A kind of powdery denitrating catalyst and preparation method thereof
阅读说明：本技术 一种粉状脱硝催化剂及其制备方法 (A kind of powdery denitrating catalyst and preparation method thereof ) 是由 祝社民 李喜红 陶兴军 金奇杰 于 2019-07-03 设计创作，主要内容包括：本发明涉及一种新型粉状脱硝催化剂及其制备方法,其特征在于各组分占粉状脱硝催化剂的百分含量分别为：活性组分为5-30％,助剂为15-50％,添加剂为20-80％；其中活性组分为Fe的氧化物和Mn的氧化物；助剂为Ce、La、Er、Si、Al、Ca、Ti的氧化物、Au或Pt中的一种或多种；添加剂为活性炭或尿素中的一种或两种和三聚氰胺或葡萄糖中的一种或两种的混合物。将焙烧制得的活性组分、助剂和添加剂充分混合球磨,制得新型粉状脱硝催化剂。本发明催化剂组分环境友好,脱除NO<Sub>x</Sub>活性温度高且窗口宽范,在700-1200℃温度范围内,可以有效的实现脱硝。(The present invention relates to a kind of new powdered denitrating catalysts and preparation method thereof, it is characterised in that it is 5-30%, auxiliary agent 15-50%, additive 20-80% that the percentage composition that each component accounts for powdery denitrating catalyst, which is respectively as follows: active component,；Wherein active component is the oxide of Fe and the oxide of Mn；Auxiliary agent is one of oxide, Au or Pt of Ce, La, Er, Si, Al, Ca, Ti or a variety of；Additive is the mixture of one or both of active carbon or urea and one or both of melamine or glucose.Active component, auxiliary agent and additive obtained will be roasted and be sufficiently mixed ball milling, new powdered denitrating catalyst is made.Catalytic component of the present invention is environmental-friendly, removes NO x Active temperature is high and the wide model of window can effectively realize denitration in 700-1200 DEG C of temperature range.)
1. a kind of powdery denitrating catalyst, it is characterised in that its group is divided into active component, auxiliary agent and additive, and each component accounts for powdery It is 5-30%, auxiliary agent 15-50%, additive 20-80% that the percentage composition of denitrating catalyst, which is respectively as follows: active component,；Its Middle active component is the oxide of Fe and the oxide of Mn；Auxiliary agent is oxide, the Si of the oxide of Ce, the oxide of La, Er Oxide, the oxide of Al, the oxide of Ca, Ti one of oxide, Au or Pt or a variety of；Additive is active carbon Or the mixture of one or both of urea and one or both of melamine or glucose, wherein active carbon or urea One or both of account for the 11~100% of additive gross mass.
2. according to right want 1 described in powdery denitrating catalyst, it is characterised in that the oxygen of the oxide of Fe and Mn in active component Compound mass ratio is 1:(0.1-10).
3. a kind of method for preparing powdery denitrating catalyst as described in claim 1, the specific steps are that:
(1) preparation of active component
It weighs after molysite roasts in air atmosphere, hydrogen atmosphere handles 30-45min；Manganese salt is weighed to roast in air atmosphere；
(2) preparation of auxiliary agent
If auxiliary agent is the oxide of the oxide of Ce, the oxide of La, Er, weighs the precursor salt containing Ce, La or Er and exist It is roasted under air atmosphere；If auxiliary agent is the oxide of Si, the oxide of Al, the oxide of Ca, the oxide of Ti, Au or Pt Directly weigh；
(3) preparation of monolithic catalyst
Weigh active component made from step (1) by the percentage composition of each component, the oxide of Si, the oxide of Al, Ca oxygen One in the oxide of the oxide of Ce, the oxide of La or Er is prepared in compound, the oxide of Ti, Au, Pt, step (2) Kind or a variety of and additive, mixing and ball milling sieving, are made powdery denitrating catalyst.
4. according to the method described in claim 2, it is characterized in that the molysite is Fe(NO3)39H2O；The manganese salt is Four nitric hydrate manganese.
5. according to the method described in claim 2, it is characterized in that the precursor salt containing Ce, La or Er is containing Ce, La Or the nitrate of Er.
6. according to the method described in claim 2, it is characterized in that maturing temperature described in step (1) and (2) is 500- 600 DEG C, the time is 2-3h.
7. according to the method described in claim 2, it is characterized in that the sieving was 20 meshes.
Technical field
The present invention relates to a kind of novel powdery denitrating catalyst and preparation method thereof, belong to environment protection catalytic material and big Gas pollution control field.
Background technique
Nitrogen oxides is one of the important origin cause of formation of haze, acid rain, and cement industry is main NOxStationary source is discharged, simultaneously It is also the emphasis of air contaminant treatment.Cement industry discharges NO due to lacking efficient, practical denitration technology at presentxDischarge one As area be 400mg/m3, key area 320mg/m3Standard.And power industry has been carried out NOxDischarging general area is 50mg/m3, key area 25mg/m3Standard.With the increase of environmental protection pressure, cement industry NOxDischarge standard will be carried out 100mg/m3, some areas have been carried out minimum discharge, it is desirable that are less than 50mg/m3.And currently used denitration technology is difficult to meet.
Cement industry main denitration technology in China's has: low-NO_x combustion technology, selective non-catalytic reduction (SNCR) denitration skill Art and SCR denitration technology.Kong Xuebiaos etc. are improved by low NO to promote denitration efficiency, but denitration efficiency can only still reach To 50% or so；Yellow distance of travel of roc, Wang Fan etc. is designed and is optimized cement plant SNCR denitration system, the experimental results showed that denitration efficiency 70% can be reached, somebody adds SNCR denitration technology by low nitrogen burning, can only meet 100mg/m3Discharge limit, but Still it cannot achieve minimum discharge, and there are serious the escaping of ammonia, cause the secondary pollution and equipment corrosion of environment.SCR denitration Technology, denitration efficiency can be greater than 90%, though the minimum discharge in power industry is used widely, cement industry it is high-alkali Flue dust easily inactivates catalyst poisoning, and Gao Chenyi makes catalyst blockage, it is difficult to be applied.
Summary of the invention
A kind of novel powdery denitration catalyst is provided the purpose of the invention is to improve the deficiencies in the prior art Agent, further object of the present invention are to provide the preparation method of above-mentioned catalyst.
The technical solution of the present invention is as follows: a kind of powdery denitrating catalyst, it is characterised in that its group is divided into active component, helps Agent and additive；It is 5-30%, auxiliary agent 15- that the percentage composition that each component accounts for powdery denitrating catalyst, which is respectively as follows: active component, 50%, additive 20-80%；Wherein active component is the oxide of Fe and oxide (ferroso-ferric oxide and the titanium dioxide of Mn Manganese)；Auxiliary agent be the oxide of Ce, the oxide of La, the oxide of Er, the oxide of Si, the oxide of Al, Ca oxide, One of oxide, Au or Pt of Ti or a variety of；Additive is one or both of active carbon or urea and melamine Or the mixture of one or both of glucose, wherein one or both of active carbon or urea account for additive gross mass 11~100%.
It is preferred that the oxide mass of the oxide of Fe and Mn ratio are 1:(0.1-10 in above-mentioned active component).
The present invention also provides the methods for preparing above-mentioned powdery denitrating catalyst, the specific steps are that:
(1) preparation of active component
It weighs after molysite roasts in air atmosphere, maturing temperature is 500-600 DEG C, time 2-3h, at hydrogen atmosphere Manage 30-45min；Manganese salt is weighed to roast in air atmosphere；Maturing temperature is 500-600 DEG C, time 2-3h；
(2) preparation of auxiliary agent
If auxiliary agent is oxide, the oxide of La or the oxide of Er of Ce, the forerunner containing Ce, La or Er is weighed Body salt roasts in air atmosphere, and maturing temperature is 500-600 DEG C, time 2-3h；If auxiliary agent is oxide, the Al of Si Oxide, the oxide of Ca, the oxide of Ti, Au or Pt then directly weigh；
(3) preparation of monolithic catalyst
Active component made from step (1), the oxide of Si, the oxide of Al, Ca are weighed by the percentage composition of each component Oxide, the oxide of Ti, Au, Pt, step (2) be prepared in the oxide of the oxide of Ce, the oxide of La or Er One or more and additive, mixing and ball milling sieving, be made powdery denitrating catalyst.
It is preferred that above-mentioned molysite is Fe(NO3)39H2O；The manganese salt is four nitric hydrate manganese.
It is preferred that the above-mentioned precursor salt containing Ce, La or Er is the nitrate containing Ce, La or Er.
It is preferred that above-mentioned mixing and ball milling sieving was 20 meshes.
The utility model has the advantages that
Catalytic component of the present invention is environmental-friendly, removes NOxIt is the wide model of active temperature windows, high-efficient, at 700-1200 DEG C In temperature range, denitration can be effectively realized.Compared with traditional high temperature denitration mode, main advantage is that denitration is imitated Rate is high, equipment one-time investment is low.It can reduce using NH3, the problem of reducing ammonia excess and the escaping of ammonia, prevent equipment Corrosion, there is no the influences of water sulfur poisoning.
Specific embodiment
Example 1
(1) preparation of active component
After taking 2355.54g Fe(NO3)39H2O to roast in air atmosphere, maturing temperature is 500 DEG C, time 2h, hydrogen Gas atmosphere handles 45min；Tetra- nitric hydrate manganese of 144.25g is taken to roast in air atmosphere；Maturing temperature is 500 DEG C, and the time is 2h；Wherein the mass ratio of ferroso-ferric oxide and manganese dioxide is 9:1；
(2) preparation of auxiliary agent
Take 265.64g lanthanum nitrate hexahydrate, six nitric hydrate cerium of 252.32g, five nitric hydrate erbium of 115.97g in air It is roasted under atmosphere, maturing temperature is 500 DEG C, time 2h；Take 500g alumina powder, 500g silicon oxide powder, 200g oxidation Calcium powder, 0.005g nanogold are uniformly mixed with 0.005g platinum；
(3) preparation of monolithic catalyst
By active component obtained above, auxiliary agent and 3000g active carbon, 2000g melamine, 1000g glucose, The mixing of 2000 urea, is sufficiently milled to 20-80 mesh；Novel powder denitrating catalyst is made, wherein active component: auxiliary agent: complexing The mass ratio of additive is 5:15:80；
(4) activity rating
Test condition NO=900ppm, O2=5%, N2For Balance Air, air speed 3000h-1, gas flow=1000 mL/ Min, catalyst usage amount are 5g/min, and test result shows catalyst in 700-1200 DEG C of denitration activity 86% or more.
Example 2
(1) preparation of active component
After taking 785.16g Fe(NO3)39H2O to roast in air atmosphere, maturing temperature is 500 DEG C, time 3h, hydrogen Gas atmosphere handles 35min；Tetra- nitric hydrate manganese of 432.76g is taken to roast in air atmosphere；Maturing temperature is 600 DEG C, and the time is 3h；Wherein the mass ratio of ferroso-ferric oxide and manganese dioxide is 1:1；
(2) preparation of auxiliary agent
Take 106.26g lanthanum nitrate hexahydrate, six nitric hydrate cerium of 151.40g, five nitric hydrate erbium of 57.98g in air gas It is roasted under atmosphere, maturing temperature is 600 DEG C, time 3h；Take 300g alumina powder, 300g silicon oxide powder, 50g calcium oxide Powder, 0.0005g nanogold are uniformly mixed with 0.0005g platinum；
(3) preparation of monolithic catalyst
Active component obtained above, auxiliary agent are mixed with 50g active carbon, 150g urea, are sufficiently milled to 20-80 mesh； Novel powder denitrating catalyst is made, wherein active component: auxiliary agent: the mass ratio that additive is complexed is 30:50:20；
(4) activity rating
Test condition NO=900ppm, O2=5%, N2For Balance Air, air speed 3000h-1, gas flow=1000 mL/ Min, catalyst usage amount are 5g/min, and test result shows catalyst in 700-1200 DEG C of denitration activity 80% or more.
Example 3
(1) preparation of active component
After taking 1046.91g Fe(NO3)39H2O to roast in air atmosphere, maturing temperature is 600 DEG C, time 2h, hydrogen Gas atmosphere handles 40min；Tetra- nitric hydrate manganese of 57.70g is taken to roast in air atmosphere；Maturing temperature is 500 DEG C, and the time is 2h；Wherein the mass ratio of ferroso-ferric oxide and manganese dioxide is 10:1；
(2) preparation of auxiliary agent
26.56g lanthanum nitrate hexahydrate, six nitric hydrate cerium of 50.46g is taken to roast in air atmosphere, maturing temperature is 500 DEG C, time 2h；100g alumina powder, 50g silicon oxide powder 0.0005g nanogold is taken to mix with 0.0005g platinum It is even；
(3) preparation of monolithic catalyst
Active component obtained above, auxiliary agent are mixed with 300g melamine, 100g glucose, 200g urea, sufficiently It is milled to 20-80 mesh；Novel powder denitrating catalyst is made, wherein active component: auxiliary agent: the mass ratio that additive is complexed is 22:18:60；
(4) activity rating
Test condition NO=900ppm, O2=5%, N2For Balance Air, air speed 3000h-1, gas flow=1000 mL/ Min, catalyst usage amount are 5g/min, and test result shows catalyst in 700-1200 DEG C of denitration activity 83% or more.
Example 4
(1) preparation of active component
After taking 104.70g Fe(NO3)39H2O to roast in air atmosphere, maturing temperature is 500 DEG C, time 3h, hydrogen Gas atmosphere handles 30min；Tetra- nitric hydrate manganese of 577.01g is taken to roast in air atmosphere；Maturing temperature is 600 DEG C, and the time is 3h；Wherein the mass ratio of ferroso-ferric oxide and manganese dioxide is 1:10；
(2) preparation of auxiliary agent
Six nitric hydrate cerium of 75.70g is taken to roast in air atmosphere, maturing temperature is 600 DEG C, time 3h；Take 250g Alumina powder, 50g silicon oxide powder, 0.0005g nanogold are uniformly mixed with 0.0005g platinum；
(3) preparation of monolithic catalyst
Active component obtained above, auxiliary agent are mixed with 50g active carbon, 300g melamine, 100g glucose, filled Bulb separation is milled to 20-80 mesh；Novel powder denitrating catalyst is made, wherein active component: the mass ratio of additive auxiliary agent: is complexed For 22:33:45；
(4) activity rating
Test condition NO=900ppm, O2=5%, N2For Balance Air, air speed 3000h-1, gas flow=1000 mL/ Min, catalyst usage amount are 5g/min, and test result shows catalyst in 700-1200 DEG C of denitration activity 81% or more.
Example 5
(1) preparation of active component
After taking 785.16g Fe(NO3)39H2O to roast in air atmosphere, maturing temperature is 500 DEG C, time 3h, hydrogen Gas atmosphere handles 35min；Tetra- nitric hydrate manganese of 432.76g is taken to roast in air atmosphere；Maturing temperature is 600 DEG C, and the time is 3h；Wherein the mass ratio of ferroso-ferric oxide and manganese dioxide is 1:1；
(2) preparation of auxiliary agent
500g silicon oxide powder is weighed, as auxiliary agent；
(3) preparation of monolithic catalyst
Active component obtained above, auxiliary agent are mixed with 50g active carbon, 150g urea, be sufficiently milled to 20 mesh with Under；Novel powder denitrating catalyst is made, wherein active component: auxiliary agent: the mass ratio that additive is complexed is 30:50:20；
(4) activity rating
Test condition NO=900ppm, O2=5%, N2For Balance Air, air speed 3000h-1, gas flow=1000 mL/ Min, catalyst usage amount are 5g/min, and test result shows catalyst in 700-1200 DEG C of denitration activity 78% or more.
Example 6
(1) preparation of active component
After taking 104.70g Fe(NO3)39H2O to roast in air atmosphere, maturing temperature is 500 DEG C, time 3h, hydrogen Gas atmosphere handles 30min；Tetra- nitric hydrate manganese of 577.01g is taken to roast in air atmosphere；Maturing temperature is 600 DEG C, and the time is 3h；Wherein the mass ratio of ferroso-ferric oxide and manganese dioxide is 1:10；
(2) preparation of auxiliary agent
Six nitric hydrate cerium of 832.68g is taken to roast in air atmosphere, maturing temperature is 600 DEG C, time 3h；
(3) preparation of monolithic catalyst
Active component obtained above, auxiliary agent are mixed with 50g active carbon, 300g melamine, 100g glucose, filled Bulb separation is milled to 20 mesh or less；Novel powder denitrating catalyst is made, wherein active component: the mass ratio of additive auxiliary agent: is complexed For 22:33:45；
(4) activity rating
Test condition NO=900ppm, O2=5%, N2For Balance Air, air speed 3000h-1, gas flow=1000 mL/ Min, catalyst usage amount are 5g/min, and test result shows catalyst in 700-1200 DEG C of denitration activity 80% or more.