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Adjust oven racks to upper-middle and lower-middle positions and heat oven to 450 degrees.
Combine chili powder, 2 teaspoons salt, and 1 teaspoon pepper in small bowl.
Toss cauliflower with oil and 2 teaspoons spice mixture on rimmed baking sheet until well coated, then arrange in single layer.
Line second rimmed baking sheet with foil.
Place salmon, skin side down, on foil-lined sheet and brush tops of fillets with honey.
Sprinkle remaining 3 teaspoons spice mixture evenly over salmon.
Roast cauliflower on lower rack until well browned and tender, about 25 minutes.
After about 10 minutes, place salmon on upper rack and roast until center is still translucent when checked with tip of paring knife and registers 125 degrees (for medium-rare), about 12 minutes.
Sprinkle cauliflower with cilantro.
Serve cauliflower with salmon and lime wedges.