The risk with step one of the Solvay process is the intense heat needed to break apart the calcium carbonate. According to this paper on calcium carbonate, an activation energy of 40.6 kcal/mole (about 1000 degrees centigrade) is required to begin decomposition. In addition, the release of free CO2 could be harmful, and the quicklime (CaO) is an irritant and releases heat in contact with water.
The risk with step two is the ammonia. Ammonia can be toxic and causes lung damage.
Step six makes a strong base solution of calcium hydroxide, so protective equipment should be worn while using the solution. Calcium hydroxide can cause skin irritation, burns, lung damage, and blindness.
I suggest wearing safety goggles during most of the process, and a mask if possible while working with ammonia and any of the lime products.
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