DE392280C - Process for the extraction of sulfur and sulfur dioxide from calcium sulfate - Google Patents

Process for the extraction of sulfur and sulfur dioxide from calcium sulfate

Info

Publication number
DE392280C
DE392280C DEA30442D DEA0030442D DE392280C DE 392280 C DE392280 C DE 392280C DE A30442 D DEA30442 D DE A30442D DE A0030442 D DEA0030442 D DE A0030442D DE 392280 C DE392280 C DE 392280C
Authority
DE
Germany
Prior art keywords
calcium sulfate
sulfur
reducing
extraction
gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
DEA30442D
Other languages
German (de)
Inventor
Dr Arthur Bibergeil
Dr Sigmar Muench
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Aktiengesellschaft fuer Anilinfabrikation GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aktiengesellschaft fuer Anilinfabrikation GmbH filed Critical Aktiengesellschaft fuer Anilinfabrikation GmbH
Priority to DEA30442D priority Critical patent/DE392280C/en
Priority to DEA33984D priority patent/DE413376C/en
Application granted granted Critical
Publication of DE392280C publication Critical patent/DE392280C/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/48—Sulfur dioxide; Sulfurous acid
    • C01B17/50—Preparation of sulfur dioxide
    • C01B17/501—Preparation of sulfur dioxide by reduction of sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/06—Preparation of sulfur; Purification from non-gaseous sulfides or materials containing such sulfides, e.g. ores

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Description

Verfahren zur Gewinnung von Schwefel und Schwefeldioxyd aus Kalziumsulfat. über die Zerlegung von Kalziumsulfat existieren in der Literatur sehr widerspre- chende Angaben. So geben H o f n1 a n n un.d 11 o s t o w i t s c 1i (Chemisches "Lentralblat, 1911, I, S. 1737) an, daß Gips durch Glühen in einer Atmosphäre von Kohlenoxyd, XVasser- stoff oder Wasserstoffgas zu Schwefelk.alziuln reduziert wird, welches geringe Mengen von 1,Zalzitunoxv(1 enthalten kann. Dieser Vor- gang verläuft also bei Anwendung von @@-<1sserstoff nach folgender Gleichung: I. Ca SO, +4H_=CaS+4H@0. Andererseits soll nach den Beobachtungen von Glasenapp und Schott Gips bei i4oo bis i-E3o@ flach Gleichung II zerfallen. Nach Hofmann und Mostowitsch soll die- ser Zerfall schon bei iooo° eintreten und bei 120o^ sehr stark werden: II. Ca SO,-Ca0+SO'.+O. Geln.'#iß der französischen Patentschrift -l'700-,2 wird Kalziumsulfat durch Erhitzen lnit einer zur vollkommenen Verbrennung ausreichenden Gaslnischunr in schweflige Säure und Kalk zerlegt, oder aber man führt den Gips mit Hilfe einer reduzierenden hlanlme in Ca S über, das dann mit Hilfe eileer oxydierenden Flamme in S0._, und Ca O übergeführt wird. Die Erfinderin stellt nun fest, daß Gips weder bei iooo bis 120o' noch bei 140o bis 143o" und selbst bei erheblich darüberliegen- den 'Temperaturen nicht nennenswert nach Gleichung II zerfällt. Dagegen wurde die überraschende Beobach- tung gelllacht, daß 111a11 I`a1ziumsulfat 111 weitgehendstem Maße, unter Umständen so- gar quantitativ, in halziumox@-(1 und schwef- lige Säure verwandeln kann, wenn ,nan das Kalziulnstilfat vorzugsweise hei Temperaturen oberhalb looo' abwechselnd mit Reduktions-- lnitteln, wie Kohlenoxyd, Wasserstoff oder Wasserstoffgas, und mit Oxvdationslnitteln, wie Sauerstoff oder Luft, behandelt. Dabei verläuft die Reaktion in der reduzierenden Periode nach der Gleichung: 11I. Ca SO, +H_-Ca0+SO_+H=O. Es wurde jedoch gefunden, (laß die Ein- wirkung der Reduktionsmittel auf den Gips nur sehr kurze Zeit, z. B. bei Anwendung l an Leuchtgas nur etwa ';`_ -Minute nach Gleichung 1L'1. verläuft, während nach dieser "Zeit der weitere --erlauf der Reaktion wahr- #,cheinlich teilweise im Sinne der Gleichung 1 vor sich (yelit. Unterbricht inan daher nach kurzer Zeit das reduzierende Blasen in der @@'eise, daß nian kurze Zeit die -lasse mit einem ox-,Idierenden Gasgemisch, behandelt, so kann niali (las reduzierende Blasen mit gleicbein Erfolge *iederholen, so daß es ge- liegt, einen gleichmäßigen Strom von hochprozentigem SO, in der l@edttl@tionsperiode zti erhalten.Process for the extraction of sulfur and sulfur dioxide from calcium sulfate. on the decomposition of calcium sulfate exist in the literature very contradicting appropriate information. So give H of n1 ann und.d 11 ostowitsc 1i (chemical "Lentralblat, 1911, I, p. 1737) that plaster of paris by glowing in an atmosphere of carbon dioxide, water or hydrogen gas to form sulfuric salts is reduced, which is small amounts of 1, Zalzitunoxv (may contain 1. This pro gang runs when using @@ - <hydrogen according to the following equation: I. Ca SO, + 4H_ = CaS + 4H @ 0. On the other hand, according to the observations of Glasenapp and Schott Gips at i4oo decay until i-E3o @ flat equation II. To Hofmann and Mostowitsch should This decay can already occur at iooo ° and at 120o ^ become very strong: II. Ca SO, -Ca0 + SO '. + O. Gels. '' In the French patent specification -l'700-, 2 becomes calcium sulfate by heating With one for complete combustion Sufficient gas mixture in sulphurous Acid and lime decomposed, or else one leads the plaster of paris with the help of a reducing hlanlme in Ca S over, which then with the help eileer oxidizing flame in S0._, and Ca O is convicted. The inventor now finds that plaster of paris neither at iooo to 120o 'nor at 140o to 143o "and even with considerably higher the temperatures are not noticeable Equation II breaks down. In contrast, the surprising observation it was laughing that 111a11 I`a1ziumsulfat 111 to the greatest possible extent, possibly also even quantitative, in halziumox @ - (1 and sulfur oily acid can transform, if, nan that Calculus nilphate preferably at high temperatures above looo 'alternating with reduction-- agents such as carbon dioxide, hydrogen or Hydrogen gas, and with oxidizing agents, like oxygen or air. Included the reaction proceeds in the reducing Period according to the equation: 11I. Ca SO, + H_-Ca0 + SO_ + H = O. It was found, however, (let the entrance effect of reducing agents on the plaster of paris only for a very short time, e.g. B. when using l of coal gas only about '; `_ minutes after Equation 1L'1. runs while after this "Time of the further course of the reaction true- #, apparently partly in the sense of equation 1 in front of him (yelit. interrupts inan after short time the reducing bubbles in the @@ 'eise that nian let the -lassen with for a short time an oxidizing gas mixture, treated so can niali (las reducing bubbles with repeat successes so that it is a steady stream of high percentage SO, zti received in the l @ edttl @ tion period.

Zlan kann das Verfahren praktisch in der Weise durchführen, daß inan als reduzierendes Gas Leuchtgas, Generatorgas. Wassergas n. dgl., entweder für sich oder mit Verbrennungsgasen verdünnt, anwendet. 'Man heizt zunächst den Ofeninhalt in beliebiger Weise auf Temperaturen über tooo° und läßt das reduzierende Gas einwirken. Nach kurzer Zeit, z. B. bei Anwendung von Wassergas nach % bis i Minute, wird das reduzierende Blasen unterbrochen und Luft oder Sauerstoff eingeführt. Hierauf wird wieder reduzierend geblasen und so fort ini schnellen Wechsel, wobei das entstehende S02 Gas auf geeignete Weise aus dem Ofen entfernt wird. Der Rückstand stellt Ca O dar.Zlan can practically carry out the procedure in such a way that inan as reducing gas, luminous gas, generator gas. Water gas n. The like, either by itself or diluted with combustion gases. 'First you heat the contents of the oven in any way to temperatures above tooo ° and allows the reducing gas to act. After a short time, e.g. B. when using water gas after% to i minute, that will reducing bubbles interrupted and air or oxygen introduced. Then will blown again in a reducing manner and so on in rapid change, whereby the resulting S02 gas is removed from the furnace in a suitable manner. The residue represents approx O dar.

Statt ein geeignetes Gas in den Ofen einzublasen, kann man es im Ofen direkt erzeugen, indem man z. B. Kalziumsulfat finit Koks oder anderem kohlehaltigen Material mischt und Luft, gegebenenfalls unter Zusatz von Wasserdampf, einbläst. Der Reduktionsprozeß und der oxydierende Teil des Verfahrens werden dann in der Weise erzielt, daß man die Menge der einzublasenden Luft der jeweils gewünschten Wirkung anpaßt. Man kann auch die beiden Ausführungsarten in der Weise kombinieren, daß man das Kalzitttnsulfat mit weniger Koks bzw. kohlehaltigen Materialien mischt, als zur Durchführung des Prozesses erforderlich ist, und außerdem noch die erforderliche Menge Generatorgas o. dgl. einbläst. Die abwechselnd reduzierende und oxydierende Wirkung wird wiederuni durch die abwechselnd größere und geringere Menge der einzublasenden Luft bewirkt.Instead of blowing a suitable gas into the furnace, you can put it in the furnace generate directly by z. B. calcium sulfate finite coke or other carbonaceous Mixes the material and blows in air, if necessary with the addition of steam. The reduction process and the oxidizing part of the process are then in the Way achieved that the amount of air to be blown is desired in each case Effect adjusts. You can also combine the two types of execution in such a way that that the calcium sulfate is mixed with less coke or carbonaceous materials, than is necessary to carry out the process, and also the necessary Amount of generator gas or the like. The alternating reducing and oxidizing The effect is again achieved by the alternating larger and smaller quantities of the injected Air causes.

Schließlich kann man auch den Prozeß in von außen heizbaren Retorten durchführen, «-obei man die reduzierenden und oxydierenden Gase getrennt nacheinander über d'as Kalziumsulfat führt.Finally, the process can also be carried out in retorts that can be heated from the outside carry out, «- the reducing and oxidizing gases being separated one after the other over d'as calcium sulfate leads.

Claims (1)

PATENT-AxSPRUCH: Verfahren zur Gewinnung von Schwefel und schwefliger Säure aus Kalziumsulfat, dadurch gekennzeichnet, daß man bei Temperaturen von zweckmäßig oberhalb iooo` Kalziunisulfat in schnellem Wechsel mit reduzierend und oxydierend wirkenden Mitteln behandelt, wobei eine Beheizung des Kalziumsulfats durch flammenlose Oberflächenverbrenntmg ausgenommen ist.PATENT-AxSPRUCH: Process for the production of sulfur and sulphurous Acid from calcium sulfate, characterized in that it is expedient at temperatures of above 100% calcium sulfate in rapid alternation with reducing and oxidizing acting agents treated, with a heating of the calcium sulfate by flameless Surface combustion is excluded.
DEA30442D 1918-04-16 1918-04-16 Process for the extraction of sulfur and sulfur dioxide from calcium sulfate Expired DE392280C (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DEA30442D DE392280C (en) 1918-04-16 1918-04-16 Process for the extraction of sulfur and sulfur dioxide from calcium sulfate
DEA33984D DE413376C (en) 1918-04-16 1920-08-27 Production of sulfur and sulfur dioxide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA30442D DE392280C (en) 1918-04-16 1918-04-16 Process for the extraction of sulfur and sulfur dioxide from calcium sulfate

Publications (1)

Publication Number Publication Date
DE392280C true DE392280C (en) 1924-04-15

Family

ID=6927224

Family Applications (1)

Application Number Title Priority Date Filing Date
DEA30442D Expired DE392280C (en) 1918-04-16 1918-04-16 Process for the extraction of sulfur and sulfur dioxide from calcium sulfate

Country Status (1)

Country Link
DE (1) DE392280C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE767756C (en) * 1937-05-23 1953-05-18 Metallgesellschaft Ag Process for the thermal decomposition of sulphates of magnesium or other metals
EP0015333A1 (en) * 1979-03-08 1980-09-17 Exxon Research And Engineering Company Converting calcium sulphide to calcium oxide

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE767756C (en) * 1937-05-23 1953-05-18 Metallgesellschaft Ag Process for the thermal decomposition of sulphates of magnesium or other metals
EP0015333A1 (en) * 1979-03-08 1980-09-17 Exxon Research And Engineering Company Converting calcium sulphide to calcium oxide

Similar Documents

Publication Publication Date Title
DE1199243B (en) Process for the production of gases containing sulfur dioxide from waste sulfuric acid containing ammonium salts
DE392280C (en) Process for the extraction of sulfur and sulfur dioxide from calcium sulfate
DE600269C (en) Process for the preparation of citrate-soluble calcium alkali metal phosphates
DE394362C (en) Process for the production of sulfur dioxide from the sulphates of the alkaline earths, magnesium or iron
DE438172C (en) Method of processing gypsum
DE483286C (en) Process for the extraction of elemental sulfur from the end gases of carbon disulfide production
DE682261C (en) Process for the production of sulfur dioxide with simultaneous production of a phosphate fertilizer
DE371978C (en) Process for the continuous extraction of sulfur dioxide from gypsum
DE581656C (en) Manufacture of potash nitrate
DE426669C (en) Process for the rapid and complete decomposition of any products containing selenium with distillation of the selenium
DE377409C (en) Process for the production of sulfur dioxide from mixtures of sulphates with heavy metal sulphides
AT71752B (en) Process for the production of a fertilizer from silicate rocks containing potash and minerals containing phosphoric acid (especially phosphorites).
DE432099C (en) Process for the production of sulphurous acid and oxides from sulphates
DE669500C (en) Process for producing a liquid, basic iron-iron oxide / lime slag for refining pig iron and raw steel
DE380999C (en) Process for the production of sulphurous acid by reducing alkaline earth sulphates
DE951007C (en) Process for the production of low-nitrogen steel by blowing pig iron in a basic converter with a mixture of gases of very different strengths of oxidation, such as oxygen and carbon dioxide
DE352115C (en) Process for the production of sulphate by the Hargreaves process
DE715845C (en) Process for the extraction of elemental sulfur from sulfur dioxide and gases containing such
AT123841B (en) Process for the production of citrate-soluble calcium alkali metal phosphates by treating rock phosphates with alkali metal sulfates and reducing agents.
DE584375C (en) Process for the production of fertilizers from chalk phosphates
DE526258C (en) Process for the direct manufacture of solid, dry ammonium sulphate from its components
DE530564C (en) Manufacture of the compounds of metals with the elements sulfur, selenium and tellurium
DE508394C (en) Oxidation of ammonia salts
DE406673C (en) Extraction of antimony chlorine and elemental sulfur
DE348408C (en) Process for removing carbon oxysulphide from gases