CN101829472A

CN101829472A - Method for removing sulfur and nitric oxides from flue gas

Info

Publication number: CN101829472A
Application number: CN200910119515A
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: 2010-09-15
Anticipated expiration: 2029-03-12
Also published as: CN101829472B

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 are subject to 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 to be solved in the present invention provides the method for sulphur, nitrogen oxide in a kind of simultaneous removing flue gas new, that efficient is higher.

A kind ofly remove sulphur in the flue gas, the method of nitrogen oxide, be included under the absorption separation condition, with sulfur-bearing, the flue gas of nitrogen oxide contacts with adsorbent, described adsorbent contains heat-resistant inorganic oxide matrix and metal component I and metal component II, wherein, described metal component I is selected from the I A of the periodic table of elements, in the II A family one or more, metal component II is selected from the VIB of the periodic table of elements, VIIB, VIII, in the IIB family one or more, with described adsorbent is benchmark, 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 described adsorbent is benchmark, the content of heat-resistant inorganic oxide matrix is preferably 65 weight %-98 weight % in the described 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.

Described metal component I is selected from Ba, the Mg of the Na of I A family and K and composition thereof and II A family and Ca and composition thereof; Described 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 described 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, described 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 described 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 represents the chemical valence of chromium, for example Cr ⁶⁺And Cr ³⁺, its i value is respectively 6+ and 3+, and S represents 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, described 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 described 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 represents the chemical valence of manganese, for example Mn ⁴⁺, Mn ²⁺, its i value is respectively 4+ and 2+, and S represents 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, described 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 described 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 represents the chemical valence of cobalt, 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 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, described 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 described 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 represents the chemical valence of zinc, for example Zn ¹⁺And Zn ²⁺, its i value is respectively 1+ and 2+, and S represents 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.

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 one or more components that are selected from I B, III B, IV B, the V B family, one or more among further preferred wherein Cu, Ce, La, the V.Total amount with described composition is a benchmark, the described component that is selected from I B, III B, IV B, V B 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 described 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 described composition;

Wherein, described metal component I is selected from the I A of the periodic table of elements, in the II A family one or more, metal component II is selected from the VIB of the periodic table of elements, VIIB, VIII, in the IIB family one or more, with described adsorbent is benchmark, the consumption of each component makes in the final described adsorbent in the described step (1), 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 %, be 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 described step (2) is 620 ℃-1000 ℃, and more preferably 650 ℃-960 ℃, roasting time is 3 hours-12 hours, more preferably 4 hours-11 hours.

Wherein, the method for introducing metal component I and metal component II in the precursor of heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix described in the described step (1) is not particularly limited.Can be that the method that the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix and the compound of compound that contains described metal component I and/or metallic components II directly mix is introduced, 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 described metal component I and/or metallic components II 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 described compound that contains described metal component I and/or metallic components II 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 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 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, III B, IV B, V B 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, 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 metal component I and metal component II, to introduce, also can be introduced separately into.For example, can be with the precursor of described heat-resistant inorganic oxide matrix and/or heat-resistant inorganic oxide matrix with when the compound of described metallic components I and/or metal component II directly mixes, the method that will contain the compound of described 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 described 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 described metal component I and/or the metal component II.Can also be to introduce with the method for dipping afterwards in described step (2).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, here be not particularly limited, described method of roasting is a conventional method, and 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 adsorbent is a benchmark, the consumption of each component makes in the final described adsorbent, the described 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 be no more than 17 weight %, be more preferably and be no more than 15 weight %.

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

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

According to the invention provides method, optionally comprise the regeneration step of described adsorbent.Under the prerequisite that is enough to make performance of the adsorbent to recover, the inventive method is not particularly limited the regeneration of described adsorbent.In preferred embodiment, the regeneration of described adsorbent comprises:

(1) under 200 ℃ of-800 ℃ of temperature, the described regenerative compositions for the treatment of 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.

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

Described reducing gas can be any under described 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 described step (1), more preferably 0.5 hour-3.5 hours, be preferably 0.5 hour-4 hours the time of contact of step (3), more preferably 0.5 hour-3.5 hours.Wherein, under the prerequisite that is enough to form to the reduction atmosphere of described adsorbent, the consumption of reducing gas is not particularly limited.The volume space velocity of preferred steps (1) is 5000/ hour-50000/ hour, more preferably 5000/ hour-35000/ hour; The volume space velocity of preferred steps (3) is 5000/ hour-50000/ hour, further preferred 5000/ hour-30000/ hour.

Described oxygen-containing gas can be any material that can discharge oxygen under described temperature, 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 described step (2) was preferably 0.5 hour-3 hours, more preferably 0.5 hour-3 hours.Wherein, under the prerequisite that is enough to form to the oxidation atmosphere of described adsorbent, the consumption of described oxygen-containing gas is not particularly limited.The volume space velocity of preferred steps (2) is 5000/ hour-50000/ hour, more 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 described composition contacts with reducing gas or oxygen-containing gas.Described inert gas is selected from one or more in nitrogen, helium, argon gas, neon, krypton gas, xenon, the radon gas, under the prerequisite that is being enough to satisfy to purge require, the consumption and the purge time of described purge gas is not particularly limited.The volume space velocity of preferred described 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 described 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 described regeneration, oxidation and restoring in same tower hockets, when adsorbing separation between multitower during handover operation, reduction in the described regeneration, oxidation and restore and can hocket in same tower also can be carried out respectively in two or several towers.

The method of the invention provides is suitable for removing SOx and/or the 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

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 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.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 1-1

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 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 1-1

Illustrate and be suitable for adsorbent that the invention provides 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 restrains SiO with L1, L2, L3 dipping 1000 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 of the present 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-r-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-Cu-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 restrains SiO with L1, L2, L3 dipping 1000 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 of the present invention ₂

Wherein, chromium is with Cr ³⁺Form occurs.

Embodiment 1-8

The effect that the invention provides method synchronized desulfuring, nitrogen is described.

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.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 1.314 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, 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 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 CO gas that switched air speed and be 15000/ hour makes it contact 2 hours with SORB1-1 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 SORB1-1 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 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 restrains γ-Al with L1, L2, L3 dipping 1000 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 of the present 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 restrains γ-Al with L1, L2, L3 dipping 1000 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 of the present 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 restrains γ-Al with L1, L2 dipping 1000 ₂O ₃Carrier 2 hours, each dipping back obtains composition K-Mn-SiO of the present invention in 110 ℃ of dryings, 750 ℃ of roastings in 12 hours 8 hours ₂

Preparation is formed respectively with K ₂CO 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 restrains γ-Al with L1, L2, L3 dipping 1000 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 of the present 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.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.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 embodiment 2-1 preparation is described.

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 CO gas that switched air speed and be 15000/ hour makes it contact 2 hours with SORB2-1 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 SORB2-1 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 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 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 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-Cu-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 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

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.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.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 explanation 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 embodiment 3-1 preparation is described.

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 CO gas that switched air speed and be 15000/ hour makes it contact 2 hours with SORB3-1 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 SORB3-1 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 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 restrains SiO with L1, L2, L3 dipping 1000 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 of the present 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 the 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 restrains SiO with L1, L2, L3 dipping 1000 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 of the present 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.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 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

The performance that the invention provides adsorbent is described.

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 CO gas that switched air speed and be 15000/ hour makes it contact 2 hours with SORB4-1 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 SORB4-1 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 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 method for the invention provides has 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. one kind removes sulphur in the flue gas, the method of nitrogen oxide, be included under the absorption separation condition, with sulfur-bearing, the flue gas of nitrogen oxide contacts with adsorbent, described adsorbent contains heat-resistant inorganic oxide matrix and metal component I and metal component II, wherein, described metal component I is selected from the IA of the periodic table of elements, in the II A family one or more, metal component II is selected from the VIB of the periodic table of elements, VIIB, VIII, in the IIB family one or more, with described adsorbent is benchmark, 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 %.

2. method according to claim 1, it is characterized in that, with described adsorbent is benchmark, the content of heat-resistant inorganic oxide matrix is 65 weight %-98 weight % in the described 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, described metal component I is selected from Ba, the Mg of the Na of I A family and K and composition thereof and II A family and Ca and composition thereof; Described 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 characterize with X-ray photoelectron spectroscopy, the metal component II in the described adsorbent exists with two kinds of different valence states at least.

5. method according to claim 4 is characterized in that, described 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%.

6. method according to claim 5 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%.

7. method according to claim 4 is characterized in that, described 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, described Mn ²⁺Content be 10-30%, Mn ⁴⁺Content be 90-70%.

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

9. method according to claim 4 is characterized in that, described 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, described Co ³⁺Content be 10-30%, Co ⁴⁺Content be 90-70%.

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

11. method according to claim 4 is characterized in that, described 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, described Zn ¹⁺Content be 10-28%, Zn ²⁺Content be 90-72%.

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

13. method 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.

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

15. 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 described 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 %.

16. method according to claim 15, it is characterized in that, one or more components in the described 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 %.

17. method according to claim 16 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 %.

18. 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.

19. method according to claim 18 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.

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

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

22. method according to claim 20 is characterized in that, the temperature of described step (1) is 280 ℃-650 ℃, and the temperature of described step (2) is 280 ℃-650 ℃, and the temperature of described step (3) is 280 ℃-650 ℃.

23. method according to claim 20, it is characterized in that, described 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 described step (1), and be 0.5 hour-4 hours the time of contact of step (3).

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

25. method according to claim 20, it is characterized in that, described 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 described step (2).

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