You could try though. Hang on to the advice line until a really sensible person comes on (usually the final option) then make a case. We got that far with a phone jockey but, for some reason, we forgot to fill in the application form. I see no reason that home educating children should NOT get EMA. We are a viable alternative to schools so we should we be treated as a lesser group. I bet if we tried a legal challenge we would win.
I just had a quick look at http://www.direct.gov.uk/en/EducationAndLearning/14To19/MoneyToLearn/EMA/DG_067575
and it says
"If you’re 16, 17 or 18 and studying in Northern Ireland, Scotland or Wales, you may be eligible for an Education Maintenance Allowance (EMA). You can get up to £30 a week to help you with the cost of learning.....
* Please note EMA in England has closed to new applicants.
EMA helpline (Wales): 0845 602 8845
EMA helpline (Northern Ireland): 0845 601 7646"