CN104549356A - 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 PDF

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CN104549356A
CN104549356A CN201510036816.4A CN201510036816A CN104549356A CN 104549356 A CN104549356 A CN 104549356A CN 201510036816 A CN201510036816 A CN 201510036816A CN 104549356 A CN104549356 A CN 104549356A
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catalytic material
denitrification
manganese
acid hydrolysis
catalysis material
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CN104549356B (en
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崔素萍
田国兰
马晓宇
郭红霞
王亚丽
王剑锋
张良静
项泽强
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Beijing University of Technology
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Beijing University of Technology
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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

A kind of acid hydrolysis residue prepares the method for low-temperature denitration catalysis material
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 low temperature SCR denitration catalysis material.
Background technology
Nitrogen oxide is the one of the main reasons causing acid rain, photochemical fog and PM2.5.SCR (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 SCR reactor 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.
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.But the major defect of this method produces a large amount of refuses, 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.
Relatively less to the research of acid hydrolysis residue recycling at present.General also just for recovery section titanium.The acid hydrolysis residue of Titanium White Production By Sulfuric Acid Process carries out washing, preparing slag slurry, two-stage flotation by patent CN102764689A, obtains titanium ore, obtains the raw material for titanium white production after drying; The titanium ore grade > 46%, rate of recovery > 85% reclaimed.Patent CN101469367 by washing acid hydrolysis residue, smash, roughly select, magnetic separation, drying, must TiO be contained 2the ilmenite product of 47-49%.Though foregoing invention can by the TiO in acid hydrolysis residue 2recycle, but still acid hydrolysis residue can not be made full use of, really turn waste into wealth.
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 low-temperature denitration catalysis material.
Acid hydrolysis residue prepares a method for denitration catalyst material, it is characterized in that preparation process is as follows:
Acid hydrolysis residue is mixed with manganese salt solution, magnetic agitation 15 ~ 45min; Add ammoniacal liquor, to pH=10 ~ 11, magnetic agitation 15 ~ 45min; Or add hydrogen peroxide again and no longer change to suspension color, magnetic agitation 15 ~ 45min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 75 ~ 105 DEG C of drying 10 ~ 15h; 250 ~ 400 DEG C of roasting 3h obtain catalysis material powder.
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 ~ 350 DEG C temperature conditions, and catalysis material transformation efficiency of the oxides of nitrogen prepared by the present invention can reach 99%.
Further, acid hydrolysis residue in described step: manganese salt mol ratio (Si+Ti): Mn=1:0.6.
Further, manganese salt in described 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, and protect environment, obtained low temperature, high activity denitration catalyst material, more bring huge social benefit.
Detailed description of the invention
Embodiment one:
20g acid hydrolysis residue and 25.12g manganese acetate are added in 300g water, magnetic agitation 30min; Add the ammoniacal liquor 100g of mass percentage 25%, to pH=11, magnetic agitation 40min; The hydrogen peroxide 75g adding mass percentage 30% more no longer changes to suspension color, magnetic agitation 30min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 75 DEG C of dry 15h; 400 DEG C of roasting 2h obtain catalysis material powder.
Denitration rate is tested: NO 1000ppm, NH 31000ppm, O 25%, N 2for carrier gas, gas flow rate 2000ml/min, air speed is 27000h -1.Can more than 80% be reached 190 DEG C ~ 340 DEG C denitration rates, can more than 90% be reached 220 DEG C ~ 300 DEG C denitration rates.
Embodiment two:
20g acid hydrolysis residue and 25.12g manganese acetate are added in 300g water, magnetic agitation 30min; Add the ammoniacal liquor 100g of mass percentage 25%, to pH=11, magnetic agitation 40min; The hydrogen peroxide 75g adding mass percentage 30% more no longer changes to suspension color, magnetic agitation 30min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 75 DEG C of dry 15h; 350 DEG C of roasting 2h obtain catalysis material powder.
Denitration rate is tested: NO 1000ppm, NH 31000ppm, O 25%, N 2for carrier gas, gas flow rate 2000ml/min, air speed is 27000h -1.Can more than 80% be reached 150 DEG C ~ 330 DEG C denitration rates, can more than 90% be reached 180 DEG C ~ 300 DEG C denitration rates.
Embodiment three:
20g acid hydrolysis residue and 25.12g manganese acetate are added in 300g water, magnetic agitation 30min; Add the ammoniacal liquor 100g of mass percentage 25%, to pH=11, magnetic agitation 40min; The hydrogen peroxide 75g adding mass percentage 30% more no longer changes to suspension color, magnetic agitation 30min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 75 DEG C of dry 15h; 300 DEG C of roasting 4h obtain catalysis material powder.
Denitration rate is tested: NO 1000ppm, NH 31000ppm, O 25%, N 2for carrier gas, gas flow rate 2000ml/min, air speed is 27000h -1.Can more than 80% be reached 150 DEG C ~ 320 DEG C denitration rates, can more than 90% be reached 170 DEG C ~ 280 DEG C denitration rates.
Embodiment four:
20g acid hydrolysis residue and 25.12g manganese acetate are added in 300g water, magnetic agitation 30min; Add the ammoniacal liquor 100g of mass percentage 25%, to pH=11, magnetic agitation 40min; The hydrogen peroxide 75g adding mass percentage 30% more no longer changes to suspension color, magnetic agitation 30min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 75 DEG C of dry 15h; 250 DEG C of roasting 3h obtain catalysis material powder.
Denitration rate is tested: NO 1000ppm, NH 31000ppm, O 25%, N 2for carrier gas, gas flow rate 2000ml/min, air speed is 27000h -1.React under 90 DEG C ~ 350 DEG C temperature conditions, the denitration rate of catalysis material reaches as high as 99.1%, can reach more than 80% 100 DEG C ~ 290 DEG C denitration rates, can reach more than 90% 120 DEG C ~ 260 DEG C denitration rates.
Embodiment five:
25g acid hydrolysis residue and 32.03g manganese nitrate are added in 300g water, magnetic agitation 20min; Add the ammoniacal liquor 100g of mass percentage 25%, to pH=10, magnetic agitation 20min; The hydrogen peroxide 100g adding mass percentage 30% more no longer changes to suspension color, magnetic agitation 30min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 95 DEG C of dry 12h; 250 DEG C of roasting 3h obtain catalysis material powder.
Denitration rate is tested: NO 1000ppm, NH 31000ppm, O 25%, N 2for carrier gas, gas flow rate 2000ml/min, air speed is 27000h -1.Can more than 80% be reached 130 DEG C ~ 300 DEG C denitration rates, can more than 90% be reached 160 DEG C ~ 220 DEG C denitration rates.
Embodiment six:
25g acid hydrolysis residue and 19.35g manganese sulfate are added in 300g water, magnetic agitation 30min; Add the ammoniacal liquor 110g of mass percentage 25%, to pH=11, magnetic agitation 30min; The hydrogen peroxide 80g adding mass percentage 30% more no longer changes to suspension color, magnetic agitation 30min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 95 DEG C of dry 12h; 250 DEG C of roasting 3h obtain catalysis material powder.
Denitration rate is tested: NO 1000ppm, NH 31000ppm, O 25%, N 2for carrier gas, gas flow rate 2000ml/min, air speed is 27000h -1.Can more than 80% be reached 140 DEG C ~ 310 DEG C denitration rates, can more than 90% be reached 170 DEG C ~ 260 DEG C denitration rates.
Embodiment seven:
25g acid hydrolysis residue and 16.12g manganese chloride are added in 300g water, magnetic agitation 40min; Add the ammoniacal liquor 100g of mass percentage 25%, to pH=11, magnetic agitation 40min; The hydrogen peroxide 75g adding mass percentage 30% more no longer changes to suspension color, magnetic agitation 30min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 95 DEG C of dry 13h; 250 DEG C of roasting 3h obtain catalysis material powder.
Denitration rate is tested: NO 1000ppm, NH 31000ppm, O 25%, N 2for carrier gas, gas flow rate 2000ml/min, air speed is 27000h -1.Can more than 80% be reached 130 DEG C ~ 290 DEG C denitration rates, can more than 90% be reached 170 DEG C ~ 250 DEG C denitration rates.
Embodiment eight:
25g acid hydrolysis residue and 20.15g potassium permanganate are added in 300g water, magnetic agitation 30min; Add the ammoniacal liquor 100g of mass percentage 25%, to pH=11, magnetic agitation 40min; Centrifugation goes out bottom precipitation, washing, alcohol wash; 95 DEG C of dry 11h; 250 DEG C of roasting 3h obtain catalysis material powder.
Denitration rate is tested: NO 1000ppm, NH 31000ppm, O 25%, N 2for carrier gas, gas flow rate 2000ml/min, air speed is 27000h -1.Can more than 80% be reached in the denitration rate of 100 DEG C ~ 240 DEG C of catalysis materials, can more than 90% be reached 140 DEG C ~ 220 DEG C denitration rates.

Claims (3)

1. acid hydrolysis residue prepares a method for low-temperature denitration catalysis material, it is characterized in that: mixed with manganese salt solution by acid hydrolysis residue, and the mol ratio of acid hydrolysis residue and manganese salt is (Si+Ti): Mn=1:0.6, magnetic agitation 15 ~ 45min; Add ammoniacal liquor, to pH=10 ~ 11, magnetic agitation 15 ~ 45min; Or add hydrogen peroxide more no longer to change to suspension color, magnetic agitation 15 ~ 45min; Centrifugation goes out bottom precipitation, and washing drying and roasting obtains catalysis material powder; 250 ~ 400 DEG C of roasting-2-4h obtain catalysis material powder.
2. a kind of acid hydrolysis residue according to claim 1 prepares the method for low-temperature denitration catalysis material, it is characterized in that: manganese salt is any one in manganese acetate, manganese nitrate, manganese sulfate, manganese chloride, potassium permanganate.
3. a kind of acid hydrolysis residue according to claim 1 prepares the method for low-temperature denitration catalysis material, it is characterized in that: manganese: the mol ratio of hydrogen peroxide is 1:5 ~ 7.
CN201510036816.4A 2015-01-25 2015-01-25 Method for preparing low-temperature denitrification catalytic material from acidolysis residues Active CN104549356B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103240081A (en) * 2013-05-01 2013-08-14 北京工业大学 Manganese-based low-temperature denitration catalyst taking TiO2-SiO2 as carrier and preparation method thereof
CN104001501A (en) * 2014-05-27 2014-08-27 北京工业大学 Method for preparing denitration catalytic material by using acidolysis residues

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103240081A (en) * 2013-05-01 2013-08-14 北京工业大学 Manganese-based low-temperature denitration catalyst taking TiO2-SiO2 as carrier and preparation method thereof
CN104001501A (en) * 2014-05-27 2014-08-27 北京工业大学 Method for preparing denitration catalytic material by using acidolysis residues

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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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