CN106268755A - A kind of preparation method without vanadium denitration catalyst - Google Patents
A kind of preparation method without vanadium denitration catalyst Download PDFInfo
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- CN106268755A CN106268755A CN201610652524.8A CN201610652524A CN106268755A CN 106268755 A CN106268755 A CN 106268755A CN 201610652524 A CN201610652524 A CN 201610652524A CN 106268755 A CN106268755 A CN 106268755A
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention discloses a kind of preparation method without vanadium denitration catalyst, comprise the steps, cerous nitrate, Lanthanum (III) nitrate, zirconium nitrate, antimony acetate are dissolved completely in water by (1) respectively, then above-mentioned solution mix homogeneously are obtained mixed solution A；(2) in mixed solution A, nano-TiO is added2, stir, prepare muddy mixed liquid B, wherein add nano-TiO2Amount accounts for 50% the 90% of mixed liquid B；(3) in mixed liquid B, it is separately added into the carboxymethyl cellulose accounting for gross mass 0.2% 0.8% and the polyethylene glycol oxide accounting for gross mass 0.9% 1.5%, mix homogeneously, calcining, prepares C；(4) C being ground to particle diameter is 03 microns, obtains product without vanadium denitration catalyst D.It is an advantage of the current invention that and prepare without vanadium, low cost in raw material, specific surface area is high, and operating temperature width has preferable sulfur resistance simultaneously.
Description
Technical field
The invention belongs to catalyst preparation technical field, be specifically related to a kind of preparation method without vanadium denitration catalyst.
Background technology
Coal is the main source of China's energy, but the burning of coal is our life, works offer easily together
Time also bring serious atmospheric pollution, air quality declines, and haze have impact on daily life, limits especially
The further enforcement of Zhi Liao China strategy of sustainable development.Oxynitride (the NO particularly generated after burningx), can cause
The problem of environmental pollution such as ozone and acid rain, therefore, eliminates NO the most effectivelyxBecome the important class in current field of Environment Protection
Topic.Commonplace general way is to utilize ammonia that conversion of nitrogen oxides becomes harmless nitrogen, namely selective catalytic reduction
(SCR), SCR (selective catalytic reduction, SCR) method is relatively low with its reaction temperature, only
Rate is high, reliable, the advantages such as secondary pollution is little, has become the prefered method of removing NOx in developed country.At SCR technology
In, catalyst is core, and its cost accounts for the 20%～40% of SCR system totle drilling cost, and the performance of catalyst directly affects NOx's
Removal effect.Ammonia selective catalysis reducing process (NH3-SCR) it is the method that application is relatively broad, efficiency is higher at present, remove NOx
Efficiency is the highest, the denitration technology being most widely used, the most commercial NH3-SCR catalyst, mainly V2O5-TiO2Or V2O5-
WO3(MoO3)-TiO2.Such catalyst shows higher NOx clearance and good sulfur resistance at 350～400 DEG C.But
It is that this catalyst still suffers from some problems in actual use: active component V2O5Predecessor toxicity general the biggest, to people
Body and environment all have toxic action；The preparation condition of catalyst is the most wayward；Operation temperature window is narrower, and control
System is strict, is not suitable for existing power plant of China production status；A kind of have in the range of wider temperature window accordingly, it would be desirable to develop
Excellent NOx removal effect without vanadium catalyst.
The patent document of Patent No. 200910087773.7 discloses a kind of low-vanadium denitration catalyst, and this catalyst exists
There is in the range of 200～450 DEG C the conversion rate of NOx higher than 90%, but this catalyst contains a small amount of v element, to environment and people
Body still has certain damaging effect.The Chinese invention patent of Publication No. CN102310001A discloses a kind of ceramic honeycomb
Ferrous sulfate, without vanadium denitration catalyst, is supported on molecular sieve and is prepared by formula, has certain anti-toxic and mechanical strength,
But the ferrous sulfate active component used, at high temperature carries out easily aoxidizing during denitration, causes catalyst to lose work
Property, shorten service life.Therefore developing a kind of low cost of the present invention, specific surface area is high, operating temperature width, has good simultaneously
Sulfur resistance without vanadium denitration catalyst, there is wide market prospect.
Summary of the invention
The present invention is directed to the deficiency in prior art, it is provided that a kind of low cost, specific surface area are high, operating temperature width, simultaneously
Have good sulfur resistance without vanadium denitration catalyst.
In order to solve above-mentioned technical problem, the technical scheme is that
A kind of preparation method without vanadium denitration catalyst of the present invention, comprises the steps:
1) cerous nitrate, Lanthanum (III) nitrate, zirconium nitrate, antimony acetate are dissolved completely in respectively water, then by the mixing of above-mentioned solution all
Even mixed solution A；
2) in mixed solution A, nano-TiO is added2, stir, prepare muddy mixed liquid B, wherein add nanometer
TiO2Amount accounts for the 50%-90% of mixed liquid B；
3) in mixed liquid B, it is separately added into the carboxymethyl cellulose accounting for gross mass 0.2%-0.8% and accounts for gross mass
The polyethylene glycol oxide of 0.9%-1.5%, mix homogeneously, calcining, prepare C；
4) C being ground to particle diameter is 0-3 micron, prepares product without vanadium denitration catalyst D.
Further, in order to make each solvent fully dissolve, in step (1), cerous nitrate, Lanthanum (III) nitrate, zirconium nitrate and antimony acetate
It is 1:10-20 with the mass ratio of water.
Further, cerous nitrate, Lanthanum (III) nitrate, zirconium nitrate and antimony acetate 1:15 all preferred with the mass ratio of water.
Further, in order to improve the specific surface area of catalyst, in step (2), nano-TiO2Particle diameter be 1nm
250nm。
Further, nano-TiO2The preferred 100nm of particle diameter.
Further, nano-TiO2Addition is solution B gross mass 80%.
Further, in order to make catalyst fully activate, in step (3), calcining heat is 400 DEG C-800 DEG C, during calcining
Between be 25h-40h.
Further, calcining heat preferably 600 DEG C, the preferred 33h of calcination time.
Further, in step (3), the quality of preferably carboxymethyl cellulose is the 0.5% of gross mass, preferably polyoxyethylene
The quality of alkene is the 1.2% of gross mass.
The present invention propose a kind of without vanadium denitration catalyst and preparation method thereof, addition carboxymethyl cellulose as bonding
Agent and thickening agent, polyethylene glycol oxide, as pore creating material and thickening agent, selects nano-TiO2, the specific surface of catalyst can be improved
Long-pending.Compared with the conventional method, the invention has the advantages that: without vanadium in the raw material preparing denitrating catalyst in method, use
Nano-TiO2Powder body improves the specific surface area of catalyst, operating temperature width, has preferable sulfur resistance simultaneously
Detailed description of the invention
The invention is further illustrated by the following examples, but the present invention is not limited only to following example.
Embodiment 1
1) cerous nitrate, Lanthanum (III) nitrate, zirconium nitrate, antimony acetate are dissolved completely in water respectively, obtain settled solution, the most above-mentioned respectively
Raw material is 1:15 with the mass ratio of water.Then above-mentioned settled solution mix homogeneously is obtained mixed solution A.
2) adding particle diameter in mixed solution A is the nano-TiO of 100nm2, prepare muddy mixed liquid B, stir,
Wherein add nano-TiO2Quality account for the 80% of solution B.
3) in mixed liquid B, it is separately added into the carboxymethyl cellulose accounting for gross mass 0.5% and the polyoxy accounting for gross mass 1.2%
Change ethylene, mix homogeneously, calcine 33h at 600 DEG C, prepare C；
4) C being ground to particle diameter is 0-3 micron, i.e. prepares product without vanadium denitration catalyst D.Embodiment 2
1) cerous nitrate, Lanthanum (III) nitrate, zirconium nitrate, antimony acetate are dissolved completely in water respectively, obtain settled solution, the most above-mentioned respectively
Raw material is 1:10 with the mass ratio of water.Then above-mentioned settled solution mix homogeneously is obtained mixed solution A.
2) adding particle diameter in mixed solution A is the nano-TiO of 1nm2, prepare muddy mixed liquid B, stir, its
Middle addition nano-TiO2Quality account for the 50% of solution B.
3) in mixed liquid B, it is separately added into the carboxymethyl cellulose accounting for gross mass 0.2% and the polyoxy accounting for gross mass 1.5%
Change ethylene, mix homogeneously, calcine 25h at 400 DEG C, prepare C；
4) C being ground to particle diameter is 0-3 micron, i.e. prepares product without vanadium denitration catalyst D.
Embodiment 3
1) cerous nitrate, Lanthanum (III) nitrate, zirconium nitrate, antimony acetate are dissolved completely in water respectively, obtain settled solution, the most above-mentioned respectively
Raw material is 1:20 with the mass ratio of water.Then above-mentioned settled solution mix homogeneously is obtained mixed solution A.
2) adding particle diameter in mixed solution A is the nano-TiO of 250nm2, prepare muddy mixed liquid B, stir,
Wherein add nano-TiO2Quality account for the 90% of solution B.
3) in mixed liquid B, it is separately added into the carboxymethyl cellulose accounting for gross mass 0.8% and the polyoxy accounting for gross mass 0.9%
Change ethylene, mix homogeneously, calcine 40h at 800 DEG C, prepare C；
4) C being ground to particle diameter is 0-3 micron, i.e. prepares product without vanadium denitration catalyst D.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any amendment, equivalent and the improvement etc. made within god and principle, should be included within the scope of the present invention.
Claims (9)
1. the preparation method without vanadium denitration catalyst, it is characterised in that comprise the steps:
1) cerous nitrate, Lanthanum (III) nitrate, zirconium nitrate, antimony acetate are dissolved completely in respectively water, then above-mentioned solution mix homogeneously are obtained
Mixed solution A；
2) in mixed solution A, nano-TiO is added2, stir, prepare muddy mixed liquid B, wherein add nano-TiO2Amount
Account for the 50%-90% of mixed liquid B；
3) in mixed liquid B, it is separately added into the carboxymethyl cellulose accounting for gross mass 0.2%-0.8% and accounts for gross mass 0.9%-
The polyethylene glycol oxide of 1.5%, mix homogeneously, calcining, prepare C；
4) C being ground to particle diameter is 0-3 micron, obtains product without vanadium denitration catalyst D.
A kind of preparation method without vanadium denitration catalyst the most according to claim 1, is characterised by, in step (1), described
Cerous nitrate, Lanthanum (III) nitrate, zirconium nitrate and antimony acetate are 1:10-20 with the mass ratio of water.
A kind of preparation method without vanadium denitration catalyst the most according to claim 2, is characterised by, in step (1), described
Cerous nitrate, Lanthanum (III) nitrate, zirconium nitrate and antimony acetate are 1:15 with the mass ratio of water.
A kind of preparation method without vanadium denitration catalyst the most according to claim 1, is characterised by, in step (2), described
Nano-TiO2Particle diameter be 1nm 250nm.
A kind of preparation method without vanadium denitration catalyst the most according to claim 4, is characterised by, described nano-TiO2's
Particle diameter is 100nm.
A kind of preparation method without vanadium denitration catalyst the most according to claim 1, is characterised by, in step (2), described
Nano-TiO2Addition is miscible fluid B gross mass 80%.
A kind of preparation method without vanadium denitration catalyst the most according to claim 1, is characterised by, in step (3), described
Calcining, temperature is 400 DEG C-800 DEG C, and the time is 25h-40h.
A kind of preparation method without vanadium denitration catalyst the most according to claim 7, is characterised by, in step (3), described
Calcining, temperature is 600 DEG C, and the time is 33h.
A kind of preparation method without vanadium denitration catalyst the most according to claim 1, is characterised by, in step (3), described
Addition quality is gross mass the 0.5% of carboxymethyl cellulose, the addition quality of described polyethylene glycol oxide is gross mass
1.2%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101947443A (en) * | 2010-09-03 | 2011-01-19 | 浙江省环境保护科学设计研究院 | Cellular Mn-Ti-based catalyst for low-temperature selective catalytic reduction denitration reaction and preparation method and using method |
| CN103596678A (en) * | 2011-02-07 | 2014-02-19 | 水晶美国股份公司 | Ce containing, V-free mobile denox catalyst |
| CN105521777A (en) * | 2015-12-31 | 2016-04-27 | 安徽省元琛环保科技有限公司 | A preparing method of a catalyst for low-temperature denitrification |
-
2016
- 2016-08-10 CN CN201610652524.8A patent/CN106268755A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101947443A (en) * | 2010-09-03 | 2011-01-19 | 浙江省环境保护科学设计研究院 | Cellular Mn-Ti-based catalyst for low-temperature selective catalytic reduction denitration reaction and preparation method and using method |
| CN103596678A (en) * | 2011-02-07 | 2014-02-19 | 水晶美国股份公司 | Ce containing, V-free mobile denox catalyst |
| CN105521777A (en) * | 2015-12-31 | 2016-04-27 | 安徽省元琛环保科技有限公司 | A preparing method of a catalyst for low-temperature denitrification |
Non-Patent Citations (3)
| Title |
|---|
| 《煤炭技术》 * |
| 《第十四届全国稀土催化学术会议论文集》 * |
| 张蕾: "《烟气脱硫脱硝技术及催化剂的研究进展》", 31 July 2016, 中国矿业大学出版社 * |
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