748076 A EP05748076 A EP 05748076A EP 1751253 B1 EP1751253 B1 EP 1751253B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coke
- additive
- resid
- coker
- coking
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000000571 coke Substances 0.000 title claims description 136
- 238000004939 coking Methods 0.000 title claims description 32
- 238000000034 method Methods 0.000 title claims description 26
- 230000003111 delayed effect Effects 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000000654 additive Substances 0.000 claims description 46
- 230000000996 additive effect Effects 0.000 claims description 35
- 238000009835 boiling Methods 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011874 heated mixture Substances 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 239000011331 needle coke Substances 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003518 caustics Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 241000894007 species Species 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- -1 clays Chemical compound 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 229910021485 fumed silica Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000003303 reheating Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical class [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000002010 green coke Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 2
- 125000005608 naphthenic acid group Chemical class 0.000 description 2
- 239000005445 natural material Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011329 calcined coke Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000001907 polarising light microscopy Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KQSJSRIUULBTSE-UHFFFAOYSA-M sodium;3-(3-ethylcyclopentyl)propanoate Chemical compound [Na+].CCC1CCC(CCC([O-])=O)C1 KQSJSRIUULBTSE-UHFFFAOYSA-M 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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Images
Classifications
-
- 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
-
- 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
- C10B57/045—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing mineral oils, bitumen, tar or the like or mixtures thereof
Definitions
- the invention relates to a modified vacuum distillation and delayed coking process for making substantially free-flowing coke, preferably free-flowing shot coke.
- a vacuum resid feedstock is used which contains less than 10 wt.% material boiling between 900°F and 1040°F (482.22°C to 560°C) as determined by HTSD (High-temperature Simulated Distillation).
- HTSD High-temperature Simulated Distillation
- Delayed coking involves thermal decomposition of hydrocarbonaceous feedstocks (HFs) including petroleum residua (resids) and deasphalter bottoms etc. to produce gas, liquid streams of various boiling ranges, and coke. Delayed coking of HFs from heavy and heavy sour (high sulfur) crude oils is carried out primarily as a means of disposing of these low value feedstocks by converting part of the HFs to more valuable liquid and gas products.
- HFs hydrocarbonaceous feedstocks
- resids petroleum residua
- deasphalter bottoms etc. to produce gas, liquid streams of various boiling ranges, and coke.
- Delayed coking of HFs from heavy and heavy sour (high sulfur) crude oils is carried out primarily as a means of disposing of these low value feedstocks by converting part of the HFs to more valuable liquid and gas products.
- a resid feedstock is rapidly heated in a fired heater or tubular furnace at from 480°C to 520°C and pressures of 50 to 550 psig (344.74 to 3792.12 kPag) .
- the heated feedstock is then passed to a coking drum that is maintained at conditions under which coking occurs, generally at temperatures above 800°F (426.6 °C), typically between 480°C to 520°C (895°F to 970°F), under super-atmospheric pressures of 15 to 80 psig (103.42 to 551.58 kPag) to allow volatiles that form in the coker drum to be removed overhead and passed to a fractionator, leaving coke behind.
- the heated feed is switched to another drum and additional hydrocarbon vapors are purged from the coke drum with steam.
- the drum is then quenched with water to lower the temperature to below 300°F (148.89°C) after which the water is drained.
- the drum is opened and the coke is removed after drilling and/or cutting using high velocity water jets.
- a high speed, high impact water jet is used to cut the coke from the drum.
- a hole is typically bored in the coke from water jet nozzles located on a boring tool. Nozzles oriented horizontally on the head of a cutting tool then cut the coke from the drum.
- the coke removal step adds considerably to the throughput time of the overall process.
- it would be desirable to be able to produce a free-flowing coke, in a coker drum that would not require the expense and time associated with conventional coke removal, i.e., it could be drained out of the bottom of the drum.
- hot spots may be the result of a combination of morphologies of coke being present in the drum, which may contain a combination of more than one type of solid coke product, i.e., sponge coke and shot coke. Since unagglomerated shot coke may cool faster than other coke morphologies, such as large shot coke masses or sponge coke, it would be desirable to predominantly produce free-flowing shot coke in a delayed coker, in order to avoid or minimize hot drums.
- a delayed coking process comprising:
- the coking zone is in a delayed coker drum, and a substantially free-flowing shot coke product is removed from the coker drum.
- an additive is introduced into the feedstock either prior to heating or just prior to it being introduced in the coker vessel, which additive can be a metals-containing or metals-free additive. If a metals containing it is preferably an organic soluble, organic insoluble, or non-organic miscible metals-containing additive that is effective for the formation of substantially free-flowing coke.
- the metal of the additive is selected from the group consisting of sodium, potassium, iron, nickel, vanadium, tin, molybdenum, manganese, aluminum, cobalt, calcium, magnesium, and mixtures thereof.
- the metals-containing additive is a finely ground solid with a high surface area, a natural material of high surface area, or a fine particle/seed producing additive.
- high surface area materials include fumed silica and alumina, catalytic cracker fines, FLEXICOKER cyclone fines, magnesium sulfate, calcium sulfate, diatomaceous earth, clays, magnesium silicate, vanadium-containing fly ash and the like.
- the additives may be used either alone or in combination.
- substantially metals-free additives can be used in the practice of the present invention.
- Non-limiting examples include elemental sulfur, high surface area substantially metals-free solids, such as rice hulls, sugars, cellulose, ground coals, ground auto tires and mineral acids such as sulfuric acid, phosphoric acid, and their acid anhydrides.
- a caustic species preferably in aqueous form, may optionally be added.
- the caustic can be added before, during, or after the resid is passed to the coker furnace and heated to coking temperatures.
- Spent caustic obtained from hydrocarbon processing can be used.
- Such spent caustic can contain dissolved hydrocarbons, and salts of organic acids, e.g., carboxylic acids, phenols, naphthenic acids and the like.
- the process is used in conjunction with automated coke drum bottom deheading valves, and the product coke plus cooling water mixture is throttled out the bottom of the coke drum through the bottom valve.
- Dispersing of the additive is accomplished by any number of ways, preferably by introducing a side stream of the additive into the feedstream at the desired location.
- the additive can be added by solubilization of the additive into the vacuum resid, or by reducing the viscosity of the vacuum resid prior to mixing in the additive, e.g., by heating, solvent addition, etc.
- High energy mixing or use of static mixing devices may be employed to assist in dispersal of the additive agent, especially additive agents that have relatively low solubility in the feedstream.
- all or substantially all of the coke formed in the process is substantially free-flowing coke, more preferably, free-flowing shot coke. It is also preferred that at least a portion of volatile species present in the coker drum during and after coking be separated and conducted away from the process, preferably overhead of the coker drum.
- Petroleum vacuum residua (“resid”) feedstocks are suitable for delayed coking.
- Such petroleum residua are frequently obtained after removal of distillates from crude feedstocks under vacuum and are characterized as being comprised of components of large molecular size and weight, generally containing: (a) asphaltenes and other high molecular weight aromatic structures that would inhibit the rate of hydrotreating/hydrocracking and cause catalyst deactivation; (b) metal contaminants occurring naturally in the crude or resulting from prior treatment of the crude, which contaminants would tend to deactivate hydrotreating/hydrocracking catalysts and interfere with catalyst regeneration; and (c) a relatively high content of sulfur and nitrogen compounds that give rise to objectionable quantities of SO 2 , SO 3 , and NO x upon combustion of the petroleum residuum. Nitrogen compounds present in the resid also have a tendency to deactivate catalytic cracking catalysts.
- Coke bed morphology is typically described in simplified terms such as sponge coke, shot coke, transition coke, and needle coke.
- Needle coke is the highest quality of the three varieties. Needle coke, upon further thermal treatment, has high electrical conductivity (and a low coefficient of thermal expansion) and is used in electric arc steel production. It is relatively low in sulfur and metals and is frequently produced from some of the higher quality coker feedstocks that include more aromatic feedstocks such as slurry and decant oils from catalytic crackers and thermal cracking tars. Typically, it is not formed by delayed coking of resid feeds.
- a sandy coke is a coke that after cutting looks to the naked eye much like coarse black beach sand.
- resid feedstocks include but are not limited to residues from the atmospheric and vacuum distillation of petroleum crudes or the atmospheric or vacuum distillation of heavy oils, visbroken resids, tars from deasphalting units, coal liquids, shale oil or combinations of these materials. Atmospheric and vacuum topped heavy bitumens can also be employed. Feedstocks typically used in delayed coking are high-boiling hydrocarbonaceous materials with an API gravity of 20° or less, and a Conradson Carbon Residue content of 0 to 40 weight percent.
- Vacuum resids are characterized by a number of parameters, including their boiling point distributions.
- the boiling point distribution can be obtained by a physical distillation in a laboratory, but it is costly to perform this type of analysis.
- Another method for determining the boiling point distribution is to use specialized gas chromatographic techniques that have been developed for the petroleum industry.
- One such GC method is High-temperature Simulated Distillation (HTSD). This method is described by D.C. Villalanti, et al. In "High-temperature Simulated Distillation Applications in Petroleum Characterization" in Encyclopedia of Analytical Chemistry, R.A. Meyers (Ed.), pp.
- Boiling point distributions are reported as wt.% off versus atmospheric equivalent boiling point (AEBP) and are report in increments of 1 wt.%.
- Vacuum distillation is well known in the industry. A number of variables affect the boiling point distribution of the vacuum distillation unit bottoms. As refiners tend to try to push ever more flow through existing units, however, the boiling point distributions of the vacuum bottoms tend to pick up a higher percentage of the lowest boiling components.
- Such deeper cuts of resids can be obtained by any means available in a petroleum refinery.
- One means is represented in Figure 1 hereof wherein atmospheric resid bottoms is conducted via line 19 through a furnace 1 wherein it is heated to a temperature of 700°F to 800°F (371.11°C to 426.67°C) then sent via line 20 to vacuum distillation tower 2 wherein non-condensable material, such as steam and any small amount of remaining light ends are collected overhead via line 6 preferably by use of an ejector system (not shown).
- a heavy vacuum gas oil cut is removed via line 5 .
- An intermediate cut is removed via line 4 where it is combined with vacuum bottoms of line 3 and conducted to outboard stripper 7 where a lighter stream, such as one containing at least a fraction of any remaining gas oil, is stripped by use of steam injected via line 8 and sent back to the vacuum distillation tower via line 80.
- the stripped vacuum resid bottoms is then conducted via line 9 to a delayed coker where it is typically introduced near the bottom of the main fractionator 10' although it can be fed directly to the coker furnace 11 .
- the bottoms of the main fractionator line 100 are fed to the coker furnace wherein recycle distillate is introduced via line 12 . Any additives to aid in the desired coking reaction can be introduced via line 13 .
- the resid stream is heated in coker furnace 11 to coking temperatures then sent via line 14 to one or more coker drums (not shown).
- Figure 2 hereof shows another preferred process scheme for obtaining a deep cut vacuum resid feed for producing substantially free-flowing shot coke in a delayed coker.
- the process scheme is similar to that shown in Figure 1 hereof except the intermediate cut removed from distillation tower 2 is conducted via line 50 and combined with vacuum distillation bottoms on line 55 and sent through outboard stripper furnace 15 for reheating to substantially the same temperature as that of furnace 1.
- the reheated vacuum bottoms/intermediate cut stream is conducted via line 60 to outboard stripper 7 .
- a distillate stream can be added to the coker feed.
- the boiling point distribution of the distillate recycle stream is such that it is an effective mitigator of furnace fouling yet its endpoint is low enough that it does not affect the coke morphology.
- An example of this would be a coker distillate stream with a boiling range of 450°F to 750°F (232.22°C to 398 .89°C).
- the resid feed pumped to a heater at a pressure of 50 to 550 psig (344.74 to 3792.12 kPag) , where it is heated to a temperature from 480°F (248.89°C) to 520°F (271.11°C). It is then discharged into a coking zone, typically a vertically-oriented, insulated coker drum through an inlet at the base of the drum. Pressure in the drum is usually relatively low, such as 15 to 80 psig (103.42 to 551.58 kPag) to allow volatiles to be removed overhead. Typical operating temperatures of the drum will be between 410°C and 475°C.
- the hot feedstock thermally cracks over a period of time (the "coking time") in the coker drum, liberating volatiles composed primarily of hydrocarbon products, that continuously rise through the coke mass and are collected overhead.
- the volatile products are sent to a coker fractionator for distillation and recovery of coker gases, gasoline, light gas oil, and heavy gas oil.
- a portion of the heavy coker gas oil present in the product stream introduced into the coker fractionator can be captured for recycle and combined with the fresh feed (coker feed component), thereby forming the coker heater or coker furnace charge.
- delayed coking also forms solid coke product.
- Coke bed morphology is typically described in simplified terms such as sponge coke, shot coke, transition coke, and needle coke.
- Sponge coke as the name suggests, has a sponge-like appearance with various sized pores and bubbles "frozen into” a solid coke matrix.
- One key attribute of sponge coke produced by routine coker operating conditions is that the coke is self-supporting, and typically will not fall out of the bottom of an un-headed coker drum, which typically has a head diameter of 6 feet (1.83 m) .
- the head of the coker drum can be removed either manually or by use of a throttled slide valve.
- Needle coke refers to a specialty coke that has a unique anisotropic structure. Preparation of coke whose major component is needle coke is known to those skilled in the art and is not the subject of this invention.
- Shot coke is a distinctive type of coke. It is comprised of individual substantially spherical particles that look like BBs. These individual particles range from substantially spherical to slightly ellipsoidal with average diameters of 1 mm to 10 mm. The particles may be aggregated into larger-sized particles, e.g., from tennis-ball size to basketball or larger sizes.
- the shot coke can sometimes migrate through the coke bed and to the bottom drain lines of the coke drum and slow, or even block, the quench water drain process. While shot coke has a lower economic value that sponge coke, it is the desired product coke for purposes of this invention because its ease of removal from the coker drum results in effectively increasing the process capacity which more than offsets its reduced economic valve.
- bonded shot coke At times there appears to be a binder material present between the individual shot coke particles, and such a coke is sometimes referred to as "bonded shot” coke.
- the bed may not be self-supporting, and can flow out of the drum when the drum is opened. This can be referred to as “fall-out' or “avalanche” and if unexpected it can be dangerous to operating personnel and it can also damage equipment.
- transition coke refers to coke that has morphology between that of sponge coke and shot coke.
- coke that has a mostly sponge-like physical appearance, but with evidence of small shot spheres that are just beginning to form as discrete particles in one type of transition coke.
- Coke beds are not necessarily comprised of all of one type of coke morphology.
- the bottom of a coke drum can contain large aggregates of shot, transitioning into a section of loose shot coke, and finally have a layer of sponge-rich coke at the top of the bed of coke.
- additional descriptors for coke although less common.
- Such additional descriptors include: sandy coke which is a coke that after cutting looks to the naked eye much like coarse black beach sand; and needle coke that refers to a specialty coke that has a unique anisotropic structure. Preparation of coke whose major component is needle coke is well known to those having ordinary skill in the art and is not a subject of this invention.
- free-flowing means that 500 tons (508.02 Mg) of coke plus its interstitial water in a coker drum can be drained in less than 30 minutes through a 60-inch (152.4 cm) diameter opening .
- substantially free-flowing shot coke can be produced by the practice of the present invention by insuring that the resid feed is one having a substantially higher initial boiling point than resides conventionally used for delay coking.
- conventional delayed coking resid feeds typically have an initial boiling point from 500°C to 526°C, but the resid feeds of the present invention having an initial boiling point from 549°C to 566°C will unexpected produce shot coke over sponge coke.
- Conventional coke processing aids including an antifoaming agent, can be employed in the process, for example, delayed coking wherein a resid feedstock is air-blown to a target softening point as described in U.S. Patent No. 3,960,704 .
- shot coke has been produced by conventional methods it is typically agglomerated to such a degree that water-jet technology is needed for its removal.
- Additives are employed to provide for the formation of the desired, substantially free-flowing shot coke.
- the additive is an organic soluble metal, such as a metal naphthenate or a metal acetylacetonate, including mixtures thereof.
- Preferred metals are potassium, sodium, iron, nickel, vanadium, tin, molybdenum, manganese, aluminum, cobalt, calcium, magnesium and mixtures thereof. Potassium, sodium, iron, aluminum and calcium are preferred.
- Additives in the form of species naturally present in refinery stream can be used.
- the refinery stream may act as a solvent for the additive, which may assist in the dispersing the additive in the resid feed.
- Additives naturally present in refinery streams include nickel, vanadium, iron, sodium, and mixtures thereof naturally present in certain resid and resid fractions (i.e., certain feed streams).
- the contacting of the additive and the feed can be accomplished by blending a feed fraction containing additive species (including feed fractions that naturally contain such species) into the feed.
- the metals-containing additive is a finely ground solid with a high surface area, a natural material of high surface area, or a fine particle/seed producing additive.
- high surface area materials include fumed silica and alumina, catalytic cracker fines, FLEXICOKER cyclone fines, magnesium sulfate, calcium sulfate, diatomaceous earth, clays, magnesium silicate, vanadium-containing fly ash and the like.
- the additives may be used either alone or in combination.
- a metals-free additive be used.
- substantially metals-free additives that can be used in the practice of the present invention include elemental sulfur, high surface area substantially metals-free solids, such as rice hulls, sugars, cellulose, ground coals, ground auto tires.
- Other additives include inorganic oxides such as fumed silica and alumina; salts of oxides, such as ammonium silicate and mineral acids such as sulfuric acid and phosphoric acid, and their acid anhydrides.
- a caustic species is added to the resid coker feedstock.
- the caustic species may be added before, during, or after heating in the coker furnace. Addition of caustic will reduce the Total Acid Number (TAN) of the resid coker feedstock and also convert naphthenic acids to metal naphthanates, e.g., sodium naphthenate.
- TAN Total Acid Number
- Uniform dispersal of the additive into the vacuum resid feed is desirable to avoid heterogeneous areas of shot coke formation.
- Dispersing of the additive is accomplished by any number of ways, for example, by solubilization of the additive into the vacuum resid, or by reducing the viscosity of the vacuum resid prior to mixing in the additive, e.g., by heating, solvent addition, use of organometallic agents, etc. High energy mixing or use of static mixing devices may be employed to assist in dispersal of the additive agent.
- Polarizing light microscopy was used in the examples (illustrated in Figures 1 and 2 ) for comparing and contrasting structures of green coke (i.e., non-calcined coke) samples.
- thermal anisotropy refers to coke bulk thermal properties such as coefficient of thermal expansion, which is typically measured on cokes which have been calcined, and fabricated into electrodes.
- metals-free additives be used to encourage the production of free-flowing coke, preferably free-flowing shot coke.
- metals-free additives include elemental sulfur, high surface area substantially metals-free solids, such as rice hulls, sugars, cellulose, ground coals, ground auto tires; inorganic oxides such as fumed silica and alumina; salts of oxides, such as ammonium silicate and mineral acids such as sulfuric acid, phosphoric acid, and acid anhydrides.
- a vacuum resid is produced in a refinery and has had the vacuum overflash reincorporated into it.
- the refinery is pushing throughput, and consequently the resid boiling point distribution is having an increased amount of the lightest portion.
- the vacuum resid has an API gravity of 3.7, contains 5.4 wt.% S, and 10.0 wt.% hydrogen.
- the boiling point distribution of the front end as determined by HTSD is as follows in the column labeled "base case vacuum resid" in the table below. TABLE Base Case Vacuum Resid Resid with second stage vacuum distillation HTSD Wt.% Off AEBP, Deg. F (Deg. C) AEBP, Deg. F (Deg. F (Deg.
- the resid contains 12 wt.% 900°F to 1040°F (482.22°C to 560°C) material.
- the base case resid is coked in a pilot plant coker with a drum overhead temperature of 820°F (437.78°C), drum overhead pressure of 15 psig (103.42 kPag) and zero recycle.
- the product coke has a bonded morphology which appears highly fused throughout the bed. Microscopic examination of the coke under cross polarized light reveals mostly small domains (10-20 microns) with coarse mosaic (5-10 micron). Percentage shot coke by the micrographic technique is estimate to be 25%. By a known relationship with a commercial-scale coker, it is projected that this coke would yield a bonded shot that would be self-supporting in the commercial scale coke drum.
- the base case resid then has a second stage vacuum distillation which removes a portion of the lightest components.
- the boiling point distribution of the resid after distillation is shown in the right column of the table, i.e., after the second stage vacuum distillation, the resid contains 7 wt.% 900°F to 1040°F (482.22°C to 560°C) material.
- the deeper cut resid is coked in the pilot plant coker with a drum overhead temperature of 820°F (437.78°C), a drum overhead pressure of 15 psig (103.42 kPag) , and zero recycle.
- the product coke is 80% shot coke. Microscopic examination of the coke under cross-polarized light reveals mostly medium/coarse mosaic (2-10 microns). Percentage shot coke by the micrographic technique is estimate to be 75%. By a known relationship with a commercial-scale coker, it is projected that this coke would yield a relatively loose shot that would be non-self supporting in the commercial scale coke drum.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Coke Industry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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US57134604P | 2004-05-14 | 2004-05-14 | |
PCT/US2005/016708 WO2005113709A1 (en) | 2004-05-14 | 2005-05-12 | Delayed coking process for the production of substantially fre-flowing coke from a deeper cut of vacuum resid |
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EP1751253A1 EP1751253A1 (en) | 2007-02-14 |
EP1751253B1 true EP1751253B1 (en) | 2015-08-12 |
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US (1) | US20060006101A1 (es) |
EP (1) | EP1751253B1 (es) |
JP (1) | JP2007537344A (es) |
CN (1) | CN1954050A (es) |
AU (1) | AU2005245864A1 (es) |
BR (1) | BRPI0510547A (es) |
CA (1) | CA2564048A1 (es) |
ES (1) | ES2550260T3 (es) |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11359148B2 (en) | 2019-09-18 | 2022-06-14 | Saudi Arabian Oil Company | Methods and systems to produce needle coke from aromatic recovery complex bottoms |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8147676B2 (en) * | 2001-12-04 | 2012-04-03 | Exxonmobil Research And Engineering Company | Delayed coking process |
BRPI0603016B1 (pt) * | 2006-07-28 | 2015-10-27 | Petróleo Brasileiro S A Petrobras | processo de modificação de uma carga em uma unidade de coqueamento retardado |
BRPI0603024B1 (pt) | 2006-07-28 | 2015-08-25 | Petroleo Brasileiro Sa | Processo de coqueamento retardado com carga modificada |
US7871510B2 (en) * | 2007-08-28 | 2011-01-18 | Exxonmobil Research & Engineering Co. | Production of an enhanced resid coker feed using ultrafiltration |
US7794587B2 (en) * | 2008-01-22 | 2010-09-14 | Exxonmobil Research And Engineering Company | Method to alter coke morphology using metal salts of aromatic sulfonic acids and/or polysulfonic acids |
US8202480B2 (en) * | 2009-06-25 | 2012-06-19 | Uop Llc | Apparatus for separating pitch from slurry hydrocracked vacuum gas oil |
US8540870B2 (en) * | 2009-06-25 | 2013-09-24 | Uop Llc | Process for separating pitch from slurry hydrocracked vacuum gas oil |
US8231775B2 (en) | 2009-06-25 | 2012-07-31 | Uop Llc | Pitch composition |
RU2469068C1 (ru) * | 2011-11-25 | 2012-12-10 | Государственное унитарное предприятие "Институт нефтехимпереработки Республики Башкортостан" (ГУП "ИНХП РБ") | Способ получения кокса |
US9150470B2 (en) | 2012-02-02 | 2015-10-06 | Uop Llc | Process for contacting one or more contaminated hydrocarbons |
CN102944667B (zh) * | 2012-10-30 | 2015-08-12 | 中国石油化工股份有限公司 | 一种双反应器焦化原料评价系统 |
US10053630B2 (en) | 2014-05-14 | 2018-08-21 | Exxonmobil Research And Engineering Company | Control of coke morphology in delayed coking |
US10421914B2 (en) * | 2016-03-06 | 2019-09-24 | David Ledo Perez | Solid residue separation: a new way of transporting and processing heavy feedstocks |
US10591456B2 (en) | 2016-03-30 | 2020-03-17 | Exxonmobil Research And Engineering Company | In situ monitoring of coke morphology in a delayed coker using AC impedance |
CN109749775A (zh) * | 2017-11-06 | 2019-05-14 | 江苏新海石化有限公司 | 一种通过改变焦化原料组成延迟焦化的工艺 |
Family Cites Families (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3475323A (en) * | 1967-05-01 | 1969-10-28 | Exxon Research Engineering Co | Process for the preparation of low sulfur fuel oil |
US3558474A (en) * | 1968-09-30 | 1971-01-26 | Universal Oil Prod Co | Slurry process for hydrorefining petroleum crude oil |
US3852047A (en) * | 1969-06-09 | 1974-12-03 | Texaco Inc | Manufacture of petroleum coke |
US3617514A (en) * | 1969-12-08 | 1971-11-02 | Sun Oil Co | Use of styrene reactor bottoms in delayed coking |
US3707459A (en) * | 1970-04-17 | 1972-12-26 | Exxon Research Engineering Co | Cracking hydrocarbon residua |
US3684697A (en) * | 1970-12-17 | 1972-08-15 | Bernard William Gamson | Petroleum coke production |
US3769200A (en) * | 1971-12-06 | 1973-10-30 | Union Oil Co | Method of producing high purity coke by delayed coking |
US4140623A (en) * | 1977-09-26 | 1979-02-20 | Continental Oil Company | Inhibition of coke puffing |
US4298455A (en) * | 1979-12-31 | 1981-11-03 | Texaco Inc. | Viscosity reduction process |
CA1125686A (en) * | 1980-07-03 | 1982-06-15 | Zacheria M. George | Hydrodesulfurization of coke |
US4612109A (en) * | 1980-10-28 | 1986-09-16 | Nl Industries, Inc. | Method for controlling foaming in delayed coking processes |
JPS5790093A (en) * | 1980-11-27 | 1982-06-04 | Cosmo Co Ltd | Treatment of petroleum heavy oil |
US4440625A (en) * | 1981-09-24 | 1984-04-03 | Atlantic Richfield Co. | Method for minimizing fouling of heat exchanges |
US4455219A (en) * | 1982-03-01 | 1984-06-19 | Conoco Inc. | Method of reducing coke yield |
US4430197A (en) * | 1982-04-05 | 1984-02-07 | Conoco Inc. | Hydrogen donor cracking with donor soaking of pitch |
US4411770A (en) * | 1982-04-16 | 1983-10-25 | Mobil Oil Corporation | Hydrovisbreaking process |
US4518487A (en) * | 1983-08-01 | 1985-05-21 | Conoco Inc. | Process for improving product yields from delayed coking |
US4616308A (en) * | 1983-11-15 | 1986-10-07 | Shell Oil Company | Dynamic process control |
US4549934A (en) * | 1984-04-25 | 1985-10-29 | Conoco, Inc. | Flash zone draw tray for coker fractionator |
US4659543A (en) * | 1984-11-16 | 1987-04-21 | Westinghouse Electric Corp. | Cross brace for stiffening a water cross in a fuel assembly |
US4592830A (en) * | 1985-03-22 | 1986-06-03 | Phillips Petroleum Company | Hydrovisbreaking process for hydrocarbon containing feed streams |
US4659453A (en) * | 1986-02-05 | 1987-04-21 | Phillips Petroleum Company | Hydrovisbreaking of oils |
US4927561A (en) * | 1986-12-18 | 1990-05-22 | Betz Laboratories, Inc. | Multifunctional antifoulant compositions |
US5160602A (en) * | 1991-09-27 | 1992-11-03 | Conoco Inc. | Process for producing isotropic coke |
US5258115A (en) * | 1991-10-21 | 1993-11-02 | Mobil Oil Corporation | Delayed coking with refinery caustic |
US5248410A (en) * | 1991-11-29 | 1993-09-28 | Texaco Inc. | Delayed coking of used lubricating oil |
FR2689137B1 (fr) * | 1992-03-26 | 1994-05-27 | Inst Francais Du Petrole | Procede d'hydro conversion de fractions lourds en phase liquide en presence d'un catalyseur disperse et d'additif polyaromatique. |
US5286371A (en) * | 1992-07-14 | 1994-02-15 | Amoco Corporation | Process for producing needle coke |
US6264829B1 (en) * | 1994-11-30 | 2001-07-24 | Fluor Corporation | Low headroom coke drum deheading device |
US5820750A (en) * | 1995-02-17 | 1998-10-13 | Exxon Research And Engineering Company | Thermal decomposition of naphthenic acids |
US6169054B1 (en) * | 1997-04-11 | 2001-01-02 | Intevep, S.A. | Oil soluble coking additive, and method for making and using same |
US5645711A (en) * | 1996-01-05 | 1997-07-08 | Conoco Inc. | Process for upgrading the flash zone gas oil stream from a delayed coker |
US5853565A (en) * | 1996-04-01 | 1998-12-29 | Amoco Corporation | Controlling thermal coking |
US5954949A (en) * | 1998-03-25 | 1999-09-21 | Unipure Corporation | Conversion of heavy petroleum oils to coke with a molten alkali metal hydroxide |
US6387840B1 (en) * | 1998-05-01 | 2002-05-14 | Intevep, S.A. | Oil soluble coking additive |
AU8906998A (en) * | 1998-06-11 | 1999-12-30 | Conoco Inc. | Delayed coking with external recycle |
US6168709B1 (en) * | 1998-08-20 | 2001-01-02 | Roger G. Etter | Production and use of a premium fuel grade petroleum coke |
US6048904A (en) * | 1998-12-01 | 2000-04-11 | Exxon Research And Engineering Co. | Branched alkyl-aromatic sulfonic acid dispersants for solublizing asphaltenes in petroleum oils |
US6611735B1 (en) * | 1999-11-17 | 2003-08-26 | Ethyl Corporation | Method of predicting and optimizing production |
US6800193B2 (en) * | 2000-04-25 | 2004-10-05 | Exxonmobil Upstream Research Company | Mineral acid enhanced thermal treatment for viscosity reduction of oils (ECB-0002) |
US6544411B2 (en) * | 2001-03-09 | 2003-04-08 | Exxonmobile Research And Engineering Co. | Viscosity reduction of oils by sonic treatment |
US6489368B2 (en) * | 2001-03-09 | 2002-12-03 | Exxonmobil Research And Engineering Company | Aromatic sulfonic acid demulsifier for crude oils |
EP1379604B1 (en) * | 2001-03-12 | 2010-02-24 | Curtiss-Wright Flow Control Corporation | Improved coke drum bottom de-heading system |
US20040035749A1 (en) * | 2001-10-24 | 2004-02-26 | Khan Motasimur Rashid | Flow properties of heavy crude petroleum |
US20030127314A1 (en) * | 2002-01-10 | 2003-07-10 | Bell Robert V. | Safe and automatic method for removal of coke from a coke vessel |
US20030191194A1 (en) * | 2002-04-09 | 2003-10-09 | Ramesh Varadaraj | Oil/water viscoelastic compositions and method for preparing the same |
-
2005
- 2005-05-12 AU AU2005245864A patent/AU2005245864A1/en not_active Abandoned
- 2005-05-12 US US11/127,730 patent/US20060006101A1/en not_active Abandoned
- 2005-05-12 WO PCT/US2005/016708 patent/WO2005113709A1/en active Application Filing
- 2005-05-12 CN CNA2005800155603A patent/CN1954050A/zh active Pending
- 2005-05-12 ES ES05748076.6T patent/ES2550260T3/es active Active
- 2005-05-12 CA CA002564048A patent/CA2564048A1/en not_active Abandoned
- 2005-05-12 BR BRPI0510547-1A patent/BRPI0510547A/pt not_active Application Discontinuation
- 2005-05-12 JP JP2007513379A patent/JP2007537344A/ja active Pending
- 2005-05-12 EP EP05748076.6A patent/EP1751253B1/en not_active Not-in-force
- 2005-05-12 MX MXPA06011746A patent/MXPA06011746A/es unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US11359148B2 (en) | 2019-09-18 | 2022-06-14 | Saudi Arabian Oil Company | Methods and systems to produce needle coke from aromatic recovery complex bottoms |
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ES2550260T3 (es) | 2015-11-05 |
EP1751253A1 (en) | 2007-02-14 |
US20060006101A1 (en) | 2006-01-12 |
BRPI0510547A (pt) | 2007-10-30 |
WO2005113709A1 (en) | 2005-12-01 |
JP2007537344A (ja) | 2007-12-20 |
AU2005245864A1 (en) | 2005-12-01 |
MXPA06011746A (es) | 2007-01-16 |
CN1954050A (zh) | 2007-04-25 |
CA2564048A1 (en) | 2005-12-01 |
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