CN101732986A - Method for removal of sulfur and nitrogen oxides in smoke - Google Patents
Method for removal of sulfur and nitrogen oxides in smoke Download PDFInfo
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- CN101732986A CN101732986A CN200810226916A CN200810226916A CN101732986A CN 101732986 A CN101732986 A CN 101732986A CN 200810226916 A CN200810226916 A CN 200810226916A CN 200810226916 A CN200810226916 A CN 200810226916A CN 101732986 A CN101732986 A CN 101732986A
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Abstract
The invention discloses a method for the removal of sulfur and nitrogen oxides in smoke, comprising the steps: the smoke containing sulfur and nitrogen oxides comes into contact with an adsorbent on condition of adsorption separation and the adsorbent contacting with the smoke containing sulfur and nitrogen oxides is then subject to regeneration, the method is characterized in that, the regeneration is performed according to the method comprising the following steps: (1) at the temperature ranging from 200 to 800 DEG C, the composite to be regenerated comes into contact with reducing gas for 0.5 to 5 hours; (2) at the temperature ranging from 200 to 800 DEG C, the product resulted from the step (1) comes into contact with oxygen-containing gas for 0.5 to 3 hours; and (3) at the temperature ranging from 200 to 800 DEG C, the product resulted from the step (2) comes into contact with the reducing gas for 0.5 to 5 hours once again. Compared with the prior art, the method according to the invention is obviously enhanced in the recovery of sulfur and nitrogen removal performance after the regeneration of the adsorbent, thereby further prominently improving the use efficiency of the adsorbent.
Description
Technical field
The present invention relates to a kind of method that removes sulphur in the flue gas, nitrogen oxide.
Background technology
Atmosphere sulphur oxide SOx (is SO more than 95%
2), the pollution problem of nitrogen oxide NOx (being NO more than 90%) is serious day by day, the flue gas of generations such as fuel combustion, metal smelt is the main source of SOx and NOx.These pernicious gases cause serious destruction to ecological environment and health.
At present the emission control technique to SOx is comparatively ripe in the world, and to the emission control of NOx, though carried out a series of research both at home and abroad, effect is person of modern times's meaning not still.
US6521559 discloses a kind of pillared clays catalyst, is applicable to and utilizes NH
3The SCR technology (SCR) of reductive NO.The characteristics of this catalyst are mainly introduced metal oxide such as V in the middle of argillic horizon
2O
5, CuO, Fe
2O
3, Cr
2O
3, Fe
2O
3-Cr
2O
3, Nb
2O
5Deng, utilize the catalytic reduction character of metal oxide that NO is carried out catalytic reduction.The NOx removal efficiency of this material reaches more than 95%.
US5451387 has reported a kind of Fe-ZSM-5 catalyst, is suitable for the SCR technology, and the NOx removal efficiency of this material can reach 98%.
US6165934 reported a kind of can be from flue gas the material of adsorbing and removing NOx, this material support is TiO
2, SiO
2, Al
2O
3Deng, active component comprises alkali metal, copper, noble metal etc., the NOx removal efficiency of this material reaches 70%.
Desulfurization simultaneously, denitride technology more and more are subject to people's attention in recent years owing to have advantages such as reduced investment, operating cost are low.
For example, people such as Chen Ying discloses about " new adsorbent-catalyst La-Cu-Na-γ-Al
2O
3Remove SO simultaneously
2Experimental study with NO " and achievement (colleges and universities' Chemical Engineering journal, the 21st the 1st phase of volume, in February, 2007,64-69).Point out: " with the adsorbent Na-Al of NOXSO technology
2O
3Compare La-Cu-Na-γ-Al
2O
3Adsorb SO simultaneously
2With the big (SO of NO ability
2When/NO is 5.1-3.5, La-Cu-Na-γ-Al
2O
3Adsorb SO simultaneously
2With the adsorbance of NO be respectively Na-γ-Al
2O
31.25 and 4.7 times) ".This result shows, is similar to La-Cu-Na-γ-Al
2O
3The composition of forming has and takes off SO preferably synchronously
2With the NO performance.
Although point out as people such as Chen Ying, La-Cu-Na-γ-Al
2O
3Have and recycle performance preferably, but the said composition after regeneration take off SO synchronously
2Still bigger with the NO performance loss.
Summary of the invention
The technical problem to be solved in the present invention is in the prior art, the adsorbent composition after regeneration take off SO
2The deficiency bigger with the NO performance loss provides a kind of new method that can be used for sulphur, nitrogen oxide in the simultaneous removing flue gas.
A kind of method that removes sulphur in the flue gas, nitrogen oxide, be included under the absorption separation condition, the flue gas of sulfur-bearing, nitrogen oxide is contacted with adsorbent, adsorbent reactivation after will contacting with the flue gas of sulfur-bearing, nitrogen oxide afterwards, it is characterized in that described regeneration adopts the method that may further comprise the steps to carry out:
(1) under 200 ℃ of-800 ℃ of temperature, will treat that reproducing adsorbent contacted 0.5 hour-5 hours with reducing gas; (2) under 200 ℃ of-800 ℃ of temperature, will contact 0.5 hour with oxygen-containing gas-3 hours through the product of step (1) reduction; (3) under 200 ℃ of-800 ℃ of temperature, will contact 0.5 hour with reducing gas once more-5 hours through the product of step (2) oxidation.
Compared with prior art, method provided by the invention has adopted a kind of more efficiently adsorbent regeneration method, when this method being used for adsorption method of separation removing flue gas sulphur and/or nitrogen oxide, the recovery of adsorbent desulfurization, nitrogen performance obviously improves, and then can obviously improve the service efficiency of adsorbent.
For example, for identical adsorbent, when adopting the inventive method to regenerate, regeneration back absorption SO
2Saturated extent of adsorption be 1.125 mM/grams (for fresh dose 90.7%), the saturated extent of adsorption of NO reaches 0.359 mM/gram (be fresh dose 87.3%).And when adopting existing method regeneration, regeneration back adsorbent SO
2Saturated extent of adsorption be 0.785 mM/gram (for fresh dose 63.3%), the saturated extent of adsorption of NO reaches 0.241 mM/gram (be fresh dose 58.6%).
Description of drawings
Fig. 1 is a kind of schematic flow sheet that the invention provides method.
The specific embodiment
According to method provided by the invention, described regeneration can be carried out in the original position adsorbent equipment, also can carry out in the regenerating unit outside habitual device.For example, outside the fixed bed device, carry out in the regeneration reactor.Wherein, the temperature of described step (1) is preferably 250 ℃-700 ℃, more preferably 280 ℃-650 ℃; The temperature of described step (2) is preferably 250 ℃-700 ℃, more preferably 280 ℃-650 ℃; The temperature of described step (3) is preferably 250 ℃-700 ℃, more preferably 280 ℃-650 ℃.
Described reducing gas can be any under described temperature gasifiable material with reducing property, for example, can be preferably carbon monoxide, hydrogen, carbon number is one or more in 1～4 the hydrocarbon compound, described carbon number is that 1～4 hydrocarbon compound further is preferably selected from methane, ethene, ethane, propylene, in the propane one or more, be preferably 0.5 hour-4 hours the time of contact of described step (1), more preferably 0.5 hour-3.5 hours, be preferably 0.5 hour-4 hours the time of contact of step (3), more preferably 0.5 hour-3.5 hours.Wherein, under the prerequisite that is enough to form to the reduction atmosphere of described composition, the consumption of reducing gas is not particularly limited.The volume space velocity of preferred steps (1) is 5000/ hour-50000/ hour, more preferably 5000/ hour-35000/ hour; The volume space velocity of preferred steps (3) is 5000/ hour-50000/ hour, further preferred 5000/ hour-30000/ hour.
Described oxygen-containing gas can be any material that can discharge oxygen under described temperature, for example, can be preferably in the mist of mist, oxygen and helium of mist, oxygen and argon of oxygen, air, oxygen and nitrogen one or more, the contact of described step (2) was preferably 0.5 hour-3 hours, more preferably 0.5 hour-3 hours.Wherein, under the prerequisite that is enough to form to the oxidation atmosphere of described composition, the consumption of described oxygen-containing gas is not particularly limited.The volume space velocity of preferred steps (2) is 5000/ hour-50000/ hour, more preferably 5000/ hour-25000/ hour.
According to method provided by the invention,, also comprise the step of adsorbent equipment being cleaned and replacing with inert gas for satisfying the condition that described composition contacts with reducing gas or oxygen-containing gas.Described inert gas is selected from one or more in nitrogen, helium, argon gas, neon, krypton gas, xenon, the radon gas, under the prerequisite that is being enough to satisfy to purge require, the consumption and the purge time of described purge gas is not particularly limited.The volume space velocity of preferred described purging is 5000/ hour-25000/ hour, and the time is 0.5 hour-3.0 hours, and the further preferred volume space velocity that purges is 10000/ hour-20000/ hour, and the time is 0.5-2 hour.
According to method provided by the invention, all kinds of regeneration that can be used for removing the adsorbent composition of sulphur in the flue gas and/or nitrogen oxide all can be adopted this method in the prior art.For example, these adsorbent compositions can be as the disclosed V of containing of US6521559
2O
5, CuO, Fe
2O
3, Cr
2O
3, Fe
2O
3-Cr
2O
3, Nb
2O
5Pillared clays catalyst etc. component; The disclosed Fe-ZSM-5 catalyst of US5451387; US6165934 is disclosed with TiO
2, SiO
2, Al
2O
3Deng the catalyst that is the component such as alkali metal containing, copper, noble metal of carrier; The disclosed La-Cu-Na-γ-Al of people such as Chen Ying
2O
3Adsorbent composition.
In preferred embodiment, the inventive method is particularly suitable for the regeneration of following adsorbent composition, said composition contains at least a I B that is selected from, IIB, IIIB, IVB, VB, VIB, VIIB, the oxide of the transition metal of VIII family, at least a I A that is selected from, the metal oxide of II A family, at least a heat-resistant inorganic oxide matrix, with described composition is benchmark, be selected from I B, II B, IIIB, IVB, V B, VIB, VIIB, the content of the transition metal oxide of VIII family is 0.5 weight %-35 weight %, be selected from I A, the content of the metal oxide of II A family is 0.5 weight %-35 weight %, the content of heat-resistant inorganic oxide matrix is 50 weight %-99 weight %, and described catalyst is prepared by the method that may further comprise the steps:
(1) in the precursor of heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix, introduces at least a oxide that is selected from the transition metal of I B, II B, IIIB, IVB, V B, VIB, VIIB, VIII family, at least a metal oxide that is selected from I A, II A family;
(2) product 2 hours-12 hours of calcination steps (1) under greater than 600 ℃ to 1100 ℃ conditions obtains described composition.
Wherein, the sintering temperature of preferred described step (2) is 620 ℃-1000 ℃, and more preferably 650 ℃-960 ℃, roasting time is 3 hours-12 hours, more preferably 4 hours-11 hours.
Described transition metal is preferably from I B, II B, IIIB, VIB, VIIB, VIII family, one or more among further preferred wherein Mn, Cr, Co, Cu, Fe, Ni, Zn, Ce, La, Pt, the Re.
Among the preferred Na of metal of described I A, II A family, K, Ba, Mg, the Ca one or more.
Described heat-resistant inorganic oxide matrix is the heat-resistant inorganic oxide of Chang Zuowei catalyst support substrate.For example, be selected from aluminium oxide, silica, titanium oxide, magnesia, silica-alumina, silica-magnesia, silica-zirconia, silica-thorium oxide, silica-beryllium oxide, silica-titanium oxide, silica-zirconia, oxidation titania-zirconia, silica-alumina-thorium oxide, silica-alumina-titanium oxide, silica-alumina-magnesia, the silica-alumina-zirconia one or more.Preferred aluminium oxide, silica, silica-alumina wherein.
With described composition is benchmark, preferably the content from the transition metal oxide of IIIB, IVB, V B, VIB, VIIB, VIII family is 1 weight %-18 weight %, preferably the content from the metal oxide of I A, II A family is 1 weight %-20 weight %, and the content of heat-resistant inorganic oxide matrix is 65 weight %-98 weight %.
The described composition that provides according to the method described above, wherein, to at least a oxide that is selected from the transition metal of I B, IIB, IIIB, IVB, VB, VIB, VIIB, VIII family of introducing in the precursor of heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix described in described preparation method's the step (1), at least a method that is selected from the metal oxide of I A, II A family is not particularly limited.Can be with the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and describedly contain at least a I B that is selected from, IIB, IIIB, IVB, VB, VIB, VIIB, the compound of the transition metal component of VIII family and/or at least a I A that is selected from, the method that the compound of the metal component of II A family directly mixes is introduced, and also can be with containing the described at least a I B that is selected from, II B, IIIB, IVB, V B, VIB, VIIB, the compound of the transition metal component of VIII family and/or at least a I A that is selected from, the method of the described heat-resistant inorganic oxide matrix of solution impregnation of the compound of the metal component of II A family and/or the precursor of heat-resistant inorganic oxide matrix is introduced.
The described composition that provides is according to the method described above looked different the article shaped that require can be made into various easy operatings, for example microballoon, sphere, tablet or bar shaped etc.Moulding can be carried out according to a conventional method, for example, can be with the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and describedly contain at least a compound that is selected from the transition metal component of I B, IIB, IIIB, IVB, VB, VIB, VIIB, VIII family that the compound of at least a metal component that is selected from I A, II A family is after the method preparation of extruded moulding and roasting.Or at first the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix is prepared into shaping carrier, introduce the described at least a transition metal component that is selected from I B, II B, IIIB, IVB, V B, VIB, VIIB, VIII family, at least a metal component that is selected from I A, II A family of containing with the method for dipping afterwards.When extrusion molding, can add an amount of extrusion aid and/or adhesive, extrusion molding then.The kind of described extrusion aid, peptizing agent and consumption are that preformed catalyst or adsorbent preparation field technical staff are known, do not give unnecessary details at this.
According to the invention provides method, preferably also comprise the step that the described composition after the regeneration is sieved, described screening is optimized the composition that finally makes after the described regeneration in follow-up use.Described method for sieving is this area conventional process.For example: the method that adopts bolting.
Described flue gas with sulfur-bearing, nitrogen oxide contacts with adsorbent, can carry out in the adsorption separation device arbitrarily, for example, carries out in ADSORPTION IN A FIXED BED tower or fluid bed adsorbing separation reactor.When described contact is carried out in the fixed bed absorption tower, according to actual conditions, be typically provided with two or more adsorption tower handover operations with implementation procedure continuously.When adsorbing separation between Liang Ta during handover operation, reduction in the described regeneration, oxidation and restoring in same tower hockets, when adsorbing separation between multitower during handover operation, reduction in the described regeneration, oxidation and restore and can hocket in same tower also can be carried out respectively in two or several towers.
According to the invention provides method, the gas sulphur oxide after being enough to make described contact make separation and the content of nitrogen oxide satisfy " emission standard of air pollutants for boilers, GB 13271 " requirement (oxysulfide content is less than 315ppm, amount of nitrogen oxides is less than 300ppm) prerequisite under, operating condition to described adsorbing separation is not particularly limited, preferably include: temperature is 0～300 ℃, more preferably 0～100 ℃; The volume space velocity of unstrpped gas is 5000/ hour-50000/ hour, more preferably 5000/ hour-35000/ hour; Pressure is 0.1-3.0MPa, further preferred 0.1-2.0MPa.
The invention provides an adsorbing separation that adopts the ADSORPTION IN A FIXED BED knockout tower to carry out of method, carry out according to flow process shown in Figure 1.
According to flow process shown in Figure 1, adsorbing separation is switched in two ADSORPTION IN A FIXED BED knockout towers and is carried out, and promptly works as one of them adsorption tower and carries out adsorbing separation, and another adsorption tower carries out adsorbent reactivation.For example, when adsorbing separation is carried out in adsorption tower 4, when adsorbent reactivation carries out at adsorption tower 11, described lock out operation comprises: closed control valve 3 and control valve 6, open control valve 2 and control valve 5, the flue gas that need are purified is introduced adsorption tower 4 through 1, and it is contacted with described adsorbent, and the gas that has removed SOX and/or NOX discharges through 8; Simultaneously, open control valve 10 and control valve 13, closed control valve 9 and control valve 12, under described adsorbent reactivation reaction condition successively through 15, control valve 10 is introduced reducing gases, displacement gas and oxic gas to realize described regeneration to adsorption tower 11, and regeneration gas is drawn adsorption tower 11 through 7.When adsorbing separation is carried out in adsorption tower 11, when adsorbent reactivation carries out at adsorption tower 4, described lock out operation comprises: closed control valve 10 and control valve 13, open control valve 9 and control valve 12, the flue gas that need purify is introduced attached tower 11 through 1, it is contacted with described adsorbent, and the gas that has removed SOX and/or NOX is through 8 dischargings; Simultaneously, open control valve 3 and control valve 6, closed control valve 2 and control valve 5, under described adsorbent reactivation reaction condition successively through 14, control valve 3 is introduced reducing gases, displacement gas and oxic gas to realize described regeneration to adsorption tower 4, and regeneration gas is drawn adsorption tower 4 through 7.And so forth to realize the continuous of described adsorbing separation.Wherein, the change in concentration of SOx and/or NOx in the employing KM9106 flue gas analyzer on-line monitoring flue gas.
The method of the invention provides is suitable for removing SOx and/or the NOx in the flue gas, for example, be applicable to the SOx and/or the NOx that remove in catalytic cracking flue gas improvement, coal-fired plant flue gas improvement, the steel mill flue gas, remove SOx and/or NOx in the flue gas of refuse burning, and other contain the smoke gas treatment of SOx and/or NOx.
The following examples will the invention will be further described, but not thereby limiting the invention.
Remove and specify that used chemical reagent is chemical pure among the embodiment.
Described adsorbent composition that preferably is suitable for desulfurization simultaneously, nitrogen oxide of embodiment 1-7 explanation and preparation method thereof.
Embodiment 1
Raw material: γ-Al
2O
3Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product.Na
2CO
3, Cu (NO
3)
2, La (NO
3)
3Be Beijing Chemical Plant's product.
Preparation method: take by weighing 8.5 gram Na
2CO
3, 15.8 gram Cu (NO
3)
2With 12.4 gram La (NO
3)
3Be dissolved into 100 ml solns with deionized water, normal temperature is down with this solution impregnation 100 gram γ-Al
2O
3Carrier 2 hours, afterwards in 110 ℃ of dryings 12 hours, 950 ℃ of roastings 10 hours obtain composition SORB-1 of the present invention.
SORB-1 forms: each component load capacity is respectively with Na
2CO
3, CuO and La
2O
3Meter, the content of sodium are that the content of 8 weight %, copper is that the content of 5 weight %, lanthanum is 5 weight % (metal component content adopts the X-ray fluorescence spectra analyses, down with).
Embodiment 2
Raw material: γ-Al
2O
3Carrier (with embodiment 1); Ba (NO
3)
2, La (NO
3)
3, 50 weight % Mn (NO
3)
2Solution is Beijing Chemical Plant's product.
Preparation method: with 1.7 gram Ba (NO
3)
2Be dissolved into 100 ml soln L1 with deionized water, with 10 gram La (NO
3)
3With 54.2 gram Mn (NO
3)
2Solution is dissolved into 100 ml soln L2 with deionized water.Order restrains γ-Al with L1, L2 dipping 100
2O
3Carrier 2 hours, each dipping back be in 110 ℃ of dryings 12 hours, and 900 ℃ of roastings 10 hours obtain combination articles SORB-2 of the present invention.
SORB-2 forms: each component load capacity is respectively with BaO, MnO
2And La
2O
3Meter, the content of Ba are that the content of 1 weight %, manganese is that the content of 13 weight %, lanthanum is 4 weight %.
Embodiment 3
Raw material: silica support, sphere, 1.22 millimeters of average grain diameters, Chang Ling catalyst plant product; Mg (NO
3)
2, Cr (NO
3)
3Be Beijing Chemical Plant's product.
Except that sintering temperature is 800 ℃, other preparation methods are with embodiment 1.Preparation is formed respectively with Cr
2O
3, MgO meter, the content of chromium is that the content of 1 weight %, magnesium is 19 weight % composition SORB-3.
Embodiment 4
Raw material: silica support (with embodiment 3); Mn (NO
3)
2(being 50% weight solution), K
2CO
3Be Beijing Chemical Plant's product.
Except that sintering temperature is 750 ℃, other preparation methods are with embodiment 1.Preparation is formed respectively with K
2CO
3, MnO
2Meter, the content of potassium is that the content of 4 weight %, manganese is 13 weight % composition SORB-4.
Embodiment 5
Raw material: γ-Al
2O
3Carrier (with embodiment 1); Mg (NO
3)
2, Co (NO
3)
2Be Beijing Chemical Plant's product.
Except that sintering temperature is 700 ℃, other preparation methods form respectively with MgO, Co with embodiment 1. preparations
2O
3Meter, the content of magnesium is that the content of 7 weight %, cobalt is 15 weight % composition SORB-5.
Embodiment 6
Raw material: γ-Al
2O
3Carrier (with embodiment 1); Mg (NO
3)
2, Zn (NO
3)
2, Fe (NO
3)
3Be Beijing Chemical Plant's product.
Except that sintering temperature is 650 ℃, other preparation methods are with embodiment 1.Preparation is formed respectively with MgO, ZnO, Fe
2O
3Meter, the content of magnesium are that the content of 3 weight %, zinc is that the content of 11 weight %, iron is 8 weight % composition SORB-6.
Embodiment 7
Except that sintering temperature and roasting time were 600 ℃ of roastings 10 hours, other were with embodiment 1.Each component load capacity is respectively with Na
2CO
3, CuO and La
2O
3Meter is consisted of: the content of sodium is that the content of 8 weight %, copper is that the content of 5 weight %, lanthanum is the composition SORB-7 of 5 weight %.
Embodiment 8-11 illustrates the performance of described adsorbent composition.
Embodiment 8
The SORB-1 performance is described.
Experiment is carried out on fixed bed continuous-flow adsorbent equipment.Absorber is the reaction tube of 8 millimeters of internal diameters, and the SORB-1 consumption is 1 gram, and adsorption temp is 175 ℃, and the feed gas volume flow is 300 ml/min.Feed gas volume consists of: SO
2, 0.3%; NO, 0.1%; O
2, 4.5%, surplus is N
2Use N before feeding unstripped gas
2Volume flow with 300 ml/min purged desulfurization removing nitric material bed down 1 hour at 300 ℃, and was cooled to adsorption temp.When tending towards stability, absorption tail gas concentration stops adsorption experiment.The absorber outlet meets SO
2, SO in the NO analyzer monitoring flue gas
2, NO content variation, adopt the SO of FIREFOX software calculation composition
2With NO saturated extent of adsorption (following other embodiment therewith together).Wherein, SO
2Saturated extent of adsorption reach 1.241 mM/grams, the saturated extent of adsorption of NO reaches 0.411 mM/gram.
Embodiment 9
The SORB-2 performance is described
Experiment with embodiment 8 same apparatus on carry out.The SORB-2 consumption is 1 gram, and adsorption temp is 50 ℃, and the feed gas volume flow is 300 ml/min.Feed gas volume consists of: SO
2, 0.3%; NO, 0.1%; O
2, 4.5%; Surplus is N
2Use N before feeding unstripped gas
2Volume flow with 300 ml/min purged desulfurization removing nitric material bed down 1 hour at 300 ℃, and was cooled to adsorption temp.When tending towards stability, absorption tail gas concentration stops adsorption experiment.Reactor outlet meets SO
2, SO in the NO analyzer monitoring flue gas
2, NO content variation.Wherein, SO
2Saturated extent of adsorption reach 1.312 mM/grams, the saturated extent of adsorption of NO reaches 0.445 mM/gram.
Embodiment 10
The SORB-3 performance is described.
Experiment with embodiment 8 same apparatus on carry out.The SORB-3 consumption is 1 gram, and adsorption temp is 100 ℃, and the feed gas volume flow is 300 ml/min.Feed gas volume consists of: SO
2, 0.3%; NO, 0.1%; O
2, 4.5%; Surplus is N
2Use N before feeding unstripped gas
2Volume flow with 300 ml/min purged desulfurization removing nitric material bed down 1 hour at 300 ℃, and was cooled to adsorption temp.When tending towards stability, absorption tail gas concentration stops adsorption experiment.Reactor outlet meets SO
2, SO in the NO analyzer monitoring flue gas
2, NO content variation.Wherein, SO
2Saturated extent of adsorption reach 1.210 mM/grams, the saturated extent of adsorption of NO reaches 0.405 mM/gram.
Embodiment 11
The SORB-7 performance is described.
Experiment with embodiment 8 same apparatus on carry out.The SORB-7 consumption is 1 gram, and adsorption temp is 175 ℃, and the feed gas volume flow is 300 ml/min.Feed gas volume consists of: SO
2, 0.3%; NO, 0.1%; O
2, 4.5%; Surplus is N
2Use N before feeding unstripped gas
2Volume flow with 300 ml/min purged desulfurization removing nitric material bed down 1 hour at 300 ℃, and was cooled to adsorption temp, stopped adsorption experiment when absorption tail gas concentration tends towards stability.Reactor outlet meets SO
2, SO in the NO analyzer monitoring flue gas
2, NO content variation.Wherein, SO
2Saturated extent of adsorption reach 1.125 mM/grams, the saturated extent of adsorption of NO reaches 0.292 mM/gram.
Embodiment 12
The inventive method is described.
Treat that regenerative agent is the saturated back of embodiment 8 a conditions absorption sample.
Regeneration is carried out on the regenerating unit outside device, and regeneration reactor is the tubular reactor of 10 millimeters of internal diameters.
SORB-1 to be regenerated places regeneration reactor with 1 gram, be under 10000/ hour the nitrogen purging condition in air speed, with 10 ℃/minute programming rate temperature programmings to 350 ℃, stablize after 30 minutes and stop to feed nitrogen, under 350 ℃, the CO gas that switched air speed and be 15000/ hour makes it contact 2 hours with SORB-1 to be regenerated; With air speed is that 10000/ hour nitrogen purged 30 minutes, and the oxygen that switched air speed and be 15000/ hour makes it contact 30 minutes with the SORB-1 to be regenerated that reduces through back; With air speed is that 10000/ hour nitrogen purged 30 minutes, switch air speed and be 15000/ hour methane gas and contact 1 hour with SORB-1 to be regenerated through the back oxidation, afterwards, the nitrogen that fed air speed and be 10000/ hour purges to temperature of reactor reduces to normal temperature, the adsorbent composition SORB-1-1 after obtaining regenerating.
Estimate SORB-1-1 according to embodiment 8 appreciation conditions.Experimental result is: SO
2Saturated extent of adsorption be 1.125 mM/grams (for fresh dose 90.7%), the saturated extent of adsorption of NO reaches 0.359 mM/gram (be fresh dose 87.3%).
Comparative Examples 1
The renovation process of reference is described.
Regeneration reactor is with to treat regenerated catalyst identical with embodiment 12.
SORB-1 to be generated places regeneration reactor with 1 gram, be under 10000/ hour the nitrogen purging condition in air speed, be warming up to 600 ℃ with 10 ℃/minute speed programs, stablize after 30 minutes and stop to feed nitrogen, under 600 ℃, the hydrogen that switched air speed and be 15000/ hour makes it contact 1 hour with SORB-1 to be regenerated; With air speed is that 10000/ hour nitrogen purged 30 minutes, and the oxygen that switched air speed and be 15000/ hour makes it contact 30 minutes with the SORB-1 to be regenerated that reduces through back; Be 10000/ hour nitrogen purging, be cooled to normal temperature, the adsorbent composition SORB-1-C1 after obtaining regenerating with air speed.
Estimate SORB-1-C1 according to embodiment 8 appreciation conditions.Experimental result is: SO
2Saturated extent of adsorption be 0.785 mM/gram (for fresh dose 63.3%), the saturated extent of adsorption of NO reaches 0.241 mM/gram (be fresh dose 58.6%).
Embodiment 13-16 illustrates the influence of this operating condition to the inventive method.
Embodiment 13
Regenerating unit is with to treat regenerated catalyst identical with embodiment 12.
SORB-1 to be generated places reaction unit with 1 gram, be under 20000/ hour the nitrogen purging condition in air speed, be warming up to 300 ℃ with 10 ℃/minute speed programs, stablize after 30 minutes and stop to feed nitrogen, under 300 ℃, the CO gas that switched air speed and be 20000/ hour makes it contact 30 minutes with SORB-1 to be regenerated; With air speed is that 20000/ hour nitrogen purged 30 minutes, and the oxygen that switched air speed and be 15000/ hour makes it contact 30 minutes with SORB-1 to be regenerated that back reduces; With air speed is that 20000/ hour nitrogen purged 30 minutes, the switching air speed is that 25000/ hour hydrogen contacts 3.5 hours with the SORB-1 to be regenerated of back oxidation, afterwards, the nitrogen that fed air speed and be 20000/ hour purges to temperature of reactor reduces to normal temperature, the adsorbent composition SORB-1-2 after obtaining regenerating.
Estimate SORB-1-2 according to embodiment 8 appreciation conditions.Experimental result is: SO
2Saturated extent of adsorption be 1.120 mM/grams (for fresh dose 90.2%), the saturated extent of adsorption of NO reaches 0.351 mM/gram (be fresh dose 85.4%).
Embodiment 14
Regenerating unit is with to treat regenerated catalyst identical with embodiment 12.
SORB-1 to be generated places reaction unit with 1 gram, be under 10000/ hour the nitrogen purging condition in air speed, be warming up to 350 ℃ with 10 ℃/minute speed programs, stablize after 30 minutes and stop to feed nitrogen, under 350 ℃, the methane gas that switched air speed and be 30000/ hour makes it contact 30 minutes with SORB-1 to be regenerated; Be 10000/ hour nitrogen purging 30 minutes and be warming up to 400 ℃ that the switching air speed is that 20000/ hour air makes its SORB-1 to be regenerated with the back reduction contact 2.5 hours with air speed; Be 10000/ hour nitrogen purging 30 minutes and be warming up to 630 ℃ with air speed; The switching air speed is that 5000/ hour CO gas contacts 30 minutes with the SORB-1 to be regenerated of back oxidation, afterwards, the nitrogen that fed air speed and be 10000/ hour purges to temperature of reactor reduces to normal temperature, the adsorbent composition SORB-1-3 after obtaining regenerating.
Estimate SORB-1-3 according to embodiment 8 appreciation conditions.Experimental result is: SO
2Saturated extent of adsorption be 1.130 mM/grams (for fresh dose 91.1%), the saturated extent of adsorption of NO reaches 0.381 mM/gram (be fresh dose 92.7%).
Embodiment 15
Regenerating unit is with to treat regenerated catalyst identical with embodiment 12.
SORB-1 to be generated places reaction unit with 1 gram, be under 10000/ hour the nitrogen purging condition in air speed, with 10 ℃ of per minute temperature programmings to 500 ℃, stablize after 30 minutes and stop to feed nitrogen, under 500 ℃, the propylene gas of switching air speed and being 35000/ hour makes it contact 30 minutes with SORB-1 to be regenerated; Be 10000/ hour nitrogen purging 30 minutes and be warming up to 630 ℃ with air speed; The switching air speed is that 10000/ hour oxygen helium mixture (oxygen accounts for 75 volume %) makes its SORB-1 to be regenerated with the back reduction contact 2 hours; With air speed be 10000/ hour nitrogen purge and be cooled to 450 ℃ after constant temperature, the switching air speed is that 25000/ hour ethane gas contacts 1.5 hours with the SORB-1 to be regenerated of back oxidation, afterwards, the nitrogen that fed air speed and be 10000/ hour purges to temperature of reactor reduces to normal temperature, the adsorbent composition SORB-1-4 after obtaining regenerating.
Estimate SORB-1-4 according to embodiment 8 appreciation conditions.Experimental result is: SO
2Saturated extent of adsorption be 1.119 mM/grams (for fresh dose 90.1%), the saturated extent of adsorption of NO reaches 0.369 mM/gram (be fresh dose 89.8%).
Embodiment 16
Regenerating unit is with to treat regenerated catalyst identical with embodiment 12.
SORB-1 to be generated places reaction unit with 1 gram, be under 10000/ hour the nitrogen purging condition in air speed, with 10 ℃ of per minute temperature programmings to 650 ℃, stablize after 30 minutes and stop to feed nitrogen, under 650 ℃, the hydrogen that switched air speed and be 5000/ hour makes it contact 3.5 hours with SORB-1 to be regenerated; With air speed be 10000/ hour nitrogen purge and be cooled to 500 ℃ after constant temperature, the oxygen argon mixture (oxygen accounts for 30 volume %) that switched air speed and be 10000/ hour makes it contact 1 hour with SORB-1 to be regenerated that back reduces; With air speed be 10000/ hour nitrogen purge and be cooled to 380 ℃ after constant temperature, the switching air speed is that 25000/ hour ethylene gas contacts 1.5 hours with the SORB-1 to be regenerated of back oxidation, afterwards, the nitrogen that fed air speed and be 10000/ hour purges to temperature of reactor reduces to normal temperature, the adsorbent composition SORB-1-5 after obtaining regenerating.
Estimate SORB-1-5 according to embodiment 8 appreciation conditions.Experimental result is: SO
2Saturated extent of adsorption be 1.140 mM/grams (for fresh dose 91.9%), the saturated extent of adsorption of NO reaches 0.386 mM/gram (be fresh dose 93.9%).
The result that embodiment 13-16 provides can illustrate that the inventive method flexible operation and catalyst performance recover.
Claims (10)
1. method that removes sulphur in the flue gas, nitrogen oxide, be included under the absorption separation condition, the flue gas of sulfur-bearing, nitrogen oxide is contacted with adsorbent, adsorbent reactivation after will contacting with the flue gas of sulfur-bearing, nitrogen oxide afterwards, it is characterized in that described regeneration adopts the method that may further comprise the steps to carry out:
(1) under 200 ℃ of-800 ℃ of temperature, will treat that reproducing adsorbent contacted 0.5 hour-5 hours with reducing gas; (2) under 200 ℃ of-800 ℃ of temperature, will contact 0.5 hour with oxygen-containing gas-3 hours through the product of step (1) reduction; (3) under 200 ℃ of-800 ℃ of temperature, will contact 0.5 hour with reducing gas once more-5 hours through the product of step (2) oxidation.
2. method according to claim 1 is characterized in that, the temperature of described step (1) is 250 ℃-700 ℃, and the temperature of described step (2) is 250 ℃-700 ℃, and the temperature of described step (3) is 250 ℃-700 ℃.
3. method according to claim 1 is characterized in that, the temperature of described step (1) is 280 ℃-650 ℃, and the temperature of described step (2) is 280 ℃-650 ℃, and the temperature of described step (3) is 280 ℃-650 ℃.
4. method according to claim 1, it is characterized in that, it is in 1～4 the hydrocarbon compound one or more that described reducing gas is selected from carbon monoxide, hydrogen, carbon number, and be 0.5 hour-4 hours the time of contact of described step (1), and be 0.5 hour-4 hours the time of contact of step (3).
5. method according to claim 4 is characterized in that, described carbon number is that 1～4 hydrocarbon compound is selected from one or more in methane, ethene, ethane, propylene, the propane.
6. method according to claim 4 is characterized in that, be 0.5 hour-3.5 hours the time of contact of described step (1), and be 0.5 hour-3.5 hours the time of contact of step (3).
7. method according to claim 1, it is characterized in that, described oxygen-containing gas is selected from one or more in the mist of mist, oxygen and helium of mist, oxygen and argon of oxygen, air, oxygen and nitrogen, and be 0.5 hour-3 hours the time of contact of described step (2).
8. method according to claim 7 is characterized in that, be 0.5 hour-2.5 hours the time of contact of described step (2).
9. method according to claim 1 is characterized in that, described absorption separation condition comprises: temperature is 0～300 ℃, and the volume space velocity of unstrpped gas is 5000/ hour-50000/ hour, and pressure is 0.1-3MPa.
10. method according to claim 9 is characterized in that, described absorption separation condition comprises: temperature is 0～100 ℃, and the volume space velocity of unstrpped gas is 5000/ hour-35000/ hour, and pressure is 0.1-2MPa.
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| CN200810226916.3A CN101732986B (en) | 2008-11-20 | 2008-11-20 | Method for removal of sulfur and nitrogen oxides in smoke |
| MYPI20094591A MY175209A (en) | 2008-10-31 | 2009-10-30 | A sorbent composition, the preparation method thereof, and the process for removing sulfur oxides and nitrogen oxides in a flue gas by the sorbent composition |
| KR1020090104966A KR101646630B1 (en) | 2008-10-31 | 2009-11-02 | A sorbent composition, the preparation method thereof, and the process for removing sulfur oxides and nitrogen oxides in a flue gas by the sorbent composition |
| US12/611,094 US20100107874A1 (en) | 2008-10-31 | 2009-11-02 | Sorbent composition, the preparation method thereof, and the process for removing sulfur oxides and nitrogen oxides in a flue gas by the sorbent composition |
| EP09174759.2A EP2181751B1 (en) | 2008-10-31 | 2009-11-02 | A sorbent composition, the preparation method thereof, and the process for removing sulfur oxides and nitrogen oxides in a flue gas by the sorbent composition |
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| CN103191677A (en) * | 2013-04-26 | 2013-07-10 | 华东理工大学 | Analog moving bed reactor and operating method and application thereof |
| CN108211791A (en) * | 2018-02-26 | 2018-06-29 | 山东大学 | A kind of dual chamber modularization alternating denitrating system and method for denitration |
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| CN85109321A (en) * | 1984-04-26 | 1987-06-03 | 无比石油公司 | The reactivation that contains the precious metal catalyst agent material |
| CN1080593C (en) * | 1998-08-06 | 2002-03-13 | 南京四力化工有限公司 | Fluidized bed gas-phase catalytic hydrogenation catalyst non-nitrogen regeneration activating method |
| CN101209391B (en) * | 2006-12-30 | 2011-06-15 | 中国石油化工股份有限公司 | Method for removing oxysulfide and/or nitrogen oxide from flue gas and hydrocarbon oil cracking method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103191677A (en) * | 2013-04-26 | 2013-07-10 | 华东理工大学 | Analog moving bed reactor and operating method and application thereof |
| CN108211791A (en) * | 2018-02-26 | 2018-06-29 | 山东大学 | A kind of dual chamber modularization alternating denitrating system and method for denitration |
| CN110433642A (en) * | 2019-08-28 | 2019-11-12 | 苏州仕净环保科技股份有限公司 | A kind of double-tower type desulfuring and denitrifying apparatus |
| CN111068511A (en) * | 2019-12-18 | 2020-04-28 | 东南大学 | Deacidifying agent for removing acid gas in high-temperature flue gas and preparation method thereof |
| CN111068511B (en) * | 2019-12-18 | 2022-02-15 | 东南大学 | Deacidifying agent for removing acid gas in high-temperature flue gas and preparation method thereof |
| CN112221301A (en) * | 2020-09-30 | 2021-01-15 | 武汉钢铁有限公司 | Activated carbon flue gas purification system and method thereof |
| CN112221301B (en) * | 2020-09-30 | 2022-12-23 | 武汉钢铁有限公司 | Activated carbon flue gas purification system and method thereof |
| CN114377512A (en) * | 2021-12-24 | 2022-04-22 | 松山湖材料实验室 | Method and device for purifying nitrogen oxides in underground space |
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