CN108889316A - A kind of denitrating catalyst and preparation method thereof - Google Patents
A kind of denitrating catalyst and preparation method thereof Download PDFInfo
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- CN108889316A CN108889316A CN201810965896.5A CN201810965896A CN108889316A CN 108889316 A CN108889316 A CN 108889316A CN 201810965896 A CN201810965896 A CN 201810965896A CN 108889316 A CN108889316 A CN 108889316A
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- denitrating catalyst
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- tailings
- vanadium extraction
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 50
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 48
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 48
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000605 extraction Methods 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 239000000470 constituent Substances 0.000 claims abstract description 11
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 10
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910001868 water Inorganic materials 0.000 claims description 19
- 238000001125 extrusion Methods 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 7
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 7
- 229910021538 borax Inorganic materials 0.000 claims description 6
- 239000004328 sodium tetraborate Substances 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 5
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003546 flue gas Substances 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 15
- 239000007789 gas Substances 0.000 abstract description 11
- 239000000779 smoke Substances 0.000 abstract description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 25
- 238000012360 testing method Methods 0.000 description 19
- 238000007598 dipping method Methods 0.000 description 12
- 239000012047 saturated solution Substances 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 230000032683 aging Effects 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229940080314 sodium bentonite Drugs 0.000 description 5
- 229910000280 sodium bentonite Inorganic materials 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229940092782 bentonite Drugs 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
Abstract
The present invention provides a kind of denitrating catalyst, including carrier, the carrier includes：Tailings in vanadium extraction, pore creating material and binder；The active constituent of load on the carrier, the active constituent includes alkali formula ferrous sulfate and ferrous sulfate.Compared with prior art, denitrating catalyst mechanical property provided by the invention is good, denitration efficiency is high, and using tailings in vanadium extraction and industrial green vitriol as primary raw material, raw material sources are extensive, and preparation cost is low, while can be realized the high-efficiency comprehensive utilization of residue resource.Denitrating catalyst provided by the invention has a good application prospect, and can be applied to sintering flue gas and administers and thermal power plant smoke gas treatment.The present invention also provides a kind of preparation methods of denitrating catalyst.
Description
Technical field
The present invention relates to catalyst technical fields more particularly to a kind of denitrating catalyst and preparation method thereof.
Background technique
The tailings in vanadium extraction that steel generates 350,000 tons every year is climbed, utilization of resources difficulty is larger.Contain Fe in tailings in vanadium extraction2O3、
TiO2、V2O5、MnO2Isoreactivity ingredient.University Of Chongqing scientific research personnel uses tailings in vanadium extraction for raw material, by adjusting component to prepare flue gas
Denitrating catalyst, denitration efficiency reach 60%, and Northeastern University scientific research personnel, as primary raw material, develops titanium-based using tailings in vanadium extraction
Catalysis material achieves certain effect.In addition, there is research institution to propose that using tailings in vanadium extraction, as primary raw material, exploitation is useless
Treatment catalyst material achieves preferable effect in field of waste water treatment.
But the denitrating catalyst denitration efficiency that the prior art is prepared using tailings in vanadium extraction as primary raw material is lower, limits
The practical application of this denitrating catalyst.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of denitrating catalysts, including：
Carrier, the carrier is by including that the material of tailings in vanadium extraction, pore creating material and binder is prepared；
The active constituent of load on the carrier, the active constituent includes alkali formula ferrous sulfate and ferrous sulfate.
In the present invention, the mass ratio of the tailings in vanadium extraction, pore creating material and binder is preferably (75~85):(10~
20)：(1~7), more preferably (78~82):(12~18)：(2~6), most preferably 80:(14~16)：(3~5).
The present invention does not have special limitation to the type of the tailings in vanadium extraction and source, using known to those skilled in the art
Tailings in vanadium extraction, i.e., the described tailings in vanadium extraction be in vanadic anhydride production process, steel slag (Converter Vanadium-bearing Slag) is through peroxidating
Exhaust gas gurry after sodium roasting, leaching, the tailings in vanadium extraction are preferably sodium tailings in vanadium extraction.In the present invention, the vanadium extraction
Tailings preferably includes：
Fe2O3、TiO2、V2O5、MnO2And sodium salt.
In the present invention, the Fe2O3Mass content in tailings in vanadium extraction is preferably 40~45%, more preferably 41~
44%, most preferably 42~43%；The TiO2Mass content in tailings in vanadium extraction is preferably 10~15%, and more preferably 11
~14%, most preferably 12~13%；The V2O5Mass content in tailings in vanadium extraction is preferably 1~3%, and more preferably 1.5
~2.5%, most preferably 2%；The MnO2Mass content in tailings in vanadium extraction is preferably 7~12%, more preferably 8~
11%, most preferably 9~10%；The sodium salt is preferably sodium metasilicate, and mass content of the sodium salt in tailings in vanadium extraction is preferred
It is 3~8%, more preferably 4~7%, most preferably 5~6%.
In the present invention, the granularity of the tailings in vanadium extraction is preferably 0.1~0.2mm, more preferably 0.12~0.18mm, most
Preferably 0.14~0.16mm.Present invention preferably employs the tailings in vanadium extraction of above-mentioned granularity, the tailings in vanadium extraction of this granularity can be mentioned
The porosity for the carrier that height is prepared, to improve the denitration efficiency for the denitrating catalyst being prepared.
In the present invention, the pore creating material is preferably coke powder.In the present invention, the preferred < of the granularity of the pore creating material
0.1mm, more preferably 0.02~0.08mm, most preferably 0.04~0.06mm, present invention preferably employs the pore-creating of above-mentioned granularity
Agent is entrained in tailings in vanadium extraction, is aoxidized by sintering process, and the porosity for the carrier being prepared is improved, and is prepared into improve
The denitration efficiency of the denitrating catalyst arrived.
In the present invention, the binder preferably includes bentonite, and the bentonite is preferably sodium bentonite.In this hair
In bright, it is also preferable to include boraxs for the binder.In the present invention, the borax and bentonitic mass ratio are preferably A：(1~
5), 0 A≤2 <, more preferably (0.1~1.5)：(2~4), most preferably (0.5~1)：(2.5~3.5).The present invention preferably adopts
With the binder of mentioned kind, these binders have preferable high temperature sintering effect, the carrier tool that the present invention is prepared
There is good mechanical property, to make the denitrating catalyst obtained that there is good mechanical property.
In the present invention, the preparation method of the carrier is preferably：
Tailings in vanadium extraction, pore creating material, binder and water are mixed, mixture is obtained；
The mixture be dried again after extrusion forming, is sintered, carrier is obtained.
In the present invention, described in the type and dosage and above-mentioned technical proposal of the tailings in vanadium extraction, pore creating material and binder
Tailings in vanadium extraction, pore creating material and the type of binder are consistent with dosage, and details are not described herein.In the present invention, the water is mixing
Mass content in material is preferably 3~5%, and more preferably 3.5~4.5%, most preferably 4%.
In the present invention, the mixture is preferably subjected to ageing mixture after obtaining mixture, the ageing mixture is that will obtain
Mixture place a period of time, make binder therein and moisture distribution with improve the uniformity and mouldability of mixture.?
In the present invention, the time of the ageing mixture is preferably 2~5 hours, more preferably 3~4 hours, most preferably 3.5 hours.
In the present invention, the equipment of the extrusion forming is preferably single lead screw ex truding briquetting machine.In the present invention, the extrusion forming
Shaping strength be preferably 1~5MPa, more preferably 2~4MPa, most preferably 2.5~3.5MPa.
In the present invention, temperature dry after the extrusion forming is preferably 100~120 DEG C, more preferably 105~115
DEG C, most preferably 110 DEG C.
In the present invention, the temperature of the sintering is preferably 900~1100 DEG C, and more preferably 950~1050 DEG C, most preferably
It is 1000 DEG C.
The present invention is sintered using special materials such as tailings in vanadium extraction and in 900~1100 DEG C of temperature range, can be had
There is the above-mentioned carrier compared with high porosity.
In the present invention, the active constituent is the alkali formula ferrous sulfate and ferrous sulfate that green vitriol is formed after Overheating Treatment
Molysite ingredient.In the present invention, the load factor of the active constituent in the carrier is preferably 10~20%, more preferably 12~
18%, most preferably 14~16%.
The present invention provides a kind of preparation methods of denitrating catalyst described in above-mentioned technical proposal, including：
Then industrial green vitriol solution loadings are dried and are heat-treated on carrier, denitrating catalyst is obtained.
The present invention does not have special limitation to the type of the industrial green vitriol and source, using known to those skilled in the art
Industrial green vitriol.In the present invention, the industrial green vitriol is preferably the by-product in sulfate process titanium dioxide production process, this hair
Bright is preferably the raw material for preparing denitrating catalyst with this industrial green vitriol, to reduce production cost, realizes the synthesis of waste resource
It utilizes.In the present invention, the mass content of ferrous sulfate heptahydrate is preferably 90% or more in the industrial green vitriol, and more preferably 91
~94%, most preferably 92~93%.In the present invention, the industrial green vitriol solution is preferably the saturated solution of industrial green vitriol,
The present invention preferably is mixed with the industrial green vitriol and water to obtain industrial green vitriol saturated solution.
In the present invention, the method for the load is preferably to be loaded using the method for dipping, more preferably using true
The method of sky dipping is loaded.In the present invention, the time of the dipping is preferably 2~5 hours, and more preferably 3~4 is small
When, most preferably 3.5 hours.In the present invention, the vacuum degree of the dipping is preferably 0.06~0.1MPa, and more preferably 0.07
~0.09MPa, most preferably 0.08MPa.
In the present invention, the carrier is consistent with carrier described in above-mentioned technical proposal, and details are not described herein.In the present invention
In, the load factor of the industry green vitriol is consistent with the load factor of active constituent described in above-mentioned technical proposal, and details are not described herein.
In the present invention, the drying after the load preferably carries out under protective atmosphere, and the protective atmosphere is preferred
For inert gas, the inert gas is preferably argon gas.In the present invention, the drying temperature after the load be preferably 100~
120 DEG C, more preferably 105~115 DEG C, most preferably 110 DEG C.
In the present invention, the temperature of the heat treatment is preferably 200~500 DEG C, and more preferably 250~450 DEG C, most preferably
It is 300~400 DEG C.In the present invention, preferably under protective atmosphere, the protective atmosphere is preferably inertia for the heat treatment
Gas, more preferably nitrogen.
The preparation method process flow of denitrating catalyst provided in an embodiment of the present invention is as shown in Figure 1, include：
Tailings in vanadium extraction is sieved, the tailings in vanadium extraction that granularity is 0.1~0.2mm is obtained；
Above-mentioned tailings in vanadium extraction and coke powder, bentonite, borax and water are mixed, ageing mixture is then carried out, obtains mixture；
The mixture is subjected to extrusion forming, obtains green body；
The idiosome is dried, is sintered, catalyst carrier is obtained；
Industrial green vitriol and water are mixed, the saturated solution of industrial green vitriol is prepared；
Catalyst carrier is subjected to vacuum impregnation in the saturated solution of the industrial green vitriol；
Product after vacuum impregnation is dried in nitrogen atmosphere；
Product after drying is heat-treated (sintering) in nitrogen atmosphere, obtains denitrating catalyst.
The present invention uses above-mentioned specified raw material and raw material proportioning and the denitration being prepared in conjunction with above-mentioned ad hoc approach is urged
Agent has good mechanical performance, and compressive resistance has reached 7MPa or more, and has good denitration performance, optimal
For denitration temperature at 300~400 DEG C, denitration efficiency reaches 70% or more.
Denitrating catalyst provided by the invention is using tailings in vanadium extraction and industrial green vitriol as primary raw material, using extrusion forming process
And sintering process is prepared, and forms the denitrating catalyst having compared with high porosity, denitration efficiency reaches 70% or more.With
Traditional V-Ti system denitrating catalyst is compared, and denitrating catalyst provided by the invention has raw material sources extensive, and preparation cost is low
Advantage, while can be realized the high-efficiency comprehensive utilization of residue resource.Denitrating catalyst provided by the invention has good answer
It can be applied to sintering flue gas under the increasingly stringent form of current environmental protection standard with prospect and administer and thermal power plant flue gas
It administers.
Climb steel generates about 350,000 tons of tailings in vanadium extraction every year at present, and complicated component comprehensive utilization difficulty is big in tailings, and industry is green
Alum generates 200,000 tons or more every year, and comprehensive utilization difficulty is big.The invention proposes using tailings in vanadium extraction and industrial green vitriol as
The raw material of denitrating catalyst meets the Environmental Protection Situation of current rigorous and the demand for development of circular economy.It is provided by the invention de-
The denitration efficiency of denox catalyst is 70% or more, can administer in sintering flue gas and firepower finds to answer in factory's smoke gas treatment engineering
With significantly reducing the input cost of catalyst.
Compared with prior art, the preparation method raw material sources of denitrating catalyst provided by the invention are extensive, cheap and easy to get,
Catalyst simple production process, cost is relatively low, can significantly reduce the cost input of catalyst；It can be realized tailings in vanadium extraction and industry
The high-efficiency comprehensive utilization of green vitriol resource meets the requirement of previous cycle economic policy.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the process flow chart of denitrating catalyst preparation method provided in an embodiment of the present invention；
Fig. 2 is the apparatus structure schematic diagram that the embodiment of the present invention detects denitration efficiency.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff it is improved or retouching all other example, shall fall within the protection scope of the present invention.
The ingredient of tailings in vanadium extraction used in following embodiment of the present invention includes：The Fe of 43wt%2O3, 12wt% TiO2、
The V of 2wt%2O5, 10wt% MnO2With the Na of 5wt%2SiO3。
Industrial green vitriol used is the by-product in sulfate process titanium dioxide production process, the quality of ferrous sulfate heptahydrate therein
Content is 90.1%.
Embodiment 1
75 parts by weight of tailings in vanadium extraction for being 0.1~0.2mm by granularity, 20 parts by weight of coke powder of granularity < 0.1mm, granularity <
3 parts by weight of sodium bentonite of 0.1mm are mixed ageing mixture 2 hours after 2 parts by weight of borax and the water mixing of granularity < 0.1mm
Expect, the mass content of water is 3% in the mixture.
Obtained mixture is used into single lead screw ex truding briquetting machine extrusion forming, the shaping strength during extrusion forming is 2MPa,
Obtain green body.
By obtained green body at 110 DEG C it is dry after at 1000 DEG C sinter molding, obtain catalyst carrier.
Industrial green vitriol and water are mixed with to obtain the saturated solution of industrial green vitriol；
The saturated solution of the industrial green vitriol is supported on said catalyst carrier surface using vacuum-impregnated method, is obtained
Carrier after to dipping, the vacuum degree during the vacuum impregnation are 0.08MPa, and dip time is 4 hours, industrial green vitriol
Load capacity is 18%.
Carrier after dipping is dry under nitrogen atmosphere at 110 DEG C, hot place is then carried out under nitrogen atmosphere at 300 DEG C
Reason, obtains denitrating catalyst.
According to GB T 5072-2208《Refractory material cold crushing strength experimental method》, prepared by the embodiment of the present invention 1
Obtained catalyst carrier carries out compressive resistance test, and testing result is the catalyst carrier that the embodiment of the present invention 1 is prepared
Compressive resistance be 10.7MPa.
According to GB T 2997-1982《Fine and close shaping refractory product apparent porosity, water absorption rate, bulk density and true porosity
Test method》, porosity test is carried out to the catalyst carrier that the embodiment of the present invention 1 is prepared, testing result is the present invention
The porosity for the catalyst carrier that embodiment 1 is prepared is 62%.
The denitration efficiency for the denitrating catalyst that the embodiment of the present invention 1 is prepared is detected, detection method is：
It is detected using laboratory simulation flue gas, the structural schematic diagram of detection device is as shown in Fig. 2, using simulated flue gas
As experimental gas, in practical flue gas, NO accounts for NOxIt is total to represent nitrogen oxides with NO in simulated flue gas for 95% or more of total amount
It measures, the gas componant in simulated flue gas is：N2、NO、O2、SO2、CO2, laboratory uses steel cylinder calibrating gas, is mixed by metering
It is used as simulated flue gas afterwards.The activity rating of denitrating catalyst is to carry out in 19mm stainless steel fixed bed reactors in internal diameter, each road
Reaction gas (simulated flue gas ingredient) is respectively adopted mass flowmenter and is measured, subsequently into mixer, by certain volume
Denitrating catalyst is fitted into the reaction tube of fixed bed reactors, in N2After being heated to test temperature under atmosphere, it is passed through simulated flue gas
With certain density NH3(reducing agent).Laboratory denitration simulation test gas working condition be：Simulated flue gas mixed gas flow
3000mL/min, ammonia nitrogen molar ratio are (NH3/ NO) it is 1；The volumetric concentration of NO is 0.1%, NH3Volumetric concentration be 0.1%, O2
Volumetric concentration be 2%, reaction temperature be 200~500 DEG C, using flue gas analyzer to reaction front and back NO concentration examine
It surveys, calculates denitration efficiency using following formula：
Wherein, CNO inFor the concentration for reacting preceding nitrogen oxides (NO)；
CNO outFor the concentration of nitrogen oxides (NO) after reaction.
Testing result is that the best denitration temperature for the denitrating catalyst that the embodiment of the present invention 1 is prepared is 300~400
DEG C, denitration efficiency 75.6%.
Embodiment 2
85 parts by weight of tailings in vanadium extraction for being 0.1~0.2mm by granularity, 10 parts by weight of coke powder of granularity < 0.1mm, granularity <
Ageing mixture 5 hours after 5 parts by weight of sodium bentonite and the water mixing of 0.1mm, mixture is obtained, the quality of water contains in the mixture
Amount is 5%.
Obtained mixture is used into single lead screw ex truding briquetting machine extrusion forming, the shaping strength during extrusion forming is 5MPa,
Obtain green body.
By obtained green body at 110 DEG C it is dry after at 900 DEG C sinter molding, obtain catalyst carrier.
Industrial green vitriol and water are mixed with to obtain the saturated solution of industrial green vitriol；
The saturated solution of the industrial green vitriol is supported on said catalyst carrier surface using vacuum-impregnated method, is obtained
Carrier after to dipping, the vacuum degree during the vacuum impregnation are 0.08MPa, and dip time is 2 hours, industrial green vitriol
Load capacity is 11.5%.
Carrier after dipping is dry under nitrogen atmosphere at 110 DEG C, hot place is then carried out under nitrogen atmosphere at 500 DEG C
Reason, obtains denitrating catalyst.
According to the method for embodiment 1, compressive resistance survey is carried out to the catalyst carrier that the embodiment of the present invention 2 is prepared
Examination, testing result are that the compressive resistance for the catalyst carrier that the embodiment of the present invention 2 is prepared is 7.2MPa.
According to the method for embodiment 1, porosity test is carried out to the catalyst carrier that the embodiment of the present invention 2 is prepared,
Testing result is that the porosity for the catalyst carrier that the embodiment of the present invention 2 is prepared is 55%.
According to the method for embodiment 1, the denitration efficiency for the denitrating catalyst embodiment of the present invention 2 being prepared is examined
It surveys, testing result is that the best denitration temperature for the denitrating catalyst that the embodiment of the present invention 2 is prepared is 300~400 DEG C, is taken off
Nitre efficiency is 72.6%.
Embodiment 3
80 parts by weight of tailings in vanadium extraction for being 0.1~0.2mm by granularity, 15 parts by weight of coke powder of granularity < 0.1mm, granularity <
Ageing mixture 3 hours after 4 parts by weight of sodium bentonite of 0.1mm, 1 parts by weight of borax of granularity < 0.1mm and water mixing, mixed
Expect, the mass content of water is 4% in the mixture.
Obtained mixture is used into single lead screw ex truding briquetting machine extrusion forming, the shaping strength during extrusion forming is 2MPa,
Obtain green body.
By obtained green body at 110 DEG C it is dry after at 1100 DEG C sinter molding, obtain catalyst carrier.
Industrial green vitriol and water are mixed with to obtain the saturated solution of industrial green vitriol；
The saturated solution of the industrial green vitriol is supported on said catalyst carrier surface using vacuum-impregnated method, is obtained
Carrier after to dipping, the vacuum degree during the vacuum impregnation are 0.08MPa, and dip time is 4 hours, industrial green vitriol
Load capacity is 17.5%.
Carrier after dipping is dry under nitrogen atmosphere at 110 DEG C, hot place is then carried out under nitrogen atmosphere at 200 DEG C
Reason, obtains denitrating catalyst.
According to the method for embodiment 1, compressive resistance survey is carried out to the catalyst carrier that the embodiment of the present invention 3 is prepared
Examination, testing result are that the compressive resistance for the catalyst carrier that the embodiment of the present invention 3 is prepared is 13.5MPa.
According to the method for embodiment 1, porosity test is carried out to the catalyst carrier that the embodiment of the present invention 3 is prepared,
Testing result is that the porosity for the catalyst carrier that the embodiment of the present invention 3 is prepared is 48%.
According to the method for embodiment 1, the denitration efficiency for the denitrating catalyst embodiment of the present invention 3 being prepared is examined
It surveys, testing result is that the best denitration temperature for the denitrating catalyst that the embodiment of the present invention 3 is prepared is 300~400 DEG C, is taken off
Nitre efficiency is 68.9%.
Embodiment 4
75 parts by weight of tailings in vanadium extraction for being 0.1~0.2mm by granularity, 20 parts by weight of coke powder of granularity < 0.1mm, granularity <
Ageing mixture 2 hours after 3 parts by weight of sodium bentonite of 0.1mm, 2 parts by weight of borax of granularity < 0.1mm and water mixing, mixed
Expect, the mass content of water is 3% in the mixture.
Obtained mixture is used into single lead screw ex truding briquetting machine extrusion forming, the shaping strength during extrusion forming is 2MPa,
Obtain green body.
By obtained green body at 110 DEG C it is dry after at 1050 DEG C sinter molding, obtain catalyst carrier.
Industrial green vitriol and water are mixed with to obtain the saturated solution of industrial green vitriol；
The saturated solution of the industrial green vitriol is supported on said catalyst carrier surface using vacuum-impregnated method, is obtained
Carrier after to dipping, the vacuum degree during the vacuum impregnation are 0.08MPa, and dip time is 3 hours, industrial green vitriol
Load capacity is 16%.
Carrier after dipping is dry under nitrogen atmosphere at 110 DEG C, hot place is then carried out under nitrogen atmosphere at 300 DEG C
Reason, obtains denitrating catalyst.
According to the method for embodiment 1, compressive resistance survey is carried out to the catalyst carrier that the embodiment of the present invention 4 is prepared
Examination, testing result are that the compressive resistance for the catalyst carrier that the embodiment of the present invention 4 is prepared is 12MPa.
According to the method for embodiment 1, porosity test is carried out to the catalyst carrier that the embodiment of the present invention 4 is prepared,
Testing result is that the porosity for the catalyst carrier that the embodiment of the present invention 4 is prepared is 59%.
According to the method for embodiment 1, the denitration efficiency for the denitrating catalyst embodiment of the present invention 4 being prepared is examined
It surveys, testing result is that the best denitration temperature for the denitrating catalyst that the embodiment of the present invention 4 is prepared is 300~400 DEG C, is taken off
Nitre efficiency is 77%.
As seen from the above embodiment, the present invention provides a kind of denitrating catalyst, including carrier, the carrier includes：It mentions
Vanadium tailing soil, pore creating material and binder；The active constituent of load on the carrier, the active constituent includes alkali formula ferrous sulfate
And ferrous sulfate.Compared with prior art, denitrating catalyst mechanical property provided by the invention is good, denitration efficiency is high, and with
Tailings in vanadium extraction and industrial green vitriol are primary raw material, and raw material sources are extensive, and preparation cost is low, while can be realized the height of residue resource
Effect comprehensive utilization.Denitrating catalyst provided by the invention has a good application prospect, can be applied to sintering flue gas administer and
Thermal power plant smoke gas treatment.
What has been described above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill of the art
For personnel, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of denitrating catalyst, including：
Carrier, the carrier is by including that the material of tailings in vanadium extraction, pore creating material and binder is prepared；
The active constituent of load on the carrier, the active constituent includes alkali formula ferrous sulfate and ferrous sulfate.
2. denitrating catalyst according to claim 1, which is characterized in that the tailings in vanadium extraction, pore creating material and binder
Mass ratio is (75~85):(10~20):(1~7).
3. denitrating catalyst according to claim 1, which is characterized in that the tailings in vanadium extraction includes：
Fe2O3、TiO2、V2O5、MnO2And sodium salt.
4. denitrating catalyst according to claim 1, which is characterized in that the pore creating material is coke powder.
5. denitrating catalyst according to claim 1, which is characterized in that the binder includes bentonite.
6. denitrating catalyst according to claim 5, which is characterized in that the binder further includes borax.
7. a kind of preparation method of denitrating catalyst described in claim 1, including：
Then industrial green vitriol solution loadings are heat-treated on carrier, denitrating catalyst is obtained；
The preparation method of the carrier is：
Tailings in vanadium extraction, pore creating material, binder and water are mixed, mixture is obtained；
It will be sintered after the mixture extrusion forming, obtain carrier.
8. the method according to the description of claim 7 is characterized in that the temperature of the heat treatment is 200~500 DEG C.
9. the method according to the description of claim 7 is characterized in that the temperature of the sintering is 900~1100 DEG C.
10. the method according to the description of claim 7 is characterized in that the shaping strength of the extrusion forming is 1~5MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111729666A (en) * | 2020-06-18 | 2020-10-02 | 北京科技大学 | Method for preparing denitration catalyst from vanadium titano-magnetite |
| CN112473694A (en) * | 2019-09-12 | 2021-03-12 | 国家能源投资集团有限责任公司 | Catalyst support composition, catalyst support and preparation method thereof |
| CN113908847A (en) * | 2021-10-13 | 2022-01-11 | 河钢承德钒钛新材料有限公司 | Method for preparing denitration catalyst by using vanadium tailings extracted by alkaline leaching |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219385A (en) * | 2008-01-23 | 2008-07-16 | 清华大学 | Catalyst, method for producing the same, flue gas denitrating technique by using the catalyst |
| CN102380384A (en) * | 2011-07-22 | 2012-03-21 | 丁珂 | Preparation method of novel environmentally-friendly non-toxic catalyst |
| CN102580743A (en) * | 2011-12-30 | 2012-07-18 | 浙江大学 | Method for preparing oxidation catalyst from gold ore tailing slag, and prepared oxidation catalyst and application thereof |
| CN103394358A (en) * | 2013-08-12 | 2013-11-20 | 武汉理工大学 | Method for preparing manganese-base low-temperature denitration catalyst by utilizing gold copper tailings |
-
2018
- 2018-08-23 CN CN201810965896.5A patent/CN108889316A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219385A (en) * | 2008-01-23 | 2008-07-16 | 清华大学 | Catalyst, method for producing the same, flue gas denitrating technique by using the catalyst |
| CN102380384A (en) * | 2011-07-22 | 2012-03-21 | 丁珂 | Preparation method of novel environmentally-friendly non-toxic catalyst |
| CN102580743A (en) * | 2011-12-30 | 2012-07-18 | 浙江大学 | Method for preparing oxidation catalyst from gold ore tailing slag, and prepared oxidation catalyst and application thereof |
| CN103394358A (en) * | 2013-08-12 | 2013-11-20 | 武汉理工大学 | Method for preparing manganese-base low-temperature denitration catalyst by utilizing gold copper tailings |
Non-Patent Citations (1)
| Title |
|---|
| 苏步青 等: "《中学百科全书 化学卷》", 31 December 1994, 华东师范大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112473694A (en) * | 2019-09-12 | 2021-03-12 | 国家能源投资集团有限责任公司 | Catalyst support composition, catalyst support and preparation method thereof |
| CN111729666A (en) * | 2020-06-18 | 2020-10-02 | 北京科技大学 | Method for preparing denitration catalyst from vanadium titano-magnetite |
| CN113908847A (en) * | 2021-10-13 | 2022-01-11 | 河钢承德钒钛新材料有限公司 | Method for preparing denitration catalyst by using vanadium tailings extracted by alkaline leaching |
| CN113908847B (en) * | 2021-10-13 | 2023-08-04 | 河钢承德钒钛新材料有限公司 | Method for preparing denitration catalyst by utilizing alkaline leaching vanadium tailings |
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