解:设$EC = x,$$AB = 2a。$
在$\triangle ABC$中,$∠ACB = 90^\circ ,$$∠BAC = 30^\circ ,$则$BC = a,$$AC = \sqrt {3}a。$
因为$\triangle ABD$是等边三角形,
所以$AD = AB = 2a,$$∠DAB = 60^\circ ,$
故$∠EAC = ∠DAB + ∠BAC = 90^\circ 。$
由于折叠使点$D$与$C$重合,
所以$DE = EC = x,$则$AE = AD - DE = 2a - x。$
在$\text{Rt}\triangle AEC$中,由勾股定理得$(2a - x)^2 + (\sqrt {3}a)^2 = x^2,$
解得$x = \frac {7}{4}a,$
所以$AE = 2a - \frac {7}{4}a = \frac {1}{4}a。$
因此,$\sin ∠ACE = \frac {AE}{EC} = \frac {\frac {1}{4}a}{\frac {7}{4}a} = \frac {1}{7}。$