CN1123382C - Process for preparing compound Ti-base oxide for reversible adsorption of nitrogen oxide - Google Patents
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Abstract
The present invention relates to a method for preparing compound Ti-base oxides used for reversible adsorption of nitrogen oxides, which belongs to the technical field of environmental protection. In the present invention, firstly, a sol-gel method is adopted to prepare compound Ti-base oxides with a high specific surface area and an anatase structure, then the solid powder of the compound Ti-base oxides is immersed in the solution of soluble salts of transition metal compounds, and finally, after the process of drying and roasting, a desired solid adsorbing material is obtained. The present invention is suitable for adsorbing nitrogen oxides in the temperature range of 10 to 300 DEG C, and has high nitrogen oxide adsorption capacity; adsorbents that have adsorbed nitrogen oxides can be quickly regenerated by heating and temperature rising in an inert atmosphere or a reducing atmosphere, and meanwhile, the adsorbed nitrogen oxides are released or converted into nitrogen gas.
Description
Technical field
The invention belongs to field of environment protection, specially refer to a kind of preparation method who is used for the titanium base adsorbent of adsorption cleaning nitrogen oxide.
Background technology
Nitrogen oxide is one of a kind of important atmosphere pollution.It can cause acid rain and city photochemical fog, and the respiratory tract and the cardiopulmonary organ of human body had bigger toxicity.Except selective catalytic reduction, the purification that absorption method is used for low concentration of NO x has also caused great concern.This method can be carried out the absorption of NOx earlier, from solid absorbent, after concentrating, discharge again by changing temperature and dividing potential drop then, so both improved the purification efficiency of per volume of catalyst, the purification for the NOx under the excess oxygen provides a selectable approach again.Used sorbing material has Y-Ba-Cu-O (the K.Tabaki et al of alkaline including earth metal element, Chem.Lett., 1988:799), Ba-Cu-O (Machida etal, J.Chem.Soc., Chem.Commu., 1990:1165) and Y-Sr-Co-O etc., its shortcoming is that this type of sorbing material element is easily poisoned by the carbon dioxide of acidity.Zeolite molecular sieve, mixed oxide and active carbon all have suction-operated to NOx.Wherein, (Journal of Catalysis 1996,158:420) mol ratio with the coprecipitation preparation is Mn: Zr=1: 1 amorphous state mixed oxide can reach 1.43wt% 200 ℃ of adsorbances to NO, and its absorption property is not subjected to CO to Eguchi etc.
2Influence, its shortcoming is that the heat endurance of non-crystal oxide is bad.
(Chinese patent Granted publication number:, made a kind of NOx in the waste gas and SOx and can be of adsorbing such as the neat Bath of MS at the alumina adsorbant of thermal regeneration more than 600 ℃ 1039973) by one or more stabilizing agents in silica, lanthana, other rare earth, titanium dioxide, zirconia and the alkaline earth are added in aluminium oxide.They are being precipitated as aluminium salt in the alumina process, add the aforementioned stable agent.Subsequently, the powder of precipitation is made the spherical alumina particle of slurry, grinding, drippage formation stabilisation.At last, with these impregnated with particles alkali metal or alkaline-earth metal, make stabilized sorbent.This method is main base material with aluminium oxide, and desired adsorbent reactivation temperature is very high, is generally 650 ℃.
(Chinese patent publication number: 1147416), obtain a kind of crystalline titanium oxide, be used as SO such as Li Daji with rutile and anatase mixing crystal formation with the porous titanium oxide of dilute sulfuric acid processing through sintering, Quenching Treatment
2With the adsorbent of NOx etc., this process will be used the sulfuric acid of the severe corrosive of 5-30% concentration.
The city comes (Chinese patent Granted publication number: 1063353) add the titania support of the interpolation Mn that Mn salt obtains in noncrystalline titanium dioxide after burning till such as justice.Then, on above-mentioned titania support, support by the oxide of noble metal Ru and/or Ce and the NOx adsorbent of forming by oxide at least a among Ag, Cu and the Mn.What they used is unformed titanium oxide, and specific area is lower, only is 70-140m
2/ g, heat endurance is relatively poor, loses specific area and adsorption activity becoming rutile phase more than 600 ℃, and will use noble metal Ru, and the adsorbent cost is raise.
M moral crust etc. (the Chinese patent publication number: 1190909) a kind of NOx adsorbent material that contains alkaline metal oxide (or metal carbonate or metal hydroxides or mixed-metal oxides) and cerium oxide composition is disclosed, and a kind of catalyzed conversion NOx catalyst that contains platinum.They use the technical process of multistep complexity, NOx catalytic component and NOx adsorbent component are dispersed on the same alumina support separated from one anotherly, and further be coated on the cordierite honeycomb carrier, be used for reducing the NOx gas of discharging in engine lean operating period and stoichiometry/rich oil periodic adjustment process between operating period.The complex process of this method is the base material of main absorption with the aluminium oxide, and sulfur resistance is relatively poor.
(Energy ﹠amp such as W.B.Li; Fuels 1997, find that 11:428) titanium base material of support type support type has stronger anti-sulphur ability, and they are at Cu/TiO
2And Ce-Cu/TiO
2On obtained very high adsorption activity, but the heat endurance of such adsorbent is bad.
Summary of the invention
The objective of the invention is in order to overcome the weak point of prior art, a kind of preparation method who is used for the Ti-base composite oxide of reversible adsorption nitrogen oxide is proposed, have that the cost of material is low, higher heat endurance, can in very wide adsorption temp scope, use, higher advantages such as adsorbance are arranged when the high temperature adsorption process.
The present invention proposes a kind of preparation method who is used for the Ti-base composite oxide of reversible adsorption nitrogen oxide, may further comprise the steps: the first step: at first adopt sol-gel process to prepare a kind of anatase structured Ti-base composite oxide of high-specific surface area; This process is to get a certain amount of titaniferous predecessor earlier to join in the organic solvent wiring solution-forming A; Respectively with certain density catalyst solution and the solution that contains stabilizing agent, join wiring solution-forming B in the organic solvent again; Then, two solution are evenly mixed, the control reaction temperature is 0～80 ℃, in the process in the control reaction system mol ratio between the reactant be the titanium precursor thing: organic solvent: catalyst: water: stabilizing agent=1: w: x: y: z, wherein w is between 5～60, x is between 0.001～2, and y is between 0.5～10, and z is between 0.01～0.45; After forming gel in the reaction system, aging a period of time, remove moisture and partial solvent through further drying, again through 450～800 ℃ of calcination process, obtain a kind of Ti-base composite oxide pressed powder that contains stabilizing agent.
Second step: Jin Zi method routinely, the Ti-base composite oxide pressed powder of above-mentioned gained be impregnated in a certain amount of one or more to have in the solution of soluble-salt of transistion metal compound, oven dry then, and, obtain required solid absorbent 200～800 ℃ of calcination process;
The present invention places the thermogravimetric analyzer of flowable state with above-mentioned solid absorbent, and the concentration of nitrogen oxide is several to 5000ppm in the air-flow, and oxygen concentration is 0～20%, and remaining balance gas is nitrogen; Detect adsorbent with thermogravimetry and be worth over time, obtain the adsorption curve of adsorbent at the gain in weight under the assigned temperature; When marked change does not take place in gain in weight in time, the absorption that promptly reaches capacity, this moment, resulting gain in weight was designated as equilibrium adsorption capacity, with the quality representation of the adsorbent nitrogen oxide of every gram; Adsorbent of the present invention reaches the time of equilibrium adsorption capacity generally in 10-120 minute;
Adsorbent of the present invention reaches capacity after the absorption, can be by in inert atmosphere or reducing atmosphere, and heat temperature raising adsorbent to 200～600 ℃ discharge the nitrogen oxide of absorption or reaction is converted into nitrogen; From the weight-loss curve of thermogravimetric analyzer, can detect the desorption rate of gas, determine complete desorption temperature.
Above-mentioned catalyst can be a kind of of hydrochloric acid, nitric acid, sulfuric acid, acetic acid and ammoniacal liquor; Said organic solvent can be a kind of of ethanol, methyl alcohol, propyl alcohol, benzene.
Said titaniferous predecessor is titanyl sulfate, chlorination oxygen titanium or alkoxytitanium (Ti (OR)
4, wherein R is the alkoxyl that contains carbon to four carbon) a kind of.
The stabilizing agent that is added is one or more of alkoxide compound that contain the soluble-salt of magnesium, calcium, strontium, barium, cerium, aluminium, silicon or aluminium, silicon.
Said transition metal salt is one or more in copper, manganese, cobalt, nickel and the chromium, and its quality percentage composition in final Ti-base composite oxide adsorbent is 0.1～30%.
The temperature of the absorption that the present invention is used can be 0～300 ℃; To adsorb in the regenerative process of adsorbent of nitrogen oxide, used inert atmosphere is air, nitrogen and rare gas, and used reducibility gas can be hydrogen, carbon monoxide, alkene, alkane or alcohol compound.
The present invention can choose sample segment, records the specific area of sample and the crystalline phase of investigating sample with the X-ray diffraction diffractometer by nitrogen adsorption.
Characteristics of the present invention:
The present invention adopts sol-gel process to prepare a kind of Ti-base composite oxide with high-specific surface area, is used for nitric oxide adsorption absorption.The Ti-base composite oxide that is synthesized is a kind of sorbing material with anatase structured high-specific surface area, and it is suitable for the absorption of nitrogen oxide in 10～300 ℃ of temperature ranges, can obtain high nitrogen oxide adsorption capacity.The main feature of this adsorbent is that cost is low without Pt family precious metal element; Can obtain to have the adsorbent of the high-specific surface area of anatase phase structure by adding stabilizing agent; This adsorbent still can be kept anatase phase rather than rutile phase at 800 ℃, has higher heat endurance, can use in very wide adsorption temp scope, and higher adsorbance is arranged when being used for the high temperature adsorption process.
The adsorbent that nitrogen oxide has been adsorbed in the present invention can pass through the fast rapid regeneration of heat temperature raising quilt in inert atmosphere or reducing atmosphere, and the nitrogen oxide that is adsorbed simultaneously is released or is converted into nitrogen.The present invention can be used for the purified treatment in room, flue gas, industrial tail gas and vehicle exhaust nitrogen oxides pollution source.
The specific embodiment
Embodiment 1
Get 8.66 milliliters of butyl titanates (TBT) and a certain amount of silicic acid four butyl esters (Si (OC
2H
5)
4) be diluted to wiring solution-forming A in the absolute ethyl alcohol of controlled amounts, an amount of rare nitric acid and water are joined wiring solution-forming B in a certain amount of absolute ethyl alcohol.Acid solution B is added drop-wise in the solution A under stirring condition, and keeping the mol ratio between the reactant in the process is TBT: ethanol: nitric acid: water: Si (OC
2H
5)
4=1: 30: 0.05: 4: 0.1.Under 20 ℃, be stirred to form gel after, aging a period of time, repeatedly behind the suction filtration, place 80 ℃ of water-baths dry with deionized water again.The mol ratio that obtains like this is 0.1: 1 SiO
2/ TiO
2Pressed powder, after 450 ℃ of calcination process, recording its BET specific area is 246m
2/ g.
With the pressed powder of top gained, with nickel nitrate solution dipping, 100 ℃ of oven dry then, obtaining containing the nickel oxide weight ratio through 450 ℃ of roastings again is 2% 2%NiO-Al
2O
3/ TiO
2Pressed powder.
Embodiment 2
Get wiring solution-forming A in the absolute ethyl alcohol that 8.66 milliliters of butyl titanates (TBT) are diluted to controlled amounts, with an amount of Al (NO
3)
3Join wiring solution-forming B in a certain amount of absolute ethyl alcohol with an amount of diluted nitric acid aqueous solution.Acid solution B is added drop-wise in the solution A under stirring condition, and keeping the mol ratio between the reactant in the process is TBT: methyl alcohol: hydrochloric acid: water: aluminum nitrate=1: 45: 0.015: 6: 0.2.Under 50 ℃, be stirred to form gel after, aging a period of time, repeatedly behind the suction filtration, place 80 ℃ of water-baths dry with deionized water again.The mol ratio that obtains like this is 0.2: 1 Al
2O
3/ TiO
2Pressed powder, after 450 ℃ of calcination process, recording its BET specific area is 180m
2/ g.
With the pressed powder of top gained, overflow stain with nickel nitrate solution, 100 ℃ of oven dry then, obtaining containing the nickel oxide weight ratio through 450 ℃ of roastings again is 2% 2%NiO-Al
2O
3/ TiO
2Pressed powder.
With above-mentioned 2%NiO-Al
2O
3/ TiO
2Pressed powder places the thermogravimetric analyzer of flowable state, and the concentration of nitrogen oxide is 2000ppm in the air-flow, and oxygen concentration is 8%, and remaining balance gas is nitrogen.At 200 ℃, the maximal absorptive capacity that every gram adsorbent can nitric oxide adsorption is 5.1mg/ (a g adsorbent).
With the above-mentioned 2%NiO-Al that adsorbs nitrogen oxide
2O
3/ TiO
2Be rapidly heated to 450 ℃, from the weight-loss curve of thermogravimetric analyzer, the gas that can observe absorption is desorption fully.
Embodiment 3
Get 8.66 milliliters of metatitanic acids, four fourth fat and be diluted to wiring solution-forming 1 in a certain amount of absolute ethyl alcohol, in proportion a certain amount of barium acetate being joined wiring solution-forming in an amount of glacial acetic acid and the deionized water 2., to keep the mol ratio between the reactants be TBT: ethanol: acetic acid: water: barium acetate=1: 6: 2: 5: 0.1.Under 30 ℃, be stirred to form gel after, aging a period of time, repeatedly behind the suction filtration, place 80 ℃ of water-baths dry with deionized water again.The mol ratio that obtains like this is 0.1: 1 BaO/TiO
2Pressed powder, after 450 ℃ of calcination process, recording its BET specific area is 150m
2/ g.
With the pressed powder of top gained, with manganese nitrate solution dipping, 100 ℃ of oven dry then, obtaining containing the manganese oxide weight ratio through 450 ℃ of roastings again is 3.2% 3.2%MnO
2-BaO/TiO
2Pressed powder.
With above-mentioned 3.2%MnO
2-Al
2O
3/ TiO
2Pressed powder places the thermogravimetric analyzer of flowable state, and the concentration of nitrogen oxide is 3000ppm in the air-flow, and oxygen concentration is 12%, and remaining balance gas is nitrogen.At 200 ℃, the maximal absorptive capacity that every gram adsorbent can nitric oxide adsorption is 15.0mg/ (a g adsorbent).
With the above-mentioned 3.2%MnO that adsorbs nitrogen oxide
2-BaO/TiO
2Be rapidly heated in nitrogen atmosphere to 450 ℃, from the weight-loss curve of thermogravimetric analyzer, the gas that can observe absorption can be by complete desorption.
Embodiment 4
With the method for similar embodiment 3, with manganese nitrate solution dipping, 120 ℃ of oven dry then, obtaining containing the manganese oxide weight ratio through 500 ℃ of roastings again is 9.5%MnO
2-BaO/TiO
2Pressed powder, and adopt similar condition to carry out the experiment of nitrogen oxide absorption, different is that adsorption temp is 200 ℃ among 100 ℃ of replacement embodiment 3, nitrous oxides concentration in the air-flow is the 3000ppm among the 2000ppm embodiment 3, and it is 26mg/ (g adsorbent) that the result obtains the maximal absorptive capacity that every gram adsorbent can nitric oxide adsorption.
With adsorption temp is 20 ℃, carries out similar adsorption experiment, and it is 42mg/ (g adsorbent) that the result obtains the maximal absorptive capacity that every gram adsorbent can nitric oxide adsorption.Under nitrogen atmosphere, be heated to 500 ℃, the complete desorption of nitrogen oxide in this adsorbent can be come out.
Embodiment 5
With the method for similar embodiment 3, replace manganese nitrate solution to prepare 3.2%Cu-2.2%Ni-BaO/TiO with the mixed solution of copper nitrate and nickel nitrate
2Pressed powder.Adopting similar adsorption method, is 500ppm at nitrous oxides concentration, and oxygen concentration is 2%, and adsorption temp is under 200 ℃, and the maximal absorptive capacity that every gram adsorbent can nitric oxide adsorption is 13.0mg/ (a g adsorbent).
Embodiment 6
With the method for similar embodiment 3, the mol ratio of keeping between the reactant is TBT: ethanol: acetic acid: water: barium acetate=1: 6: 2: 5: 0.2, prepared mol ratio and be 0.2: 1 BaO/TiO
2Pressed powder, after 450 ℃ of calcination process, with copper nitrate solution dipping, 100 ℃ of oven dry then, obtaining containing the manganese oxide weight ratio through 450 ℃ of roastings again is 5.1%CuO-BaO/TiO
2Adsorbent.Concentration at nitrogen oxide is 2000ppm then, and oxygen concentration is in 2% the air-flow, at 100 ℃ of adsorption experiments that carry out nitrogen oxide, the result for every gram adsorbent can nitric oxide adsorption maximal absorptive capacity be 35.0mg/ (g adsorbent).
With the above-mentioned 5.1CuO%-BaO/TiO that adsorbs nitrogen oxide
2Be rapidly heated in nitrogen atmosphere to 520 ℃, from the weight-loss curve of thermogravimetric analyzer, the gas that can observe absorption can be by complete desorption.
Also can be with the above-mentioned 5.1CuO%-BaO/TiO that adsorbs nitrogen oxide
2Be rapidly heated to 330 ℃ in the propylene atmosphere of 2000ppm, from the weight-loss curve of thermogravimetric analyzer, the gas that can observe absorption can be by complete desorption.
Can also be with the above-mentioned 5.1CuO%-BaO/TiO that adsorbs nitrogen oxide
2Be rapidly heated in the carbon monoxide atmosphere of 2000ppm to 280 ℃, from the weight-loss curve of thermogravimetric analyzer, the gas that can observe absorption can be by complete desorption.
Embodiment 7
Get 1.0 gram titanyl sulfates and 0.07 gram strontium nitrate is dissolved in wiring solution-forming A in the deionized water, will an amount of positive silicic acid four butyl esters (Si (OC
2H
5)
4) and an amount of ammoniacal liquor join wiring solution-forming B in a certain amount of absolute ethyl alcohol.Acid solution B is added drop-wise in the solution A under stirring condition, and keeping the mol ratio between the reactant in the process is titanyl sulfate: methyl alcohol: ammoniacal liquor: water: Si (OC
2H
5)
4=1: 45: 0.005: 50: 0.4.Under 50 ℃, be stirred to form gel after, aging a period of time, repeatedly behind the suction filtration, place 70 ℃ of water-baths dry with deionized water again.The mol ratio that obtains like this is 0.05: 0.4: 1 SrO/SiO
2/ TiO
2Pressed powder, after 450 ℃ of calcination process, recording its BET specific area is 310m
2/ g.
With the pressed powder of top gained, with nickel nitrate solution dipping, 100 ℃ of oven dry then, obtaining containing the nickel oxide weight ratio through 450 ℃ of roastings again is 7.5% 7.5%NiO-SrO/SiO
2/ TiO
2Pressed powder.Concentration at nitrogen oxide is 2000ppm then, and oxygen concentration is in 2% the air-flow, at 100 ℃ of adsorption experiments that carry out nitrogen oxide, the result for every gram adsorbent can nitric oxide adsorption maximal absorptive capacity be 25.5mg/ (g adsorbent).
Embodiment 8
Get wiring solution-forming A in the absolute ethyl alcohol that 8.66 milliliters of butyl titanates (TBT) are diluted to controlled amounts, an amount of rare nitric acid and the rare aqueous solution of a certain amount of cerous nitrate are joined wiring solution-forming B in a certain amount of absolute ethyl alcohol.Acid solution B is added drop-wise in the solution A under stirring condition, and keeping the mol ratio between the reactant in the process is TBT: ethanol: nitric acid: water: cerous nitrate=1: 30: 0.015: 4: 0.1.Under 20 ℃, be stirred to form gel after, aging a period of time, repeatedly behind the suction filtration, place 60 ℃ of water-baths dry with deionized water again.The mol ratio that obtains like this is the CeO of 0.1:1
2/ TiO
2Pressed powder, after 450 ℃ of calcination process, recording its BET specific area is 141m
2/ g.
With the pressed powder of top gained, with manganese nitrate solution dipping, 100 ℃ of oven dry then, obtaining containing the manganese oxide weight ratio through 450 ℃ of roastings again is 5.9% 5.9%MnO-CeO
2/ TiO
2Pressed powder.Concentration at nitrogen oxide is 2000ppm then, and oxygen concentration is in 2% the air-flow, at 200 ℃ of adsorption experiments that carry out nitrogen oxide, the result for every gram adsorbent can nitric oxide adsorption maximal absorptive capacity be 5.5mg/ (g adsorbent).
Claims (2)
1. preparation method who is used for the Ti-base composite oxide of reversible adsorption nitrogen oxide comprises following step:
1) at first adopt sol-gel process to prepare a kind of anatase structured Ti-base composite oxide of high-specific surface area; This process is to get a certain amount of titaniferous predecessor earlier to join in the organic solvent wiring solution-forming A; Respectively with certain density aqueous catalyst solution and the solution that contains stabilizing agent, join wiring solution-forming B in the organic solvent again; Then, two solution are evenly mixed, the control reaction temperature is 0～80 ℃, in the process in the control reaction system mol ratio between the reactant be the titanium precursor thing: organic solvent: catalyst: water: stabilizing agent=1: w: x: y: z, wherein w is between 5～60, x is between 0.001～2, and y is between 0.5～10, and z is between 0.01～0.45; After forming gel in the reaction system, aging a period of time, remove moisture and partial solvent through further drying, again through 450～800 ℃ of calcination process, obtain a kind of Ti-base composite oxide pressed powder that contains stabilizing agent;
2) method of flooding routinely, the Ti-base composite oxide pressed powder of above-mentioned gained be impregnated in a certain amount of one or more to have in the solution of soluble-salt of transistion metal compound, oven dry then, and, obtain required solid absorbent 200～800 ℃ of calcination process;
Said catalyst is a kind of of hydrochloric acid, nitric acid, sulfuric acid, acetic acid and ammoniacal liquor; Said organic solvent is a kind of of ethanol, methyl alcohol, propyl alcohol, benzene; Said titaniferous predecessor is a kind of of titanyl sulfate, chlorination oxygen titanium or alkoxytitanium; Said stabilizing agent is one or more of alkoxide compound that contain the soluble-salt of magnesium, calcium, strontium, barium, cerium, aluminium, silicon or aluminium, silicon.
2. as the right 1 described preparation method who is used for the Ti-base composite oxide of reversible adsorption nitrogen oxide, it is characterized in that, said transition metal salt is one or more in copper, manganese, cobalt, nickel and the chromium, and its quality percentage composition in final adsorbent is 0.1～30%.
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