CN110252332A - A method of honeycomb VOCs catalyst is prepared using useless SCR catalyst - Google Patents
A method of honeycomb VOCs catalyst is prepared using useless SCR catalyst Download PDFInfo
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- CN110252332A CN110252332A CN201910559464.9A CN201910559464A CN110252332A CN 110252332 A CN110252332 A CN 110252332A CN 201910559464 A CN201910559464 A CN 201910559464A CN 110252332 A CN110252332 A CN 110252332A
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- scr catalyst
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- useless
- vocs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
Abstract
The invention discloses a kind of method for preparing honeycomb VOCs catalyst using useless SCR catalyst, include the following steps: 1) to carry out dust suction processing to useless SCR catalyst module by vacuumizing dust exhaust apparatus；2) it will be cleaned in the useless SCR catalyst module merging acid solution after dust suction, rinse in deionized water, then useless SCR catalyst module is placed in lye and is cleaned, rinsed in deionized water；3) the useless SCR catalyst module after cleaning is put into hot-blast stove and is dried, then crushed using Raymond mill, obtain SCR catalyst powder；4) by obtained SCR catalyst powder and active material, binder and mix lubricant it is uniform after mediated, extrusion molding, drying and calcination, obtain the honeycombed catalyst for being catalyzed VOCs.A kind of method for preparing honeycomb VOCs catalyst using useless SCR catalyst of the present invention, the resource for realizing useless SCR catalyst maximally utilize, and reduce production cost, active material is uniformly dispersed, is not easily to fall off, and improves the efficiency of catalysis VOCs.
Description
Technical field
The present invention relates to a kind of methods for preparing honeycomb VOCs catalyst using useless SCR catalyst.
Background technique
As country requires to be increasingly stringenter to air contaminant treatment, SCR technology (SCR) has become de-
Most mature technology in nitre engineering, wherein SCR catalyst is core.In the process of running, the high-content in flue gas is grey for catalyst
Heavy metal contaminants in point and wait substances at alkali (soil) metal, sulfur dioxide, cause SCR catalyst poisoning, abrasion, block, make
Catalyst denitration performance decline, be unable to satisfy use.Therefore useless SCR catalyst is produced, it is a large amount of due to containing in useless SCR
Heavy metal, belongs to the scope of hazardous waste HW50, and processing cost is high.
Useless SCR catalyst is that have very large access area by modular structure, containing a large amount of titaniums, tungsten and vanadium and silicon,
The oxides such as aluminium, calcium, therefore, useless SCR catalyst still have certain catalytic capability, can be used among other catalyst systems.
VOCs refer to boiling point 50-260 DEG C, at room temperature the volatile organic compound hydro carbons of saturated vapour pressure 133.3pa,
Chlorohydrocarbon, aromatic hydrocarbon, polycyclic aromatic hydrocarbons (PAH) etc..Mainly from the exhaust gas of the discharges such as petrochemical industry, printing, spray painting, motor vehicle.Such
Eye, nose, respiratory tract irritating effect of the organic compounds to people, causes acute and chronic poisoning, can be carcinogenic.It is this in order to eliminate
Hypertoxicity pollutant develops many correlation processing techniques, and wherein catalysis method is a kind of efficient method of comparison.VOCs catalysis combustion
Catalyst in burning technology mainly includes noble metal, molecular sieve and catalyst of transition metal oxide.Currently, transition metal V,
The oxide of Cu, Mn, Fe, Co and La are welcome because its is at low cost, stability and sulfur poisoning-resistant are good by people.Patent
201810003889.7 using ceramic honey comb matrix as skeleton, and aluminium oxide is that coating Co, La and Ce are that active component is prepared for VOCs
It is catalyzed the catalyst of burning, when temperature is 350 DEG C, toluene conversion 93.67%-95.97%, ethyl acetate conversion ratio is
92.65%-95.64%.Patent CN201711289741.6 coats rare-earth oxidation aluminium layer with honeycomb ceramic carrier, with Pt, Pd,
The mixture of seven kinds of substances of Rh, Cu, Fe, Mn, Co is that active component is prepared for VOCs combustion catalyst, layered coated operation side
Just quick and coating consistency.The VOCs catalyst of patent CN201710964536.9 is with three-dimensional porous honeycomb skeleton knot
Three ternary solid solution Cex-Zry-Ti1-x-y-O of structure2For coating, using Co and Ce composite oxides as active component.It is above special
Though sharp catalyst can be catalyzed burning VOCs, preparation process is complicated, and is all to coat active group using ceramic honey comb as carrier
Point and auxiliary agent.Active material is easy to fall off, and dispersion is uneven, catalysis burning VOCs low efficiency, and higher cost.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for preparing honeycomb VOCs catalyst using useless SCR catalyst, realize
The resource of useless SCR catalyst maximally utilizes, and reduces production cost, and active material is uniformly dispersed, is not easily to fall off, be conducive to
Improve the efficiency of catalysis VOCs.
To achieve the above object, the present invention provides a kind of method for preparing honeycomb VOCs catalyst using useless SCR catalyst,
Include the following steps:
1) dust suction processing 20-40min is carried out to useless SCR catalyst module by vacuumizing dust exhaust apparatus, it is described to vacuumize dust suction
The vacuum degree of device is 200-235mbar, air quantity 200-265m3/h；
2) the useless SCR catalyst module after dust suction is placed in 0.1-0.5mol/l acid solution and cleans 10-20min, in deionized water
3-5min is rinsed, then useless SCR catalyst module is placed in 0.1-0.5mol/l lye and cleans 10-20min, is floated in deionized water
Wash 3-5min；
3) the useless SCR catalyst module after cleaning is put into hot-blast stove and is dried, drying temperature is 130-180 DEG C, dry
Time is 3-5h, then the useless SCR catalyst module after drying is crushed using Raymond mill, obtains granularity d50≤5 μm
SCR catalyst powder；
4) by obtained SCR catalyst powder and active material, binder and lubricant with weight ratio meter for 100:(10-17):
(0.5-1.5): (0.5-0.8) mediated after mixing, extrusion molding, drying and calcination, is obtained for being catalyzed VOCs's
Honeycombed catalyst.
Preferably, active material presoma described in step 4) is ammonium metavanadate, copper nitrate and manganese nitrate, and metavanadic acid
Ammonium, copper nitrate and manganese nitrate are with weight ratio meter for (2-4): (3-5): (5-8).
Preferably, adhesive described in step 4) is methylcellulose, in hydroxypropyl methyl cellulose, hydroxyethyl cellulose
One kind.
Preferably, lubricant described in step 4) is one of tung oil, glycerine, oleic acid, stearic acid.
Preferably, acid solution described in step 2 is the mixture of one or more of sulfuric acid, nitric acid, acetic acid, oxalic acid.
Preferably, lye described in step 2 is one of sodium hydroxide, calcium hydroxide, potassium hydroxide, ammonium hydroxide or several
The mixture of kind.
The advantages and beneficial effects of the present invention are: preparation process of the invention is simple, active material is uniformly dispersed, is not easy
It falls off, is conducive to extend catalytic life, and improve the efficiency of catalysis VOCs；Also, realize the resource of useless SCR catalyst most
Bigization utilizes, and reduces environmental pollution, reduces production cost, has preferable economy and application value.
Specific embodiment
With reference to embodiment, the specific embodiment of the present invention is further described.Following embodiment is only used for more
Add and clearly demonstrate technical solution of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1
A method of honeycomb VOCs catalyst being prepared using useless SCR catalyst, is included the following steps:
1) dust suction processing 20min is carried out to useless SCR catalyst module by vacuumizing dust exhaust apparatus, it is described to vacuumize dust exhaust apparatus
Vacuum degree be 235mbar, air quantity 265m3/h；
2) 10min will be cleaned in the useless SCR catalyst module merging 0.5mol/l sulfuric acid solution after dust suction, is rinsed in deionized water
5min, then useless SCR catalyst module is placed in 0.1mol/l sodium hydroxide solution and cleans 10min, it is rinsed in deionized water
5min；
3) the useless SCR catalyst module after cleaning is put into hot-blast stove and is dried, drying temperature is 180 DEG C, drying time
For 3h, then the useless SCR catalyst module after drying crushed using Raymond mill, the SCR for obtaining granularity d50=4.54 μm is urged
Agent powder；
4) by obtained SCR catalyst powder and active material, binder and lubricant with weight ratio meter for 100:10:0.5:
It 0.5 is mediated after mixing, extrusion molding, drying and calcination, obtains the honeycombed catalyst for being catalyzed VOCs；Its
In, active material be ammonium metavanadate, copper nitrate and manganese nitrate, and ammonium metavanadate, copper nitrate and manganese nitrate with weight ratio meter be 2:
3:5；Binder is methylcellulose, and lubricant is tung oil.
Embodiment 2
A method of honeycomb VOCs catalyst being prepared using useless SCR catalyst, is included the following steps:
1) dust suction processing 40min is carried out to useless SCR catalyst module by vacuumizing dust exhaust apparatus, it is described to vacuumize dust exhaust apparatus
Vacuum degree be 200mbar, air quantity 200m3/h；
2) 20min will be cleaned in the useless SCR catalyst module merging 0.1mol/l nitric acid solution after dust suction, is rinsed in deionized water
3min, then useless SCR catalyst module is placed in 0.5mol/l calcium hydroxide solution and cleans 20min, it is rinsed in deionized water
3min；
3) the useless SCR catalyst module after cleaning is put into hot-blast stove and is dried, drying temperature is 130 DEG C, drying time
For 5h, then the useless SCR catalyst module after drying crushed using Raymond mill, the SCR for obtaining granularity d50=4.23 μm is urged
Agent powder；
4) by obtained SCR catalyst powder and active material, binder and lubricant with weight ratio meter for 100:17:1.5:
It 0.8 is mediated after mixing, extrusion molding, drying and calcination, obtains the honeycombed catalyst for being catalyzed VOCs；Its
In, active material be ammonium metavanadate, copper nitrate and manganese nitrate, and ammonium metavanadate, copper nitrate and manganese nitrate with weight ratio meter be 4:
5:8；Adhesive is hydroxypropyl methyl cellulose, and lubricant is glycerine.
Embodiment 3
A method of honeycomb VOCs catalyst being prepared using useless SCR catalyst, is included the following steps:
1) dust suction processing 40min is carried out to useless SCR catalyst module by vacuumizing dust exhaust apparatus, it is described to vacuumize dust exhaust apparatus
Vacuum degree be 235mbar, air quantity 265m3/h；
2) 15min will be cleaned in the useless SCR catalyst module merging 0.5mol/l acetum after dust suction, is rinsed in deionized water
5min, then useless SCR catalyst module is placed in 0.1mol/l potassium hydroxide solution and cleans 10min, it is rinsed in deionized water
5min；
3) the useless SCR catalyst module after cleaning is put into hot-blast stove and is dried, drying temperature is 150 DEG C, drying time
For 3h, then the useless SCR catalyst module after drying crushed using Raymond mill, the SCR for obtaining granularity d50=4.54 μm is urged
Agent powder；
4) by obtained SCR catalyst powder and active material, binder and lubricant with weight ratio meter for 100:14:0.5:
It 0.5 is mediated after mixing, extrusion molding, drying and calcination, obtains the honeycombed catalyst for being catalyzed VOCs；Its
In, active material be ammonium metavanadate, copper nitrate and manganese nitrate, and ammonium metavanadate, copper nitrate and manganese nitrate with weight ratio meter be 4:
5:5；Binder is hydroxyethyl cellulose, and lubricant is oleic acid.
Embodiment 4
A method of honeycomb VOCs catalyst being prepared using useless SCR catalyst, is included the following steps:
1) dust suction processing 30min is carried out to useless SCR catalyst module by vacuumizing dust exhaust apparatus, it is described to vacuumize dust exhaust apparatus
Vacuum degree be 235mbar, air quantity 200m3/h；
2) 15min will be cleaned in the useless SCR catalyst module merging 0.5mol/l oxalic acid solution after dust suction, is rinsed in deionized water
5min, then useless SCR catalyst module is placed in 0.3mol/l ammonia spirit and cleans 10min, 5min is rinsed in deionized water；
3) the useless SCR catalyst module after cleaning is put into hot-blast stove and is dried, drying temperature is 150 DEG C, drying time
For 3h, then the useless SCR catalyst module after drying crushed using Raymond mill, the SCR for obtaining granularity d50=4.12 μm is urged
Agent powder；
4) by obtained SCR catalyst powder and active material, binder and lubricant with weight ratio meter for 100:16:1:0.6
It is mediated after mixing, extrusion molding, drying and calcination, obtains the honeycombed catalyst for being catalyzed VOCs；Wherein, living
Property substance be ammonium metavanadate, copper nitrate and manganese nitrate, and ammonium metavanadate, copper nitrate and manganese nitrate are 4:5:7 with weight ratio meter；It is viscous
Knot agent is hydroxypropyl methyl cellulose, and lubricant is stearic acid.
Comparative example 1
A method of honeycomb VOCs catalyst being prepared using useless SCR catalyst, is included the following steps:
1) useless SCR catalyst module is crushed using Raymond mill, obtains the SCR catalyst powder of granularity d50=4.54 μm；
2) by obtained SCR catalyst powder and active material, binder and lubricant with weight ratio meter for 100:10:0.5:
It 0.5 is mediated after mixing, extrusion molding, drying and calcination, obtains the honeycombed catalyst for being catalyzed VOCs；Its
In, active material be ammonium metavanadate, copper nitrate and manganese nitrate, and ammonium metavanadate, copper nitrate and manganese nitrate with weight ratio meter be 2:
3:5；Adhesive is methylcellulose, and lubricant is tung oil.
Catalyst performance test
By honeycomb VOCs catalyst made from embodiment 1-4 and comparative example 1 in air speed 20000h-1, oxygen content 20%, toluene is dense
Spending is 2000ppm, and N2 examines to import and export concentration with GC9800 type gas-chromatography on-line checking under the same test conditions of Balance Air
Survey the results are shown in Table 1.
1 catalyst performance testing result of table
As it can be seen from table 1 the efficiency of VOCs catalyst VOCs made from embodiment 1-4 is better than comparative example 1.It can be seen that
The honeycomb VOCs catalyst of invention preparation effectively raises the efficiency of catalysis VOCs.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (6)
1. a kind of method for preparing honeycomb VOCs catalyst using useless SCR catalyst, which comprises the steps of:
1) dust suction processing 20-40min is carried out to useless SCR catalyst module by vacuumizing dust exhaust apparatus, it is described to vacuumize dust suction
The vacuum degree of device is 200-235mbar, air quantity 200-265m3/h；
2) the useless SCR catalyst module after dust suction is placed in 0.1-0.5mol/l acid solution and cleans 10-20min, in deionized water
3-5min is rinsed, then useless SCR catalyst module is placed in 0.1-0.5mol/l lye and cleans 10-20min, is floated in deionized water
Wash 3-5min；
3) the useless SCR catalyst module after cleaning is put into hot-blast stove and is dried, drying temperature is 130-180 DEG C, dry
Time is 3-5h, then the useless SCR catalyst module after drying is crushed using Raymond mill, obtains granularity d50≤5 μm
SCR catalyst powder；
4) by obtained SCR catalyst powder and active material, binder and lubricant with weight ratio meter for 100:(10-17):
(0.5-1.5): (0.5-0.8) mediated after mixing, extrusion molding, drying and calcination, is obtained for being catalyzed VOCs's
Honeycombed catalyst.
2. the method according to claim 1 for preparing honeycomb VOCs catalyst using useless SCR catalyst, which is characterized in that
Active material presoma described in step 4) is ammonium metavanadate, copper nitrate and manganese nitrate, and ammonium metavanadate, copper nitrate and manganese nitrate
With weight ratio meter for (2-4): (3-5): (5-8).
3. the method according to claim 2 for preparing honeycomb VOCs catalyst using useless SCR catalyst, which is characterized in that
Adhesive described in step 4) is one of methylcellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose.
4. the method according to claim 3 for preparing honeycomb VOCs catalyst using useless SCR catalyst, which is characterized in that
Lubricant described in step 4) is one of tung oil, glycerine, oleic acid, stearic acid.
5. the method according to claim 4 for preparing honeycomb VOCs catalyst using useless SCR catalyst, which is characterized in that
Acid solution described in step 2 is the mixture of one or more of sulfuric acid, nitric acid, acetic acid, oxalic acid.
6. the method according to claim 5 for preparing honeycomb VOCs catalyst using useless SCR catalyst, which is characterized in that
Lye described in step 2 is the mixture of one or more of sodium hydroxide, calcium hydroxide, potassium hydroxide, ammonium hydroxide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111138164A (en) * | 2019-12-30 | 2020-05-12 | 安徽元琛环保科技股份有限公司 | Denitration catalyst module frame based on ceramic matrix and preparation method thereof |
| CN111167490A (en) * | 2020-02-14 | 2020-05-19 | 江苏龙净科杰环保技术有限公司 | Method for preparing antitoxic low-temperature denitration catalyst by using waste SCR catalyst |
| CN114471745A (en) * | 2022-04-06 | 2022-05-13 | 山东万达环保科技有限公司 | Regeneration method of SCR denitration catalyst and application of SCR denitration catalyst in denitration |
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| CN114471745A (en) * | 2022-04-06 | 2022-05-13 | 山东万达环保科技有限公司 | Regeneration method of SCR denitration catalyst and application of SCR denitration catalyst in denitration |
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