CN107537492A - A kind of method that iron system denitrating catalyst is directly prepared by the activation of red mud soda acid - Google Patents

A kind of method that iron system denitrating catalyst is directly prepared by the activation of red mud soda acid Download PDF

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CN107537492A
CN107537492A CN201711000654.4A CN201711000654A CN107537492A CN 107537492 A CN107537492 A CN 107537492A CN 201711000654 A CN201711000654 A CN 201711000654A CN 107537492 A CN107537492 A CN 107537492A
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red mud
slurry
acid
obtains
catalyst
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余剑
杨娟
李长明
刘周恩
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Nanjing Weiheng Experiment Equipment Co ltd
Institute of Process Engineering of CAS
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Nanjing Weiheng Experiment Equipment Co ltd
Institute of Process Engineering of CAS
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Abstract

The invention provides a kind of method for directly preparing iron system denitrating catalyst by the activation of red mud soda acid.Methods described method comprises the following steps：(1) acid is added into red mud, after 70 DEG C of 200 DEG C of reactions, obtains the first slurry, first slurry is Acid Slurry；(2) alkaline matter is added into step (1) first slurry, regulation pH value obtains the second slurry to 5 10；(3) separation of solid and liquid is carried out to step (2) second slurry and obtains filter cake, the filter cake is calcined, obtains the ferrotitanium sieve and silica-sesquioxide catalyst with denitration activity.The method harmless treatment red mud discarded object of the present invention, turns waste into wealth, is directly used in denitrating flue gas process, greatly reduce the cost of existing denitration, have extensive prospects for commercial application simultaneously；The ferrotitanium sieve and silica-sesquioxide catalyst that the method for the present invention obtains can be used for coal-fired flue gas denitration process, substitute the denitrating catalyst of existing vanadium tungsten titanium.

Description

A kind of method that iron system denitrating catalyst is directly prepared by the activation of red mud soda acid
Technical field
The invention belongs to the processing of aluminum oxide smelting industry danger solid waste and application field, is related to one kind by red mud system Method of the standby iron system without vanadium high temperature denitrating catalyst.
Background technology
The pollution strong basicity waste residue that red mud is discharged when being aluminium industry extraction aluminum oxide, average often produce 1 ton of oxidation Aluminium, incidentally produce 1.0~2.0 tons of red muds.Substantial amounts of red mud belongs to strong alkaline substance, stacks, takes by the stockyard of large area It must be avoided causing environment serious pollution by cement barrier wall while a large amount of soils.Most of country will be red Mud is classified as danger wastes, and the generation production to the mankind, the life of red mud cause many influences directly or indirectly, So to greatest extent reduce red mud yield and harm, realize by all kinds of means, the recycling of big quantity it is extremely urgent.
Not only contain the composition such as iron oxide, silica, aluminum oxide, sodium oxide molybdena and other transition metal oxides in red mud. The existing more Patents report of the higher value application conversion of these compositions in red mud, for example, CN102234171A and Red mud is subjected to dealkalize then as the raw material of production cement disclosed in CN101468866A；CN101891406A and CN1837121A discloses the method that red mud using red mud or after iron is selected in dealkalize and desulfurated plaster prepare cement； CN103373815A is disclosed using Bayer process red mud as main material production porous devitrified glass；CN103420359A discloses red The method that mud catalysis prepares CNT；CN102757060A is disclosed by way of lime disappears sodium, then separates wherein aluminium With part ferriferous oxide, the depth extraction of aluminium compound is realized.CN105536797 A propose loads substantial amounts of oxygen using red mud Denitrating catalyst is prepared after changing copper, denitration activity is only 80%, and temperature window is narrow.However, in these above-mentioned inventions, red mud The dealkalize of neutral and alkali compound or other processing procedures, obtain iron oxide therein and other transition metal oxides Utilize well.Particularly realize the catalytic activity of iron oxide.Pollution and Synthetical Utilization Situation with reference to red mud, it is seen that existing Stage also realizes the higher value application method and approach of iron in red mud, and red mud high-valued and that amount is big without feasible technology Application approach.
And in the investigation of denitrating catalyst, commercialized middle temperature catalyst is with vanadium tungsten titanium or vanadium molybdenum titanium oxide body System, the catalyst need to expend added value high titanium dioxide and vanadium tungsten oxide, and cost is high, and high temperature oxidation stability is strong, it is difficult to should For more than 400 DEG C flue gas conditions.And with increasingly strict, the depth of building materials field cement revolving tubular kiln flue gas of national environmental protection policy It is imperative to spend denitration, new requirement is proposed to catalyst practical under the conditions of high-temperature high dust.Iron oxide is as active component Or catalyst aid prepare denitrating catalyst patent it is a lot, such as patent CN103949267A, all mention and adopting in CN102658161A By the use of iron oxide as active component in carrier TiO2Or Al2O3Surface is loaded or mixing prepares denitrating catalyst, makes catalysis Agent has high intensity and high activity.It is complete with regulation and control method by suitably preparing containing abundant iron oxide composition in red mud The excellent catalyst of coal-fired flue gas denitration can be translated into, moreover also contains micro transition metal oxide in red mud, Such as Cr2O3、TiO2, Nb2O5And ZrO2, these all to NO catalysis reduction play an important role.
Therefore a kind of method that red mud is more efficiently converted into denitrating catalyst is developed, can not only solves dangerous waste processing Problem, and existing denitrating flue gas cost can be effectively reduced, be significant.
The content of the invention
To solve the above-mentioned problems in the prior art, iron system is prepared by red mud it is an object of the invention to provide one kind The method of denitrating catalyst.The method of the present invention regulates and controls to react by soda acid, the alkali metal in red mud is removed and system Middle active Fe content is adjusted, and realizes the preparation of the ferrotitanium sial composite oxides with high temperature denitration activity.The present invention Both solved the problem of red mud processing, and reduced existing denitrating flue gas cost again, reach the purpose of the treatment of wastes with processes of wastes against one another.
To use following technical scheme up to this purpose, the present invention：
The present invention provides a kind of method that iron system denitrating catalyst is prepared by red mud, the described method comprises the following steps：
(1) acid is added into red mud, after 70 DEG C of -200 DEG C of reactions, obtains the first slurry, first slurry is acidity Slurry；
(2) alkaline matter is added into step (1) first slurry, regulation pH value obtains the second slurry to 5-10；
(3) separation of solid and liquid is carried out to step (2) second slurry and obtains filter cake, the filter cake is calcined, obtained Ferrotitanium sieve and silica-sesquioxide catalyst with denitration activity.
The present invention prepares the high-specific surface area iron with high temperature denitration activity using aluminum oxide smelting by-product iron content red mud Titanium silicon-aluminium compound catalyst.In the present invention, by liquid phase acid-base reaction at a certain temperature, by ferrotitanium sial chemical combination in red mud Thing carries out molecular recombination and activation, realizes the work of the transition metal oxide such as red mud neutral and alkali devolatilization and ferrous oxide Change, and improve the specific surface area of material, realize the high temperature denitration activity of catalyst, then be catalyzed by filtering and calcining Agent product.The ferrotitanium sieve and silica-sesquioxide catalyst with denitration activity that the present invention obtains is with Al2O3、SiO2And TiO2 Micro heavy oxide to contain in carrier, iron oxide and red mud is the high temperature denitration catalyst agent material of active component, The catalyst material is represented by Fe2O3/SiO2-Al2O3-TiO2Compound.
In the present invention, acid reaction temperature is limited as 70 DEG C -200 DEG C in step (1), for example, 70 DEG C, 90 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C or 200 DEG C etc., it is not limited to cited numerical value, other are unrequited in the number range Numerical value it is equally applicable.Here, the transition metal oxide that 70 DEG C -200 DEG C of temperature can allow in red mud is to a certain extent Acidification reaction is carried out, forms corresponding salting liquid；It is transition metal hydroxide in follow-up alkalimetric titration process again hydrolysis Thing, by follow-up washing, drying, roasting process, so that it becomes gamma-iron oxide, this can make the ferrotitanium that the present invention ultimately produces The catalytic performance of sieve and silica-sesquioxide catalyst is significantly improved.In the step, selection and sour use by temperature, not only Help to realize the dealkalize of red mud, the effect of the iron oxide activation caused in red mud is also acted, simultaneously for ferrotitanium in red mud The raising of the molecular recombination of silicoaluminate and final obtained specific surface area of catalyst all has good facilitation.This In, if temperature is less than 70 DEG C, the activation of iron oxide can not be realized, that can cause the ferrotitanium sieve and silica-sesquioxide catalyst finally obtained Catalytic performance be decreased obviously；If temperature is higher than 200 DEG C, equipment and materials requirement can be caused too high, production cost is complicated, and High-temperature hydrolysis directly occur for some transition metal salts, reduce the catalytic activity of product.
In the present invention, acid and alkaline matter regulation pH value are added in step (1) and (2), realize main iron in red mud, titanium, The reformation of silicon, aluminum material forms new compound and ensure that the removing of red mud neutral and alkali material.In step (2), regulation PH value is to 5-10, such as 5,6,7,8,9 or 10 etc., it is not limited to cited numerical value, interior other of the number range do not arrange The numerical value of act is equally applicable.
Currently preferred technical scheme is used as below, but not as the limitation to technical scheme provided by the invention, is led to Following preferable technical scheme is crossed, can preferably reach and realize the technical purpose and beneficial effect of the present invention.
As currently preferred technical scheme, in step (1), the acid is sulfuric acid, hydrochloric acid, phosphoric acid, oxalic acid, acetic acid or Organic sulfonic acid any one or at least two combination, preferably sulfuric acid.In the present invention,
The denitration catalyst of ferrotitanium sieve and silica-sesquioxide catalyst of the sour species used in step (1) for finally giving is lived Property there is important influence, if use acid decompose at a lower temperature, such as nitric acid, then be unable to reach red mud activation mesh , decomposed at a temperature of will being limited in step of the present invention (1), and then be difficult to play dealkalize, lift what is finally given The specific surface area of ferrotitanium sieve and silica-sesquioxide catalyst and the effect of the iron oxide in activation red mud.Here preferably sulfuric acid is because sulphur Acid has high stability.
Preferably, the pH of first slurry is 0-2, such as 0,0.5,1,1.5 or 2 etc., it is not limited to cited Numerical value, other unrequited numerical value are equally applicable in the number range, preferably 1.
As currently preferred technical scheme, step (1) described red mud is Bayer process red mud, sub-molten salt red mud or sintering In method red mud any one or at least two combination.
Preferably, the content of iron oxide is 10%-60% in the red mud, such as 10%, 20%, 30%, 40%, 50% Or 60% etc., it is not limited to cited numerical value, other interior unrequited numerical value of the number range are equally applicable.
As currently preferred technical scheme, step (1) acid is industrial waste acid, such as Producing Titanium Dioxide process produces Spent acid (sulfuric acid and hydrochloric acid) etc..
Preferably, mass fraction sour in the industrial waste acid is 20%-60%.
Preferably, in step (1), the mass ratio of the red mud and acid is 1:(0.1-5), such as 1:0.1、1:0.5、1:1、 1:2、1:3、1:4、1:5 etc., it is not limited to cited numerical value, other interior unrequited numerical value of the number range are equally suitable With.Here sour quality refers to the quality of the acid solute in acid solution rather than the quality that acid solution is overall.If red mud and acid Mass ratio be higher than 1:0.1 (i.e. red mud is excessive), key component in red mud can be caused to react insufficient, alkali metal removing is endless Entirely；If the mass ratio of red mud and acid is less than 1:5 (i.e. excessive acids), acid consumption can be caused too big, separation of solid and liquid cost height, yielded poorly.
As currently preferred technical scheme, in step (1), the temperature of the reaction is 80 DEG C -180 DEG C, such as 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C or 180 DEG C etc., it is not limited to cited numerical value, in the number range other Unrequited numerical value is equally applicable.
Preferably, in step (1), time of the reaction is 3h-20h, such as 3h, 5h, 8h, 10h, 13h, 16h, 18h Or 20h etc., it is not limited to cited numerical value, other interior unrequited numerical value of the number range are equally applicable.
Preferably, in step (1), the reaction is carried out under the conditions of being stirred.
As currently preferred technical scheme, in step (2), the alkaline matter is alkaline hydrated oxide, carbonate In ammoniate any one or at least two combination, preferably sodium hydroxide and/or ammonium carbonate.Here, described " hydrogen Sodium oxide molybdena and/or ammonium carbonate " refers to：Can be sodium hydroxide, or ammonium carbonate, can also be sodium hydroxide and ammonium carbonate Combination.
As currently preferred technical scheme, in step (2), the addition manner of the alkaline matter is gradually adds. Here, described gradually add refers to add several times, rather than is disposably added completely into.
As currently preferred technical scheme, in step (3), the mode of the separation of solid and liquid is plate compression, leaf is filtered Or any one in vacuum filtration.
Preferably, in step (3), in addition to：The filter cake obtained after separation of solid and liquid is washed and dried.
Preferably, the washing is carried out multiple, until the alkali metal mass fraction in the filter cake is less than 0.5wt%, example Such as 0.4wt%, 0.3wt%, 0.2wt%, 0.1wt%, 0.05wt% or 0.01wt%.
In the method for the present invention, step (3), which carries out separation of solid and liquid and the purpose of washing, just includes removing alkali metal compound, Washing process carries out repeatedly making the content of the alkali metal compound in filter cake lower.
Preferably, in step (3), return at red mud raw material and carry out after the aqueous phase progress desalting processing that separation of solid and liquid obtains Recycle.
Preferably, in step (3), discharged again after the aqueous phase progress desalting processing that separation of solid and liquid obtains.The desalting processing So that the requirement that the aqueous phase that separation of solid and liquid obtains is up to state standards.
As currently preferred technical scheme, in step (3), the temperature of the roasting is 300 DEG C -800 DEG C, such as 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C or 800 DEG C etc., but simultaneously not only It is limited to cited numerical value, other unrequited numerical value are equally applicable in the number range.
Preferably, in step (3), time of the roasting is 1h-20h, for example, 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h or 20h etc., it is not limited to cited numerical value, other interior unrequited numerical value of the number range are same It is applicable.
Preferably, in step (3), in addition to：The ferrotitanium sieve and silica-sesquioxide catalyst with denitration activity is carried out It is broken.
As the further preferred technical scheme of the method for the invention, the described method comprises the following steps：
(1) sulfuric acid is added into red mud, after 80 DEG C of -180 DEG C of reaction 3h-20h, obtains the first slurry, first slurry The pH of material is 0-2, and the mass ratio of the red mud and sulfuric acid is 1:(0.1-5)；
(2) sodium hydroxide and/or ammonium carbonate are added into step (1) first slurry, regulation pH value obtains to 5-10 Second slurry；
(3) filter cake is obtained after separation of solid and liquid and washing being carried out to step (2) second slurry, the filter cake is dried 1h-20h is calcined at 300 DEG C -800 DEG C after dry, then is crushed, obtains having the ferrotitanium sieve and silica-sesquioxide of denitration activity to be catalyzed Agent.
Compared with the prior art, the present invention has the advantages that：
(1) method provided by the invention that iron system denitrating catalyst is prepared by red mud can use red mud system by plain mode Standby nanosized iron-based catalyst material, harmless treatment red mud discarded object, turns waste into wealth, is directly used in denitrating flue gas process simultaneously, The processing procedure of the treatment of wastes with processes of wastes against one another and the higher value application of red mud are realized, greatly reduces the cost of existing denitration, is had extensive Prospects for commercial application；
(2) method provided by the invention is suitable sour by being added at a proper temperature into red mud in step (1) Carry out react, not only facilitate the dealkalize for realizing red mud, also effectively activated the bloodstone in red mud, improve final The denitration activity of the ferrotitanium sieve and silica-sesquioxide catalyst arrived；
(3) the ferrotitanium sieve and silica-sesquioxide specific surface area of catalyst that method provided by the invention obtains is high, and intensity is high, and catalysis is lived Property it is high, suitable for high-temperature high dust denitrating flue gas processing procedure, such as coal-fired flue gas denitration process, substitute existing vanadium tungsten titanium Denitrating catalyst, fully meet industrial requirement.
Brief description of the drawings
Fig. 1 is the process chart for the method for preparing iron system denitrating catalyst in the embodiment of the present invention 1 by red mud.
Embodiment
Technical scheme is further illustrated below by embodiment.But following embodiments are only The simple example of the present invention, the scope of the present invention is not represented or limits, the scope of the present invention is with claim Book is defined.
Embodiment 1
The present embodiment provides a kind of method that iron system denitrating catalyst is prepared by red mud, and its specific method is：
(1) to 1kg red mud (Fe in red mud2O3Mass fraction is 35%) middle addition 3kg waste hydrochloric acid (concentration 20%) Afterwards, it is reacted into 10h at 80 DEG C, obtains the first homogeneous slurry, the first slurry solid content is 25%, pH 2；
(2) ammoniacal liquor (mass fraction of ammonia is 10% in ammoniacal liquor) is gradually added into the first slurry, solution ph is about 9, Silicon-aluminum sol precipitates again, and system viscosity diminishes, and obtains the second slurry；
(3) after the second slurry being carried out into separation of solid and liquid and washing, dried under the conditions of 100 DEG C, and then under the conditions of 600 DEG C Roasting 5h obtains solid matter, i.e. ferrotitanium sieve and silica-sesquioxide denitrating catalyst.The aqueous phase that separation of solid and liquid obtains carries out desalting processing After return at red mud raw material and recycled.
In the present embodiment, the technological process that iron system denitrating catalyst is prepared by red mud is as shown in Figure 1.
The specific surface area for the ferrotitanium sieve and silica-sesquioxide denitrating catalyst that the present embodiment obtains is 205m2/ g, intensity 5Mpa, Composition is as shown in table 1.
Table 1
The sample of ferrotitanium silicon-aluminium compound obtained by the present embodiment is 10 in air speed5Under/h, 600ppm SO2With 10% In the presence of water, and NH3Under conditions of/NO is 1,300 DEG C, 350 DEG C, 400 DEG C and 450 DEG C of denitration rates be respectively 60%, 83%th, 90% and 90%.
Embodiment 2
The present embodiment provides a kind of method that iron system denitrating catalyst is prepared by red mud, and its specific method is：
(1) to 1kg red mud (Fe in red mud2O3Mass fraction is 45%) middle addition 10kg Waste Sulfuric Acid (concentration 40%) Afterwards, it is reacted into 10h at 120 DEG C, obtains the first homogeneous slurry, the pH of the first slurry is 0.5；
(2) the slow gradually ammonium carbonate powder into the first slurry, control solution terminal pH value is about 6, obtains the second slurry；
(3) after the second slurry being carried out into separation of solid and liquid and washing, dried under the conditions of 100 DEG C, and then under the conditions of 500 DEG C Roasting 10h obtains solid matter, i.e. ferrotitanium sieve and silica-sesquioxide denitrating catalyst.
The specific surface area for the ferrotitanium sieve and silica-sesquioxide denitrating catalyst that the present embodiment obtains is 190m2/ g, intensity are 4.5Mpa, composition are as shown in table 2.
Table 2
The sample of ferrotitanium silicon-aluminium compound is 10 obtained by the present embodiment5Under/h space velocities, 600ppm SO2With 10% water In the presence of, and NH3Under conditions of/NO is 1,300 DEG C, 350 DEG C, 400 DEG C and 450 DEG C of denitration rates be respectively 68.7%, 94%th, 98% and 99%.
Embodiment 3
The present embodiment provides a kind of method that iron system denitrating catalyst is prepared by red mud, and its specific method is：
(1) to 1kg red mud (Fe in red mud2O3Mass fraction is 10%) middle addition 1kg waste phosphoric acid (concentration 10%) Afterwards, it is reacted into 20h at 70 DEG C, obtains the first homogeneous slurry, the pH of the first slurry is 0；
(2) the slow gradually ammonium carbonate powder into the first slurry, control solution terminal pH value is about 5, obtains the second slurry；
(3) after the second slurry being carried out into separation of solid and liquid and washing with plate compression, dried under the conditions of 100 DEG C, Jin Er 20h is calcined under the conditions of 400 DEG C and obtains solid matter, i.e. ferrotitanium sieve and silica-sesquioxide denitrating catalyst.
The specific surface area for the ferrotitanium sieve and silica-sesquioxide denitrating catalyst that the present embodiment obtains is 150m2/ g, intensity are 4.5Mpa, composition are as shown in table 3.
Table 3
The sample of ferrotitanium silicon-aluminium compound is 10 obtained by the present embodiment5Under/h space velocities, 600ppm SO2With 10% water In the presence of, and NH3Under conditions of/NO is 1,300 DEG C, 350 DEG C, 400 DEG C and 450 DEG C of denitration rates be respectively 50%, 60%th, 75% and 90%.
Embodiment 4
The present embodiment provides a kind of method that iron system denitrating catalyst is prepared by red mud, and its specific method is：
(1) to 1kg red mud (Fe in red mud2O3Mass fraction is 60%) middle addition 10kg useless oxalic acid (concentration 50%) Afterwards, it is reacted into 3h at 200 DEG C, obtains the first homogeneous slurry, the pH of the first slurry is 1；
(2) the slow gradually ammonium carbonate powder into the first slurry, control solution terminal pH value is about 10, obtains the second slurry Material；
(3) after the second slurry being carried out into separation of solid and liquid and washing with leaf filter mode, dried under the conditions of 100 DEG C, Jin Er 1h is calcined under the conditions of 800 DEG C and obtains solid matter, i.e. ferrotitanium sieve and silica-sesquioxide denitrating catalyst.
The specific surface area for the ferrotitanium sieve and silica-sesquioxide denitrating catalyst that the present embodiment obtains is 159m2/ g, intensity 3Mpa, Composition is as shown in table 4.
Table 4
The sample of ferrotitanium silicon-aluminium compound is 10 obtained by the present embodiment5Under/h space velocities, 600ppm SO2With 10% water In the presence of, and NH3Under conditions of/NO is 1, it is respectively in the denitration rate of 300 DEG C, 350 DEG C, 400 DEG C and 450 DEG C scopes 80%th, 90%, 95% and 100%.
Embodiment 5
A kind of method that iron system denitrating catalyst is prepared by red mud of the present embodiment offer, its specific method reference embodiment 2, Difference is：
In step (1), reaction temperature is 180 DEG C；In step (3), solid-liquid separation method is vacuum filtration.
The specific surface area for the ferrotitanium sieve and silica-sesquioxide denitrating catalyst that the present embodiment obtains is 185, intensity 4.5, composition As shown in table 5.
Table 5
The sample of ferrotitanium silicon-aluminium compound is 10 obtained by the present embodiment5Under/h space velocities, 600ppm SO2With 10% water In the presence of, and NH3Under conditions of/NO is 1,300 DEG C, 350 DEG C, 400 DEG C and 450 DEG C of denitration rates be respectively 70.7%, 95%th, 99% and 99%.
Comparative example 1
This comparative example is with reference to embodiment 2, and difference is, in step (1), reaction temperature is 50 DEG C.
The specific surface area for the ferrotitanium sieve and silica-sesquioxide denitrating catalyst that this comparative example obtains is 20m2/ g, intensity 1Mpa, Composition is as shown in table 6.
Table 6
The sample of ferrotitanium silicon-aluminium compound is 10 obtained by this comparative example5Under/h space velocities, 600ppm SO2With 10% water In the presence of, and NH3Under conditions of/NO is 1,300 DEG C, 350 DEG C, 400 DEG C and 450 DEG C of denitration rates be respectively 10%, 20%th, 30% and 50%.
Comparative example 2
This comparative example is with reference to embodiment 2, and difference is, in step (1), the acid used is nitric acid.
The specific surface area for the ferrotitanium sieve and silica-sesquioxide denitrating catalyst that this comparative example obtains is 80m2/ g, intensity are 1.5Mpa, composition are as shown in table 7.
Table 7
The sample of ferrotitanium silicon-aluminium compound is 10 obtained by this comparative example5Under/h space velocities, 600ppm SO2With 10% water In the presence of, and NH3Under conditions of/NO is 1,300 DEG C, 350 DEG C, 400 DEG C and 450 DEG C of denitration rates be respectively 20%, 30%th, 40% and 60%.
From above example and comparative example, a kind of side that iron system denitrating catalyst is prepared by red mud of the application offer Method, by liquid phase acid-base reaction, ferrotitanium silicoaluminate in red mud is subjected to molecular recombination, realizes red mud neutral and alkali devolatilization With the activation of the transition metal oxide such as ferrous oxide, and the specific surface area of material is improved, realize that the high temperature of catalyst takes off Nitre activity, then obtain catalyst prod by filtering and calcining.Reaction temperature and the sour kind used especially in step (1) Class, influenceed substantially for the activation effect of iron oxide in red mud in the scheme of the application offer.Comparative example is not using the present invention The scheme of offer, therefore the product finally obtained does not reach the excellent results acquired by the method for the present invention.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.

Claims (10)

  1. A kind of 1. method that iron system denitrating catalyst is prepared by red mud, it is characterised in that the described method comprises the following steps：
    (1) acid is added into red mud, after 70 DEG C of -200 DEG C of reactions, obtains the first slurry, first slurry is Acid Slurry；
    (2) alkaline matter is added into step (1) first slurry, regulation pH value obtains the second slurry to 5-10；
    (3) separation of solid and liquid is carried out to step (2) second slurry and obtains filter cake, the filter cake is calcined, had The ferrotitanium sieve and silica-sesquioxide catalyst of denitration activity.
  2. 2. according to the method for claim 1, it is characterised in that in step (1), the acid is sulfuric acid, hydrochloric acid, phosphoric acid, grass Acid, acetic acid or organic sulfonic acid any one or at least two combination, preferably sulfuric acid；
    Preferably, the pH of first slurry is 0-2, preferably 1.
  3. 3. method according to claim 1 or 2, it is characterised in that step (1) described red mud is Bayer process red mud, Asia is molten In salt red mud or red mud from sintering process any one or at least two combination；
    Preferably, the content of iron oxide is 10%-60% in the red mud.
  4. 4. according to the method described in claim any one of 1-3, it is characterised in that step (1) acid is industrial waste acid；
    Preferably, mass fraction sour in the industrial waste acid is 20%-60%；
    Preferably, in step (1), the mass ratio of the red mud and acid is 1:(0.1-5).
  5. 5. according to the method described in claim any one of 1-4, it is characterised in that in step (1), the temperature of the reaction is 80 ℃-180℃；
    Preferably, in step (1), the time of the reaction is 3h-20h；
    Preferably, in step (1), the reaction is carried out under the conditions of being stirred.
  6. 6. according to the method described in claim any one of 1-5, it is characterised in that in step (2), the alkaline matter is alkalescence In hydroxide, carbonate or ammoniate any one or at least two combination, preferably sodium hydroxide and/or carbonic acid Ammonium.
  7. 7. according to the method described in claim any one of 1-6, it is characterised in that in step (2), the addition of the alkaline matter Mode is gradually to add.
  8. 8. according to the method described in claim any one of 1-7, it is characterised in that in step (3), the mode of the separation of solid and liquid For any one in plate compression, leaf filter or vacuum filtration；
    Preferably, in step (3), in addition to：The filter cake obtained after separation of solid and liquid is washed and dried；
    Preferably, the washing is carried out multiple, until the alkali metal mass fraction in the filter cake is less than 0.5wt%；
    Preferably, in step (3), returned to after the aqueous phase progress desalting processing that separation of solid and liquid obtains at red mud raw material and carry out profit again With；
    Preferably, in step (3), discharged again after the aqueous phase progress desalting processing that separation of solid and liquid obtains.
  9. 9. according to the method described in claim any one of 1-8, it is characterised in that in step (3), the temperature of the roasting is 300℃-800℃；
    Preferably, in step (3), the time of the roasting is 1h-20h；
    Preferably, in step (3), in addition to：The ferrotitanium sieve and silica-sesquioxide catalyst with denitration activity is crushed.
  10. 10. according to the method described in claim any one of 1-9, it is characterised in that the described method comprises the following steps：
    (1) sulfuric acid is added into red mud, after 80 DEG C of -180 DEG C of reaction 3h-20h, obtains the first slurry, first slurry PH is 0-2, and the mass ratio of the red mud and sulfuric acid is 1:(0.1-5)；
    (2) sodium hydroxide and/or ammonium carbonate are added into step (1) first slurry, regulation pH value obtains second to 5-10 Slurry；
    (3) filter cake is obtained after separation of solid and liquid and washing being carried out to step (2) second slurry, after being dried to the filter cake 1h-20h is calcined at 300 DEG C -800 DEG C, then is crushed, obtains the ferrotitanium sieve and silica-sesquioxide catalyst with denitration activity.
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CN111450841A (en) * 2020-05-22 2020-07-28 福州大学 Reduction method simultaneous desulfurization and denitrification catalyst prepared from red mud and preparation method thereof
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CN108479845A (en) * 2018-03-22 2018-09-04 李俊霞 A kind of high-efficiency denitration catalyst and preparation method thereof
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CN109433217B (en) * 2018-11-29 2020-07-17 山东大学 Red mud denitration catalyst and preparation method thereof
CN110694474A (en) * 2019-11-25 2020-01-17 徐书敏 Green and low-cost flue gas demercuration method
CN110833830A (en) * 2019-11-25 2020-02-25 徐书敏 Method for preparing demercuration catalyst by using natural ore soil and waste residues
CN110694474B (en) * 2019-11-25 2021-05-18 泰州清润环保科技有限公司 Green and low-cost flue gas demercuration method
CN111450841A (en) * 2020-05-22 2020-07-28 福州大学 Reduction method simultaneous desulfurization and denitrification catalyst prepared from red mud and preparation method thereof
CN112295400A (en) * 2020-10-29 2021-02-02 中国铝业股份有限公司 Preparation method of activated red mud composite calcium-based dry desulfurizing agent and desulfurizing agent
CN112316947A (en) * 2020-11-26 2021-02-05 上海应用技术大学 Method for preparing denitration catalyst by red mud in-situ modification
CN115594380A (en) * 2022-10-26 2023-01-13 中铝环保节能集团有限公司（Cn） Hydrogen sulfide removing agent and preparation method thereof

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