A hexagonal ring with the radius of N consists of 6 straight lines, each with length N - see my extremely crude example below :) For N=2:

The arrows cover 2 hexes each.
I assume you have some functions which give you the neighbouring tile in a specific direction, like north(), southeast() etc. So your algorithm, in pseudocode, should be something like this:
var point = startingPoint.north(N)
for i = 0..N-1:
result.add(point)
point = point.southeast(1);
for i = 0..N-1:
result.add(point)
point = point.south(1);
for i = 0..N-1:
result.add(point)
point = point.southwest(1);
for i = 0..N-1:
result.add(point)
point = point.northwest(1);
for i = 0..N-1:
result.add(point)
point = point.north(1);
for i = 0..N-1:
result.add(point)
point = point.northeast(1);
Note that this should work also for edge cases N=1, returning 6 tiles, and N=0 returning an empty set.
I know the code isn't perfect :) There is some redundancy here. In my projects using regularly tiled maps (hexagonal or otherwise) I usually have an enum "Direction", which allows me to do this more smoothly:
var point = startingPoint.inDir(N, Direction.North)
var dir = Direction.SouthEast.
for d = 0..Direction.count():
for i = 0..N-1:
result.add(point)
point = point.inDir(1, dir);
dir = nextDirection(dir);