bc 41 chars
I guess this kind of problems is what bc was invented for:
for(n=read();n>1;){if(n%2)n=n*6+2;n/=2;n}
Test:
bc1 -q collatz.bc
21
64
32
16
8
4
2
1
Proper code:
for(n=read();n>1;){if(n%2)n=n*3+1else n/=2;print n,"\n"}
bc handles numbers with up to INT_MAX digits
Edit: The Wikipedia article mentions this conjecture has been checked for all values up to 20x258 (aprox. 5.76e18). This program:
c=0;for(n=2^20000+1;n>1;){if(n%2)n=n*6+2;n/=2;c+=1};n;c
tests 220,000+1 (aprox. 3.98e6,020) in 68 seconds, 144,404 cycles.