CN101757911B - Manganese-containing adsorbent composition - Google Patents
Manganese-containing adsorbent composition Download PDFInfo
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- CN101757911B CN101757911B CN2008102465205A CN200810246520A CN101757911B CN 101757911 B CN101757911 B CN 101757911B CN 2008102465205 A CN2008102465205 A CN 2008102465205A CN 200810246520 A CN200810246520 A CN 200810246520A CN 101757911 B CN101757911 B CN 101757911B
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Abstract
The invention relates to a manganese-containing adsorbent composition, which contains heat-resistant inorganic oxide matrix, a manganese component and at least one of metal components selected from the I A group and/or the II A group; based on the composition, the content of the heat-resistant inorganic oxide matrix is 50 percent to 99 percent by weight; and by oxides, the content of the manganese component is 0.5 percent to 35 percent by weight, and the content of the metal components selected from the I A group and/or the II A group is 0.5 percent to 35 percent by weight. Compared with the prior art, on the premise of maintaining the high performance of removing sulfur and oxynitride in flue gas, the composition has high regeneration stability.
Description
Technical field
The present invention relates to a kind of adsorbent, particularly relate to a kind of adsorbent composition that contains manganese.
Background technology
Atmospheric Sulfur oxide S Ox (is SO more than 95%
2), the pollution problem order of nitrogen oxide NOx (being NO more than 90%) benefit is 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 the emission control technique to SOx is comparatively ripe in the world, and to the emission control of NOx, although 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 utilize 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, applicable 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 more and more are subject to people's attention in recent years owing to having the advantages such as reduced investment, operating cost are low.
The people such as Chen Ying disclose about " new adsorbent-catalyst La-Cu-Na-γ-Al
2O
3Remove simultaneously SO
2Experimental study with NO " and achievement (colleges and universities' Chemical Engineering journal, the 1st phase of the 21st 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 simultaneously SO
2With the large (SO of NO ability
2When/NO is 5.1-3.5, La-Cu-Na-γ-Al
2O
3Adsorb simultaneously SO
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 that forms has and takes off synchronously preferably SO
2With the NO performance.
Summary of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, and a kind of new, better adsorbent composition of performance is provided.
The invention provides a kind of adsorbent composition that contains manganese, said composition contains heat-resistant inorganic oxide matrix, manganese metal component and at least a IA and/or the IIA family metal component of being selected from, take described composition as benchmark, the content of heat-resistant inorganic oxide matrix is 50 % by weight-99 % by weight, in oxide, the content of manganese metal component is 0.5 % by weight-35 % by weight, and the content that is selected from IA and/or IIA family metal component is 0.5 % by weight-35 % by weight.
Described composition provided by the invention can use as adsorbent in various gas cleanings.Because this adsorbent has excellent sulphur, nitrogen oxide absorption property, be particularly suitable for removing simultaneously sulphur, nitrogen oxide is the purification of the industrial waste gas of purpose.Compared with prior art, when this adsorbent being used for when removing simultaneously sulphur, nitrogen oxide as the industrial waste gas purifying process of purpose, this adsorbent not only has higher desulfurization, nitrogen performance, and has better regenerating stability.
The specific embodiment
According to adsorbent provided by the invention, take described composition as benchmark, the content of heat-resistant inorganic oxide matrix is preferably 65 % by weight-98 % by weight, in oxide, the content of manganese metal component is preferably 1 % by weight-18 % by weight, and the content that is selected from IA and/or IIA family metal component is preferably 1 % by weight-20 % by weight.
Wherein, described manganese can be to exist with oxide and/or with the equiprobable form of salt that other components form in described adsorbent composition.Described IA and/or IIA family metal component can be to exist with its oxide and/or with the equiprobable form of salt that other components form in described adsorbent composition.
Characterize with X-ray photoelectron spectroscopy, further the manganese in the preferred described adsorbent exists with two kinds of different valence states at least, for example, and Mn
4+And Mn
2+The form of two kinds of valence states exists, take the total amount of manganese metal component as benchmark, and in element, Mn
4+Content be 90-70%, Mn
2+Content be 10-30%, be more preferably Mn
4+Content be 85-70%, Mn
2+Content be 15-30%.
Here,
Wherein, M represents manganese, and i represents the chemical valence of manganese, for example Mn
4+, Mn
2+, its i value be respectively 4 and 2, S represent the area integral value at different valence state manganese characteristic of correspondence peak in ev～I figure, ∑ S
Mn iSummation for the characteristic peak area integrated value of different valence state manganese.
The described metal that is selected from IA family is preferably a kind of and composition thereof among Na and the K, one or more among the preferred Ba of IIA family metal component, Mg and the Ca.
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 and composition thereof.
According to adsorbent provided by the invention, wherein can also contain any component that maybe can improve composition properties provided by the invention that do not affect.For example, can contain one or more components that are selected from IB, IIB, IIIB, VIB, the VIII family, further the component of one or more among preferred wherein Cr, Co, Cu, Fe, Ni, Zn, Ce, La, the Pt.In oxide and take the total amount of described composition as benchmark, the described component that is selected from IB, IIB, IIIB, VIB, VIII family, further the content of the component of one or more among preferred wherein Cr, Co, Cu, Fe, Ni, Zn, Ce, La, the Pt is no more than 35 % by weight, further preferably be no more than 17 % by weight, be more preferably and be no more than 15 % by weight.
Adsorbent composition provided by the invention can adopt the method preparation that may further comprise the steps:
(1) in the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix, introduces manganese metal component and at least a metal component that is selected from IA, IIA family;
(2) product 2 hours-12 hours of calcination steps (1) under greater than 600 ℃ to 1100 ℃ conditions obtains described composition;
The consumption of each component makes in the final described composition in the wherein said step (1), take described composition as benchmark, the content of heat-resistant inorganic oxide matrix is 50 % by weight-99 % by weight, be preferably 65 % by weight-98 % by weight, in oxide, the content of manganese metal component is 0.5 % by weight-35 % by weight, is preferably 1 % by weight-18 % by weight, the content that is selected from IA and/or IIA family metal component is 0.5 % by weight-35 % by weight, is preferably 1 % by weight-20 % by weight.
The sintering temperature of preferred described step (2) is preferably 620 ℃-1000 ℃, and more preferably 650 ℃-960 ℃, roasting time was preferably 3 hours-12 hours, more preferably 4 hours-11 hours.
Wherein, to described in the described step (1) introduce the manganese metal component in the precursor of heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and at least a method that is selected from the metal component of IA, IIA family is not particularly limited.Can be that the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix is contained the compound of manganese metal component and/or method that at least a compound that is selected from the metal component of IA, IIA family directly mixes is introduced with described, also can be to introduce with the method for the precursor of the described heat-resistant inorganic oxide matrix of solution impregnation of the compound of the compound that contains the manganese metal component and/or at least a metal component that is selected from IA, IIA family and/or heat-resistant inorganic oxide matrix.
According to described composition provided by the invention, depending on the different article shaped that require can be made into various easy operatings, such as microballoon, sphere, tablet or bar shaped etc.Moulding can be carried out according to a conventional method, for example, can be with the method preparation by extruded moulding and roasting of the compound of the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and the described compound that contains the manganese metal component and/or at least a metal component that is selected from IA, IIA family.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 manganese metal component and/or at least a metal component that is selected from IA, IIA family with the method for dipping afterwards.When extrusion molding, can add an amount of 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.
In described adsorbent composition, also contain any other components that maybe can improve composition properties provided by the invention that do not affect, for example, contain the component that is selected from IB, IIB, IIIB, VIB, VIII family, further during the component of one or more among preferred wherein Cr, Co, Cu, Fe, Ni, Zn, Ce, La, the Pt, described preparation method also comprises the step of introducing these components.
Wherein, introducing method to described other components is not particularly limited, can be in step (1) with when in the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix, introducing manganese metal component and at least a metal component that is selected from IA, IIA family, to introduce, also can be introduced separately into.For example, can be at precursor and described compound and/or at least a IA that is selected from that contains the manganese metal component with described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix, the compound of the metal component of IIA family directly mixes the method for the compound that will contain simultaneously described other components to be introduced, also can be with the compound that contains other components and the compound and/or at least a IA that is selected from that contain the manganese metal component, the compound preparation mixed solution of the metal component of IIA family, the method for flooding afterwards the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix is introduced.Also can configure separately dipping solution, the method for flooding before or after the metal component of introducing described manganese and/or IA, IIA family is introduced.Can also be to introduce with the method for dipping afterwards in described step (2), when when step (2) is introduced with the method for dipping afterwards, the step that after dipping, also comprises dry and roasting, described drying is conventional method and condition, is not particularly limited here, and described method of roasting is conventional method, described roasting condition preferably includes: sintering temperature 600-1100 ℃, more preferably 650-960 ℃, roasting time 2-12 hour, more preferably 4-11 hour.Take the total amount of described composition as benchmark, the consumption of each component makes in the final described adsorbent composition, the described component that is selected from IB, IIB, IIIB, VIB, VIII family, further the content of the component of one or more among preferred wherein Cr, Co, Cu, Fe, Ni, Zn, Ce, La, the Pt is no more than 35 % by weight, preferably be no more than 17 % by weight, be more preferably and be no more than 15 % by weight.
Described composition provided by the invention can be used as adsorbent and is directly used in and adopts adsorption method to remove SOx and/or NOx process in the flue gas.Therefore, be applicable to catalytic cracking flue gas improvement, coal-fired plant flue gas improvement, steel mill smoke gas treatment, flue gas of refuse burning is administered and other contain the smoke gas treatment of SOx and NOx.Wherein, the operating temperature in the described adsorption method can be usual operating temperature.Preferred operating temperature is 0～300 ℃, more preferably 0～100 ℃.
The following examples illustrate the present invention further, but not thereby limiting the invention.Except specifying, used chemical reagent is chemical pure among the embodiment.
Adopt X-ray photoelectron spectroscopy to measure the content of different valence state manganese.Concrete operations comprise: x-ray photoelectron spectroscopy is the PHI Quantera SXM of ULVAC-PH INC.Adopt monochromator, select the Al plate target, X-ray beam 9 μ m-1.5mm
2, energy resolution 0.5eV, sensitivity 3M CPS, incidence angle is 45 °, analysis room's vacuum 6.7 * 10
-8Pa.
Sputtering condition: sweep type Ar
+Rifle, area 1 * 1mm
2, sputter rate is about 20nm/min, and energy is 2.0KV, and emission current is 20mA, and standard specimen is thermal oxide SiO
2/ Si.The sputter result calculates each characteristic peak area integrated value by Origin 7.0 Software Create ev (electronic energy)～I (intensity) spectrogram.According to
S
M i/ ∑ S
M i* 100% calculates the content of different valence state metal.
(determine with reference to handbook " (Handbook of X Ray Photoelectron Spectroscopy " (second edition in 1992) by the characteristic peak among the ev～I) in the x-ray photoelectron power spectrum for the different valence state metal.
Comparative Examples 1
The composition and method of making the same that can be used for removing sulfureous in flue gas, nitrogen oxide that explanation provides according to prior art.
Raw material: γ-Al
2O
3Carrier (with embodiment 1).Na
2CO
3, Cu (NO
3)
2, La (NO
3)
3Be Beijing Chemical Plant's product.
Preparation method: take by weighing 85 gram Na
2CO
3, 158 gram Cu (NO
3)
2With 124 gram La (NO
3)
3Be dissolved into 1 liter of solution with deionized water, restrain γ-Al with this solution impregnation 1000 under the normal temperature
2O
3Carrier 2 hours, afterwards in 110 ℃ of dryings 12 hours, 600 ℃ of roastings 10 hours obtain described reference composition La-Cu-Na-γ-Al
2O
3
Form: 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 % by weight, copper is that the content of 5 % by weight, lanthanum is 5 % by weight.
Embodiment 1-7 illustrates composition and method of making the same provided by the invention.
Embodiment 1
Raw material: γ-Al
2O
3Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Ba (NO
3)
2, La (NO
3)
3, 50 % by weight Mn (NO
3)
2Solution (being Beijing Chemical Plant's product).
Preparation method: with 25 gram Ba (NO
3)
2Be dissolved into 1 liter of solution L1 with deionized water, with 100 gram La (NO
3)
3Be dissolved into 1 liter of solution L2 with deionized water, with 542 gram Mn (NO
3)
2Solution is dissolved into 1 liter of solution L3 with deionized water.Order restrains γ-Al with L1, L2, L3 dipping 1000
2O
3Carrier 2 hours, in 110 ℃ of dryings 12 hours, 900 ℃ of roastings 10 hours obtained composition La-Mn-Ba-γ-Al of the present invention behind each dipping
2O
3
Form: each component load capacity is respectively with BaO, MnO
2And La
2O
3Meter, the content of barium are that the content of 1 % by weight, manganese is that the content of 13 % by weight, lanthanum is 4 % by weight (metal component content adopts x-ray fluorescence method to measure, lower with).
Manganese is respectively with Mn
4+And Mn
2+Two kinds of different valence state exist, in element, and Mn
4+Content be 75%, Mn
2+Content be 25%.
Embodiment 2
Raw material: with embodiment 1.
Preparation method: with 25 gram Ba (NO
3)
2Be dissolved into 1 liter of solution L1 with deionized water, with 100 gram La (NO
3)
3Be dissolved into 1 liter of solution L2 with deionized water, with 542 gram Mn (NO
3)
2Solution is dissolved into 1 liter of solution L3 with deionized water.Order restrains γ-Al with L1, L2, L3 dipping 1000
2O
3Carrier 2 hours, in 110 ℃ of dryings 12 hours, 600 ℃ of roastings 10 hours obtained composition La-Mn-Ba-γ-Al of the present invention behind each dipping
2O
3
Form: each component load capacity is respectively with BaO, MnO
2And La
2O
3Meter, the content of barium are that the content of 1 % by weight, manganese is that the content of 13 % by weight, lanthanum is 4 % by weight.
Manganese is with Mn
4+Form does not detect other valence state forms of Mn.
Embodiment 3
Raw material: silica support, sphere, 1.22 millimeters of average grain diameters, Chang Ling catalyst plant product; Mn (NO
3)
2(being 50% weight solution), K
2CO
3Be Beijing Chemical Plant's product.
With 40 gram K
2CO
3Be dissolved into 1 liter of solution L1 with deionized water, with 535 gram Mn (NO
3)
2Solution is dissolved into 1 liter of solution L2 with deionized water.Order restrains γ-Al with L1, L2 dipping 1000
2O
3Carrier 2 hours in 110 ℃ of dryings, 750 ℃ of roastings in 12 hours 8 hours, obtains composition K-Mn-SiO of the present invention behind each dipping
2
Preparation forms respectively with K
2CO
3, MnO
2Meter, composition K-Mn-SiO
2The content of middle potassium is that the content of 4 % by weight, manganese is 13 % by weight.
Manganese is respectively with Mn
4+And Mn
2+Two kinds of different valence state exist, in element, and Mn
4+Content be 71%, Mn
2+Content be 29%.
Embodiment 4
Raw material: γ-Al
2O
3Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Mn (NO
3)
2(being 50% weight solution), Cr (NO
3)
3, Na
2CO
3Be Beijing Chemical Plant's product.
With 160 gram Na
2CO
3Be dissolved into 1 liter of solution L1 with deionized water, with 535 gram Mn (NO
3)
2Solution is dissolved into 1 liter of solution L2, with 684 gram Cr (NO
3)
3Solution melts into 1 liter of solution L3 with deionized water.Order restrains γ-Al with L1, L2, L3 dipping 1000
2O
3Carrier 2 hours, in 110 ℃ of dryings 12 hours, 700 ℃ of roastings 5 hours obtained composition Na-Mn-Cr-γ-Al of the present invention behind each dipping
2O
3
Composition Na-Mn-Cr-γ-Al
2O
3Composition respectively with Na
2CO
3, MnO
2, Cr
2O
3Meter, the content of sodium are that the content of 16 % by weight, manganese is that the content of 5 % by weight, chromium is 13 % by weight.
Manganese is respectively with Mn
4+And Mn
2+Two kinds of different valence state exist, in element, and Mn
4+Content be 85%, Mn
2+Content be 15%.
Embodiment 5
Raw material: γ-Al
2O
3Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Mn (NO
3)
2(being 50% weight solution), Co (NO
3)
2, Na
2CO
3, Ba (NO
3)
2Be Beijing Chemical Plant's product.
The method of step impregnation is carried out in sample preparation, and in 110 ℃ of dryings 12 hours, 680 ℃ of lower roastings 6 hours, other preparation methods were with embodiment 1 behind each step dipping.Preparation forms respectively with Na
2CO
3, MnO
2, Co
3O
4, BaO meter, the content of sodium is that the content of 6 % by weight, manganese is that the content of 10 % by weight, cobalt is that the content of 8 % by weight, barium is the composition Na-Mn-Co-Ba-γ-Al of 5 % by weight
2O
3
Manganese is respectively with Mn
4+And Mn
2+Two kinds of different valence state exist, in element, and Mn
4+Content be 80%, Mn
2+Content be 20%.
Embodiment 6
Raw material: γ-Al
2O
3Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Mn (NO
3)
2(being 50% weight solution), Cu (NO
3)
2, Na
2CO
3Be Beijing Chemical Plant's product.
The method of step impregnation is carried out in sample preparation, and in 110 ℃ of dryings 12 hours, 750 ℃ of lower roastings 4 hours, other preparation methods were with embodiment 1 behind each step dipping.Preparation forms respectively with Na
2CO
3, MnO
2, CuO meter, the content of sodium is that the content of 8 % by weight, manganese is that the content of 3 % by weight, copper is the composition Na-Mn-Cu-γ-Al of 15 % by weight
2O
3
Manganese is respectively with Mn
4+And Mn
2+Two kinds of different valence state exist, in element, and Mn
4+Content be 84%, Mn
2+Content be 16%.
Embodiment 7
Raw material: γ-Al
2O
3Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Mn (NO
3)
2(being 50% weight solution), Zn (NO
3)
2, Na
2CO
3Be Beijing Chemical Plant's product.
The method of step impregnation is carried out in sample preparation, and in 110 ℃ of dryings 12 hours, 950 ℃ of lower roastings 4 hours, other preparation methods were with embodiment 1 behind each step dipping.Preparation forms respectively with Na
2CO
3, MnO
2, ZnO meter, the content of sodium is that the content of 18 % by weight, manganese is that the content of 8 % by weight, zinc is the composition Na-Mn-Zn-γ-Al of 10 % by weight
2O
3
Manganese is respectively with Mn
4+And Mn
2+Two kinds of different valence state exist, in element, and Mn
4+Content be 77%, Mn
2+Content be 23%.
Embodiment 8
La-Mn-Ba-γ-the Al of embodiment 1 preparation is described
2O
3Performance.
Experiment is carried out at preventing fixed bed adsorber.Tube inner diameter is 8 millimeters, and the adsorbent 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 passing into unstripped gas
2Volume flow with 300 ml/min purges desulfurization removing nitric material beds 1 hour under 300 ℃, and is 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, adopt the SO of FIREFOX software calculation composition
2With NO saturated extent of adsorption (lower same).Wherein, SO
2Saturated extent of adsorption reach 1.320 mMs/gram, the saturated extent of adsorption of NO reach 0.446 mM/gram.
Comparative Examples 2
La-Cu-Na-γ-Al that this Comparative Examples explanation is provided by Comparative Examples 1
2O
3Performance.
Experiment is carried out at fixed bed continuous-flow reaction unit.Tube inner diameter is 8 millimeters, and the desulfurization removing nitric material usage 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 passing into unstripped gas
2Volume flow with 300 ml/min purges desulfurization removing nitric material beds 1 hour under 300 ℃, and is cooled to adsorption temp, stops 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 mMs/gram, the saturated extent of adsorption of NO reach 0.292 mM/gram.
Embodiment 9
La-Mn-Ba-γ-the Al of embodiment 2 preparations is described
2O
3Performance.
Experiment is carried out at fixed bed continuous-flow reaction unit.Tube inner diameter is 8 millimeters, and the desulfurization removing nitric material usage 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 passing into unstripped gas
2Volume flow with 300 ml/min purges desulfurization removing nitric material beds 1 hour under 300 ℃, and is cooled to adsorption temp.When absorption tail gas concentration tends towards stability, stop adsorption experiment, use again N
2Purge mist remaining in the tube wall 10 minutes.Reactor outlet meets SO
2, SO in the NO analyzer monitoring flue gas
2, NO content variation.Wherein, SO
2Saturated extent of adsorption reach 1.209 mMs/gram, the saturated extent of adsorption of NO reach 0.308 mM/gram.
Embodiment 10
Desulfurization removing nitric performance after the sample regeneration of embodiment 1 preparation is described.
Be that embodiment 8 conditions are adsorbed saturated rear sample until regenerative agent.
Regeneration regenerating unit outside device carries out, and regeneration reactor is the tubular reactor of 10 millimeters of internal diameters.Restrain SORB-1 to be regenerated with 1 and place reaction unit, be under 10000/ hour the nitrogen blowing condition in air speed, with 10 ℃/minute programming rate temperature programmings to 350 ℃, stablize after 30 minutes and stop to pass into 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; Be 10000/ hour nitrogen blowing 30 minutes with air speed, 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; It is 10000/ hour nitrogen blowing 30 minutes with air speed, switch air speed and be 15000/ hour methane gas and contact 1 hour with SORB-1 to be regenerated through the 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-1-1 after obtaining regenerating.
Estimate SORB-1-1 according to embodiment 8 appreciation conditions.Experimental result is: SO
2Saturated extent of adsorption be 1.152 mMs/gram (for fresh dose 87.3%), the saturated extent of adsorption of NO reach 0.396 mM/gram (for fresh dose 88.8%).
Comparative Examples 3
Sample La-Cu-Na-γ-Al that explanation is provided by Comparative Examples 1
2O
3Desulfurization removing nitric performance after the regeneration.The regeneration tests step is with embodiment 10.
The appreciation condition of sample is with Comparative Examples 2 after the regeneration.Experimental result shows, the saturated extent of adsorption of the desulfurization removing nitric material SO2 after the regeneration 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%).
Evaluation result shows, the invention provides the desulfurization of adsorbent composition and regrowth thereof and adsorbent composition and the regrowth thereof that nitrogen removal performance all provides apparently higher than prior art.
Claims (10)
1. adsorbent composition that contains manganese, said composition contains heat-resistant inorganic oxide matrix, manganese metal component and at least a I A and/or the IIA family metal component of being selected from, take described composition as benchmark, the content of heat-resistant inorganic oxide matrix is 50 % by weight-99 % by weight, in oxide, the content of manganese metal component is 0.5 % by weight-35 % by weight, the content that is selected from I A and/or IIA family metal component is 0.5 % by weight-35 % by weight, characterize with X-ray photoelectron spectroscopy, described manganese metal component exists with at least two kinds of different valence states.
2. composition according to claim 1, it is characterized in that, take described composition as benchmark, the content of heat-resistant inorganic oxide matrix is 65 % by weight-98 % by weight, in oxide, the content of manganese metal component is 1 % by weight-18 % by weight, and the content that is selected from I A and/or II A family metal component is 1 % by weight-20 % by weight.
3. composition according to claim 1 is characterized in that, the manganese metal component of described different valence state comprises Mn
4+And Mn
2+, in element, take the total amount of manganese metal component as benchmark, Mn
4+Content be 90%-70%, Mn
2+Content be 10%-30%.
4. composition according to claim 3 is characterized in that, in element, and take the total amount of manganese metal component as benchmark, described Mn
4+Content be 85%-70%, Mn
2+Content be 15%-30%.
5. composition according to claim 1 is characterized in that, the metal of described I A, IIA family is selected from one or more among Na, K, Ba, Mg, the Ca.
6. composition according to claim 1, it is characterized in that, described heat-resistant inorganic oxide matrix is 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, the silica-alumina-zirconia.
7. composition according to claim 6 is characterized in that, described heat-resistant inorganic oxide matrix is selected from one or more in aluminium oxide, silica, the silica-alumina.
8. composition according to claim 1, it is characterized in that, also contain one or more components that are selected from I B, IIB, IIIB, IVB, VB, VIB, the VIII family in the described composition, in oxide and take the total amount of described composition as benchmark, the content of one or more components in the described I of being selected from B, II B, IIIB, IVB, VB, VIB, the VIII family is no more than 35 % by weight.
9. composition according to claim 8, it is characterized in that, the component of described I B, IIB, IIIB, IVB, VB, VIB, VIII family is selected from one or more among Cr, Co, Cu, Fe, Ni, Zn, Ce, La, the Pt, in oxide and take the total amount of described composition as benchmark, the content of one or more components among the described Cr of being selected from, Co, Cu, Fe, Ni, Zn, Ce, La, the Pt is no more than 17 % by weight.
10. composition according to claim 9 is characterized in that, in oxide and take the total amount of described composition as benchmark, the content of one or more components among the described Cr of being selected from, Co, Cu, Fe, Ni, Zn, Ce, La, the Pt is no more than 15 % by weight.
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| CN2008102465205A CN101757911B (en) | 2008-12-25 | 2008-12-25 | Manganese-containing adsorbent composition |
| 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 |
| 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 |
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| CN2008102465205A CN101757911B (en) | 2008-12-25 | 2008-12-25 | Manganese-containing adsorbent composition |
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