Process of producing a distilled butanediol product of high quality in high yield

Abstract

In accordance with the present invention, there is provided herein a process for producing a distilled butanediol product of high quality in high yield. The process begins with a crude butynediol solution which is made by an ethynylation reaction between aqueous formaldehyde and acetylene. The crude butynediol solution contains at least a metallic ion, usually sodium, magnesium and/or calcium ion, and an anion, particularly, formate ion, and usually also acetate ion, and often silicic acids and silicic acid salts, as impurities, and unreacted formaldehyde. After substantially stripping the solution of the unreacted formaldehyde, the stripped solution is treated with ion exchange resin, including at least a cation exchange resin to remove one or more of the metallic ions present, and as an anion exchange resin to remove the formate ion, and the acetate ion and silicic acids and silicic acid salts, should they be present in the solution. The deionized butynediol solution then is hydrogenated to form a purified butanediol solution, which is fractionally distilled while maintaining the residue thereof in a fluid state to provide a butanediol product of high quality in high yield.

I claim: 
     
       1. In the process of producing distilled butanediol product from an aqueous butynediol solution which contains metallic and formate ions, which process comprises hydrogenating said butynediol to butanediol and distilling said butanediol, the improvement which is characterized by: treating said butynediol solution prior to said hydrogenation treatment with a cationic exchange resin to remove said metallic ion, and an anionic resin to remove formate ion, then hydrogenating and distilling the butanediol at .[.about 160°-200° C..]. .Iadd.a pot temperature of 110°-200° C. at a subatmospheric pressure of 40 mm Hg or less .Iaddend.to obtain a distilled butanediol product .[.having a purity of at least 99.7%,.]. in a yield of at least 93%, and a residue which is fluid and pumpable at the distillation temperature for recycling or disposal thereof.   
     
     
       2. A process according to claim 1 wherein said metallic ion is at least one of the group consisting of magnesium, sodium and calcium. 
     
     
       3. A process according to claim 1 wherein said impurities include acetate ion which is removed along with said formate ion. 
     
     
       4. A process according to claim 1 wherein said cation exchange resin is a strong acid type resin. 
     
     
       5. A process according to claim 1 wherein said anion exchange resin is either a weak or a strong base type resin. 
     
     
       6. A process according to claim 1 wherein said butynediol solution is passed successively through a strong acid cation exchange resin bed and a weak base anion exchange resin bed. 
     
     
       7. A process according to claim 1 wherein said butynediol solution is passed successively through a strong acid cation exchange resin bed and a strong base anion exchange resin bed. 
     
     
       8. A process according to claim 7 wherein said resins are contained in a mixed bed. 
     
     
       9. A process according to claim 1 wherein said anion exchange resin includes both weak and strong base type resins. 
     
     
       10. A process according to claim 9 wherein said resins are contained in separate beds. 
     
     
       11. A process according to claim 9 wherein said butynediol solution is passed successively through a strong acid cation and a weak base anion, and a strong base anion exchange resin bed. 
     
     
       12. A process according to claim 1 wherein said strong acid cation exchange resin is a sulfonated polystyrene type resin. 
     
     
       13. A process according to claim 1 wherein said weak anion exchange resin is a tertiary amine polystyrenedivinylbenzene type resin. 
     
     
       14. A process according to claim 9 wherein said strong base anion exchange resin is a polyammonium hydroxide-polystyrene-divinylbenzene type resin. 
     
     
       15. A process according to claim 1 wherein said impurities also includes silicic acids and silicic acid salts, and said anion exchange resin includes at least a strong base resin to remove such impurities.