The maximum volunteers you can send to Spain IIRC is seven, limited by their province count when you have enough divisions to send seven of them.
According to the HOI4 wiki
Influencing ongoing civil wars:
The number of divisions that can be deployed is 1 division for every 20 active divisions (rounded down, so with 19 or fewer no Volunteers can be sent). For example 176 active divisions means 8 divisions where 181 would mean 9 divisions could be deployed as volunteers. Note that a division with only 1 battalion in it counts as much as one that has 25. The minimum of 20 divisions with 1 infantry will enable 1 volunteer division to be sent. The sending country must have at least 30 divisions to send volunteers at all. Added to this is one division per 20 provinces in the destination country.
EDIT: The HOI4 description above is supported by the HOI4 defines file
VOLUNTEERS_PER_TARGET_PROVINCE = 0.05, -- Each province owned by the target country contributes this amount of volunteers to the limit.
VOLUNTEERS_PER_COUNTRY_ARMY = 0.05, -- Each army unit owned by the source country contributes this amount of volunteers to the limit.
VOLUNTEERS_DIVISIONS_REQUIRED = 30, -- This many divisons are required for the country to be able to send volunteers.
EDIT: Republican Spain and Nationalist Spain corrected.
At the start of the Spanish Civil War,
Republican Nationalist Spain has a total of 135 provinces while
Nationalist Republican Spain has a total of 110 provinces. When control of provinces increase, then the ability to send additional volunteers should also increase per the wiki.
Republican Nationalist Spain province summary -
| State ID | State Name | Province Count |
|---|
| 166 | Western Aragón | 11 |
| 169 | Sevilla | 14 |
| 170 | Extremadura | 17 |
| 171 | Galicia | 13 |
| 172 | Navarra | 5 |
| 174 | León | 13 |
| 176 | Burgos | 13 |
| 177 | Islas Baleares | 3 |
| 178 | Islas Canarias | 1 |
| 290 | Spanish Africa | 6 |
| 297 | Equatorial Guinea | 2 |
| 699 | Rio de Oro | 6 |
| 788 | Salamanca | 6 |
| 789 | Córdoba | 12 |
| 791 | Valladolid | 13 |
Republican Nationalist Spain Totals | Total States = 15 | Total Provinces = 135 |
Nationalist Republican Spain province summary -
| State ID | State Name | Province Count |
|---|
| 41 | Madrid | 13 |
| 165 | Cataluña | 14 |
| 167 | Valencia | 10 |
| 168 | Murcia | 11 |
| 173 | Granada | 11 |
| 175 | Ciudad Real | 10 |
| 790 | Asturias | 9 |
| 792 | País Vasco | 4 |
| 793 | Guadalajara | 14 |
| 794 | Eastern Aragón | 14 |
Nationalist Republican Spain Totals | Total States = 10 | Total Provinces = 110 |