Observation of Gravitional waves by LIGO from binary black hole merger
Neutron stars are less massive but larger than black holes. The frequency of the gravitational waves is due to the orbital period of the objects as they spiral together. A neutron star merger would have a different orbital speed, so the frequency would be different and lower. It would rise at a different rate. The signal from neutron stars is also much weaker, so couldn't be detected from the same range.

Prior to the detection of the signal, numerical simulations of merging black holes of various sizes were done, so the theoretical shape of the waveform expected from the merger of black holes (and neutron stars) was known. It was possible from this theoretical work to estimate the mass of the two black holes taking part in the merger by matching the observed signal to a theoretical one. You can see the theoretical signal for black holes with 36 and 29 in the diagrams labelled as "numerical relativity"