CN101829472B

CN101829472B - Method for removing sulfur and nitric oxides from flue gas

Info

Publication number: CN101829472B
Application number: CN2009101195152A
Authority: CN
Inventors: 杜冰; 宗保宁; 罗一斌; 王维家
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2009-03-12
Filing date: 2009-03-12
Publication date: 2012-08-15
Anticipated expiration: 2029-03-12
Also published as: CN101829472A

Abstract

The invention relates to a method for removing sulfur and nitric oxides from flue gas, which comprises the step of contacting the flue gas containing sulfur and nitric oxides with an adsorbent under the condition of adsorption separation, wherein the adsorbent contains a heat-resisting inorganic oxide matrix, a metal component I and a metal component II; the metal component I is selected from one or more of groups of IA and IIA in a periodic table of elements, and the metal component II is selected from one or more of groups of VIB, VIIB, VIII and IIB in the periodic table of elements; the heat-resisting inorganic oxide matrix is 50 to 99 weight percent of the adsorbent; and the metal component I is 0.5 to 35 weight percent of the oxides, and the metal component II is 0.5 to 35 weight percent of the oxides. Compared with the prior art, the method provided by the invention has high desulfuration and denitrification performance and regeneration stability.

Description

A kind of method that removes sulphur in the flue gas, nitrogen oxide

Technical field

The present invention relates to a kind of method that removes sulphur in the flue gas, nitrogen oxide.

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 receive people's attention in recent years owing to have advantages such as reduced investment, operating cost are low.

For example, people such as Chen Ying discloses 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 provides the method for sulphur, nitrogen oxide in a kind of simultaneous removing flue gas new, that efficient is higher.

A kind of method that removes sulphur in the flue gas, nitrogen oxide; Be included under the absorption separation condition, the flue gas of sulfur-bearing, nitrogen oxide is contacted with adsorbent, said adsorbent contains heat-resistant inorganic oxide matrix and metal component I and metal component II; Wherein, Said metal component I is selected from the IA of the periodic table of elements, in the IIA family one or more, and metal component II is selected from one or more among the VIB, VIIB, VIII, IIB family of the periodic table of elements, is benchmark with said adsorbent; The content of heat-resistant inorganic oxide matrix is 50 weight %-99 weight %; In oxide, the content of metal component I is 0.5 weight %-35 weight %, and the content of metal component II is 0.5 weight %-35 weight %.

Method provided by the invention has adopted a kind ofly has the adsorbent of better absorption property to sulphur, nitrogen oxide, 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.

According to method provided by the invention; Wherein, With said adsorbent is benchmark, and the content of heat-resistant inorganic oxide matrix is preferably 65 weight %-98 weight % in the said adsorbent, in oxide; The content of metal component I is preferably 1 weight %-20 weight %, and the content of metal component II is preferably 1 weight %-18 weight %.

Described metal component I and metal component II exist with oxide and/or with any one or a few possible forms such as salt that other components form.

Said metal component I is selected from Ba, Mg and Ca of Na and K of IA family and composition thereof and IIA family and composition thereof; Said metal component II is selected from the chromium of group vib, the manganese of VIIB family, the cobalt of group VIII, the zinc of IIB family and their mixture.

Characterize with X-ray photoelectron spectroscopy, further the metal component II in the preferred said adsorbent is at least with M _II ^I1+And M _II ^I2+Two kinds of different valence states exist.Here, M _IIExpression metal component II, i1+ and i2+ represent M _IIDifferent chemical valences.

One preferred embodiment in, said metal component II is a chromium, described chromium is with Cr ⁶⁺And Cr ³⁺The form of valence state exists.In element and with the total amount of chromium is benchmark, M in the said different valence state metal component _II ^I1+Content be 90-70%, be more preferably 85-70%, M _II ^I2+Content be 10%-30%, be more preferably 15%-30%, i1 wherein is less than i2.

Here,

Wherein, M _IIExpression chromium, i representes the chemical valence of chromium, for example Cr ⁶⁺And Cr ³⁺, its i value is respectively 6+ and 3+, and S representes the area integral value at different valence state chromium characteristic of correspondence peak in ev～I figure, Summation for the area integral value of the characteristic peak of different valence state chromium.

One preferred embodiment in, said metal component II is a manganese, described manganese is with Mn ⁴⁺And Mn ²⁺The form of valence state exists.In element and with the total amount of manganese is benchmark, M in the said different valence state metal component _Ii ^I1+Content be 10-30%, be more preferably 15-30%, M _II ^I2+Content be 90-70%, be more preferably 85-70%, i1 wherein is less than i2.

Here,

Wherein, M _IIExpression manganese, i representes the chemical valence of manganese, for example Mn ⁴⁺, Mn ²⁺, its i value is respectively 4+ and 2+, and S representes the area integral value at different valence state manganese characteristic of correspondence peak in ev～I figure, Summation for the area integral value of the characteristic peak of different valence state manganese.

One preferred embodiment in, said metal component II is a cobalt, described cobalt is with Co ³⁺And Co ⁴⁺The form of valence state exists.In element and with the total amount of cobalt is benchmark, M in the said different valence state metal component _Ii ^I1+Content be 10-30%, be more preferably 15-30%, M _II ^I2+Content be 90-70%, be more preferably 85-70%, i1 wherein is less than i2.

Here,

Wherein, M _IIThe expression cobalt, i representes the chemical valence of cobalt, 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 cobalt characteristic of correspondence peak in ev～I figure,

Summation for the area integral value of the characteristic peak of different valence state cobalt.

Another preferred embodiment in, said metal component II is a zinc, described zinc Zn ¹⁺And Zn ²⁺The form of two kinds of valence states exists.In element and with the total amount of zinc is benchmark, M in the said different valence state metal component _II ^I1+Content be 10-28%, be more preferably 12-25%, M _II ^I2+Content be 90%-72%, be more preferably 88%-75%, i wherein ₁Less than i ₂

Here, Wherein, M _IIExpression zinc, i representes the chemical valence of zinc, for example Zn ¹⁺And Zn ²⁺, its i value is respectively 1+ and 2+, and S representes the area integral value at different valence state zinc characteristic of correspondence peak in ev～I figure, Summation for the area integral value of the characteristic peak of different valence state zinc.

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. one or more in titanium oxide, magnesia, silica one aluminium oxide, 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.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 one or more components that are selected from IB, IIIB, IVB, the VB family, one or more among further preferred wherein Cu, Ce, La, the V.Total amount with said composition is a benchmark; The said component that is selected from IB, IIIB, IVB, VB family; The components contents of one or more among further preferred wherein Cu, Ce, La, the V is no more than 35 weight %, preferably is no more than 17 weight %, is more preferably and is no more than 15 weight %.

Adsorbent 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 metal component I and metal component II;

(2) product 2 hours-12 hours of calcination steps (1) under greater than 600 ℃ to 1100 ℃ conditions obtains said composition;

Wherein, said metal component I is selected from the IA of the periodic table of elements, in the IIA family one or more, and metal component II is selected from one or more among the VIB, VIIB, VIII, IIB family of the periodic table of elements; With said adsorbent is benchmark, and the consumption of each component makes in the final said adsorbent in the said step (1), 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 metal component I is 0.5 weight %-35 weight %, is preferably 1 weight %-20 weight %; The content of metal component II is 0.5 weight %-35 weight %, is preferably 1 weight %-18 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 the not special restriction of the method for in the precursor of heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix, introducing metal component I and metal component II described in the said step (1).Can be that compound with the precursor of said heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and compound that contains said metal component I and/or metallic components II directly carries out method of mixing and introduces, also can be to introduce with the method for the precursor of the said heat-resistant inorganic oxide matrix of solution impregnation of the compound of compound that contains said metal component I and/or metallic components II and/or heat-resistant inorganic oxide matrix.

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 precursor of said heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and said is contained said metal component I the compound of compound and/or metallic components II 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 metal component I and metal component II with the method for dipping afterwards.When extrusion molding, can add an amount of extrusion aid and/or adhesive, extrusion molding then for making to extrude smoothly.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, IIIB, IVB, VB family; During the component of one or more among further preferred wherein Cu, Ce, La, the V, 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 metal component I and metal component II, to introduce, also can introduce separately.For example; Can be with the precursor of said heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix with when the compound of said metallic components I and/or metal component II directly mixes; The method that will contain the compound of said other components is introduced; Also can be the compound preparation mixed solution with the compound that contains other components and metallic components I and/or metal component II, the method for flooding the precursor of said heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix be afterwards introduced.Also can dispose dipping solution separately, introduce the method introducing of flooding before or after said metal component I and/or the metal component II.Can also be to introduce with the method for dipping afterwards in said step (2).When step (2) is introduced with the method for dipping afterwards, after dipping, also comprise the step of dry and roasting, said drying is conventional method and condition; Here not special restriction; Said method of roasting is a conventional method, and 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 adsorbent is a benchmark; The consumption of each component makes in the final said adsorbent; The said component that is selected from IB, IIIB, IVB, VB family; The content of one or more among further preferred wherein Cu, Ce, La, the V is no more than 35 weight %, preferably is no more than 17 weight %, is more preferably and is no more than 15 weight %.

Said flue gas with sulfur-bearing, nitrogen oxide contacts with adsorbent, can carry out in the adsorption separation device arbitrarily, for example, in ADSORPTION IN A FIXED BED tower or fluid bed adsorbing separation reactor, carries out.

According to the present invention method is provided; The gas sulphur oxide after being enough to make said contact make separation and the content of nitrogen oxide satisfy " emission standard of air pollutants for boilers; GB13271 " the prerequisite of requirement (oxysulfide content is less than 315ppm, and amount of nitrogen oxides is less than 300ppm) under, to the not special restriction of the operating condition of said adsorbing separation; Preferably include: temperature is 0～300 ℃, further is preferably 0～100 ℃; The volume space velocity of unstrpped gas is 5000/ hour-50000/ hour, further is preferably 5000/ hour-35000/ hour; Pressure is 0.1-3.0MPa, further preferred 0.1-2.0MPa.

According to the present invention method is provided, optionally comprises the regeneration step of said adsorbent.Be enough to make under the prerequisite of performance of the adsorbent recovery, the inventive method is to the not special restriction of the regeneration of said adsorbent.In preferred embodiment, the regeneration of said adsorbent comprises:

(1) under 200 ℃ of-800 ℃ of temperature, the said regenerative compositions of treating was contacted 0.5 hour-5 hours with reducing gas;

(2) under 200 ℃ of-800 ℃ of temperature, the product that step (1) is obtained contacted 0.5 hour-3 hours with oxygen-containing gas;

(3) under 200 ℃ of-800 ℃ of temperature, the product that step (2) is obtained contacted 0.5 hour-5 hours once more with reducing gas.

Said regeneration can be carried out in the original position adsorbent equipment, also can outside habitual device, carry out in the regenerating unit.For example, outside the fixed bed device, carry out in the regeneration reactor.Wherein, the temperature of said step (1) is preferably 250 ℃-700 ℃, further is preferably 280 ℃-650 ℃; The temperature of said step (2) is preferably 250 ℃-700 ℃, further is preferably 280 ℃-650 ℃; The temperature of said step (3) is preferably 250 ℃-700 ℃, further is preferably 280 ℃-650 ℃.

Said reducing gas can be any under said temperature gasifiable material with reducing property; For example; Can be preferably in carbon monoxide, hydrogen, methane, ethene, ethane, propylene, the propane one or more, be preferably 0.5 hour-4 hours the time of contact of said step (1), further was preferably 0.5 hour-3.5 hours; Be preferably 0.5 hour-4 hours the time of contact of step (3), further was preferably 0.5 hour-3.5 hours.Wherein, under the prerequisite that is enough to form to the reduction atmosphere of said adsorbent, to the not special restriction of the consumption of reducing gas.The volume space velocity of preferred steps (1) is 5000/ hour-50000/ hour, further is preferably 5000/ hour-35000/ hour; The volume space velocity of preferred steps (3) is 5000/ hour-50000/ hour, further preferred 5000/ hour-30000/ hour.

But said oxygen-containing gas can be any under said temperature the material of release of oxygen; For example; Can be preferably in the mist of mist, oxygen and helium of mist, oxygen and argon of oxygen, air, oxygen and nitrogen one or more; The contact of said step (2) was preferably 0.5 hour-3 hours, further was preferably 0.5 hour-3 hours.Wherein, under the prerequisite that is enough to form to the oxidation atmosphere of said adsorbent, to the not special restriction of the consumption of said oxygen-containing gas.The volume space velocity of preferred steps (2) is 5000/ hour-50000/ hour, further is preferably 5000/ hour-25000/ hour.

According to method provided by the invention,, also comprise the step of adsorbent equipment being cleaned and replacing with inert gas for satisfying the condition that said composition contacts with reducing gas or oxygen-containing gas.Said inert gas is selected from one or more in nitrogen, helium, argon gas, neon, krypton gas, xenon, the radon gas, is being enough to satisfy under the prerequisite that purges requirement, to the consumption and the not special restriction of purge time of said purge gas.The volume space velocity of preferred said purging is 5000/ hour-25000/ hour, and the time is 0.5 hour-3.0 hours, and the further preferred volume space velocity that purges is 10000/ hour-20000/ hour, and the time is 0.5-2 hour.

According to method provided by the invention, when said contact is carried out in the fixed bed absorption tower, according to actual conditions, be typically provided with two or more adsorption tower handover operations with implementation procedure continuously.When adsorbing separation between Liang Ta during handover operation; Reduction in the said regeneration, oxidation and restoring in same tower hockets; When adsorbing separation between multitower during handover operation; Reduction in the said regeneration, oxidation and restore and can in same tower, hocket also can be carried out respectively in two or several tower.

The present invention provides method to be suitable for removing SOx and/or NOx in the flue gas; For example; Be applicable to the SOx and/or the NOx that remove in catalytic cracking flue gas improvement, coal-fired plant flue gas improvement, the steel mill flue gas; Remove SOx and/or NOx in the flue gas of refuse burning, and other contain the smoke gas treatment of SOx and/or NOx.

The specific embodiment

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 metal component II 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.Calculate the content of different valence state metal according to

.

(confirm 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 1-1

Adsorbent that can be used for removing sulphur in the flue gas, nitrogen oxide that explanation provides according to prior art and preparation method thereof.

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 1-1

Explain that being suitable for the present invention provides adsorbent of method and preparation method thereof.

Raw material: silica support, sphere, 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: with 263 gram Cr (NO ₃) ₃Be dissolved into 1 liter of solution L1 with deionized water, with 123 gram La (NO ₃) ₃Be dissolved into 1 liter of solution L2 with deionized water, with 592 gram Mg (NO ₃) ₂Solution is dissolved into 1 liter of solution L3 with deionized water.Order is with L1, L2, L3 dipping 1000 gram SiO ₂Carrier 2 hours, each dipping back be in 110 ℃ of dryings 12 hours, and 950 ℃ of roastings 10 hours obtain combination articles La-Mg-Cr-SiO according to the invention ₂

Form: with MgO, Cr ₂O ₃And La ₂O ₃Meter, the content of magnesium are that the content of 16 weight %, chromium is that the content of 5 weight %, lanthanum is 4 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 1-2

Raw material:: γ-Al ₂O ₃Carrier, sphere, 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: adopt the method for step impregnation to prepare composition K-Cr-γ-Al with embodiment 1-1 ₂O ₃Each step dipping back is in 110 ℃ of dryings 12 hours, 900 ℃ of following roastings 8 hours.

Form: with K ₂CO ₃, Cr ₂O ₃Meter, K-Cr-γ-Al ₂O ₃The content of middle potassium is that the content of 4 weight %, chromium is 17 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 1-3

Raw material: γ-Al ₂O ₃Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Mn (NO ₃) ₂(being 50% weight solution), Cr (NO ₃) ₃, Na ₂CO ₃Be Beijing Chemical Plant's product.

Preparation method: adopt the method for step impregnation to prepare composition Na-Mn-Cr-γ-Al with embodiment 1-1 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, Cr ₂O ₃Meter, Na-Mn-Cr-γ-Al ₂O ₃In the content of sodium be that the content of 16 weight %, manganese is that the content of 5 weight %, chromium is 13 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 1-4

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, Na ₂CO ₃, Ba (NO3) 2 is Beijing Chemical Plant's product.

Preparation method: adopt the method for step impregnation to prepare composition Na-Cr-Co-Ba-γ-Al with embodiment 1-1 ₂O ₃Each step dipping back is in 110 ℃ of dryings 12 hours, 680 ℃ of following roastings 5 hours.

Form: with Na ₂CO ₃, Cr ₂O ₃, Co ₃O ₄, BaO meter, Na-Cr-Co-Ba-γ-Al ₂O ₃In the content of sodium be that the content of 3 weight %, chromium is that the content of 10 weight %, cobalt is that the content of 8 weight %, barium is 8 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 1-5

Raw material: γ-Al ₂O ₃Carrier, sphere, 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: adopt the method for step impregnation to prepare composition Na-Cr-Gu-γ-Al with embodiment 1-1 ₂O ₃Each step dipping back is in 110 ℃ of dryings 12 hours, 750 ℃ of following roastings 4 hours.

Form: with Na ₂CO ₃, Cr ₂O ₃, CuO meter, Na-Cr-Cu-γ-Al ₂O ₃In the content of sodium be that the content of 8 weight %, chromium is that the content of 3 weight %, copper is 15 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 1-6

Raw material: γ-Al ₂O ₃Carrier, sphere, 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: adopt the method for step impregnation to prepare composition Na-Cr-Zn-γ-Al with embodiment 1-1 ₂O ₃Each step dipping back is in 110 ℃ of dryings 12 hours, 950 ℃ of following roastings 6 hours.

Form: with Na ₂CO ₃, Cr ₂O ₃, ZnO meter, Na-Cr-Zn-γ-Al ₂O ₃In the content of sodium be that the content of 18 weight %, chromium is that the content of 8 weight %, zinc is 10 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 1-7

Preparation method: with 263 gram Cr (NO ₃) ₃Be dissolved into 1 liter of solution L1 with deionized water, with 123 gram La (NO ₃) ₃Be dissolved into 1 liter of solution L2 with deionized water, with 592 gram Mg (NO ₃) ₂Solution is dissolved into 1 liter of solution L3 with deionized water.Order is with L1, L2, L3 dipping 1000 gram SiO ₂Carrier 2 hours, each dipping back be in 110 ℃ of dryings 12 hours, and 600 ℃ of roastings 10 hours obtain combination articles La-Mg-Cr-SiO according to the invention ₂

Wherein, chromium is with Cr ³⁺Form occurs.

Embodiment 1-8

Explain that the present invention provides the effect of method synchronized desulfuring, nitrogen.

Adsorbent is the La-Mg-Cr-SiO of embodiment 1-1 preparation ₂, 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 1.314 mM/grams, the saturated extent of adsorption of NO reaches 0.423 mM/gram.

Comparative Examples 1-2

The effect of reference method synchronized desulfuring, nitrogen is described.

La-Cu-Na-γ-Al that adsorbent provides for Comparative Examples 1-1 ₂O ₃, 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 1-9

Adsorbent is the La-Mg-Cr-SiO of embodiment 1-7 preparation ₂Experiment 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 1.201 mM/grams, the saturated extent of adsorption of NO reaches 0.310 mM/gram.

Embodiment 1-10

The regenerability that is suitable for adsorbent of the present invention is described.

Treat that regenerative agent is the saturated back of embodiment 8 a conditions absorption sample, counts SORB1-1.Regeneration is carried out on the regenerating unit outside device, and regeneration reactor is the tubular reactor of 10 millimeters of internal diameters.

SORB1-1 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 SORB1-1 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 SORB1-1 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 SORB1-1 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 SORB1-1-1 after obtaining regenerating.

Estimate SORB1-1-1 according to embodiment 1-9 appreciation condition.Experimental result is: SO ₂Saturated extent of adsorption be 1.182 mM/grams (for fresh dose 89.9%), the saturated extent of adsorption of NO reaches 0.401 mM/gram (be fresh dose 94.8%).

Comparative Examples 1-3

The regenerability of reference method with adsorbent is described.

Treat that regenerative agent is the saturated back of a Comparative Examples 1-2 condition absorption sample, the regeneration tests step is with embodiment 1-10.

The appreciation condition of regeneration back sample is with Comparative Examples 1-2.Experimental result is: SO ₂Saturated extent of adsorption be 0.785 mM/gram (for fresh dose 63.3%), the saturated extent of adsorption of NO reaches 0.241 mM/gram (be fresh dose 58.6%).

Embodiment 2-1

Raw material: γ-Al ₂O ₃Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Ba (NO ₃) ₂, La (NO ₃) ₃, 50 weight % Mn (NO ₃) ₂Solution (being Beijing Chemical Plant's product).

Preparation method: with 25 gram Ba (NO ₃) ₂Be dissolved into 1 liter of solution L1 with deionized water, with 100 gram La (NO ₃) ₃Be dissolved into 1 liter of solution L2 with deionized water, with 542 gram Mn (NO ₃) ₂Solution is dissolved into 1 liter of solution L3 with deionized water.Order is with L1, L2, L3 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 composition La-Mn-Ba-γ-Al according to the invention ₂O ₃

Form: each component load capacity is respectively with BaO, MnO ₂And La ₂O ₃Meter, the content of barium are that the content of 1 weight %, manganese is that the content of 13 weight %, lanthanum is 4 weight %.

Manganese is respectively with Mn ⁴⁺And Mn ²⁺Two kinds of different valence state exist, in element, and Mn ⁴⁺Content be 75%, Mn ²⁺Content be 25%.

Embodiment 2-2

Raw material: with embodiment 2-1.

Preparation method: with 25 gram Ba (NO ₃) ₂Be dissolved into 1 liter of solution L1 with deionized water, with 100 gram La (NO ₃) ₃Be dissolved into 1 liter of solution L2 with deionized water, with 542 gram Mn (NO ₃) ₂Solution is dissolved into 1 liter of solution L3 with deionized water.Order is with L1, L2, L3 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 composition La-Mn-Ba-γ-Al according to the invention ₂O ₃

Manganese is with Mn ⁴⁺Form does not detect other valence state forms of Mn.

Embodiment 2-3

Raw material: silica support, sphere, 1.22 millimeters of average grain diameters, Chang Ling catalyst plant product; Mn (NO ₃) ₂(being 50% weight solution), K ₂CO ₃Be Beijing Chemical Plant's product.

With 40 gram K ₂CO ₃Be dissolved into 1 liter of solution L1 with deionized water, with 535 gram Mn (NO ₃) ₂Solution is dissolved into 1 liter of solution L2 with deionized water.Order is with L1, L2 dipping 1000 gram γ-Al ₂O ₃Carrier 2 hours, each dipping back obtains composition K-Mn-SiO according to the invention in 110 ℃ of dryings, 750 ℃ of roastings in 12 hours 8 hours ₂

Preparation is formed respectively with K ₂GO ₃, MnO ₂Meter, composition K-Mn-SiO ₂The content of middle potassium is that the content of 4 weight %, manganese is 13 weight %.

Manganese is respectively with Mn ⁴⁺And Mn ²⁺Two kinds of different valence state exist, in element, and Mn ⁴⁺Content be 71%, Mn ²⁺Content be 29%.

Embodiment 2-4

With 160 gram Na ₂CO ₃Be dissolved into 1 liter of solution L1 with deionized water, with 535 gram Mn (NO ₃) ₂Solution is dissolved into 1 liter of solution L2, with 684 gram Cr (NO ₃) ₃Solution fuses into 1 liter of solution L3 with deionized water.Order is with L1, L2, L3 dipping 1000 gram γ-Al ₂O ₃Carrier 2 hours, each dipping back be in 110 ℃ of dryings 12 hours, and 700 ℃ of roastings 5 hours obtain composition Na-Mn-Cr-γ-Al according to the invention ₂O ₃

Composition Na-Mn-Cr-γ-Al ₂O ₃Composition respectively with Na ₂CO ₃, MnO ₂, Cr ₂O ₃Meter, the content of sodium are that the content of 16 weight %, manganese is that the content of 5 weight %, chromium is 13 weight %.

Manganese is respectively with Mn ⁴⁺And Mn ²⁺Two kinds of different valence state exist, in element, and Mn ⁴⁺Content be 85%, Mn ²⁺Content be 15%.

Embodiment 2-5

Raw material: γ-Al ₂O ₃Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Mn (NO ₃) ₂(being 50% weight solution), Co (NO ₃) ₂, Na ₂CO ₃, Ba (NO ₃) ₂Be Beijing Chemical Plant's product.

The method of step impregnation is carried out in sample preparation, and each step dipping back was in 110 ℃ of dryings 12 hours, and 680 ℃ of following roastings 6 hours, other preparation methods were with embodiment 2-1.Preparation is formed respectively with Na ₂CO ₃, MnO ₂, Co ₃O ₄, BaO meter, the content of sodium is that the content of 6 weight %, manganese is that the content of 10 weight %, cobalt is that the content of 8 weight %, barium is composition Na-Mn-Co-Ba-γ-Al of 5 weight % ₂O ₃

Manganese is respectively with Mn ⁴⁺And Mn ²⁺Two kinds of different valence state exist, in element, and Mn ⁴⁺Content be 80%, Mn ²⁺Content be 20%.

Embodiment 2-6

Raw material: γ-Al ₂O ₃Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Mn (NO ₃) ₂(being 50% weight solution), Cu (NO ₃) ₂, Na ₂CO ₃Be Beijing Chemical Plant's product.

The method of step impregnation is carried out in sample preparation, and each step dipping back was in 110 ℃ of dryings 12 hours, and 750 ℃ of following roastings 4 hours, other preparation methods were with embodiment 2-1.Preparation is formed respectively with Na ₂CO ₃, MnO ₂, CuO meter, the content of sodium is that the content of 8 weight %, manganese is that the content of 3 weight %, copper is composition Na-Mn-Cu-γ-Al of 15 weight % ₂O ₃

Manganese is respectively with Mn ⁴⁺And Mn ²⁺Two kinds of different valence state exist, in element, and Mn ⁴⁺Content be 84%, Mn ²⁺Content be 16%.

Embodiment 2-7

Raw material: γ-Al ₂O ₃Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Mn (NO ₃) ₂(being 50% weight solution), Zn (NO ₃) ₂, Na ₂CO ₃Be Beijing Chemical Plant's product.

The method of step impregnation is carried out in sample preparation, and each step dipping back was in 110 ℃ of dryings 12 hours, and 950 ℃ of following roastings 4 hours, other preparation methods were with embodiment 2-1.Preparation is formed respectively with Na ₂CO ₃, MnO ₂, ZnO meter, the content of sodium is that the content of 18 weight %, manganese is that the content of 8 weight %, zinc is composition Na-Mn-Zn-γ-Al of 10 weight % ₂O ₃

Manganese is respectively with Mn ⁴⁺And Mn ²⁺Two kinds of different valence state exist, in element, and Mn ⁴⁺Content be 77%, Mn ²⁺Content be 23%.

Embodiment 2-8

Adsorbent is the La-Mn-Ba-γ-Al of embodiment 2-1 preparation ₂O ₃, experiment is carried out on the ADSORPTION IN A FIXED BED device.Tube inner diameter is 8 millimeters, and the adsorbent consumption is 1 gram, and adsorption temp is 175 ℃, and the feed gas volume flow is 300 ml/min.Feed gas volume consists of: SO ₂, 0.3%; NO, 0.1%; O ₂, 4.5%, surplus is N ₂Use N before 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.Wherein, SO ₂Saturated extent of adsorption reach 1.320 mM/grams, the saturated extent of adsorption of NO reaches 0.446 mM/gram.

Embodiment 2-9

Adsorbent is the La-Mn-Ba-γ-Al of embodiment 2-2 preparation ₂O ₃, 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 1.209 mM/grams, the saturated extent of adsorption of NO reaches 0.308 mM/gram.

Embodiment 2-10

Desulfurization removing nitric performance after the sample regeneration of illustrative embodiment 2-1 preparation.

Treat that regenerative agent is the saturated back of an embodiment 2-8 condition absorption sample, count SORB2-1 regeneration and outside device, carry out on the regenerating unit that regeneration reactor is the tubular reactor of 10 millimeters of internal diameters.

SORB2-1 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 SORB2-1 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 SORB2-1 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 SORB1-1 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 SORB2-1-1 after obtaining regenerating.

Estimate SORB2-1-1 according to embodiment 2-8 appreciation condition.Experimental result is: SO ₂Saturated extent of adsorption be 1.152 mM/grams (for fresh dose 87.3%), the saturated extent of adsorption of NO reaches 0.396 mM/gram (be fresh dose 88.8%).

Embodiment 3-1

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 3-2

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 3-1 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 3-3

Raw material: γ-Al ₂O ₃Carrier (with embodiment 3-1); 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 3-1 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 3-4

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 3-1 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.

Embodiment 3-5

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 3-1 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 3-6

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-Gu-γ-Al with embodiment 3-1 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 3-7

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 3-1 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 3-8

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

Wherein, cobalt is with Co ⁴⁺Form occurs.

Embodiment 3-9

Adsorbent is the Mg-Co-γ-Al of embodiment 3-1 preparation ₂O ₃, 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.Wherein, SO ₂Saturated extent of adsorption reach 1.256 mM/grams, the saturated extent of adsorption of NO reaches 0.431 mM/gram.

Embodiment 3-10

Adsorbent is the Mg-Co-γ-Al of illustrative embodiment 3-8 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 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 3-11

Desulfurization removing nitric performance after the sample regeneration of illustrative embodiment 3-1 preparation.

Treat that regenerative agent is the saturated back of an embodiment 3-9 condition absorption sample, counts SORB3-1.Regeneration is carried out on the regenerating unit outside device, and regeneration reactor is the tubular reactor of 10 millimeters of internal diameters.

SORB3-1 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 SORB3-1 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 SORB3-1 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 SORB3-1 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 SORB3-1-1 after obtaining regenerating.

Estimate SORB3-1-1 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%).

Embodiment 4-1

Raw material: silica support, sphere, 1.22 millimeters of average grain diameters, Chang Ling catalyst plant product; Mg (NO ₃) ₂, Zn (NO ₃) ₂, La (NO ₃) ₃Be Beijing Chemical Plant's product.

Preparation method: with 109.6 gram Zn (NO ₃) ₂Be dissolved into 1 liter of solution L1 with deionized water, with 172 gram La (NO ₃) ₃Be dissolved into 1 liter of solution L2 with deionized water, with 592 gram Mg (NO ₃) ₂Solution is dissolved into 1 liter of solution L3 with deionized water.Order is with L1, L2, L3 dipping 1000 gram SiO ₂Carrier 2 hours, each dipping back be in 110 ℃ of dryings 12 hours, and 950 ℃ of roastings 10 hours obtain combination articles La-Mg-Zn-SiO according to the invention ₂

Form: with MgO, ZnO and La ₂O ₃Meter, the content of magnesium are that the content of 16 weight %, zinc is that the content of 3 weight %, lanthanum is 7 weight %.

Wherein, zinc is respectively with Zn ¹⁺And Zn ²⁺Occur, in element, Zn ¹⁺Content be 13%, Zn ²⁺Content be 87%.

Embodiment 4-2

Raw material: γ-Al ₂O ₃Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Zn (NO ₃) ₂, K ₂CO ₃Be Beijing Chemical Plant's product.

Preparation method: adopt the method for step impregnation to prepare composition K-Zn-γ-Al with embodiment 4-1 ₂O ₃Each step dipping back is in 110 ℃ of dryings 12 hours, 900 ℃ of following roastings 8 hours.

Form: with K ₂CO ₃, ZnO meter, K-Zn-γ-Al ₂O ₃The content of middle potassium is that the content of 4 weight %, zinc is 17 weight %.

Wherein, zinc is respectively with Zn ¹⁺And Zn ²⁺Occur, in element, Zn ¹⁺Content be 15%, Zn ²⁺Content be 85%.

Embodiment 4-3

Preparation method: adopt the method for step impregnation to prepare composition Na-Mn-Zn-γ-Al with embodiment 4-1 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, ZnO meter, Na-Mn-Zn-γ-Al ₂O ₃In the content of sodium be that the content of 16 weight %, manganese is that the content of 8 weight %, zinc is 15 weight % composition Na-Mn-Zn-γ-Al ₂O ₃

Wherein, zinc is respectively with Zn ¹⁺And Zn ²⁺Occur, in element, Zn ¹⁺Content be 17%, Zn ²⁺Content be 83%.

Embodiment 4-4

Raw material: γ-Al ₂O ₃Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Zn (NO ₃) ₂, Co (NO ₃) ₂, Na ₂CO ₃, Ba (NO3) ₂Be Beijing Chemical Plant's product.

Preparation method: adopt the method for step impregnation to prepare composition Na-Zn-Co-Ba-γ-Al with embodiment 4-1 ₂O ₃Each step dipping back is in 110 ℃ of dryings 12 hours, 680 ℃ of following roastings 5 hours.

Form: with Na ₂CO ₃, ZnO, Co ₃O ₄, BaO meter, Na-Zn-Co-Ba-γ-Al ₂O ₃In the content of sodium be that the content of 3 weight %, zinc is that the content of 12 weight %, cobalt is that the content of 9 weight %, barium is 8 weight %.

Wherein, zinc is respectively with Zn ¹⁺And Zn ²⁺Occur, in element, Zn ¹⁺Content be 19%, Zn ²⁺Content be 81%.

Embodiment 4-5

Raw material: γ-Al ₂O ₃Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Cr (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-Zn-Cr-γ-Al with embodiment 4-1 ₂O ₃Each step dipping back is in 110 ℃ of dryings 12 hours, 750 ℃ of following roastings 4 hours.

Form: with Na ₂CO ₃, Cr ₂O ₃, ZnO meter, Na-Cr-Zn-γ-Al ₂O ₃In the content of sodium be that the content of 8 weight %, chromium is that the content of 3 weight %, zinc is 15 weight %.

Wherein, zinc is respectively with Zn ¹⁺And Zn ²⁺Occur, in element, Zn ¹⁺Content be 21%, Zn ²⁺Content be 79%.

Embodiment 4-6

Raw material: γ-Al ₂O ₃Carrier, sphere, 1.3 millimeters of average grain diameters, Chang Ling catalyst plant product; Cu (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-Cu-Zn-γ-Al with embodiment 4-1 ₂O ₃Each step dipping back is in 110 ℃ of dryings 12 hours, 950 ℃ of following roastings 6 hours.

Form: with Na ₂CO ₃, CuO, ZnO meter, Na-Cu-Zn-γ-Al ₂O ₃In the content of sodium be that the content of 14 weight %, zinc is that the content of 8 weight %, zinc is 12 weight %.

Wherein, zinc is respectively with Zn ¹⁺And Zn ²⁺Occur, in element, Zn ¹⁺Content be 14%, Zn ²⁺Content be 86%.

Embodiment 4-7

Preparation method: with 109.6 gram Zn (NO ₃) ₃Be dissolved into 1 liter of solution L1 with deionized water, with 172 gram La (NO ₃) ₃Be dissolved into 1 liter of solution L2 with deionized water, with 592 gram Mg (NO ₃) ₂Solution is dissolved into 1 liter of solution L3 with deionized water.Order is with L1, L2, L3 dipping 1000 gram SiO ₂Carrier 2 hours, each dipping back be in 110 ℃ of dryings 12 hours, and 600 ℃ of roastings 10 hours obtain combination articles La-Mg-Zn-SiO according to the invention ₂

Wherein, zinc is with Zn ²⁺Form occurs.

Embodiment 4-8

Adsorbent is the La-Mg-Zn-SiO of embodiment 4-1 preparation ₂, 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 the NO saturated extent of adsorption.Wherein, SO ₂Saturated extent of adsorption reach 1.188 mM/grams, the saturated extent of adsorption of NO reaches 0.344 mM/gram.

Embodiment 4-9

Adsorbent is the La-Mg-Zn-SiO of embodiment 4-7 preparation ₂, 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 1.153 mM/grams, the saturated extent of adsorption of NO reaches 0.323 mM/gram.

Embodiment 4-10

Explain that the present invention provides the performance of adsorbent.

Adsorbent is the Na-Cu-Zn-γ-Al of embodiment 4-6 preparation ₂O ₃Experiment 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 100 ℃, 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 1.180 mM/grams, the saturated extent of adsorption of NO reaches 0.340 mM/gram.

Embodiment 4-11

The regenerability that the present invention is sorbent used is described.

Treat that regenerative agent is the saturated back of an embodiment 4-8 condition absorption sample, counts SORB4-1.

Regeneration is carried out on the regenerating unit outside device, and regeneration reactor is the tubular reactor of 10 millimeters of internal diameters.SORB4-1 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 SORB4-1 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 SORB4-1 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 SORB5-1 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 SORB4-1-1 after obtaining regenerating.

Estimate SORB4-1-1 according to embodiment 4-8 appreciation condition.Experimental result is: SO ₂Saturated extent of adsorption be 1.100 mM/grams (for fresh dose 92.5%), the saturated extent of adsorption of NO reaches 0.297 mM/gram (be fresh dose 86.3%).

The result shows that the present invention provides method to have higher desulfuration, nitric efficiency.In addition, the adsorbent that also provides of the regenerability of the adsorbent that uses of the inventive method apparently higher than prior art.

Claims

1. method that removes sulphur in the flue gas, nitrogen oxide; Be included under the absorption separation condition, the flue gas of sulfur-bearing, nitrogen oxide is contacted with adsorbent, said adsorbent contains heat-resistant inorganic oxide matrix and metal component I and metal component II; Wherein, Said metal component I is selected from the IA of the periodic table of elements, in the II A family one or more, and metal component II is selected from one or more among the VI B, VIIB, VIII, IIB family of the periodic table of elements, is benchmark with said adsorbent; The content of heat-resistant inorganic oxide matrix is 50 weight %-99 weight %; In oxide, the content of metal component I is 0.5 weight %-35 weight %, and the content of metal component II is 0.5 weight %-35 weight %; Characterize with X-ray photoelectron spectroscopy, the metal component II in the said adsorbent exists with two kinds of different valence states at least.

2. method according to claim 1; It is characterized in that; With said adsorbent is benchmark, and the content of heat-resistant inorganic oxide matrix is 65 weight %-98 weight % in the said adsorbent, in oxide; The content of metal component I is 1 weight %-20 weight %, and the content of metal component II is 1 weight %-18 weight %.

3. method according to claim 1 is characterized in that, said metal component I is selected from Ba, Mg and Ca of Na and K of I A family and composition thereof and II A family and composition thereof; Said metal component II is selected from the chromium of group vib, the manganese of VIIB family, the cobalt of group VIII, the zinc of IIB family and their mixture.

4. according to claim 1 or 3 described methods, it is characterized in that said metal component II is with Cr ⁶⁺And Cr ³⁺The chromium that valence state exists.In element and with the total amount of chromium is benchmark, Cr ³⁺Content be 90-70%, Cr ⁶⁺Content be 15%-30%.

5. method according to claim 4 is characterized in that, is benchmark in element and with the total amount of chromium, Cr ³⁺Content be 85-70%, Cr ⁶⁺Content be 15%-30%.

6. according to claim 1 or 3 described methods, it is characterized in that said metal component II is with Mn ⁴⁺And Mn ²⁺The manganese that valence state exists is benchmark in element and with the total amount of manganese, said Mn ²⁺Content be 10-30%, Mn ⁴⁺Content be 90-70%.

7. method according to claim 6 is characterized in that, is benchmark in element and with the total amount of manganese, said Mn ²⁺Content be 15-30%, Mn ⁴⁺Content be 85-70%.

8. according to claim 1 or 3 described methods, it is characterized in that said metal component II is with Co ³⁺And Co ⁴⁺The cobalt that valence state exists is a benchmark in element and with the total amount of cobalt, said Co ³⁺Content be 10-30%, Co ⁴⁺Content be 90-70%.

9. method according to claim 8 is characterized in that, is benchmark in element and with the total amount of cobalt, said Co ³⁺Content be 15-30%, Co ⁴⁺Content be 85-70%.

10. according to claim 1 or 4 described methods, it is characterized in that said metal component II is with Zn ¹⁺And Zn ²⁺The zinc that valence state exists is benchmark in element and with the total amount of zinc, said Zn ¹⁺Content be 10-28%, Zn ²⁺Content be 90-72%.

11. method according to claim 10 is characterized in that, is benchmark in element and with the total amount of zinc, said Zn ¹⁺Content be 12-25%, Zn ²⁺Content be 88-75%.

12. method 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, silica-zirconia, oxidation titania-zirconia, silica-alumina-thorium oxide, silica-alumina-titanium oxide, silica-alumina-magnesia, the silica-alumina-zirconia.

13. method according to claim 12 is characterized in that, said heat-resistant inorganic oxide matrix is selected from one or more in aluminium oxide, silica, the silica-alumina.

14. method according to claim 1; It is characterized in that; Contain one or more components that are selected from IB, IIIB, IVB, the VB family in the said adsorbent; Total amount with adsorbent is a benchmark, and one or more components contents that are selected from IB, IIIB, IVB, the VB family are no more than 35 weight %.

15. method according to claim 14; It is characterized in that; One or more components in the said IB of being selected from, IIIB, IVB, the VB family are one or more among Cu, Ce, La, the V; Total amount with adsorbent is a benchmark, and one or more components contents that are selected from IB, IIIB, IVB, the VB family are no more than 17 weight %.

16. method according to claim 15 is characterized in that, is benchmark with the total amount of adsorbent, one or more components contents that are selected from IIIB, IVB, the VB family are no more than 15 weight %.

17. method according to claim 1 is characterized in that, described absorption separation condition comprises: temperature is 0～300 ℃, and the volume space velocity of unstrpped gas is 5000/ hour-50000/ hour, and pressure is 0.1-3MPa.

18. method according to claim 17 is characterized in that, described absorption separation condition comprises: temperature is 0～100 ℃, and the volume space velocity of unstrpped gas is 5000/ hour-35000/ hour, and pressure is 0.1-2MPa.

19. method according to claim 1 is characterized in that, said method also comprises the regeneration step of adsorbent, comprising:

20. method according to claim 19 is characterized in that, the temperature of said step (1) is 250 ℃-700 ℃, and the temperature of said step (2) is 250 ℃-700 ℃, and the temperature of said step (3) is 250 ℃-700 ℃.

21. method according to claim 19 is characterized in that, the temperature of said step (1) is 280 ℃-650 ℃, and the temperature of said step (2) is 280 ℃-650 ℃, and the temperature of said step (3) is 280 ℃-650 ℃.

22. method according to claim 19; It is characterized in that; Said reducing gas is selected from one or more in carbon monoxide, hydrogen, methane, ethene, ethane, propylene, the propane; Be 0.5 hour-4 hours the time of contact of said step (1), and be 0.5 hour-4 hours the time of contact of step (3).

23. method according to claim 22 is characterized in that, be 0.5 hour-3.5 hours the time of contact of said step (1), and be 0.5 hour-3.5 hours the time of contact of step (3).

24. method according to claim 19; It is characterized in that; Said oxygen-containing gas is selected from one or more in the mist of mist, oxygen and helium of mist, oxygen and argon of oxygen, air, oxygen and nitrogen, and be 0.5 hour-3 hours the time of contact of said step (2).

25. method according to claim 24 is characterized in that, be 0.5 hour-2.5 hours the time of contact of said step (2).