5 Must-Have Features in a 5-8 Calcined Petroleum Coke

Author: Ada

Aug. 04, 2025

USA - Non-puffing petroleum coke - Google Patents

Non-puffing petroleum coke Download PDF

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Publication number: USA
Authority: US; United States
Prior art keywords: feedstock; puffing; coke; inhibitor; coking
Prior art date: -02-02
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.): Expired - Lifetime

Application number

US06/135,717

Inventor

Harry L. Hsu

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

GREAT LAKES CARBON Corp

SGL Carbon Corp

Original Assignee

GREAT LAKES CARBON Corp

Priority date (The priority date 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 date listed.)

-02-02

Filing date

-03-31

Publication date

-06-15

-03-31 Application filed by GREAT LAKES CARBON Corp filed Critical GREAT LAKES CARBON Corp

-03-31 Priority to US06/135,717 priority Critical patent/USA/en

-03-27 Priority to PCT/US/ priority patent/WOA1/en

-03-27 Priority to EP priority patent/EPA4/en

-03-19 Assigned to GREAT LAKES CARBON CORPORATION, A CORP OF DE reassignment GREAT LAKES CARBON CORPORATION, A CORP OF DE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HSU, HARRY L.

-06-15 Application granted granted Critical

-06-15 Publication of USA publication Critical patent/USA/en

-03-18 Assigned to MANUFACTURERS HANOVER TRUST COMPANY A NY CORP. reassignment MANUFACTURERS HANOVER TRUST COMPANY A NY CORP. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GREAT LAKES CARBON CORPORATION, A DE CORP

-02-08 Assigned to CHASE MANHATTAN BANK, N.A., THE, AS CO-AGENT, MANUFACTURERS HANOVER TRUST COMPANY, AS CO-AGENT reassignment CHASE MANHATTAN BANK, N.A., THE, AS CO-AGENT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GREAT LAKES CARBON CORPORATION

-08-20 Assigned to MANUFACTURERS HANOVER TRUST COMPANY AS ADMINISTRATIVE AGENT reassignment MANUFACTURERS HANOVER TRUST COMPANY AS ADMINISTRATIVE AGENT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GREAT LAKES CARBON CORPORATION, A CORP. OF DE F/K/A GREAT LAKES CARBON HOLDING CORPORATION

-06-23 Assigned to GREAT LAKES CARBON CORPORATION reassignment GREAT LAKES CARBON CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHASE MANHATTAN BANK, THE

-11-06 Assigned to BANKERS TRUST COMPANY reassignment BANKERS TRUST COMPANY SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GREAT LAKES CARBON CORPORATION

-06-15 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

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petroleum coke Substances 0.000 title 1
puffing effect Effects 0.000 claims abstract description 69
UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 24
NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
sulfur Substances 0.000 claims abstract description 17
sulfur Inorganic materials 0.000 claims abstract description 17
coking Methods 0.000 claims abstract description 16
delayed effect Effects 0.000 claims abstract description 16
petroleum Substances 0.000 claims abstract description 9
WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 8
calcium fluoride Inorganic materials 0.000 claims abstract description 8
needle coke Substances 0.000 claims abstract description 7
heat treatment Methods 0.000 claims abstract description 6
inhibitor Substances 0.000 claims description 57
coke Substances 0.000 claims description 53
OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
mixture Substances 0.000 claims description 21
particle Substances 0.000 claims description 21
graphite Substances 0.000 claims description 20
graphite Inorganic materials 0.000 claims description 20
method Methods 0.000 claims description 18
manufacturing process Methods 0.000 claims description 7
dispersion Substances 0.000 claims description 6
material Substances 0.000 claims description 6
irreversible effect Effects 0.000 claims description 5
chemical reaction Methods 0.000 claims description 4
VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 3
liquid Substances 0.000 claims description 3
CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
iron(III) sulfate Inorganic materials 0.000 claims description 2
iron compounds Chemical class 0.000 claims 2
-1 pyrites Chemical compound 0.000 claims 1
rendering Methods 0.000 claims 1
graphitization Methods 0.000 abstract description 6
fine particle Substances 0.000 abstract description 3
XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
addition Methods 0.000 description 9
carbon Inorganic materials 0.000 description 8
additive Substances 0.000 description 7
iron oxide Nutrition 0.000 description 7
iron Inorganic materials 0.000 description 6
binding agent Substances 0.000 description 5
PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
Steel Inorganic materials 0.000 description 4
steel Substances 0.000 description 4
inert gas Substances 0.000 description 3
product Substances 0.000 description 3
salts Chemical class 0.000 description 3
OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
antifoaming agent Substances 0.000 description 2
approach Methods 0.000 description 2
calcination Methods 0.000 description 2
calcium Inorganic materials 0.000 description 2
calcium Substances 0.000 description 2
chromium Inorganic materials 0.000 description 2
chromium Substances 0.000 description 2
compounds Chemical class 0.000 description 2
decrease Effects 0.000 description 2
distribution Methods 0.000 description 2
effects Effects 0.000 description 2
hydrocarbons Chemical class 0.000 description 2
hydrogen sulfide Inorganic materials 0.000 description 2
magnesium Inorganic materials 0.000 description 2
magnesium Substances 0.000 description 2
mixing Methods 0.000 description 2
nickel Inorganic materials 0.000 description 2
powder Substances 0.000 description 2
suspension Substances 0.000 description 2
titanium Substances 0.000 description 2
titanium Inorganic materials 0.000 description 2
ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
Calcium carbide Substances 0.000 description 1
VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
Fe2 O3 Inorganic materials 0.000 description 1
Fe3 O4 Inorganic materials 0.000 description 1
UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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 description 1
NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
Vitellaria paradoxa Nutrition 0.000 description 1
QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
additive effect Effects 0.000 description 1
aluminium Inorganic materials 0.000 description 1
XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
barium Inorganic materials 0.000 description 1
DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical class [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
boron Inorganic materials 0.000 description 1
calcined coke Substances 0.000 description 1
calcium compound Drugs 0.000 description 1
calcium compounds Chemical class 0.000 description 1
STRTXDFFNXSZQB-UHFFFAOYSA-N calcium;cyanamide Chemical compound [Ca+2].NC#N STRTXDFFNXSZQB-UHFFFAOYSA-N 0.000 description 1
carbon atom Chemical group C* 0.000 description 1
catalyst Substances 0.000 description 1
chemical substances by application Substances 0.000 description 1
chromium oxide Inorganic materials 0.000 description 1
coating agent Substances 0.000 description 1
coating method Methods 0.000 description 1
cobalt Substances 0.000 description 1
cobalt Inorganic materials 0.000 description 1
GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
colloidal system Substances 0.000 description 1
concentrate Substances 0.000 description 1
copper Inorganic materials 0.000 description 1
copper Substances 0.000 description 1
crystal Substances 0.000 description 1
decreasing effect Effects 0.000 description 1
desulfuration reaction Methods 0.000 description 1
desulfurization Effects 0.000 description 1
desulfurizing effect Effects 0.000 description 1
dual effect Effects 0.000 description 1
elimination Effects 0.000 description 1
elimination reaction Methods 0.000 description 1
final product Substances 0.000 description 1
gas Substances 0.000 description 1
grinding Methods 0.000 description 1
hydrocarbon Natural products 0.000 description 1
hydrogen Inorganic materials 0.000 description 1
hydrogen Substances 0.000 description 1
hydrogenation reaction Methods 0.000 description 1
impurity Substances 0.000 description 1
inhibitory process Effects 0.000 description 1
inorganic mineral Inorganic materials 0.000 description 1
VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
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 description 1
marcasite Inorganic materials 0.000 description 1
measurement Methods 0.000 description 1
melting Methods 0.000 description 1
melting Effects 0.000 description 1
metal Inorganic materials 0.000 description 1
metal Substances 0.000 description 1
metallic ions Chemical class 0.000 description 1
migration Methods 0.000 description 1
migration Effects 0.000 description 1
mineral Substances 0.000 description 1
moulding Methods 0.000 description 1
organometallic compounds Chemical class 0.000 description 1
NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
poly(methylsilsesquioxane) Polymers 0.000 description 1
NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
pyrite Inorganic materials 0.000 description 1
resin Substances 0.000 description 1
resin Polymers 0.000 description 1
sand Substances 0.000 description 1
scavenging effect Effects 0.000 description 1
slurry Substances 0.000 description 1
sodium Inorganic materials 0.000 description 1
sodium Substances 0.000 description 1
sodium carbonate Inorganic materials 0.000 description 1
spalling Methods 0.000 description 1
strontium Inorganic materials 0.000 description 1
CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
strontium compounds Chemical class 0.000 description 1
sulfides Chemical class 0.000 description 1
sulfur atom Chemical group 0.000 description 1
synergetic effect Effects 0.000 description 1
CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
testing method Methods 0.000 description 1
zirconium Inorganic materials 0.000 description 1
zirconium compounds Chemical class 0.000 description 1

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
- 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
- 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

Definitions

Electrode grade graphite is manufactured from a commercial grade of coke having an acicular, anisotropic microstructure called needle coke, see U.S. Pat. No. 2,775,549 to Shea, Dec. 25, , Cl. 201-42, made by delayed coking of certain petroleum residues under specific conditions of heat and pressure. To produce graphite from such coke, it is necessary to heat it to a temperature in the range of °-° C., which has the dual function of supplying energy for the conversion of the carbon in the coke to the graphitic crystalline form and of volatilizing impurities.
puffing When carbon bodies made from such cokes are heated at temperatures in the vicinity of °-° C., various sulfur-containing compounds decompose, attended by a rapid and irreversible expansion of the carbon body. This phenomenon is termed "puffing". During the production of graphite articles, particularly high performance graphite electrodes, puffing is extremely undesirable as it may destroy the structural integrity of the piece and render it marginal or useless for its intended purpose.
Puffing of a carbon article made from high sulfur cokes generally starts at about ° C., and may result in a volumetric expansion of as much as 25%. It is not simply an elastic expansion but should be characterized as an inelastic, irreversible expansion.
puffing phenomenon in acicular needle cokes with a relatively large amount of sulfur, sulfur atoms are bonded to carbon atoms by covalent bonds, either in carbon ring structures or linking rings. These bonds are less stable at high temperatures than the carbon-to-carbon bonds. On heating, the carbon-sulfur bonds rupture, the sulfur is freed, then reacts with hydrogen to form hydrogen sulfide. The simultaneous rupture of these bonds and evolution of hydrogen sulfide and other sulfur containing materials causes the physical expansion called puffing.
additives have usually been added during the mixing stage when various sizes and grades of coke particles are mixed, before being wetted with pitch, formed into the desired shape, baked at an intermediate temperature and graphitized at high temperatures.
Additives have included primarily metal salts and oxides, as disclosed in British Pat. No. 733,073, Greenhalgh, July 6, , Cl. 90 b; French Pat. No. 1,491,497, Gillot et al., Aug. 11, , Cl. C 01 b; French Pat. No. 2,035,273, Continental Oil, Dec. 18, , Cl. C 10 b 57; U.S. Pat. No.
French Pat. No. 1,491,497 discloses the use of chromium oxide at 0.2-5% in a mixture with coke and a binder as a catalyst, enabling graphitization to occur at temperatures in the range of °-° C.
French Pat. No. 2,035,273 discloses a low sulfur coke produced by the addition of 0.3-5% of sodium carbonate to the coking stream mixture and subsequent hydrogenation of the coke at high temperature.
British Pat. No. 733,073 discloses the use of oxides of chromium, iron, copper, or nickel incorporated in the grinding stage of coke, mixed with pitch, shaped, baked at ° C., and graphitized at °-° C.
U.S. Pat. No. 3,563,705 discloses the use of mixtures of iron or calcium compounds with small amounts of titanium or zirconium compounds as puffing inhibitors incorporated into the coke-binder mixture.
U.S. Pat. No. 3,338,993 discloses the use of calcium, magnesium, strontium, and barium fluorides as puffing inhibitors with raw or calcined coke and binder, mixed, shaped, baked and graphitized.
U.S. Pat. No. 3,642,962 discloses the use of 1-3% calcium cyanamid or calcium carbide as desulfurizing agents and puffing inhibitors, mixed with raw coke prior to calcining.
CTE coefficient of thermal expansion
Electrodes for electric furnace melting of steel must have a low CTE to avoid excessive differential expansion at operating temperatures and the resultant spalling, which in turn causes excessive consumption of the electrode and cost in operation.
Other applications requiring dimensional stability at high temperatures are well-known although of somewhat less economic importance.
any foreign material to a graphitizing carbonaceous mix will have, in addition to its desired effect, such as puffing inhibition, the effect of increasing the CTE of the graphite body.
a needle coke is distinguished by its physical structure when microscopically examined, showing long needle-like acicular particles.
Such cokes to be suitable for manufacture of graphite electrodes to be used in ultra-high powered electric steel furnaces, should have a graphite CTE characteristic of less than 5 ⁇ 10 -7 /°C. measured over the range of 0°-50° C.
Needle cokes for lower powered electric steel furnaces may have a graphite CTE characteristic of as much as 7 ⁇ 10 -7 /°C. over the 0°-50° C. range.
the cokes or blends of cokes must be thoroughly mixed with the puffing inhibitor to avoid the difficulties present in making uniform homogeneous blends and in thoroughly coating the particles, which are often as much as 7 mm. in diameter. Both of these difficulties can lead to non-uniform dispersion of the inhibitor and to puffing, even though there is sufficient inhibitor present in the total mix to prevent puffing. This non-uniformity is particularly troublesome when operating under the newer type of graphitization processes, which raise the temperature of the carbon bodies (i.e. electrodes) at a much higher rate than the older processes. The combination of high sulfur with high rate of temperature rise exacerbates the problem and requires undesirably slow heating rates to overcome puffing.
the puffing problem is further increased with the rate of graphitization of the carbon bodies.
Optimum distribution of the inhibitor throughout the structure of the carbon body to be graphitized is essential as the degree of puffing for any coke particle blend is highly rate sensitive, being directly related to the rate of temperature increase during the graphitization cycle.
the figures in certain of the examples given will show a much higher dynamic puffing at a 14° C./min. temperature rise than for a 5° C./min. rise.
a petroleum coker feedstock which would normally produce a puffing coke due to its high sulfur content is rendered non-puffing by the addition of an effective amount of puffing inhibitor to the feedstock as a fine particle size powder.
Puffing inhibitors such as iron oxide and/or calcium fluoride may be pre-dispersed in a high concentration in a small quantity of the feedstock (fresh feed or coker furnace feed), or in compatible material miscible with the feedstock, or dispersed in the total coker stream and added either batchwise to a batch type coker, continuously to the main stream in a delayed coker, or near the top of a delayed coker (as in the case of anti-foam additives) while the coker stream is admitted into the coker at or near the bottom of the unit.
the feedstock fresh feed or coker furnace feed
compatible material miscible with the feedstock or dispersed in the total coker stream and added either batchwise to a batch type coker, continuously to the main stream in a delayed coker, or near the top of a delayed coker (as in the case of anti-foam additives) while the coker stream is admitted into the coker at or near the bottom of the unit.
a current of inert gas or steam bubbled slowly through the hydrocarbons in a batch type coker during the run aids in keeping the puffing inhibitor in suspension without significantly increasing the CTE of the finished product. In a commercial delayed coker this is not essential.
delayed coking see R. J. Diwoky, Continuous Coking of Residuum by the Delayed Coking Process, Refiner and Natural Gasoline Manufacturer, Vol. 17, No. 11, November .
Iron oxide is formed when any of numerous iron bearing materials is calcined, including organometallic compounds and salts. Minerals such as magnetite (Fe 3 O 4 ), limonite (2Fe 2 O 3 .3H 2 O); and pyrites (FeS 2 ) and salts such as ferric sulfate and nitrate when roasted in air are converted to ferric oxide, and may be used to form the oxide.
Minerals such as magnetite (Fe 3 O 4 ), limonite (2Fe 2 O 3 .3H 2 O); and pyrites (FeS 2 ) and salts such as ferric sulfate and nitrate when roasted in air are converted to ferric oxide, and may be used to form the oxide.
the reactive species may be elemental iron, produced by reduction of the Fe 2 O 3 by coke during graphitization.
Calcium fluoride is also highly effective as an inhibitor with slightly superior performance as compared to iron oxide. Mixtures of the two inhibitors have shown a synergistic result, being more effective than either of the two when used alone.
inhibitor in this manner produces a coke which is lower puffing and produces a graphite which has a lower CTE than from a coke conventionally inhibited by a dry mix.
CTE of the graphitized coke was determined by preparing small 5/8" ⁇ 5"(1.6 ⁇ 12.7 cm.) electrodes by the procedure disclosed in U.S. Pat. No. 2,775,549, (except for calcination of the coke to ° C.), and measuring their elongation over the temperature range of 0° to 50° C.
the drawing is a schematic representation of an apparatus for carrying out the process of the invention.
a decant oil the fractionater tower bottoms from a catalytically cracked gas oil fraction, also termed slurry oil, or other equivalent hydrocarbon residue, is conveyed from the fractionater 33 through line 10 and meter 14 to diversion valve 17, where a portion of the feedstock is diverted through valve 13, and meter 15 to disperser 18. Simultaneously a portion of inhibitor 12 is weighed in scale 16 and conveyed to disperser 18 where it is dispersed in the feedstock to a specific concentration by weight. Alternately a compatible liquid and additives from supply 19 are metered through valve 11 to valve 13 and meter 15 to disperser 18.
a compatible liquid and additives from supply 19 are metered through valve 11 to valve 13 and meter 15 to disperser 18.
the inhibitor is dispersed and discharged through line 22 and meter 23 preferably to valve 34 and through line 36 to top inlets 38 and 38A of the coker drums.
the inhibitor may also be fed through valve 34 to mixer 24 where it is mixed with the principal portion of the feedstock through pump 27, line 26; furnace 29 and line 31 to the bottom inlets of the coker drums 28 and 28A.
the overheads are taken off through line 32 and sent to the fractionater 33.
the disperser which may be any of several types of equipment well known in the art, preferably a high shear or colloid mill. Alternately, a sand or ball mill could be used.
the puffing inhibitor dispersion and feedstock are metered in the correct proportions to give a concentration of approximately 0.05-0.5 wt. % puffing inhibitor in the feedstock.
the viscosity of the feedstock is extremely low and some means is necessary to minimize settling and a concentration of the puffing inhibitor in the lower portion of the coker during batchwise coker operation.
the puffing inhibitor is maintained in a uniform suspension without significantly raising the CTE of the finished product or lowering the acicular crystal content of the coke. It is preferable to add the inhibitor at or near the top of the coke drum, through either the ports normally used to inject anti-foam or a special fitting.
micronized puffing inhibitors calcium fluoride and iron oxide (having approximately the same particle size distribution) were individually mixed with samples of a fresh feed decant oil coker feedstock, at 0.1 wt. % level in a high speed blender for about 5 minutes. The mixtures were coked under identical conditions in 4 liter resin flasks.
Dynamic puffing of the cokes was then determined in comparison with uninhibited samples, and with samples inhibited in the normal manner with dry-mixed iron oxide.
the coke samples had 50% ⁇ 200 mesh (79 mesh/cm.) particles and 100% ⁇ 65 mesh (26 mesh/cm.) particles.
Puffing was measured by taking representative samples by the method of ASTM D346-35, crushing, mixing 100 g coke and 25 g pitch, and molding plugs at 12,500 psi (879 kg./cm. 2 ). The plugs were measured by micrometer and placed in a dilatometer. The temperature was raised to ° C. over a period of 50 ⁇ 10 min., then the test was run at a temperature increase of 5° or 12°-16° C./min. over the °-° C. range, with measurements taken every five minutes. The reported DP is the maximum degree of elongation (or shrinkage) measured. All of the DP's below were at 14° C./min. rise except as noted.
the calcium fluoride was found to be the more effective.
the addition of either inhibitor to the feedstock significantly decreased puffing of the resulting coke.
the CTE of the resulting cokes was within the range (under 5 ⁇ 10 -7 /°C.) considered necessary for a needle coke.
a CTE of the graphite body of as much as 7 ⁇ 10 -7 /°C. may be acceptable, but for ultra high power electrodes for electric steel furnaces the upper limit is generally 5 ⁇ 10 -7 /°C.
Some feedstocks may well need and be beneficially treated with inhibitor additions of as much as 0.5%, resulting in a 2% ash level which is almost totally inhibitor in the final coke.

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Abstract

Very fine particle size iron oxide or calcium fluoride is dispersed in a high sulfur petroleum coker feedstock before delayed coking to produce a needle coke with low CTE and negligible puffing on heating to the temperature of graphitization.

Description

This application is a continuation-in-part of Ser. No. 8,838, filed Feb. 2, , and now abandoned. BACKGROUND OF THE INVENTION Electrode grade graphite is manufactured from a commercial grade of coke having an acicular, anisotropic microstructure called needle coke, see U.S. Pat. No. 2,775,549 to Shea, Dec. 25, , Cl. 201-42, made by delayed coking of certain petroleum residues under specific conditions of heat and pressure. To produce graphite from such coke, it is necessary to heat it to a temperature in the range of °-° C., which has the dual function of supplying energy for the conversion of the carbon in the coke to the graphitic crystalline form and of volatilizing impurities. When carbon bodies made from such cokes are heated at temperatures in the vicinity of °-° C., various sulfur-containing compounds decompose, attended by a rapid and irreversible expansion of the carbon body. This phenomenon is termed "puffing". During the production of graphite articles, particularly high performance graphite electrodes, puffing is extremely undesirable as it may destroy the structural integrity of the piece and render it marginal or useless for its intended purpose. Puffing of a carbon article made from high sulfur cokes generally starts at about ° C., and may result in a volumetric expansion of as much as 25%. It is not simply an elastic expansion but should be characterized as an inelastic, irreversible expansion. The generally accepted explanation of the puffing phenomenon is that in acicular needle cokes with a relatively large amount of sulfur, sulfur atoms are bonded to carbon atoms by covalent bonds, either in carbon ring structures or linking rings. These bonds are less stable at high temperatures than the carbon-to-carbon bonds. On heating, the carbon-sulfur bonds rupture, the sulfur is freed, then reacts with hydrogen to form hydrogen sulfide. The simultaneous rupture of these bonds and evolution of hydrogen sulfide and other sulfur containing materials causes the physical expansion called puffing. Puffing has been avoided in the past by using coke made from petroleum residues low in sulfur content. This approach is of only limited utility at present since the principal petroleum crudes currently in use have high sulfur contents, and the cokes made from their residues will normally exhibit an undesirable degree of puffing. Another approach to elimination or alleviation of the puffing problem in manufacture of graphite articles has been by the use of additives. These additives have usually been added during the mixing stage when various sizes and grades of coke particles are mixed, before being wetted with pitch, formed into the desired shape, baked at an intermediate temperature and graphitized at high temperatures. Additives have included primarily metal salts and oxides, as disclosed in British Pat. No. 733,073, Greenhalgh, July 6, , Cl. 90 b; French Pat. No. 1,491,497, Gillot et al., Aug. 11, , Cl. C 01 b; French Pat. No. 2,035,273, Continental Oil, Dec. 18, , Cl. C 10 b 57; U.S. Pat. No. 3,642,962, Wallouch, Feb. 15, , Cl. 201-17; U.S. Pat. No. 3,563,705, Grindstaff et al., Feb. 16, , C. C 01 b 31/04, Cl. 423-375; U.S. Pat. No. 3,842,165, Grindstaff et al. Oct. 15, , Cl. C 01 b 31/04, Cl. 264-29.1; and U.S. Pat. No. 3,338,993, Juel et al. Aug. 29, , Cl. 106-56. The patents above disclose the use of iron, sodium, chromium, nickel, cobalt, boron, aluminum, titanium, calcium, zirconium, manganese, magnesium, barium and strontium compounds as puffing inhibitors. Some compounds of this group are in general usage and of these a choice is naturally made based upon the effectiveness as a puffing inhibitor and upon other properties of the graphite article such as electrical resistivity, tensile strength, modulus of rupture, modulus of elasticity, coefficient of thermal expansion, and cost. Of the above, French Pat. No. 1,491,497 discloses the use of chromium oxide at 0.2-5% in a mixture with coke and a binder as a catalyst, enabling graphitization to occur at temperatures in the range of °-° C. French Pat. No. 2,035,273 discloses a low sulfur coke produced by the addition of 0.3-5% of sodium carbonate to the coking stream mixture and subsequent hydrogenation of the coke at high temperature. British Pat. No. 733,073 discloses the use of oxides of chromium, iron, copper, or nickel incorporated in the grinding stage of coke, mixed with pitch, shaped, baked at ° C., and graphitized at °-° C. U.S. Pat. No. 3,563,705 discloses the use of mixtures of iron or calcium compounds with small amounts of titanium or zirconium compounds as puffing inhibitors incorporated into the coke-binder mixture. U.S. Pat. No. 3,338,993 discloses the use of calcium, magnesium, strontium, and barium fluorides as puffing inhibitors with raw or calcined coke and binder, mixed, shaped, baked and graphitized. U.S. Pat. No. 3,642,962 discloses the use of 1-3% calcium cyanamid or calcium carbide as desulfurizing agents and puffing inhibitors, mixed with raw coke prior to calcining. U.S. Pat. No. 3,873,427, Long, issued Mar. 25, , Cl. 201-17, discloses the addition of metallic chloride and ferruginous material for desulfurization of coke. U.S. Pat. No. 4,043,898, Kegler, issued Aug. 23, , Cl. 208/50, discloses delayed coking of selected feedstocks to produce needle coke. At present, the most common methods of the above are those using iron oxides mixed dry in the coke-pitch binder blend as puffing inhibitors. These are effective puffing inhibitors but must be used with caution, as their use tends to increase the coefficient of thermal expansion or CTE, of the finished product, to an undesirable level. The coefficient of thermal expansion (CTE), which is conventionally expressed in in./in./°C. or cm./cm./°C., is also of vital importance in the production of graphite for certain applications. Electrodes for electric furnace melting of steel must have a low CTE to avoid excessive differential expansion at operating temperatures and the resultant spalling, which in turn causes excessive consumption of the electrode and cost in operation. Other applications requiring dimensional stability at high temperatures are well-known although of somewhat less economic importance. In general, the addition of any foreign material to a graphitizing carbonaceous mix will have, in addition to its desired effect, such as puffing inhibition, the effect of increasing the CTE of the graphite body. A needle coke is distinguished by its physical structure when microscopically examined, showing long needle-like acicular particles. Such cokes, to be suitable for manufacture of graphite electrodes to be used in ultra-high powered electric steel furnaces, should have a graphite CTE characteristic of less than 5×10-7 /°C. measured over the range of 0°-50° C. Needle cokes for lower powered electric steel furnaces may have a graphite CTE characteristic of as much as 7×10-7 /°C. over the 0°-50° C. range. The cokes or blends of cokes must be thoroughly mixed with the puffing inhibitor to avoid the difficulties present in making uniform homogeneous blends and in thoroughly coating the particles, which are often as much as 7 mm. in diameter. Both of these difficulties can lead to non-uniform dispersion of the inhibitor and to puffing, even though there is sufficient inhibitor present in the total mix to prevent puffing. This non-uniformity is particularly troublesome when operating under the newer type of graphitization processes, which raise the temperature of the carbon bodies (i.e. electrodes) at a much higher rate than the older processes. The combination of high sulfur with high rate of temperature rise exacerbates the problem and requires undesirably slow heating rates to overcome puffing. It should be emphasized that overcoming the puffing problem becomes increasingly more difficult in the larger graphite electrode sizes (above 20 in. ((51 cm.)) diam) because in such sizes, larger particles of coke are used. Since the puffing inhibitor only coats the surface of the particles, the coke surface area to inhibitor weight ratio decreases, for a given weight addition ratio, giving a higher concentration of inhibitor on the coke particle surfaces for the larger particle blends. Thus a large amount of the inhibitor is at relatively greater distance from the centers of the coke particles in the larger coke particle mixes as opposed to the smaller particle mixes used in smaller electrodes. Migration of the inhibitor into the centers of the large particles becomes progressively more difficult and less effective as the coke particles increase in size. The puffing problem is further increased with the rate of graphitization of the carbon bodies. Optimum distribution of the inhibitor throughout the structure of the carbon body to be graphitized is essential as the degree of puffing for any coke particle blend is highly rate sensitive, being directly related to the rate of temperature increase during the graphitization cycle. Thus, the figures in certain of the examples given will show a much higher dynamic puffing at a 14° C./min. temperature rise than for a 5° C./min. rise. The amount of puffing for any given coke-inhibitor blend could be expressed as a proportionality in the general form:

DP=K(S,P,ΔT)/l

where DP=dynamic puffing S=sulfur content of coke P=mean particle size ΔT=rate of temperature increase l=amount of inhibitor K=proportionality factor Thus it may be seen that increases in sulfur content, particle size, and temperature rise will increase puffing, while an increase in the inhibitor level will decrease puffing. SUMMARY OF THE INVENTION A petroleum coker feedstock which would normally produce a puffing coke due to its high sulfur content is rendered non-puffing by the addition of an effective amount of puffing inhibitor to the feedstock as a fine particle size powder. Puffing inhibitors such as iron oxide and/or calcium fluoride may be pre-dispersed in a high concentration in a small quantity of the feedstock (fresh feed or coker furnace feed), or in compatible material miscible with the feedstock, or dispersed in the total coker stream and added either batchwise to a batch type coker, continuously to the main stream in a delayed coker, or near the top of a delayed coker (as in the case of anti-foam additives) while the coker stream is admitted into the coker at or near the bottom of the unit. The use of a fine particle size powder of 100% less than 5 micron diameter, predispersed in a portion of the feedstock, insures that the final product will be a homogeneous coke with puffing inhibitor uniformly distributed throughout. A current of inert gas or steam bubbled slowly through the hydrocarbons in a batch type coker during the run aids in keeping the puffing inhibitor in suspension without significantly increasing the CTE of the finished product. In a commercial delayed coker this is not essential. For a description of delayed coking, see R. J. Diwoky, Continuous Coking of Residuum by the Delayed Coking Process, Refiner and Natural Gasoline Manufacturer, Vol. 17, No. 11, November . Iron oxide is formed when any of numerous iron bearing materials is calcined, including organometallic compounds and salts. Minerals such as magnetite (Fe3 O4), limonite (2Fe2 O3.3H2 O); and pyrites (FeS2) and salts such as ferric sulfate and nitrate when roasted in air are converted to ferric oxide, and may be used to form the oxide. The reactive species may be elemental iron, produced by reduction of the Fe2 O3 by coke during graphitization. Calcium fluoride is also highly effective as an inhibitor with slightly superior performance as compared to iron oxide. Mixtures of the two inhibitors have shown a synergistic result, being more effective than either of the two when used alone. The addition of inhibitor in this manner to the feedstock to the coker produces a coke which is lower puffing and produces a graphite which has a lower CTE than from a coke conventionally inhibited by a dry mix. The mode of operation of these puffing inhibitors is probably a scavenging reaction, sulfur reacting with the metallic ions to form the sulfides, then decomposing slowly at higher temperatures to give a controlled evolution of vaporized elemental sulfur. In general the use of any of the additives listed above, when added to a coke particle-pitch binder mix, will lower the extent of puffing, but at the same time significantly increase the CTE, of the graphite bodies made from such cokes. I have found that the use of puffing inhibitor dispersed in the coker feedstock in appropriate amounts prior to coking gives an unexpected advantage in that it controls puffing of the coke while increasing the CTE only to a smaller degree (or in some instances not at all), when compared to the CTE of a graphite body in which the puffing has been eliminated by adding the same additive to the electrode mix by the conventional dry-mix practice. CTE of the graphitized coke was determined by preparing small 5/8"×5"(1.6×12.7 cm.) electrodes by the procedure disclosed in U.S. Pat. No. 2,775,549, (except for calcination of the coke to ° C.), and measuring their elongation over the temperature range of 0° to 50° C. DESCRIPTION OF THE DRAWING The drawing is a schematic representation of an apparatus for carrying out the process of the invention. In FIG. 1 a decant oil, the fractionater tower bottoms from a catalytically cracked gas oil fraction, also termed slurry oil, or other equivalent hydrocarbon residue, is conveyed from the fractionater 33 through line 10 and meter 14 to diversion valve 17, where a portion of the feedstock is diverted through valve 13, and meter 15 to disperser 18. Simultaneously a portion of inhibitor 12 is weighed in scale 16 and conveyed to disperser 18 where it is dispersed in the feedstock to a specific concentration by weight. Alternately a compatible liquid and additives from supply 19 are metered through valve 11 to valve 13 and meter 15 to disperser 18. The inhibitor is dispersed and discharged through line 22 and meter 23 preferably to valve 34 and through line 36 to top inlets 38 and 38A of the coker drums. The inhibitor may also be fed through valve 34 to mixer 24 where it is mixed with the principal portion of the feedstock through pump 27, line 26; furnace 29 and line 31 to the bottom inlets of the coker drums 28 and 28A. The overheads are taken off through line 32 and sent to the fractionater 33. In the above flowsheet, 18 is the disperser which may be any of several types of equipment well known in the art, preferably a high shear or colloid mill. Alternately, a sand or ball mill could be used. In practice, a dispersion of approximately 5-50% by wt. of puffing inhibitor in the feedstock is used as a concentrate. The puffing inhibitor dispersion and feedstock are metered in the correct proportions to give a concentration of approximately 0.05-0.5 wt. % puffing inhibitor in the feedstock. At the operating temperature the viscosity of the feedstock is extremely low and some means is necessary to minimize settling and a concentration of the puffing inhibitor in the lower portion of the coker during batchwise coker operation. By the introduction of a small flow of inert gas bubbled up from the bottom of the coker drum the puffing inhibitor is maintained in a uniform suspension without significantly raising the CTE of the finished product or lowering the acicular crystal content of the coke. It is preferable to add the inhibitor at or near the top of the coke drum, through either the ports normally used to inject anti-foam or a special fitting. The following are examples of specific methods of practicing the invention: EXAMPLE 1 The micronized puffing inhibitors, calcium fluoride and iron oxide (having approximately the same particle size distribution) were individually mixed with samples of a fresh feed decant oil coker feedstock, at 0.1 wt. % level in a high speed blender for about 5 minutes. The mixtures were coked under identical conditions in 4 liter resin flasks. In an insulated glass resin flask, an inert gas at the rate of 0.16 SCFH/kg (4.5 l/hr./kg.) mixture was bubbled up from the bottom of the coking pot to keep the inhibitor uniformly dispersed in feedstock. The following time-temperature cycle was used:

______________________________________                                    
Temperature   Elapsed Time   Rate ΔC.°/hr                    
______________________________________                                    
Room to 350° C.                                                    
              3 hours        110                                          
350-450° C.                                                        
              4.5-5 hours    20                                           
450° C.                                                            
              16 hours       --                                           
450-530° C.                                                        
              4.0-4.5 hours  20                                           
530° C.                                                            
              1 hour         --                                           
530° C.-RT                                                         
              Cool-down, power off                                        
______________________________________

Dynamic puffing of the cokes was then determined in comparison with uninhibited samples, and with samples inhibited in the normal manner with dry-mixed iron oxide. The coke samples had 50%<200 mesh (79 mesh/cm.) particles and 100%<65 mesh (26 mesh/cm.) particles. Puffing was measured by taking representative samples by the method of ASTM D346-35, crushing, mixing 100 g coke and 25 g pitch, and molding plugs at 12,500 psi (879 kg./cm.2). The plugs were measured by micrometer and placed in a dilatometer. The temperature was raised to ° C. over a period of 50±10 min., then the test was run at a temperature increase of 5° or 12°-16° C./min. over the °-° C. range, with measurements taken every five minutes. The reported DP is the maximum degree of elongation (or shrinkage) measured. All of the DP's below were at 14° C./min. rise except as noted.

______________________________________                                    
           Coke Properties                                                
                           CTE ×                                    
                                    DP,                                   
Inhibitor Coke             10.sup.-7 /°C.**                        
                                    % Δ L***                        
Added to  Yld.   Ash    S    pph  Fe.sub.2 O.sub.3 *                      
                                        pph  Fe.sub.2 O.sub.3 *           
Feedstock %      %      %    0    1/2   0    1/2                          
______________________________________                                    
0         23.3   0.01   1.17 3.0  --    +6.8 --                           
0         23.3   0.01   1.17 --   3.8   --   +1.7                         
0.1% CaF.sub.2                                                            
          24.9   0.65   1.26 4.2  --    +1.2 --                           
0.1% Fe.sub.2 O.sub.3                                                     
          23.0   0.50   1.22 4.1  --    +1.6 --                           
______________________________________                                    
 *(Iron oxide drymixed into the coke)                                     
 **(Coefficient of Thermal Expansion over the range of 0°-50.degree
 C. × 10.sup.-7 /°C., 5/8" × 5" (1.6 × 12.7 cm.) 
 sample, 10 min. time)                                                    
 ***(Dynamic Puffing over the range of °-° C.)

Of the two puffing inhibitors, the calcium fluoride was found to be the more effective. The addition of either inhibitor to the feedstock significantly decreased puffing of the resulting coke. The CTE of the resulting cokes was within the range (under 5×10-7 /°C.) considered necessary for a needle coke. For less demanding applications, a CTE of the graphite body of as much as 7×10-7 /°C. may be acceptable, but for ultra high power electrodes for electric steel furnaces the upper limit is generally 5×10-7 /°C. EXAMPLE 2 Another fresh feed sample was tested as in Example 1 using the inhibitors at a higher level of addition, with the following results:

______________________________________                                    
Inhibitor     Coke Properties                                             
Added to      CTE                                                         
Feedstock     10.sup.-7 /°C.                                       
                           DP, % Δ L                                
______________________________________                                    
0             2.9          8.3                                            
CaF.sub.2 (0.2%)                                                          
              4.7          0.7                                            
Fe.sub.2 O.sub.3 (0.2%)                                                   
              5.1          0.7                                            
______________________________________

Some feedstocks may well need and be beneficially treated with inhibitor additions of as much as 0.5%, resulting in a 2% ash level which is almost totally inhibitor in the final coke. The examples above are not shown as limitations but merely samples from the wide variety of petroleum residues currently available.

Claims (9)

I claim: 1. In a process for the manufacture of non-puffing needle coke having a graphite CTE characteristic of not higher than 7×10-7 /°C. over the range of 0° to 50° C. by delayed coking of petroleum feedstock having a level of sulfur content combined molecularly in components of said feedstock sufficiently high enough to contribute to an irreversible volumetric expansion on heating to a temperature of ° C. or higher, the improvement consisting of the addition of from 0.05 to 0.5% by wt. of puffing inhibitor selected from the group consisting of iron oxide and calcium fluoride or mixtures thereof to said feedstock prior to or during the coking of said feedstock in a delayed coker, thereby rendering said coke non-puffing. 2. The process of claim 1 wherein from 0.05 to 0.5% by wt. of puffing inhibitor is added to the feedstock in the form of a predispersed liquid concentrated dispersion of said puffing inhibitor in a liquid medium compatible with said feedstock. 3. The process of claim 1 wherein the puffing inhibitor used has a particle size diameter such that 100% of said particles are less than 5 microns and 70% are less than 2 microns. 4. The process of claim 1 wherein the puffing inhibitor is dispersed in a portion of the coker feedstock. 5. In a process for the manufacture of non-puffing coke suitable for conversion to graphite with a CTE characteristic of not higher than 5×10-7 /°C. over the range of 0° to 50° C. by delayed coking of petroleum feedstocks having sulfur molecularly combined in components of said feedstock in sufficient quantity to contribute to an irreversible volumetric expansion on heating to a temperature of ° C. or higher, the improvement consisting of selecting an effective amount of puffing inhibitor selected from the group consisting of iron oxide and calcium fluoride or mixtures thereof of particle size less than 5μ (5×10-6 m) to be added to said feedstock at a concentration by wt. of 0.05 to 0.5% of said feedstock, dispersing said puffing inhibitor in a portion of said feedstock or other compatible material to form a uniform dispersion of said puffing inhibitor; adding said dispersion to the principal portion of said feedstock at or near the top of a delayed coker drum and coking said feedstock in said delayed coker. 6. The process of claims 1 or 5 in which the puffing inhibitor is iron oxide. 7. The process of claims 1 or 5 in which the puffing inhibitor is calcium fluoride. 8. In a process for the manufacture of non-puffing needle coke having a graphite CTE characteristic not higher than 7×10-7 /°C. over the range of 0° to 50° C. suitable for conversion to electrode grade graphite by delayed coking of petroleum feedstock having a level of sulfur content in said feedstock sufficiently high enough to contribute to an irreversible volumetric expansion on heating said coke to a temperature of ° C. or higher, the improvement comprising the addition of an iron compound selected from the group consisting of ferric nitrate, ferric sulfate, pyrites, and limonite to said feedstock before or during coking said feedstock in a delayed coker, to render said coke non-puffing, said iron compound added in an amount effectively equivalent to 0.05% to 0.5% iron oxide by wt. of said feedstock. 9. The process of claims 1 or 8 wherein the puffing inhibitor is added to the feedstock during the coking process at or near the top of a delayed coker. US06/135,717 -02-02 -03-31 Non-puffing petroleum coke Expired - Lifetime USA (en)

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Cited By (14)

Citations (6)

* Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title GBA (en) * -04-08 -07-06 Nat Res Dev Improvements in or relating to production of artificial graphite masses USA (en) * -01-25 -12-25 Great Lakes Carbon Corp Production of coke from petroleum hydrocarbons USA (en) * -05-29 -04-14 Great Lakes Carbon Corp Method of eliminating puffing in the manufacture of electrodes from puffing petroleum coke USA (en) * -11-24 -03-25 Lummus Co Desulfurizing coke using a ferruginous material and a metal chloride USA (en) * -08-25 -08-23 Continental Oil Company Control of feedstock for delayed coking USA (en) * -09-26 -02-20 Continental Oil Company Inhibition of coke puffing

- -03-31 US US06/135,717 patent/USA/en not_active Expired - Lifetime
- -03-27 WO PCT/US/ patent/WOA1/en not_active Application Discontinuation
- -03-27 EP EP patent/EPA4/en not_active Withdrawn

Patent Citations (6)

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party Title Fundamentals of Paint, Varnish, and Lacquer Technology, Singer, American Paint Journal Co., St. Louis, , pp. 63-71. * Kirk-Othmer Encyclopedia of Chemical Technology, 2nd Ed., Interscience, New York, , vol. 15, pp. 555, 517-520. * Mellor, Inorganic and Theoretical Chemistry, Longmans Green, London, , vol. XIV, pp. 310, 381. * The Solubility of Nonelectrolytes, Hildebrand and Scott, Dover, New York, , pp. 4-5, 26-27. *

Cited By (29)

* Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title JPSA (en) * -09-11 -03-16 Nippon Steel Corp Manufacturing method of artificial graphite electrode DEC1 (en) * -03-06 -03-22 Sigri Gmbh, Meitingen, De DEC1 (en) * -03-06 -04-19 Sigri Gmbh, Meitingen, De DEA1 (en) * -03-06 -09-13 Sigri Gmbh METHOD FOR INHIBITING THE PUFFING OF COCKS MADE FROM CARBON TECH DEA1 (en) * -03-06 -09-20 Sigri Gmbh METHOD FOR PRODUCING NON-PUBLIC CARBON BODIES USA (en) * -03-06 -11-26 Sigri Gmbh Process for the production of non-puffing shaped carbon bodies USA (en) * -03-06 -04-14 Sigri Gmbh Process for the inhibition of the puffing of cokes produced from coal tar pitches GBB (en) * -03-06 -03-24 Sigri Gmbh Process for the production of graphitized shaped carbon bodies USA (en) * -04-13 -10-09 Amoco Corporation Antifoam process for delayed coking USA1 (en) * -08-20 -02-16 Etter Roger G Production and use of a premium fuel grade petroleum coke USB2 (en) -08-20 -10-25 Roger G. Etter Production and use of a premium fuel grade petroleum coke USA1 (en) * -11-17 -07-08 Etter Roger G Selective Cracking and Coking of Undesirable Components in Coker Recycle and Gas Oils USB2 (en) -11-17 -11-18 Roger G. Etter System and method for introducing an additive into a coking process to improve quality and yields of coker products USA1 (en) * -11-17 -08-20 Etter Roger G System and Method of Introducing an Additive with a Unique Catalyst to a Coking Process USA1 (en) * -11-17 -06-11 Etter Roger G Addition of a Reactor Process to a Coking Process USB2 (en) -11-17 -06-26 Etter Roger G Addition of a reactor process to a coking process USB2 (en) -11-17 -01-29 Etter Roger G System and method of introducing an additive with a unique catalyst to a coking process USB2 (en) -11-17 -02-12 Roger G. Etter System and method for introducing an additive into a coking process to improve quality and yields of coker products USB2 (en) -11-17 -02-12 Roger G. Etter Catalytic cracking of undesirable components in a coking process USB2 (en) -11-17 -03-12 Roger G. Etter Addition of a reactor process to a coking process USA1 (en) * -11-17 -06-18 Etter Roger G System and Method for Introducing an Additive into a Coking Process to Improve Quality and Yields of Coker Products WOA3 (en) * -11-17 -07-17 Roger G Etter Selective cracking and coking of undesirable components in coker recycle and gas oils USB2 (en) -11-17 -03-03 Roger G. Etter Catalytic cracking of undesirable components in a coking process USB2 (en) -11-17 -04-21 Roger G. Etter System and method of introducing an additive with a unique catalyst to a coking process USB2 (en) -11-17 -10-06 Roger G. Etter Addition of a modified vapor line reactor process to a coking process USB2 (en) -11-17 -11-17 Roger G. Etter Reactions with undesirable components in a coking process EPA4 (en) * -02-14 -02-18 Etter Roger G System and method for introducing an additive to a coking process for improving the yields and properties of desired products WOA1 (en) * -01-29 -08-03 Sgl Carbon Se Catalytically active additives for coke origintiang from petrol or coal USB2 (en) -01-29 -01-26 Sgl Carbon Se Catalytically active additives for coke originating from petrol or coal

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