CN102302944A - Ceramic honeycomb type denitrating catalyst and preparation method thereof - Google Patents
Ceramic honeycomb type denitrating catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a ceramic honeycomb type denitrating catalyst. The ceramic honeycomb type denitrating catalyst is formed by mixing, forming and calcining a catalyst active ingredient, a catalyst carrier and a forming aid, wherein the catalyst active ingredient is ferrous sulphate. In an embodiment, the catalyst active ingredient comprises 20 to 40 weight parts of the ferrous sulphate; the catalyst carrier comprises 60 to 90 weight parts of molecular sieve; the forming aid comprises 2 to 4 weight parts of citric acid, 2 to 6 weight parts of sodium carboxymethylcellulose, 2 to 6 weight parts of polyoxyethylene, 0.2 to 1.0 weight part of glycerol, 2 to 4 weight parts of nitric acid, 90 to 120 weight parts of pseudoboehmite, 30 to 40 weight parts of Suzhou clay, 2 to 6 weight parts of sesbania cannabina pers powder and 10 to 30 weight parts of glass fiber. The raw materials of the catalyst have low cost and do not have toxicity. The denitrating catalyst module has high denitrating efficiency and certain anti-poisoning property and mechanical strength.
Description
Technical field
Present invention relates in general to be used for the catalyst of denitrating flue gas, more particularly, the present invention relates to a kind of ceramic honeycomb denitrating catalyst and preparation method.
Background technology
As everyone knows, nitrogen oxide NO
X(mainly be NO and NO
2) be one type of main atmosphere pollution.Contain NO
XIf the not treated atmosphere that enters of flue gas, then can cause serious harm to health and human residential environment.In " 12 " of China planning, also NO
XReduction of discharging as binding performance assessment criteria.Therefore, control NO
XDischarging be extremely urgent.
Have been found that in the prior art that (Selective caalytic reduction SCR) is a kind of effective denitrating flue gas (that is, removing nitrogen oxide) method to selective catalytic reduction.The principle of SCR method denitration is in the discharging flue gas, to spray into NH
3Deng reducing agent, under catalyst action with flue gas in NO
XGenerate harmless N
2And H
2O.At present, the SCR method has become at present the mainstream technology of power plant's denitration comparative maturity both at home and abroad.
In industrialized SCR denitration technology, catalyst is placed in the flue with the form of module usually.The pattern of SCR denitrating catalyst module mainly contains honeycomb fashion, flat and corrugated.Wherein, the honeycomb fashion catalyst is used widely owing to its strong durability, high rotproofness, high reliability, height are recycled rate, low pressure degradation characteristic.From the SCR method denitration unit that has put into operation at present, adopt the honeycomb fashion catalyst more than 75%.
This ceramic honeycomb Preparation of catalysts generally includes blend step, forming step and calcining step.In blend step, will comprise that the various materials of catalyst activity composition, catalyst carrier and shaping assistant mixes with solvent (for example water), form and have plastic pug, this step is carried out in kneader usually.In forming step, utilizing extruder (add and be made into type die) usually is the honeycomb ceramics blank with the pug extrusion molding.In calcining step, the honeycomb ceramics blank is calcined, to form ceramic honeycomb denitrating catalyst module.
The core technology of ceramic honeycomb denitrating catalyst that can industrial applications is its composition of raw materials and preparation technology.At present, the SCR ceramic honeycomb denitrating catalyst that uses in the industry is mainly vanadium titanium class catalyst, and this type catalyst is with V
2O
5Be main active, add WO
3Or MoO
3As co-catalyst, and with anatase TiO
2As catalyst carrier.This type catalyst existing relatively ripe composition of raw materials and preparation technology.But vanadium titanium class catalyst exists cost height, big, the easy secondary pollution problems of post processing of vanadium toxicity.
At present, discover ferrous sulfate FeSO
4Can in the SCR method, remove the nitrogen oxide in the flue gas effectively as the denitrating catalyst active component.And, than vanadium titanium class catalyst, advantage such as ferrous sulfate catalyst has cheapness, is easy to get, the life-span is long, disposable.
Although that kind as indicated above has been found ferrous sulfate and can be used as the active component of SCR denitrating catalyst; And the technology of preparing of existing ripe ceramic honeycomb denitrating catalyst in the prior art; But it is a kind of successful with the ceramic honeycomb denitrating catalyst of ferrous sulfate as active component to it will be understood by those skilled in the art that this can not obviously obtain.In order to obtain a kind of like this denitrating catalyst; Also need be in the selection of raw material, proportion of raw materials, in preparation process, carry out meticulous research and design on one or more technological difficulties such as addition sequence (time point), technological parameter of raw material, and carry out a large amount of experiments and could realize.
Summary of the invention
Therefore, an object of the present invention is to overcome above-mentioned one or more technological difficulties.
According to one aspect of the present invention, a kind of ceramic honeycomb denitrating catalyst is provided, be that catalyst activity composition, catalyst carrier and shaping assistant are formed through mixing, moulding and calcining, wherein, said catalyst activity composition is a ferrous sulfate.
Preferably, said catalyst carrier is a molecular sieve.
Preferably, said shaping assistant comprises the combination of nitric acid and boehmite.
Preferably, said shaping assistant also comprises Suzhou soil.
Preferably, said shaping assistant also comprises citric acid.
Preferably, said shaping assistant comprises citric acid, sodium carboxymethylcellulose, polyethylene glycol oxide or this three's combination in any.
Preferably, said shaping assistant comprises glycerine and/or field mountain valley with clumps of trees and bamboo powder.
Preferably, said shaping assistant comprises glass fibre.
According to another aspect of the present invention; A kind of ceramic honeycomb denitrating catalyst is provided; Be that catalyst activity composition, catalyst carrier and shaping assistant are formed through mixing, moulding and calcining; Wherein, Said catalyst activity composition comprises the ferrous sulfate of 20-40 weight portion; Catalyst carrier comprises the molecular sieve of 60-90 weight portion, and said shaping assistant comprises: the Suzhou soil of the nitric acid of the polyethylene glycol oxide of the citric acid of 2-4 weight portion, 2-6 weight portion sodium carboxymethylcellulose, 2-6 weight portion, the glycerine of 0.2-1.0 weight portion, 2-4 weight portion, the boehmite of 90-120 weight portion, 30-40 weight portion, the field mountain valley with clumps of trees and bamboo powder of 2-6 weight portion, the glass fibre of 10-30 weight portion.
According to another aspect of the present invention, a kind of preparation method of ceramic honeycomb denitrating catalyst is provided, comprising:
Blend step is used for various materials and solvent, forms to have plastic pug;
Old step and/or pugging step are used to improve the characteristic of said pug;
Forming step, being used for said mud material forming is the honeycomb ceramics blank;
Drying steps is used for removing the moisture of said honeycomb ceramics blank;
Calcining step is used for said honeycomb ceramics blank is calcined, to form said ceramic honeycomb denitrating catalyst;
Wherein, order comprises in blend step:
1) water of getting 100 weight portions is as solvent, and the polyethylene glycol oxide of getting citric acid, 2-6 weight portion sodium carboxymethylcellulose, the 2-6 weight portion of 2-4 weight portion again joins in the solvent and dissolves;
2) ferrous sulfate of 20-40 weight portion is joined in the solution dissolve again;
3) nitric acid of getting glycerine and the 2-4 weight portion of 0.2-1.0 weight portion joins in the solution and dissolves.
4) with the boehmite of the molecular screen primary powder of 60-90 weight portion, 90-120 weight portion, the Suzhou soil of 30-40 weight portion, and the field mountain valley with clumps of trees and bamboo powder of 2-6 weight portion and the solution for preparing before join in the kneader and mediate;
5) when basically forming toughness and plastic pug in the kneader, in kneader, progressively add the glass fibre of 10-30 weight portion; Kneader continues to mediate then, fully mixes in kneader until all materials, forms to have plastic pug uniformly.
Preferably, said pug was placed in the environment of base closed old 24-48 hour.
Preferably, in the environment of said base closed, charge into nitrogen.
Preferably, in said drying steps, said honeycomb ceramics blank is admitted to and carries out drying in the drying machine, and wherein, the average heating speed of said drying machine is between 5-10 ℃/day, until the baking temperature that reaches 60-150 ℃.
Preferably, said baking temperature is between 80-120 ℃.
Preferably, in said calcining step, the honeycomb ceramics blank is sent into calcining kiln and is calcined, and in calcination process, average heating speed is between 10-20 ℃/hour, until the calcining heat that reaches 450-550 ℃.
Preferably, in calcination process, average heating speed is between 15-20 ℃/hour.
Preferably, in calcination process, said calcining heat is between 480-520 ℃.
The present invention has following beneficial effect:
The present invention the selection of raw material, proportion of raw materials, in preparation process raw material addition sequence (time point), technological parameter this several aspect to being that the ceramic honeycomb denitrating catalyst of active component has proposed the improvement means with the ferrous sulfate, improve the performance and/or the yield rate of the final ceramic honeycomb denitrating catalyst that obtains.It should be noted that the present invention can use in above-mentioned improvement aspect several independently or jointly, so that the industrial applications of ferrous sulfate ceramic honeycomb denitrating catalyst becomes possibility.Than the iron ceramic honeycomb denitrating catalyst of existing other type, 1) catalyst of the present invention can select cheap raw material for use, greatly reduces the production cost of denitrating catalyst; 2) all avirulences of selecting materials of the present invention have reduced ambient influnence and have reduced the post processing cost of discarded catalyst; 3) denitrating catalyst module of the present invention has high denitration efficiency, and has certain anti-poisoning performance and mechanical strength.
The specific embodiment
To combine the specific embodiment to further explain of the present invention below.
The selection of material
The catalyst activity composition adopts ferrous sulfate.
Solvent can be water or deionized water, or other solvent that is fit to.Consider the factor of cost, preferably make water as solvent.
Catalyst carrier can be used molecular sieve, as draws together A type zeolite molecular sieve, X type zeolite molecular sieve, y-type zeolite molecular sieve, ZSM series molecular sieve, MFI molecular sieve, MOR molecular sieve or the like, also can adopt the molecular sieve that is applicable to ferrous sulfate of other type.In other embodiments, catalyst carrier also can adopt other non-molecular sieve material that is applicable to ferrous sulfate, like cordierite, mullite or pillared clay etc.
Shaping assistant can comprise adhesive, extrusion aid, pore creating material and/or reinforcing agent or the like, one of ordinary skill in the art will readily recognize that a kind of sometimes material can play the effect of multiple auxiliary agent simultaneously.Preferably, at least a material in the shaping assistant also can be made simultaneously the anti-oxidant of ferrous sulfate.
For example, in a preferred embodiment of the invention, the shaping assistant of being selected for use can comprise:
1) citric acid, nitric acid and boehmite, wherein, citric acid and nitric acid can form colloid with the boehmite reaction respectively, thereby can be used as adhesive.
2) polyethylene glycol oxide (PEO) because its viscosity can be used as adhesive, can also play the effect of pore creating material, to improve the pore property of finished catalyst.
3) sodium carboxymethylcellulose (CMC) can be used as adhesive, can also play the effect of pore creating material, to improve pore property.
4) glycerine and field mountain valley with clumps of trees and bamboo powder can be used as extrusion aid.
5) Suzhou soil can be used as adhesive.
6) glass fibre can be used as reinforcing agent.
In the preferred embodiment; Citric acid, polyethylene glycol oxide and sodium carboxymethylcellulose all have oxidation resistant effect to ferrous sulfate separately; Promptly; These three kinds of materials also can be used as the anti-oxidant of ferrous sulfate as in the shaping assistant, with prevent ferrous sulfate with the process of solvent in oxidized.
Certainly, those skilled in the art can adopt other shaping assistant scheme, and preferably, at least a material in the shaping assistant also can be made simultaneously the anti-oxidant of ferrous sulfate.
For the anti-oxidant of ferrous sulfate, in other embodiments, anti-oxidant can be to be selected from citric acid, polyethylene glycol oxide and the sodium carboxymethylcellulose one or both, or in other shaping assistant scheme to the material of ferrous sulfate Wheat Protein.
For adhesive, the combination (reaction generates colloid) of preferably adopting nitric acid and boehmite is as adhesive.And because the oxidisability of nitric acid is stronger, the combination of the preferred acid of also using weak oxide property in addition and boehmite is as adhesive, citric acid for example, and as previously mentioned, citric acid also can be used as the anti-oxidant of ferrous sulfate simultaneously.In addition, for the deficiency of the viscosity that further remedies the adhesive that nitric acid and/or citric acid and boehmite form, adhesive preferably also comprises Suzhou soil.Preferably, also can add polyethylene glycol oxide and/or sodium carboxymethylcellulose in addition as adhesive, these two kinds of materials also can be used as the anti-oxidant of ferrous sulfate.In other embodiments, also can use other proper adhesive.
For extrusion aid, preferably include glycerine, more preferably, extrusion aid also comprises field mountain valley with clumps of trees and bamboo powder.In other embodiments, also can use other suitable extrusion aid.
For pore creating material, preferably include polyethylene glycol oxide and/or sodium carboxymethylcellulose, these two kinds of materials also can be used as the anti-oxidant of ferrous sulfate.In other embodiments, also can use other suitable pore creating material.
For reinforcing agent, preferably include glass fibre.Reinforcing agent is carbon fiber, glass fibre, mullite, calcium sulfate or their combination in any also.In other embodiments, also can use other suitable reinforcing agent.
Blend step
In this blend step, with selected various materials and solvent, formation has plastic pug, and this step is carried out in kneader usually.As previously mentioned, these materials comprise the ferrous sulfate as the catalyst activity composition, the catalyst carrier that is used for the load ferrous sulfate and shaping assistant.Shaping assistant generally includes adhesive, extrusion aid, pore creating material and/or reinforcing agent etc., is used to help the moulding of pug.
In one embodiment, can solvent all be joined in the mixing apparatus with said various materials and mix, for example join kneader and fully mediate.
In another embodiment, this blend step can comprise two sub-steps: formulations prepared from solutions step and pug form step.In the formulations prepared from solutions step, a part of material dissolution that can in solvent, dissolve in the said various materials is formed solution in said solvent.Preferably, in the dissolving preparation process, all soluble material are all joined in the solvent dissolve.Through such mode, can be so that soluble material distributing very evenly in finished catalyst, to improve the performance of catalyst.Form in the step at pug, again rest materials is mixed with formed solution, for example join kneader and fully mediate, form pug.
It should be noted that; For two kinds of embodiments of above-mentioned blend step any one; Preferably control the order by merging of material; Made before ferrous sulfate and solvent, earlier will be as the material and the solvent of anti-oxidant, so that oxidized when preventing ferrous sulfate and solvent best.
Below, according to one more specifically preferred embodiment describe this blend step in detail.
1) formulations prepared from solutions step
The water of at first getting 100 weight portions is as solvent, and the polyethylene glycol oxide of getting citric acid, 2-6 weight portion sodium carboxymethylcellulose, the 2-6 weight portion of 2-4 weight portion again joins in the solvent and dissolves.Of preamble, here, citric acid, sodium carboxymethylcellulose and polyethylene glycol oxide are shaping assistant, also are the anti-oxidants of ferrous sulfate.
Then, again with the dissolving that is added to the water of the ferrous sulfate of 20-40 weight portion.Since before in solvent, added the anti-oxidant of ferrous sulfate, this can prevent in the process that ferrous sulfate dissolves in water oxidized effectively, thereby makes and after whole preparation process is accomplished, keep its catalytic activity.
It should be noted that when having used sodium carboxymethylcellulose and/or polyethylene glycol oxide in the anti-oxidant,, can heat solution in order to promote its dissolving.Before adding ferrous sulfate, preferably earlier solution is cooled to room temperature.
Subsequently, again the material that is prone in solvent, dissolve in other shaping assistant is joined in the solution.Particularly, getting the glycerine of 0.2-1.0 weight portion and the nitric acid of 2-4 weight portion joins in the solution.
2) pug forms step
The solution for preparing in the abovementioned steps and remaining other material joined in the kneader mediate.These other material can comprise as other shaping assistant that does not join in the molecular screen primary powder of catalyst carrier and the abovementioned steps in the solution.
Particularly, with the boehmite of the molecular screen primary powder of 60-90 weight portion, 90-120 weight portion, the Suzhou soil of 30-40 weight portion, and the field mountain valley with clumps of trees and bamboo powder of 2-6 weight portion and the solution for preparing before join in the kneader and mediate.When these materials basically form toughness and plastic pug in kneader, after for example kneader was mediated about 20-45 minute, in kneader, progressively add the glass fibre of 10-30 weight portion.Kneader continues to mediate then, fully mixes in kneader until all materials, forms to have plastic pug uniformly.
In order further to improve the characteristic of pug, preferably also to carry out old and/or pugging to the pug that forms in the kneader.Can pug be closed when old in that pug is carried out, for example be enclosed in the polybag, under nitrogen atmosphere old 24-48 hour.When pug is carried out pugging, can pug be sent in the vacuum deairing machine pugging 1-3 time, be used for removing the bubble and the impurity of pug.
More specifically among the embodiment, the proportioning raw materials in the blend step can be selected according to the instance that provides in the following form at some:
Table one unit: weight portion
| Instance 1 | Instance 2 | Instance 3 | Instance 4 | Instance 5 | Instance 6 | |
| Citric acid | 2 | 3 | 4 | 2.5 | 3.5 | 0 |
| Sodium carboxymethylcellulose | 2 | 4 | 6 | 3 | 0 | 4 |
| Polyethylene glycol oxide | 2 | 4 | 6 | 0 | 5 | 4 |
| Ferrous sulfate | 20 | 30 | 40 | 25 | 35 | 30 |
| Glycerine | 0.2 | 0.6 | 1.0 | 0.4 | 0.8 | 0.6 |
| Nitric acid | 2 | 3 | 4 | 2.5 | 3.5 | 4 |
| Molecular screen primary powder | 60 | 75 | 90 | 68 | 82 | 75 |
| Boehmite | 90 | 105 | 120 | 98 | 112 | 105 |
| Suzhou soil | 30 | 35 | 40 | 33 | 0 | 35 |
| Field mountain valley with clumps of trees and bamboo powder | 2 | 4 | 6 | 3 | 5 | 0 |
| Glass fibre | 10 | 20 | 30 | 15 | 25 | 20 |
Forming step
The pug that forms in the blend step is sent in the extruder.The outlet of extruder adds the honeycomb moulding mould of being furnished with certain specification as required, and like this, extruder then is shaped to continuous honeycomb ceramics blank after pug is extruded through mould.Through automatic synchronization cutting mechanism cutting, then formation has the honeycomb ceramics blank module of certain size again.
Here, the selection of mould and the selection of module size all are well-known to those skilled in the art, repeat no more at this.
Calcining step
Before the calcining beginning, preferably the honeycomb ceramics blank for preparing in the forming step is sent into drying machine and carry out drying.In dry run, the average heating speed of drying machine is preferably between 5-10 ℃/day, until the baking temperature that reaches between 60-150 ℃, preferably reaches the baking temperature between 80-120 ℃.Under this baking temperature, the honeycomb ceramics blank is carried out drying then, until making the weight of honeycomb ceramics blank basically no longer change.Such drying time is usually at 15-20 days.
At last, the honeycomb ceramics blank that drying is good is sent into calcining kiln and is calcined, and forms the ceramic honeycomb denitrating catalyst.In calcination process, average heating speed is preferably between 10-20 ℃/hour, more preferably between 15-20 ℃/hour, until the calcining heat that reaches between 450-550 ℃, preferred 480-520 ℃.Whole calcination process continues 24-48 hour, thereby obtains required ceramic honeycomb denitrating catalyst finished product module.
Adopt the denitrating catalyst module of this method preparation; In the ammonia nitrogen mol ratio is that NH3/NOx=1 and SV air speed are under the true flue gas condition of 40000/h; Denitration efficiency is all more than 80% in 280-380 ℃ temperature range; Behind the operation 60h, tangible decline does not appear in activity, shows that this catalyst module possesses certain anti-poisoning performance and mechanical strength continuously.
Claims (17)
1. a ceramic honeycomb denitrating catalyst is that catalyst activity composition, catalyst carrier and shaping assistant are formed through mixing, moulding and calcining, it is characterized in that, said catalyst activity composition is a ferrous sulfate.
2. ceramic honeycomb denitrating catalyst according to claim 1 is characterized in that, said catalyst carrier is a molecular sieve.
3. ceramic honeycomb denitrating catalyst according to claim 2 is characterized in that said shaping assistant comprises the combination of nitric acid and boehmite.
4. ceramic honeycomb denitrating catalyst according to claim 3 is characterized in that, said shaping assistant also comprises Suzhou soil.
5. according to claim 3 or 4 or described ceramic honeycomb denitrating catalyst, it is characterized in that said shaping assistant also comprises citric acid.
6. according to each described ceramic honeycomb denitrating catalyst among the claim 1-4, it is characterized in that said shaping assistant comprises citric acid, sodium carboxymethylcellulose, polyethylene glycol oxide or this three's combination in any.
7. according to each described ceramic honeycomb denitrating catalyst among the claim 1-6, it is characterized in that said shaping assistant comprises glycerine and/or field mountain valley with clumps of trees and bamboo powder.
8. according to each described ceramic honeycomb denitrating catalyst among the claim 1-7, it is characterized in that said shaping assistant comprises glass fibre.
9. ceramic honeycomb denitrating catalyst; Be that catalyst activity composition, catalyst carrier and shaping assistant are formed through mixing, moulding and calcining; It is characterized in that; Said catalyst activity composition comprises the ferrous sulfate of 20-40 weight portion; Catalyst carrier comprises the molecular sieve of 60-90 weight portion, and said shaping assistant comprises: the Suzhou soil of the nitric acid of the polyethylene glycol oxide of the citric acid of 2-4 weight portion, 2-6 weight portion sodium carboxymethylcellulose, 2-6 weight portion, the glycerine of 0.2-1.0 weight portion, 2-4 weight portion, the boehmite of 90-120 weight portion, 30-40 weight portion, the field mountain valley with clumps of trees and bamboo powder of 2-6 weight portion, the glass fibre of 10-30 weight portion.
10. the preparation method of a ceramic honeycomb denitrating catalyst comprises:
Blend step is used for various materials and solvent, forms to have plastic pug;
Old step and/or pugging step are used to improve the characteristic of said pug;
Forming step, being used for said mud material forming is the honeycomb ceramics blank;
Drying steps is used for removing the moisture of said honeycomb ceramics blank;
Calcining step is used for said honeycomb ceramics blank is calcined, to form said ceramic honeycomb denitrating catalyst;
It is characterized in that order comprises in blend step:
1) water of getting 100 weight portions is as solvent, and the polyethylene glycol oxide of getting citric acid, 2-6 weight portion sodium carboxymethylcellulose, the 2-6 weight portion of 2-4 weight portion again joins in the solvent and dissolves;
2) ferrous sulfate of 20-40 weight portion is joined in the solution dissolve again;
3) nitric acid of getting glycerine and the 2-4 weight portion of 0.2-1.0 weight portion joins in the solution and dissolves.
4) with the boehmite of the molecular screen primary powder of 60-90 weight portion, 90-120 weight portion, the Suzhou soil of 30-40 weight portion, and the field mountain valley with clumps of trees and bamboo powder of 2-6 weight portion and the solution for preparing before join in the kneader and mediate;
5) when basically forming toughness and plastic pug in the kneader, in kneader, progressively add the glass fibre of 10-30 weight portion; Kneader continues to mediate then, fully mixes in kneader until all materials, forms to have plastic pug uniformly.
11. preparation method according to claim 10 is characterized in that, in said old step, said pug is placed in the environment of base closed old 24-48 hour.
12. preparation method according to claim 11 is characterized in that, in the environment of said base closed, charges into nitrogen.
13. preparation method according to claim 10 is characterized in that, in said drying steps; Said honeycomb ceramics blank is admitted to and carries out drying in the drying machine; Wherein, the average heating speed of said drying machine is between 5-10 ℃/day, until the baking temperature that reaches 60-150 ℃.
14. preparation method according to claim 13 is characterized in that, said baking temperature is between 80-120 ℃.
15. preparation method according to claim 10 is characterized in that, in said calcining step; The honeycomb ceramics blank is sent into calcining kiln and is calcined; In calcination process, average heating speed is between 10-20 ℃/hour, until the calcining heat that reaches 450-550 ℃.
16. preparation method according to claim 15 is characterized in that, in calcination process, average heating speed is between 15-20 ℃/hour.
17. preparation method according to claim 15 is characterized in that, in calcination process, said calcining heat is between 480-520 ℃.
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| CN102698810A (en) * | 2012-05-14 | 2012-10-03 | 清华大学 | Honeycomb type denitration catalyst and preparation method thereof |
| CN102824922A (en) * | 2012-09-07 | 2012-12-19 | 浙江天蓝环保技术股份有限公司 | Integrated honeycomb SCR (selective catalytic reduction) catalyst for low-temperature smoke denitration and preparation method of catalyst |
| CN103301831A (en) * | 2012-03-16 | 2013-09-18 | 中国科学院大连化学物理研究所 | Catalyst for removing nitrogen oxide in emission exhaust and preparation method thereof |
| CN103691489A (en) * | 2013-11-29 | 2014-04-02 | 湖北广净环保催化剂有限公司 | Denitration catalyst carrier for loading high-dust flue gas and preparation method thereof |
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| 任雯等: "FeSO4催化剂模块的制备及对其脱硝性能影响的研究", 《环境科学学报》 * |
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