DE216747C - - Google Patents
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- Publication number
- DE216747C DE216747C DENDAT216747D DE216747DA DE216747C DE 216747 C DE216747 C DE 216747C DE NDAT216747 D DENDAT216747 D DE NDAT216747D DE 216747D A DE216747D A DE 216747DA DE 216747 C DE216747 C DE 216747C
- Authority
- DE
- Germany
- Prior art keywords
- calcium
- alkaline earth
- equation
- acid
- nitrite
- Prior art date
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- IOVCWXUNBOPUCH-UHFFFAOYSA-M nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 229910052500 inorganic mineral Chemical class 0.000 claims description 5
- 239000011707 mineral Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- MNWRMTPYEUYRSI-UHFFFAOYSA-N hydroxy(sulfo)sulfamic acid Chemical compound OS(=O)(=O)N(O)S(O)(=O)=O MNWRMTPYEUYRSI-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 150000002826 nitrites Chemical class 0.000 claims 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L cacl2 Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims 1
- CSABAZBYIWDIDE-UHFFFAOYSA-L sulfinato sulfite Chemical class [O-]S(=O)OS([O-])=O CSABAZBYIWDIDE-UHFFFAOYSA-L 0.000 claims 1
- 239000011734 sodium Substances 0.000 description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L Calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- GBAOBIBJACZTNA-UHFFFAOYSA-L Calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 235000010261 calcium sulphite Nutrition 0.000 description 6
- AONJRPXZCVADKF-UHFFFAOYSA-L calcium;dinitrite Chemical compound [Ca+2].[O-]N=O.[O-]N=O AONJRPXZCVADKF-UHFFFAOYSA-L 0.000 description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 6
- -1 alkali metal salts Chemical class 0.000 description 5
- 230000001264 neutralization Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VGYYSIDKAKXZEE-UHFFFAOYSA-L Hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000001175 calcium sulphate Substances 0.000 description 4
- 235000011132 calcium sulphate Nutrition 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000015450 Tilia cordata Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- LVGQIQHJMRUCRM-UHFFFAOYSA-L Calcium bisulfite Chemical compound [Ca+2].OS([O-])=O.OS([O-])=O LVGQIQHJMRUCRM-UHFFFAOYSA-L 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M Sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 235000010260 calcium hydrogen sulphite Nutrition 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- JXRVKYBCWUJJBP-UHFFFAOYSA-L calcium;hydrogen sulfate Chemical compound [Ca+2].OS([O-])(=O)=O.OS([O-])(=O)=O JXRVKYBCWUJJBP-UHFFFAOYSA-L 0.000 description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N Sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- HXPBDISMDAKVLJ-UHFFFAOYSA-N [Ca][H]NO Chemical compound [Ca][H]NO HXPBDISMDAKVLJ-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 229910000099 calcium monohydride Inorganic materials 0.000 description 1
- 239000004295 calcium sulphite Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- NXPHCVPFHOVZBC-UHFFFAOYSA-N hydroxylamine;sulfuric acid Chemical compound ON.OS(O)(=O)=O NXPHCVPFHOVZBC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
- C01B21/1409—Preparation
- C01B21/1427—Preparation by reduction of nitrogen oxides or nitrites with bisulfite or sulfur dioxide, e.g. by the Raschig process
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
M 216747 KLASSE 12 #. GRUPPEM 216747 CLASS 12 #. GROUP
Dr. F. RASCHIG in LUDWIGSHAFEN a. Rh.Dr. F. RASCHIG in LUDWIGSHAFEN a. Rh.
In der Patentschrift 41987 der Kl. 12 ist angegeben, wie man aus Alkalinitrit und Alkalibisulfit hydroxylamindisulfosaure Alkalisalze herstellt, die man dann in Hydroxylaminsulfat und Alkalisulfat spalten kann. Es hat sich später herausgestellt, daß die dort angegebene Reaktionsgleichung:In the patent specification 41987 Cl. 12 it is indicated how to make alkali metal salts from alkali metal nitrite and alkali metal bisulfite hydroxylamindisulfosaure which can then be split into hydroxylamine sulphate and alkali sulphate. It has later found out that the reaction equation given there:
1. NaNO2 + 2HSO3Na 1. NaNO 2 + 2HSO 3 Na
= HON : (SO3 Na)2 + NaOH = HON : (SO 3 Na) 2 + NaOH
nicht richtig ist, und daß, wenn man Nitrit und Bisülfit in den durch diese Gleichung angezeigten Mengenverhältnissen zusammenbringt, keine großen Ausbeuten an Hydroxylamin zu erreichen sind. . Denn in Wirklichkeit tritt bei dieser Reaktion, solange sie sich in der Kälte vollzieht, kein freies Alkali auf, sondern das entstehende Alkali sättigt ein Drittel des Bisulfits zu Monosulfit ab; der wirklich und quantitativ zwischen Nitrit und Bisulfit in der Kälte verlaufende Vorgang . entspricht daher der Gleichung:is not correct, and that if you put nitrite and bisulite in by this equation brings together indicated proportions, no large yields of hydroxylamine can be reached. . Because in reality this reaction occurs as long as it is in the cold takes place, no free alkali, but the resulting alkali saturates One third of the bisulfite turns into monosulfite; who really and quantitatively between nitrite and Bisulphite process that runs in the cold. therefore corresponds to the equation:
2. NaNO2 + 3HSO3Na 2. NaNO 2 + 3HSO 3 Na
= HON : (SO3Na)2 + Na2S O3 + H2 O. = HON : (SO 3 Na) 2 + Na 2 S O 3 + H 2 O.
Natürlich bedeutet der Verlauf der ReaktionOf course means the course of the reaction
nach dieser Gleichung einen Verlust von einem Drittel des Bisulfits, außerdem aber auch einen ■ Verlust an Hydroxylamin, insofern als, wenn man später durch Ansäuren hydrolysiert, sich schweflige Säure abspaltet und teilweise mit schon gebildetem Hydroxylamin zu wertloser Aminosulfosäure zusammentritt:according to this equation a loss of one Third of the bisulfite, but also a ■ loss of hydroxylamine, insofar as if later hydrolyzed by acidic acids, sulphurous acid is split off and partly with already formed hydroxylamine comes together to form worthless aminosulfonic acid:
NH2-OH + SO2= NH,NH 2 -OH + SO 2 = NH,
SO3H.SO 3 H.
Es wurde daher nach Mitteln gesucht, den Reaktionsverlauf möglichst vollständig im Sinne der Gleichung 1 zu gestalten, und gerunden (wie bereits in der Zeitschrift für angew. Chemie 17 [1904], S. 1400 und 1402 ausgeführt wurde), daß dies gelingt, wenn man durch nachträglichen Zusatz der gerade notwendigen Menge Mineralsäure (Salz- oder Schwefelsäure) das nach der Gleichung 1 frei werdende Alkali zu neutralem Chlorid oder Sulfat absättigt. Man hat also die Reagenzien in den durch die Gleichung: . :It was therefore searched for means, the course of the reaction as completely as possible in Shape the sense of equation 1, and round (As already stated in the Zeitschrift für angew. Chemie 17 [1904], pp. 1400 and 1402 was) that this succeeds if one adds the just necessary Amount of mineral acid (hydrochloric or sulfuric acid) the alkali released according to equation 1 saturates to neutral chloride or sulfate. So you have the reagents in the Equation:. :
3. NaNO2 + 2HSO3Na +-HCl 3. NaNO 2 + 2HSO 3 Na + -HCl
" = HON -.(SO3Na)2+ NaCl + H2O "= HON -. (SO 3 Na) 2 + NaCl + H 2 O
angegebenen Mengenverhältnissen aufeinander einwirken zu lassen und bekommt dann hydroxylamindisulfosaures Alkali in. so gut wie berechneter Menge.Let the specified proportions act on each other and then get hydroxylaminedisulfosaures Alkali in. As good as the calculated amount.
Man kann aber auch das frei werdende Alkali mit schwefliger Säure übersättigen und hat dann den weiteren Vorteil, daß man gerade so viel. Bisulfit erhalt, wie nötig ist, um ein zweites Molekül Nitrit in hydroxylamindisulfosaures Natrium überzuführen. Dabei wird, was für die Reindarstellung von. Hydroxylaminsulfat, die ja das Endziel ist, von großem Vorteil ist, das Disulfosalz frei von sonstigen Salzbeimengungen erhalten. Die Reaktion verläuft so gut wie quantitativ im Sinne. der Gleichung: .But you can also supersaturate the liberated alkali with sulphurous acid and then has the further advantage that you can do just that much. Bisulfite received as necessary to one to convert the second nitrite molecule into sodium hydroxylamine disulfate. In doing so, what for the pure representation of. Hydroxylamine sulfate, which is the ultimate goal, it is of great advantage that the disulfosalt is free from others Received salt admixtures. The reaction is as good as quantitative in the sense. the Equation:.
4. 2NaNO2 + 2HSO3 Na + 2 S O2 4.2NaNO 2 + 2HSO 3 Na + 2 S O 2
-. = 2HON : (SO3Na)2. -. = 2HON: (SO 3 Na) 2 .
Die Darstellung des hydroxylamindisulfo-. sauren Alkalisalzen nach Gleichung 4 ist an sich bereits durch die Angaben von Divers (Journ. of the Chem. Soc. 77 [1900], S. 681) nahegelegt..The representation of the hydroxylamindisulfo-. acidic alkali salts according to equation 4 is on already through the information from Divers (Journ. Of the Chem. Soc. 77 [1900], p. 681) suggested ..
Die Ausführung der in den Gleichungen 3 und 4 dargestellten Vorgänge gestaltet' sich so, daß man zuerst zum Nitrit allmählich das Bisulfit gibt, indem man die -Temperatur des Gemisches entweder durch Zugabe von Eis oder durch Kühlung von außen unter + 100C. hält. Dabei werden, wenn man nach Gleichung 3 arbeiten will, nur zwei Drittel und nach Gleichung 4 sogar nur ein Drittel des Nitrits in hydroxylamindisulfosaures Salz umgesetzt, und ein Drittel des Bisulfits geht in neutrales Sulfit über. Alsdann fügt man wieder unter Kühlung entweder die nach 3. berechnete Menge Mineralsäure zu, oder man leitet nach 4. die berechnete Menge von Schwefligsäuregas ein. Nur wenn man diese Reihenfolge innehält, kann man auf einen glatten Verlauf der Reaktion rechnen.The execution of the operations shown in equations 3 and 4, designed 'so that first gradually outputs the bisulfite to nitrite, by maintaining the -temperature of the mixture either by the addition of ice or external cooling below + 10 0 C. . If you want to work according to equation 3, only two thirds and according to equation 4 even only one third of the nitrite are converted into hydroxylamine disulphonic acid salt, and one third of the bisulphite is converted into neutral sulphite. Then either the amount of mineral acid calculated according to 3. is added again with cooling, or the amount of sulfurous acid gas calculated according to 4. is introduced. Only if you follow this sequence can you count on a smooth course of the reaction.
Wie vorauszusehen ist, kann man im NitritPredictably, you can in nitrite
oder im Bisulfit oder in beiden das Natrium durch Kalium oder andere Alkalimetalle ersetzen. Aber nicht vorauszusehen war, daß man an ihrer Stelle auch die Kalziumsalze der salpetrigen und schwefligen Säure anwenden kann. Denn, da neutrales Kalziumsulfit unlöslich ist, so muß sich, wenn man Kalziumnitrit und Kalziumbisulfit aufeinanderwirken läßt, neutrales Kalziumsulfit abscheiden und ein Teil des Kalziumnitrits in Lösung bleiben. Fügt man dann Mineralsäure hinzu oder leitet schweflige Säure ein, so war zu erwarten, daß diese eher auf das gelöste Kalziumnitrit als auf das ungelöste Kalziumsulfit einwirken, daß sich also freie, salpetrige Säure bilden und bald zersetzen würde. Nichts von dem tritt ein; das abgeschiedene Kalziumsulfit geht vielmehr in der zugesetzten Salzsäure oder schwefligen Säure in Lösung, und die Reaktion verläuft mit ■ Kalziumsalzen wie auch mit Strontium- und Bariumsalzen ebenso glatt und quantitativ wie mit den Alkalisalzen. or replace the sodium in bisulfite or both with potassium or other alkali metals. But it was not foreseeable that the calcium salts of nitrous and sulphurous acids would also be used in their place can. Because, since neutral calcium sulphite is insoluble, if one uses calcium nitrite and calcium bisulfite interacts, depositing neutral calcium sulfite and some of the calcium nitrite will remain in solution. Mineral acid is then added or passed sulphurous acid, it was to be expected that this was more due to the dissolved calcium nitrite than act on the undissolved calcium sulfite, so that free, nitrous acid is formed and would soon decompose. None of this occurs; the deposited calcium sulfite rather goes into solution in the added hydrochloric acid or sulphurous acid, and the Reaction proceeds with calcium salts as well as with strontium and barium salts smooth and quantitative as with the alkali salts.
Diese Ersetzbarkeit der Alkalisalze durch Kalksalze ist von großem technischen Wert; denn Kalziumnitrit ist durch Leiten der in der Hochspannungsflamme aus Luft entstehenden nitrosen Gase über wasserberieselten Kalk viel billiger herzustellen als Natriumnitrit, und Kalziumbisulfit ist das billigste aller Bisulfite, weil es — wie in der Zellstoff fabrikation allgemein üblich — unmittelbar aus .Röstgasen, Kalk und Wasser hergestellt wird. Außerdem vollzieht sich die Gewinnung von Hydroxylamin aus dem hydroxylamindisulfosauren. Kalzium besonders leicht, weil bei dessen Hydrolyse unlösliches Kalziumsulfat entsteht, das sich glatt von· dem leicht löslichen Hydroxylaminsulfat trennen läßt.This substitutability of the alkali salts by lime salts is of great technical value; because calcium nitrite is produced by conducting the air produced in the high voltage flame nitrous gases to be produced much cheaper than sodium nitrite using water-sprinkled lime, and calcium bisulfite is the cheapest of all bisulfites because it is - just like in pulp manufacture common practice - produced directly from roasting gases, lime and water will. In addition, the extraction of hydroxylamine takes place from the hydroxylamine disulfonic acid. Calcium is particularly easy because its hydrolysis produces insoluble calcium sulphate, which is easily removed from it soluble hydroxylamine sulfate can be separated.
1. Zu 1001 Kalziumnitritlösung (10 fach normal = 660 g Ca (N O%)2 im Liter) gibt man 4000 1 technische Kalziumbisülfitlösung (V2 n. '= 30,5 g CaH2(SO3J2 im Liter). Es scheidet sich neutrales Kalziumsulfit.als milchige· ■ Trübung aus. Nunmehr läßt man, während durch Kühlen von außen die Temperatur unter + 100C. gehalten wird, unter Umrühren 100 1 10 fach normale Schwefelsäure zufließen. Dabei löst sich das Kalziumsulfit auf, und an seine Stelle tritt Kalziumsulfat. Man filtriert von diesem ab und erhält eine klare Lösung von fast der berechneten Menge von hydroxylamindisulfosaurem Kalzium HON: (S O3) 2 · Ca, die man auf bekannte Weise durch Erwärmen in Hydroxylaminsulfat, Kalziumsulfat und Schwefelsäure spaltet und auf Hydroxylamin verarbeitet.1. To 100 liters of calcium nitrite solution (10 times normal = 660 g Ca (NO % ) 2 per liter) add 4000 liters of technical calcium bisulfate solution (V 2 n. '= 30.5 g CaH 2 (SO 3 I 2 per liter) Neutral calcium sulfite separates out as a milky cloudiness. Now, while the temperature is kept below + 10 ° C. by external cooling, 100 1 10 times normal sulfuric acid is allowed to flow in with stirring Calcium sulphate is used instead of calcium sulphate, which is filtered off and a clear solution of almost the calculated amount of calcium hydroxylamine disulphonate HON: (SO 3 ) 2 · Ca is obtained, which is split and split in a known manner by heating in hydroxylamine sulphate, calcium sulphate and sulfuric acid Hydroxylamine processed.
2. Zu 1001 Kalziumnitritlösung gibt man '-20001 Kalziumbisülfitlösung, kühlt wieder von außen und leitet 64 kg schweflige Säure ein. Dabei löst sich das anfänglich ausgefallene Kalziumsulfit wieder auf, und man hat zum Schluß eine klare Lösung von fast der berechneten Menge reinen hydroxylamindisulfosauren Kalziums.2. Add '-20001 to 1001 calcium nitrite solution Calcium bisulfate solution, cools again from the outside and introduces 64 kg of sulphurous acid. The initially precipitated calcium sulfite dissolves again, and you have to In the end a clear solution of almost the calculated amount of pure hydroxylamine disulphonic acids Calcium.
Claims (2)
= 2HON : (SO3J2- Ca+ CaCl2+ 2H2O ne. Ca (NOJ 2 + 2 Ca (HS O 3 ) 2 + 2 H Cl
= 2HON : (SO 3 I 2 - Ca + CaCl 2 + 2H 2 O ne .
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE756961C (en) * | 1939-04-30 | 1952-08-21 | Ig Farbenindustrie Ag | Production of hydroxylammonium sulfate by reducing nitrites with the help of bisulfites and / or sulphurous acid |
-
0
- DE DENDAT216747D patent/DE216747C/de active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE756961C (en) * | 1939-04-30 | 1952-08-21 | Ig Farbenindustrie Ag | Production of hydroxylammonium sulfate by reducing nitrites with the help of bisulfites and / or sulphurous acid |
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