When the environment variable TCL_LIBRARY is defined, Tcl's default initialization sequence takes its value to be a file system directory in which the init.tcl file should be sought first. In a proper Tcl installation, use of this environment variable should not be needed. The main use for it is in Tcl's own build and test procedures to direct initialization of a freshly built Tcl program so that it can be tested before it is installed. Other than that, it should be considered a tool for "last-resort" workarounds of broken installations, not a tool for routine use.
If what you are trying to do is set an environment variable to point to directories containing other Tcl packages, check TCLLIBPATH.
See also magic names and tclvars.