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PL126287B1 - Method of removal of sulfur compounds and nitrogen compounds from gas fuels - Google Patents

Method of removal of sulfur compounds and nitrogen compounds from gas fuels Download PDF

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Publication number
PL126287B1
PL126287B1 PL22624780A PL22624780A PL126287B1 PL 126287 B1 PL126287 B1 PL 126287B1 PL 22624780 A PL22624780 A PL 22624780A PL 22624780 A PL22624780 A PL 22624780A PL 126287 B1 PL126287 B1 PL 126287B1
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PL
Poland
Prior art keywords
gas
sulfur compounds
compounds
temperature
removal
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Application number
PL22624780A
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Polish (pl)
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PL226247A1 (en
Inventor
Jadwiga Pasynkiewicz
Zbigniew Kulicki
Stefan Ermich
Jerzy Gutowski
Krystyna Falecka
Grazyna Jasinska
Krzysztof Tatarczuk
Karol Gawad
Miroslaw Ptak
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Inst Gornictwa Naftowego I Gaz
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Priority to PL22624780A priority Critical patent/PL126287B1/en
Publication of PL226247A1 publication Critical patent/PL226247A1/xx
Publication of PL126287B1 publication Critical patent/PL126287B1/en

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Description

Przedmiotem wynalazku jest sposób usuwania z pa¬ liw gazowych zwiazkW siarki i zwiazków azotu otrzy¬ manych z termicznego rozkladu paliw.Wedlug znanych dotychczas sposobów usuwanie zwiazków siarki i zwiazków azotu z paliw gazowych polega na usuwaniu wszystkich zanieczyszczen me¬ toda niskotemperaturowej absorpcji w metanolu (pro¬ ces rectisol) lub odrebnego usuwania zwiazków siar¬ ki i zwiazków azotu np. w kolejnych etapach: pluczki cjanowe, absorbery siarkowodoru.Metoda pierwsza jest nie selektywna, powoduje miedzy innymi usuniecie z gazów skladników palnych.Metoda druga nie zapewnia dostatecznego stopnia usuniecia organicznych polaczen siarki oraz powoduje powstawanie scieków o znacznych zawartosciach ro¬ danków, cjanków, zelazocjanków i mrówczanów trud¬ nych do utylizacji.Istota sposobu wedlug wynalazku polega na tym, ze gaz z wysokotemperaturowego zgazowania wegla po sprezeniu do cisnienia 0,8—3,6 MPa, a nastepnie po podgrzaniu w wymiennikach ciepla do temperatury 560—730 K wchodzi do reaktora katalitycznego, w którym na katalizatorze, najkorzystniej kobaltowo-mo- libdenowym osadzonym na tlenku glinu zachodzi pod wplywem zawartego w gazie wodoru redukcja GOS i innych zwiazków siarki do H2S oraz redukcja HCN do NH3. Nastepnie goracy gaz poprzez wymiennik ciepla przechodzi do pluczki NH3, gdzie jest schla¬ dzany bezprzeponowo woda oraz gdzie absorbowany jest amoniak, po czym przechodzi do absorbera, gdzie w temperaturze 290—360 K zachodzi selektywne usu¬ wanie siarkowodoru zawartego w gazie surowym i wy¬ tworzonego na drodze redukcji pozostalych polaczen siarkowych przez 15—30% wodny roztwór weglanu. 5 Amoniak wydzielony z kondensatów wodnych jest utylizowany.Zaleta sposobu usuwania zwiazków siarki i zwiaz¬ ków azotu z paliw gazowych jest to, ze redukcja HCN do amoniaku eliminuje tworzenie sie rodanków, zela- 10 zocjanków i mrówczanów w roztworze absorpcyjnym stosowanym do selektywnego odsiarczania gazu.Ponadto proponowane rozwiazanie technologiczne ogranicza powstanie w roztworze absorpcyjnym mrów¬ czanów i tlenku wegla zawartego w gazie surowym. 15 Podany przyklad objasnia sposób wedlug wynalazku.Przyklad. Gaz z wysokotemperaturowego zga¬ zowania wegla o skladzie objetosciowym: 30% H2 58% CO, 10% C02, 1,8% H2S, 0,2% COS oraz nie¬ znacznej ponizej 100 mg S/m3, zawartosci innych 20 polaczen siarkowych oraz azotowych w ilosci ok. 200 mg/m3 HCN, 100 mg/m3 NH3, po sprezeniu do cis¬ nienia 3+ 3,6 MPa i podgrzaniu w wymiennikach ciepla/gazem wychodzacym z reaktora i para) do tem¬ peratury 673 K wchodzi do reaktora katalitycznego. 25 W reaktorze tym zawierajacym 15% wag Mo03 i 3% CoO, pod wplywem zawartego w gazie wodoru, za¬ chodzi redukcja COS i innych polaczen siarkowych do H2S oraz redukcja HCN do HN3. Goracy gaz po o- puszczeniu reaktora przez wymiennik ciepla przechodzi 30 do pluczki NH3, gdzie gaz schladzany jest bezprze- 126 287126 287 ponowo woda oraz gdzie absorbowany jest amoniak.Nastepnie gaz przechodzi do absorbera, gdzie w tem¬ peraturze 303 K zachodzi selektywne usuwanie siarko¬ wodoru zawartego w gazie surowym i wytworzonego na drodze redukcji pozostalych polaczen siarkowych przez 20% wodny roztwór K2C03.Gaz oczyszczany wychodzacy z góry absorbera zawiera glównie H2, CO, C02 oraz sladowe ilosci zwiazków siarki w tym ~1 ppm H2S. Gaz kwasny siarkowodorowy o zawartosci H2S50%, zdesorbo- wany podczas regeneracji roztworu absorpcyjnego, w regeneratorze kierowany jest poprzez separator do dalszej utylizacji. Amoniak zaleznie od warunków lokalnych moze byc odpedzany z kondensatów wod¬ nych i niszczony lub utylizowany albo w postaci kon¬ densatu kierowany do zakladowej oczyszczalni scie¬ ków.Zastrzezenie patentowe Sposób usuwania z paliw gazowych zwiazków siar- 10 15 ki i zwiazków azotu, znamienny tym, ze gaz z wyso¬ kotemperaturowego zgazowania wegla po sprezeniu do cisnienia 0,8—3,6 MPa, a nastepnie po podgrza¬ niu w wymiennikach ciepla do temperatury 560—730 K wprowadza sie do reaktora katalitycznego, w którym na katalizatorze, najkorzystniej kobaltowo-molibde- nowym osadzonym na tlenku glinu, pod wplywem za¬ wartego w gazie wodoru redukuje sie COS i inne zwiaz¬ ki siarki do H2S a HCN do NH3, nastepnie goracy gaz poprzez wymiennik ciepla przechodzi do pluczki NH3 gdzie jest schladzany bezprzeponowo woda oraz gdzie absorbowany jest amoniak po czym przecho¬ dzi do absorbera gdzie w temperaturze 290—360 K. selektywne usuwa sie zawarte w gazie surowym i wy¬ tworzone na drodze redukcji pozostale polaczenia .siarkowe przez 15—30% wodny roztwór weglanu* a wydzielony z kondensatów wodnych amoniak uty- lizuje sie.LDD Z-d 2, Z. 101/1400/85/36, n. 90+20 egz.Cena 100 zl PLThe subject of the invention is a method of removing sulfur compounds and nitrogen compounds obtained from thermal decomposition of fuels from gaseous fuels. According to the methods known so far, the removal of sulfur compounds and nitrogen compounds from gaseous fuels consists in removing all impurities by the method of low-temperature absorption in methanol (pro ¬ ces rectisol) or separate removal of sulfur compounds and nitrogen compounds, e.g. in the following stages: cyan rinses, hydrogen sulfide absorbers. The first method is not selective, it removes flammable components from the gases. The second method does not ensure a sufficient degree of removal of organic compounds. sulfur and causes the formation of wastewater with a significant content of yeast, cyanides, ferrocyanides and formates difficult to utilize. The essence of the method according to the invention consists in the fact that the gas from high-temperature coal gasification is compressed to a pressure of 0.8-3.6 MPa, and then, when heated in heat exchangers to a temperature of 560-730 K, it enters to a catalytic reactor, in which, on the catalyst, most preferably cobalt-molybdenum supported on alumina, the hydrogen contained in the gas is influenced by the reduction of GOS and other sulfur compounds to H2S and the reduction of HCN to NH3. Then the hot gas passes through the heat exchanger to the NH3 scrub, where the water is directly cooled and where ammonia is absorbed, and then it passes to the absorber, where at a temperature of 290-360 K there is a selective removal of hydrogen sulphide contained in the crude gas and depletion of the gas. formed by reduction of the residual sulfur compounds with a 15-30% aqueous solution of carbonate. The ammonia separated from the aqueous condensates is recycled. An advantage of the method of removing sulfur compounds and nitrogen compounds from gaseous fuels is that the reduction of HCN to ammonia eliminates the formation of radicals, ferricides and formates in the absorption solution used for selective gas desulfurization. Moreover, the proposed technological solution limits the formation of formates and carbon monoxide contained in the raw gas in the absorption solution. The example given illustrates the method according to the invention. Gas from high-temperature coal gasification with a volumetric composition: 30% H2, 58% CO, 10% CO2, 1.8% H2S, 0.2% COS and not much less than 100 mg S / m3, the content of other 20 sulfur compounds and 200 mg / m3 of HCN, 100 mg / m3 of NH3, compressed to a pressure of 3+ 3.6 MPa and heated in heat exchangers / gas coming from the reactor and steam) to the temperature of 673 K catalytic converter. In this reactor containing 15% by weight of MoO3 and 3% of CoO, under the influence of the hydrogen contained in the gas, the reduction of COS and other sulfur compounds to H2S and the reduction of HCN to HN3 takes place. After leaving the reactor through the heat exchanger, the hot gas passes into the NH3 scrub, where the gas is directly cooled down again with water and where ammonia is absorbed. Then the gas passes to the absorber, where selective sulfur removal takes place at a temperature of 303 K ¬ Hydrogen contained in the crude gas and produced by reducing the remaining sulfur compounds by a 20% aqueous solution of K2CO3. The purge gas coming from the top of the absorber contains mainly H2, CO, CO2 and traces of sulfur compounds including ~ 1 ppm H2S. Hydrogen sulphide acid gas with the content of H2S50%, desorbed during regeneration of the absorption solution, in the regenerator is directed through the separator for further disposal. Depending on local conditions, ammonia can be drained from water condensates and destroyed or utilized, or in the form of condensate directed to the on-site wastewater treatment plant. Patent claim A method of removing sulfur and nitrogen compounds from gas fuels, characterized by that the gas from high-temperature coal gasification after compression to a pressure of 0.8-3.6 MPa, and then after heating in heat exchangers to a temperature of 560-730 K, is fed to the catalytic reactor, in which, on the catalyst, preferably cobalt -molybdenum deposited on alumina, under the influence of hydrogen contained in the gas, COS and other sulfur compounds are reduced to H2S and HCN to NH3, then the hot gas passes through the heat exchanger to the NH3 flush, where it is directly cooled down with water and where ammonia is absorbed and then goes to the absorber, where at a temperature of 290-360 K. the selective removal of the crude gas contained in the gas and the residue formed by reduction remains No sulfur connections through 15-30% aqueous carbonate solution * and ammonia separated from water condensates is utilized. LDD Z-d 2, Z. 101/1400/85/36, No. 90 + 20 copies Price PLN 100 PL

Claims (1)

1. Zastrzezenie patentowe Sposób usuwania z paliw gazowych zwiazków siar- 10 15 ki i zwiazków azotu, znamienny tym, ze gaz z wyso¬ kotemperaturowego zgazowania wegla po sprezeniu do cisnienia 0,8—3,6 MPa, a nastepnie po podgrza¬ niu w wymiennikach ciepla do temperatury 560—730 K wprowadza sie do reaktora katalitycznego, w którym na katalizatorze, najkorzystniej kobaltowo-molibde- nowym osadzonym na tlenku glinu, pod wplywem za¬ wartego w gazie wodoru redukuje sie COS i inne zwiaz¬ ki siarki do H2S a HCN do NH3, nastepnie goracy gaz poprzez wymiennik ciepla przechodzi do pluczki NH3 gdzie jest schladzany bezprzeponowo woda oraz gdzie absorbowany jest amoniak po czym przecho¬ dzi do absorbera gdzie w temperaturze 290—360 K. selektywne usuwa sie zawarte w gazie surowym i wy¬ tworzone na drodze redukcji pozostale polaczenia .siarkowe przez 15—30% wodny roztwór weglanu* a wydzielony z kondensatów wodnych amoniak uty- lizuje sie. LDD Z-d 2, Z. 101/1400/85/36, n. 90+20 egz. Cena 100 zl PLClaim 1. A method of removing sulfur compounds and nitrogen compounds from gaseous fuels, characterized in that the gas from high-temperature coal gasification is compressed to a pressure of 0.8-3.6 MPa, and then heated in in heat exchangers to a temperature of 560-730 K, they are fed to a catalytic reactor, in which, on a catalyst, preferably cobalt-molybdenum supported on alumina, COS and other sulfur compounds are reduced to H2S under the influence of hydrogen contained in the gas. HCN to NH3, then the hot gas, through the heat exchanger, goes to the NH3 scrub, where it is directly cooled with water and where ammonia is absorbed, and then it goes to the absorber where, at a temperature of 290-360 K., the raw gas contained in the raw gas and produced by reduction, the remaining sulfur compounds through a 15-30% aqueous carbonate solution are utilized, and the ammonia separated from the aqueous condensates is utilized. LDD Z-d 2, Z. 101/1400/85/36, n. 90 + 20 copies. Price PLN 100 PL
PL22624780A 1980-08-14 1980-08-14 Method of removal of sulfur compounds and nitrogen compounds from gas fuels PL126287B1 (en)

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PL126287B1 true PL126287B1 (en) 1983-07-30

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