CN101455956B - Molecular sieve absorbent - Google Patents
Molecular sieve absorbent Download PDFInfo
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- CN101455956B CN101455956B CN2007101794427A CN200710179442A CN101455956B CN 101455956 B CN101455956 B CN 101455956B CN 2007101794427 A CN2007101794427 A CN 2007101794427A CN 200710179442 A CN200710179442 A CN 200710179442A CN 101455956 B CN101455956 B CN 101455956B
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Abstract
The invention relates to a molecular sieve sorbent, in particular to a flue gas desulphurization sorbent applicable to the treatment of SO2 in boiler flue gas. The sorbent comprises the following compositions by mass percentage: 0.1 to 5 percent of V2O5, 4 to 30 percent of CuO and 65 to 95.9 percent of silicon-aluminum molecular sieve. The molecular sieve sorbent takes molecular sieve as a carrier and contains vanadium and copper at the same time; moreover, a small amount of boron, aluminum, magnesium, titanium, chromium, manganese, iron, cobalt, nickel, zinc, zirconium, molybdenum, argentum, platinum, rhenium, or one or more elements in lanthanide or corresponding oxides can be added in the molecular sieve sorbent. The sorbent has the advantages of high adsorption capacity, excellent reproducing property, long service life and the like, and is not only applicable to flue gas desulphurization, but also applicable in gas purification fields such as CO removal and nitrogen oxide reduction.
Description
Technical field
The present invention relates to a kind of adsorbent of molecular sieve, particularly a kind of flue gas desulfurization adsorbent of handling SO2 in the boiler smoke that is applicable to.
Background technology
Fossil fuels such as coal occupy critical role in China's energy resource structure midium or long term, and the oxysulfide that contains in coal-burning power plant, the smeltery's exhaust gas discharged is because atmosphere pollution and acid deposition have formed environmental hazard.For administering the environmental hazard that sulfur dioxide (SO2) emissions cause, (flue gas desulphurization, FGD) technology is arisen at the historic moment in flue gas desulfurization.In various sulfur methods, the regeneration absorption method is that a kind of atmospheric sulfer of can administering pollutes, but can reclaim the resource technology of sulphur resource again, obtains extensive studies in recent years.
The regeneration absorption method is that adsorbent with a fixed structure is the SO in the flue gas
2Be adsorbed in the surface, discharge sulfide with heating or other way then, make adsorbent recover adsorption activity, obtain regeneration cycle and use, the key problem in technology of regeneration absorption method is an adsorbent.Carried molecular sieve is one of adsorbent of using always, and according to the application target difference, the component of load is different, generally is in the metal component one or more, or metal component and nonmetallic ingredient be used, sometimes also some organic matters of load.
CN86107272A discloses a kind of catalyst that is used for reducing nitrogen oxides, by 5～40% anatases, 50～90% zeolites, 0～30% adhesive and content are at least 0.1% promoter formation, wherein promoter is the oxide of vanadium, molybdenum, copper, and its preparation method is with the above-mentioned substance mixing or will floods promoter behind first three kind material mixing granulation.
CN1594505A discloses a kind of method of gasoline absorbing desulfurization, adsorbent employing is wherein soaked altogether or is divided the method for soaking to make, carrier is silica, aluminium oxide, diatomite, zeolite, the mixture of one or more in the porous materials such as zirconia, the metal in metal oxide-loaded be in cobalt, molybdenum, nickel, tungsten, vanadium, chromium, copper, calcium, potassium, the phosphorus one or more, metal oxide accounts for 2～50% of adsorbent total amount.
USP5041272 discloses a kind of method that removes nitrogen oxides of exhaust gas, its catalyst adopts silica alumina ratio greater than 5 zeolite, in metals such as loaded Cu, Zn, V, Cr, Mn, Fe, Co, Ni, Pt, Pd or the metal oxide one or more are used immersion process for preparing.
As SO
2Adsorbent is studied the more CuO/Al that has at present
2O
3, CuO/SiO
2And the adsorbent of making carrier to load metal with carbonaceous material such as activated coke, activated carbon etc.
For example: CN1569325A discloses a kind of absorbent charcoal based SO
2The preparation of adsorbent method, this adsorbent is a raw material with lignite semi-coke or bituminous coal semicoke, floods KI after the modification;
It is active component with the cupric oxide that CN1089034C discloses a kind of, is the SO of carrier with the raw material of wood-charcoal material
2The preparation of adsorbent method.
Because the sulfur-containing solid thing easily is deposited on charcoal material surface and stops up the absorption duct, has reduced the adsorption capacity of charcoal base adsorbent, and can cause the regeneration difficulty, reduced the desulfurized effect of adsorbent.
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of load type molecular sieve adsorbant, the flue gas desulfurization adsorbent that particularly a kind of adsorption capacity is high adds component by screening, optimize preparation condition, further improve the serviceability of carried molecular sieve.
Adsorbent of molecular sieve of the present invention is used for flue gas desulfurization, and in mass percent, its composition contains:
V
2O
5: 0.1%～5%, CuO:4%～30%, Si-Al molecular sieve 65%～95.9%; Adsorbent of molecular sieve is to adopt oxide or the salt that adds vanadium in Si-Al molecular sieve, extrusion, granulation behind the adding adhesive, 350～650 ℃ of following roastings 5～24 hours, put it in the soluble copper salting liquid, dipping 30～720min, filtration, dry under 100～140 ℃ obtains in 5～24 hours method of 450 ℃～650 ℃ following roastings then.
V in the adsorbent of molecular sieve of the present invention
2O
5Content is preferably 1%～4%, and the content of CuO is preferably 10%～25%.
In the adsorbent of molecular sieve of the present invention except that containing vanadium and copper, also can contain one or more elements in boron, aluminium, magnesium, titanium, chromium, manganese, iron, cobalt, nickel, zinc, zirconium, molybdenum, silver, platinum, rhenium or the lanthanide series, preferably contain in magnesium, iron, nickel, zinc, cobalt, chromium, titanium, silver, zirconium, the molybdenum one or more, its oxide content is 0%～5%, and generally the form dissolving dipping with soluble-salt adds.
The Si-Al molecular sieve of indication of the present invention can be y-type zeolite, X type zeolite, A type zeolite, chabasie, ZSM-5, modenite etc., can be in y-type zeolite, X type zeolite, A type zeolite, chabasie, ZSM-5, the modenite one or more, y-type zeolite preferably, SiO
2/ Al
2O
3Be preferably 2～7.
Adsorbent of molecular sieve of the present invention is made carrier with molecular sieve, contain vanadium and copper simultaneously, and can add a kind of or several elements or its oxide in small amount of boron, aluminium, magnesium, titanium, chromium, manganese, iron, cobalt, nickel, zinc, zirconium, molybdenum, silver, platinum, rhenium or the lanthanide series.Because Cu becomes Cu with V-arrangement
3V
2O
8Crystal formation is evenly distributed on Si-O-Al active structure surface, makes adsorbent to SO
2Very strong absorption is arranged; The adding of a small amount of V is played certain cutting apart and restraining function to the surface-active center of adsorbent, has stablized the surface-active structure of adsorbent, improved the stability of adsorbent, but the amount of V can not be too much, (general V
2O
5Be not higher than 5.5%) otherwise V occupies the activity site of Cu, influences adsorption activity, reduces absorption property on the contrary.Utilize cavitation effect of ultrasonic waves, can change absorption phase equilibrium relationship and selectivity, improve the dispersiveness of Cu on carrier, thereby improve its activity.
In the preparation process of adsorbent of molecular sieve, can adopt infusion process, can also adopt co-precipitation, do methods such as mixed, recommend the preparation of adsorbent method to select infusion process for use; Si-Al molecular sieve both can be commercially available, also can be to use known method preparation and got.Can be that first vanadium impregnated adds copper again in carrier in flue gas desulfurization preparation of adsorbent process, also can be to flood copper earlier to add vanadium again in carrier, will get well from the former effect of effect of adsorbent.Preferably copper adds before the carrier moulding, and vanadium adds with impregnation method.
The oxide of vanadium or salt can be a kind of in the vanadium-containing compounds such as vanadic anhydride, ammonium metavanadate, sodium metavanadate, vanadic sulfate.
Adhesive can be polyacrylic acid, polyvinyl alcohol, one or more in the adhesives such as polyacrylamide, Ludox, aluminium colloidal sol.The present invention is not specially limited the kind and the addition of adhesive, the commonly used adhesive of general Preparation of Catalyst, addition all can, get final product so long as can satisfy the moulding requirement.The addition of adhesive is 100% in the quality of adsorbent of molecular sieve, is preferably 0～5%.
In order to improve load effect, also can in the second step adsorbent preparation process, the copper salt solution that is added with carrier can be placed on the supersonic oscillations instrument, under 40～100 ℃, carry out ultrasonic immersing, the ultrasound wave irradiation frequency is preferably 10～60kHz.
More specifically, can use following steps and obtain adsorbent of molecular sieve:
1, preparing carriers:
With silicon source material, aluminium source material, the oxide of vanadium or salt are raw material, adopt guiding crystallization legal system to be equipped with carrier: under agitation add aluminium source material, water, silicon source material, heat temperature raising to 60～100 ℃, regulate pH=8～10, add directed agents and allow its crystallization, continue to stir 30～120min, filter, washing, the oxide or the salt that in silicon-aluminum mixture, add vanadium, extrusion, granulation 350～650 ℃ of following roastings 5～24 hours, promptly make the Si-Al molecular sieve that contains vanadium behind the adding adhesive.
Sial feed molar proportioning is: (2.5～7.5) Na
2O: Al
2O
3: (2.0～12) SiO
2: (150～400) H
2O.
Directed agents mole proportioning is: (5～15) Na
2O: Al
2O
3: (2.0～8) SiO
2: (200～320) H
2O.
Above-mentioned silicon source material can adopt the used silicon source of common preparation molecular sieve, and the present invention is not limited especially, as being waterglass, Na
2SiO
39H
2O, Na
2SiO
4Deng in a kind of;
Above-mentioned aluminium source material can adopt the used aluminium source of common preparation molecular sieve, and the present invention is not limited especially, as can being that aluminium hydroxide, aluminum sulfate, aluminum nitrate, aluminium chloride etc. contain a kind of in the aluminium inorganic compound;
2, adsorbent preparation:
The Si-Al molecular sieve that contains vanadium for preparing is put into the copper salt solution of preparation, dipping 30～720min, filtration, dry under 100～140 ℃ then 450 ℃～650 ℃ following roastings 5～24 hours, promptly makes the adsorbent among the present invention.Dipping, step dry, roasting preferably repeat one to three time.
In the second step adsorbent preparation process, preferably use the supersonic oscillations instrument, equally at 40～100 ℃ of following ultrasonic immersing copper.
The adsorbent that adopts the present invention to obtain has advantages such as adsorption capacity height, reproducibility are good, prolongation in service life.The saturated Sulfur capacity of adsorbent can be stablized and remains on more than the 7.0gS/100g adsorbent among the present invention, apparently higher than the data of domestic relevant bibliographical information.The adsorbent of molecular sieve that use the present invention makes also is applicable to gas purification fields such as CO removes, nitrogen oxide reduction except that being applicable to flue gas desulfurization.
The specific embodiment
Method of testing:
Each components contents adopts following methods analyst respectively among the present invention:
Al
2O
3: EDTA titration among the GB/T3286.3-1998 " mensuration of lime stone, dolomite chemical analysis method alumina amount ";
SiO
2: perchloric acid dehydrated weight method among the GB/T3286.2-1998 " mensuration of lime stone, dolomite chemical analysis method silica volume ";
V
2O
5: GB/T 3257.12-1999 " bauxitic ore chemical analysis method benzoylphenylhydroxyamine spectrphotometric method for measuring vanadic anhydride amount "
CuO content: GB/T 6609.9-2004 " the new cuprous halo degree method of aluminium oxide chemical analysis method and method for measuring physical properties is measured cupric oxide content "
The evaluation method that adsorbent of the present invention is used for flue gas desulfurization is as follows:
The 5g adsorbent is packed in the fixed bed reactors, at 350 ℃, volume space velocity 5000h
-1Feeding the normal pressure flue gas under the condition estimates.Simulated flue gas consists of: SO
2: 800ppm; O
2: 5%; H
2O:5%; Air is a balance gas.SO in the reactant
2Content by gas chromatograph for determination, calculate saturated Sulfur capacity according to analysis result.
The calculating of saturated Sulfur capacity is carried out according to following formula among the present invention:
In the formula: f
i(t), be with L
iC
iTo adsorption time mapping, the fitting function that obtains;
f
o(t), be with L
oC
oTo adsorption time mapping, the fitting function that obtains;
T---adsorption time, min;
The quality of m---adsorbent, g;
L
i---the gas flow of reactor inlet, ml/min;
L
o---the gas flow of reactor outlet, ml/min;
C
i---SO in the reactor inlet gas
2Content, V%;
C
o---SO in the reactor outlet gas
2Content, V%;
Embodiment 1
Be slowly to drip 20g waterglass (SiO in 10% the aluminum sulfate aqueous solution under agitation to 50ml concentration
225.5%, Na
2O9.3%, H
2O65.2%), be warming up to 70 ℃, regulate pH=8.5, add directed agents (12Na
2O: Al
2O
3: 5SiO
2: 28OH
2O), stir filtration washing behind the 30min, add 10g concentration again and be the ammonia spirit of 5% vanadic anhydride, add the granulation of 2ml polyacrylic acid extrusion, drying 400 ℃ of following roastings 4 hours, promptly makes the molecular sieve that contains vanadium, its SiO
2/ Al
2O
3Be 3.4.
Embodiment 2
Under agitation in 20ml 10% aluminum nitrate aqueous solution, slowly drip the Na of 160g20%
2SiO
39H
2O solution is warming up to 90 ℃, regulates pH=9.5, adds directed agents (8Na
2O: Al
2O
3: 8SiO
2: 300H
2O), filtration washing behind the stirring 60min adds 10g 5%NH
4VO
3Ammonia spirit, add the granulation of 2ml polyvinyl alcohol extrusion, dry back promptly makes the molecular sieve that contains vanadium, its SiO 600 ℃ of following roastings 2 hours
2/ Al
2O
3Be 6.8.
Embodiment 3
Take by weighing the molecular sieve that 5g embodiment 1 makes, after vacuumizing, adding 100ml concentration is 10% Cu (SO
4)
2Solution places on the supersonic oscillations instrument, floods 600min down for 50 ℃ in supersonic frequency 30kHz, temperature, and 450 ℃ of roastings of Muffle furnace 12 hours are put in filtration, dry under 120 ℃ then, promptly make adsorbent XF-1.
Embodiment 4
Take by weighing the product that 5g embodiment 1 makes, after vacuumizing, adding 150ml concentration is 10% Cu (NO
3)
2Solution places on the supersonic oscillations instrument, floods 240min down for 85 ℃ in supersonic frequency 45kHz, temperature, and 500 ℃ of roastings of Muffle furnace 8 hours are put in filtration, dry under 100 ℃ then, promptly make adsorbent XF-2.
Embodiment 5
Take by weighing the product that 5g embodiment 2 makes, after vacuumizing, adding 100ml concentration is 10% Cu (NO
3)
2Solution places on the supersonic oscillations instrument, at 90 ℃ of supersonic frequency 50kHz, temperature dipping 120min down, filter, 100 ℃ dry down, put into 550 ℃ of roastings of Muffle furnace 4 hours then, repeat above dipping, baking operation 2 times, promptly make adsorbent XF-3.
Embodiment 6
Take by weighing the product that 5g embodiment 2 makes, after vacuumizing, adding 100ml concentration is 30% CuCl
2Solution places on the supersonic oscillations instrument, floods 60min down for 90 ℃ in supersonic frequency 60kHz, temperature, and 500 ℃ of roastings of Muffle furnace 16 hours are put in filtration, dry under 120 ℃ then, promptly make adsorbent XF-4.
Embodiment 7
Take by weighing the 5g modenite (commercially available, SiO
2/ Al
2O
3: 5), add 10g concentration and be the ammonia spirit of 5% vanadic anhydride, add the 2ml polyacrylic acid, the extrusion granulation of dry back places 600 ℃ of roastings of Muffle furnace 6 hours.Take by weighing the good particle of 5g roasting, adding 100ml concentration is 30% Cu (NO
3)
2Solution floods 600min down for 60 ℃ in temperature, and 650 ℃ of roastings of Muffle furnace 12 hours are put in filtration, dry under 120 ℃ then, promptly make adsorbent XF-5.
Embodiment 8
Take by weighing the 5g Y zeolite (commercially available, SiO
2/ Al
2O
3: 7), add the 0.8g vanadic anhydride, 550 ℃ of roastings of Muffle furnace 12 hours are put in the granulation of 5ml polyacrylamide extrusion, add 100ml concentration then and be 10% Cu (NO
3)
2Solution floods 120min down for 90 ℃ in temperature, and filtration washing is dry under 120 ℃, 550 ℃ of following roastings 8 hours, promptly makes adsorbent XF-6.
Embodiment 9
Take by weighing 5g ZSM-5 molecular sieve (commercially available, SiO
2/ Al
2O
3: 10), add 15ml concentration and be the ammonia spirit of 10% vanadic anhydride, add the 5ml polyacrylic acid, the extrusion granulation, 500 ℃ of following roastings are 8 hours in Muffle furnace.Particle after the title 5g roasting, adding 100ml concentration are 30% Cu (NO
3)
2Solution floods 100min down for 95 ℃ in temperature, and filtration washing, dry under 100 ℃ is put into 550 ℃ of roastings of Muffle furnace then and promptly made adsorbent XF-7 in 4 hours.
Embodiment 10
Take by weighing 5g 5A molecular sieve (commercially available, SiO
2/ Al
2O
3: 2), add 10ml 5%NH
4VO
3Ammonia spirit, add 5ml five polyaluminium chlorides, the extrusion granulation, 550 ℃ of roastings are 4 hours in Muffle furnace, claim the particle after the 5g roasting, add 20% Cu (SO
4)
2Solution 300ml and 10% MgSO
4Solution 50ml places on the supersonic oscillations instrument, floods 120min down for 100 ℃ in supersonic frequency 50kHz, temperature, and 550 ℃ of roastings of Muffle furnace 4 hours are put in filtration, dry under 100 ℃ then, promptly make adsorbent XF-8.
Embodiment 11
Take by weighing the adsorbent XF-2 that 5g embodiment 4 makes, add 10% Ti (SO
4)
2Solution 50ml adds 10% Fe (NO again
3)
3Solution 50ml floods 240min down for 90 ℃ in temperature, and 500 ℃ of roastings of Muffle furnace 4 hours are put in filtration, dry under 100 ℃ then, promptly make adsorbent XF-9.
Embodiment 12
Take by weighing the adsorbent XF-2 that 5g embodiment 4 makes, add 10% Ni (NO
3)
2Solution 50ml adds 10% Co (NO again
3)
3Solution 50ml floods 240min down for 85 ℃ in temperature, and 500 ℃ of roastings of Muffle furnace 4 hours are put in filtration, dry under 100 ℃ then, promptly make adsorbent XF-10.
Embodiment 13
Take by weighing the adsorbent XF-1 that 5g embodiment 3 makes, add 10% ZnCl
2Solution 50ml adds 10% Cr (NO again
3)
3Solution 50ml places on the supersonic oscillations instrument, floods 120min down for 90 ℃ in supersonic frequency 50kHz, temperature, filters, and is dry under 100 ℃, puts into 500 ℃ of roastings of Muffle furnace 4 hours, promptly makes adsorbent XF-11.
Embodiment 14
Take by weighing the adsorbent XF-1 that 5g embodiment 3 makes, add 10% AgNO
3Solution 50ml,, flood 240min down for 90 ℃ in temperature, 550 ℃ of roastings of Muffle furnace 4 hours are put in filtration, dry under 120 ℃, promptly make adsorbent XF-12.
Embodiment 15
Take by weighing the adsorbent XF-3 that 5g embodiment 5 makes, add 10% (NH
4)
6Mo
7O
24Solution 100ml places on the supersonic oscillations instrument, floods 120min down for 90 ℃ in supersonic frequency 50kHz, temperature, and 550 ℃ of roastings of Muffle furnace 4 hours are put in filtration, dry under 120 ℃, promptly make adsorbent XF-13.
Embodiment 16
Take by weighing respectively 2.5gY type molecular sieve (commercially available, SiO
2/ Al
2O
3: 7) and the 2.5g modenite (commercially available, SiO
2/ Al
2O
3: 6), mix, add the 1.5g vanadic anhydride, 550 ℃ of roastings of Muffle furnace 12 hours are put in the granulation of 5ml polyacrylamide extrusion, add 100ml concentration then and be 30% Cu (NO3)
2Solution floods 120min down for 90 ℃ in temperature, and filtration washing is dry under 120 ℃, 550 ℃ of following roastings 8 hours, promptly makes adsorbent XF-14.
Comparative Examples 1
Method by embodiment 2 prepares molecular sieve, but does not add NH
4VO
3Ammonia spirit, prepared molecular sieve according to the method for embodiment 3 dipping Cu, is made adsorbent DB-1.
Comparative Examples 2
Take by weighing the molecular sieve that 5g embodiment 2 makes, after vacuumizing, adding 100ml concentration is 30% FeCl
3Solution places on the supersonic oscillations instrument, floods 60min down for 90 ℃ in supersonic frequency 60kHz, temperature, and 500 ℃ of roastings of Muffle furnace 16 hours are put in filtration, dry under 120 ℃ then, promptly make adsorbent DB-2.
Comparative Examples 3
Take by weighing the adsorbent DB-1 of preparation in the 5g Comparative Examples 1, add 20% Co (NO
3)
3Solution 100ml floods 240min down at 80 ℃, and 450 ℃ of roastings of Muffle furnace 12 hours are put in filtration, dry under 120 ℃ then, promptly make adsorbent DB-3.
Comparative Examples 4
Method according to embodiment 8 prepares adsorbent, and the amount of vanadic anhydride changes into and adds 3g, and other preparation conditions are constant, make adsorbent DB-4.
Through evaluation test, the saturated Sulfur capacity of adsorbent is as shown in table 1 in each embodiment and the Comparative Examples:
Table 1 adsorbent evaluation test result
Claims (9)
1. an adsorbent of molecular sieve is used for flue gas desulfurization, it is characterized in that in mass percent, and its composition contains: Si-Al molecular sieve: 65%～95.9%, and V
2O
5: 0.1%～5%, CuO:4%～30%; Adsorbent of molecular sieve is to adopt oxide or the salt that adds vanadium in Si-Al molecular sieve, extrusion, granulation behind the adding adhesive, 350～650 ℃ of following roastings 5～24 hours, put it in the soluble copper salting liquid, dipping 30～720min, filtration, dry under 100～140 ℃ obtains in 5～24 hours method of 450 ℃～650 ℃ following roastings then.
2. adsorbent of molecular sieve according to claim 1 is characterized in that V
2O
5Content is 1%～4%.
3. adsorbent of molecular sieve according to claim 1, the content that it is characterized in that CuO is 10%～25%.
4. adsorbent of molecular sieve according to claim 1, it is characterized in that adsorbent also contains one or more elements in boron, aluminium, magnesium, titanium, chromium, manganese, iron, cobalt, nickel, zinc, zirconium, molybdenum, silver, platinum, rhenium or the lanthanide series, its oxide content is 0%～5%.
5. adsorbent of molecular sieve according to claim 4 is characterized in that containing in the adsorbent one or more elements in magnesium, iron, nickel, zinc, cobalt, chromium, titanium, silver, zirconium, the molybdenum.
6. adsorbent of molecular sieve according to claim 1 is characterized in that Si-Al molecular sieve is selected from one or more in y-type zeolite, chabasie, ZSM-5, the modenite.
7. adsorbent of molecular sieve according to claim 1 is characterized in that Si-Al molecular sieve is a y-type zeolite.
8. adsorbent of molecular sieve according to claim 1 is characterized in that the SiO of y-type zeolite
2/ Al
2O
3Be 2～7.
9. adsorbent of molecular sieve according to claim 1 is characterized in that flooding 30～720min and is meant that the copper salt solution that will be added with carrier places on the supersonic oscillations instrument, carries out ultrasonic immersing under 40～100 ℃, and the ultrasound wave irradiation frequency is 10～60kHz.
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