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(12) Patent Application Publication (10) Pub. No.: US 2002/0179493 A1 Etter (43) Pub US 2002O179493A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2002/0179493 A1 Etter (43) Pub. Date: Dec. 5, 2002 (54) PRODUCTION AND USE OF A PREMIUM (52) U.S. Cl. .................... 208/131; 208/108; 208/111.01; FUEL GRADE PETROLEUM COKE 208/142; 208/143; 208/144; 208/145 (75) Inventor: Roger G. Etter, Cardington, OH (US) Correspondence Address: (57) ABSTRACT STANDLEY & GLCREST LLP 495 METRO PLACE SOUTH A premium "fuel-grade' petroleum coke is produced by SUTE 210 modifying petroleum coking technology. Coking process DUBLIN, OH 43017 (US) parameters are controlled to consistently produce petroleum coke within a predetermined range for Volatile combustible (73) Assignee: Environmental & Energy Enterprises, material (VCM) content. The invention includes a process of LLC producing a coke fuel, the method comprising Steps: (a) obtaining a coke precursor material derived from crude oil (21) Appl. No.: 10/027,677 and having a volatile organic component; and (b) Subjecting the coke precursor material to a thermal cracking proceSS for (22) Filed: Dec. 20, 2001 Sufficient time and at Sufficient temperature and under Suf ficient preSSure So as to produce a coke product having Related U.S. Application Data volatile combustible materials (VCMs) present in an amount (63) Continuation-in-part of application No. 09/556,132, in the range of from about 13% to about 50% by weight. filed on Apr. 21, 2000. Continuation-in-part of appli Most preferably, the volatile combustible materials in the coke product typically may be in the range of from about cation No. 09/763,282, filed on Feb. 20, 2001. 15% to about 30% by weight. The present invention also (30) Foreign Application Priority Data provides methods for (1) altering the coke crystalline struc ture, (2) improving the quality of the coke VCM, and (3) Aug. 20, 1999 (US)............................. PCT/US99/19091 reducing the concentration of coke contaminants. Fuels made from the inventive coke product and methods of Publication Classification producing energy through the combustion of Such fuels are also included. Finally, novel environmental control tech (51) Int. Cl." ............................ C10G 9/00; C10G 47/00; niques are developed to take optimal advantage of the C10G 45/00 unique characteristics of this upgraded petroleum coke. Patent Application Publication Dec. 5, 2002 Sheet 1 of 12 US 2002/0179493 A1 S. & S. CO CN s N CN %. QO CN CO y S w C © 2. 1N C-Dé QC w r CN O se s y S Patent Application Publication Dec. 5, 2002 Sheet 4 of 12 US 2002/0179493 A1 s S s s s i & É >- & 5 c É Dec. 5, 2002 Sheet 5 of 12 003 20? Patent Application Publication Dec. 5, 2002. Sheet 6 of 12 US 2002/0179493 A1 30 e - Co l, H (9 A N\/- (104 Patent Application Publication Dec. 5, 2002. Sheet 7 of 12 US 2002/0179493 A1 & 3 Oc tli Oe Patent Application Publication Dec. 5, 2002. Sheet 8 of 12 US 2002/0179493 A1 l, loe Patent Application Publication Dec. 5, 2002. Sheet 9 of 12 US 2002/0179493 A1 Patent Application Publication Dec. 5, 2002 Sheet 10 of 12 US 2002/0179493 A1 FIG - 7A Patent Application Publication Dec. 5, 2002 Sheet 11 of 12 US 2002/0179493 A1 S s s S. N S. N w CO Patent Application Publication Dec. 5, 2002 Sheet 12 of 12 US 2002/0179493 A1 FIG - 4 Negligible Rediction 'i' 2\ WX XXXXXXXXX &X S&N Activity Temperature N N Operation 1 XXXXXXXXXX X. Operation 2 W/ Operation 3 US 2002/0179493 A1 Dec. 5, 2002 PRODUCTION AND USE OF A PREMUM FUEL “theoretical” because these materials coke or crack from GRADE PETROLEUM COKE thermal decomposition before they reach Such temperatures. 0001. This application is a continuation-in-part of U.S. 0011 Coking feedstocks normally consist of refinery application Ser. No. 09/556,132, filed Apr. 21, 2000, which process Streams which cannot economically be further dis claimed the benefit of International Application No. PCT/ tilled, catalytically cracked, or otherwise processed to make US99/19091, filed Aug. 20, 1999, which claimed the benefit fuel-grade blend Streams. Typically, these materials are not of U.S. application Ser. No. 09/137,283, filed Aug. 20, 1998, Suitable for catalytic operations because of catalyst fouling now U.S. Pat. No. 6,168,709. and/or deactivation by ash and metals. Common coking feedstocks include atmospheric distillation residuum, 0002 This application is also a continuation-in-part of Vacuum distillation residuum, catalytic cracker residual oils, U.S. application Ser. No. 09/763,282, filed Feb. 20, 2001, hydrocracker residual oils, and residual oils from other which claimed the benefit of International Application No. refinery units. Consequently, coking feedstockS vary Sub PCT/US99/19091, filed Aug. 20, 1999, which claimed the Stantially among refineries. Their composition and quantity benefit of U.S. application Ser. No. 09/137,283, filed Aug. primarily depend on (1) the input crude oil blend, (2) 20, 1998, now U.S. Pat. No. 6,168,709. refinery processing equipment, and (3) the optimized opera tion plan for any particular refinery. In addition, contaminant 0003. The entirety of each of the above priority docu compounds, which occur naturally in the crude oil, generally ments is hereby incorporated by reference. have relatively high boiling points and relatively complex molecular Structures. Consequently, these contaminant com BACKGROUND OF THE INVENTION pounds, containing Sulfur and heavy metals, tend to con 0004) 1. Field of the Invention centrate in these residua. Many of the worst process Streams in the refinery have become coker feedstock, and their 0005. This invention relates generally to the field of contaminants usually end up in the petroleum coke by petroleum coking processes, and more Specifically to modi product. For this reason, the coking processes have often fications of petroleum coking processes for the production of been labeled as the "garbage can' of the refinery. a premium-quality, "fuel-grade’ petroleum coke. This invention also relates generally to the use of this new 0012. There are three major types of modern coking formulation of petroleum coke for the production of energy, processes currently used in refineries to convert the heavy and more Specifically to modifications in conventional, crude oil fractions into lighter hydrocarbons and petroleum Solid-fuel furnaces and environmental control Systems to coke: Delayed Coking, Fluid CokinTM, and Flexicoking TM. take optimal advantage of its unique properties. In all three of these coking processes, the petroleum coke is considered a by-product that is tolerated in the interest of 0006 2. Description of Prior Art more complete conversion of refinery residues to lighter hydrocarbon compounds, referred to as “cracked liquids' 0007 Since initial efforts to refine crude oil in the U.S. throughout this discussion. These cracked liquids range during the late 1800s, the Search for an appropriate use for from pentanes to complex hydrocarbons with boiling ranges the heaviest fractions of crude oil (i.e. the “bottom of the typically between 350 and 950 F. The heavier cracked barrel') has been a perplexing problem. Initially, many liquids (e.g. gas oils) are commonly used as feedstocks for refineries received little to no value from the heaviest further refinery processing that transforms them into trans fractions of crude oil. Some were noted to Simply discard the portation fuel blend StockS. “bottom of the barrel.” Over time, some of the heavy crude oil fractions were used in asphalt products and residual fuel 0013 The delayed coking process has evolved with many oils. However, the demand for these products was not improvements since the mid-1930s. Essentially, delayed Sufficient to consume increasing production. coking is a Semi-continuous process in which the heavy feedstock is heated to a high temperature (between 900 F. 0008 AS demand for transportation fuels (e.g. gasoline, and 1000 F) and transferred to large coking drums. Suffi diesel, and aviation fuels) increased in the early 1900s, cient residence time is provided in the coking drums to allow thermal cracking processes were developed to convert the the thermal cracking and coking reactions to proceed to heavy crude oil fractions into lighter products. These refin completion. The heavy residua feed is thermally cracked in ery processes evolved into the modern coking processes that the drum to produce lighter hydrocarbons and Solid, petro predominate the technology currently used to upgrade the leum coke. One of the initial patents for this technology heaviest fractions of the crude oil. These processes typically (U.S. Pat. No. 1,831,719) discloses “The hot vapor mixture reduce the quantity of heavy oil fractions, but Still produce from the vapor phase cracking operation is, with advantage, unwanted by-products (e.g. petroleum coke) with marginal introduced into the coking receptacle before its temperature value. falls below 950 F., or better 1050 F., and usually it is, with advantage, introduced into the coking receptacle at the 0009. A. Production of Petroleum Coke; Coking Pro maximum possible temperature.” The "maximum possible CCSSCS temperature' in the coke drum favors the cracking of the 0010. In general, modern coking processes employ high heavy residua, but is limited by the initiation of coking in the Severity, thermal decomposition (or "cracking”) to maxi heater and downstream feed lines, as well as excessive mize the conversion of Very heavy, low-value residuum cracking of hydrocarbon vapors to gases (butane and feeds to lower boiling hydrocarbon products. Coker feed lighter). When other operational variables are held constant, StockS typically consist of non-volatile, asphaltic and aro the "maximum possible temperature' normally minimizes matic materials with “theoretical' boiling points exceeding the Volatile material remaining in the petroleum coke by 1000 F.
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