A production method of 4-A molecular sieve is disclosed, wherein raw materials comprise sodium silicate solution which is obtained through resolving intermediate product sodium silicate solution or product white carbon black in alkaline solution or sodium silicate solution with low modulus and low concentration in the manufacturing process of silicon dioxde which is extracted by adopting the coal ash alkali-soluble method, intermediate product sodium aluminate solution or product aluminum hydroxide, and aluminum oxide solution which are obtained in the production process of aluminum oxide through the coal ash desiliconisation sintering method, sodium-hydroxide and water, the components satisfy the following mole proportion conditions: SiO2: Al2O3=1.5-2.5, Na2O: SiO2=1-10, and filled water H2O: Na2O=10-80, the raw materials are mixed, are stirred into glue, and are added with guiding agent, the temperature rises to 70-100 DEG C, the mixed solution is stationarily placed for crystallization, then the soultion is led out, filtered and washed until the pH value is smaller than 11, and finally the solution is dried in 70-80 DEG C for abtaining 4-A molecular sieve.