Petroleum Coke

Petroleum coke (often abbreviated pet coke or petcoke) is a carbonaceous solid delivered from oil refinery coker units or other cracking processes. Coking processes that can be employed for making petcoke include contact coking, fluid coking, flexicoking and delayed coking. Other coke has traditionally been delivered from coal.

There are two distinctive grades of Petroleum Coke, those are Calcinable or Green Petcoke or anode grade (low in sulfur and metals) and Fuel Grade Petcoke (high in sulfur and metals) . The raw coke directly out of the coker is often referred to as green coke. In this context, “green” means unprocessed. The further processing of green coke by calcining in a rotary kiln removes residual volatile hydrocarbons from the coke. The calcined petroleum coke can be further processed in an anode baking oven in order to produce anode coke of the desired shape and physical properties. The anodes are mainly used in the aluminium and steel industry.

Petcoke is over 90 percent carbon and emits 5 to 10 percent more carbon dioxide (CO₂) than coal on a per-unit-of-energy basis when it is burned. As petcoke has a higher energy content, petcoke emits between 30 and 80 percent more CO₂ than coal per unit of weight. The difference between coal and coke in CO₂ production per unit energy produced depends upon the moisture in the coal (increases the CO₂ per unit energy – heat of combustion) and volatile hydrocarbon in coal and coke (decrease the CO₂ per unit energy).

Types of petroleum coke:

There are at least four basic types of petroleum coke, namely, needle coke, honeycomb coke, sponge coke and shot coke. Different types of petroleum coke have different microstructures due to differences in operating variables and nature of feedstock. Significant differences are also to be observed in the properties of the different types of coke, particularly ash and volatile matter contents.

Needle coke, also called acicular coke, is a highly crystalline petroleum coke used in the production of electrodes for the steel and aluminium industries and is particularly valuable because the electrodes must be replaced regularly. Needle coke is produced exclusively from either FCC decant oil or coal tar pitch.

Honeycomb coke is an intermediate coke, with ellipsoidal pores that are uniformly distributed. Compared to needle coke, honeycomb coke has a lower coefficient of thermal expansion and a lower electrical conductivity.

Fuel grade coke: Fuel grade coke is classified as either sponge coke or shot coke morphology. While oil refiners have been producing coke for well over 100 years, the mechanisms that cause sponge coke or shot coke to form are not well understood and cannot be accurately predicted. In general, lower temperatures and higher pressures promote sponge coke formation. Additionally, the amount of heptane insolubles present, and fraction of light components in the coker feed contribute.

While its high heat and low ash content make it a decent fuel for power generation in coal fired boilers, petroleum coke is high in sulfur and low in volatile content, and this poses environmental (and technical) problems with its combustion. To meet current North American emissions standards, some form of sulfur capture is required, a common choice of sulfur recovering unit for burning petroleum coke is the SNOX Flue gas desulfurisation technology,[4] which is based on the well-known WSA Process. Fluidized bed combustion is commonly used to burn petroleum coke. Gasification is increasingly used with this feedstock (often using gasifiers placed in the refineries themselves).

Calcined petroleum coke: Calcined petroleum coke (CPC) is the product from calcining petroleum coke. This coke is the product of the coker unit in a crude oil refinery. The calcined petroleum coke is used to make anodes for the aluminium, steel and titanium smelting industry. The green coke must have sufficiently low metals content in order to be used as anode material. Green coke with this low metals content is referred to as anode grade coke. The green coke with too high metals content will not be calcined and is used for burning. This green coke is called fuel grade coke.

Desulfurization of petcoke: A high sulfur content in petcoke reduces its market value and may prevent its use as fuel due to restrictions on sulfur oxides emissions for environmental reasons. Methods have thus been proposed to reduce or eliminate the sulfur content of petcoke. Most of them involve the desorption of the inorganic sulfur present in the pores or surface of the coke, and the partition and removal of the organic sulfur attached to the aromatic carbon skeleton.

Potential petcoke desulfurization techniques can be classified as follows:

Solvent extraction

Chemical treatment

Thermal desulfurization

Desulfurization in an oxidizing atmosphere

Desulfurization in an atmosphere of sulfur-bearing gas

Desulfurization in an atmosphere of hydrocarbon gases

Hydrodesulfurization

Applications

Petcoke in cement production

Depending on the process there are 3 types of petcock: Green Delayed petcoke, Fluid petcoke and Flexicoke. There is use Green delayed petcoke in cement production but we can make mix with other types of petcoke

Benefits of Fuel grade Petcoke over coal

• Petcoke is a direct replacement of coal as a fuel but has higher calorific value (>7800Kcal/Kg as compared to 3500-4500 Kcal/Kg for coal).
• Petcoke is hydrophobic as compared to coal which is hydrophilic, thereby having edge during rainy season.
• Being solid fuel, Petcoke has low volatile matter thus no evaporation losses. Helps saving in transportation cost due to higher density compared to liquid fuels.
• Low ash content.