Patent GB-988356-A (GB)
Title: Improvements in or relating to permonosulphates and the preparation thereof
Inventor: LEAVER JOHN PHILIP
IPC: C11D3/39
Filed: 1960-08-23
Abstract: Permonosulphates have the general formula Kx(NH4)5-x(HSO5)2(HSO4) (SO4) where 2.5<x<4.5.  The reaction is effected by forming an aqueous solution or paste containing potassium and ammonium cations in the ratio of from 1:1 to 9:1 and permonosulphate, bisulphate, and sulphate anions in the ratio 2:1:1 and thereafter either crystallising out the product or evaporating the solution or paste to dryness.  Specifically oleum may be reacted with concentrated hydrogen peroxide followed by either partial neutralization with an ammonium or potassium based alkali or partial neutralization with a mixture of these alkalis, after which sufficient ammonium and/or potassium sulphate and bisulphate are added to give the final product.  Alternatively potassium pyrosulphate, which may be prepared by reacting potassium sulphate with liquid sulphur trioxide, is reacted with concentrated hydrogen peroxide to give a mixture of the permonosulphate and bisulphate, and if a sufficient excess of potassium sulphate is initially used to give the desired sulphate content, then the final product is obtained by adding a suitable amount of an ammonium based alkali.  Alternatively potassium permonosulphate may be passed down a column of strong acid cation exchange resin in the ammonium form, the appropriate amount of bisulphate and sulphate being added to the product.  Alternatively the necessary sulphates may be added to permonosulphuric acid together with the required amount of alkalis.  Permonosulphate compositions thus formed are useful as bleaching agents and may be obtained in a dry free flowing state with an active oxygen content of 5% or more.  Boron compounds, e.g. boric acid and oxide, the alkali metal borates and perborates, and alkali metal carbonates, sesquicarbonates, phosphates, and silicates may be present in the dry product as extenders.  Example (1) refers to 65% oleum being added to 86% /w/w hydrogen peroxide below 5 DEG  C., after which a 35% solution of potassium carbonate was added until the pH was 1.5.  The reaction mixture was then vacuum concentrated at 50 DEG  C. to obtain a wet solid when sufficient ammonium sulphate and bisulphate was added so that the mole ratio of HSO5-: HSO4-: SO42- became 2:1:1. After thorough mixing the product was heated in an air current at 50 DEG  C. for 24 hours.  Example (3) refers to dried potassium sulphate reacted under dry carbon tetrachloride with liquid sulphur trioxide and 95% hydrogen peroxide, below 40 DEG  C.  The filtered product was then mixed with ammonium carbonate and water to form a smooth paste which was dried under vacuum at 50 DEG  C. for 48 hours.  Example (5) refers to anhydrous potassium permonosulphate being mixed with potassium bisulphate, ammonium sulphate and water to form a smooth paste which was dried in air at 50 DEG  C. for 24 hours.ALSO:Bleaching compositions may contain mono-persulphates of the general formula. Kx(NH4)5-x (HSO5)2(HSO4)(SO4) where 2.5 < x < 4.5, and 1-12% of boron compounds preferably boric acid and oxide and the alkali metal borates and perborates.  Alkali metal carbonates, sesquicarbonates, phosphates, sulphates and silicates may also be present.