ST_SetSkew — Sets the georeference X and Y skew (or rotation parameter). If only one is passed in, sets X and Y to the same value.
raster ST_SetSkew(raster  rast, float8  skewxy);
raster ST_SetSkew(raster  rast, float8  skewx, float8  skewy);
Sets the georeference X and Y skew (or rotation parameter). If only one is passed in, sets X and Y to the same value. Refer to World File for more details.
-- Example 1
UPDATE dummy_rast SET rast = ST_SetSkew(rast,1,2) WHERE rid = 1;
SELECT rid, ST_SkewX(rast) As skewx, ST_SkewY(rast) As skewy,
    ST_GeoReference(rast) as georef
FROM dummy_rast WHERE rid = 1;
rid | skewx | skewy |    georef
----+-------+-------+--------------
  1 |     1 |     2 | 2.0000000000
                    : 2.0000000000
                    : 1.0000000000
                    : 3.0000000000
                    : 0.5000000000
                    : 0.5000000000
                
-- Example 2 set both to same number:
UPDATE dummy_rast SET rast = ST_SetSkew(rast,0) WHERE rid = 1;
SELECT rid, ST_SkewX(rast) As skewx, ST_SkewY(rast) As skewy,
    ST_GeoReference(rast) as georef
FROM dummy_rast WHERE rid = 1;
 rid | skewx | skewy |    georef
-----+-------+-------+--------------
   1 |     0 |     0 | 2.0000000000
                     : 0.0000000000
                     : 0.0000000000
                     : 3.0000000000
                     : 0.5000000000
                     : 0.5000000000