CN104556147A - Process for preparing SCR reducing agent from coking residual ammonia wastewater as raw material - Google Patents
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- CN104556147A CN104556147A CN201410785680.2A CN201410785680A CN104556147A CN 104556147 A CN104556147 A CN 104556147A CN 201410785680 A CN201410785680 A CN 201410785680A CN 104556147 A CN104556147 A CN 104556147A
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Abstract
The invention provides a process for preparing an SCR reducing agent from a coking residual ammonia wastewater as a raw material. The process is characterized by comprising the following steps: condensing ammonia vapor generated by a dephlegmator of an ammonia stripping system of a gas purification workshop in a coking plant to obtain coking strong ammonia water; removing impurities from the coking strong ammonia water by a filter and deoiling by an adsorption tower; adding an NaOH alkali liquor to the ammonia water, mixing evenly, and then conveying to a distillation tower to carry out secondary distillation; processing the ammonia vapor at the tower top through the dephlegmator and then processing by the condenser, so as to obtain refined strong ammonia water; adopting coking ammonia water generated by ammonia distillation of the coking residual ammonia wastewater as a preparation raw material of the SCR reducing agent, and refining the coking strong ammonia water to reach the requirements of the reducing agent used for SCR catalytic reduction, so that the denitration cost is reduced when the denitration efficiency is ensured.
Description
Technical field
The present invention relates to coal chemical enterprise exhaust emission control technology field, being specifically related to a kind of take residual coking ammonia water as the technique that SCR reducing agent prepared by raw material.
Background technology
The SO of China
2and NO
xdischarge capacity is in prostatitis, countries in the world.Research shows, gas phase SO
2, NO
xthe presoma of PM2.5, by SO
2, NO
x, the amount of PM2.5 that changes of the presoma such as VOCs is more than what directly discharge.SO
2, NO
xbe one of main matter forming acid rain, the atmosphere pollution caused and acid rain problem are day by day serious, serious to the harm such as human health and the ecosystem, have become the factor of restriction China sustainable development of socio-economy.
On June 27th, 2012 national environmental protection portion and State Administration for Quality Supervision and Inspection and Quarantine jointly issued " coking chemistry emission of industrial pollutants standard " (GB16171-2012), require from 1 day January in 2015, existing enterprise performs " table 5 " regulation; From 1 day January in 2012, newly-built enterprise execution table 1 specified; Area performs " table 6 " stricter regulation especially, and concrete regulation sees the following form.
Table 1 GB16171-2012 coke oven chimney Air Pollutant Emission concentration limit
Document " low NOx combusting technology progress " (" fuel and chemical industry ", 2013 (1): 6 ~ 9) and " during coke oven heating burning the formation mechenism of nitrogen oxide and control " (" fuel and chemical industry ", 2009 (6): 5 ~ 12), paper coke oven NO
xthe mechanism formed, show that the nitrogen oxide that coke-stove gas burning produces is mainly temperature heating power type conclusion, and proposes to adopt the mode of Combustion System to improve.
Document " coke oven chimney NOx emission controls modest proposal " (" fuel and chemical industry ", 2013 (5): 1 ~ 3), the design from coke oven heating system and 2 aspects of the post processing to coke oven stack gases discuss coke oven chimney NO
xthe technical measures of emission control, briefly introduce SCR(SCR) gas denitrifying technology, propose pilot scale and the engineering experience of Japanese Tokyo Gas Company, SCR denitration technology is adopted to carry out post processing to coke oven stack gases, to be up to state standards to the NOx emission control overflow of " especially area " coke oven chimney.
Above document Main Analysis coke oven NO
xthe mechanism formed, suppresses coke oven NO by the mode, design, structure etc. controlling coke oven heating
xthe NO that heating flame produces
x, do not propose concrete method and solve coke oven flue waste gas SO
2, NO
xand reclaim the method for heat.The pilot process of Tokyo Gas Company needs to heat coke oven exhaust gas again.
Application publication number CN 103816796 A, name is called the application for a patent for invention of " a kind of low temperature coke oven flue gas desulfurization systems denitrating technique ", with Authorization Notice No. CN 203853017 U, name is called the utility model patent of " a kind of low temperature coke oven flue gas desulfurization systems denitrification apparatus ", individually disclose a kind of low temperature coke oven flue gas desulfurization systems denitrating technique and device, propose to spray into fluidised NaHCO in flue gas conveyance conduit
3fine powder, the SO of the overwhelming majority in dry removal flue gas
2, denitrating catalyst structure sheaf is combined with except ammonia catalyst structure layer, the NO in efficient removal flue gases of cock oven simultaneously
x, denitrating catalyst adopts filter bag shaped structure, except ammonia catalyst adopts V-shape structure; The system that this technique prepares unit by air inducing unit, desulfurization unit, ammonia, denitration forms except ammonia unit, compressed air unit, particle supply unit realizes NO_x Reduction by Effective, desulfurization; Utilize coke-oven plant's remained ammonia, adopt the technique that dry desulfurization combines with the denitration of SCR method, and denitrating catalyst is combined with except ammonia catalyst, realize carrying out high-efficiency desulfurization denitration to coalitenessity kiln gas.This patent uses residual coking ammonia water direct denitration, because residual coking ammonia water concentration is low, only containing the ammonia of 3g/l, also has the impurity such as oil, hydrogen sulfide, hydrogen cyanide, does not therefore reach the technological requirement that denitration uses ammonia.
Application publication number CN101717096A, the patent of invention that name is called " utilizing residual coking ammonia water to prepare the technique of desulfurizing agent ammoniacal liquor in sintering flue gas desulfurization ", discloses a kind of technique utilizing residual coking ammonia water to prepare ammoniacal liquor desulfurizing agent in sintering flue gas desulfurization.Residual coking ammonia water in technology utilization coking gas purification system after ammonia still ammonia dephlegmator, i.e. 15% ~ 20% concentration ammoniacal liquor of ammonia steam-condensation generation is as the source sintering desulfurizing agent ammoniacal liquor in ammonia type flue gas desulfurizing.Remained ammonia is used for flue gas desulfurization by this patent, the ammonium salt of hydrogen sulfide in remained ammonia, hydrogen cyanide and formation can not all decompose in extracting tower, sulfide hydrogen after entering ammonia still in solution, the ammonium salt of hydrogen cyanide continue to decompose, still containing impurity such as phenol, oil, hydrogen sulfide, hydrogen cyanide in ammoniacal liquor, do not reach the technological requirement that denitration uses ammonia equally.
Summary of the invention
Do not reach to solve residual coking ammonia water the technical problem that denitration uses ammonia process requirement, the invention provides a kind of take residual coking ammonia water as the technique that SCR reducing agent prepared by raw material.Adopt the raw materials of coking concentrated ammonia liquor as SCR reducing agent of remained ammonia ammonia still process generation in the ammonia still process workshop section of gas purification workshop, coke-oven plant, coking concentrated ammonia liquor is refined the requirement reaching the reducing agent that SCR catalytic reduction uses, while ensureing denitration efficiency, reduce the expense of denitration.
In order to realize foregoing invention object, the present invention adopts following technical scheme:
Take residual coking ammonia water as the technique that SCR reducing agent prepared by raw material, it is characterized in that: the ammonia vapour that gas purification workshop, coke-oven plant ammonia steaming device dephlegmator produces obtains coking concentrated ammonia liquor through condensation, coking concentrated ammonia liquor is after filter removal of impurities and adsorption tower de-oiling, NaOH alkali lye is added again in ammoniacal liquor, deliver to destilling tower after mixing and carry out second distillation, the ammonia vapour of tower top, by after dephlegmator, obtains refining concentrated ammonia liquor through condenser.
Owing to containing the impurity such as phenol, oil, hydrogen sulfide, hydrogen cyanide in coking concentrated ammonia liquor, these impurity can affect the activity of SCR catalyst or cause poisoning.The present invention by first for coking concentrated ammonia liquor filtering and impurity removing, then after absorption de-oiling, adds NaOH alkali lye in ammoniacal liquor, and ammonium hydro sulfide, ammonium cyanide etc. in NaOH alkali lye and coking concentrated ammonia liquor are converted into Na
2the thermal-stable salts such as S, NaCN, coking concentrated ammonia liquor hydrogen sulfide, hydrogen cyanide etc. when second distillation are remained in deposed ammonia and does not enter into ammonia vapour, the coking concentrated ammonia liquor adding alkali lye is delivered to destilling tower and carries out second distillation, the ammonia vapour of tower top is only containing the impurity such as phenol, oil, hydrogen sulfide, hydrogen cyanide of trace, after dephlegmator, condensation obtains pure refining concentrated ammonia liquor, meets the technological requirement that SCR denitration uses ammonia.
Refining concentrated ammonia liquor of the present invention contains ammonia 16 ~ 26%, containing H
2s is less than 5mg/l, hydrogen cyanide is less than 5mg/l, without the visible mechanical admixture of naked eyes and oil, can not affect the activity of low-temperature SCR catalyst, meets the technological requirement that denitration uses ammonia completely.
Preferably, add in coking concentrated ammonia liquor per ton mass fraction be 31% alkali lye 15 ~ 100kg or mass fraction be 42% alkali lye 12 ~ 70kg.In ammoniacal liquor, add excessive NaOH alkali lye, be converted into Na with the ammonium hydro sulfide in coking concentrated ammonia liquor, ammonium cyanide etc.
2the thermal-stable salts such as S, NaCN, make coking concentrated ammonia liquor hydrogen sulfide, hydrogen cyanide etc. when second distillation remain in deposed ammonia and do not enter into ammonia vapour.
Pass into live (open) steam at the bottom of destilling tower of the present invention, effectively can reduce investment.
Deliver to coking ammonia steaming device containing the deposed ammonia of alkali lye at the bottom of destilling tower of the present invention and decompose ammonium salt.
The mass fraction of coking concentrated ammonia liquor of the present invention is 14-18%.
What absorption de-oiling of the present invention adopted is activated carbon.
The SCR that refining concentrated ammonia liquor of the present invention is used for coke oven flue waste gas is catalytic-reduction denitrified.
Preferably, the catalyst of described SCR denitration to be temperature range the be low temperature SCR denitration catalyst of 160 DEG C ~ 290 DEG C.
Because flue gases of cock oven temperature is 220 ~ 290 DEG C, under this temperature conditions, carry out denitration reaction, the SCR catalyst at selecting 160 DEG C ~ 290 DEG C has very high denitration efficiency, and the escaping of ammonia rate is very low, can effectively by the NO in coke oven flue gas
xbe converted into N
2, denitration efficiency is high.
Preferably, described coke oven combustion uses the coke-stove gas after purification, the dry desulfurizing process that its process for purifying adopts desulfurizing tower to connect with adsorption tower.
In order to ensure the denitration efficiency of catalyst, first adopting dry desulfurizing process to purify coke-stove gas, flow process being formed as the serial operation mode of desulfurizing tower and adsorption tower, being removed the most of H in coal gas by desulfurizing tower
2s, then enter adsorption tower and remove H further
2s, organic sulfur and most of tar, naphthalene, NH
3with the impurity such as HCN, control by the total sulfur content reduced in coke-stove gas the SO that coke-stove gas burns in the coke oven flue waste gas that produces
2concentration, at reduction SO
2while outer row's concentration, prevent SO
2sO is changed under denitrating catalyst effect
3, with NH
3blocking catalyst after reaction generation ammonium sulfate deliquescence, has a strong impact on catalyst service efficiency.
Coke oven flue exhuast gas desulfurization denitration generally uses semi-dry desulphurization+low temperature SCR denitration at present, in denitrating technique, preposition sulfur removal technology removes the sulphur in stack gases, because preposition sulfur removal technology is semi-dry desulphurization, flue-gas temperature can reduce by 40 ~ 60 DEG C, then because flue-gas temperature decreases, denitration efficiency can be reduced further.Although this problem can be solved by heating coke oven flue waste gas, can energy waste be caused, increase once investment and operating cost simultaneously.Adopt dry desulfurizing process first by the inorganic sulfur delivered in the firing tunnel in coking furnace of coke oven and organic sulfur removal, flue gas does not need heating, and directly can carry out denitration, denitration efficiency can reach the highest standard (table 6) that GB16171-2012 specifies, containing NO
x<150 mg/m
3, SO
2<30mg/m
3, both reduced investment, in turn save the energy, coke per ton can by-product 100kg steam simultaneously.
Further preferably, the coke-stove gas total sulfur <40mg/m after described purification
3.By the total sulfur content in the coke-stove gas after reduction purification in this scope, thus SO in the coke oven flue waste gas of generation after controlling coke-stove gas burning
2concentration <20mg/m
3, ensure the use of low temperature SCR denitration catalyst, ensure the service life of denitration efficiency, extending catalyst, save the use amount of catalyst.
Described total sulfur comprises the sulfur-containing compound such as hydrogen sulfide and organic sulfur.
Beneficial effect of the present invention is:
1, owing to containing the impurity such as phenol, oil, hydrogen sulfide, hydrogen cyanide in coking concentrated ammonia liquor, these impurity can affect the activity of SCR catalyst or cause poisoning.Coking concentrated ammonia liquor first by filtering and impurity removing, then after absorption de-oiling, is added NaOH alkali lye by the present invention in ammoniacal liquor, and ammonium hydro sulfide, ammonium cyanide etc. in NaOH alkali lye and coking concentrated ammonia liquor are converted into Na
2the thermal-stable salts such as S, NaCN, coking concentrated ammonia liquor hydrogen sulfide, hydrogen cyanide etc. when second distillation are remained in deposed ammonia and does not enter into ammonia vapour, the coking concentrated ammonia liquor adding alkali lye is delivered to destilling tower and carries out second distillation, the ammonia vapour of tower top is only containing the impurity such as phenol, oil, hydrogen sulfide, hydrogen cyanide of trace, after dephlegmator, condensation obtains pure refining concentrated ammonia liquor, this refining concentrated ammonia liquor is used for the reducing agent of SCR denitration, the activity of SCR catalysts can not be affected, ensure that the efficiency of SCR denitration.
2, the refining concentrated ammonia liquor that present invention process obtains contains ammonia 16 ~ 26%, containing H
2s is less than 5mg/l, hydrogen cyanide is less than 5mg/l, without the visible mechanical admixture of naked eyes and oil, can not affect the activity of SCR catalyst, is the high efficiency guarantee of SCR denitration.
3, the present invention add in coking concentrated ammonia liquor per ton mass fraction be 31% alkali lye 15 ~ 100kg or mass fraction be 42% alkali lye 12 ~ 70kg.In ammoniacal liquor, add excessive NaOH alkali lye, be converted into Na with the ammonium hydro sulfide in coking concentrated ammonia liquor, ammonium cyanide etc.
2the thermal-stable salts such as S, NaCN, make coking concentrated ammonia liquor hydrogen sulfide, hydrogen cyanide etc. when second distillation remain in deposed ammonia and do not enter into ammonia vapour, ensure that the purity of refining ammoniacal liquor.
4, the refining concentrated ammonia liquor that obtains of present invention process is for the SCR denitration technique of coke oven flue waste gas, utilizes the ammoniacal liquor that coking produces, and storage, transport are just very simple, achieve and reduce denitration expense, reduce investment, and the coke-oven plant of 1,000,000 tons/year saves about 1,400,000; Meanwhile, denitration efficiency can reach the highest standard (table 6) that GB16171-2012 specifies, containing NO
x<150 mg/m
3, SO
2<30mg/m
3.
5, the prior art of coke oven flue exhaust gas denitration generally uses power plant's High-temperature scr catalyst, and efficiency is low, and the complete ammonia of unreacted is high; The present invention is 220 ~ 290 DEG C according to flue gases of cock oven temperature, and the low temperature SCR denitration catalyst at selecting 160 DEG C ~ 290 DEG C, not only directly can carry out denitration reaction to flue gases of cock oven, meet the feature that coke oven flue EGT is lower, and do not need heating, energy consumption is low; Also have very high denitration efficiency, the escaping of ammonia rate is very low, can effectively by the NO in coke oven flue gas
xbe converted into N
2, denitration efficiency is high.
6, coke oven combustion adopts the coke-stove gas after purifying, and adopts dry desulfurizing process, removes the sulfur-containing compound in coke-stove gas, then enter the further imurity-removal of adsorption tower in desulfurizing tower.Remove the sulphur in stack gases relative to sulfur removal technology preposition in the denitrating technique of prior art, because preposition sulfur removal technology is semi-dry desulphurization, flue-gas temperature can reduce by 40 ~ 60 DEG C, then because flue-gas temperature decreases, can reduce denitration efficiency further.Although this problem can be solved by heating coke oven flue waste gas, can energy waste be caused, increase once investment and operating cost simultaneously.Adopt dry desulfurizing process first by the inorganic sulfur delivered in the firing tunnel in coking furnace of coke oven and organic sulfur removal, make the total sulfur <40mg/m in the coal gas after purification
3, make flue gases of cock oven SO after gas-fired
2reach 20 mg/m
3below, flue gas does not need heating, and directly can carry out denitration, denitration efficiency can reach the highest standard that GB16171-2012 specifies, saves the consumption of the energy and catalyst, reduce further investment, and coke per ton can by-product 100kg steam.
Accompanying drawing explanation
Fig. 1 is the flow chart of SCR reducing agent preparation technology of the present invention.
Be labeled as in figure: 1, coking concentrated ammonia liquor groove, 2, concentrated ammonia liquor pump, 3, filter, 4, adsorption tower, 5, ammonia still, 6, dephlegmator, 7, condenser, 8, refining ammoniacal liquor storage tank.
Detailed description of the invention
Below in conjunction with detailed description of the invention, essentiality content of the present invention is described in further detail.
Embodiment 1
Take residual coking ammonia water as the technique that SCR reducing agent prepared by raw material, the ammonia vapour that gas purification workshop, coke-oven plant ammonia steaming device dephlegmator produces obtains coking concentrated ammonia liquor through condensation, coking concentrated ammonia liquor is after filter removal of impurities and adsorption tower de-oiling, NaOH alkali lye is added again in ammoniacal liquor, deliver to destilling tower after mixing and carry out second distillation, the ammonia vapour of tower top, by after dephlegmator, obtains refining concentrated ammonia liquor through condenser.
Embodiment 2
Take residual coking ammonia water as the technique that SCR reducing agent prepared by raw material, the ammonia vapour that gas purification workshop, coke-oven plant ammonia steaming device dephlegmator produces obtains coking concentrated ammonia liquor through condensation, coking concentrated ammonia liquor is after filter removal of impurities and adsorption tower de-oiling, NaOH alkali lye is added again in ammoniacal liquor, deliver to destilling tower after mixing and carry out second distillation, the ammonia vapour of tower top, by after dephlegmator, obtains refining concentrated ammonia liquor through condenser.
Described refining concentrated ammonia liquor contains ammonia 16%, containing H
2s 3.5mg/l, hydrogen cyanide 3.2mg/l.
Embodiment 3
Take residual coking ammonia water as the technique that SCR reducing agent prepared by raw material, the ammonia vapour that gas purification workshop, coke-oven plant ammonia steaming device dephlegmator produces obtains coking concentrated ammonia liquor through condensation, coking concentrated ammonia liquor is after filter removal of impurities and adsorption tower de-oiling, NaOH alkali lye is added again in ammoniacal liquor, deliver to destilling tower after mixing and carry out second distillation, the ammonia vapour of tower top, by after dephlegmator, obtains refining concentrated ammonia liquor through condenser.
The alkali lye 15kg that mass fraction is 31% is added in coking concentrated ammonia liquor per ton.
Described refining concentrated ammonia liquor contains ammonia 26%, containing H
2s 3.2mg/l, hydrogen cyanide 2.6mg/l.
Embodiment 4
Take residual coking ammonia water as the technique that SCR reducing agent prepared by raw material, the ammonia vapour that gas purification workshop, coke-oven plant ammonia steaming device dephlegmator produces obtains coking concentrated ammonia liquor through condensation, coking concentrated ammonia liquor is after filter removal of impurities and adsorption tower de-oiling, NaOH alkali lye is added again in ammoniacal liquor, deliver to destilling tower after mixing and carry out second distillation, the ammonia vapour of tower top, by after dephlegmator, obtains refining concentrated ammonia liquor through condenser.
The alkali lye 100kg that mass fraction is 31% is added in coking concentrated ammonia liquor per ton.
Live (open) steam is passed at the bottom of described destilling tower.
Described refining concentrated ammonia liquor contains ammonia 20%, containing H
2s 4.2mg/l, hydrogen cyanide 3.2mg/l.
The mass fraction of described coking concentrated ammonia liquor is 14%.
Embodiment 5
Take residual coking ammonia water as the technique that SCR reducing agent prepared by raw material, the ammonia vapour that gas purification workshop, coke-oven plant ammonia steaming device dephlegmator produces obtains coking concentrated ammonia liquor through condensation, coking concentrated ammonia liquor is after filter removal of impurities and adsorption tower de-oiling, NaOH alkali lye is added again in ammoniacal liquor, deliver to destilling tower after mixing and carry out second distillation, the ammonia vapour of tower top, by after dephlegmator, obtains refining concentrated ammonia liquor through condenser.
The alkali lye 55kg that mass fraction is 31% is added in coking concentrated ammonia liquor per ton.
Live (open) steam is passed at the bottom of described destilling tower.
Described refining concentrated ammonia liquor contains ammonia 24%, containing H
2s 3.8mg/l, hydrogen cyanide 2.5mg/l.
Deliver to coking ammonia steaming device containing the deposed ammonia of alkali lye at the bottom of described destilling tower and decompose ammonium salt.
The mass fraction of described coking concentrated ammonia liquor is 18%.
Embodiment 6
Take residual coking ammonia water as the technique that SCR reducing agent prepared by raw material, the ammonia vapour that gas purification workshop, coke-oven plant ammonia steaming device dephlegmator produces obtains coking concentrated ammonia liquor through condensation, coking concentrated ammonia liquor is after filter removal of impurities and adsorption tower de-oiling, NaOH alkali lye is added again in ammoniacal liquor, deliver to destilling tower after mixing and carry out second distillation, the ammonia vapour of tower top, by after dephlegmator, obtains refining concentrated ammonia liquor through condenser.
The alkali lye 12kg that mass fraction is 42% is added in coking concentrated ammonia liquor per ton.
Live (open) steam is passed at the bottom of described destilling tower.
Described refining concentrated ammonia liquor contains ammonia 22%, containing H
2s 3.6mg/l, hydrogen cyanide 3.1mg/l.
Deliver to coking ammonia steaming device containing the deposed ammonia of alkali lye at the bottom of described destilling tower and decompose ammonium salt.
The mass fraction of described coking concentrated ammonia liquor is 15%.
Embodiment 7
Take residual coking ammonia water as the technique that SCR reducing agent prepared by raw material, the ammonia vapour that gas purification workshop, coke-oven plant ammonia steaming device dephlegmator produces obtains coking concentrated ammonia liquor through condensation, coking concentrated ammonia liquor is after filter removal of impurities and adsorption tower de-oiling, NaOH alkali lye is added again in ammoniacal liquor, deliver to destilling tower after mixing and carry out second distillation, the ammonia vapour of tower top, by after dephlegmator, obtains refining concentrated ammonia liquor through condenser.
The alkali lye 70kg that mass fraction is 42% is added in coking concentrated ammonia liquor per ton.
Live (open) steam is passed at the bottom of described destilling tower.
Described refining concentrated ammonia liquor contains ammonia 23%, containing H
2s 2.8mg/l, hydrogen cyanide 2.5mg/l.
Deliver to coking ammonia steaming device containing the deposed ammonia of alkali lye at the bottom of described destilling tower and decompose ammonium salt.
The mass fraction of described coking concentrated ammonia liquor is 16%.
Embodiment 8
Take residual coking ammonia water as the technique that SCR reducing agent prepared by raw material, the ammonia vapour that gas purification workshop, coke-oven plant ammonia steaming device dephlegmator produces obtains coking concentrated ammonia liquor through condensation, coking concentrated ammonia liquor is after filter removal of impurities and adsorption tower de-oiling, NaOH alkali lye is added again in ammoniacal liquor, deliver to destilling tower after mixing and carry out second distillation, the ammonia vapour of tower top, by after dephlegmator, obtains refining concentrated ammonia liquor through condenser.
The alkali lye 60kg that mass fraction is 42% is added in coking concentrated ammonia liquor per ton.
Live (open) steam is passed at the bottom of described destilling tower.
Described refining concentrated ammonia liquor contains ammonia 18%, containing H
2s 2.9mg/l, hydrogen cyanide 2.3mg/l.
Deliver to coking ammonia steaming device containing the deposed ammonia of alkali lye at the bottom of described destilling tower and decompose ammonium salt.
The mass fraction of described coking concentrated ammonia liquor is 15%.
Embodiment 9
Refining concentrated ammonia liquor of the present invention is used for the SCR denitration technique of coke oven flue waste gas.
Qualified discharge after the nitrogen oxide removing in stack gases by SCR reaction, discharge flue gas reaches the highest standard that GB16171-2012 specifies.
Embodiment 10
Refining concentrated ammonia liquor of the present invention is used for the SCR denitration technique of coke oven flue waste gas.
The catalyst of described SCR denitration to be temperature range the be low temperature SCR denitration catalyst of 160 DEG C ~ 290 DEG C.
Qualified discharge after the nitrogen oxide removing in stack gases by SCR reaction, discharge flue gas reaches the highest standard that GB16171-2012 specifies.
Embodiment 11
The present embodiment is substantially the same manner as Example 10, on this basis:
Described coke oven combustion uses the coke-stove gas after purification, the dry desulfurizing process that its process for purifying adopts desulfurizing tower to connect with adsorption tower.
Dry desulfurizing process of the present invention is conventional coke oven gas dry sulfur removal technology:
Desulfurizing agent in described desulfurizing tower is iron oxide, and desulfurizing agent regularly replaces after losing desulfurizing function.
Adsorbent in described adsorption tower is active carbon, active carbon regular regeneration.Be adsorption tower to after the impurity absorption a period of times such as the organic sulfur in coke-stove gas, by heating gas adsorption tower regenerated and superheated steam regeneration.Heating gas regeneration adopts the coke-stove gas after adsorbing through steam indirect to 130 ~ 160 DEG C, and another mistake is to passing through adsorption tower, and the coal gas after regeneration returns to the cleaning shop of coking.The heating gas recovery time is 10 ~ 30h/ time, need to carry out superheated steam regeneration after 3 ~ 8 heating gas regeneration, take out of with water vapour after sulphur in adsorbent is gasified by high-temperature heating, water vapour obtains sulphur by condensation, superheat steam temperature 400 ~ 450 DEG C, the recovery time is 10 ~ 50h/ time.
Embodiment 12
The present embodiment is substantially the same manner as Example 10, on this basis:
Described coke oven combustion uses the coke-stove gas after purification, the dry desulfurizing process that its process for purifying adopts desulfurizing tower to connect with adsorption tower.
Coke-stove gas total sulfur <40mg/m after described purification
3.
Claims (10)
1. be the technique that SCR reducing agent prepared by raw material with residual coking ammonia water, it is characterized in that: the ammonia vapour that gas purification workshop, coke-oven plant ammonia steaming device dephlegmator produces obtains coking concentrated ammonia liquor through condensation, coking concentrated ammonia liquor is after filter removal of impurities and adsorption tower de-oiling, NaOH alkali lye is added again in ammoniacal liquor, deliver to destilling tower after mixing and carry out second distillation, the ammonia vapour of tower top, by after dephlegmator, obtains refining concentrated ammonia liquor through condenser.
2. according to claim 1 is the technique that SCR reducing agent prepared by raw material with residual coking ammonia water, it is characterized in that: described refining concentrated ammonia liquor contains ammonia 16 ~ 26%, containing H
2s is less than 5mg/l, hydrogen cyanide is less than 5mg/l.
3. according to claim 1 is the technique that SCR reducing agent prepared by raw material with residual coking ammonia water, it is characterized in that: add in coking concentrated ammonia liquor per ton mass fraction be 31% alkali lye 15 ~ 100kg or mass fraction be 42% alkali lye 12 ~ 70kg.
4. according to claim 1 is the technique that SCR reducing agent prepared by raw material with residual coking ammonia water, it is characterized in that: pass into live (open) steam at the bottom of described destilling tower.
5. according to claim 1 is the technique that SCR reducing agent prepared by raw material with residual coking ammonia water, it is characterized in that: deliver to coking ammonia steaming device containing the deposed ammonia of alkali lye at the bottom of described destilling tower and decompose ammonium salt.
6. according to claim 1 is the technique that SCR reducing agent prepared by raw material with residual coking ammonia water, it is characterized in that: the mass fraction of described coking concentrated ammonia liquor is 14-18%.
7. according to claim 1 is the technique that SCR reducing agent prepared by raw material with residual coking ammonia water, it is characterized in that: the SCR that described refining concentrated ammonia liquor is used for coke oven flue waste gas is catalytic-reduction denitrified.
8. according to claim 7 is the technique that SCR reducing agent prepared by raw material with residual coking ammonia water, it is characterized in that: the catalytic-reduction denitrified catalyst of described SCR to be temperature range the be low temperature SCR denitration catalyst of 160 DEG C ~ 290 DEG C.
9. according to claim 7 take residual coking ammonia water as the technique that SCR reducing agent prepared by raw material, it is characterized in that: described coke oven combustion uses the coke-stove gas after purification, the dry desulfurizing process that its process for purifying adopts desulfurizing tower to connect with adsorption tower.
10. according to claim 9 is the technique that SCR reducing agent prepared by raw material with residual coking ammonia water, it is characterized in that: the coke-stove gas total sulfur <40mg/m after described purification
3.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109248564A (en) * | 2018-11-15 | 2019-01-22 | 山东海科化工集团有限公司 | A kind of recycle device and technique of the ammonia liquor that petrochemical industry refinery acidity water treatment facilities generates |
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| CN113617199A (en) * | 2021-09-03 | 2021-11-09 | 山西化美环保科技有限公司 | Process method for treating tail gas containing hydrogen sulfide by using double-alkali method |
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