CN104801296A - Novel dioxin removing catalyst and preparation method thereof - Google Patents
Novel dioxin removing catalyst and preparation method thereof Download PDFInfo
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- CN104801296A CN104801296A CN201510171820.1A CN201510171820A CN104801296A CN 104801296 A CN104801296 A CN 104801296A CN 201510171820 A CN201510171820 A CN 201510171820A CN 104801296 A CN104801296 A CN 104801296A
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Abstract
The invention discloses a novel dioxin removing catalyst and a preparation method thereof. The novel dioxin removing catalyst comprises, in percentage by weight, 75%-95% of TiO2, 0%-3% of WO3, 3%-10% of V2O5 and 2%-10% of silicon dioxide. The dioxin removing catalyst has the excellent decomposition removing ability on dioxins at the lower temperature and is large in specific surface area, high in strength, convenient to prepare and suitable for large-scale industrial production.
Description
Technical field
The invention belongs to incineration treatment of garbage field, particularly relate to and a kind of novelly remove bioxin Catalysts and its preparation method.
Background technology
Along with the rapid raising of China's rapid development of economy, living standards of the people and the continuous quickening of urbanization process, the generation of China's municipal refuse sharply increases, and growth is growing on and on.The annual production of current China municipal refuse has reached 1.4 hundred million tons, and refuse production is 450 ~ 500 kilograms per capita, and constantly increases in the annual growth with 8 ~ 10%.
In order to protection of the environment; generally have employed the waste disposal methods such as landfill method, composting process and burning method in the world; wherein waste incineration because its compatible amount is large, process the high and series of advantages such as recyclable heat energy of timely, innoxious degree and receive much concern, the major way having become garbage disposal obtains fast development.
But rubbish inevitably produces a large amount of pollutant in burning process, as particle, HCl, NOX, heavy metal and bioxin etc.These pollutants especially bioxin also exist great harm to health.Bioxin is the general name of many chloros hexichol bioxin (PCDDS) and many chloros dibenzofuran (PCDFS), there is severe toxicity, toxicity is 1000 times of potassium cyanide, and have the slow poisonings such as carcinogenicity, teratogenesis, mutagenicity in addition, various countries are proposed strict control objectives to it.
Along with national environmental protection policy is more and more stricter, the exploitation that begins one's study of domestic many colleges and universities, institutes and enterprise removes bioxin catalyst, but the bioxin catalyst that removes of domestic research and development exists that running temperature is high, specific area is little and the shortcoming such as bioxin removal efficiency is low.
Summary of the invention
The object of the present invention is to provide and a kind of novelly remove bioxin Catalysts and its preparation method, there is the problem that running temperature is high, specific area little Ji bioxin removal efficiency is low in the bioxin catalyst that removes being intended to solve domestic research and development.
The present invention is achieved in that a kind of novel TiO removing bioxin catalyst and comprise 75%-95% weight percentage
2, the WO of 0%-3% weight percentage
3, the V of 3%-10% weight percentage
2o
5, the silica of 2%-10% weight percentage.
Further, describedly novelly TiO in bioxin catalyst is removed
2weight percentage be 80%-92%.
Further, describedly novelly bioxin catalyst WO is removed
3weight percentage be 0.5%-3%.
Further, describedly novelly V in bioxin catalyst is removed
2o
5weight percentage be 4%-8%.
Further, the described novel weight percentage removing silica in bioxin catalyst is 2%-6%.
Another object of the present invention is to provide a kind of novel preparation method removing bioxin catalyst, concrete steps comprise:
Step one, take TiO
2, ammonium metatungstate, ammonium metavanadate, silica four kinds of raw material for standby, make TiO
2weight accounts for 75%-95% in four kinds of raw material gross weights, WO
3weight accounts for 0%-3% in four kinds of raw material gross weights, V
2o
5weight accounts for 3%-10% in four kinds of raw material gross weights, and silica weight accounts for 2%-10% in four kinds of raw material gross weights;
Step 2, get TiO
2, ammonium metatungstate is with silica and mix, by deionized water, TiO
2the carboxymethyl cellulose of weight 1%-4%, TiO
2the polyethylene glycol oxide of weight 2%-5% adds TiO
2, ammonium metatungstate and silica mixture in, stir;
Step 3, in the mixture of step 2, add TiO
2weight 2%-5%, weight percentage is the lactic acid solution of 20%, fully stirs the plasticity lotion obtaining mixing;
Lubricant is added in step 4, the plasticity lotion that obtains in step 3;
Step 5, in the mixture of step 4, add the ammonium metavanadate that step one takes, mix the catalyst blank that clover shape extruded by rear extruder;
Step 6, by catalyst blank dry 10-20 hour under 30-50 DEG C of condition, then dry 10-20 hour under the temperature conditions of 50-65 DEG C;
Step 7, dried catalyst blank is calcined 3-6 hour under 250-300 DEG C of condition, then under 380-450 DEG C of condition, calcine 3-7 hour, obtain finished catalyst.
Further, described lubricant is glycerine or stearic acid.
Further, described TiO
2diameter of particle < 0.1mm, and specific area is greater than 150m
2/ g.
Further, described silicon-dioxide powdery particle diameter < 0.1mm, and specific area is greater than 300m
2/ g.
The bioxin catalyst that removes of the present invention adds binding agent, dispersant, water-loss reducer, lubricant etc. by substep in manufacturing process, ceaselessly stir in mixing roll and react, namely the obtained bioxin catalyst that removes has excellent [jfg-ip1] to be applicable to industrialization large-scale production to bioxin at a lower temperature.
Accompanying drawing explanation
Fig. 1 is the novel preparation method's flow chart removing bioxin catalyst that the embodiment of the present invention provides.
Detailed description of the invention
For summary of the invention of the present invention, Characteristic can be understood further, hereby exemplify following examples, and coordinate accompanying drawing to be described in detail as follows: the present invention does not exist the innovation of software or method.
The present invention is achieved in that a kind of novel TiO removing bioxin catalyst and comprise 75%-95% weight percentage
2, the WO of 0%-3% weight percentage
3, the V of 3%-10% weight percentage
2o
5, the silica of 2%-10% weight percentage.
Further, describedly novelly TiO in bioxin catalyst is removed
2weight percentage be 80%-92%.
Further, describedly novelly bioxin catalyst WO is removed
3weight percentage be 0.5%-3%.
Further, describedly novelly V in bioxin catalyst is removed
2o
5weight percentage be 4%-8%.
Further, the described novel weight percentage removing silica in bioxin catalyst is 2%-6%.
Another object of the present invention is to provide a kind of novel preparation method removing bioxin catalyst, as shown in Figure 1, concrete steps comprise:
S101, take TiO
2, ammonium metatungstate, ammonium metavanadate, silica four kinds of raw material for standby, make TiO
2weight accounts for 75%-95% in four kinds of raw material gross weights, WO
3weight accounts for 0%-3% in four kinds of raw material gross weights, V
2o
5weight accounts for 3%-10% in four kinds of raw material gross weights, and silica weight accounts for 2%-10% in four kinds of raw material gross weights;
S102, get TiO
2, ammonium metatungstate is with silica and mix, by deionized water, TiO
2the carboxymethyl cellulose of weight 1%-4%, TiO
2the polyethylene glycol oxide of weight 2%-5% adds TiO
2, ammonium metatungstate and silica mixture in, stir;
S103, in the mixture of step S102, add TiO
2weight 2%-5%, weight percentage is the lactic acid solution of 20%, fully stirs the plasticity lotion obtaining mixing;
Lubricant is added in S104, the plasticity lotion that obtains in step S103;
S105, in the mixture of step S104, add the ammonium metavanadate that step S101 takes, mix the catalyst blank that clover shape extruded by rear extruder;
S106, by catalyst blank dry 10-20 hour under 30-50 DEG C of condition, then dry 10-20 hour under the temperature conditions of 50-65 DEG C;
S107, dried catalyst blank is calcined 3-6 hour under 250-300 DEG C of condition, then under 380-450 DEG C of condition, calcine 3-7 hour, obtain finished catalyst.
Further, described lubricant is glycerine or stearic acid.
Further, described TiO
2diameter of particle < 0.1mm, and specific area is greater than 150m
2/ g.
Further, described silicon-dioxide powdery particle diameter < 0.1mm, and specific area is greater than 300m
2/ g.
embodiment 1
A, take the TiO of 80kg
2, the ammonium metatungstate of 3.3kg, the ammonium metavanadate of 10.2kg, silica four kinds of raw material for standby of 6kg, make TiO
2weight accounts for 80%, WO in four kinds of raw material gross weights
3weight accounts for 3%, V in four kinds of raw material gross weights
2o
5weight accounts for 8% in four kinds of raw material gross weights, and silica weight accounts for 6% in four kinds of raw material gross weights;
B, get TiO
2, ammonium metatungstate is with silica and mix, by carboxymethyl cellulose, the TiO of 30Kg deionized water and 2kg
2the polyethylene glycol oxide of weight 2%-5% adds TiO
2, ammonium metatungstate and silica mixture in, stir;
C, add in the mixture of step b 4kg, weight percentage is the lactic acid solution of 20%, fully stirs the plasticity lotion obtaining mixing;
Glycerine is added as lubricant in d, the plasticity lotion that obtains in step c;
E, in the mixture of steps d, add the ammonium metavanadate that step a takes, mix the catalyst blank that clover shape extruded by rear extruder;
F, by catalyst blank dry 15-20 hour under 30 DEG C of conditions, then dry 15-20 hour under the temperature conditions of 50 DEG C;
G, dried catalyst blank to be calcined 6 hours under 250 DEG C of conditions, then calcine 7 hours under 380 DEG C of conditions, obtain finished catalyst.
embodiment 2
A, take the TiO of 92kg
2, the ammonium metatungstate of 0.56kg, the ammonium metavanadate of 5.1kg, silica four kinds of raw material for standby of 2kg, make TiO
2weight accounts for 92%, WO in four kinds of raw material gross weights
3weight accounts for 0.5%, V in four kinds of raw material gross weights
2o
5weight accounts for 4% in four kinds of raw material gross weights, and silica weight accounts for 2% in four kinds of raw material gross weights;
B, get TiO
2, ammonium metatungstate is with silica and mix, by the carboxymethyl cellulose of 30Kg deionized water, 3kg, TiO
2the polyethylene glycol oxide of weight 2% ~ 5% adds TiO
2, ammonium metatungstate and silica mixture in, stir;
C, add in the mixture of step b 4.5kg, weight percentage is the lactic acid solution of 20%, fully stirs the plasticity lotion obtaining mixing;
Stearic acid is added as lubricant in d, the plasticity lotion that obtains in step c;
E, in the mixture of steps d, add the ammonium metavanadate that step a takes, mix the catalyst blank that clover shape extruded by rear extruder;
F, by catalyst blank dry 10-12 hour under 50 DEG C of conditions, then dry 10-12 hour under the temperature conditions of 65 DEG C;
G, dried catalyst blank to be calcined 3 hours under 300 DEG C of conditions, then calcine 4 hours under 420 DEG C of conditions, obtain finished catalyst.
embodiment 3
A, take the TiO of 85kg
2, the ammonium metatungstate of 3.75kg, the ammonium metavanadate of 6.4kg, silica four kinds of raw material for standby of 4kg, make TiO
2weight accounts for 85%, WO in four kinds of raw material gross weights
3weight accounts for 3%, V in four kinds of raw material gross weights
2o
5weight accounts for 5% in four kinds of raw material gross weights, and silica weight accounts for 4% in four kinds of raw material gross weights;
B, get TiO
2, ammonium metatungstate is with silica and mix, by the carboxymethyl cellulose of 30Kg deionized water, 3kg, TiO
2the polyethylene glycol oxide of weight 2%-5% adds TiO
2, ammonium metatungstate and silica mixture in, stir;
C, add in the mixture of step b 3.5kg, weight percentage is the lactic acid solution of 20%, fully stirs the plasticity lotion obtaining mixing;
Glycerine is added as lubricant in d, the plasticity lotion that obtains in step c;
E, in the mixture of steps d, add the ammonium metavanadate that step a takes, mix the catalyst blank that clover shape extruded by rear extruder;
F, by catalyst blank dry 12-15 hour under 40 DEG C of conditions, then under the temperature conditions of 55 DEG C dry 12-15 hour;
G, dried catalyst blank to be calcined 5 hours under 275 DEG C of conditions, then calcine 5 hours under 400 DEG C of conditions, obtain finished catalyst.
embodiment 4
A, take the TiO of 86kg
2, the ammonium metatungstate of 0.56kg, the ammonium metavanadate of 7.7kg, silica four kinds of raw material for standby of 5kg, make TiO
2weight accounts for 86%, WO in four kinds of raw material gross weights
3weight accounts for 0.5%, V in four kinds of raw material gross weights
2o
5weight accounts for 6% in four kinds of raw material gross weights, and silica weight accounts for 5% in four kinds of raw material gross weights;
B, get TiO
2, ammonium metatungstate is with silica and mix, by the carboxymethyl cellulose of 30Kg deionized water, 2kg, TiO
2the polyethylene glycol oxide of weight 2%-5% adds TiO
2, ammonium metatungstate and silica mixture in, stir;
C, add in the mixture of step b 3kg, weight percentage is the lactic acid solution of 20%, fully stirs the plasticity lotion obtaining mixing;
Lubricant is added in d, the plasticity lotion that obtains in step c;
E, in the mixture of steps d, add the ammonium metavanadate that step a takes, mix the catalyst blank that clover shape extruded by rear extruder;
F, by catalyst agent dry 12-15 hour under 40 DEG C of conditions, then dry 18-20 hour under the temperature conditions of 50 DEG C;
G, dried catalyst blank to be calcined 4 hours under 290 DEG C of conditions, then calcine 4 hours under 410 DEG C of conditions, obtain finished catalyst.
embodiment 5
A, take the TiO of 86kg
2, the ammonium metatungstate of 1.1kg, the ammonium metavanadate of 7.7kg, silica four kinds of raw material for standby of 4kg, make TiO
2weight accounts for 86%, WO in four kinds of raw material gross weights
3weight accounts for 1%, V in four kinds of raw material gross weights
2o
5weight accounts for 6% in four kinds of raw material gross weights, and silica weight accounts for 4% in four kinds of raw material gross weights;
B, get TiO
2, ammonium metatungstate is with silica and mix, by the carboxymethyl cellulose of 30Kg deionized water, 3.2kg, TiO
2the polyethylene glycol oxide of weight 2%-5% adds TiO
2, ammonium metatungstate and silica mixture in, stir;
C, add in the mixture of step b 2.6kg, weight percentage is the lactic acid solution of 20%, fully stirs the plasticity lotion obtaining mixing;
Glycerine is added as lubricant in d, the plasticity lotion that obtains in step c;
E, in the mixture of steps d, add the ammonium metavanadate that step a takes, mix the catalyst blank that clover shape extruded by rear extruder;
F, by catalyst blank dry 18-20 hour under 35 DEG C of conditions, then under the temperature conditions of 60 DEG C dry 15-18 hour;
G, dried catalyst blank to be calcined 6 hours under 260 DEG C of conditions, then calcine 3 hours under 450 DEG C of conditions, obtain finished catalyst.
Respectively the clover catalyst of embodiment 1,2,3,4,5 and reference are tested as follows:
1, the method for testing of mechanical detection
Undertaken by the regulation of GB/T2782-2011, mechanical strength measures and adopts Intelligent testing machine for particle, precision I level, range 0-250N.
The sample detecting catalyst granules mechanical strength is finished product sample, and its granule number is 30.Directly take out at random from laboratory sample, and make its length between 5-5.5mm.Its length is measured one by one with caliper-gauge.
Table 1 intensity and specific area test result
2, bioxin removes performance test
The catalytic activity test of catalyst is carried out on homemade dynamic fixed bed reactors.Sample simulating-estimating device is tested the catalytic conversion of its Dui bioxin presoma o-dichlorohenzene.Experiment condition is as follows: air speed GHSV is 22500h
-1, o-dichlorohenzene concentration is 1250mg/m
3. test result, in table 2, can find out that the sample 4 that the present invention obtains has higher catalyzed conversion activity than reference catalyst to bioxin presoma o-dichlorohenzene.
table 2 bioxin removal efficiency test result
As can be seen from the test result that upper table provides, cellular catalyst provided by the invention has that specific area is large, intensity high and low temperature removes bioxin advantages of higher.
The above is only to preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, every according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent variations and modification, all belong in the scope of technical solution of the present invention.
Claims (9)
1. novelly remove a bioxin catalyst, it is characterized in that, this novel TiO removing bioxin catalyst and comprise 75%-95% weight percentage
2, the WO of 0%-3% weight percentage
3, the V of 3%-10% weight percentage
2o
5, the silica of 2%-10% weight percentage.
2. novelly as claimed in claim 1 remove bioxin catalyst, it is characterized in that, described novelly remove TiO in bioxin catalyst
2weight percentage be 80%-92%.
3. novelly as claimed in claim 1 remove bioxin catalyst, it is characterized in that, described novelly remove bioxin catalyst WO
3weight percentage be 0.5%-3%.
4. novelly as claimed in claim 1 remove bioxin catalyst, it is characterized in that, described novelly remove V in bioxin catalyst
2o
5weight percentage be 4%-8%.
5. novelly as claimed in claim 1 remove bioxin catalyst, it is characterized in that, the described novel weight percentage removing silica in bioxin catalyst is 2%-6%.
6. the novel preparation method removing bioxin catalyst, is characterized in that, these novel concrete steps removing the preparation method of bioxin catalyst comprise:
Step one, take TiO
2, ammonium metatungstate, ammonium metavanadate, silica four kinds of raw material for standby, make TiO
2weight accounts for 75%-95% in four kinds of raw material gross weights, WO
3weight accounts for 0%-3% in four kinds of raw material gross weights, V
2o
5weight accounts for 3%-10% in four kinds of raw material gross weights, and silica weight accounts for 2%-10% in four kinds of raw material gross weights;
Step 2, get TiO
2, ammonium metatungstate is with silica and mix, by deionized water, TiO
2the carboxymethyl cellulose of weight 1%-4%, TiO
2the polyethylene glycol oxide of weight 2%-5% adds TiO
2, ammonium metatungstate and silica mixture in, stir;
Step 3, in the mixture of step 2, add TiO
2weight 2%-5%, weight percentage is the lactic acid solution of 20%, fully stirs the plasticity lotion obtaining mixing;
Lubricant is added in step 4, the plasticity lotion that obtains in step 3;
Step 5, in the mixture of step 4, add the ammonium metavanadate that step one takes, mix the catalyst blank that clover shape extruded by rear extruder;
Step 6, by catalyst blank dry 10-20 hour under 30-50 DEG C of condition, then dry 10-20 hour under the temperature conditions of 50-65 DEG C;
Step 7, dried catalyst blank is calcined 3-6 hour under 250-300 DEG C of condition, then under 380-450 DEG C of condition, calcine 3-7 hour, obtain finished catalyst.
7. the novel preparation method removing bioxin catalyst as claimed in claim 6, it is characterized in that, described lubricant is glycerine or stearic acid.
8. the novel preparation method removing bioxin catalyst as claimed in claim 6, is characterized in that, described TiO
2diameter of particle < 0.1mm, and specific area is greater than 150m
2/ g.
9. the novel preparation method removing bioxin catalyst as claimed in claim 6, it is characterized in that, described silicon-dioxide powdery particle diameter < 0.1mm, and specific area is greater than 300m
2/ g.
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CN105597736A (en) * | 2016-03-10 | 2016-05-25 | 珠海市云筒环保科技有限公司 | Dioxin catalyst for production of cellular bricks |
CN107376895A (en) * | 2017-07-04 | 2017-11-24 | 清华大学 | A kind of Collaborative Control NOxWith the preparation method and applications of CVOCs trifolium-shaped catalyst |
CN109647190A (en) * | 2019-01-25 | 2019-04-19 | 湖南宏福环保股份有限公司 | A kind of de- integrative coordinated processing equipment of dioxin of combined denitration |
CN112588293A (en) * | 2020-12-13 | 2021-04-02 | 江苏百茂源环保科技有限公司 | Novel catalyst for degrading dioxin and preparation method thereof |
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Application publication date: 20150729 |