US812124A - Formaldehyde hydrosulfite and process of making same. - Google Patents

Description

I the formaldehyde compound oi sodium bihv manufacture o certain Cl: mounds obtained. by the action of aldehyde, on'hydrosulfites,'

sulfite, to which he assigns the formula:

UNITED sTA rns PATENT OFFICE.

EMILE A. RJURNEAUX OF NEW 'EGRK. N. Y, ASSIGNOR TO HERMAN A.

METZ, OF NEW YORK. i. Y.

FORMALDEHYDE HYnRosuLFwe 41%!) PROCESS OF MAKING SAME.

Specification of Letters Patent.

Application filed 'nmh 30,1so5. 3451531 in, 262,865",

Patented Feb. 6, 1966.

To all whom it may oolwern: I 3

Be it known that I, EM LE A. Foumgm 1374, a citizen of the United States, residing at New'York, in the county of New York end York, have invented certain eases of ii eking Same, of which the folhm-ing is a specification.

In the Unified States Patent No. 769,593

Louis Descam s describe-1 and claims the and more piirtieularly the body obtained by the action of formaldehyde on sodium hydro- On December 1, 1904, Messrs. IAH'.'BRU- mann, G. Thesmur, and Jos. Frossard pub lished a ieper in the Revue Germ-ale rles Meiieres 0 om'ntes in which they prove that the compound described by Mr. Desemnps is not a chemical individual, but merely a mechanical mixture in more or less molecular proportions of two bodies: the formaldehyde compound of sodium bisulfite,

NaHSO UH O i i1 0,

and the body termed by them the formaldell de compound of" sodium bihydrosulfite, Na. SO CH O+2H Q which result from Bernthsens sodium hydrosulfite by the following reaction:

Nais20i+2omo+m0= mnsotcnios Nausotonio.

Of these two bodies, which constitute the material eom'mereielly known as hyraldite or h dresulfite NF, the fornmldehyde sodium ihydrosulfito is the active constituent, whereas the formaldehyde eompmlnd of sodium bisuhite is merely an unavoidable and undesirable impurity.

The method described by Messrs. Baumenu, Thesmar, and Frossard for producing drosulfite is so lengthy and onerous us to he of little or no commercial value.

If it were possible econor'nieally to manufacture the active constituent of hydrosulfite l NF or hymldite in a pure state, free froni the iofnmldellyde compound of sodium liisulfite,

this would constitute {Livery material improvement and progress over the present methods, because it )osscsses almost twine the reducing power oi the -zil)m'e-nmne(l hydriiisuliites and is materially more stable, owing to its purity.

To avoid confusion of terms, the salts corresponding to the general formula M,s,o (Me indicating any univelent metal) heretofore considered as derived from the hypo theiia: hydrosulfurous acid of Bernthsen, H 8 0 are herein termed hydrosullites in m-eordnnce with common usage and the salts derived from the hy )ot-hetie hydrosulfurous acid of Sehuet-zenlierger, H 89 are hcreinafterreferrcd to as hydrosuliites, (S).

I have found :1 incl hod by which formaldehyde compounds of lgdrosuliites (S) can he prepared eeonomieolly and in a state of great unity and have also discovered a" new and heretofore unknown basic zin furlnuldehyde hydrosulfitc (S) which is instrumenlnl in our- I'ying out myim'ention. This salt separates quentitativcl 1 es :1. white erystelline precipitate upon addition of the required umount of a suitable alkaline salt, )refcrnbly sodium carbonate, to a solution 0 zinc hydrosullite which has been trentcd with fornialdelwde until'it ceases to reduce it solution of indigo sulfonic acid at ordinary temperature. This new basic zine-salt is characterized by its great reducing power, one part reducing in the neighbor-howl of one and one-half parts of pure indigo intho form of indigo sulfonii: acid and by its great stability, as it can be dried on the weter imth in the open air without decomposing, which is entirely unprecedented in hydrosulfite compounds and quite unexpected. The actual composition of lhis eom )ound has not yet been ascertained with absolute exactness, but it is believed in correspend in the formuln: ZI1S() ll ().ll and to be formed by the followingrcip'tion:

eznsgo. +401 120+ NazU0n+til ii )5 2ZnS()2.UlhOJLOi-QNM1503.01MH-( YOQ.

By treating this zine-salt. with e solutlou of sodium carbonate the eorrespondingsoiliuni sslt is formed qunntitetively and can be sepsruted from its solution by ereporation. It appears to be identical with the remarkably stable.

roduct, NaHSO,.CH 0+ 211,0, described yMessrs. Baumann, T 0 mar, and Frossard.

If the basic zinc-salt is treated with an acid, the free acid is liberated and can be used for the preparation of other salts by the well-known methods. This free acid is also Its solution decomposes only when heated for some time, when sulfurous acid is given off and a yellow oil separates, which becomes crystalline on cooling. The basic zinc-salt may be prepared by various methods, a satisfactory rocedure being asfollows: One hundred an twenty parts zinc-dust are pasted up with three hundred parts boiling water and added to nine hun-. dred parts cold water in a lead-lined kettle provided witha stirrer and the amount of sulfurous acid introduced, which is just suflicient to dissolve the total amount of zincapproximately two hundred parts. The temperature during this whole process should not exceed 45 centigrade. The resulting solution of zinc hydrosulfite is then cooled to a temperature not exceeding 30 centigrade, filtered to separate it from zinc sulfite and other impurities, and formaldehyde added until the product no longer reduces a solution of indigo sulfonic acid at ordinary temperature. The amount of formaldehyde reuired is about two hundred and fifty arts. "hen add a highly-concentrated solution of sodium carbonate until the basic zinc-salt is completely preci itated and the mother-liquors, which shou d still be slightly acid to litmus no longer or but very slightly, reduce indigo sulfonlc acid at atemperature exceeding 4. centigrade. The amount of sodium car. bonate required is about eighty arts. The white crystalline precipitate is t en filtered and washed in the usual way anddried; It can be applied as such for reducing and dis charging purposes or for the manufacture of other formaldehyde liydrosulfites (S) in the manner above described.

The formation of this zinc-salt appears to be a secondary reaction. There is at first recipitation of a heavy flocculent white ody, which soon decomposes, giving off carbon dioxid and separating the crystalline basic zinc-salt.

The basic zinc-salt may be prepared by other methods-as, for instance, by reaction of zinc-dust and a suitable acid on sodium bisulfite formaldehyde under suitable conditions, as described in my co )ending application, Serial No. 259,469, filed May 8, 1905.

l. The process of making basic zinc formaldehyde h *drosulfite (S) which consists in reacting wit I a suitable alkali compound upon a solution of zinc hydrosulfite treated with formaldehyde, substantially as described.

2. As a new article of manufacture, basic zinc formaldehyde hydrosulfite (S) occurring as a white crystalline precipitate, capable of being dried on the water-bath in the open air without decomposing, and one )art capable of reducing about one and one-half parts of pure indigo in the form of indigo sulfonic acid, substantially as described.

3. The process of making alkali formaldehyde hydrosulfitc (S) which consists in reacting with a suitable alkali'compound upon the basic zinc formaldehyde hydrosulfite (S), substantially as described.

4. Theproeess of making sodium formaldehyde hydrosulfite (S) whlch consists in reacting with sodium carbonate upon basic zinc formaldehyde hydrosulfite (S), substantially as described.

5. The process which consists in reacting with a suitable alkali compound upon a s o lp tion of zinc hydrosulfite treated with formal dehyde, thereb forming basic zinc formaldehyde h 'drosul ite (S), andithen reacting with a suitable alkali compound upon. said basic zinc formaldehyde hydrosulfite (S) to form alkali formaldehyde hydrosulfite (S), substantially as described.

In testimony whereof I affix my signature in presence of two witnesses.

EMILE A. FOURNEAUX.

Witnesses H. S. NEIMAN, PAUL LoasER.