DE2145293A1 - 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
DE2145293A1
DE2145293A1 DE19712145293 DE2145293A DE2145293A1 DE 2145293 A1 DE2145293 A1 DE 2145293A1 DE 19712145293 DE19712145293 DE 19712145293 DE 2145293 A DE2145293 A DE 2145293A DE 2145293 A1 DE2145293 A1 DE 2145293A1
Authority
DE
Germany
Prior art keywords
added
gas
arsenic
water
ammonia
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
DE19712145293
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 DE19712145293 priority Critical patent/DE2145293A1/en
Priority to GB504374A priority patent/GB1387257A/en
Priority to GB990772A priority patent/GB1379624A/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 DE2145293A1 publication Critical patent/DE2145293A1/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
    • C10K1/12—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
    • 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

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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)
  • Treatment Of Water By Oxidation Or Reduction (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 dem bei der Ammoniakwäsche von Gas, insbesondere von Koksofengas, anfallenden Waschwasser" Die Erfindung betrifft ein Verfahren zur Entfernung von Schwefelwasserstoff aus dem bei der Ammoniakwäsche von Gas, insbesondere von Koksofengas anfallenden Waschwasser."Process for the removal of hydrogen sulfide from the Ammonia scrubbing of gas, in particular of coke oven gas, resulting scrubbing water "The The invention relates to a method for removing hydrogen sulfide from the in the ammonia scrubbing of gas, in particular of coke oven gas resulting scrubbing water.

Das Auswaschen von Ammoniak aus Gas spielt insbesondere bei der Aufbereitung von Koksofengas eine große Rolle. Dazu wird Wasser benutzt. Insbesondere kann es sich um Wasser handeln, das bei der Kühlung des Kokofengases als Kondensat anfällt In diesem Fall enthält schon das Waschwasser beträchtliche Mengen an Schwefelwasserstoff0 Das Waschwasser wird allgemein bei der Ammoniakwäsche im Gegenstrom zu dem Gas geführt und nimmt dabei das Ammoniak auf, Die spätere Entfernung des Ammoniaks aus dem Waschwasser ist aus verschiedenen Gritnden erforderlich. Im Aninoniakabtreiber wird das Kondensat zumeist auch thermisch behandelt. Daher ist die Entfernung des Schwefelwasserstoffes vor dem Ammoniakabtreiber erforderlich, um die Emission dieser Verbindung zu verhindern oder auf ein ungefährliches Maß herabzusetzen. Außerdem werden dadurch auch apparative Kosten, zaBo ftlr die Entsäuerungsstufen bei der Aufbereitung des Gaswassers eingespart0 Es wurde nun gefunden, daß die Entfernung von Schwefelwasserstoff aus dem bei der Ammoniakwäsche von Gas, insbesondere von Koksofengas anfallenden Wasser ohne weiteres möglich ist, wenn dean Waschwasser wasserlösliche Chinonderivate zugesetzt und das hieraus entstehende Gemisch bei pH-Werten von > 8 zu Disulfid oder Thiosulfat oxydiert wird.The scrubbing of ammonia from gas is particularly important during processing of coke oven gas plays a major role. Water is used for this. In particular, it can are water that is produced as condensate when cooling the coke oven gas In this case, the washing water already contains considerable amounts of hydrogen sulfide In the case of ammonia scrubbing, the washing water is generally fed in countercurrent to the gas and thereby absorbs the ammonia, The later removal of the ammonia from the washing water is required for various reasons. The condensate is in the ammonia expeller mostly also thermally treated. Therefore is the removal of the hydrogen sulfide required before the ammonia expeller to prevent the emission of this compound or to reduce it to a safe level. In addition, this also means that apparatus Costs saved, e.g. for the deacidification stages in the treatment of the gas water0 It has now been found that the removal of hydrogen sulfide from the Ammonia scrubbing of gas, in particular of water produced by coke oven gas, easily is possible if water-soluble quinone derivatives are added to the wash water and that resulting mixture at pH values of> 8 to disulfide or thiosulfate is oxidized.

Das diesen Prozeß verlassende Waschwasser hat keinen nennenswerten Schwefelwasserstoffpartialdruck¢ Infolgedessen können derart behandelte Waschwässer ohne Entsäuerungsstufe direkt entammoniakalisiert werden. Die dabei entstehenden ammoniakhaltigen Brüden können in einer Verbrennungs- oder Ammoniaksersetzungsanlage umgesetzt werden, ohne daß Schwefelwasserstoff frei wird.The wash water leaving this process has no significant Hydrogen sulfide partial pressure ¢ As a result, wash water treated in this way can be de-ammoniated directly without a deacidification stage. The resulting Ammonia-containing vapors can be used in an incineration or ammonia replacement plant be reacted without hydrogen sulfide being released.

Zur Beeinflussung der Sauerstoffiibertragung an den Schwefel empfiehlt sich die.Zugabe eines Katalysators zu dem ablaufenden Waschwasser. Dafür kommen insbesondere Arsen-, Antimon oder Ziniwerbindungen in Betracht. Der Zusatz der katalytisch wirkenden Verbindungen betrugt zweckmEßig 0,5 bis 5 g/l, vorzugsweise Jedoch 2 g/l.Recommended for influencing the oxygen transfer to the sulfur die.Zugabe a catalyst to the draining wash water. Come for it arsenic, antimony or zinc compounds in particular. The addition of the catalytic active compounds was expediently 0.5 to 5 g / l, but preferably 2 g / l.

Im übrigen ist der Zusatz von 5 bis 100 mg Hydrochinon pro 1 Flüssigkeit zum Waschwasser ausreichend; vorzugsweise beträgt er 10 bis 30 mg/l.Incidentally, the addition of 5 to 100 mg of hydroquinone per 1 liquid sufficient for washing water; preferably it is 10 to 30 mg / l.

Besondere Bedeutung kommt der automatischen Steuerung des Prozesses zu. Nach der Erfindung wird deshalb die zur Oxydation erforderliche Luftmenge durch die Messung des Redoxpotentials der Blussigkeit vor und nach der Luftzugabe gesteuert. Dabei empfiehlt es sich, die Einstellung des Redoxpotentials so vor zunehmen, daß bevorzugt Sauerstoffsäuren des Schwefels gebildet werden.The automatic control of the process is of particular importance to. According to the invention, the amount of air required for oxidation is therefore through the measurement of the redox potential of the bloodiness before and after the addition of air is controlled. It is advisable to adjust the redox potential so that preferably oxygen acids of sulfur are formed.

In der Zeichnung ist ein Schema des Verfahrens als Ausfiiifrungs beispiel wiedergegeben.In the drawing is a scheme of the process as an embodiment reproduced.

Das in den Wascher 1 bei 2 eintretende Ammoniak und schwefelwasserstoffhaltige Gas wird im Gegenstrom durch Waschwasser, das bei 4 in den Gaswascher eintritt, vom Ammoniak und Schwefelwasserstoff befreit. Aus dem Behälter 7 wird mittels einer Dosierpumpe 6 eine wässrige Lösung von Chinonderivaten bei 5 dem Waschwasser zugegeben. Das bei 8 anfallende, angereicherte Waschwasser wird mittels einer Pumpe in den Behälter 10 geleitet.The ammonia entering the washer 1 at 2 and containing hydrogen sulfide Gas is countercurrently through washing water entering the gas washer at 4, freed from ammonia and hydrogen sulfide. From the container 7 is by means of a Dosing pump 6 an aqueous solution of quinone derivatives added at 5 to the wash water. The enriched wash water accumulating at 8 is pumped into the Container 10 passed.

Bei 9 wird das Redoxpotential der Mischlösung mittels einer Platin-Xalomel-Kette gemessen.At 9, the redox potential of the mixed solution is determined by means of a platinum-xalomel chain measured.

In den Behälter wird über die Leitung 11 Luft durch ein Dilsenverteilungssystem eingeleitet und die Mischlösung oxydiert.Air is introduced into the container via line 11 through a dilsen distribution system initiated and the mixed solution oxidized.

las Oxydationspotential der bei 12 ablaufenden Lösung wird durch eine weitere Meßkette, z.B. eine Platin-Ealomel-Neßkette registriert.the oxidation potential of the solution running off at 12 is determined by a Another electrode, e.g. a platinum-Ealomel chain, is registered.

Durch eine vorgegebene Differenzbildung zwischen den Ketten 12 und 9 kann ein Meßwert eingeleitet werden, der als FUbrungegröße die Luftmenge bei 11, z.3. über ein Regelventil steuert PatentansprücheBy a predetermined difference formation between the chains 12 and 9, a measured value can be initiated which, as a fueling variable, is the amount of air at 11, z.3. Controls claims via a control valve

Claims (3)

r a t e n t a n s p r ü c h e =================== lo Verfahren zur Entfernung von Schwefelwasserstoff aus dem bei der Ammoniakwäsche von Gas, insbesondere von Koksofengas, anfallenden Waschwasser, d a d u r c h g e -k e n n z e i c h n e t , daß dem Waschwasser wasserlösliche Chinonderivate zugesetzt und das hieraus entstehende Gemisch bei pH-Werten von - 8 zu Disulfid oder Thiosulfat oxydiert wird0 r a t e n t a n s p r ü c h e ==================== lo Procedure for Removal of hydrogen sulfide from the ammonia scrubbing of gas, in particular of coke oven gas, incidental washing water, d u r c h g e -k e n n n z e i c h n e t that water-soluble quinone derivatives are added to the wash water and that from this The resulting mixture is oxidized to disulphide or thiosulphate at pH-8 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 SauerstoffUbertragi1ng an den Schwefel dem ablaufenden Gaskiiblerkondensat ein Katalysator zugegeben wird 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 for Influence of the oxygen transfer to the sulfur of the draining gas bubble condensate a catalyst is added 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 Zinnverbindungen als Katalysatoren.3. The method according to claim 2, g e k e n n z e i c arsenic, antimony or tin compounds as catalysts. 4. Verfahren nach den Ansprüchen 1 bis 3, da d u r c h g e k e n n z e i c h n e t , daß die katalytisch wirkenden Verbindungen in Mengen von 0,5 bis 5 g/l zugesetzt werden.4. The method according to claims 1 to 3, since d u r c h g e k e n n z e i c h n e t that the catalytically active compounds in amounts of 0.5 to 5 g / l can be added. 5. Verfahren nach den Ansprüchen 1 bis 4, d a d u r c h g e k e n n z e i c h n e t , daß der Zusatz der katalytisch wirkenden Verbindungen 2 g/l beträgt.5. The method according to claims 1 to 4, d a d u r c h g e k e n nz e i c h n e t that the addition of the catalytically active compounds 2 g / l amounts to. 6o 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 Waschwasser 5 bis 100 mg Hydrochinon pro 1 Flüssigkeit zugesetzt werden0 70 Verfahren nach Anspruch 6, 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 bis 30 mg/l Hydrochinon zugesetzt werden.6o The method according to claim 1 and one or more of the following Claims that the washing water 5 to 100 mg hydroquinone per 1 liquid are added0 70 procedure according to claim 6, that the gas cooler condensate 10 to 30 mg / l hydroquinone can be added. 8. 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 -net, daß die zur Oxydation erforderliche Luftmenge durch die Messung des Redoxpotentials der Flüssigkeit am Ein-und Austritt des Oxydationsbehälters gesteuert wird.8. The method of claim 1 and one or more of the following Claims that the necessary for oxidation Air volume by measuring the redox potential of the liquid at the inlet and outlet of the oxidation tank is controlled. 9. 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 die Einstellung des Redoxpotentiales so erfolgt, daß bevorzugt Sauerstoffsäuren des Schwefels gebildet werden.9. 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 the setting of the redox potential takes place in such a way that oxygen acids are preferred of sulfur are formed. L e e r s e i t eL e r s e i t e
DE19712145293 1971-03-12 1971-09-10 Ammonia hydrogen sulphide removal from coking gases - by arsenic catalysed reaction to ammonium polythionate Pending DE2145293A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
DE19712145293 DE2145293A1 (en) 1971-09-10 1971-09-10 Ammonia hydrogen sulphide removal from coking gases - by arsenic catalysed reaction to ammonium polythionate
GB504374A GB1387257A (en) 1971-03-12 1972-03-02 Separation process
GB990772A GB1379624A (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
DE19712145293 DE2145293A1 (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
DE2145293A1 true DE2145293A1 (en) 1973-03-22

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Family Applications (1)

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DE19712145293 Pending DE2145293A1 (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) DE2145293A1 (en)

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