Unless I'm missing something, this has an equal sign in the second row that's aligned with the first, and an equal sign in the math tip. Is this what you wanted?
$$\begin{aligned}
\frac{a}{b}&=\frac{a}{b}\\
&=\mathtip{\frac{a}{b}}{=hi}
\end{aligned}$$
Or did you mean you don't want the equals in the second line, but the expression should line up? If so, this hack will get you very close:
$$\begin{aligned}
\frac{a}{b}&=\frac{a}{b}\\
&\hspace{13.5pt} \mathtip{\frac{a}{b}}{=hi}
\end{aligned}$$
The fractions line up nicely:
Regards