DE2145292A1 - Ammonia hydrogen sulphide removal from coking gases - by arsenic catalysed reaction to ammonium polythionate - Google Patents

Ammonia hydrogen sulphide removal from coking gases - by arsenic catalysed reaction to ammonium polythionate

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Publication number
DE2145292A1
DE2145292A1 DE19712145292 DE2145292A DE2145292A1 DE 2145292 A1 DE2145292 A1 DE 2145292A1 DE 19712145292 DE19712145292 DE 19712145292 DE 2145292 A DE2145292 A DE 2145292A DE 2145292 A1 DE2145292 A1 DE 2145292A1
Authority
DE
Germany
Prior art keywords
gas
condensate
arsenic
hydrogen sulphide
ammonia hydrogen
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.)
Pending
Application number
DE19712145292
Other languages
German (de)
Inventor
Fritz Goetza
Otto Grossenbach
Gustav Kloss
Horst Kurapkat
Guenter Dipl Chem Voigt
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.)
RAG AG
Original Assignee
Ruhrkohle AG
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 Ruhrkohle AG filed Critical Ruhrkohle AG
Priority to DE19712145292 priority Critical patent/DE2145292A1/en
Priority to GB990772A priority patent/GB1379624A/en
Priority to GB504374A priority patent/GB1387257A/en
Priority to ES400499A priority patent/ES400499A1/en
Priority to AU39801/72A priority patent/AU3980172A/en
Priority to AR24086872A priority patent/AR195165A1/en
Priority to FR7208447A priority patent/FR2128831B1/fr
Priority to BE780509A priority patent/BE780509A/en
Priority to SE310072A priority patent/SE366558B/xx
Priority to IT6778472A priority patent/IT960890B/en
Publication of DE2145292A1 publication Critical patent/DE2145292A1/en
Priority to ES427858A priority patent/ES427858A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/105—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids containing metal compounds other than alkali- or earth-alkali carbonates, -hydroxides, oxides, or salts of inorganic acids derived from sulfur
    • C10K1/107—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids containing metal compounds other than alkali- or earth-alkali carbonates, -hydroxides, oxides, or salts of inorganic acids derived from sulfur containing As-, Sb-, Sn compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • C10K1/128—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors containing organic oxygen transferring compounds, e.g. sulfoxides

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Industrial Gases (AREA)

Abstract

Removal of H2S (and also NH3, HCN, org. cpds. such as benzene) from coking plant gases by washing the precooled, compressed gases with a solvent contg. As which catalyses reaction between NH3 and H2S to form ammonium polythionate, and then oxidising this to S, using another catalyst (e.g. cpds. of as, Sb, or Sn).

Description

"Verfahren zur Entfernung von Schwefelwasserstoff aus Gaskondensaten, insbesondere aus Kosofengaskondensat11 Die Erfindung betrifft ein Verfahren zum Entfernen von Schwefelwasserstoff aus Gaskondensat, insbesondere aus Koksofengaskondensate Bei der Abkühlung von Koksofengas fällt sogenanntes Gaswasser an, das u.a. Schwefelwasserstoff enthält. Die Entfernung des Schwefelwasserstoffes aus dem Gaswasser ist erforderlich, weil das Kondensat zum Beispiel in Aimnoniakabtreibern thermisch behandelt wird. Durch die Entfernung des Schwefelwasserstoffes wird die Emission dieser Verbindung verhindert oder auf ein ungefährliches Maß herabgesetzt. AuBerdem werden dadurch auch apparative Kosten, z.B. für die Entsuerungsstufen bei der Aufbereitung des Gaswassers eingespart."Process for removing hydrogen sulfide from gas condensates, in particular from Kosofengaskondensat11 The invention relates to a method for Removal of hydrogen sulfide from gas condensate, especially from coke oven gas condensate When coke oven gas is cooled, so-called gas water is produced, including hydrogen sulfide contains. The removal of the hydrogen sulfide from the gas water is necessary, because the condensate is thermally treated in, for example, ammonia expellers. Removal of the hydrogen sulfide reduces the emission of this compound prevented or reduced to a safe level. It also means that also equipment costs, e.g. for the deaeration stages in the preparation of the Saved gas water.

Es wurde nun gefunden, daß die Entfernung von Schwefelwasserstoff aus Gaskondensat, insbesondere aus Koksofengaskondensat ohne weiteres möglich ist, wenn dem Gaskondensat wasserlösliche Chinonderivate zugesetzt und das hieraus entstehende Gemisch bei pH-Werten von > 8 zu Disulfid oder zu Thiosulfat oxydiert wird.It has now been found that the removal of hydrogen sulfide from gas condensate, in particular from coke oven gas condensate just like that is possible if water-soluble quinone derivatives are added to the gas condensate and that resulting mixture at pH values of> 8 to disulphide or thiosulphate is oxidized.

Das diesen Prozeß verlassende Gaskühlerkondensat hat keinen nennenswerten Schwefelwasserstoffpartialdruck. Infolgedessen können derart behandelte GaskUhlerkondensate ohne Entsäuerungsstufe direkt entammoniakalisiert werden. Die dabei entstehenden annoniakhaltigen Brüden können in einer Verbrennungs- oder Ammoniakzersetzungsanlage umgesetzt werden, ohne daß Schwefelwasserstoff frei wird.The gas cooler condensate leaving this process has no significant condensate Hydrogen sulfide partial pressure. As a result, gas cooler condensates treated in this way can occur can be de-ammoniated directly without a deacidification stage. The resulting Annonia-containing vapors can be used in an incineration or ammonia decomposition plant be reacted without hydrogen sulfide being released.

Zur Beeinflussung der Sauerstoffübertragung an den Schwefel empfiehlt sich die Zugabe eines Katalysators zu dem ablaufenden Gaskkhlerkondensat. Rasur kommen insbesondere Arsen-, Antimon- oder Zinnverbindungen in Betracht.To influence the oxygen transfer to the sulfur is recommended the addition of a catalyst to the draining gas cooler condensate. shave arsenic, antimony or tin compounds are particularly suitable.

Im übrigen ist der Zusatz von 5 - 100 mg Hydrochinon pro 1 Liter Flüssfgkeit zum Waschwasser ausreichend; vorzugsweise beträgt er 10 - 30 mg/lG Besondere Bedeutung kommt der automatischen Steuerung des Prosessel zu. Nach der Erfindung wird deshalb die zur Oxydation erforderliche Luftmenge durch die Messung des Redoxpotentiales der BlUssigkeit am Ein- und Austritt des Oxydationsbehälters gesteuert. Dabei empfiehlt es sich, die Einstellung des Redoxpotentiales so vorzunehmen, daß bevorzugt Sauerstoffsäuren des Schwefels gebildet werden.Incidentally, the addition of 5-100 mg hydroquinone per 1 liter of liquid sufficient for washing water; it is preferably 10-30 mg / Ig, of particular importance is the responsibility of the automatic control of the pros chair. According to the invention is therefore the amount of air required for oxidation by measuring the redox potential controlled by the fluidity at the inlet and outlet of the oxidation tank. Here recommends it is advisable to adjust the redox potential in such a way that oxygen acids are preferred of sulfur are formed.

In der Zeichnung ist ein Schema des Verfahrens als Ausführungsbeispiel wiedergegeben.The drawing shows a scheme of the method as an exemplary embodiment reproduced.

In den Sammelbehälter 2 tritt bei 1 das GaskWhlerkondensat ein; es wird mit Hilfe einer Pumpe 4 in einen behalter 9 gepumpt.The gas radiator condensate enters the collecting container 2 at 1; it is pumped into a container 9 with the aid of a pump 4.

Aus einem Vorratsbehälter 5 entnimmt eine Dosierpumpe 6 eine wässerige Lösung von Chinonderivaten und setzt die Lösung in dosierter Menge dem Flüssigkeitsstrom der Pumpe 4 an einer Mischzelle 7 ZUe Bei 8 wird das Redoxpotential der Mischlösung mittels einer, z.B. Platin-Kalomel-Kette gemessen. In den Bhälter 9 wird über die Leitung 11 Luft durch ein Düsenverteilungssystem eingeleitet und die Mischlösung oxydiert.A metering pump 6 removes an aqueous one from a storage container 5 Solution of quinone derivatives and adds the solution to the liquid stream in a metered amount the pump 4 to a mixing cell 7 ZUe At 8, the redox potential of the mixed solution measured by means of a, e.g. platinum-calomel chain. In the station 9 is about the Line 11 introduced air through a nozzle distribution system and the mixed solution oxidized.

Das Oxydationspotential der bei 10 ablaufenden Lösung wird durch eine weitere, z.B. Platin-Ealomel-Meßkette registriert. Durch eine vorgegebene Differenzbildung zwischen den Ketten 10 und 8 kann ein Meßwert abgeleitet werden, der als FUhrungsgröße die Luftmenge bei 11, z.B. uer ein Steuerventil dosiert.The oxidation potential of the solution running off at 10 is determined by a other, e.g. platinum-Ealomel electrode registered. By forming a specified difference A measured value can be derived between the chains 10 and 8, which is used as a guide variable the amount of air at 11, e.g. metered by a control valve.

PatentansprücheClaims

Claims (7)

PatentansprUche ===================== 1. Verfahren zur Entfernung von Schwefelwasserstoff aus Gaskondensaten, insbesondere aus Koksofengaskondensat, d a d u r c h g e k e n n z e i c h n e t , daß dem Gaskondensat wasserlösliche Chinonderivate zugesetzt und das hieraus entstehende Gemisch bei pH-Werten von 8 zu Disulfid oder zu Thiosulfat oxydiert wird. Claims ====================== 1. Removal procedure of hydrogen sulfide from gas condensates, in particular from coke oven gas condensate, it is noted that the gas condensate is water-soluble Quinone derivatives added and the resulting mixture at pH values of 8 is oxidized to disulfide or thiosulfate. 2. Verfahren nach Anspruch 1, d a d u r c h g e k e n n -z e i c h n e t , daß zur Beeinflussung der Sauerstoff-Übertragung an den Schwefel dem ablaufenden Gaskühlerkondensat ein Katalysator zugegeben wird0 2. The method according to claim 1, d a d u r c h g e k e n n -z e i c h n e t that to influence the oxygen transfer to the sulfur the expiring Gas cooler condensate a catalyst is added 0 3. Verfahren nach Anspruch 2, g e k e n n z e i c h n e t d u r c h Arsen-, Antimon- oder Zinnverbindunge&ls Katalysatoren.3. The method according to claim 2, not shown by arsenic, antimony or tin compounds Catalysts. 4. Verfahren nach Anspruch 1 und einem oder mehreren der folgenden Ansprüche, d a d u r c h g e k e n n z e i c h -n e t , daß dem Gaskondensat 5 - 100 mg Hydrochinon pro Liter Flüssigkeit zugesetzt werden0 4. The method of claim 1 and one or more of the following Claims that the gas condensate 5 - 100 mg hydroquinone per liter of liquid are added0 5. Verfahren nach Anspruch 4, d a d u r c h g e k e n n -z e i c h n e t , daß dem Gaskühlerkondensat 10 - 30 mg/l Hydrochinon zugesetzt werden0 5. The method according to claim 4, that the gas cooler condensate 10 - 30 mg / l hydroquinone can be added0 6. Verfahren nach Anspruch 1 und einem oder mehreren der folgenden Ansprüche, d a d u r c h g e k e n n z e i c h -n e t , daß die zur Oxydation erforderliche luftmenge durch die Messung des edoxpotentials der Plüssigkeit am Bin- und Austritt des Oxydationsbehälters (9) gesteuert wird.6. The method according to claim 1 and one or several of the following claims, d a d u r c h g e n n n z e i c h -n e t that the amount of air required for oxidation by measuring the edox potential of the Pluidity on the bin and The outlet of the oxidation tank (9) is controlled will. 7. Verfahren nach den Ansprüchen 1 bis 6, d a d u r c h g e k e n n z e i c h n e t , daß Einstellung des Redoxpotentales so erfolgt, daß bevorzugt Sauerstoffsäuren des Schwefels gebildet werden.7. The method according to claims 1 to 6, d a d u r c h g e k e n It is not indicated that the redox potential is set in such a way that it is preferred Oxygen acids of sulfur are formed. L e e r s e i t eL e r s e i t e
DE19712145292 1971-03-12 1971-09-10 Ammonia hydrogen sulphide removal from coking gases - by arsenic catalysed reaction to ammonium polythionate Pending DE2145292A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
DE19712145292 DE2145292A1 (en) 1971-09-10 1971-09-10 Ammonia hydrogen sulphide removal from coking gases - by arsenic catalysed reaction to ammonium polythionate
GB990772A GB1379624A (en) 1971-03-12 1972-03-02 Separation process
GB504374A GB1387257A (en) 1971-03-12 1972-03-02 Separation process
ES400499A ES400499A1 (en) 1971-03-12 1972-03-07 Treatment procedure, for example, of cooking gases. (Machine-translation by Google Translate, not legally binding)
AU39801/72A AU3980172A (en) 1971-09-10 1972-03-08 a PROCESS FORTHE REMOVAL OF HYDROGEN SULPHIDE AND AMMONIA FROM OTHER GASES
AR24086872A AR195165A1 (en) 1971-03-12 1972-03-09 TREATMENT PROCEDURE, FOR EXAMPLE OF COKE GASES
FR7208447A FR2128831B1 (en) 1971-03-12 1972-03-10
BE780509A BE780509A (en) 1971-03-12 1972-03-10 TREATMENT PROCESS FOR REMOVING SULPHYDRIC ACID AND AMMONIA FROM GASES WHICH ARE POLLUTED THEREOF
SE310072A SE366558B (en) 1971-03-12 1972-03-10
IT6778472A IT960890B (en) 1971-03-12 1972-03-11 PROCESS OF PROCESS TO ELIMINATE AMMONIA AND HYDROGEN SULFURATE FROM GAS WITH THEM COUNTING MINES
ES427858A ES427858A1 (en) 1971-03-12 1974-07-01 Procedure for the elimination of hydrogen sulfide from the washing waters resulting in the washing with ammonia of gases. (Machine-translation by Google Translate, not legally binding)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19712145292 DE2145292A1 (en) 1971-09-10 1971-09-10 Ammonia hydrogen sulphide removal from coking gases - by arsenic catalysed reaction to ammonium polythionate

Publications (1)

Publication Number Publication Date
DE2145292A1 true DE2145292A1 (en) 1973-03-22

Family

ID=5819199

Family Applications (1)

Application Number Title Priority Date Filing Date
DE19712145292 Pending DE2145292A1 (en) 1971-03-12 1971-09-10 Ammonia hydrogen sulphide removal from coking gases - by arsenic catalysed reaction to ammonium polythionate

Country Status (1)

Country Link
DE (1) DE2145292A1 (en)

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