これがひとり飲【の】みだと、自然【しぜん】と自分【じぶん】と向【む】き合【あ】う時間【じかん】ができる(source)
When you drink alone, you naturally have time to face yourself.
When I looked up the vocabulary in this sentence in WWWJDIC, the English definitions do not suggest a great difference in meaning between 【しぜん】 and 【じねん】:
自然 【しぜん】 (n) (1) nature; (adj-na,n) (2) natural; spontaneous; automatic; (adv,adv-to) (3) naturally; spontaneously; automatically; (P); 【じねん】 ; (n,adv) occurring naturally (without human influence)
On Goo, there are many more entries and examples with the reading 【しぜん】, but there is also this
じ‐ねん【自然】 の解説
1 (「に」や「と」を伴って副詞的に用いる)おのずからそうであること。ひとりでにそうなること。
Explanation of "ji-nen" (natural)
1 (used adverbially with "ni" or "to") To be naturally so. To be naturally so.
If I understand both the WWWJDIC and Goo entries, it seems that 自然 + と should produce this reading:
これがひとり飲【の】みだと、自然【じねん】と自分【じぶん】と向【む】き合【あ】う時間【じかん】ができる
In summary, if 自然 stands all by itself, it is read 【しぜん】, but if 自然 is followed by と, it is read 【じねん】. Is my understanding correct?