CN105032389B - Mn Ce bimetal-doped activated carbon base desulphurization catalysts and preparation method thereof - Google Patents
Mn Ce bimetal-doped activated carbon base desulphurization catalysts and preparation method thereof Download PDFInfo
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- CN105032389B CN105032389B CN201510439617.8A CN201510439617A CN105032389B CN 105032389 B CN105032389 B CN 105032389B CN 201510439617 A CN201510439617 A CN 201510439617A CN 105032389 B CN105032389 B CN 105032389B
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- activated carbon
- nitrate solution
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- nitric acid
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 254
- 239000003054 catalyst Substances 0.000 title claims abstract description 150
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 110
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 66
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000011572 manganese Substances 0.000 claims abstract description 53
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 33
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 31
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 10
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 49
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 238000001354 calcination Methods 0.000 claims description 20
- 238000000967 suction filtration Methods 0.000 claims description 18
- 230000007935 neutral effect Effects 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 46
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 abstract description 27
- 239000011593 sulfur Substances 0.000 abstract description 27
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 52
- 230000023556 desulfurization Effects 0.000 description 26
- 239000007789 gas Substances 0.000 description 25
- 239000003546 flue gas Substances 0.000 description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 238000010306 acid treatment Methods 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000003009 desulfurizing effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009102 absorption Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- -1 Nitric Acid Modified Activated carbon Chemical class 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical class [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical class O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of Mn Ce bimetal-dopeds activated carbon base desulphurization catalyst and preparation method thereof, desulphurization catalyst is using the activated carbon through Nitric Acid Modified as carrier, using metal Mn and Ce as active component, active component is supported on carrier by dipping, nitrogen atmosphere high-temperature calcination, and wherein Mn and Ce load capacity are 1 7wt% of catalyst weight.Desulphurization catalyst preparation method, first activated carbon is immersed in nitric acid and is modified, modified activated carbon is immersed in the mixed solution of manganese nitrate solution and iron nitrate solution again, active component Mn and Ce is set to be supported on modified active high-area carbon, then the modified activated carbon for having loaded Mn and Ce is inserted in calciner, it is fully calcined in 250 DEG C 650 DEG C under nitrogen atmosphere, that is, prepare desulphurization catalyst.Desulphurization catalyst prepared by the present invention, the desulfuration efficiency at a temperature of 80 DEG C is up to 100%, and work Sulfur capacity may be up to 207mgSO2/ g catalyst.
Description
Technical field
The present invention relates to a kind of activated carbon base desulphurization catalyst, more specifically, it is related to a kind of for flue gas desulfurization
The activated carbon base desulphurization catalyst of Mn, Ce bimetal-doped using activated carbon as carrier.
Background technology
Activated carbon because of it there is higher stability, bigger serface and special surface chemistry to be widely used in cigarette
Desulfurization.Commercial charcoal base desulphurization catalyst typically has the pore structure of prosperity and various functional groups, for SO in removing flue gas2Carry
The activated centre of absorption and catalysis oxidation has been supplied, its adsorption capacity is improved by improving its pore structure and surface chemistry
And Sulfur capacity, it prepares general also all to take into account simultaneously and regenerates the factors such as difficulty or ease, mechanical strength, raw material sources and price.Existing skill
The preparation of the charcoal base desulphurization catalyst of art, mainly has two methods, a kind of is by activearm parting by way of dipping at present
Belong to ion load on the activated carbon, another is reshaping after active component, carrier and binding agent etc. are blended.
Publication No. CN103706228A patent document discloses a kind of pre-reduction type manganese systems desulfurizing agent, mainly by following
The raw material of weight/mass percentage composition is made：Activity oxidation manganese 30%~85%, metal oxide 0%~40%, auxiliary agent 12.7%~
30%；The metal oxide is the one or more in activated ferric oxide, active copper oxide and activated zinc oxide；The auxiliary agent
It is made up of the composition of following weight/mass percentage composition：Mineral additive 93.3%~96.7%, sodium carboxymethylcellulose 3.3%~
6.7%；The mineral additive is the one or more in high-alumina fly, kaolin and bentonite.In addition, it is pre- also to also disclose this
The preparation method of prototype manganese systems desulfurizing agent.
Publication No. CN103706227A discloses a kind of preparation method of normal temperature compound desulfurizer, by soluble cobalt
0.05-0.5mol/L urea is added in salt and the mixed solution of soluble ferric iron salt, the pH of manganese hydrogen sodium regulating solution is added
It is worth for 7.2-7.5；It it is 130-140 DEG C in temperature, pressure is prepared for 0.5-2 hours for reaction under the conditions of 0.12-0.15Mpa to be contained
The FeOOH precipitation particle of cobalt；After the FeOOH precipitation particle dipping zinc salt, in oxygen-containing atmosphere, 250-300
Fluosolids roasting under the conditions of DEG C, produces desulfurizing agent product.The patent inventor thinks, the composite desulfurizing agent prepared using this method,
Compared to desulfurizing agent of the prior art, there is higher Sulfur capacity under normal temperature condition.
Activated carbon is widely used in flue gas desulfurization as a kind of adsoption catalysis material.Active carbon desulfurization is to utilize activated carbon
Sulphur ressource in sulfur dioxide in the absorption of material and catalytic performance removing flue gas, flue gas can be more with product sulfuric acid or sulphur etc.
The form of kind is recycled, the Sulphur ressource in recovered flue gas during smoke gas treatment.The desulfurization performance of activated carbon is by its table
What face physical arrangement and Surface chemical characteristic were together decided on.At present, the surface modifying method of activated carbon mainly has following several：With
Oxidant carries out oxidation processes to activated carbon, changes the oxygen-containing functional group species and content of activated carbon surface；It is thermally treated to change
The adsorption activity position of activated carbon surface；In activated carbon surface carried metal or metal oxide, to strengthen the catalysis oxygen of activated carbon
Change ability.It can significantly strengthen the desulphurizing activated of activated carbon in activated carbon surface carried metal compound, and metal is negative
Carrying capacity, species and calcining heat etc. and the desulfurization performance of carbon base catalyst are closely related.The quality of desulphurization catalyst, current ability
The main desulphurizing ability from desulphurization catalyst in domain, Sulfur capacity are evaluated.
With the intensification of haze weather harm understanding healthy to people, people are more next to the hope for improving atmospheric environment
More urgent, desulfurization catalyst of flue gas of the research and development with higher desulphurizing ability and Sulfur capacity, is still this area scientific worker
The key subjects of facing.
The content of the invention
For the desulphurization catalyst state of the art and not enough, of the invention goal of the invention for smoke gas treatment of prior art
A kind of Mn-Ce bimetal-dopeds activated carbon base desulfurization catalyst of flue gas and preparation method thereof is aimed to provide, to improve desulfurization catalyst
The Sulfur capacity and desulphurizing ability of agent.
The Mn-Ce bimetal-doped activated carbon base desulphurization catalysts that the present invention is provided, its composition is with through Nitric Acid Modified
Activated carbon is carrier, using metal Mn and Ce as active component, and active component is supported on load by dipping, nitrogen atmosphere high-temperature calcination
On body, wherein Mn load capacity is the 1-7wt% of desulphurization catalyst weight, and Ce load capacity is the 1- of desulphurization catalyst weight
7wt%.
In the above-mentioned technical proposal of the present invention, Mn load capacity is preferably the 4-6wt% of desulphurization catalyst weight, enters one
Step, be the 5wt% of desulphurization catalyst weight；Ce load capacity is preferably the 2-4wt% of desulphurization catalyst weight, further
, it is the 3wt% of desulphurization catalyst weight.
Above-described Mn-Ce bimetal-dopeds activated carbon base desulphurization catalyst, can be walked by mainly including following technique
It is prepared by rapid method：
(1) activated carbon is immersed in the nitric acid that weight concentration is 15-55%, stands and be no less than 2 hours after stirring；
(2) activated carbon being sufficiently impregnated through nitric acid, it is neutral, then suction filtration, drying to be cleaned after filtering with water to eluate,
Obtain the activated carbon through Nitric Acid Modified；
(3) manganese nitrate is prepared respectively according to desulphurization catalyst Mn load capacity, Ce load capacity and element conservation law
Solution and iron nitrate solution, then mix two kinds of solution；
(4) activated carbon through Nitric Acid Modified is immersed in the mixed solution of manganese nitrate solution and iron nitrate solution, stirs
Stand and be no less than 2 hours afterwards, being evaporated liquid phase makes Mn and Ce be immersed on modified activated carbon；
(5) modified activated carbon impregnated of Mn and Ce is placed in calciner, under nitrogen atmosphere in 250 DEG C -650 DEG C
It is fully calcined, that is, obtain the desulphurization catalyst to be prepared.
In the technical scheme of the above-mentioned preparation method of the present invention, activated carbon is immersed in nitric acid and is modified, and typically adopts
With weight concentration 15-55wt.% nitric acid, activated carbon is immersed in stirred in nitric acid after, the time of standing is generally 8-12
Hour, usually stay overnight, be modified activated carbon.When the concentration of nitric acid is higher, it can be diluted, made by adding water
Salpeter solution just submerged activated carbon.
In the technical scheme of the above-mentioned preparation method of the present invention, the activated carbon after hydrogen nitrate dipping is cleaned through filtering, water, taken out
After filter, most it is better than 80 DEG C of -120 DEG C of drying.
In the technical scheme of the above-mentioned preparation method of the present invention, the activated carbon through Nitric Acid Modified is immersed in manganese nitrate solution
After being stirred in the mixed solution of iron nitrate solution, the time of standing is generally 8-12 hours, usually stays overnight, Zhi Houxian
Water bath method is carried out, liquid phase is dried again after being evaporated, and Mn and Ce is immersed on modified activated carbon；Further, through nitric acid
Modified activated carbon is immersed in manganese nitrate solution and the mixed solution of iron nitrate solution stirred standing after 8-12 hours, preferentially
It is used in water bath method at 50 DEG C -70 DEG C；Liquid phase is preferentially used at 80 DEG C -120 DEG C after being evaporated and dried.
In the technical scheme of the above-mentioned preparation method of the present invention, it is placed in calcining impregnated of Mn and Ce modified activated carbon and sets
In standby, preferentially it is used in nitrogen gas purity and is not less than the high pure nitrogen atmosphere of weight fraction 99.99% and calcined；Calcining heat is excellent
First select 400 DEG C -500 DEG C.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present invention is provided, is with the work through Nitric Acid Modified
Property charcoal be matrix, using metal Mn and Ce as active component, active component is supported on by base by dipping, nitrogen atmosphere high-temperature calcination
A kind of activated carbon base desulphurization catalyst for being totally different from prior art obtained on body.The double gold of Mn-Ce provided by the present invention
Belong to dopped activated carbon base desulphurization catalyst, with very high desulfurization performance, the desulfuration efficiency at a temperature of 80 DEG C is reachable
100%, work Sulfur capacity is more than 85mgSO2/ g catalyst, reaches as high as 207mgSO2/ g catalyst, than the activity of prior art
The Sulfur capacity of charcoal base desulphurization catalyst is greatly improved.
Brief description of the drawings
The desulphurization catalyst desulfuration efficiency and the graph of relation of time of Fig. 1 difference cerium load capacity.
The desulphurization catalyst desulfuration efficiency and the graph of relation of time of Fig. 2 difference calcining heats.
Fig. 3 differences manganese, the desulphurization catalyst desulfuration efficiency and the graph of relation of time of cerium load capacity.
The desulphurizing activated evaluating apparatus schematic diagram of Fig. 4 desulphurization catalysts.
Each shown by reference numeral represents that object is respectively in Fig. 4：1- gases (sulfur dioxide, nitrogen) steel cylinder；2- pressure-reducing valves；3- turns
Subflow gauge；4- air pumps；5- hybrid bottles；6- surge flasks；7- saturation humidifiers；8- thermostatic water-circulator baths；9- reactor jackets
Water-circulating pump；10- triple valves；11- reactors；12- sampling bottles；13- tail gas absorptions bottle；14- wet gas flow meters.
Specific embodiment
The present invention is specifically described below by embodiment, but it is necessarily pointed out that, embodiment is only used
It is further detailed in the present invention, it is impossible to be interpreted as limiting the scope of the invention, person skilled in art
It is to be not required to pay creative labor to make some nonessential modifications and adaptations to carry out specific implementation according to the content of the invention described above
Dynamic, protection scope of the present invention should be still fallen within.
In the various embodiments of the invention, the relative content of each component and number content, in addition to special instruction, be
Percetage by weight content and parts by weight content.
The desulphurization catalyst of various embodiments of the present invention, its desulphurizing activated evaluates is carried out using the system shown in accompanying drawing 4.Simulation
Gas (SO2、N2、O2) first pass through after spinner flowmeter control flow into well mixed in gas mixing bottle then slow by gas
Bottle is rushed to mix with 80 DEG C of vapor into saturation humidifier.All via the hydrogen peroxide and SO that over-richness is 3% before and after gas reaction2
The absorbing liquid that indicator is prepared into, when solution colour is gradually reddened by blue-green, illustrates there is SO2Penetrate, and be with concentration
0.01mol/L NaOH titration determines SO in solution2Content, the total flow of mixed gas is determined with wet flow indicator.With SO2Go out
Mouth concentration is just over 200mg/m3For catalyst breakthrough point, calculate catalyst Sulfur capacity and draw catalyst desulfurizing curve.
Embodiment 1
Activated carbon (AC) is placed in beaker, the nitric acid that weight fraction is 39% is added, nitric acid submergence AC is well mixed close
After envelope stands about 12 hours, it is neutral to be cleaned with water to eluate, and suction filtration obtains changing through nitric acid treatment after about 110 DEG C of drying
The activated carbon of property, is designated as NAC.30g NAC are weighed, the load capacity according to Mn is the 5wt% of catalyst weight, Ce load capacity is
The 1wt% of catalyst weight, and element conservation law, the consumption of manganese nitrate solution and cerous nitrate solution needed for calculating,
Manganese nitrate solution and cerous nitrate solution are prepared respectively.NAC is added after the manganese nitrate solution prepared and cerous nitrate solution are mixed,
Stir after one evening of standing, be evaporated in 60 DEG C or so water-baths, be finally placed in drying box and a 12h left sides are dried in about 105 DEG C
It is right.Inserted after drying in resistance furnace, with N2(high pure nitrogen, 99.99%) is protection gas, in calcining 2h or so at about 650 DEG C, is obtained
To desulphurization catalyst, labeled as 5%Mn+1%Ce/NAC.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present embodiment is provided, be in reaction velocity
1809h-1, bed temperature are 80 DEG C, SO2Entrance concentration is 2500ppm or so, O2Content is that 10%, water vapour content is
Under conditions of 10.4%, evaluate desulphurizing activated.Desulfuration efficiency and the graph of a relation of time are shown in Fig. 1, work Sulfur capacity (SO2Exit concentration
Reach 200mg/m3When catalyst remove SO2Amount) be 90mgSO2/ g catalyst, the working time is 161min (table 1).
Embodiment 2
Activated carbon (AC) is placed in beaker, the nitric acid that weight fraction is 25% is added, nitric acid submergence AC is well mixed close
After envelope stands about 12 hours, it is neutral to be cleaned with water to eluate, and suction filtration obtains changing through nitric acid treatment after about 105 DEG C of drying
The activated carbon of property, is designated as NAC.30g NAC are weighed, the load capacity according to Mn is the 5wt% of catalyst weight, Ce load capacity is
The 2wt% of catalyst weight, and element conservation law, the consumption of manganese nitrate solution and cerous nitrate solution needed for calculating,
Manganese nitrate solution and cerous nitrate solution are prepared respectively.NAC is added after the manganese nitrate solution prepared and cerous nitrate solution are mixed,
Stir after one evening of standing, be evaporated in 70 DEG C or so water-baths, be finally placed in drying box and a 12h left sides are dried in about 115 DEG C
It is right.Inserted after drying in resistance furnace, with N2(high pure nitrogen, 99.99%) is protection gas, in calcining 2h or so at about 650 DEG C, is obtained
To desulphurization catalyst, labeled as 5%Mn+2%Ce/NAC.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present embodiment is provided, be in reaction velocity
1809h-1, bed temperature are 80 DEG C, SO2Entrance concentration is 2500ppm or so, O2Content is that 10%, water vapour content is
Under conditions of 10.4%, evaluate desulphurizing activated.Desulfuration efficiency and the graph of a relation of time are shown in Fig. 1, work Sulfur capacity (SO2Exit concentration
Reach 200mg/m3When catalyst remove SO2Amount) be 85mgSO2/ g catalyst, the working time is 162min (table 1).
Embodiment 3
Activated carbon (AC) is placed in beaker, the nitric acid that weight fraction is 45% is added, nitric acid submergence AC is well mixed close
After envelope stands about 10 hours, it is neutral to be cleaned with water to eluate, and suction filtration obtains changing through nitric acid treatment after about 100 DEG C of drying
The activated carbon of property, is designated as NAC.30g NAC are weighed, the load capacity according to Mn is the 5wt% of catalyst weight, Ce load capacity is
The 3wt% of catalyst weight, and element conservation law, the consumption of manganese nitrate solution and cerous nitrate solution needed for calculating,
Manganese nitrate solution and cerous nitrate solution are prepared respectively.NAC is added after the manganese nitrate solution prepared and cerous nitrate solution are mixed,
Stir after one evening of standing, be evaporated in 55 DEG C or so water-baths, be finally placed in drying box and a 10h left sides are dried in about 115 DEG C
It is right.Inserted after drying in resistance furnace, with N2(high pure nitrogen, 99.99%) is protection gas, in calcining 2h or so at about 650 DEG C, is obtained
To desulphurization catalyst, labeled as 5%Mn+3%Ce/NAC.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present embodiment is provided, be in reaction velocity
1809h-1, bed temperature are 80 DEG C, SO2Entrance concentration is 2500ppm or so, O2Content is that 10%, water vapour content is
Under conditions of 10.4%, evaluate desulphurizing activated.Desulfuration efficiency and the graph of a relation of time are shown in Fig. 1, work Sulfur capacity (SO2Exit concentration
Catalyst removes SO when reaching 200mg/m32Amount) be 114mgSO2/g catalyst, the working time be 213min (table 1).
Embodiment 4
Activated carbon (AC) is placed in beaker, the nitric acid that weight fraction is 30% is added, nitric acid submergence AC is well mixed close
After envelope stands about 12 hours, it is neutral to be cleaned with water to eluate, and suction filtration obtains changing through nitric acid treatment after about 100 DEG C of drying
The activated carbon of property, is designated as NAC.30g NAC are weighed, the load capacity according to Mn is the 5wt% of catalyst weight, Ce load capacity is
The 4wt% of catalyst weight, and element conservation law, the consumption of manganese nitrate solution and cerous nitrate solution needed for calculating,
Manganese nitrate solution and cerous nitrate solution are prepared respectively.NAC is added after the manganese nitrate solution prepared and cerous nitrate solution are mixed,
Stir after one evening of standing, be evaporated in 65 DEG C or so water-baths, be finally placed in drying box and a 12h left sides are dried in about 105 DEG C
It is right.Inserted after drying in resistance furnace, with N2(high pure nitrogen, 99.99%) is protection gas, in calcining 2h or so at about 650 DEG C, is obtained
To desulphurization catalyst, labeled as 5%Mn+4%Ce/NAC.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present embodiment is provided, be in reaction velocity
1809h-1, bed temperature are 80 DEG C, SO2Entrance concentration is 2500ppm or so, O2Content is that 10%, water vapour content is
Under conditions of 10.4%, evaluate desulphurizing activated.Desulfuration efficiency and the graph of a relation of time are shown in Fig. 1, work Sulfur capacity (SO2Exit concentration
Reach 200mg/m3When catalyst remove SO2Amount) be 113mgSO2/ g catalyst, the working time is 207min (table 1).
Embodiment 5
Activated carbon (AC) is placed in beaker, the nitric acid that weight fraction is 50% is added, nitric acid submergence AC is well mixed close
After envelope stands about 12 hours, it is neutral to be cleaned with water to eluate, and suction filtration obtains changing through nitric acid treatment after about 105 DEG C of drying
The activated carbon of property, is designated as NAC.30g NAC are weighed, the load capacity according to Mn is the 5wt% of catalyst weight, Ce load capacity is
The 5wt% of catalyst weight, and element conservation law, the consumption of manganese nitrate solution and cerous nitrate solution needed for calculating,
Manganese nitrate solution and cerous nitrate solution are prepared respectively.NAC is added after the manganese nitrate solution prepared and cerous nitrate solution are mixed,
Stir after one evening of standing, be evaporated in 60 DEG C or so water-baths, be finally placed in drying box and a 11h left sides are dried in about 105 DEG C
It is right.Inserted after drying in resistance furnace, with N2(high pure nitrogen, 99.99%) is protection gas, in calcining 2h or so at about 650 DEG C, is obtained
To desulphurization catalyst, labeled as 5%Mn+5%Ce/NAC.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present embodiment is provided, be in reaction velocity
1809h-1, bed temperature are 80 DEG C, SO2Entrance concentration is 2500ppm or so, O2Content is that 10%, water vapour content is
Under conditions of 10.4%, evaluate desulphurizing activated.Desulfuration efficiency and the graph of a relation of time are shown in Fig. 1, work Sulfur capacity (SO2Exit concentration
Reach 200mg/m3When catalyst remove SO2Amount) be 118mgSO2/ g catalyst, the working time is 208min (table 1).
Embodiment 6
Activated carbon (AC) is placed in beaker, the nitric acid that weight fraction is 39% is added, nitric acid submergence AC is well mixed close
After envelope stands about 12 hours, it is neutral to be cleaned with water to eluate, and suction filtration obtains being modified through nitric acid treatment after about 85 DEG C of drying
Activated carbon, be designated as NAC.30g NAC are weighed, the load capacity according to Mn is the 5wt% of catalyst weight, Ce load capacity is to urge
The 3wt% of agent weight, and element conservation law, the consumption of manganese nitrate solution and cerous nitrate solution needed for calculating, point
Pei Zhi not manganese nitrate solution and cerous nitrate solution.NAC is added after the manganese nitrate solution prepared and cerous nitrate solution are mixed, is stirred
Mix after one evening of uniform standing, be evaporated in 60 DEG C or so water-baths, be finally placed in drying box and dry 12h or so in about 105 DEG C.
Inserted after drying in resistance furnace, with N2(high pure nitrogen, 99.99%) is protection gas, in calcining 2h or so at about 250 DEG C, is obtained
Desulphurization catalyst, labeled as 5%Mn+3%Ce/NAC-250.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present embodiment is provided, be in reaction velocity
1809h-1, bed temperature be 80 DEG C, SO2Entrance concentration is 2500ppm or so, O2Content is that 10%, water vapour content is
Under conditions of 10.4%, evaluate desulphurizing activated.Desulfuration efficiency and the graph of a relation of time are shown in Fig. 2, work Sulfur capacity (SO2Exit concentration
Reach 200mg/m3When catalyst remove SO2Amount) be 85mgSO2/ g catalyst, the working time is 161min (table 2).
Embodiment 7
Activated carbon (AC) is placed in beaker, the nitric acid that weight fraction is 20% is added, nitric acid submergence AC is well mixed close
After envelope stands about 12 hours, it is neutral to be cleaned with water to eluate, and suction filtration obtains changing through nitric acid treatment after about 110 DEG C of drying
The activated carbon of property, is designated as NAC.30g NAC are weighed, the load capacity according to Mn is the 5wt% of catalyst weight, Ce load capacity is
The 3wt% of catalyst weight, and element conservation law, the consumption of manganese nitrate solution and cerous nitrate solution needed for calculating,
Manganese nitrate solution and cerous nitrate solution are prepared respectively.NAC is added after the manganese nitrate solution prepared and cerous nitrate solution are mixed,
Stir after one evening of standing, be evaporated in 60 DEG C or so water-baths, be finally placed in drying box and a 12h left sides are dried in about 105 DEG C
It is right.Inserted after drying in resistance furnace, with N2(high pure nitrogen, 99.99%) is protection gas, in calcining 2h or so at about 350 DEG C, is obtained
To desulphurization catalyst, labeled as 5%Mn+3%Ce/NAC-350.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present embodiment is provided, be in reaction velocity
1809h-1, bed temperature be 80 DEG C, SO2Entrance concentration is 2500ppm or so, O2Content is that 10%, water vapour content is
Under conditions of 10.4%, evaluate desulphurizing activated.Desulfuration efficiency and the graph of a relation of time are shown in Fig. 2, work Sulfur capacity (SO2Exit concentration
Reach 200mg/m3When catalyst remove SO2Amount) be 189mgSO2/ g catalyst, the working time is 350min (table 2).
Embodiment 8
Activated carbon (AC) is placed in beaker, the nitric acid that weight fraction is 20% is added, nitric acid submergence AC is well mixed close
After envelope stands about 12 hours, it is neutral to be cleaned with water to eluate, and suction filtration obtains changing through nitric acid treatment after about 110 DEG C of drying
The activated carbon of property, is designated as NAC.30g NAC are weighed, the load capacity according to Mn is the 5wt% of catalyst weight, Ce load capacity is
The 3wt% of catalyst weight, and element conservation law, the consumption of manganese nitrate solution and cerous nitrate solution needed for calculating,
Manganese nitrate solution and cerous nitrate solution are prepared respectively.NAC is added after the manganese nitrate solution prepared and cerous nitrate solution are mixed,
Stir after one evening of standing, be evaporated in 60 DEG C or so water-baths, be finally placed in drying box and a 12h left sides are dried in about 105 DEG C
It is right.Inserted after drying in resistance furnace, with N2(high pure nitrogen, 99.99%) is protection gas, in calcining 2h or so at about 450 DEG C, is obtained
To desulphurization catalyst, labeled as 5%Mn+3%Ce/NAC-450.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present embodiment is provided, be in reaction velocity
1809h-1, bed temperature be 80 DEG C, SO2Entrance concentration is 2500ppm or so, O2Content is that 10%, water vapour content is
Under conditions of 10.4%, evaluate desulphurizing activated.Desulfuration efficiency and the graph of a relation of time are shown in Fig. 2, work Sulfur capacity (SO2Exit concentration
Reach 200mg/m3When catalyst remove SO2Amount) be 207mgSO2/ g catalyst, the working time is 384min (table 2).
Embodiment 9
Activated carbon (AC) is placed in beaker, the nitric acid that weight fraction is 45% is added, nitric acid submergence AC is well mixed close
After envelope stands about 12 hours, it is neutral to be cleaned with water to eluate, and suction filtration obtains changing through nitric acid treatment after about 100 DEG C of drying
The activated carbon of property, is designated as NAC.30g NAC are weighed, the load capacity according to Mn is the 5wt% of catalyst weight, Ce load capacity is
The 3wt% of catalyst weight, and element conservation law, the consumption of manganese nitrate solution and cerous nitrate solution needed for calculating,
Manganese nitrate solution and cerous nitrate solution are prepared respectively.NAC is added after the manganese nitrate solution prepared and cerous nitrate solution are mixed,
Stir after one evening of standing, be evaporated in 60 DEG C or so water-baths, be finally placed in drying box and a 12h left sides are dried in about 105 DEG C
It is right.Inserted after drying in resistance furnace, with N2(high pure nitrogen, 99.99%) is protection gas, in calcining 2h or so at about 550 DEG C, is obtained
To desulphurization catalyst, labeled as 5%Mn+3%Ce/NAC-550.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present embodiment is provided, be in reaction velocity
1809h-1, bed temperature be 80 DEG C, SO2Entrance concentration is 2500ppm or so, O2Content is that 10%, water vapour content is
Under conditions of 10.4%, evaluate desulphurizing activated.Desulfuration efficiency and the graph of a relation of time are shown in Fig. 2, work Sulfur capacity (SO2Exit concentration
Reach 200mg/m3When catalyst remove SO2Amount) be 165mgSO2/ g catalyst, the working time is 306min (table 2).
Embodiment 10
Activated carbon (AC) is placed in beaker, the nitric acid that weight fraction is 35% is added, nitric acid submergence AC is well mixed close
After envelope stands about 12 hours, it is neutral to be cleaned with water to eluate, and suction filtration obtains changing through nitric acid treatment after about 100 DEG C of drying
The activated carbon of property, is designated as NAC.30g NAC are weighed, the load capacity according to Mn is the 1wt% of catalyst weight, Ce load capacity is
The 7wt% of catalyst weight, and element conservation law, the consumption of manganese nitrate solution and cerous nitrate solution needed for calculating,
Manganese nitrate solution and cerous nitrate solution are prepared respectively.NAC is added after the manganese nitrate solution prepared and cerous nitrate solution are mixed,
Stir after one evening of standing, be evaporated in 60 DEG C or so water-baths, be finally placed in drying box and a 12h left sides are dried in about 105 DEG C
It is right.Inserted after drying in resistance furnace, with N2(high pure nitrogen, 99.99%) is protection gas, in calcining 2h or so at about 450 DEG C, is obtained
To desulphurization catalyst, labeled as 1%Mn+7%Ce/NAC-450.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present embodiment is provided, be in reaction velocity
1809h-1, bed temperature be 80 DEG C, SO2Entrance concentration is 2500ppm or so, O2Content is that 10%, water vapour content is
Under conditions of 10.4%, evaluate desulphurizing activated.Desulfuration efficiency and the graph of a relation of time are shown in Fig. 3, work Sulfur capacity (SO2Exit concentration
Reach 200mg/m3When catalyst remove SO2Amount) be 114mgSO2/ g catalyst, the working time is 211min (table 3).
Embodiment 11
Activated carbon (AC) is placed in beaker, the nitric acid that weight fraction is 39% is added, nitric acid submergence AC is well mixed close
After envelope stands about 12 hours, it is neutral to be cleaned with water to eluate, and suction filtration obtains changing through nitric acid treatment after about 110 DEG C of drying
The activated carbon of property, is designated as NAC.30g NAC are weighed, the load capacity according to Mn is the 2wt% of catalyst weight, Ce load capacity is
The 6wt% of catalyst weight, and element conservation law, the consumption of manganese nitrate solution and cerous nitrate solution needed for calculating,
Manganese nitrate solution and cerous nitrate solution are prepared respectively.NAC is added after the manganese nitrate solution prepared and cerous nitrate solution are mixed,
Stir after one evening of standing, be evaporated in 60 DEG C or so water-baths, be finally placed in drying box and a 12h left sides are dried in about 105 DEG C
It is right.Inserted after drying in resistance furnace, with N2(high pure nitrogen, 99.99%) is protection gas, in calcining 2h or so at about 450 DEG C, is obtained
To desulphurization catalyst, labeled as 2%Mn+6%Ce/NAC-450.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present embodiment is provided, be in reaction velocity
1809h-1, bed temperature be 80 DEG C, SO2Entrance concentration is 2500ppm or so, O2Content is that 10%, water vapour content is
Under conditions of 10.4%, evaluate desulphurizing activated.Desulfuration efficiency and the graph of a relation of time are shown in Fig. 3, work Sulfur capacity (SO2Exit concentration
Reach 200mg/m3When catalyst remove SO2Amount) be 105mgSO2/ g catalyst, the working time is 194min (table 3).
Embodiment 12
Activated carbon (AC) is placed in beaker, the nitric acid that weight fraction is 39% is added, nitric acid submergence AC is well mixed close
After envelope stands about 12 hours, it is neutral to be cleaned with water to eluate, and suction filtration obtains changing through nitric acid treatment after about 110 DEG C of drying
The activated carbon of property, is designated as NAC.30g NAC are weighed, the load capacity according to Mn is the 3wt% of catalyst weight, Ce load capacity is
The 5wt% of catalyst weight, and element conservation law, the consumption of manganese nitrate solution and cerous nitrate solution needed for calculating,
Manganese nitrate solution and cerous nitrate solution are prepared respectively.NAC is added after the manganese nitrate solution prepared and cerous nitrate solution are mixed,
Stir after one evening of standing, be evaporated in 60 DEG C or so water-baths, be finally placed in drying box and a 12h left sides are dried in about 105 DEG C
It is right.Inserted after drying in resistance furnace, with N2(high pure nitrogen, 99.99%) is protection gas, in calcining 2h or so at about 450 DEG C, is obtained
To desulphurization catalyst, labeled as 3%Mn+5%Ce/NAC-450.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present embodiment is provided, be in reaction velocity
1809h-1, bed temperature be 80 DEG C, SO2Entrance concentration is 2500ppm or so, O2Content is that 10%, water vapour content is
Under conditions of 10.4%, evaluate desulphurizing activated.Desulfuration efficiency and the graph of a relation of time are shown in Fig. 3, work Sulfur capacity (SO2Exit concentration
Reach 200mg/m3When catalyst remove SO2Amount) be 95mgSO2/ g catalyst, the working time is 176min (table 3).
Embodiment 13
Activated carbon (AC) is placed in beaker, the nitric acid that weight fraction is 39% is added, nitric acid submergence AC is well mixed close
After envelope stands about 12 hours, it is neutral to be cleaned with water to eluate, and suction filtration obtains changing through nitric acid treatment after about 110 DEG C of drying
The activated carbon of property, is designated as NAC.30g NAC are weighed, the load capacity according to Mn is the 4wt% of catalyst weight, Ce load capacity is
The 4wt% of catalyst weight, and element conservation law, the consumption of manganese nitrate solution and cerous nitrate solution needed for calculating,
Manganese nitrate solution and cerous nitrate solution are prepared respectively.NAC is added after the manganese nitrate solution prepared and cerous nitrate solution are mixed,
Stir after one evening of standing, be evaporated in 60 DEG C or so water-baths, be finally placed in drying box and a 12h left sides are dried in about 105 DEG C
It is right.Inserted after drying in resistance furnace, with N2(high pure nitrogen, 99.99%) is protection gas, in calcining 2h or so at about 450 DEG C, is obtained
To desulphurization catalyst, labeled as 4%Mn+4%Ce/NAC-450.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present embodiment is provided, be in reaction velocity
1809h-1, bed temperature are 80 DEG C, SO2Entrance concentration is 2500ppm or so, O2Content is that 10%, water vapour content is
Under conditions of 10.4%, evaluate desulphurizing activated.Desulfuration efficiency and the graph of a relation of time are shown in Fig. 3, work Sulfur capacity (SO2Exit concentration
Reach 200mg/m3When catalyst remove SO2Amount) be 120mgSO2/ g catalyst, the working time is 222min (table 3).
Embodiment 14
Activated carbon (AC) is placed in beaker, the nitric acid that weight fraction is 39% is added, nitric acid submergence AC is well mixed close
After envelope stands about 12 hours, it is neutral to be cleaned with water to eluate, and suction filtration obtains changing through nitric acid treatment after about 110 DEG C of drying
The activated carbon of property, is designated as NAC.30g NAC are weighed, the load capacity according to Mn is the 6wt% of catalyst weight, Ce load capacity is
The 2wt% of catalyst weight, and element conservation law, the consumption of manganese nitrate solution and cerous nitrate solution needed for calculating,
Manganese nitrate solution and cerous nitrate solution are prepared respectively.NAC is added after the manganese nitrate solution prepared and cerous nitrate solution are mixed,
Stir after one evening of standing, be evaporated in 60 DEG C or so water-baths, be finally placed in drying box and a 12h left sides are dried in about 105 DEG C
It is right.Inserted after drying in resistance furnace, with N2(high pure nitrogen, 99.99%) is protection gas, in calcining 2h or so at about 450 DEG C, is obtained
To desulphurization catalyst, labeled as 6%Mn+2%Ce/NAC-450.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present embodiment is provided, be in reaction velocity
1809h-1, bed temperature are 80 DEG C, SO2Entrance concentration is 2500ppm or so, O2Content is that 10%, water vapour content is
Under conditions of 10.4%, evaluate desulphurizing activated.Desulfuration efficiency and the graph of a relation of time are shown in Fig. 3, work Sulfur capacity (SO2Exit concentration
Reach 200mg/m3When catalyst remove SO2Amount) be 138mgSO2/ g catalyst, the working time is 255min (table 3).
Embodiment 15
Activated carbon (AC) is placed in beaker, the nitric acid that weight fraction is 39% is added, nitric acid submergence AC is well mixed close
After envelope stands about 12 hours, it is neutral to be cleaned with water to eluate, and suction filtration obtains changing through nitric acid treatment after about 110 DEG C of drying
The activated carbon of property, is designated as NAC.30g NAC are weighed, the load capacity according to Mn is the 7wt% of catalyst weight, Ce load capacity is
The 1wt% of catalyst weight, and element conservation law, the consumption of manganese nitrate solution and cerous nitrate solution needed for calculating,
Manganese nitrate solution and cerous nitrate solution are prepared respectively.NAC is added after the manganese nitrate solution prepared and cerous nitrate solution are mixed,
Stir after one evening of standing, be evaporated in 60 DEG C or so water-baths, be finally placed in drying box and a 12h left sides are dried in about 105 DEG C
It is right.Inserted after drying in resistance furnace, with N2(high pure nitrogen, 99.99%) is protection gas, in calcining 2h or so at about 450 DEG C, is obtained
To desulphurization catalyst, labeled as 7%Mn+1%Ce/NAC-450.
The Mn-Ce bimetal-doped activated carbon base desulfurization catalyst of flue gas that the present embodiment is provided, be in reaction velocity
1809h-1, bed temperature are 80 DEG C, SO2Entrance concentration is 2500ppm or so, O2Content is that 10%, water vapour content is
Under conditions of 10.4%, evaluate desulphurizing activated.Desulfuration efficiency and the graph of a relation of time are shown in Fig. 3, work Sulfur capacity (SO2Exit concentration
Reach 200mg/m3When catalyst remove SO2Amount) be 137mgSO2/ g catalyst, the working time is 255min (table 3).
The work Sulfur capacity and time of break-through of the Mn-Ce/NAC catalyst of table 1
The work Sulfur capacity and time of break-through of the Mn-Ce/NAC catalyst of table 2
The work Sulfur capacity and time of break-through of the Mn-Ce/NAC catalyst of table 3
Claims (5)
1. a kind of Mn-Ce bimetal-dopeds activated carbon base desulphurization catalyst, it is characterised in that using the activated carbon through Nitric Acid Modified as
Carrier, using metal Mn and Ce as active component, active component is supported on carrier by dipping, nitrogen atmosphere high-temperature calcination, its
Middle Mn load capacity is the 1-7wt% of desulphurization catalyst weight, and Ce load capacity is the 1-7wt% of desulphurization catalyst weight；
The preparation method of the desulphurization catalyst is mainly comprised the following steps that：
(1) activated carbon is immersed in the nitric acid that weight concentration is 15-55%, 8-12 hours is stood after stirring；
(2) activated carbon being sufficiently impregnated through nitric acid, it is neutral to be cleaned after filtering with water to eluate, and then suction filtration, drying, are obtained
Activated carbon through Nitric Acid Modified；
(3) manganese nitrate solution is prepared respectively according to desulphurization catalyst Mn load capacity, Ce load capacity and element conservation law
And cerous nitrate solution, then two kinds of solution are mixed；
(4) activated carbon through Nitric Acid Modified is immersed in the mixed solution of manganese nitrate solution and cerous nitrate solution, stands 8-12 small
Shi Hou, first in 50 DEG C of -70 DEG C of progress water bath methods, liquid phase is dried at 80 DEG C -120 DEG C again after being evaporated, and impregnates Mn and Ce
On modified activated carbon；
(5) modified activated carbon impregnated of Mn and Ce is placed in calciner, under nitrogen atmosphere in 400 DEG C -500 DEG C fully
Calcining, that is, obtained the desulphurization catalyst to be prepared.
2. Mn-Ce bimetal-dopeds activated carbon base desulphurization catalyst according to claim 1, it is characterised in that the Mn
Load capacity be desulphurization catalyst weight 4-6wt%, Ce load capacity is the 2-4wt% of desulphurization catalyst weight.
3. Mn-Ce bimetal-dopeds activated carbon base desulphurization catalyst according to claim 2, it is characterised in that the Mn
Load capacity be desulphurization catalyst weight 5wt%, Ce load capacity is the 3wt% of desulphurization catalyst weight.
4. Mn-Ce bimetal-dopeds activated carbon base desulphurization catalyst according to claim 1, it is characterised in that nitric acid soaks
Activated carbon after stain is after filtering, water cleaning, suction filtration, in 80 DEG C of -120 DEG C of drying.
5. Mn-Ce bimetal-dopeds activated carbon base desulphurization catalyst according to claim 1, it is characterised in that the nitrogen
Atmosphere encloses the high pure nitrogen atmosphere for being not less than weight fraction 99.99% for nitrogen gas purity.
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