CA1052537A - Process and apparatus for the purification of coke oven gas - Google Patents
Process and apparatus for the purification of coke oven gasInfo
- Publication number
- CA1052537A CA1052537A CA221,686A CA221686A CA1052537A CA 1052537 A CA1052537 A CA 1052537A CA 221686 A CA221686 A CA 221686A CA 1052537 A CA1052537 A CA 1052537A
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- CA
- Canada
- Prior art keywords
- washing
- gas
- hydrogen sulphide
- ammonia
- liquid
- 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
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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
-
- 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
- C01B17/16—Hydrogen sulfides
-
- 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
- C10K1/122—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 only carbonates, bicarbonates, hydroxides or oxides of alkali-metals (including Mg)
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Industrial Gases (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The invention relates to a process for the purification of cooled and deterred coke oven gas of the type wherein the said crude gas is passed through a washing circulation or flow to remove ammonia by washing with water, or water acidified with sulphuric acid, and to remove hydrogen sulphide by washing with an alkaline washing liquid, the improvement com-prising the use of a washing liquid, for the removal of hydrogen sulphide, containing sodium or potassium carbonate, removal of the hydrogen sulphide by the addition of caustic soda or caustic potash solution, corresponding amount of wash liquid being withdrawn from the circulation or flow. It is preferred to introduce the caustic soda or caustic potash before the hydro-gen sulphide washing and to remove the wash liquid before addition of the carbon dioxide. The carbon dioxide supplied for the hydrogen sulphide wash-ing step may be derived from the glue gases of the coke oven heating plant or from an ammonia separation plant. The invention also provides apparatus for use in the process of the invention, including gas washing devices con-structed as integrated components of the gas conduits.
The invention relates to a process for the purification of cooled and deterred coke oven gas of the type wherein the said crude gas is passed through a washing circulation or flow to remove ammonia by washing with water, or water acidified with sulphuric acid, and to remove hydrogen sulphide by washing with an alkaline washing liquid, the improvement com-prising the use of a washing liquid, for the removal of hydrogen sulphide, containing sodium or potassium carbonate, removal of the hydrogen sulphide by the addition of caustic soda or caustic potash solution, corresponding amount of wash liquid being withdrawn from the circulation or flow. It is preferred to introduce the caustic soda or caustic potash before the hydro-gen sulphide washing and to remove the wash liquid before addition of the carbon dioxide. The carbon dioxide supplied for the hydrogen sulphide wash-ing step may be derived from the glue gases of the coke oven heating plant or from an ammonia separation plant. The invention also provides apparatus for use in the process of the invention, including gas washing devices con-structed as integrated components of the gas conduits.
Description
105;~5~7 The invention relates to a process and an apparatus for the purification of coke oven ~as in which am~onia is washed out with water, if necessary with addition of sulphuric acid, and hydrogen sulphide is washed out with an alkaline w~shing liquid from the detarred and cooled crude gas, from which wash liquid the combined hydrogen sulphide is subsequently removed.
In the gas purification processes known lC. accordin~ to the state of the art the alkaline wet gas desulphurisation in particular operates unsatisfactorily. In fact in the known alkaline wet gas desulphurisation the degree of separation is relatively s~all (about 8C~' - 9C~ sO that the wet purified @as must su~sequently be subjected to a fine purification in a dry gas desulphurisation plant.
The residues of this dry operating plant are not able to be deposited and must be m2de accessible to an environmentally pleasant disposal through costly 20. further procedure. In addition in the known alkaline wet gas desulphurisation for the separation of the hydrogen sulphide washed out a relatively large quantity of energy (heat) is required. Finally in the removal from the wash liquid of the hydrogen sulphide washed out the maximum attainable degree of separation is relatively small, about 8~c.
It is accordingly an object of the invention to 1 .
`-` lC~S;~53~
develop a ~as purification process, startin~ from the initially mentioned type, so that the alkaline wet gas ~esulphurisation is already so good that the subseouent fine purification can be dispensed with. In addition the energy and other expenditure should be as small as possible.
According to the invention there is provided a process for the purification of coke o~en gas, in which a~monia is washed out with water, if necessary with 10. the addition of sulphuric acid, and hydrogen sulphide is washed with an alkaline wash liquid from the detarred and cooled crude gas from which wash liquid the combined sulphur is subsequently re~oved, characterised in that the hydrogen sulphide washing takes place with a wash liquid containing sodiu~ or potassiu~ carbonate introduced into the wash circulation from which wash liquid the hydrogen sulphide is removed by the addition of carbon dioxide, wherein caustic soda solution or caustic potash solution is introduced into the circulation whilst 20. corresponding amounts of wash liquid are removed from the circulation.
There is first of all attained through the process according to the invention an almost complete gas desulphurisation so thatas~equent fine purification of the gases is rendered unnecessary. Moreover any hydro~en cyanide and other related compounds present in the crude gas are separated at the same time with the hydrogen sulphide, the degree of separation totalling up to 99.9S~. Since the separation of the combined S;~S37 ~hydrogen sulphide in the wash liquid and related compounds is efrected by carbon dioxide, which is cheaply available in the flue gases of coke oven heating or other combustion plants the costs for the chemicals employed are limited substantially to the small quantities of caustic soda solution or caustic potash solution introduced. Since the flue gases used for the addition of carbon dioxide are as a rule also hot, an additional introduction 10. of heat in the removal of the hydrogen sulphide is rendered completely or at least partially unnecessary.
In the process accordin~ to the invention however there arises in the wash liquid alkali sulphides (sodium sulphide, sodiu~ bi-sulphide;
potassium sulphide, potassium bi-sulphide) which are often not permitted in effluents and whose disposal can create difficulties.
It is therefore a further object of the 20. invention to develop the process in the direction that these harmful materials can be caused to be removed without additional costs.
~or a solution of this problem it is proposed in the development of the process according to the invention that the wash liquid removed from the circulation of the hydro~en sulphide washing is added to the effluent of the ammonia washing for the purpose of separating the fixed ammonia present in this.
105'~537 y means of the described further step of the process, the harmful alkali sulphides occurring in the hydrogen sulphide washing are not only made unharmlul, but take over in addition a task for which otherwise slaked lime or other chemicals were required. In the separation of the ammonia from the fixed ammonium compounds of the effluent of the ammonia washing only hydrogen sulphide occurs in the gas phase, the removal of which creates no difficulties and in the aqueous phase besides the al~monium sulphate usable as fertilizer only sodium carbonate and sodium chloride, or potassium carbonate and potassium chloride, which can be passed to the effluent without further trouble.
Preferably, in the process according to the invention, the addition of caustic soda solution or caustic potash solution to the circulation of the wash liquid of the hydrogen sulphide ~rashing takes place before the hydrogen sulphide washing and the removal of th-e washing liquid from the circulation before the carbon dioxide addition. ~y this means on the one hand the introduced fresh liouor inmediately arrives in the hydrogen sulphide washing, where it particularly intensively comes into action. On the other hand the dra~rn-off washing liquid does not need first to be freed from hydrogen sulphide by means of carbon dioxide since this hydrogen sulphide causes no trouble in the separation of fixed ammonia and if necessary converts to ammonium sulphate or escapes in the gas phase.
Particularly good results are obtained when the 1~5;~537 hydro~en sulphide washing -takes place between 20 to 30 G and the treatment of the wash liquid of the hydro~en sulphide washin~ with carbon dioxide takes place at 60 to 90 C~
Preferably the hydrogen sulphide occurring in the hydro~en sulphide washing and/or in the after treatrnent of the effluent of the ammonia washing is treated in known manner in a subseguently added sulphuric acid plant to form 10. sulphuric acid or in a subsequently added Claus oven to form sulphur.
~he carbon dioxide required for treat~ent of the wash liquid of the hydrogen sulphide washing suitably comes from the flue gases of the coke oven heating and/or other combustion plants or from ammonia separation.
~or carrying out the process accordin~ to the invention in which the wash liquids must be particularly intensively mixed with the crude 20. gas to be purified, gas purification devices for the am~onia washing and/or the hydrogen sulphide washing are preferably used which have a pipe serving as mixing tube in which the gas strec~ is thoroughly mixed with the finel~
divided washing liquid and attached to it a radi~l diffuser with radially directed vanes which is surrounded by a separator provided with extractor slots, wherein the gas washing devices are constructed as inte~rated components of the l~S'~S37 gas inlet conduits.
The process accordinG to the invention is explained in more detail below with reference to the drawings in which ~igure 1 shows schematically the process flow and Figures 2 and ~ show a washing device, used in the apparatus for carryin~ out the process according to the invention, in longitudinal section and cross section respectively.
In ~igure 1 the crude gas stream, detarred and 10. cooled, to be purified, is indicated by reference numeral 1~ The crude gas stre~l is led throu~h an ammonia washer 2 into which is introduced a water strea~ 3, which if necessar~ is mi~ed with sulphuric acid. mhe effluent stream 4 of the ammonia washer 2 is led into an ammonium sulphate recovery plant 5, in which ammonia is separated from the effluent and the fixed ammonia is separated from aQmoniu~ compounds, as will be further explained below.
The crude gas stream 6, freed from ammonia, is ~ed 20. to a hydrogen sulphide wasner 7. ~he wash liquid of the hydrogen sulphide washer 7 is introduced into a circulation which is indicated collectively by reference numeral 8. This circulation contains, in aaueous solution, sodi~ carbonate, caustic soda solution, sodium sulphide and sodium bi-sulphide, as effective components for removal of hydrogen sulphide. Further, the circulation contains also different com~onents which do not react with hydrogen sulphide and which if necessary are waslled out in the hydrogen sulphide washer7.
6.
" lOS;~S37 ~ he removal of the hydrogen sulphide washed out from the circulation 8 takes place in a regener~tion plant 9 which is inserted in the circulation ~ an~ in which the wAsh liquid introduced into the circulation 8 is thorou~hly mixed with a strong flue gas stream 10 containing carbon dioxide, whereby hydrogen sulphide is separated and sodium carbonate is produced or is recovered. The flue gas stream 10 comes from the heating plant of the coke oven or from other combustion 10. plants with suitable flue gases~ If necessary carbon dioxide can also be used, which occurs in the outflow of successively connected ammonia separation columns.
In order to avoid a~ enrichment of sodium sulphide and inert components in the circulation ~, there is continuously led off from this a part-stream 11 and the quantity of wash liquid led off replaced by a supplementary stream 12 of fresh caustic soda solution.
,~he branching-off of the partial stream 11 takes place behind the hydrogen sulphide washe- 7 and in front of 20. the regeneration plant 9, whereby only a little heat energy is withdl~aw~ from the circulation 8. The supplementary stream 12 is introduced with fresh caustic soda solution before the hydrogen sulphide washer 7, so t~at the unused caustic soda solution is used immediately for washing out the hydrogen sulphide, without previously having to lose reactivity because of other reactions. ~he e~cess amount of the carbon dioxide introduced ~ith the flue gas stream 12 ~oes off with the hydro~en sulphide stream 14 from the l(~S;~53'~
regeneration plant 9. The purified gas coming from the hydrogen sulphide washer 7 is indicated by reference numeral 13.
~he hydrogen sulphide washing preferably takes place at temperatures between 20 and 30 C. ~he re~eneration takes place preferably at about 60 to 90 C. In case the quantity of heat introduced into the regeneration plant 9 with the flue gas stream 10 is not sufficient, it must be heated up. ~he branched-off part quantity 10. 11 can, when appropriate environmental conditions permit, be passed to the effluent ~7ater. When this may not be permissible, because of the sodium sulphide contained therein, this p~rtial strea~ can be used for separating .::
the combined a~onia ~rom the effluent of the a~monia washer 2. In this, the ~artial strea~ Jhich contains sodium carbonate, sodium ~i-sulphide, sodium sulphide, small quantities of caustic soda solution a~d inert components is mixed with the effluent of the ammonia washer 2 existing in the a~monium sulphate recovery 20. plant 5. ~y this the sodium sulphide contained in the partial stream 11 reacts with the fixed amronia compounds contained in the ammonia washer, wherein substantially a~monium sulphate and hydrogen sulphide result.
In the case where the sodium sulphide occurring in the sulphuric acid washin~ is not sufficient for separating the whole of the fixed ammonia~ there can if necessary be additionally lntroduced sodium sulphide elsewhere derived, the removal of which otherwise would cause high costs. The typical reactions in this 1(~5'~S;~7 separation of fixed a~monia with sodium sulphide are as follows:-Na2 S + (NH4)2 CO3 ~ a2 CO3 +(I~4)2 S
Na2 S I (~H4)2 SO4 -~ Na2 S4 +(~4)2 S
Na2 S + 2 NH~ Cl _~ 2 Na Cl + (NH4)2S
3 (NH4) S + 3 H2 SO4 ~ 3(NH4)2 SO4 + 3 2 The resultin~ .~m~onium suiphate, which is used as a fertilizer, can be withdrawn from the ammonium 10. sulphate plant 5 at 15. The hydrogen sulphide stream 16 resulting in the ammoniu~ sulphate plant ~ is supplied, together with the hydrogen sulphide stream 14 of the regeneration plant 9, to a sulphuric acid recovery plant for the production of sulphuric acid or to a Claus oven for the production of sulphur. If necessary the hydrogen sulphide stre.~m 16 can be added also to the crude gas stream 1, or the crude gas stream 6 freed from a~onia, in order subsequently to be distributed in the hydrogen sulphide llashing.
20. hs an alternative to the above described process flow the ammonia washer and the hydrogen sulphide washer can be combined into a single ~rasher. Likel~ise the two washing processes caIl be, without further trouble, interchanged in the sequence of operations.
The above described process operates with caustic soda solution and correspondingly with sodium carbonate, sodium bi-sulphide and sodium sulphide, in the circulation 8. Obviously there can be introduced in lOS;~Si37 place Or caustic soda solution caustic potash solution whereby there results in the washing liquid of the circulation 8 potassium carbonate, potassium bi-sulphide and potassiu~ sulphide.
Gas washing devices are used in accordance with the process of the invention for the ammonia washer, the hydrogen ;ulphide washer or the combined washers which are illustrated in Figures 2 and 3. ~hese gas washing devices have a pipe 21 serving as a mixing 10. tube, in which pipe the gas stream is thoroughly mixed with finely divided wash liquid, c~nd which is connected with a radial diffuser. The radial diffuser has a conically shaped body 22 which feeds the gas-washing liquid mixture to guide vanes 23 attached to it. ~hese guide vanes 2~ are so constructed a~nd arranged that they serve on the one hand for pressure recovery and on the other hand for development of angular movement in the mixture. Externally the radial diffuser is encircled by a separator 24 which 20. has extractor slots 26 opening into a collecting chamber 25. The separated licuid can be led off from the chamber 2~. The washin~ device used in accordance with the invention has the advanta~e that it can be constructed as an integrated component in the gas inlet conduits and occupies only little more space than these. The reactions in the am~onia washing and in the hydrogen sulphide washing are so intensive that the short reaction time which is available in such washing devices suffices 10.
lOSZ537 to gi~e 99.9~o separation. ~or the re~eneration plant 9 of the washing liquid circulation 8 however conventional columns with bubble tra~s or the like are required.
In the gas purification processes known lC. accordin~ to the state of the art the alkaline wet gas desulphurisation in particular operates unsatisfactorily. In fact in the known alkaline wet gas desulphurisation the degree of separation is relatively s~all (about 8C~' - 9C~ sO that the wet purified @as must su~sequently be subjected to a fine purification in a dry gas desulphurisation plant.
The residues of this dry operating plant are not able to be deposited and must be m2de accessible to an environmentally pleasant disposal through costly 20. further procedure. In addition in the known alkaline wet gas desulphurisation for the separation of the hydrogen sulphide washed out a relatively large quantity of energy (heat) is required. Finally in the removal from the wash liquid of the hydrogen sulphide washed out the maximum attainable degree of separation is relatively small, about 8~c.
It is accordingly an object of the invention to 1 .
`-` lC~S;~53~
develop a ~as purification process, startin~ from the initially mentioned type, so that the alkaline wet gas ~esulphurisation is already so good that the subseouent fine purification can be dispensed with. In addition the energy and other expenditure should be as small as possible.
According to the invention there is provided a process for the purification of coke o~en gas, in which a~monia is washed out with water, if necessary with 10. the addition of sulphuric acid, and hydrogen sulphide is washed with an alkaline wash liquid from the detarred and cooled crude gas from which wash liquid the combined sulphur is subsequently re~oved, characterised in that the hydrogen sulphide washing takes place with a wash liquid containing sodiu~ or potassiu~ carbonate introduced into the wash circulation from which wash liquid the hydrogen sulphide is removed by the addition of carbon dioxide, wherein caustic soda solution or caustic potash solution is introduced into the circulation whilst 20. corresponding amounts of wash liquid are removed from the circulation.
There is first of all attained through the process according to the invention an almost complete gas desulphurisation so thatas~equent fine purification of the gases is rendered unnecessary. Moreover any hydro~en cyanide and other related compounds present in the crude gas are separated at the same time with the hydrogen sulphide, the degree of separation totalling up to 99.9S~. Since the separation of the combined S;~S37 ~hydrogen sulphide in the wash liquid and related compounds is efrected by carbon dioxide, which is cheaply available in the flue gases of coke oven heating or other combustion plants the costs for the chemicals employed are limited substantially to the small quantities of caustic soda solution or caustic potash solution introduced. Since the flue gases used for the addition of carbon dioxide are as a rule also hot, an additional introduction 10. of heat in the removal of the hydrogen sulphide is rendered completely or at least partially unnecessary.
In the process accordin~ to the invention however there arises in the wash liquid alkali sulphides (sodium sulphide, sodiu~ bi-sulphide;
potassium sulphide, potassium bi-sulphide) which are often not permitted in effluents and whose disposal can create difficulties.
It is therefore a further object of the 20. invention to develop the process in the direction that these harmful materials can be caused to be removed without additional costs.
~or a solution of this problem it is proposed in the development of the process according to the invention that the wash liquid removed from the circulation of the hydro~en sulphide washing is added to the effluent of the ammonia washing for the purpose of separating the fixed ammonia present in this.
105'~537 y means of the described further step of the process, the harmful alkali sulphides occurring in the hydrogen sulphide washing are not only made unharmlul, but take over in addition a task for which otherwise slaked lime or other chemicals were required. In the separation of the ammonia from the fixed ammonium compounds of the effluent of the ammonia washing only hydrogen sulphide occurs in the gas phase, the removal of which creates no difficulties and in the aqueous phase besides the al~monium sulphate usable as fertilizer only sodium carbonate and sodium chloride, or potassium carbonate and potassium chloride, which can be passed to the effluent without further trouble.
Preferably, in the process according to the invention, the addition of caustic soda solution or caustic potash solution to the circulation of the wash liquid of the hydrogen sulphide ~rashing takes place before the hydrogen sulphide washing and the removal of th-e washing liquid from the circulation before the carbon dioxide addition. ~y this means on the one hand the introduced fresh liouor inmediately arrives in the hydrogen sulphide washing, where it particularly intensively comes into action. On the other hand the dra~rn-off washing liquid does not need first to be freed from hydrogen sulphide by means of carbon dioxide since this hydrogen sulphide causes no trouble in the separation of fixed ammonia and if necessary converts to ammonium sulphate or escapes in the gas phase.
Particularly good results are obtained when the 1~5;~537 hydro~en sulphide washing -takes place between 20 to 30 G and the treatment of the wash liquid of the hydro~en sulphide washin~ with carbon dioxide takes place at 60 to 90 C~
Preferably the hydrogen sulphide occurring in the hydro~en sulphide washing and/or in the after treatrnent of the effluent of the ammonia washing is treated in known manner in a subseguently added sulphuric acid plant to form 10. sulphuric acid or in a subsequently added Claus oven to form sulphur.
~he carbon dioxide required for treat~ent of the wash liquid of the hydrogen sulphide washing suitably comes from the flue gases of the coke oven heating and/or other combustion plants or from ammonia separation.
~or carrying out the process accordin~ to the invention in which the wash liquids must be particularly intensively mixed with the crude 20. gas to be purified, gas purification devices for the am~onia washing and/or the hydrogen sulphide washing are preferably used which have a pipe serving as mixing tube in which the gas strec~ is thoroughly mixed with the finel~
divided washing liquid and attached to it a radi~l diffuser with radially directed vanes which is surrounded by a separator provided with extractor slots, wherein the gas washing devices are constructed as inte~rated components of the l~S'~S37 gas inlet conduits.
The process accordinG to the invention is explained in more detail below with reference to the drawings in which ~igure 1 shows schematically the process flow and Figures 2 and ~ show a washing device, used in the apparatus for carryin~ out the process according to the invention, in longitudinal section and cross section respectively.
In ~igure 1 the crude gas stream, detarred and 10. cooled, to be purified, is indicated by reference numeral 1~ The crude gas stre~l is led throu~h an ammonia washer 2 into which is introduced a water strea~ 3, which if necessar~ is mi~ed with sulphuric acid. mhe effluent stream 4 of the ammonia washer 2 is led into an ammonium sulphate recovery plant 5, in which ammonia is separated from the effluent and the fixed ammonia is separated from aQmoniu~ compounds, as will be further explained below.
The crude gas stream 6, freed from ammonia, is ~ed 20. to a hydrogen sulphide wasner 7. ~he wash liquid of the hydrogen sulphide washer 7 is introduced into a circulation which is indicated collectively by reference numeral 8. This circulation contains, in aaueous solution, sodi~ carbonate, caustic soda solution, sodium sulphide and sodium bi-sulphide, as effective components for removal of hydrogen sulphide. Further, the circulation contains also different com~onents which do not react with hydrogen sulphide and which if necessary are waslled out in the hydrogen sulphide washer7.
6.
" lOS;~S37 ~ he removal of the hydrogen sulphide washed out from the circulation 8 takes place in a regener~tion plant 9 which is inserted in the circulation ~ an~ in which the wAsh liquid introduced into the circulation 8 is thorou~hly mixed with a strong flue gas stream 10 containing carbon dioxide, whereby hydrogen sulphide is separated and sodium carbonate is produced or is recovered. The flue gas stream 10 comes from the heating plant of the coke oven or from other combustion 10. plants with suitable flue gases~ If necessary carbon dioxide can also be used, which occurs in the outflow of successively connected ammonia separation columns.
In order to avoid a~ enrichment of sodium sulphide and inert components in the circulation ~, there is continuously led off from this a part-stream 11 and the quantity of wash liquid led off replaced by a supplementary stream 12 of fresh caustic soda solution.
,~he branching-off of the partial stream 11 takes place behind the hydrogen sulphide washe- 7 and in front of 20. the regeneration plant 9, whereby only a little heat energy is withdl~aw~ from the circulation 8. The supplementary stream 12 is introduced with fresh caustic soda solution before the hydrogen sulphide washer 7, so t~at the unused caustic soda solution is used immediately for washing out the hydrogen sulphide, without previously having to lose reactivity because of other reactions. ~he e~cess amount of the carbon dioxide introduced ~ith the flue gas stream 12 ~oes off with the hydro~en sulphide stream 14 from the l(~S;~53'~
regeneration plant 9. The purified gas coming from the hydrogen sulphide washer 7 is indicated by reference numeral 13.
~he hydrogen sulphide washing preferably takes place at temperatures between 20 and 30 C. ~he re~eneration takes place preferably at about 60 to 90 C. In case the quantity of heat introduced into the regeneration plant 9 with the flue gas stream 10 is not sufficient, it must be heated up. ~he branched-off part quantity 10. 11 can, when appropriate environmental conditions permit, be passed to the effluent ~7ater. When this may not be permissible, because of the sodium sulphide contained therein, this p~rtial strea~ can be used for separating .::
the combined a~onia ~rom the effluent of the a~monia washer 2. In this, the ~artial strea~ Jhich contains sodium carbonate, sodium ~i-sulphide, sodium sulphide, small quantities of caustic soda solution a~d inert components is mixed with the effluent of the ammonia washer 2 existing in the a~monium sulphate recovery 20. plant 5. ~y this the sodium sulphide contained in the partial stream 11 reacts with the fixed amronia compounds contained in the ammonia washer, wherein substantially a~monium sulphate and hydrogen sulphide result.
In the case where the sodium sulphide occurring in the sulphuric acid washin~ is not sufficient for separating the whole of the fixed ammonia~ there can if necessary be additionally lntroduced sodium sulphide elsewhere derived, the removal of which otherwise would cause high costs. The typical reactions in this 1(~5'~S;~7 separation of fixed a~monia with sodium sulphide are as follows:-Na2 S + (NH4)2 CO3 ~ a2 CO3 +(I~4)2 S
Na2 S I (~H4)2 SO4 -~ Na2 S4 +(~4)2 S
Na2 S + 2 NH~ Cl _~ 2 Na Cl + (NH4)2S
3 (NH4) S + 3 H2 SO4 ~ 3(NH4)2 SO4 + 3 2 The resultin~ .~m~onium suiphate, which is used as a fertilizer, can be withdrawn from the ammonium 10. sulphate plant 5 at 15. The hydrogen sulphide stream 16 resulting in the ammoniu~ sulphate plant ~ is supplied, together with the hydrogen sulphide stream 14 of the regeneration plant 9, to a sulphuric acid recovery plant for the production of sulphuric acid or to a Claus oven for the production of sulphur. If necessary the hydrogen sulphide stre.~m 16 can be added also to the crude gas stream 1, or the crude gas stream 6 freed from a~onia, in order subsequently to be distributed in the hydrogen sulphide llashing.
20. hs an alternative to the above described process flow the ammonia washer and the hydrogen sulphide washer can be combined into a single ~rasher. Likel~ise the two washing processes caIl be, without further trouble, interchanged in the sequence of operations.
The above described process operates with caustic soda solution and correspondingly with sodium carbonate, sodium bi-sulphide and sodium sulphide, in the circulation 8. Obviously there can be introduced in lOS;~Si37 place Or caustic soda solution caustic potash solution whereby there results in the washing liquid of the circulation 8 potassium carbonate, potassium bi-sulphide and potassiu~ sulphide.
Gas washing devices are used in accordance with the process of the invention for the ammonia washer, the hydrogen ;ulphide washer or the combined washers which are illustrated in Figures 2 and 3. ~hese gas washing devices have a pipe 21 serving as a mixing 10. tube, in which pipe the gas stream is thoroughly mixed with finely divided wash liquid, c~nd which is connected with a radial diffuser. The radial diffuser has a conically shaped body 22 which feeds the gas-washing liquid mixture to guide vanes 23 attached to it. ~hese guide vanes 2~ are so constructed a~nd arranged that they serve on the one hand for pressure recovery and on the other hand for development of angular movement in the mixture. Externally the radial diffuser is encircled by a separator 24 which 20. has extractor slots 26 opening into a collecting chamber 25. The separated licuid can be led off from the chamber 2~. The washin~ device used in accordance with the invention has the advanta~e that it can be constructed as an integrated component in the gas inlet conduits and occupies only little more space than these. The reactions in the am~onia washing and in the hydrogen sulphide washing are so intensive that the short reaction time which is available in such washing devices suffices 10.
lOSZ537 to gi~e 99.9~o separation. ~or the re~eneration plant 9 of the washing liquid circulation 8 however conventional columns with bubble tra~s or the like are required.
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the purification of coke oven gas, said process consisting in washing detarred and cooled gas with water having, if necessary, sulphuric acid added thereto, in order to remove ammonia from the gas, and then subjecting the washed gas to a further washing with a washing liquid circulating in a circulation system and containing sodium or potassium carbo-nate, in order to remove hydrogen sulphide from the washed gas and yield purified coke oven gas, the hydrogen sulphide being removed from the washing liquid, after it has washed the gas, by the introduction of carbon dioxide into the circulation system, said process further comprising the steps of introducing amounts of caustic soda solution or caustic potash solution into the circulating washing liquid up-stream of the point of introduction of the washed gas into the circulation system, removing corresponding amounts of washing liquid from the circulation system downstream of the point of yield of the purified gas, and adding the washing liquid thus removed to the efflu-ent from the ammonia removing washing step to separate the fixed ammonia present in such effluent.
2. Process according to claim 1, characterized in that the hydrogen sulphide washing takes place between 20 and 30°C and the treatment of the wash liquid of the hydrogen sulphide washing takes place with carbon dioxide at 60 to 90°C.
3. Process according to claim 1, characterized in that the hydrogen sulphide occurring in the hydrogen sulphide washing and/or in the after treat-ment of the effluent of the ammonia washing is further treated in known manner in a subsequently added sulphuric acid plant to form a sulphuric acid or worked up in a subsequently added Claus oven to form sulphur.
4. Process according to claim 1, 2 or 3, characterized in that the carbon dioxide required for the treatment of the wash liquid of the hydrogen sulphide washing is derived from the flue gases of the coke oven heating and/
or other combustion plants.
or other combustion plants.
5. Process according to claim 1, 2 or 3, characterized in that the carbon dioxide required for treatment of the wash liquid of the hydrogen sul-phide washing derives from ammonia separation.
6. Apparatus for carrying out the process according to claim 1, characterized by the use of gas washing devices for the ammonia washing and/
or the hydrogen sulphide washing which have a pipe serving as a mixing tube in which the gas stream is thoroughly mixed with finely divided wash liquid and to which is connected a radial diffuser with radially directed guide vanes, which diffuser is encircled by a separator provided with extractor slots, wherein the gas washing devices are constructed as integrated compo-nents of the gas conduits.
or the hydrogen sulphide washing which have a pipe serving as a mixing tube in which the gas stream is thoroughly mixed with finely divided wash liquid and to which is connected a radial diffuser with radially directed guide vanes, which diffuser is encircled by a separator provided with extractor slots, wherein the gas washing devices are constructed as integrated compo-nents of the gas conduits.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19742412026 DE2412026C3 (en) | 1974-03-13 | Process for stripping bound ammonia from ammonia water | |
| DE2441773A DE2441773A1 (en) | 1974-08-31 | 1974-08-31 | Purificn. of coke-oven gas with hydrogen sulphide removal - by scrubbing with alkali metal carbonate soln. regenerated with carbon dioxide |
| DE19742444349 DE2444349A1 (en) | 1974-09-17 | 1974-09-17 | Purificn. of coke-oven gas with hydrogen sulphide removal - by scrubbing with alkali metal carbonate soln. regenerated with carbon dioxide |
| DE19752505959 DE2505959C3 (en) | 1975-02-13 | 1975-02-13 | Process for purifying coke oven gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1052537A true CA1052537A (en) | 1979-04-17 |
Family
ID=27431824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA221,686A Expired CA1052537A (en) | 1974-03-13 | 1975-03-10 | Process and apparatus for the purification of coke oven gas |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5328321B2 (en) |
| CA (1) | CA1052537A (en) |
| FR (1) | FR2264080B3 (en) |
| GB (1) | GB1467083A (en) |
| IT (1) | IT1033456B (en) |
| NL (1) | NL7502281A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4499060A (en) * | 1982-02-12 | 1985-02-12 | Dr. C. Otto & Comp. G.M.B.H. | Process for removing hydrogen sulfide from gases, particularly coal distillation gases |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS621402Y2 (en) * | 1981-03-20 | 1987-01-13 | ||
| JPS57156056U (en) * | 1981-03-27 | 1982-09-30 | ||
| JPS621403Y2 (en) * | 1981-04-07 | 1987-01-13 | ||
| EP0336142A3 (en) * | 1988-04-04 | 1991-04-24 | American Cyanamid Company | Novel antagonists of platelet activating factor |
| DE3834847A1 (en) * | 1988-10-13 | 1990-04-19 | Krupp Koppers Gmbh | PROCESS FOR DISSOLVING COKE-FUEL GAS |
| DE102007015137B3 (en) | 2007-03-29 | 2008-09-04 | Uhde Gmbh | Preparation of sulfuric acid in sulfuric acid extraction plant, comprises preparing sulfur dioxide containing raw gas, supplying the raw gas for catalytic reaction of sulfur dioxide to sulfur trioxide and then converting to sulfuric acid |
| DE102012017045A1 (en) | 2012-08-29 | 2014-05-15 | Thyssenkrupp Uhde Gmbh | Process for washing sulfur-containing gases with a circulating ammonia-containing washing solution |
-
1975
- 1975-02-25 GB GB774375A patent/GB1467083A/en not_active Expired
- 1975-02-26 NL NL7502281A patent/NL7502281A/en unknown
- 1975-03-06 IT IT2096775A patent/IT1033456B/en active
- 1975-03-10 CA CA221,686A patent/CA1052537A/en not_active Expired
- 1975-03-12 FR FR7507756A patent/FR2264080B3/fr not_active Expired
- 1975-03-13 JP JP3063675A patent/JPS5328321B2/ja not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4499060A (en) * | 1982-02-12 | 1985-02-12 | Dr. C. Otto & Comp. G.M.B.H. | Process for removing hydrogen sulfide from gases, particularly coal distillation gases |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2264080B3 (en) | 1977-11-18 |
| NL7502281A (en) | 1975-09-16 |
| AU7903475A (en) | 1976-09-16 |
| JPS5328321B2 (en) | 1978-08-14 |
| GB1467083A (en) | 1977-03-16 |
| IT1033456B (en) | 1979-07-10 |
| FR2264080A1 (en) | 1975-10-10 |
| JPS50132003A (en) | 1975-10-18 |
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