CN104549356B - Method for preparing low-temperature denitrification catalytic material from acidolysis residues - Google Patents
Method for preparing low-temperature denitrification catalytic material from acidolysis residues Download PDFInfo
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- CN104549356B CN104549356B CN201510036816.4A CN201510036816A CN104549356B CN 104549356 B CN104549356 B CN 104549356B CN 201510036816 A CN201510036816 A CN 201510036816A CN 104549356 B CN104549356 B CN 104549356B
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- manganese
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Abstract
The invention relates to a method for preparing a low-temperature denitrification catalytic material from acidolysis residues, belonging to the fields of environmental materials, environmental catalysis and environmental protection. The method adopts a precipitation process and comprises the following steps: by using acidolysis residues, which are generated by a sulfuric acid method for producing titanium white, as the raw material, adding a manganese salt, and adding ammonia water or oxydol to prepare the denitrification catalytic material. The catalytic material preparation method adopts industrial waste residues, thereby recovering the waste. The prepared denitrification catalytic material has the advantages of low cost, simple technique and short process, and is suitable for industrial production. The denitrification catalytic material has high low-temperature denitrification activity, and the denitrification rate at 120-260 DEG C is up to 90% above. The method solves the potential hazards of the acidolysis residue stacking to the environment, and protects the environment; and the prepared low-temperature high-activity denitrification catalytic material can bring in huge social benefits.
Description
Technical field
It is specially a kind of to utilize industrial residue acid hydrolysis residue system the invention belongs to environmental catalysis material and field of environment protection
Standby low temperature SCR denitration catalysis material.
Background technology
Nitrogen oxides is the one of the main reasons for causing acid rain, photochemical fog and PM2.5.SCR
(SCR) it is a kind of denitration method for flue gas of currently the most important ones.Its with ammoniacal liquor or urea as denitrfying agent, urging in SCR reactors
Work catalysis selection absorbs under changing material effects.The composition of the business SCR catalysis materials of denitrating flue gas is V2O5(WO3)/TiO2It is (sharp
Titanium ore), its running temperature is general at 350~400 DEG C, and catalysis material high cost accounts for overall cost 30%~50%, and install
Operating cost is higher.Therefore it is crucial that research and development have inexpensive catalysis material, has responded current NOxThe emission reduction policy of compound,
Also the improvement of the ecological environment to Chinese national economy high speed development and green is significant.
Based on the denitration low temperature active that Mn oxides are excellent, manganese titanium system catalysis material is prepared both at home and abroad and all uses titanium substantially
It is in vain raw material, adds the auxiliary agents such as Fe to improve denitration activity, and add SiO2Etc. preparing complex carrier, SiO2Addition not only may be used
To increase the specific surface area of carrier, it is often more important that the alkali resistant poisoning performance of catalysis material can be improved.
China mainly use Production By Sulfuric Acid Process titanium white, with sulfuric acid, ilmenite as raw material, through acidolysis, purification, hydrolysis, washing,
Rinsing, salt treatment, calcining, crush with post processing etc. operation and be obtained.The method technique has been shaped, and is compared with chloridising, equipment
Fairly simple with operating, founding the factory, investment is relatively low, and raw material is cheap and easy to get.But the major defect of the method is to produce substantial amounts of waste, often
Production 1t titanium white discharges slag liquid about 400kg, wherein solid residue about 120kg.Solid residue major part is unreacted miberal powder.Should
After sedimentation filtration, titanium liquid is reclaimed and returns to hydrolysis procedure residue liquid, and residue is sent to slag and stacks.According to statistics, 2013, national titanium
White powder total output breaks through 2,000,000 tons first, and this means that the residue of generation is up to 240,000 tons, therefore residue is utilized and processes right
Environmental protection is significant.
It is relatively fewer to the research of acid hydrolysis residue recycling at present.Typically also it is only intended to recovery section titanium.Patent
The acid hydrolysis residue of Titanium White Production By Sulfuric Acid Process is washed, is prepared slurry, two-stage flotation by CN102764689A, obtains titanium ore,
The raw material for titanium white production is obtained after drying；The titanium ore grade ＞ 46% of recovery, rate of recovery ＞ 85%.Patent
CN101469367 is washed by acid hydrolysis residue, smashed, roughing, magnetic separation, drying, obtain containing TiO2The ferrotianium mineral products of 47-49%
Product.Though foregoing invention can be by the TiO in acid hydrolysis residue2Recycle, but still acid hydrolysis residue can not be made full use of, it is real to become useless
It is treasured.
The content of the invention
It is an object of the invention to provide a kind of industrial residue acid hydrolysis residue system for recycling Production By Sulfuric Acid Process titanium white technique
The method of standby low-temperature denitration catalysis material.
A kind of method that acid hydrolysis residue prepares denitration catalyst material, it is characterised in that preparation process is as follows：
Acid hydrolysis residue is well mixed with manganese salt solution, 15~45min of magnetic agitation；Ammoniacal liquor is added, to pH=10~11,
15~45min of magnetic agitation；Or add hydrogen peroxide to suspension color and no longer change, 15~45min of magnetic agitation；From
The heart isolates bottom precipitation, and washing, alcohol is washed；75~105 DEG C of 10~15h of drying；250~400 DEG C of roasting 3h are obtained catalysis material
Powder.
Denitration rate test of the invention is with NH3During for reducing gas, by the NO of 1000ppm, the NH of 1000ppm3, 5%
O2Mixing, carrier gas is all N2, gas flow rate 2000ml/min, reaction velocity is 27000h-1.Catalysis material powder through granulation,
The particle of 40-60 mesh is taken, 3ml is measured, reacted under 90 DEG C~350 DEG C temperature conditionss, catalysis material nitrogen oxygen prepared by the present invention
Compound conversion ratio is up to 99%.
Further, acid hydrolysis residue in the step：Manganese salt mol ratio (Si+Ti)：Mn=1:0.6.
Further, manganese salt in the step：The mol ratio of hydrogen peroxide is 1：5~7.
Further, manganese salt is any one in manganese acetate, manganese nitrate, manganese sulfate, manganese chloride, potassium permanganate.
The present invention not only solves acid hydrolysis residue and stores up potential hazard to environment, protects environment, obtained low temperature, height
Active denitration catalyst material, more brings huge social benefit.
Specific embodiment
Embodiment one：
During 20g acid hydrolysis residues and 25.12g manganese acetates added into 300g water, magnetic agitation 30min；Quality percentage is added to contain
The ammoniacal liquor 100g of amount 25%, to pH=11, magnetic agitation 40min；The hydrogen peroxide 75g of weight/mass percentage composition 30% is added to outstanding
Turbid liquid color no longer changes, magnetic agitation 30min；Centrifugation goes out bottom precipitation, and washing, alcohol is washed；75 DEG C dry 15h；
400 DEG C of roasting 2h are obtained catalysis material powder.
Denitration rate is tested：NO 1000ppm, NH31000ppm, O25%, N2It is carrier gas, gas flow rate 2000ml/min,
Air speed is 27000h-1.In 190 DEG C~340 DEG C denitration rates up to more than 80%, 220 DEG C~300 DEG C denitration rates up to 90% with
On.
Embodiment two：
During 20g acid hydrolysis residues and 25.12g manganese acetates added into 300g water, magnetic agitation 30min；Quality percentage is added to contain
The ammoniacal liquor 100g of amount 25%, to pH=11, magnetic agitation 40min；The hydrogen peroxide 75g of weight/mass percentage composition 30% is added to outstanding
Turbid liquid color no longer changes, magnetic agitation 30min；Centrifugation goes out bottom precipitation, and washing, alcohol is washed；75 DEG C dry 15h；
350 DEG C of roasting 2h are obtained catalysis material powder.
Denitration rate is tested：NO 1000ppm, NH31000ppm, O25%, N2It is carrier gas, gas flow rate 2000ml/min,
Air speed is 27000h-1.In 150 DEG C~330 DEG C denitration rates up to more than 80%, 180 DEG C~300 DEG C denitration rates up to 90% with
On.
Embodiment three：
During 20g acid hydrolysis residues and 25.12g manganese acetates added into 300g water, magnetic agitation 30min；Quality percentage is added to contain
The ammoniacal liquor 100g of amount 25%, to pH=11, magnetic agitation 40min；The hydrogen peroxide 75g of weight/mass percentage composition 30% is added to outstanding
Turbid liquid color no longer changes, magnetic agitation 30min；Centrifugation goes out bottom precipitation, and washing, alcohol is washed；75 DEG C dry 15h；
300 DEG C of roasting 4h are obtained catalysis material powder.
Denitration rate is tested：NO 1000ppm, NH31000ppm, O25%, N2It is carrier gas, gas flow rate 2000ml/min,
Air speed is 27000h-1.In 150 DEG C~320 DEG C denitration rates up to more than 80%, 170 DEG C~280 DEG C denitration rates up to 90% with
On.
Example IV：
During 20g acid hydrolysis residues and 25.12g manganese acetates added into 300g water, magnetic agitation 30min；Quality percentage is added to contain
The ammoniacal liquor 100g of amount 25%, to pH=11, magnetic agitation 40min；The hydrogen peroxide 75g of weight/mass percentage composition 30% is added to outstanding
Turbid liquid color no longer changes, magnetic agitation 30min；Centrifugation goes out bottom precipitation, and washing, alcohol is washed；75 DEG C dry 15h；
250 DEG C of roasting 3h are obtained catalysis material powder.
Denitration rate is tested：NO 1000ppm, NH31000ppm, O25%, N2It is carrier gas, gas flow rate 2000ml/min,
Air speed is 27000h-1.Reacted under 90 DEG C~350 DEG C temperature conditionss, the denitration rate of catalysis material reaches as high as 99.1%,
100 DEG C~290 DEG C denitration rates up to more than 80%, in 120 DEG C~260 DEG C denitration rates up to more than 90%.
Embodiment five：
During 25g acid hydrolysis residues and 32.03g manganese nitrates added into 300g water, magnetic agitation 20min；Quality percentage is added to contain
The ammoniacal liquor 100g of amount 25%, to pH=10, magnetic agitation 20min；Add the hydrogen peroxide 100g of weight/mass percentage composition 30% extremely
Suspension color no longer changes, magnetic agitation 30min；Centrifugation goes out bottom precipitation, and washing, alcohol is washed；95 DEG C of dryings
12h；250 DEG C of roasting 3h are obtained catalysis material powder.
Denitration rate is tested：NO 1000ppm, NH31000ppm, O25%, N2It is carrier gas, gas flow rate 2000ml/min,
Air speed is 27000h-1.In 130 DEG C~300 DEG C denitration rates up to more than 80%, 160 DEG C~220 DEG C denitration rates up to 90% with
On.
Embodiment six：
During 25g acid hydrolysis residues and 19.35g manganese sulfates added into 300g water, magnetic agitation 30min；Quality percentage is added to contain
The ammoniacal liquor 110g of amount 25%, to pH=11, magnetic agitation 30min；The hydrogen peroxide 80g of weight/mass percentage composition 30% is added to outstanding
Turbid liquid color no longer changes, magnetic agitation 30min；Centrifugation goes out bottom precipitation, and washing, alcohol is washed；95 DEG C dry 12h；
250 DEG C of roasting 3h are obtained catalysis material powder.
Denitration rate is tested：NO 1000ppm, NH31000ppm, O25%, N2It is carrier gas, gas flow rate 2000ml/min,
Air speed is 27000h-1.In 140 DEG C~310 DEG C denitration rates up to more than 80%, 170 DEG C~260 DEG C denitration rates up to 90% with
On.
Embodiment seven：
During 25g acid hydrolysis residues and 16.12g manganese chlorides added into 300g water, magnetic agitation 40min；Quality percentage is added to contain
The ammoniacal liquor 100g of amount 25%, to pH=11, magnetic agitation 40min；The hydrogen peroxide 75g of weight/mass percentage composition 30% is added to outstanding
Turbid liquid color no longer changes, magnetic agitation 30min；Centrifugation goes out bottom precipitation, and washing, alcohol is washed；95 DEG C dry 13h；
250 DEG C of roasting 3h are obtained catalysis material powder.
Denitration rate is tested：NO 1000ppm, NH31000ppm, O25%, N2It is carrier gas, gas flow rate 2000ml/min,
Air speed is 27000h-1.In 130 DEG C~290 DEG C denitration rates up to more than 80%, 170 DEG C~250 DEG C denitration rates up to 90% with
On.
Embodiment eight：
During 25g acid hydrolysis residues and 20.15g potassium permanganate added into 300g water, magnetic agitation 30min；Add quality percentage
The ammoniacal liquor 100g of content 25%, to pH=11, magnetic agitation 40min；Centrifugation goes out bottom precipitation, and washing, alcohol is washed；95 DEG C are done
Dry 11h；250 DEG C of roasting 3h are obtained catalysis material powder.
Denitration rate is tested：NO 1000ppm, NH31000ppm, O25%, N2It is carrier gas, gas flow rate 2000ml/min,
Air speed is 27000h-1.In 100 DEG C~240 DEG C denitration rates of catalysis material up to more than 80%, in 140 DEG C~220 DEG C denitration rates
Up to more than 90%.
Claims (1)
1. a kind of method that acid hydrolysis residue prepares low-temperature denitration catalysis material, it is characterised in that：By acid hydrolysis residue and manganese salt solution
Well mixed, acid hydrolysis residue is (Si+Ti) with the mol ratio of manganese salt：Mn=1:0.6,15~45min of magnetic agitation；Add ammonia
Water, to pH=10~11,15~45min of magnetic agitation；Or add hydrogen peroxide to suspension color and no longer change, magnetic
Power stirs 15~45min；Centrifugation goes out bottom precipitation, and washing drying and roasting is obtained catalysis material powder；250~400 DEG C of roastings
Burn 2-4h and catalysis material powder is obtained；Manganese salt is any one in manganese acetate, manganese nitrate, manganese sulfate, manganese chloride, potassium permanganate；
Manganese：The mol ratio of hydrogen peroxide is 1：5~7.
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