Coal is classified into different ranks based on carbon content and maturity.
The general order of coal rank is:
\[
\text{Peat} < \text{Lignite} < \text{Sub-bituminous} < \text{Bituminous} < \text{Anthracite}.
\]
As the rank of coal increases, carbon content generally increases.
Moisture and volatile matter generally decrease.
Anthracite is the highest rank of coal.
It has high fixed carbon content and low volatile matter.
Because of this, anthracite has a high calorific value compared with lignite, peat, and sub-bituminous coal.
Therefore, the coal having the highest calorific value among the given options is:
\[
\text{Anthracite}.
\]