CN101804352A - Adsorbent combination containing metal component of group VIII - Google Patents

Adsorbent combination containing metal component of group VIII Download PDF

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CN101804352A
CN101804352A CN200910077702A CN200910077702A CN101804352A CN 101804352 A CN101804352 A CN 101804352A CN 200910077702 A CN200910077702 A CN 200910077702A CN 200910077702 A CN200910077702 A CN 200910077702A CN 101804352 A CN101804352 A CN 101804352A
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metal component
weight
content
silica
group viii
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CN101804352B (en
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杜冰
宗保宁
罗一斌
王维家
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to CN2009100777029A priority Critical patent/CN101804352B/en
Priority to MYPI20094591A priority patent/MY175209A/en
Priority to US12/611,094 priority patent/US20100107874A1/en
Priority to KR1020090104966A priority patent/KR101646630B1/en
Priority to EP09174759.2A priority patent/EP2181751B1/en
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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

A kind of adsorbent composition that contains metal component of group VIII
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 95%.
US5451387 has reported a kind of Fe-ZSM-5 catalyst, is suitable for the SCR technology, and the NOx removal efficiency of this material can reach 98%.
US6165934 reported a kind of can be from flue gas the material of adsorbing and removing NOx, this material support is TiO 2, SiO 2, Al 2O 3Deng, active component comprises alkali metal, copper, noble metal etc., the NOx removal efficiency of this material reaches 70%.
Desulfurization simultaneously, denitride technology more and more are subject to people's attention in recent years owing to have advantages such as reduced investment, operating cost are low.
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 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 VIII metal component, said composition contains heat-resistant inorganic oxide matrix, at least a metal component and at least a I A and/or the II A family metal component of being selected from that is selected from group VIII, with described composition is benchmark, 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 I A and/or II A family metal component is 0.5 weight %-35 weight %.
Described 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 described 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 I A and/or II A 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 described adsorbent composition.Described I A and/or II A family metal component can be to exist with its oxide and with various possible forms such as salt that other components form in described adsorbent composition.
Characterize with X-ray photoelectron spectroscopy, further the described metal that is selected from group VIII in the preferred described 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 described different valence state metal component VIII I1+Content be 10%-30%, 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,
Figure B2009100777029D0000031
Wherein, M VIIIExpression group VIII metal, i represents the chemical valence of group VIII metal, for example Co 3+, Co 4+, its i value is respectively 3 and 4, and S represents the area integral value at different valence state group VIII metal characteristic of correspondence peak in ev～I figure,
Figure B2009100777029D0000032
Summation for the area integral value of the characteristic peak of different valence state group VIII metal.
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 II A 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 influence.For example, can contain the component that is selected from I B, II B, IIIB, IVB, V B, VI B family, the component of one or more among further preferred wherein Cr, Cu, Zn, Ce, the La.Total amount with described composition is a benchmark, the described component that is selected from I B, II B, III B, IVB, V B, VI B family, 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 described 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 I A, II A family;
(2) product 2 hours-12 hours of calcination steps (1) under greater than 600 ℃ to 1100 ℃ conditions obtains described composition;
The consumption of each component makes in the final described composition in the wherein said step (1), with described composition is benchmark, 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 I A and/or II A family metal component is 0.5 weight %-35 weight %, is preferably 1 weight %-20 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, introducing group VIII 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 I A, II A family described in the described step (1) 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 group VIII metal component and/or method that at least a compound that is selected from the metal component of I A, II A 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 compound that contains the group VIII metal component and/or at least a metal component that is selected from I A, II A family and/or heat-resistant inorganic oxide matrix.
According to described composition provided by the invention, look different the article shaped that require can be made into various easy operatings, for example microballoon, sphere, tablet or bar shaped etc.Moulding can be carried out according to a conventional method, for example, can be that compound with the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and the described compound that contains the group VIII metal component and/or at least a metal component that is selected from I A, II A family is after the method preparation of extruded moulding and roasting.Or at first the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix is prepared into shaping carrier, introduce group VIII metal component and/or at least a metal component that is selected from I A, II A 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 described extrusion aid, peptizing agent and consumption are that preformed catalyst or adsorbent preparation field technical staff are known, do not give unnecessary details at this.
In described 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 I B, II B, III B, IV B, V B, VI B family, 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, 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 group VIII metal component and at least a metal component that is selected from I A, II A family, to introduce, also can be introduced separately into.For example, can be at precursor and described compound and/or at least a I A that is selected from that contains the group VIII 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 described other components simultaneously to be introduced, also can be with the compound that contains other components and the compound and/or at least a I A that is selected from that contain the group VIII metal component, the compound preparation mixed solution of the metal component of II A family, the method for flooding the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix is afterwards introduced.Also can dispose dipping solution separately, 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 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 a conventional method, described roasting condition comprises: sintering temperature 600-1100 ℃, be preferably 650-960 ℃, roasting time 2-12 hour, be preferably 4-11 hour.Total amount with described composition is a benchmark, the consumption of each component makes in the final described adsorbent composition, the described component that is selected from I B, II B, III B, IVB, V B, VI B family, 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 %.
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 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 described adsorption method can be usual operating temperature.Preferred operating temperature is 0～300 ℃, more preferably 0～100 ℃.
The following examples will the invention will be further described, but not thereby limiting the invention.Remove and specify that used chemical reagent is chemical pure among the embodiment.
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 Origin 7.0 softwares, calculates the area integral value of each characteristic peak.According to Calculate 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 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 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 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 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; 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 restrains γ-Al with L1, L2 dipping 1000 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 of the present 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, 1.22 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-Al 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 restrains γ-Al with L1, L2 dipping 1000 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 of the present 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 embodiment 1 preparation is described 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 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 (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, stopped adsorption experiment when absorption tail gas concentration tends towards stability.Reactor outlet meets SO 2, SO in the NO analyzer monitoring flue gas 2, NO content variation.Wherein, SO 2Saturated extent of adsorption reach 1.125 mM/grams, the saturated extent of adsorption of NO reaches 0.292 mM/gram.
Embodiment 10
Mg-Co-γ-the Al of embodiment 8 preparations is described 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 embodiment 1 preparation is described.
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 CO gas that switched air speed and be 15000/ hour makes it contact 2 hours with SORB-1 to be regenerated; With air speed is that 10000/ hour nitrogen purged 30 minutes, and the oxygen that switched air speed and be 15000/ hour makes it contact 30 minutes with the SORB-1 to be regenerated that reduces through back; With air speed is that 10000/ hour nitrogen purged 30 minutes, switch air speed and be 15000/ hour methane gas and contact 1 hour with SORB-1 to be regenerated through the back oxidation, afterwards, the nitrogen that fed air speed and be 10000/ hour purges to temperature of reactor reduces to normal temperature, the adsorbent composition SORB-1-1 after obtaining regenerating.
Estimate SORB-1-1 according to embodiment 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, 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 (13)

1. 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 I A and/or the II A family metal component of being selected from that is selected from group VIII, with described composition is benchmark, 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 I A and/or II A family metal component is 0.5 weight %-35 weight %.
2. composition according to claim 1, it is characterized in that, with described composition is benchmark, 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 I A and/or II A family metal component is 1 weight %-20 weight %.
3. composition according to claim 1 is characterized in that, the described metal component that is selected from group VIII is iron and/or cobalt.
4. composition according to claim 3 is characterized in that, the described metal component that is selected from group VIII is a cobalt.
5. according to claim 1,2,3 or 4 any described compositions, it is characterized in that characterize with X-ray photoelectron spectroscopy, the described metal component of group VIII that is selected from 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.
6. composition according to claim 5 is characterized in that, in element, and is benchmark with the total amount of group VIII metal component, M in the described different valence state metal component VIII I1+Content be 10%-30%, MV III I2+Content be 90-70%.
7. composition according to claim 6 is characterized in that, in element, and is benchmark with the total amount of group VIII metal component, M in the described different valence state metal component VIII I1+Content be 15%-30%, M VIII I2+Content be 85-70%.
8. 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.
9. 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.
10. composition according to claim 8 is characterized in that described heat-resistant inorganic oxide matrix is selected from one or more in aluminium oxide, silica, the silica-alumina.
11. composition according to claim 1, it is characterized in that, also contain one or more components that are selected from I B, II B, III B, IVB, V B, the VI B family in the described composition, total amount with described composition is a benchmark, and one or more components contents in the described I of being selected from B, II B, III B, IVB, V B, the VI B family are no more than 35 weight %.
12. composition according to claim 11, it is characterized in that, one or more components in the described I of being selected from B, II B, IIIB, IVB, VB, the group vib are one or more among Cr, Cu, Zn, Ce, the La, total amount with described composition is a benchmark, and the content of one or more among described Cr, Cu, Zn, Ce, the La is no more than 17 weight %.
13. composition according to claim 12 is characterized in that, is benchmark with the total amount of described composition, the content of one or more among described Cr, Cu, Zn, Ce, the La is no more than 15 weight %.
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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
US12/611,094 US20100107874A1 (en) 2008-10-31 2009-11-02 Sorbent composition, the preparation method thereof, and the process for removing sulfur oxides and nitrogen oxides in a flue gas by the sorbent composition
KR1020090104966A KR101646630B1 (en) 2008-10-31 2009-11-02 A sorbent composition, the preparation method thereof, and the process for removing sulfur oxides and nitrogen oxides in a flue gas by the sorbent composition
EP09174759.2A EP2181751B1 (en) 2008-10-31 2009-11-02 A sorbent composition, the preparation method thereof, and the process for removing sulfur oxides and nitrogen oxides in a flue gas by the sorbent composition

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