22 times a day if you only count the minute and hour hands overlapping. The approximate times are listed below. (For the precise times, see the related question.)

2 times a day if you only count when all three hands overlap. This occurs at midnight and noon.

am

12:00
1:05
2:11
3:16
4:22
5:27
6:33
7:38
8:44
9:49
10:55

pm

12:00
1:05
2:11
3:16
4:22
5:27
6:33
7:38
8:44
9:49
10:55

A really simple way to see this is to imagine that the two hands are racing each other around a track. Every time the minute hand 'laps' the hour hand, we have the overlaps we want.

So, we can say that the number of laps completed by the minute hand every T hours, Lm = T laps. Since there are 12hours in a full rotation of the hour hand, that hand only rotates Lh = T/12 laps.

In order for the first 'lapping' to occur, the minute hand must do one more lap than the hour hand: Lm = Lh +1, so we get T = T/12 + 1 and that tells us that the first overlap happens after T = (12/11) hours. Similarly, the 2nd lapping will occur when Lm = Lh + 2.

In general, the 'Nth' lapping will occur when Lm = Lh +N, which means every N*(12/11) hours (for N = 0,1,2,3...). In other words, it will happen approximately every 1hr5mins27secs, starting at 00:00. In 24hours, this occurs a total of 24/(12/11) = 22 times.