That looks OK.
The "trick" is to keep track of persons and time.
Working with:
CMR = 0.16 / 10,000 / day
population = 5 million
The proportion of the population that dies each day is:
p = 0.16 / 10,000 = 0.000016
So the number of deaths in the 5 million population is:
Daily deaths = p * 5,000,000 = 0.000016 * 5,000,000 = 80
There are about 365 days in a year (leap years have 366) so the number of deaths in a year is:
Annual deaths = 80 * 365 = 29,200
which is what you get.
A few things to consider ...
You have to bear in mind that your estimate of CMR may not be very accurate. This is often the case with mortality estimates made from surveys.
Since we are dealing with estimates we should account for uncertainty. An easy way of doing this is to do the calculation for the lower 95% confidence limit, the point estimate, and the upper 95% confidence limit for CMR.
Populations change over time. We have a start population (5 million). If population is growing at 2.41% per year (that's the 2017 estimate for 2017 for Rwanda) then after a year that 5 million becomes:
5,000,000 * (1 + 2.41 / 100) = 5,120,500
You can use the mid-point:
(5,000,000 + 5,120,500) / 2 = 5,060,250
Using this gives:
Annual deaths = 0.000016 * 5,060,250 * 365 = 29552
Assuming (your data will likely be different) the 95% CI for the CMR is [0.09,0.25] we have:
95% LCL = 0.000009 * 5,060,250 * 365 = 16,623
95% LCL = 0.000025 * 5,060,250 * 365 = 46,175
To be able to "safely say" I think you should (if possible) check your CMR, use 95% CIs to account for imprecision in the CMR estimate, and correct the population for growth. When reporting results you should use words like "estimated" and "predicted" and present the estimate with a 95% confidence interval. With what I have above I'd say something like " an estimated 29,552 (95% CI = 16,623 - 46,175) deaths predicted to occur over the year".
I hope this is of some use.