Any natural number is either of the form 3k or 3k – 1 or 3k +1.
Sum of two numbers will be divisible by 3 if and only if either both are of the form 3k or one is of the form 3k - 1 and other is of the form 3k + 1.
This can be done in 4C2 + 4C1 x 4C1 = 6 + 16 = 22 ways