CN101804343B - Adsorbent combination containing metal component of group VIB - Google Patents
Adsorbent combination containing metal component of group VIB Download PDFInfo
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- CN101804343B CN101804343B CN2009100777033A CN200910077703A CN101804343B CN 101804343 B CN101804343 B CN 101804343B CN 2009100777033 A CN2009100777033 A CN 2009100777033A CN 200910077703 A CN200910077703 A CN 200910077703A CN 101804343 B CN101804343 B CN 101804343B
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Abstract
The invention relates to an adsorbent combination containing a metal component of group VIB. The combination comprises a heat resistant inorganic oxide substrate, at least one metal component of the group VIB and at least one metal component of the group IA and/or IIA, wherein the heat resistant inorganic oxide substrate accounts for 50-99 wt% based on the combination; and measured by oxides, the metal component of the group VIB accounts for 0.5-35 wt%, and the metal component of the group IA and/or IIA accounts for 0.5-35 wt%. Compared with the prior art, the combination maintains high performance for removing oxides and nitrogen oxides from sulfur, and achieves high regeneration stability meanwhile.
Description
Technical field
The present invention relates to a kind of adsorbent, particularly relate to a kind of adsorbent composition that contains the group vib metal component.
Background technology
Atmospheric Sulfur oxide S Ox (is SO more than 95%
2), the pollution problem of nitrogen oxide NOx (being NO more than 90%) 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 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 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, 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, owing to having the advantages such as reduced investment, operating cost are low, more and more are subject to people's attention in recent years.
The people such as Chen Ying disclose 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 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 formed has preferably synchronously de-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 the group vib metal component, said composition contains heat-resistant inorganic oxide matrix, at least one metal component that is selected from group vib is selected from I A and/or II A family metal component with at least one, 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 group vib metal component is 0.5 % by weight-35 % by weight, and the content that is selected from I A and/or II A family metal component is 0.5 % by weight-35 % by weight.
Described composition provided by the invention can be used as adsorbent in various gas cleanings.Because this adsorbent has excellent sulphur, nitrogen oxide absorption property, the purification of the industrial waste gas that to be particularly suitable for removing sulphur, nitrogen oxide be purpose simultaneously.Compared with prior art, when this adsorbent is removed to the industrial waste gas purifying process that sulphur, nitrogen oxide are purpose for take simultaneously, 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 group vib metal component is preferably 1 % by weight-18 % by weight, and the content that is selected from I A and/or II A family metal component is preferably 1 % by weight-20 % by weight.
Wherein, described group vib metal component preferred chromium, described group vib metal component can be to exist with its oxide or with the various possible forms such as salt that other components form in described adsorbent composition.Described I A and/or II A family metal component can be to exist with its oxide or with the various possible forms such as salt that other components form in described adsorbent composition.
With X-ray photoelectron spectroscopy, characterize, further the described gold of group vib that is selected from preferred described adsorbent is at least with M
vIB i1+and M
vIB i2+two kinds of different valence states exist, and take chromium as example, and preferred described chromium is with Cr
6+and Cr
3+the form of two kinds of valence states exists.The total amount of group vib metal component of take is benchmark, in element, and M in described different valence state metal component
vIB i1+content be 90-70%, be more preferably 85-70%, M
vIB i2+content be 10%-30%, be more preferably 15%-30%, i1 wherein is less than i2.
Here,
wherein, M
vIBmean VI B family metal, i means the chemical valence of VI B family metal, for example Cr
6+and Cr
3+, its i value be respectively 6 and 3, S mean the area integral value at different valence state group vib metal characteristic of correspondence peak in ev～I figure,
summation for the area integral value of the characteristic peak of different valence state VI B family metal.
The described metal that is selected from I A family is preferably a kind of and composition thereof in Na and K, one or more in the preferred Ba of II A family metal component, Mg and Ca.
The heat-resistant inorganic oxide that described heat-resistant inorganic oxide matrix is the 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.Preferably aluminium oxide wherein, silica, silica-alumina 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 I B, II B, III B, IV B, V B, VIII family, further one or more in preferred wherein Co, Cu, Fe, Ni, Zn, Ce, La, Pt.The total amount of described composition of take is benchmark, the described component that is selected from I B, II B, III B, IVB, V B, VIII family, further the content of the component of one or more in preferred wherein Co, Cu, Fe, Ni, Zn, Ce, La, 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.
Adsorbent composition provided by the invention preferably adopts the method preparation comprised the following steps:
(1) to introducing the group vib metal component in the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and at least one is selected from the metal component of I A, II A family;
(2) the product that is greater than calcination steps (1) under 600 ℃ to 1100 ℃ conditions 2 hours-12 hours, obtain described composition;
In wherein said step (1), the consumption of each component makes in final described composition, 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 group vib metal component is 0.5 % by weight-35 % by weight, is preferably 1 % by weight-18 % by weight, the content that is selected from I A and/or II A 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 620 ℃-1000 ℃, and more preferably 650 ℃-960 ℃, roasting time is 3 hours-12 hours, more preferably 4 hours-11 hours.
Wherein, the method to introducing VI B family's metal component and at least one in the precursor of heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and be selected from the metal component of IA, II A family described in described step (1) is not particularly limited.Can be that the method that the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and compound containing described VI B family metal component and/or compound that at least one is selected from the metal component of I A, II A family are directly mixed is introduced, can be also to introduce by the method for the precursor of the described heat-resistant inorganic oxide matrix of solution impregnation of the compound of the compound containing the group vib metal component and/or the metal component that at least one is selected from I A, II A 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, 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 the described compound that contains the compound of group vib metal component and/or the metal component that at least one is selected from I A, II A family the method preparation by extruded moulding roasting.Or at first the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix is prepared into to shaping carrier, introduce the group vib metal component and/or at least one is selected from the metal component of I A, II A family with the method for dipping afterwards.Can add appropriate extrusion aid and/or adhesive, then extrusion molding when 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.
Also contain any other components that maybe can improve composition properties provided by the invention that do not affect in described adsorbent composition, for example, contain the component that is selected from I B, II B, III B, IVB, V B, VIII family, further preferably wherein during the component of one or more in Co, Cu, Fe, Ni, Zn, Ce, La, 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 to introduce when introducing the metal component that VI B family's metal component and/or at least one be selected from I A, II A family in step (1) with in precursor to described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix, also can be introduced separately into.For example, can be to be selected from I A at the precursor by described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and the described compound that contains VI B family metal component and/or at least one, the compound of the metal component of II A family is directly mixed simultaneously will be introduced containing the method for the compound of described other components, can be also to be selected from I A with the compound containing other components and the compound that contains the group vib metal component and/or at least one, the compound preparation mixed solution of the metal component of II A family, the method of 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 group VIII and/or I A, II A family is introduced.Can also be with the method for dipping, to introduce afterwards in described step (2).When step (2) is introduced with the method for dipping afterwards, also comprise the step of dry and roasting after dipping, described drying is conventional method and condition, here be not particularly limited, described method of roasting is conventional method, and described roasting condition comprises: sintering temperature 600-1100 ℃ is preferably 650-960 ℃, roasting time 2-12 hour, be preferably 4-11 hour.The total amount of described composition of take is benchmark, the consumption of each component makes in final described adsorbent composition, the described component that is selected from I B, II B, III B, IVB, VB, VIII family, further the content of the component of one or more in preferred wherein Co, Cu, Fe, Ni, Zn, Ce, La, 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 the NOx process in 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 smoke gas treatments that contain SOx and NOx.Wherein, the operating temperature in 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 special instruction, in embodiment, chemical reagent used is chemical pure.
Adopt X-ray photoelectron spectroscopy to measure the content of the group vib metal component of different valence state.Concrete operations comprise: the PHI Quantera SXM that x-ray photoelectron spectroscopy is 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, by Origin 7.0 Software Create ev (electronic energy)～I (intensity) spectrogram, is calculated the area integral value of each characteristic peak.According to
calculate the content of different valence state metal.
The characteristic peak of different valence state metal in x-ray photoelectron power spectrum (ev～I) determined with reference to handbook " Handbook of X Ray Photoelectron Spectroscopy " (second edition in 1992)
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, 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 85 gram Na
2cO
3, 158 gram Cu (NO
3)
2with 124 gram La (NO
3)
3be dissolved into 1 liter of solution by deionized water, under normal temperature with this solution impregnation 1000 gram γ-Al
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 that the content that the content of sodium is 8 % by weight, copper is 5 % by weight, lanthanum is 5 % by weight.(metal component content adopts the X-ray fluorescence spectra analysis, lower same).
Embodiment 1-7 illustrates composition and method of making the same provided by the invention.
Embodiment 1
Raw material: silica support, spherical, 1.22 millimeters of average grain diameters, Chang Ling catalyst plant product; Mg (NO
3)
2, Cr (NO
3)
3, La (NO
3)
3be Beijing Chemical Plant's product.
Preparation method: by 263 gram Cr (NO
3)
3be dissolved into 1 liter of solution L1 by deionized water, by 123 gram La (NO
3)
3be dissolved into 1 liter of solution L2 by deionized water, by 592 gram Mg (NO
3)
2solution is dissolved into 1 liter of solution L3 by deionized water.Order is flooded 1000 gram SiO with L1, L2, L3
2carrier 2 hours, after each dipping, in 110 ℃ of dryings 12 hours, 950 ℃ of roastings 10 hours, obtained combination articles La-Mg-Cr-SiO of the present invention
2.
Form: with MgO, Cr
2o
3and La
2o
3meter, the content that the content that the content of magnesium is 16 % by weight, chromium is 5 % by weight, lanthanum is 4 % by weight.
Wherein, chromium is respectively with Cr
6+and Cr
3+occur, in element, Cr
3+content be 87%, Cr
6+content be 13%.
Embodiment 2
Raw material:: γ-Al
2o
3carrier, spherical, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Cr (NO
3)
3, K
2cO
3be Beijing Chemical Plant's product.
Preparation method: with embodiment 1, adopt the method for step impregnation to prepare composition K-Cr-γ-Al
2o
3.After each step dipping in 110 ℃ of dryings 12 hours, 900 ℃ of lower roastings 8 hours.
Form: with K
2cO
3, Cr
2o
3meter, K-Cr-γ-Al
2o
3the content that the content of middle potassium is 4 % by weight, chromium is 17 % by weight.
Wherein, chromium is respectively with Cr
6+and Cr
3+occur, in element, Cr
3+content be 91%, Cr
6+content be 9%.
Embodiment 3
Raw material: γ-Al
2o
3carrier, spherical, 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.
Preparation method: with embodiment 1, adopt the method for step impregnation to prepare composition Na-Mn-Cr-γ-Al
2o
3.After each step dipping in 110 ℃ of dryings 12 hours, 700 ℃ of lower roastings 6 hours.
Form: with Na
2cO
3, MnO
2, Cr
2o
3meter, Na-Mn-Cr-γ-Al
2o
3the content that the content that the content of middle sodium is 16 % by weight, manganese is 5 % by weight, chromium is 13 % by weight composition Na-Mn-Cr-γ-Al
2o
3.
Wherein, chromium is respectively with Cr
6+and Cr
3+occur, in element, Cr
3+content be 81%, Cr
6+content be 19%.
Embodiment 4
Raw material: γ-Al
2o
3carrier, spherical, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Cr (NO
3)
3, Co (NO
3)
2, Na
2cO
3, Ba (NO3) 2 is Beijing Chemical Plant's product.
Preparation method: with embodiment 1, adopt the method for step impregnation to prepare composition Na-Cr-Co-Ba-γ-Al
2o
3.After each step dipping in 110 ℃ of dryings 12 hours, 680 ℃ of lower roastings 5 hours.
Form: with Na
2cO
3, Cr
2o
3, Co
3o
4, BaO meter, Na-Cr-Co-Ba-γ-Al
2o
3the content that the content that the content that the content of middle sodium is 3 % by weight, chromium is 10 % by weight, cobalt is 8 % by weight, barium is 8 % by weight.
Wherein, chromium is respectively with Cr
6+and Cr
3+occur, in element, Cr
3+content be 85%, Cr
6+content be 15%.
Embodiment 5
Raw material: γ-Al
2o
3carrier, spherical, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Cr (NO
3)
3, Cu (NO
3)
2, Na
2cO
3be Beijing Chemical Plant's product.
Preparation method: with embodiment 1, adopt the method for step impregnation to prepare composition Na-Cr-Cu-γ-Al
2o
3.After each step dipping in 110 ℃ of dryings 12 hours, 750 ℃ of lower roastings 4 hours.
Form: with Na
2cO
3, Cr
2o
3, CuO meter, Na-Cr-Cu-γ-Al
2o
3the content that the content that the content of middle sodium is 8 % by weight, chromium is 3 % by weight, copper is 15 % by weight.
Wherein, chromium is respectively with Cr
6+and Cr
3+occur, in element, Cr
3+content be 86%, Cr
6+content be 14%.
Embodiment 6
Raw material: γ-Al
2o
3carrier, spherical, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Cr (NO
3)
3, Zn (NO
3)
2, Na
2cO
3be Beijing Chemical Plant's product.
Preparation method: with embodiment 1, adopt the method for step impregnation to prepare composition Na-Cr-Zn-γ-Al
2o
3.After each step dipping in 110 ℃ of dryings 12 hours, 950 ℃ of lower roastings 6 hours.
Form: with Na
2cO
3, Cr
2o
3, ZnO meter, Na-Cr-Zn-γ-Al
2o
3the content that the content that the content of middle sodium is 18 % by weight, chromium is 8 % by weight, zinc is 10 % by weight.
Wherein, chromium is respectively with Cr
6+and Cr
3+occur, in element, Cr
3+content be 80%, Cr
6+content be 20%.
Embodiment 7
Raw material: silica support, spherical, 1.22 millimeters of average grain diameters, Chang Ling catalyst plant product; Mg (NO
3)
2, Cr (NO
3)
3, La (NO
3)
3be Beijing Chemical Plant's product.
Preparation method: by 263 gram Cr (NO
3)
3be dissolved into 1 liter of solution L1 by deionized water, by 123 gram La (NO
3)
3be dissolved into 1 liter of solution L2 by deionized water, by 592 gram Mg (NO
3)
2solution is dissolved into 1 liter of solution L3 by deionized water.Order is flooded 1000 gram SiO with L1, L2, L3
2carrier 2 hours, after each dipping, in 110 ℃ of dryings 12 hours, 600 ℃ of roastings 10 hours, obtained combination articles La-Mg-Cr-SiO of the present invention
2.
Form: with MgO, Cr
2o
3and La
2o
3meter, the content that the content that the content of magnesium is 16 % by weight, chromium is 5 % by weight, lanthanum is 4 % by weight.
Wherein, chromium is with Cr
3+form occurs.
Embodiment 8
The La-Mg-Cr-SiO of embodiment 1 preparation is described
2performance.
Experiment is carried out on 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
2.Use N before passing into unstripped gas
2volume flow with 300 ml/min purges desulfurization removing nitric material bed 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 NO analyzer monitoring flue gas
2, NO content variation, adopt the SO of FIREFOX software calculation composition
2with the NO saturated extent of adsorption.Wherein, SO
2saturated extent of adsorption reach 1.314 mMs/gram, the saturated extent of adsorption of NO reaches 0.423 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 on 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
2.Use N before passing into unstripped gas
2volume flow with 300 ml/min purges desulfurization removing nitric material bed 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 NO analyzer monitoring flue gas
2, NO content variation (lower with).Wherein, SO
2saturated extent of adsorption reach 1.125 mMs/gram, the saturated extent of adsorption of NO reaches 0.292 mM/gram.
Embodiment 9
The La-Mg-Cr-SiO of embodiment 7 preparations is described
2performance.
Experiment is carried out on 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
2.Use N before passing into unstripped gas
2volume flow with 300 ml/min purges desulfurization removing nitric material bed 1 hour under 300 ℃, and is cooled to adsorption temp.Stop adsorption experiment when absorption tail gas concentration tends towards stability, then use N
2purge mist remaining in tube wall 10 minutes.Reactor outlet meets SO
2, SO in NO analyzer monitoring flue gas
2, NO content variation.Wherein, SO
2saturated extent of adsorption reach 1.201 mMs/gram, the saturated extent of adsorption of NO reaches 0.310 mM/gram.
Embodiment 10
Desulfurization removing nitric performance after the sample regeneration of embodiment 1 preparation is described.
Until regenerative agent be embodiment 8 conditions absorption saturated after sample, count SORB-1.
Regeneration is carried out on regenerating unit outside device, the tubular reactor that regeneration reactor is 10 millimeters of internal diameters.The SORB-1 that 1 gram is to be regenerated is placed in reaction unit, under the nitrogen blowing condition that is 10000/ hour in air speed, programming rate temperature programming to 350 ℃ with 10 ℃/minute, stablize after 30 minutes and stop passing into nitrogen, under 350 ℃, the CO gas that the switching air speed is 15000/ hour makes it with SORB-1 to be regenerated, contact 2 hours; The nitrogen blowing that is 10000/ hour by air speed 30 minutes, the oxygen that the switching air speed is 15000/ hour makes it with the SORB-1 to be regenerated through the back reduction, contact 30 minutes; The nitrogen blowing that is 10000/ hour by air speed 30 minutes, the methane gas that the switching air speed is 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 to pass into air speed be 10000/ hour is reduced to normal temperature, the adsorbent composition SORB-1-1 after being regenerated.
Estimate SORB-1-1 according to embodiment 9 appreciation conditions.Experimental result is: SO
2saturated extent of adsorption be 1.182 mMs/gram (for fresh dose 89.9%), the saturated extent of adsorption of NO reach 0.401 mM/gram (for fresh dose 94.8%).
Comparative Examples 3
Sample La-Cu-Na-γ-Al that explanation is provided by Comparative Examples 1
2o
3desulfurization removing nitric performance after regeneration.The regeneration tests step is with embodiment 10.
After regeneration, the appreciation condition of sample is with Comparative Examples 2.Experimental result shows, the desulfurization removing nitric material 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%).
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 (8)
1. the adsorbent composition containing the group vib metal component, said composition contains heat-resistant inorganic oxide matrix, at least one metal component that is selected from group vib is selected from I A and/or II A family metal component with at least one, the described metal component that is selected from group vib is chromium, described I A, the metal of II A family is selected from Na, K, Ba, Mg, one or more in Ca, 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 group vib metal component is 0.5 % by weight-35 % by weight, the content that is selected from I A and/or II A family metal component is 0.5 % by weight-35 % by weight, with X-ray photoelectron spectroscopy, characterize, the described metal component of group vib that is selected from is at least with M
vI b i1+and M
vIB i2+two kinds of different valence states exist, and i1 wherein is less than i2, and wherein, in element, and to take the total amount of VI B family metal component be benchmark, M in described different valence state metal component
vIB i1+content be 10%-30%, M
vIB i2+content be 90%-70%.
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 that is selected from the metal component of group vib 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, in element, and to take the total amount of group vib metal component be benchmark, M in described different valence state metal component
vIB i1+content be 15%-30%, M
vIB i2+content be 85%-70%.
4. 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, oxidation titania-zirconia, silica-alumina-thorium oxide, silica-alumina-titanium oxide, silica-alumina-magnesia, silica-alumina-zirconia.
5. composition according to claim 4, is characterized in that, described heat-resistant inorganic oxide matrix is selected from one or more in aluminium oxide, silica, silica-alumina.
6. composition according to claim 1, it is characterized in that, also contain one or more components in the Co, the Cu that are selected from I B, II B, III B, IV B, V B, VIII family, Fe, Ni, Zn, Ce, La, Pt in described composition, the total amount of described composition of take is benchmark, and the content of one or more components in the described I of being selected from B, II B, IIIB, IVB, VB, VIII family is no more than 35 % by weight.
7. composition according to claim 6, is characterized in that, the total amount of described composition of take is benchmark, and the content of one or more in described Co, Cu, Fe, Ni, Zn, Ce, La, Pt is no more than 17 % by weight.
8. composition according to claim 7, is characterized in that, the total amount of described composition of take is benchmark, and the content of one or more in described Co, Cu, Fe, Ni, Zn, Ce, La, Pt is no more than 15 % by weight.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100777033A CN101804343B (en) | 2009-02-12 | 2009-02-12 | Adsorbent combination containing metal component of group VIB |
| 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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| CN2009100777033A CN101804343B (en) | 2009-02-12 | 2009-02-12 | Adsorbent combination containing metal component of group VIB |
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