CN101804352B - Adsorbent combination containing metal component of group VIII - Google Patents
Adsorbent combination containing metal component of group VIII Download PDFInfo
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- CN101804352B CN101804352B CN2009100777029A CN200910077702A CN101804352B CN 101804352 B CN101804352 B CN 101804352B CN 2009100777029 A CN2009100777029 A CN 2009100777029A CN 200910077702 A CN200910077702 A CN 200910077702A CN 101804352 B CN101804352 B CN 101804352B
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Abstract
The invention relates to an adsorbent combination containing a metal component of group VIII. The combination comprises a heat resistant inorganic oxide substrate, at least one metal component of the group VIII 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 VIII 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 VIII metal component.
Background technology
Atmosphere sulphur oxide SOx (is SO more than 95%
2), the pollution problem of nitrogen oxide NOx (being NO more than 90%) is serious day by day, the flue gas of generations such as fuel combustion, metal smelt is the main source of SOx and NOx.These pernicious gases cause serious destruction to ecological environment and health.
At present the emission control technique to SOx is comparatively ripe in the world, and to the emission control of NOx, though carried out a series of research both at home and abroad, effect is person of modern times's meaning not still.
US6521559 discloses a kind of pillared clays catalyst, is applicable to and utilizes NH
3The SCR technology (SCR) of reductive NO.The characteristics of this catalyst are mainly introduced metal oxide such as V in the middle of argillic horizon
2O
5, CuO, Fe
2O
3, Cr
2O
3, Fe
2O
3-Cr
2O
3, Nb
2O
5Deng, utilize the catalytic reduction character of metal oxide that NO is carried out catalytic reduction.The NOx removal efficiency of this material reaches more than 9 5%.
US5451387 has reported a kind of Fe-ZSM-5 catalyst, is suitable for the SCR technology, and the NOx removal efficiency of this material can reach 98%.
US6165934 reported a kind of can be from flue gas the material of adsorbing and removing NOx, this material support is TiO
2, SiO
2, Al
2O
3Deng, active component comprises alkali metal, copper, noble metal etc., the NOx removal efficiency of this material reaches 70%.
Desulfurization simultaneously, denitride technology more and more receive people's attention in recent years owing to have advantages such as reduced investment, operating cost are low.
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 technology
2O
3Compare La-Cu-Na-γ-Al
2O
3Adsorb SO simultaneously
2With the big (SO of NO ability
2When/NO is 5.1-3.5, La-Cu-Na-γ-Al
2O
3Adsorb SO simultaneously
2With the adsorbance of NO be respectively Na-γ-Al
2O
31.25 and 4.7 times) ".This result shows, is similar to La-Cu-Na-γ-Al
2O
3The composition of forming has and takes off SO preferably synchronously
2With the NO performance.
Summary of the invention
The technical problem that the present invention will solve is on the basis of existing technology, and a kind of new, better adsorbent composition of performance is provided.
The present invention provides a kind of adsorbent composition that contains the group VIII metal component; Said composition contains heat-resistant inorganic oxide matrix; At least a metal component and at least a IA and/or the IIA family metal component of being selected from that is selected from group VIII; With said composition is benchmark, and the content of heat-resistant inorganic oxide matrix is 50 weight %-99 weight %, in oxide; The content of group VIII metal component is 0.5 weight %-35 weight %, and the content that is selected from IA and/or IIA family metal component is 0.5 weight %-35 weight %.
Said composition provided by the invention can use as adsorbent in the purification of all gases.Because this adsorbent has excellent sulphur, nitrogen oxide absorption property, be particularly suitable for remove sulphur simultaneously, nitrogen oxide is the purification of the industrial waste gas of purpose.Compared with prior art, when this adsorbent is used for remove sulphur simultaneously, when nitrogen oxide is 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; With said composition is benchmark; The content of heat-resistant inorganic oxide matrix is preferably 65 weight %-98 weight %; In oxide, the content of group VIII metal component is preferably 1 weight %-18 weight %, and the content that is selected from IA and/or IIA family metal component is preferably 1 weight %-20 weight %.
Wherein, preferred iron of described group VIII metal component and/or cobalt, further preferred cobalt, described group VIII metal component can be to exist with its oxide and with various possible forms such as salt that other components form in said adsorbent composition.Described IA and/or IIA family metal component can be to exist with its oxide and with various possible forms such as salt that other components form in said adsorbent composition.
Characterize with X-ray photoelectron spectroscopy, further the said metal that is selected from group VIII in the preferred said adsorbent exists with two kinds of different valence states at least, is example with the cobalt, and preferred described cobalt is with Co
3+And Co
4+The form of two kinds of valence states exists.Total amount with the group VIII metal component is a benchmark, in element, and M in the said different valence state metal component
VIII I1+Content be 10%-3 0%, be more preferably M
VIII I1+Content be 15%-30%, M
VIII I2+Content be 90-70%, be more preferably 85-70%, i1 wherein is less than i2.
Here,
Wherein, M
VIIIExpression group VIII metal, i representes the chemical valence of group VIII metal, for example Co
3+, Co
4+, its i value is respectively 3 and 4, and S representes the area integral value at different valence state group VIII metal characteristic of correspondence peak in ev～I figure,
Summation for the area integral value of the characteristic peak of different valence state group VIII metal.
The said 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.
Said 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 influence.For example, can contain the component that is selected from IB, IIB, IIIB, IVB, VB, group vib, the component of one or more among further preferred wherein Cr, Cu, Zn, Ce, the La.Total amount with said composition is a benchmark; The said component that is selected from IB, IIB, IIIB, IVB, VB, group vib; The components contents of one or more among further preferred wherein Cr, Cu, Zn, Ce, the La is no more than 35 weight %; Preferably be no more than 17 weight %, be more preferably and be no more than 15 weight %.
Adsorbent composition provided by the invention preferably adopts the method preparation that may further comprise the steps:
(1) in the precursor of said heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix, introduces group VIII 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 said composition;
The consumption of each component makes in the final said composition in the wherein said step (1), is benchmark with said composition, and the content of heat-resistant inorganic oxide matrix is 50 weight %-99 weight %; Be preferably 65 weight %-98 weight %; In oxide, the content of group VIII metal component is 0.5 weight %-35 weight %, is preferably 1 weight %-18 weight %; The content that is selected from IA and/or IIA family metal component is 0.5 weight %-35 weight %, is preferably 1 weight %-20 weight %.
The sintering temperature of preferred said step (2) is 620 ℃-1000 ℃, further is preferably 650 ℃-960 ℃, and roasting time is 3 hours-12 hours, further is preferably 4 hours-11 hours.
Wherein, to introducing group VIII metal component in the precursor of heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix described in the said step (1) and at least a not special restriction of method that is selected from the metal component of IA, IIA family.Can be compound and/or at least a compound that is selected from the metal component of IA, IIA family that the precursor of said heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and said contains the group VIII metal component directly to be carried out method of mixing introduce, also can be to introduce with the method for precursor of the said heat-resistant inorganic oxide matrix of solution impregnation and/or heat-resistant inorganic oxide matrix of compound that the compound that contains the group VIII metal component and/or at least a is selected from the metal component of IA, IIA family.
According to said composition provided by the invention, look the article shaped that demands of different can be made into various easy operatings, for example microballoon, sphere, tablet or bar shaped etc.Moulding can be undertaken by conventional method; For example, can be the compound and/or at least a that the precursor of said heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and said contains the group VIII metal component is selected from IA, IIA family the compound of metal component after the method preparation of extruded moulding and roasting.Or at first the precursor of said heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix is prepared into shaping carrier, introduce group VIII 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, extrusion molding then.The kind of said extrusion aid, peptizing agent and consumption are that preformed catalyst or adsorbent preparation field technical staff are known, do not give unnecessary details at this.
In said adsorbent composition, also contain any other components that maybe can improve composition properties provided by the invention that do not influence; For example; Contain the component that is selected from IB, IIB, IIIB, IVB, VB, group vib; During the component of one or more among further preferred wherein Cr, Cu, Zn, Ce, the La, described preparation method also comprises the step of introducing these components.
Wherein, To the not special restriction of the introducing method of said other components; 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 the metal component that group VIII metal component and at least a is selected from IA, IIA family, to introduce, also can introduce separately.For example; Can be that the precursor of said heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix is being contained the compound of group VIII metal component and/or method that at least a compound that is selected from the metal component of IA, IIA family directly mixes the compound that will contain said other components is simultaneously introduced with said; Also can be that the method for flooding the precursor of said heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix is afterwards introduced with the compound that contains other components and compound that contains the group VIII metal component and/or at least a compound preparation mixed solution that is selected from the metal component of IA, IIA family.Also can dispose dipping solution separately, the method for before or after the metal component of introducing said group VIII and/or IA, IIA family, flooding is introduced.Can also be to introduce with the method for dipping afterwards,, after dipping, also comprise the step of dry and roasting when when step (2) is introduced with the method for dipping afterwards in said step (2); Said drying is conventional method and condition, not special here restriction, and said method of roasting is a conventional method; Said roasting condition comprises: sintering temperature 600-1100 ℃; Be preferably 650-960 ℃, roasting time 2-12 hour, be preferably 4-11 hour.Total amount with said composition is a benchmark; The consumption of each component makes in the final said adsorbent composition; The said component that is selected from IB, IIB, IIIB, IVB, VB, group vib; The components contents of one or more among further preferred wherein Cr, Cu, Zn, Ce, the La is no more than 35 weight %, preferably is no more than 17 weight %, is more preferably and is no more than 15 weight %.
Said composition provided by the invention can be used as adsorbent and directly is used for the SOx and/or the NOx process that adopt adsorption method to remove flue gas.Therefore, be applicable to that catalytic cracking flue gas is administered, coal-fired plant flue gas is administered, 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 said adsorption method can be usual operating temperature.Preferred operating temperature is 0～300 ℃, further is preferably 0～100 ℃.
Following embodiment will be described further the present invention, but therefore not limit the present invention.Remove and specify that used chemical reagent is chemical pure among the embodiment.
Adopt X-ray photoelectron spectroscopy to measure the content of the group VIII metal component of different valence state.Concrete operations comprise: x-ray photoelectron spectroscopy is the PHI Quantera SXM of ULVAC-PH INC.Adopt monochromator, select the Al plate target for use, X-ray beam 9 μ m-1.5mm
2, energy resolution 0.5eV, sensitivity 3MCPS, 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 generates ev (electronic energy)～I (intensity) spectrogram by Origin7.0 software, calculates the area integral value of each characteristic peak.Calculate the content of different valence state metal according to
.
(confirm with reference to handbook " Handbook of X Ray Photoelectron Spect roscopy " (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 sulphur in the flue gas, nitrogen oxide that explanation provides according to prior art.
Raw material: γ-Al
2O
3Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product.Na
2CO
3, Cu (NO
3)
2, La (NO
3)
3Be Beijing Chemical Plant's product.
Preparation method: take by weighing 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, normal temperature is down 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 said 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 weight %, copper is that the content of 5 weight %, lanthanum is 5 weight %.(metal component content adopts the X-ray fluorescence spectra analysis, down together).
Embodiment 1-8 explains 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; Mg (NO
3)
2, Co (NO
3)
2Be Beijing Chemical Plant's product.
Preparation method: with 259 gram Mg (NO
3)
2Be dissolved into 1 liter of solution L1 with deionized water, with 544 gram Co (NO
3)
2Be dissolved into 1 liter of solution L2 with deionized water.Order is with L1, L2 dipping 1000 gram γ-Al
2O
3Carrier 2 hours, each dipping back be in 110 ℃ of dryings 12 hours, and 900 ℃ of roastings 10 hours obtain combination articles Mg-Co-γ-Al according to the invention
2O
3
Form: each component load capacity is respectively with MgO, Co
3O
4Meter, the content of magnesium is that the content of 7 weight %, cobalt is 15 weight %.
Transition metal Co is respectively with Co
3+And Co
4+Meter, Co
3+Content be 17%, Co
4+Content be 83%.
Embodiment 2
Raw material: silica support, sphere, 1.2 2 millimeters of average grain diameters, Chang Ling catalyst plant product; Co (NO
3)
2, K
2CO
3Be Beijing Chemical Plant's product.
Preparation method: adopt the method for step impregnation to prepare composition K-Co-SiO with embodiment 1
2Each step dipping back is in 110 ℃ of dryings 12 hours, 750 ℃ of following roastings 8 hours.
Form: with K
2CO
3, Co
3O
4Meter, composition K-Co-SiO
2The content of middle potassium is that the content of 4 weight %, cobalt is 13 weight %.
Wherein, cobalt is respectively with Co
3+And Co
4+Occur, in element, Co
3+Content be 11%, Co
4+Content be 89%.
Embodiment 3
Raw material: γ-Al
2O
3Carrier (with embodiment 1); Ba (NO
3)
2, Co (NO
3)
2, La (NO
3)
3Be Beijing Chemical Plant's product.
Preparation method: adopt the method for step impregnation to prepare composition Ba-Co-La-γ-Al with embodiment 1
2O
3Each step dipping back is in 110 ℃ of dryings 12 hours, 650 ℃ of following roastings 7 hours.
Form: with BaO, La
2O
3And Co
3O
4Meter, Ba-Co-La-γ-Al
2O
3The content of middle barium is that the content of 4 weight %, lanthanum is 13 weight %, and the content of cobalt is 5 weight %.
Wherein, cobalt is respectively with Co
3+And Co
4+Occur, in element, Co
3+Content be 15%, Co
4+Content be 85%.
Embodiment 4
Raw material:: γ-Al
2O
3Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Cr (NO
3)
3, Co (NO
3)
2, K
2CO
3, CaCO
3Be Beijing Chemical Plant's product.
Preparation method: adopt the method for step impregnation to prepare composition K-Co-Cr-Ca-γ-Al with embodiment 1
2O
3Each step dipping back is in 110 ℃ of dryings 12 hours, 900 ℃ of following roastings 6 hours.
Form: with K
2CO
3, Cr
2O
3, Co
3O
4, CaO meter, K-Co-Cr-Ca-γ-Al
2O
3In the content of potassium be that the content of 7 weight %, chromium is that the content of 8 weight %, cobalt is that the content of 17 weight %, calcium is 4 weight % compositions.
Wherein, cobalt is respectively with Co
3+And Co
4+Occur, in element, Co
3+Content be 15%, Co
4+Content be 85%.
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
3Be Beijing Chemical Plant's product.
Preparation method: adopt the method for step impregnation to prepare composition Na-Mn-Co-γ-Al with embodiment 1
2O
3Each step dipping back is in 110 ℃ of dryings 12 hours, 700 ℃ of following roastings 6 hours.
Form: with Na
2CO
3, MnO
2, Co
3O
4Meter, Na-Mn-Co-γ-Al
2O
3In the content of sodium be that the content of 16 weight %, manganese is that the content of 5 weight %, cobalt is 13 weight %.
Wherein, cobalt is respectively with Co
3+And Co
4+Occur, in element, Co
3+Content be 7%, Co
4+Content be 93%.
Embodiment 6
Raw material: γ-Al
2O
3Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Co (NO
3)
2, Cu (NO
3)
2, Na
2CO
3Be Beijing Chemical Plant's product.
Preparation method: adopt the method for step impregnation to prepare composition Na-Co-Cu-γ-Al with embodiment 1
2O
3Each step dipping back is in 110 ℃ of dryings 12 hours, 750 ℃ of following roastings 5 hours.
Form: with Na
2CO
3, Co
3O
4, CuO meter, Na-Co-Cu-γ-Al
2O
3In the content of sodium be that the content of 8 weight %, cobalt is that the content of 3 weight %, copper is 15 weight %.
Wherein, cobalt is respectively with Co
3+And Co
4+Occur, in element, Co
3+Content be 10%, Co
4+Content be 90%.
Embodiment 7
Raw material: γ-A l
2O
3Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Co (NO
3)
2, Zn (NO
3)
2, Na
2CO
3Be Beijing Chemical Plant's product.
Preparation method: adopt the method for step impregnation to prepare composition Na-Co-Zn-γ-Al with embodiment 1
2O
3Each step dipping back is in 110 ℃ of dryings 12 hours, 950 ℃ of following roastings 4 hours.
Form: with Na
2CO
3, Co
3O
4, ZnO meter, Na-Co-Zn-γ-Al
2O
3In the content of sodium be that the content of 18 weight %, cobalt is that the content of 8 weight %, zinc is 10 weight %.
Wherein, cobalt is respectively with Co
3+And Co
4+Occur, in element, Co
3+Content be 13%, Co
4+Content be 87%.
Embodiment 8
Raw material: γ-Al
2O
3Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Mg (NO
3)
2, Co (NO
3)
2Be Beijing Chemical Plant's product.
Preparation method: with 259 gram Mg (NO
3)
2Be dissolved into 1 liter of solution L1 with deionized water, with 544 gram Co (NO
3)
2Be dissolved into 1 liter of solution L2 with deionized water.Order is with L1, L2 dipping 1000 gram γ-Al
2O
3Carrier 2 hours, each dipping back be in 110 ℃ of dryings 12 hours, and 600 ℃ of roastings 10 hours obtain combination articles Mg-Co-γ-Al according to the invention
2O
3
Form: each component load capacity is respectively with MgO, Co
3O
4Meter, the content of magnesium is that the content of 7 weight %, cobalt is 15 weight %.
Wherein, cobalt is with Co
4+Form occurs.
Embodiment 9
Mg-Co-γ-the Al of illustrative embodiment 1 preparation
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
2Use N before feeding unstripped gas
2Volume flow with 300 ml/min purged desulfurization removing nitric material bed down 1 hour at 300 ℃, and was cooled to adsorption temp., absorption tail gas concentration stops adsorption experiment when tending towards stability.Reactor outlet meets SO
2, SO in the NO analyzer monitoring flue gas
2, NO content variation, adopt the SO of FIREFOX computed in software composition
2With NO saturated extent of adsorption (down together).Wherein, SO
2Saturated extent of adsorption reach 1.256 mM/grams, the saturated extent of adsorption of NO reaches 0.431 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
2Use N before feeding unstripped gas
2Volume flow with 300 ml/min purged desulfurization removing nitric material bed down 1 hour at 300 ℃, and was cooled to adsorption temp, when absorption tail gas concentration tends towards stability, stopped adsorption experiment.Reactor outlet meets SO
2, SO in the NO analyzer monitoring flue gas
2, NO content variation.Wherein, SO
2Saturated extent of adsorption reach 1.125 mM/grams, the saturated extent of adsorption of NO reaches 0.292 mM/gram.
Embodiment 10
Mg-Co-γ-the Al of illustrative embodiment 8 preparations
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 50 ℃, and the feed gas volume flow is 300 ml/min.Feed gas volume consists of: SO
2, 0.3%; NO, 0.1%; O
2, 4.5%; Surplus is N
2Use N before feeding unstripped gas
2Volume flow with 300 ml/min purged desulfurization removing nitric material bed down 1 hour at 300 ℃, and was cooled to adsorption temp.When absorption tail gas concentration tends towards stability, stop adsorption experiment, use N again
2Purged 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 1.207 mM/grams, the saturated extent of adsorption of NO reaches 0.303 mM/gram.
Embodiment 11
Desulfurization removing nitric performance after the sample regeneration of illustrative embodiment 1 preparation.
Treat that regenerative agent is the saturated back of embodiment 9 a conditions absorption sample, counts SORB-1.
Regeneration is carried out on the regenerating unit outside device, and regeneration reactor is the tubular reactor of 10 millimeters of internal diameters.SORB-1 to be regenerated places reaction unit with 1 gram; Be under 10000/ hour the nitrogen purging condition in air speed; With 10 ℃/minute programming rate temperature programmings to 350 ℃; Stablize after 30 minutes and stop to feed nitrogen, under 350 ℃, the switching air speed is that 15000/ hour CO gas makes it contact 2 hours with SORB-1 to be regenerated; The use air speed is that 10000/ hour nitrogen purged 30 minutes, and the switching air speed is that 15000/ hour oxygen makes it contact 30 minutes with the SORB-1 to be regenerated that reduces through back; The use air speed is that 10000/ hour nitrogen purged 30 minutes; Switch air speed and be 15000/ hour methane gas and contact 1 hour with SORB-1 to be regenerated through the back oxidation; Afterwards; The nitrogen that fed air speed and be 10000/ hour purges to temperature of reactor reduces to normal temperature, the adsorbent composition SORB-1-1 after obtaining regenerating.
Estimate SORB-1-1 according to embodiment 9 appreciation conditions.Experimental result is: SO
2Saturated extent of adsorption be 1.161 mM/grams (for fresh dose 92.4%), the saturated extent of adsorption of NO reaches 0.402 mM/gram (be fresh dose 93.3%).
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 11.
The appreciation condition of regeneration back sample is with Comparative Examples 2.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 reaches 0.241 mM/gram (be fresh dose 58.6%).
Evaluation result shows that the present 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 the group VIII metal component; Said composition contains heat-resistant inorganic oxide matrix, and at least a metal component and at least a IA and/or the IIA family metal component of being selected from that is selected from group VIII is benchmark with said composition; The content of heat-resistant inorganic oxide matrix is 50 weight %-99 weight %; In oxide, the content of group VIII metal component is 0.5 weight %-35 weight %, and the content that is selected from IA and/or IIA family metal component is 0.5 weight %-35 weight %; The said metal component that is selected from group VIII is iron and/or cobalt; The metal of said IA, IIA family is selected from one or more among Na, K, Ba, Mg, the Ca, characterizes with X-ray photoelectron spectroscopy, and the said metal component that is selected from group VIII is at least with M
VIII I1+And M
VIII I2+Two kinds of different valence states exist, and i1 wherein is less than i2.
2. composition according to claim 1; It is characterized in that; With said composition is benchmark, and the content of heat-resistant inorganic oxide matrix is 65 weight %-98 weight %, in oxide; The content that is selected from the metal component of group VIII is 1 weight %-18 weight %, and the content that is selected from IA and/or IIA family metal component is 1 weight %-20 weight %.
3. composition according to claim 1 is characterized in that, the said metal component that is selected from group VIII is a cobalt.
4. according to claim 1,2 or 3 described compositions, it is characterized in that, in element, and is benchmark with the total amount of group VIII metal component, M in the said different valence state metal component
VIII I1+Content be 10%-30%, M
VIII I2+Content be 90-70%.
5. composition according to claim 4 is characterized in that, in element, and is benchmark with the total amount of group VIII metal component, M in the said different valence state metal component
VIII I1+Content be 15%-30%, MV
III I2+Content be 85-70%.
6. composition according to claim 1; It is characterized in that said 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, the silica-alumina-zirconia.
7. composition according to claim 6 is characterized in that said 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 IB, IIB, IIIB, IVB, VB, the group vib in the said composition; Total amount with said composition is a benchmark; One or more components contents in the said IB of being selected from, IIB, IIIB, IVB, VB, the group vib are no more than 35 weight %, and one or more components in the said IB of being selected from, IIB, IIIB, IVB, VB, the group vib are one or more among Cr, Cu, Zn, Ce, the La.
9. composition according to claim 8 is characterized in that, is benchmark with the total amount of said composition, and the content of one or more among said Cr, Cu, Zn, Ce, the La is no more than 17 weight %.
10. composition according to claim 9 is characterized in that, is benchmark with the total amount of said composition, and the content of one or more among said Cr, Cu, Zn, Ce, the La is no more than 15 weight %.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100777029A CN101804352B (en) | 2009-02-12 | 2009-02-12 | Adsorbent combination containing metal component of group VIII |
| MYPI20094591A MY175209A (en) | 2008-10-31 | 2009-10-30 | A sorbent composition, the preparation method thereof, and the process for removing sulfur oxides and nitrogen oxides in a flue gas by the sorbent composition |
| KR1020090104966A KR101646630B1 (en) | 2008-10-31 | 2009-11-02 | A sorbent composition, the preparation method thereof, and the process for removing sulfur oxides and nitrogen oxides in a flue gas by the sorbent composition |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1384770A (en) * | 1999-11-01 | 2002-12-11 | 菲利浦石油公司 | Desulfurization and novel sorbents for same |
| CN101316653A (en) * | 2005-07-15 | 2008-12-03 | 中国石油化工股份有限公司 | Fuzz reduction of sulfur sorbents |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384770A (en) * | 1999-11-01 | 2002-12-11 | 菲利浦石油公司 | Desulfurization and novel sorbents for same |
| CN101316653A (en) * | 2005-07-15 | 2008-12-03 | 中国石油化工股份有限公司 | Fuzz reduction of sulfur sorbents |
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