What types of industry positions favor PhD over a masters?
I am currently employed in the biotech industry. Hopefully this is helpful but it may all just be obvious:

Concerning research industry positions, jobs are generally classified as PhD (scientist) or non-PhD (research assistant/associate). For scientists positions, sometimes someone without a PhD will be considered if they have significant experience - e.g. Masters plus 5-8 years, Bachelors plus 10+ years. However, PhDs are generally favored over non-PhDs for outside hires. For research asst/assoc positions, non-PhDs are favored over PhD holders, and many companies have policies that prohibit hiring PhDs. 

Concerning non-research industry positions, holding a PhD will give you an edge over BS/MS holders, but you have to compete with other specialized degrees. For business developement and upper management positions, you'd have to compete with MBA holders (along with internal hires from research/scientific management). For legal positions, you'd compete with JDs and certified patent agents. For project management, there are certifications as well. 

If you were to hold MBA/JD/additional certification AND a PhD, you would be extremely marketable for these types of positions. It's a lot of work to add something like that on after finishing a PhD program, but companies often love to have PhDs on staff in those types of positions - but generally you need to have the other qualifications as well. 

Edit: Also, the best people to talk to are professors from your current/old department who are on any company's board of directors. They will know exactly what kind of people a company wants to hire, and will be able to tell you how to target your job search, or what kind of experience/credentials matter most.