CN101732986B - 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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- CN101732986B CN101732986B CN200810226916.3A CN200810226916A CN101732986B CN 101732986 B CN101732986 B CN 101732986B CN 200810226916 A CN200810226916 A CN 200810226916A CN 101732986 B CN101732986 B CN 101732986B
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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 sulfureous in flue gas, nitrogen oxide.
Background technology
Atmospheric Sulfur oxide S Ox (more than 95% is SO
2), the pollution problem of nitrogen oxide NOx (more than 90% being NO) is day by day serious, the flue gas of the 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 comparatively ripe to the emission control technique of SOx in the world, to the emission control of NOx, although carried out a series of research both at home and abroad, still person of modern times's meaning not of effect.
US6521559 discloses a kind of pillared clays catalyst, is applicable to utilize NH
3the SCR technology (SCR) of reductive NO.The feature of this catalyst is mainly introduced metal oxide 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 to carry out catalytic reduction to NO.The NOx removal efficiency of this material reaches more than 95%.
US5451387 has reported a kind of Fe-ZSM-5 catalyst, is suitable for 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%.
Simultaneously desulfurization, denitride technology, owing to having the advantages such as reduced investment, operating cost are low, are more and more subject to people's attention in recent years.
For example, the people such as Chen Ying discloses about " new adsorbent-catalyst La-Cu-Na-γ-Al
2o
3remove SO simultaneously
2experimental study with NO " 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 technique
2o
3compare La-Cu-Na-γ-Al
2o
3adsorb SO simultaneously
2with the large (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 composition has synchronous de-SO preferably
2with NO performance.
Although as the people such as Chen Ying point out, La-Cu-Na-γ-Al
2o
3have and recycle preferably performance, but the synchronous de-SO of said composition after regeneration
2still larger with NO performance loss.
Summary of the invention
The technical problem to be solved in the present invention is in prior art, the de-SO of the adsorbent composition after regeneration
2the deficiency larger with NO performance loss, provides a kind of new method that can be used for simultaneous removing sulfureous in flue gas, nitrogen oxide.
A kind of method that removes sulfureous in flue gas, nitrogen oxide, be included under absorption separation condition, the flue gas of sulfur-bearing, nitrogen oxide is contacted with adsorbent, afterwards by the adsorbent reactivation after contacting with the flue gas of sulfur-bearing, nitrogen oxide, it is characterized in that, described regeneration adopts the method comprising the following steps to carry out:
(1), at 200 ℃ of-800 ℃ of temperature, will treat that reproducing adsorbent contacts 0.5 hour-5 hours with reducing gas; (2), at 200 ℃ of-800 ℃ of temperature, will contact 0.5 hour with oxygen-containing gas-3 hours through the product of step (1) reduction; (3), at 200 ℃ of-800 ℃ of temperature, will again contact 0.5 hour with reducing gas-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, in the time that the method is removed to sulfureous in flue gas and/or nitrogen oxide for adsorption method of separation, the recovery of adsorbent desulfurization, nitrogen performance obviously improves, and then can obviously improve the service efficiency of adsorbent.
For example, for identical adsorbent, in the time adopting the inventive method to regenerate, absorption SO after regeneration
2saturated extent of adsorption be 1.125 mMs/gram (for fresh dose 90.7%), the saturated extent of adsorption of NO reach 0.359 mM/gram (for fresh dose 87.3%).And while adopting the regeneration of existing method, adsorbent SO after regeneration
2saturated extent of adsorption be 0.785 mM/gram (for fresh dose 63.3%), the saturated extent of adsorption of NO reach 0.241 mM/gram (for fresh dose 58.6%).
Accompanying drawing explanation
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 original position adsorbent equipment, also can outside usual device, in regenerating unit, carry out.For example, outside fixed bed device, in regeneration reactor, carry out.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 at described temperature the gasifiable material with reducing property, for example, can be preferably carbon monoxide, hydrogen, carbon number is one or more in 1～4 hydrocarbon compound, described carbon number is that 1～4 hydrocarbon compound is further preferably selected from methane, ethene, ethane, propylene, one or more in propane, 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, being enough to form under the prerequisite of the reduction atmosphere to 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 preferably 5000/ hour-30000/ hour.
Described oxygen-containing gas can be any material that can releasing oxygen at described temperature, for example, can be preferably one or more in the mist of mist, oxygen and helium of mist, oxygen and the argon of oxygen, air, oxygen and nitrogen, the contact of described step (2) is preferably 0.5 hour-3 hours, more preferably 0.5 hour-3 hours.Wherein, being enough to form under the prerequisite of the oxidation atmosphere to 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, the condition contacting with reducing gas or oxygen-containing gas for meeting described composition, also comprises the step of adsorbent equipment being cleaned and being replaced with inert gas.Described inert gas is selected from one or more in nitrogen, helium, argon gas, neon, Krypton, xenon, radon gas, is being enough to meet under the prerequisite of purging requirement, and consumption and purge time to described purge gas are 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 volume space velocity further preferably purging is 10000/ hour-20000/ hour, and the time is 0.5-2 hour.
According to method provided by the invention, in prior art, all kinds of regeneration that can be used for the adsorbent composition that removes sulfureous in flue gas and/or nitrogen oxide all can adopt this method.For example, these adsorbent compositions can be as disclosed in US6521559 containing V
2o
5, CuO, Fe
2o
3, Cr
2o
3, Fe
2o
3-Cr
2o
3, Nb
2o
5etc. the pillared clays catalyst of 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 components such as the alkali metal containing, copper, noble metal of carrier; The disclosed La-Cu-Na-γ-Al of the people such as Chen Ying
2o
3adsorbent composition.
In a preferred embodiment, the inventive method is particularly suitable for the regeneration of following adsorbent composition, said composition contains at least one and is selected from IB, IIB, IIIB, IVB, VB, VIB, VIIB, the oxide of the transition metal of VIII family, at least one is selected from IA, the metal oxide of IIA family, at least one heat-resistant inorganic oxide matrix, take described composition as benchmark, be selected from IB, IIB, IIIB, IVB, VB, VIB, VIIB, the content of the transition metal oxide of VIII family is 0.5 % by weight-35 % by weight, be selected from IA, the content of the metal oxide of IIA family is 0.5 % by weight-35 % by weight, the content of heat-resistant inorganic oxide matrix is 50 % by weight-99 % by weight, described catalyst is prepared by the method comprising the following steps:
(1) to the oxide of introducing at least one in the precursor of heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and be selected from the transition metal of IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII family, at least one is selected from the metal oxide of IA, IIA family;
(2) being greater than the product 2 hours-12 hours of calcination steps (1) under 600 ℃ to 1100 ℃ conditions, obtain 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 IB, IIB, IIIB, VIB, VIIB, VIII family, further preferred one or more in Mn, Cr, Co, Cu, Fe, Ni, Zn, Ce, La, Pt, Re wherein.
One or more in the preferred Na of metal of described IA, IIA family, K, Ba, Mg, Ca.
Described heat-resistant inorganic oxide matrix is the heat-resistant inorganic oxide of Chang Zuowei catalyst support substrate.For example, be selected from one or more in 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, silica-alumina-zirconia.Preferred aluminium oxide, silica, silica-alumina wherein.
Take described composition as benchmark, be preferably 1 % by weight-18 % by weight from the content of the transition metal oxide of IIIB, IVB, VB, VIB, VIIB, VIII family, be preferably 1 % by weight-20 % by weight from the content of the metal oxide of IA, IIA family, the content of heat-resistant inorganic oxide matrix is 65 % by weight-98 % by weight.
The described composition providing according to the method described above, wherein, described in step (1) to described preparation method to the oxide of introducing at least one in the precursor of heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and be selected from the transition metal of IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII family, at least one method that is selected from the metal oxide of IA, IIA family is not particularly limited.Can be by the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and described containing at least one be selected from IB, IIB, IIIB, IVB, VB, VIB, VIIB, the compound of the transition metal component of VIII family and/or at least one are selected from IA, the method that the compound of the metal component of IIA family directly mixes is introduced, also can be with containing described at least one be selected from IB, IIB, IIIB, IVB, VB, VIB, VIIB, the compound of the transition metal component of VIII family and/or at least one are selected from IA, described in the solution impregnation of the compound of the metal component of IIA family, the method for the precursor of heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix is introduced.
The described composition providing according to the method described above, depending on the different article shaped that require can be made into various easy operatings, such as microballoon, spherical, tablet or bar shaped etc.Moulding can be carried out according to a conventional method, for example, can be by the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and be describedly selected from the compound of the transition metal component of IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII family containing at least one, at least one be selected from the method preparation through extruded moulding roasting after the compound of metal component of IA, IIA family.Or 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 transition metal component that is selected from IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII family containing at least one with the method for dipping afterwards, at least one is selected from the metal component of IA, IIA family.In the time of extrusion molding, can add appropriate extrusion aid and/or adhesive, then extrusion molding.The kind of described extrusion aid, peptizing agent and consumption are that preformed catalyst or absorbent preparation those skilled in the art are known, are not repeated herein.
According to the invention provides method, preferably also comprise the step that the described composition after regeneration is sieved, described screening makes finally to make the composition after described regeneration to be optimized in follow-up use.Described method for sieving is this area conventional process.For example: the method that adopts bolting.
Described the flue gas of sulfur-bearing, nitrogen oxide is contacted with adsorbent, can, carrying out in adsorption separation device arbitrarily, for example, in ADSORPTION IN A FIXED BED tower or fluid bed adsorbing separation reactor, carry out.In the time that described contact is carried out in 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 is between Liang Ta when handover operation, reduction in described regeneration, be oxidized and restore in same tower and hocket, when adsorbing separation is between multitower when handover operation, reduction in described regeneration, be oxidized and restore and can in same tower, hocket, also can in two or several towers, carry out respectively.
According to the invention provides method, gas sulphur oxide after being enough to make described contact to make to separate and the content of nitrogen oxide meet " emission standard of air pollutants for boilers, GB13271 " 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 ADSORPTION IN A FIXED BED knockout tower to carry out of method, carry out according to the flow process shown in Fig. 1.
According to the flow process shown in Fig. 1, adsorbing separation is switched and is carried out in two ADSORPTION IN A FIXED BED knockout towers, and, when one of them adsorption tower carries out adsorbing separation, another adsorption tower carries out adsorbent reactivation.For example, when adsorbing separation is carried out in adsorption tower 4, adsorbent reactivation is in the time that adsorption tower 11 carries out, 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, through 1 introducing adsorption tower 4, makes it contact with described adsorbent under described absorption separation condition, has removed the gas of SOX and/or NOX through 8 discharges; 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, adsorbent reactivation is in the time that adsorption tower 4 carries out, 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 are purified is through the attached tower 11 of 1 introducing, under described absorption separation condition, make it contact with described adsorbent, removed the gas of SOX and/or NOX through 8 discharges; 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 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 flue gas, for example, be applicable to remove SOx and/or the NOx in catalytic cracking flue gas improvement, coal-fired plant flue gas improvement, steel mill flue gas, remove SOx and/or NOx in flue gas of refuse burning, and other smoke gas treatments that contain SOx and/or NOx.
The following examples illustrate the present invention further, but not thereby limiting the invention.
Except special instruction, in embodiment, chemical reagent used is chemical pure.
Described adsorbent composition that is preferably suitable for desulfurization simultaneously, nitrogen oxide of embodiment 1-7 explanation and preparation method thereof.
Embodiment 1
Raw material: γ-Al
2o
3carrier, spherical, 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 8.5 grams of Na
2cO
3, 15.8 grams of Cu (NO
3)
2with 12.4 grams of La (NO
3)
3be dissolved into 100 ml solns by deionized water, under normal temperature with 100 grams of γ-Al of this solution impregnation
2o
3carrier 2 hours, afterwards in 110 ℃ dry 12 hours, 950 ℃ of roastings 10 hours, obtain composition SORB-1 of the present invention.
SORB-1 composition: each component load capacity is respectively with Na
2cO
3, CuO and La
2o
3meter, the content of sodium is that the content of 8 % by weight, copper is that the content of 5 % by weight, lanthanum is 5 % by weight (metal component content adopts X-ray fluorescence spectra analyses, lower with).
Embodiment 2
Raw material: γ-Al
2o
3carrier (with embodiment 1); Ba (NO
3)
2, La (NO
3)
3, 50 % by weight Mn (NO
3)
2solution is Beijing Chemical Plant's product.
Preparation method: by 1.7 grams of Ba (NO
3)
2be dissolved into 100 ml soln L1 by deionized water, by 10 grams of La (NO
3)
3with 54.2 grams of Mn (NO
3)
2solution is dissolved into 100 ml soln L2 by deionized water.100 grams of γ-Al of L1, L2 dipping for order
2o
3carrier 2 hours, after each dipping in 110 ℃ dry 12 hours, 900 ℃ of roastings 10 hours, obtain combination articles SORB-2 of the present invention.
SORB-2 composition: each component load capacity is respectively with BaO, MnO
2and La
2o
3meter, the content of Ba is that the content of 1 % by weight, manganese is that the content of 13 % by weight, lanthanum is 4 % by weight.
Embodiment 3
Raw material: silica support, spherical, 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 sintering temperature is 800 ℃, other preparation methods are with embodiment 1.Preparation composition is respectively with Cr
2o
3, MgO meter, the content of chromium is that the content of 1 % by weight, magnesium is 19 % by weight composition SORB-3.
Raw material: silica support (with embodiment 3); Mn (NO
3)
2(being 50% weight solution), K
2cO
3be Beijing Chemical Plant's product.
Except sintering temperature is 750 ℃, other preparation methods are with embodiment 1.Preparation composition is respectively with K
2cO
3, MnO
2meter, the content of potassium is that the content of 4 % by weight, manganese is 13 % by 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 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 % by weight, cobalt is 15 % by 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 sintering temperature is 650 ℃, other preparation methods are with embodiment 1.Preparation composition is respectively with MgO, ZnO, Fe
2o
3meter, the content of magnesium is that the content of 3 % by weight, zinc is that the content of 11 % by weight, iron is 8 % by weight composition SORB-6.
Except sintering temperature and roasting time are 600 ℃ of roastings 10 hours, other are 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 % by weight, copper is that the content of 5 % by weight, lanthanum is the composition SORB-7 of 5 % by weight.
Embodiment 8-11 illustrates the performance of described adsorbent composition.
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 SORB-1 consumption is 1 gram, and adsorption temp is 175 ℃, and 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
2.Before passing into unstripped gas, use N
2volume flow with 300 ml/min purges desulfurization removing nitric material bed 1 hour at 300 ℃, and is cooled to adsorption temp.In the time that tending towards stability, absorption tail gas concentration stops adsorption experiment.Absorber outlet meets SO
2, SO in 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 are same therewith).Wherein, SO
2saturated extent of adsorption reach 1.241 mMs/gram, the saturated extent of adsorption of NO reaches 0.411 mM/gram.
Embodiment 9
SORB-2 performance is described
Experiment with embodiment 8 same apparatus on carry out.SORB-2 consumption is 1 gram, and adsorption temp is 50 ℃, and 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
2.Before passing into unstripped gas, use N
2volume flow with 300 ml/min purges desulfurization removing nitric material bed 1 hour at 300 ℃, and is cooled to adsorption temp.In the time that tending towards stability, absorption tail gas concentration stops adsorption experiment.Reactor outlet meets SO
2, SO in NO analyzer monitoring flue gas
2, NO content variation.Wherein, SO
2saturated extent of adsorption reach 1.312 mMs/gram, the saturated extent of adsorption of NO reaches 0.445 mM/gram.
SORB-3 performance is described.
Experiment with embodiment 8 same apparatus on carry out.SORB-3 consumption is 1 gram, and adsorption temp is 100 ℃, and 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
2.Before passing into unstripped gas, use N
2volume flow with 300 ml/min purges desulfurization removing nitric material bed 1 hour at 300 ℃, and is cooled to adsorption temp.In the time that tending towards stability, absorption tail gas concentration stops adsorption experiment.Reactor outlet meets SO
2, SO in NO analyzer monitoring flue gas
2, NO content variation.Wherein, SO
2saturated extent of adsorption reach 1.210 mMs/gram, the saturated extent of adsorption of NO reaches 0.405 mM/gram.
SORB-7 performance is described.
Experiment with embodiment 8 same apparatus on carry out.SORB-7 consumption is 1 gram, and adsorption temp is 175 ℃, and 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
2.Before passing into unstripped gas, use N
2volume flow with 300 ml/min purges desulfurization removing nitric material bed 1 hour at 300 ℃, and is cooled to adsorption temp, stops adsorption experiment in the time that absorption tail gas concentration tends towards stability.Reactor outlet meets SO
2, SO in NO analyzer monitoring flue gas
2, NO content variation.Wherein, SO
2saturated extent of adsorption reach 1.125 mMs/gram, the saturated extent of adsorption of NO reaches 0.292 mM/gram.
Embodiment 12
The inventive method is described.
Until regenerative agent be embodiment 8 conditions absorption saturated after sample.
Regeneration is carried out on regenerating unit outside device, and regeneration reactor is the tubular reactor of 10 millimeters of internal diameters.
1 gram of SORB-1 to be regenerated is placed in to regeneration reactor, be under the nitrogen blowing condition of 10000/ hour in air speed, with the programming rate temperature programming to 350 ℃ of 10 ℃/min, stablize after 30 minutes and stop passing into nitrogen, at 350 ℃, switching air speed is that the CO gas of 15000/ hour makes it contact 2 hours with SORB-1 to be regenerated; Be the nitrogen blowing 30 minutes of 10000/ hour by air speed, the oxygen that switches air speed and be 15000/ hour makes it contact 30 minutes with the SORB-1 to be regenerated reducing through back; It is the nitrogen blowing 30 minutes of 10000/ hour by air speed, switching air speed is that the methane gas of 15000/ hour contacts 1 hour with the SORB-1 to be regenerated of premenstrual oxidation step, afterwards, nitrogen blowing to the temperature of reactor that passes into air speed and be 10000/ hour is reduced to normal temperature, the adsorbent composition SORB-1-1 after being regenerated.
Evaluate SORB-1-1 according to embodiment 8 appreciation conditions.Experimental result is: SO
2saturated extent of adsorption be 1.125 mMs/gram (for fresh dose 90.7%), the saturated extent of adsorption of NO reach 0.359 mM/gram (for fresh dose 87.3%).
Comparative example 1
The renovation process of reference is described.
Regeneration reactor and treat that regenerated catalyst is identical with embodiment 12.
1 gram of SORB-1 to be generated is placed in to regeneration reactor, be under the nitrogen blowing condition of 10000/ hour in air speed, be warming up to 600 ℃ with the speed program of 10 ℃/min, stablize after 30 minutes and stop passing into nitrogen, at 600 ℃, switching air speed is that the hydrogen of 15000/ hour makes it contact 1 hour with SORB-1 to be regenerated; Be the nitrogen blowing 30 minutes of 10000/ hour by air speed, the oxygen that switches air speed and be 15000/ hour makes it contact 30 minutes with the SORB-1 to be regenerated reducing through back; Be the nitrogen blowing of 10000/ hour, be cooled to normal temperature, the adsorbent composition SORB-1-C1 after being regenerated by air speed.
Evaluate 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 reach 0.241 mM/gram (for fresh dose 58.6%).
Embodiment 13-16 illustrates the impact of this operating condition on the inventive method.
Embodiment 13
Regenerating unit and treat that regenerated catalyst is identical with embodiment 12.
1 gram of SORB-1 to be generated is placed in to reaction unit, be under the nitrogen blowing condition of 20000/ hour in air speed, be warming up to 300 ℃ with the speed program of 10 ℃/min, stablize after 30 minutes and stop passing into nitrogen, at 300 ℃, switching air speed is that the CO gas of 20000/ hour makes it contact 30 minutes with SORB-1 to be regenerated; Be the nitrogen blowing 30 minutes of 20000/ hour by air speed, the oxygen that switches air speed and be 15000/ hour makes it contact 30 minutes with the SORB-1 to be regenerated that back reduces; It is the nitrogen blowing 30 minutes of 20000/ hour by air speed, switching air speed is that the hydrogen of 25000/ hour contacts 3.5 hours with the SORB-1 to be regenerated of back oxidation, afterwards, nitrogen blowing to the temperature of reactor that passes into air speed and be 20000/ hour is reduced to normal temperature, the adsorbent composition SORB-1-2 after being regenerated.
Evaluate SORB-1-2 according to embodiment 8 appreciation conditions.Experimental result is: SO
2saturated extent of adsorption be 1.120 mMs/gram (for fresh dose 90.2%), the saturated extent of adsorption of NO reach 0.351 mM/gram (for fresh dose 85.4%).
Regenerating unit and treat that regenerated catalyst is identical with embodiment 12.
1 gram of SORB-1 to be generated is placed in to reaction unit, be under the nitrogen blowing condition of 10000/ hour in air speed, be warming up to 350 ℃ with the speed program of 10 ℃/min, stablize after 30 minutes and stop passing into nitrogen, at 350 ℃, switching air speed is that the methane gas of 30000/ hour makes it contact 30 minutes with SORB-1 to be regenerated; Be the nitrogen blowing 30 minutes of 10000/ hour and be warming up to 400 ℃ by air speed, the air that switches air speed and be 20000/ hour makes it contact 2.5 hours with the SORB-1 to be regenerated that back reduces; Be the nitrogen blowing 30 minutes of 10000/ hour and be warming up to 630 ℃ by air speed; Switching air speed is that the CO gas of 5000/ hour contacts 30 minutes with the SORB-1 to be regenerated of back oxidation, afterwards, nitrogen blowing to the temperature of reactor that passes into air speed and be 10000/ hour is reduced to normal temperature, the adsorbent composition SORB-1-3 after being regenerated.
Evaluate SORB-1-3 according to embodiment 8 appreciation conditions.Experimental result is: SO
2saturated extent of adsorption be 1.130 mMs/gram (for fresh dose 91.1%), the saturated extent of adsorption of NO reach 0.381 mM/gram (for fresh dose 92.7%).
Regenerating unit and treat that regenerated catalyst is identical with embodiment 12.
1 gram of SORB-1 to be generated is placed in to reaction unit, be under the nitrogen blowing condition of 10000/ hour in air speed, with 10 ℃ of temperature programmings to 500 ℃ per minute, stablize after 30 minutes and stop passing into nitrogen, at 500 ℃, switching air speed is that the propylene gas of 35000/ hour makes it contact 30 minutes with SORB-1 to be regenerated; Be the nitrogen blowing 30 minutes of 10000/ hour and be warming up to 630 ℃ by air speed; Switching air speed is that the oxygen helium mixture (oxygen accounts for 75 volume %) of 10000/ hour makes it contact 2 hours with the SORB-1 to be regenerated of back reduction; With air speed be the nitrogen blowing of 10000/ hour and be cooled to 450 ℃ after constant temperature, switching air speed is that the ethane gas of 25000/ hour contacts 1.5 hours with the SORB-1 to be regenerated of back oxidation, afterwards, nitrogen blowing to the temperature of reactor that passes into air speed and be 10000/ hour is reduced to normal temperature, the adsorbent composition SORB-1-4 after being regenerated.
Evaluate SORB-1-4 according to embodiment 8 appreciation conditions.Experimental result is: SO
2saturated extent of adsorption be 1.119 mMs/gram (for fresh dose 90.1%), the saturated extent of adsorption of NO reach 0.369 mM/gram (for fresh dose 89.8%).
Embodiment 16
Regenerating unit and treat that regenerated catalyst is identical with embodiment 12.
1 gram of SORB-1 to be generated is placed in to reaction unit, be under the nitrogen blowing condition of 10000/ hour in air speed, with 10 ℃ of temperature programmings to 650 ℃ per minute, stablize after 30 minutes and stop passing into nitrogen, at 650 ℃, switching air speed is that the hydrogen of 5000/ hour makes it contact 3.5 hours with SORB-1 to be regenerated; With air speed be the nitrogen blowing of 10000/ hour and be cooled to 500 ℃ after constant temperature, switching air speed is that the oxygen argon mixture (oxygen accounts for 30 volume %) of 10000/ hour makes it contact 1 hour with the SORB-1 to be regenerated that back reduces; With air speed be the nitrogen blowing of 10000/ hour and be cooled to 380 ℃ after constant temperature, switching air speed is that the ethylene gas of 25000/ hour contacts 1.5 hours with the SORB-1 to be regenerated of back oxidation, afterwards, nitrogen blowing to the temperature of reactor that passes into air speed and be 10000/ hour is reduced to normal temperature, the adsorbent composition SORB-1-5 after being regenerated.
Evaluate SORB-1-5 according to embodiment 8 appreciation conditions.Experimental result is: SO
2saturated extent of adsorption be 1.140 mMs/gram (for fresh dose 91.9%), the saturated extent of adsorption of NO reach 0.386 mM/gram (for fresh dose 93.9%).
The result that embodiment 13-16 provides can illustrate, the inventive method flexible operation and catalyst performance recover.
Claims (10)
1. one kind removes the method for sulfureous in flue gas, nitrogen oxide, be included under absorption separation condition, the flue gas of sulfur-bearing, nitrogen oxide is contacted with adsorbent, afterwards by the adsorbent reactivation after contacting with the flue gas of sulfur-bearing, nitrogen oxide, it is characterized in that, described regeneration adopts the method comprising the following steps to carry out:
(1), at 200 ℃ of-800 ℃ of temperature, will treat that reproducing adsorbent contacts 0.5 hour-5 hours with reducing gas; (2), at 200 ℃ of-800 ℃ of temperature, will contact 0.5 hour with oxygen-containing gas-3 hours through the product of step (1) reduction; (3), at 200 ℃ of-800 ℃ of temperature, will again contact 0.5 hour with reducing gas-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, described reducing gas is selected from one or more in the hydrocarbon compound that carbon monoxide, hydrogen, carbon number are 1～4, 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, the hydrocarbon compound that described carbon number is 1～4 is selected from one or more in methane, ethene, ethane, propylene, 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 the 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 |
| 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 |
| 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 |
| 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 |
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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 |
| 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 |
| 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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| CN85109321A (en) * | 1984-04-26 | 1987-06-03 | 无比石油公司 | The reactivation that contains the precious metal catalyst agent material |
| CN1213589A (en) * | 1998-08-06 | 1999-04-14 | 南京四力化工有限公司 | Fluidized bed gas-phase catalytic hydrogenation catalyst non-nitrogen regeneration activating method |
| CN101209391A (en) * | 2006-12-30 | 2008-07-02 | 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 |
|---|---|---|---|---|
| CN85109321A (en) * | 1984-04-26 | 1987-06-03 | 无比石油公司 | The reactivation that contains the precious metal catalyst agent material |
| CN1213589A (en) * | 1998-08-06 | 1999-04-14 | 南京四力化工有限公司 | Fluidized bed gas-phase catalytic hydrogenation catalyst non-nitrogen regeneration activating method |
| CN101209391A (en) * | 2006-12-30 | 2008-07-02 | 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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