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but are limited to 25 similtaneous users.
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MSDE allows unlimited simultaneous users. However, it does employ throughput throttling when the number of concurrent users is more than 8. The additional users aren't rejected; their queries just run "slower."
Ref
http://techperformanceadvisor.com/doc/09585
The workaround for this limitation is to utilize batch type processing, and to have the users connect, run their queries, and disconnect. Although you'll have some additional time required to actually connect/disconnect from the server, the performance hit is relatively small. When you think about it, this type opf approach actually makes a lot of sense anyway. Most users pull data, then spend minutes or hours perusing it, before actually needing to access the database again.