[EDITED to include other prime powers and give the list of
27 maximal solutions]
The maximum is $42$, attained in $27$ ways (listed below); there are
$566$ runners-up with $41$, and then $6747$ with $40$,
another $52078$ with $39$, "etc.".
The counts are obtained by dynamical programming. We simplify
the computation by checking that the $a_i$ can include no multiple
of a prime power greater than $27$, and if multiples of
$11$, $13$, $16$, $17$, $19$, $25$, or $27$ appear then
they must combine to remove that factor from the denominator,
which can only be done in
$46,\phantom. 9,\phantom. 7,\phantom., 1, \phantom.
2,\phantom. 1,\phantom. 1$ ways respectively
(the last four are $(17,34,85)$, $(19,57,76)$ or $(38,76,95)$,
$(50,75)$, and $(25,54)$ respectively; $23$ does not occur).
That brings the denominator down to $D = 2^3 3^2 5 \phantom. 7 = 2520$,
small enough to make a table of the number of times each pair of integers
arises as $(n, D\sum_{i=1}^n 1/a_i)$ with $\sum_i 1/a_i \leq 1$,
and at the end extract the counts for $(n,D)$.
This approach does not immediately give the list of $27$ maximal solutions,
but it can be modified to compute this list instead: at each stage,
instead of recording the number of representations of each fraction,
keep track of the representation(s) with the largest number of terms.
The list of $42$'s is follows, in lexicographical order; each uses the
prime 17, and all use 99 except for two which have $\max_i a_i = 96$.
[12, 17, 21, 22, 24, 26, 27, 30, 32, 33, 34, 35, 36, 38, 39, 40, 42, 44, 48, 50, 52, 54, 55, 56, 60, 63, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[13, 17, 18, 21, 22, 24, 26, 27, 32, 33, 34, 35, 38, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 60, 63, 65, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[13, 17, 18, 22, 24, 26, 27, 28, 32, 33, 34, 35, 36, 38, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 60, 65, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[13, 17, 20, 21, 22, 24, 26, 27, 32, 33, 34, 35, 36, 38, 40, 42, 44, 48, 50, 52, 54, 55, 56, 60, 63, 65, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[13, 17, 20, 21, 22, 24, 26, 30, 32, 33, 34, 35, 36, 38, 40, 42, 44, 45, 48, 50, 52, 55, 56, 60, 63, 65, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[13, 17, 20, 21, 22, 26, 27, 30, 32, 33, 34, 35, 36, 38, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 60, 63, 65, 66, 70, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[13, 17, 20, 21, 24, 26, 27, 30, 32, 33, 34, 35, 36, 38, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 60, 63, 65, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96]
[13, 17, 20, 22, 24, 26, 27, 28, 30, 32, 33, 34, 35, 38, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 60, 65, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[14, 17, 21, 22, 24, 26, 27, 28, 30, 32, 33, 34, 35, 36, 38, 39, 40, 44, 48, 50, 52, 54, 55, 56, 60, 63, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[15, 17, 18, 21, 22, 24, 26, 27, 32, 33, 34, 35, 38, 39, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 60, 63, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[15, 17, 18, 22, 24, 26, 27, 28, 32, 33, 34, 35, 36, 38, 39, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 60, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[15, 17, 20, 21, 22, 24, 26, 27, 32, 33, 34, 35, 36, 38, 39, 40, 42, 44, 48, 50, 52, 54, 55, 56, 60, 63, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[15, 17, 20, 21, 22, 24, 26, 30, 32, 33, 34, 35, 36, 38, 39, 40, 42, 44, 45, 48, 50, 52, 55, 56, 60, 63, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[15, 17, 20, 21, 22, 26, 27, 30, 32, 33, 34, 35, 36, 38, 39, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 60, 63, 66, 70, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[15, 17, 20, 21, 24, 26, 27, 30, 32, 33, 34, 35, 36, 38, 39, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 60, 63, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96]
[15, 17, 20, 22, 24, 26, 27, 28, 30, 32, 33, 34, 35, 38, 39, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 60, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[17, 18, 19, 21, 22, 24, 26, 27, 30, 32, 33, 34, 35, 39, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 57, 60, 63, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 96, 99]
[17, 18, 19, 22, 24, 26, 27, 28, 30, 32, 33, 34, 35, 36, 39, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 57, 60, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 96, 99]
[17, 18, 20, 21, 22, 24, 26, 27, 28, 30, 32, 33, 34, 38, 39, 40, 44, 45, 48, 50, 52, 54, 55, 56, 60, 63, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[17, 18, 20, 21, 22, 24, 26, 27, 30, 32, 33, 34, 35, 38, 39, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 63, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[17, 18, 20, 21, 22, 24, 26, 27, 30, 32, 33, 34, 35, 38, 39, 40, 42, 44, 45, 48, 50, 54, 55, 56, 60, 63, 65, 66, 70, 72, 75, 76, 77, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[17, 18, 20, 21, 22, 24, 26, 27, 30, 32, 33, 34, 36, 38, 39, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 60, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[17, 18, 20, 21, 22, 24, 26, 27, 32, 33, 34, 35, 36, 38, 39, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 60, 63, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 91, 95, 96, 99]
[17, 18, 20, 22, 24, 26, 27, 28, 30, 32, 33, 34, 35, 36, 38, 39, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[17, 18, 20, 22, 24, 26, 27, 28, 30, 32, 33, 34, 35, 36, 38, 39, 40, 42, 44, 45, 48, 50, 54, 55, 56, 60, 65, 66, 70, 72, 75, 76, 77, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[17, 18, 21, 22, 24, 26, 27, 28, 30, 32, 33, 34, 35, 36, 38, 39, 40, 42, 44, 45, 48, 50, 52, 54, 55, 56, 60, 66, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 95, 96, 99]
[17, 19, 20, 21, 22, 24, 26, 27, 30, 32, 33, 34, 35, 36, 39, 40, 42, 44, 48, 50, 52, 54, 55, 56, 57, 60, 63, 66, 70, 72, 75, 76, 77, 78, 80, 84, 85, 88, 90, 91, 96, 99]