CN104001501B - A kind of acid hydrolysis residue prepares the method for denitration catalyst material - Google Patents
A kind of acid hydrolysis residue prepares the method for denitration catalyst material Download PDFInfo
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Abstract
The method that acid hydrolysis residue prepares denitration catalyst material belongs to environmental catalysis material and a field of environment protection, provides a kind of industrial residue acid hydrolysis residue recycling Production By Sulfuric Acid Process titanium white technique to prepare the method for denitration catalyst material.Acid hydrolysis residue is added water, and stir and form uniform suspension, then mix with manganese acetate solution, magnetic agitation 15 ~ 45min obtains mixed solution; Above-mentioned mixed solution is heated to 80 ~ 95 DEG C, adds the urea liquid of 2mol/L, magnetic agitation 15 ~ 45min; Add ammoniacal liquor, to pH=10 ~ 11, cool after magnetic agitation 15 ~ 45min; Or add hydrogen peroxide again and no longer change to suspension color, cool after magnetic agitation 15 ~ 45min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 75 ~ 105 DEG C of drying 10 ~ 15h; 450 ~ 650 DEG C of roasting 2 ~ 4h obtain catalysis material powder.Described method adopts industrial residue, and cost is low, and flow process is short, is applicable to suitability for industrialized production.Prepared catalysis material is 60% ~ 80% 260 DEG C ~ 360 DEG C denitration rates.
Description
Technical field
The invention belongs to environmental catalysis material and field of environment protection, be specially one and utilize industrial residue acid hydrolysis residue to prepare SCR denitration catalysis material.
Background technology
China mainly adopts Production By Sulfuric Acid Process titanium white, with sulfuric acid, ilmenite for raw material, obtains through operations such as acidolysis, purification, hydrolysis, washing, rinsing, Ficus caricaL, calcining, pulverizing and post processings.This method technique is shaped, and compares with chloridising, and equipment is fairly simple with operation, and investment of founding the factory is lower, and raw material is cheap and easy to get.The major defect of this method produces a large amount of refuses, and often produce 1t titanium white discharge slag liquid and be about 400kg, wherein solid residue is about 120kg.Solid residue major part is unreacted breeze.This residue liquid is after sedimentation filtration, and titanium liquid reclaims and returns hydrolysis procedure, and residue is sent to slag field and stacks.According to statistics, 2013, national titanium dioxide total output broke through 2,000,000 tons first, and this just means that the residue of generation is up to 240,000 tons, and therefore residue utilizes and processes and is significant to protection of the environment.
Nitrogen oxide is the one of the main reasons causing acid rain, photochemical fog and PM2.5.SCR (SelectiveCatalyticReduction, SCR) is current most important a kind of denitration method for flue gas.It for denitrfying agent, makes catalysis Selective absorber under the catalysis material effect in absorption tower with ammoniacal liquor or urea.The business SCR catalysis material of denitrating flue gas consist of V
2o
5(WO
3)/TiO
2(anatase), its running temperature is generally at 350 ~ 400 DEG C, and catalysis material cost is high, account for overall cost 30% ~ 50%, and installation and operation costly.Therefore research and development have low cost catalysis material is crucial, has responded current NO
xthe reduction of discharging policy of compound, is also significant to the improvement of the ecological environment of Chinese national economy high speed development and green.
Based on the denitration low temperature active of Mn oxide excellence, prepare manganese titanium system catalysis material both at home and abroad and substantially all use titanium white for raw material, add the auxiliary agents such as Fe to improve denitration activity, and add SiO
2etc. preparing complex carrier, SiO
2add the specific area that not only can increase carrier, the more important thing is the alkali resistant poisoning performance that can improve catalysis material.The acid hydrolysis residue chemical composition that the present invention selects is in table 1.
Table 1 acid hydrolysis residue chemical composition
Summary of the invention
The object of this invention is to provide a kind of method that industrial residue acid hydrolysis residue recycling Production By Sulfuric Acid Process titanium white technique prepares denitration catalyst material.
Acid hydrolysis residue prepares a method for denitration catalyst material, it is characterized in that step is as follows:
Acid hydrolysis residue is added water, and stir and form uniform suspension, then mix with manganese acetate solution, magnetic agitation 15 ~ 45min obtains mixed solution; Mn wherein in manganese acetate solution and (Ti+Si) mol ratio in acid hydrolysis residue: be 0.13 ~ 0.9:1; Above-mentioned mixed solution is heated to 80 ~ 95 DEG C, adds the urea liquid of 2mol/L, magnetic agitation 15 ~ 45min; Add ammoniacal liquor, to pH=10 ~ 11, cool after magnetic agitation 15 ~ 45min; Or add hydrogen peroxide again and no longer change to suspension color, cool after magnetic agitation 15 ~ 45min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 75 ~ 105 DEG C of drying 10 ~ 15h; 450 ~ 650 DEG C of roasting 2 ~ 4h obtain catalysis material powder.
Further, acid hydrolysis residue: the urea in urea liquid: the mass ratio of the hydrogen peroxide in hydrogen peroxide solution is 1:5 ~ 10:0 ~ 0.5.
Denitration rate of the present invention test is with NH
3during for reducing gas, by the NH of the NO of 1000ppm, 1000ppm
3, the O of 5%
2mixing, carrier gas is all N
2, gas flow rate 2000ml/min, reaction velocity is 27000h
-1.Catalysis material powder, through granulation, is got 40-60 object particle, is measured 3ml, reacts under 90 DEG C ~ 360 DEG C temperature conditions, and catalysis material transformation efficiency of the oxides of nitrogen prepared by the present invention can reach 80%.
Detailed description of the invention
Embodiment one:
A kind of acid hydrolysis residue prepares denitration catalyst material (mol ratio Mn:(Ti+Si)=0.13:1) method step as follows:
10g acid hydrolysis residue is added in 100g water, stir and form uniform suspension, 2.757g manganese acetate is dissolved in 30g water, more above-mentioned two kinds of solution is mixed, magnetic agitation 15min; Above-mentioned mixed solution is heated to 80 DEG C, adds 2mol/L urea liquid 75ml, magnetic agitation 20min; Add the ammoniacal liquor 9g of mass percentage 25%, to pH=10 ~ 11, cool after magnetic agitation 40min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 75 DEG C of dry 15h; 450 DEG C of roasting 3h obtain catalysis material powder.
Embodiment two:
A kind of acid hydrolysis residue prepares denitration catalyst material (Mn:(Ti+Si)=0.4:1) method step as follows:
10g acid hydrolysis residue is added in 100g water, stir and form uniform suspension, 8.374g manganese acetate is dissolved in 30g water, more above-mentioned two kinds of solution is mixed, magnetic agitation 25min; Above-mentioned mixed solution is heated to 95 DEG C, adds 2mol/L urea liquid 75ml, magnetic agitation 30min; Add the ammoniacal liquor 11.6g of mass percentage 25%, to pH=10 ~ 11, cool after magnetic agitation 30min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 80 DEG C of dry 13h; 550 DEG C of roasting 3h obtain catalysis material powder.
Embodiment three:
A kind of acid hydrolysis residue prepares denitration catalyst material (Mn:(Ti+Si)=0.5:1) method step as follows:
10g acid hydrolysis residue is added in 100g water, stir and form uniform suspension, 10.468g manganese acetate is dissolved in 30g water, more above-mentioned two kinds of solution is mixed, magnetic agitation 35min; Above-mentioned mixed solution is heated to 90 DEG C, adds 2mol/L urea liquid 75ml, magnetic agitation 40min; Add the ammoniacal liquor 21.5g of mass percentage 25%, to pH=10 ~ 11, cool after magnetic agitation 20min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 90 DEG C of dry 12h; 450 DEG C of roasting 4h obtain catalysis material powder.
Embodiment four:
A kind of acid hydrolysis residue prepares denitration catalyst material (Mn:(Ti+Si)=0.6:1) method step as follows:
10g acid hydrolysis residue is added in 100g water, stir and form uniform suspension, 12.561g manganese acetate is dissolved in 30g water, more above-mentioned two kinds of solution is mixed, magnetic agitation 45min; Above-mentioned mixed solution is heated to 85 DEG C, adds 2mol/L urea liquid 75ml, magnetic agitation 15min; Add the ammoniacal liquor 35.5g of mass percentage 25%, to pH=10 ~ 11, cool after magnetic agitation 15min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 100 DEG C of dry 11h; 650 DEG C of roasting 2h obtain catalysis material powder.
Embodiment five:
A kind of acid hydrolysis residue prepares denitration catalyst material (Mn:(Ti+Si)=0.7:1) method step as follows:
20g acid hydrolysis residue is added in 300g water, stir and form uniform suspension, 14.655g manganese acetate is dissolved in 70g water, more above-mentioned two kinds of solution is mixed, magnetic agitation 25min; Above-mentioned mixed solution is heated to 90 DEG C, adds 2mol/L urea liquid 100ml, magnetic agitation 25min; Add the ammoniacal liquor 110g of mass percentage 25%, to pH=10, magnetic agitation 35min; Add mass percentage 30% hydrogen peroxide 15g, cool after magnetic agitation 40min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 100 DEG C of dry 11h; 500 DEG C of roasting 3h obtain catalysis material powder.
Embodiment six:
A kind of acid hydrolysis residue prepares denitration catalyst material (Mn:(Ti+Si)=0.8:1) method step as follows:
20g acid hydrolysis residue is added in 300g water, stir and form uniform suspension, 16.749g manganese acetate is dissolved in 70g water, more above-mentioned two kinds of solution is mixed, magnetic agitation 35min; Above-mentioned mixed solution is heated to 95 DEG C, adds 2mol/L urea liquid 100ml, magnetic agitation 35min; Add the ammoniacal liquor 140g of mass percentage 25%, to pH=11, magnetic agitation 45min; Add mass percentage 30% hydrogen peroxide 20g, cool after magnetic agitation 15min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 105 DEG C of dry 10h; 600 DEG C of roasting 3h obtain catalysis material powder.
Embodiment seven:
A kind of acid hydrolysis residue prepares denitration catalyst material (Mn:(Ti+Si)=0.9:1) method step as follows:
20g acid hydrolysis residue is added in 300g water, stir and form uniform suspension, 18.843g manganese acetate is dissolved in 70g water, more above-mentioned two kinds of solution is mixed, magnetic agitation 30min; Above-mentioned mixed solution is heated to 95 DEG C, adds 2mol/L urea liquid 100ml, magnetic agitation 45min; Add the ammoniacal liquor 120g of mass percentage 25%, to pH=11, magnetic agitation 45min; Add mass percentage 30% hydrogen peroxide 30g, cool after magnetic agitation 30min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 100 DEG C of dry 12h; 600 DEG C of roasting 3h obtain catalysis material powder.
The denitration rate test of above-mentioned four kinds of catalysis materials: with NH
3during for reducing gas, by the NH of the NO of 1000ppm, 1000ppm
3, the O of 5%
2mixing, carrier gas is all N
2, gas flow rate 2000ml/min, reaction velocity is 27000h
-1.Catalysis material powder, through granulation, is got 40 ~ 60 object particles, is measured 3ml, and react under 90 DEG C ~ 360 DEG C temperature conditions, the denitration rate of catalysis material sees the following form.
Denitration rate under table 2 seven kinds of catalysis material condition of different temperatures
Claims (2)
1. acid hydrolysis residue prepares a method for denitration catalyst material, it is characterized in that step is as follows:
Acid hydrolysis residue is added water, and stir and form uniform suspension, then mix with manganese acetate solution, magnetic agitation 15 ~ 45min obtains mixed solution; Mn wherein in manganese acetate solution and (Ti+Si) mol ratio in acid hydrolysis residue: be 0.13 ~ 0.9:1; Above-mentioned mixed solution is heated to 80 ~ 95 DEG C, adds the urea liquid of 2mol/L, magnetic agitation 15 ~ 45min; Add ammoniacal liquor, to pH=10 ~ 11, cool after magnetic agitation 15 ~ 45min; Or add hydrogen peroxide again and no longer change to suspension color, cool after magnetic agitation 15 ~ 45min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 75 ~ 105 DEG C of drying 10 ~ 15h; 450 ~ 650 DEG C of roasting 2 ~ 4h obtain catalysis material powder.
2. method according to claim 1, is characterized in that: acid hydrolysis residue: the urea in urea liquid: the mass ratio of the hydrogen peroxide in hydrogen peroxide solution is 1:5 ~ 10:0 ~ 0.5.
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| CN104549356B (en) * | 2015-01-25 | 2017-05-24 | 北京工业大学 | Method for preparing low-temperature denitrification catalytic material from acidolysis residues |
| CN107754799A (en) * | 2017-11-23 | 2018-03-06 | 北京工业大学 | A kind of method that ferro-silicon slag prepares medium temperature demercuration catalysis material |
| CN108031285A (en) * | 2017-12-01 | 2018-05-15 | 南通三创机械制造有限公司 | A kind of redox denitrfying agent |
| CN108993529A (en) * | 2018-07-26 | 2018-12-14 | 北京工业大学 | A method of improving Industrial Stoves low-temperature denitration catalysis material catalytic activity using tourmaline |
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