US1010177A - Process for the manufacture of alkali earth salts of hydroxylamin disulfonic acid. - Google Patents

Process for the manufacture of alkali earth salts of hydroxylamin disulfonic acid. Download PDF

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US1010177A
US1010177A US49746509A US1909497465A US1010177A US 1010177 A US1010177 A US 1010177A US 49746509 A US49746509 A US 49746509A US 1909497465 A US1909497465 A US 1909497465A US 1010177 A US1010177 A US 1010177A
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hydroxylamin
calcium
manufacture
alkali
disulfonic acid
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US49746509A
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Friedrich Raschig
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/082Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/087Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
    • C01B21/093Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
    • C01B21/096Amidosulfonic acid; Salts thereof

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  • the nascent alkali may I be supersaturated with sulfurous acid
  • Example II To 100 liters of calcium-nitrite solution are added 2000 liters of cal cium bisulfite solution, the liquid is cooled from outside, and 64:,kilos of sulfuric acid are admitted. The previously precipitated calcium-sulfite is thereby re-dissolved, and the final result is a clear solution of almost the calculated quantity of the pure calciumsalt of hydroxylamin-disulfonic acid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

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To all whom itmayconcem." g
Be it known thatI, Famnmon Rasome, manufacturing chemist, a subject of the German Emperor, residing at Ludwigshafen-on-the-Rhine,'. Germany, have mvented certain new and useful Improve: I
- ments in Processes for the Manufacture t Alkali Earth Salts-of Hydroxylamin Disulfonic Acid, of which. the following is aspecificatio It is known, the action of alkali nitrite on alkali bisulfite hydroxylamindisulfonic acid, alkali-salts may be produced, which will easily split up into hydroxylamin sulfate' and alkali sulfate. It has'b'ee'n L NaNO +2HSO Na= I HON(SO,Na),+NaOH which was believed to represent the chemical reaction for this process, is not correct, and that it is not possible to obtain a large yield of hydroxylamin by vbringing nitrite and bisulfite together in the proportions indicated by this equation. For in reality no free alkali results from this reaction, as long as it takes place in the cold, instead of which the nascent alkali saturates a third of the bisulfite by forming monosulfite; the reaction taking place between nitrite and bisulfite in the cold may, however, be reprethe following equation also as sented by regards quantities:
. 5 2. NaNO +3HSO Na= The reaction according to this equation implies, of course, the loss of a third of the 'which-partly unites with already formed hydroxylainin to form worthless aminosulfonic acid.
It has already been recognized, that thev reaction maybe caused to run as indicated by equation I. by subsequently adding ust the necessary quantity of mineral acid bydrochloric or sulfuric acid) for saturatingthe alkali, which is set free, so as to .form
some extent .7 7/ 1900, page 681.
I mam of mar; mat. 'P t f 1* w, 35,-: Application filed as :21, 1909. serial' wo. 497,405.;
l jl e utral chloridlor' sulfatesit is *i.
necessary, that the reagents shouldact fipon which case'an alkali salt of hydroxyl'amin *disulfonic acid is obtained in practically-the {calculated quantity.
As an alternative, the nascent alkali may I be supersaturated with sulfurous acid,
thereby obtaining the further advantage 0 obtaining justenough bisulfite to trans- .form asecond molecule of nitrite intosodium hydroxylamin-disulfonate. By this process the disulfo-salt is obtained free from any other salts, which is a great advantage for the manufacture of hydroxyl-' amin-sulfate in a pure condition, which, of course, is the ultimate object.
a The reaction takesplace almost exactly (also as regards quantities) in the sense of the equation:
2110M se m I each other in the proportions-indicated by'ili Ethe equation:
hydroxylamin-disulfonic acid according to er 8e, has been suggested to y the statements of Divers 1n the Journal of the O'hemz'oal, Society equation (4) The sodium 1n the nitrite or.in the bisulfite orv in both may, of course, be replaced by potassium or other alkali metals, but it could not beexpected that in lieu of the same the calcium salts of nitrous and sulfurous acid may be employed. Neutral; calcium sulfite being insoluble, the interaction of cal- 'cium nitrite and calcium-sulfitemust cause neutral calcium-sulfite to be separated out, while a portion of the calcium-nitrite remains in solution. If afterward a mineral 1 acid is added or sulfurous acid .is introduced, it was probable that the latte'rwould act on the dissolved calcium-nitrite, rather dissolves in the added hydrochloric or sulfurous acid, and the reaction with calcium-- salts, as well as with stroniumand bariumsalts runs as smoothly and uantitatively as which liquid may be split in the known manwith alkali-salts. This possibility of replacing the alkali-salts with lime-salts is of great commercial importance, because calcium nitrite may be produced (by conducting the nitrous gases arising fromair in the flame of electric high-tension lam s over lime kept moist byrunning water much more cheaply than sodium-nitrite, and calciumbisulfite is the cheapest of all bisulfites, because it is produced, as usual in the manufacture of cellulose, directly from sulfurous gases (obtained by roasting pyrites etc.), lime and water. Moreover, the manufacture of hydroxylamin from the calcium salts of I hydroxylamin-disulfonic acid is.
very easy, because by its hydrolysis insoluble calcium-sulfate is produced, which can be readily separated from the easily soluble hydroxylamin-sulfate.
Example I: To 100 liters of calcium-nitrite solution (ten fold normal=660 grams of Ca(NO per liter) are added 4000 liters of commercial calcium-bisulfite-solution (%n=30.5 grams of .CaH,(SO per liter). Neutral calcium'sulfite separates out and forms a milky liquid. 100 liters of 10 fold normal'sulfuric acid is now caused to flow into the liquid, while stirring and, keeping the temperature below 10 C. by' external cooling. The calcium sulfite enters into solution and is replaced by calcium-sul fate. Thisis separated from the liquid by filtration, thereby obtaining a clear liquid containing almost the calculated quantity of calcium hydroxylamin-rdisulfonatener by heating, into hv droxylamin-sulfate, calcium sulfate and sul onic acid. a
Example II: To 100 liters of calcium-nitrite solution are added 2000 liters of cal cium bisulfite solution, the liquid is cooled from outside, and 64:,kilos of sulfuric acid are admitted. The previously precipitated calcium-sulfite is thereby re-dissolved, and the final result is a clear solution of almost the calculated quantity of the pure calciumsalt of hydroxylamin-disulfonic acid.
What I claim is The process for the manufacture of alkali earth salts of hydroxylamin-disulionic acid, which consists in causing a nitrite of an alkali earth, a bisulfiteof an alkali earth, and sulfurous acid to act upon one another in the cold, in the proportions indicated by the equation nitrite and bisulfite being brought together first and the sulfurous acid added afterward,
substantially as described.
In testimony whereof I have hereunto set my hand in presence of two subscribing witnesses.
FRIEDRICH RASCHIGV Witnesses: 1
ROBERT GERLAGH, A. T. MI'rroN.
US49746509A 1909-05-21 1909-05-21 Process for the manufacture of alkali earth salts of hydroxylamin disulfonic acid. Expired - Lifetime US1010177A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2555667A (en) * 1948-11-01 1951-06-05 Directie Staatsmijnen Nl Procedures for the production of hydroxylamine compounds
US2677599A (en) * 1950-02-22 1954-05-04 Directie Staatsmijnen Nl Manufacture of hydroxylamine sulfonates
US2785954A (en) * 1949-08-27 1957-03-19 Inventa Ag Process for the production of hydroxylamine sulfate solutions
US2897052A (en) * 1952-06-20 1959-07-28 Teuber Hans Joachim Method for preparing stable potassium nitroso disulfonate
US4086327A (en) * 1975-10-17 1978-04-25 Agency Of Industrial Science & Technology Process for removing nitrogen oxides from gaseous mixtures
US4203959A (en) * 1978-03-15 1980-05-20 Hoechst Aktiengesellschaft Process for the preparation of nitrous oxide

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2555667A (en) * 1948-11-01 1951-06-05 Directie Staatsmijnen Nl Procedures for the production of hydroxylamine compounds
US2785954A (en) * 1949-08-27 1957-03-19 Inventa Ag Process for the production of hydroxylamine sulfate solutions
US2677599A (en) * 1950-02-22 1954-05-04 Directie Staatsmijnen Nl Manufacture of hydroxylamine sulfonates
US2897052A (en) * 1952-06-20 1959-07-28 Teuber Hans Joachim Method for preparing stable potassium nitroso disulfonate
US4086327A (en) * 1975-10-17 1978-04-25 Agency Of Industrial Science & Technology Process for removing nitrogen oxides from gaseous mixtures
US4203959A (en) * 1978-03-15 1980-05-20 Hoechst Aktiengesellschaft Process for the preparation of nitrous oxide

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