CN110038564A - A kind of catalyst with core-casing structure and preparation method thereof of high-efficient purification burning waste gas - Google Patents
A kind of catalyst with core-casing structure and preparation method thereof of high-efficient purification burning waste gas Download PDFInfo
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- CN110038564A CN110038564A CN201910229968.4A CN201910229968A CN110038564A CN 110038564 A CN110038564 A CN 110038564A CN 201910229968 A CN201910229968 A CN 201910229968A CN 110038564 A CN110038564 A CN 110038564A
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
Abstract
The invention discloses a kind of catalyst with core-casing structure of high-efficient purification burning waste gas, are related to field of exhaust gas purification, and according to the mass fraction, raw material includes TiO2And Al2O370~85 parts of mixed carrier；6~8 parts of glass fibre；2~4 parts of wood pulp；3~5 parts of ammonium metavanadate activity；8~12 parts of ammonium paratungstate；2~6 parts of ruthenium trichloride living solution；2~4 parts of auxiliary agent；1~3 part of tristerin；1~3 part of reinforcing agent；22~24 parts of deionized water.This kind of catalyst is to the NO in combustion product gasesx、Hg0There is efficient Collaborative Control ability and long-acting anti-toxicity energy with VOCs etc., and its preparation is simply appropriate for large-scale production.
Description
Technical field
The present invention relates to field of exhaust gas purification, more specifically, it relates to a kind of nucleocapsid knot of high-efficient purification burning waste gas
Structure catalyst and preparation method thereof.
Background technique
China's fossil energy consumption amount accounts for the 86.7% of primary energy consumption, in short term up to 37.8 hundred million tons of standard coals within 2016
Energy resource structure based on interior fossil energy will be kept.The burning of fossil fuel supports thermoelectricity, heating, steel, building materials and change
The sustainable development of the important industry of the national economy such as work, but also discharged largely containing NOx、SO2, the pollutants such as Hg and VOCs cigarette
Gas.Which results in the serious compound atmosphere pollution in China, seriously threaten natural environment and human health.
Catalysis method is the important method of China's combustion product gases contamination control, and thermal power plant's SCR denitration is used widely,
Coal-burning power plant, China NO is realized in power-assistedxImportant function has been played in terms of minimum discharge.SCR method is mainly used by TiO2Load
V, W, Mo isoreactivity component, can be at 290-300 DEG C or more, in NH3Under the action of efficiently restore NOx.The catalyst have compared with
Strong redox ability, to the Hg in flue gas0(nonvalent mercury) has certain oxidation, but to Hg0Oxidation efficiency, root
According to different coal and flue gas condition, only 5 to 40%；But within the temperature range of combustion product gases, this catalyst is difficult to remove
Aoxidize the VOCs component in flue gas.
For example, application No. is 201610750324.6 Chinese patents to disclose the catalyst of de- VOC of denitration demercuration a kind of,
Although forming Mo-V-W/TiO between the catalyst components2-Al2O3System, in active component Mo, V, W and carrier
TiO2-Al2O3Under the action of realize simultaneously denitration demercuration take off VOC function, can effectively simplify the knot of tail gas filtering exhaust apparatus
Structure reduces environmentally friendly cost.But due to generally all containing element sulphur in the coal of existing burning, combustion process is easy to produce two
Sulfur oxide.And the selectivity of the catalyst is poor, is easy Sulphur Dioxide into sulfur trioxide, and then the ammonia reacted with participation
Solid/liquid/gas reactions production has more strongly adherent ammonium hydrogen sulfate, so that the active sites of catalyst are capped can not to be participated in reacting, into
And the problem of catalyst failure occurs.
Therefore a kind of NO that can efficiently in cooperation-removal combustion product gases need to be developedx、Hg0And VOCs, and have and be poisoned compared with highly resistance
The catalyst with core-casing structure of ability, in order to realize the collaboration of multiple pollutant in combustion product gases using existing SCR denitration equipment
Control synchronously completes, to meet increasingly strict environmental requirement and emission limit.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of nucleocapsid knot that high-efficient purification burning is useless
Structure catalyst can efficiently and stably remove NO in combustion product gasesx、Hg0With the pollutants such as VOCs, it is increasingly strict to meet China
Burning pollutant emission limit.The catalyst anti-poisoning capability with higher simultaneously, preparation method is easy, is suitble to scale
Production.
To achieve the above object, the present invention provides the following technical scheme that
A kind of catalyst with core-casing structure of high-efficient purification burning waste gas, according to the mass fraction, raw material includes,
TiO2And Al2O370~85 parts of mixed carrier, 6~8 parts of glass fibre, 2~4 parts of wood pulp, ammonium metavanadate activity liquid 3~
5 parts, 8~12 parts of ammonium paratungstate, 2~6 parts of ruthenium trichloride living solution, 2~4 parts of auxiliary agent, 1~3 part of tristerin, enhancing
1~3 part and 22~24 parts of deionized water of agent.
By using above-mentioned technical proposal, first with TiO2And Al2O3As carrier, on the one hand can guarantee to urge in this way
The intensity of agent, on the other hand, due to TiO2It is containing a large amount of electron-hole pairs, can is the VOCs catalysis oxidation mistake in exhaust gas
Journey provides surface oxygen species, effectively facilitates the purification efficiency to VOCs in exhaust gas.
Secondly, ammonium metavanadate activity liquid can be converted to vanadic anhydride after semi-finished product sintering, it can be in ammonia
The nitrogen oxides in exhaust gas is catalysed and reduced into nitrogen and water under effect, to reduce the pollution to environment.In addition, five oxidations two
Vanadium is difficult to and SO2Reaction, sulfur poisoning resistance with higher；And its oxidability is moderate, is not easy SO2It is converted into SO3, drop
The low generation of ammonium hydrogen sulfate, extends the active timeliness of catalyst.And ruthenium trichloride living solution is after presoma sintering
It is converted to ruthenic oxide, helps speed up Hg0Oxidation efficiency, so that the mercuryvapour in exhaust gas be made to be oxidized to mercury oxide solid
Particle is easy for precipitating during exhaust gas flows in this way, to realize the effect of removing mercuryvapour.
Furthermore tristerin is a kind of good lubricant, facilitate material during the mixing of each material
Fully dispersed, can also resolve into water and carbon dioxide during sintering later, to be not easy to catalyst
Performance impacts.
And wood pulp has longer cellulose, and the knob of each material connection can be effective as in catalyst preparation process
Band, thus facilitate shaping of catalyst, meanwhile, under the action of glass fibre, the structure that can effectively improve catalyst is strong
Degree.
Preferably, TiO2And Al2O3Mass ratio be 4: 1, the TiO2For Detitanium-ore-type TiO2, Al2O3With γ type part
Based on compound β type crystal phase is constituted.
Preferably, the auxiliary agent includes C4H6MnO4·4H2O、Ce(NO3)·6H2O、Nd(NO3)3In two or three it is mixed
Close object.
By using above-mentioned technical proposal, the addition of above-mentioned auxiliary agent can effectively improve the selectivity of catalyst, thus
Catalyst is helped to improve to the NO in combustion product gasesx、Hg0With the efficiency of the efficient cooperation-removal such as VOCs.
Preferably, the reinforcing agent is the mixture of conch meal and magnesia, and the mass ratio of conch meal and magnesia is 1
∶ 1.7。
By using above-mentioned technical proposal, since the main ingredient of conch meal is calcium carbonate, it is in catalyst preparation in this way
The shaping efficiency of catalyst is helped to improve in the process, secondly, conch meal and magnesia share, can effectively improve urge in this way
The structural strength of agent.Moreover, conch meal inherently has hole, after catalyst is made in this way, can inhale to a certain extent
Harmful substance in attached exhaust gas, consequently facilitating carrying out catalysis oxidation.
Preferably, the conch meal is by passing through the mixed enzyme solution containing alkali protease, papain and trypsase
Treated, and shell is made.
By using above-mentioned technical proposal, conch meal can generate some chitins after enzyme solution processing, and the chitin
With certain bactericidal effect, can guarantee pug during aging not vulnerable to microbial contamination, secondly chitin also has
Certain viscosity, helps to improve the bond effect of each material of catalyst, to effectively improve the molding of catalyst, is convenient for
Following process.
Preferably, the ammonium metavanadate activity liquid is mixed by ammonium metavanadate and oxalic acid, and ammonium metavanadate and oxalic acid
Mass ratio is 1: 2.
Preferably, the ruthenium trichloride living solution is mixed to prepare by ruthenium trichloride and deionized water, and ruthenium trichloride with
The mass ratio of deionized water is 1: 10.
A kind of preparation method of the catalyst with core-casing structure of high-efficient purification burning waste gas, it is characterised in that: including walking as follows
Suddenly,
Step 1: according to the mass fraction, by 35~45 parts of TiO2And Al2O3Mixed carrier, 2~3 parts of glass fibre, 0.5
~1.5 parts of tristerins and 3~5 parts of ammonium paratungstates progress are dry-mixed, and 10~12 parts of deionized waters are added later, are further continued for
Mixing is until uniformly, obtain just mixing；
Step 2: by 1~2 part of wood pulp, 1~2 part of auxiliary agent, 0.5~1 part of reinforcing agent, 1~2 part of ammonium metavanadate activity liquid and 1~
2 parts of ruthenium trichloride activity liquid are mixed with the first mixing in step 1, obtain pug one；
Step 3: remaining whole materials are mixed according to step 1 and step 2, pug two is obtained；
Step 4: pug one is placed under normal temperature state aging 6~8 hours, several spherical cores are made in pug one later, and
It is dried, obtains semi-finished product；
Step 5: pug two is all uniformly coated on the surface of semi-finished product, and the semi-finished product for being coated with pug two are dried；
Step 6: transferring them to and being sintered in sintering furnace, obtain finished catalyst when the water content of semi-finished product is 15%.
By using above-mentioned technical proposal, pug is carried out first aging, on the one hand can guarantee inside pug in this way
Substance is sufficiently reacted, during reducing follow-up sintering, the pug problem chipping because of autoreaction.Secondly, to half
It is transferred into sintering furnace when finished product is not completely dried also, can make to keep certain viscosity inside semi-finished product in this way, reduce
The chipping probability in transfer process.
Preferably, before sintering, in two outer cladding asbestos of pug.
By using above-mentioned technical proposal, since asbestos heating conduction is stronger, in such sintering process, asbestos can will be warm
The circumferential surface for measuring Transmit evenly semi-finished product, to reduce the problem of catalyst breakage occurs because of uneven heating in sintering process.
In conclusion the invention has the following advantages:
1, by the TiO of 4: 1 proportions2∶Al2O3Carrier has the advantages that porosity is higher, the acid bits number of catalyst surface is moderate,
Guarantee can be provided to effectively improve reaction efficiency and reducing production cost；
2、MnO2、CeO2、Nd2O3The addition of equal auxiliary agents composition effectively increases the redox on the catalyst with core-casing structure surface
Ability provides activable oxygen species under more low temperature, to improve Hg0With the oxidation efficiency of VOCs；
3, carrier components titanium dioxide contains a large amount of electron-hole pairs, can quickly aoxidize the VOCs in coal-fired flue-gas at high temperature；
4, conch meal is due to enzyme treated mistake, thus its surface can generate chitin, to be easier to carry out during at production
It is qualitative；
5, pug two is coated using asbestos, can guarantees that product is heated evenly during sintering in this way, and then be conducive to protect
Demonstrate,prove the quality of product.
Detailed description of the invention
Fig. 1 is a kind of preparation technology flow chart of the catalyst with core-casing structure of high-efficient purification burning waste gas.
Specific embodiment
Embodiment one,
A kind of preparation method of the catalyst with core-casing structure of high-efficient purification burning waste gas, it is characterised in that: include the following steps,
Step 1: weighing TiO2And Al2O3Mixed carrier 70kg, glass fibre 6kg, wood pulp 2kg, ammonium metavanadate activity liquid
3kg, ammonium paratungstate 8kg, ruthenium trichloride living solution 2kg, auxiliary agent 2kg, tristerin 1kg, reinforcing agent 1kg and deionization
Water 22kg；
Step 2: the mixed carrier of 35kg, the glass fibre of 2kg, 0.5kg tristerin and 3kg ammonium paratungstate are carried out
It is dry-mixed, 10kg deionized water is added later, is further continued for mixing until uniformly, obtaining just mixing；
Step 3: by the wood pulp of 1kg, 1kg auxiliary agent, 0.5kg reinforcing agent, 1kg ammonium metavanadate activity liquid and 1kg ruthenium trichloride activity
Liquid is mixed with the first mixing in step 1, obtains pug one；
Step 4: remaining material is mixed according to step 2 and step 3, pug two is obtained；
Step 5: pug one and pug two are distinguished aging 6 hours, several cores are made in pug one later, and be put in 80 DEG C
It is 1 hour dry in drying box, obtain solidification pug one；
Step 6: pug two is all uniformly coated on each surface for solidifying pug one, and it is coated with the solidification of pug two
Pug one is placed in drying 1 hour in 80 DEG C of drying boxes, obtains semi-finished product；
Step 7: carrying out asbestos cladding to semi-finished product, is sent later as being sintered 3 hours at 500 DEG C in sintering furnace, obtain finished product
Catalyst.
Wherein, TiO2And Al2O3Mass ratio be 4: 1, and TiO2For Detitanium-ore-type TiO2, Al2O3With the compound β in γ type part
Based on type crystal phase is constituted；And auxiliary agent includes C4H6MnO4·4H2O and Ce (NO3)·6H2The mixture of O, the two mass ratio are 1: 1；
Furthermore reinforcing agent is the mixture of conch meal and magnesia, and the mass ratio of conch meal and magnesia is 1: 1.7.Secondly, inclined vanadium
Sour ammonium activity liquid is mixed by ammonium metavanadate and oxalic acid, and the mass ratio of ammonium metavanadate and oxalic acid is 1: 2.And ruthenium trichloride is living
Property solution be mixed to prepare by ruthenium trichloride and deionized water, and ruthenium trichloride and the mass ratio of deionized water are 1: 10.
Meanwhile the preparation method of conch meal: the sodium sulfite buffer solution that 50ml pH is 8.0 is first prepared, with 1ml Qula
It is logical to be used as surfactant, and use the alkali protease that mass ratio is 1: 1: 1, the group synthase of papain and trypsase
5g is catalyzed；By sodium sulfite buffer solution, Qula is logical and group synthase three is mixed to get enzyme solution；Shell is soaked in enzyme solution
In, control constant temperature shaker temperature is 50 DEG C, is hydrolyzed 2 hours under conditions of revolving speed 300r/min；Later, by grinding shells at average
The conch meal that granularity is 10 μm.Wherein, the preparation of sodium sulfite buffer solution is the prior art, and is not the core of the application
Content, because without being developed in details herein.
Embodiment two,
A kind of preparation method of the catalyst with core-casing structure of high-efficient purification burning waste gas, it is characterised in that: include the following steps,
Step 1: weighing TiO2And Al2O3Mixed carrier 77kg, glass fibre 7kg, wood pulp 3kg, ammonium metavanadate activity liquid
4kg, ammonium paratungstate 10kg, ruthenium trichloride living solution 4kg, auxiliary agent 3kg, tristerin 2kg, reinforcing agent 2kg and go from
Sub- water 23kg；
Step 2: the mixed carrier of 40kg, the glass fibre of 2.5kg, 1kg tristerin and 4kg ammonium paratungstate are carried out
It is dry-mixed, 11kg deionized water is added later, is further continued for mixing until uniformly, obtaining just mixing；
Step 3: by the wood pulp of 1.5kg, 1.5kg auxiliary agent, 0.7kg reinforcing agent, 1.5kg ammonium metavanadate activity liquid and 1.5kg trichlorine
Change ruthenium activity liquid to be mixed with the first mixing in step 1, obtains pug one；
Step 4: remaining material is mixed according to step 2 and step 3, pug two is obtained；
Step 5: pug one and pug two are distinguished aging 7 hours, several cores are made in pug one later, and be put in 80 DEG C
It is 1 hour dry in drying box, obtain solidification pug one；
Step 6: pug two is all uniformly coated on each surface for solidifying pug one, and it is coated with the solidification of pug two
Pug one is placed in drying 1 hour in 80 DEG C of drying boxes, obtains semi-finished product；
Step 7: carrying out asbestos cladding to semi-finished product, is sent later as being sintered 3 hours at 500 DEG C in sintering furnace, obtain finished product
Catalyst.
Wherein, TiO2And Al2O3Mass ratio be 4: 1, and TiO2For Detitanium-ore-type TiO2, Al2O3With the compound β in γ type part
Based on type crystal phase is constituted；And auxiliary agent includes Ce (NO3)·6H2O and Nd (NO3)3Two kinds of mixtures, the mass ratio of the two are 1: 1；
Furthermore reinforcing agent is the mixture of conch meal and magnesia, and the mass ratio of conch meal and magnesia is 1: 1.7.Secondly, inclined vanadium
Sour ammonium activity liquid is mixed by ammonium metavanadate and oxalic acid, and the mass ratio of ammonium metavanadate and oxalic acid is 1: 2.And ruthenium trichloride is living
Property solution be mixed to prepare by ruthenium trichloride and deionized water, and ruthenium trichloride and the mass ratio of deionized water are 1: 10.
Meanwhile the preparation method of conch meal: the sodium sulfite buffer solution that 50ml pH is 8.0 is first prepared, with 1ml Qula
It is logical to be used as surfactant, and use the alkali protease that mass ratio is 1: 1: 1, the group synthase of papain and trypsase
5g is catalyzed；By sodium sulfite buffer solution, Qula is logical and group synthase three is mixed to get enzyme solution；Shell is soaked in enzyme solution
In, control constant temperature shaker temperature is 50 DEG C, is hydrolyzed 2 hours under conditions of revolving speed 300r/min；Later, by grinding shells at average
The conch meal that granularity is 10 μm.Wherein, the preparation of sodium sulfite buffer solution is the prior art, and is not the core of the application
Content, because without being developed in details herein.
Embodiment three,
A kind of preparation method of the catalyst with core-casing structure of high-efficient purification burning waste gas, it is characterised in that: include the following steps,
Step 1: weighing TiO2And Al2O3Mixed carrier 85kg, glass fibre 8kg, wood pulp 4kg, ammonium metavanadate activity liquid
5kg, ammonium paratungstate 12kg, ruthenium trichloride living solution 6kg, auxiliary agent 4kg, tristerin 3kg, reinforcing agent 3kg and go from
Sub- water 24kg；
Step 2: the mixed carrier of 45kg, the glass fibre of 3kg, 1.5kg tristerin and 5kg ammonium paratungstate are carried out
It is dry-mixed, 12kg deionized water is added later, is further continued for mixing until uniformly, obtaining just mixing；
Step 3: by the wood pulp of 2kg, 2kg auxiliary agent, 1kg reinforcing agent, 2kg ammonium metavanadate activity liquid and 2kg ruthenium trichloride activity liquid
It is mixed with the first mixing in step 1, obtains pug one；
Step 4: remaining material is mixed according to step 2 and step 3, pug two is obtained；
Step 5: pug one and pug two are distinguished aging 8 hours, several cores are made in pug one later, and be put in 80 DEG C
It is 1 hour dry in drying box, obtain solidification pug one；
Step 6: pug two is all uniformly coated on each surface for solidifying pug one, and it is coated with the solidification of pug two
Pug one is placed in drying 1 hour in 80 DEG C of drying boxes, obtains semi-finished product；
Step 7: carrying out asbestos cladding to semi-finished product, is sent later as being sintered 3 hours at 500 DEG C in sintering furnace, obtain finished product
Catalyst.
Wherein, TiO2And Al2O3Mass ratio be 4: 1, and TiO2For Detitanium-ore-type TiO2, Al2O3With the compound β in γ type part
Based on type crystal phase is constituted；And auxiliary agent includes C4H6MnO44H2O and Nd (NO3)3Two kinds of mixtures, the mass ratio of the two is 1:
1；Furthermore reinforcing agent is the mixture of conch meal and magnesia, and the mass ratio of conch meal and magnesia is 1: 1.7.Secondly,
Ammonium metavanadate activity liquid is mixed by ammonium metavanadate and oxalic acid, and the mass ratio of ammonium metavanadate and oxalic acid is 1: 2.And tri-chlorination
Ruthenium living solution is mixed to prepare by ruthenium trichloride and deionized water, and ruthenium trichloride and the mass ratio of deionized water are 1: 10.
Meanwhile the preparation method of conch meal: the sodium sulfite buffer solution that 50ml pH is 8.0 is first prepared, with 1ml Qula
It is logical to be used as surfactant, and use the alkali protease that mass ratio is 1: 1: 1, the group synthase of papain and trypsase
5g is catalyzed；By sodium sulfite buffer solution, Qula is logical and group synthase three is mixed to get enzyme solution；Shell is soaked in enzyme solution
In, control constant temperature shaker temperature is 50 DEG C, is hydrolyzed 2 hours under conditions of revolving speed 300r/min；Later, by grinding shells at average
The conch meal that granularity is 10 μm.Wherein, the preparation of sodium sulfite buffer solution is the prior art, and is not the core of the application
Content, because without being developed in details herein.
Example IV,
A kind of preparation method of the catalyst with core-casing structure of high-efficient purification burning waste gas, it is characterised in that: include the following steps,
Step 1: weighing TiO2And Al2O3Mixed carrier 70kg, glass fibre 8kg, wood pulp 3kg, ammonium metavanadate activity liquid
3kg, ammonium paratungstate 8kg, ruthenium trichloride living solution 6kg, auxiliary agent 3kg, tristerin 2kg, reinforcing agent 2kg and deionization
Water 23kg；
Step 2: the mixed carrier of 40kg, the glass fibre of 2kg, 1.5kg tristerin and 3kg ammonium paratungstate are carried out
It is dry-mixed, 11kg deionized water is added later, is further continued for mixing until uniformly, obtaining just mixing；
Step 3: by the wood pulp of 1kg, 2kg auxiliary agent, 0.5kg reinforcing agent, 2kg ammonium metavanadate activity liquid and 2kg ruthenium trichloride activity
Liquid is mixed with the first mixing in step 1, obtains pug one；
Step 4: remaining material is mixed according to step 2 and step 3, pug two is obtained；
Step 5: pug one and pug two are distinguished aging 6~8 hours, several cores are made in pug one later, and be put in 80
It is 1 hour dry in DEG C drying box, obtain solidification pug one；
Step 6: pug two is all uniformly coated on each surface for solidifying pug one, and it is coated with the solidification of pug two
Pug one is placed in drying 1 hour in 80 DEG C of drying boxes, obtains semi-finished product；
Step 7: carrying out asbestos cladding to semi-finished product, is sent later as being sintered 3 hours at 500 DEG C in sintering furnace, obtain finished product
Catalyst.
Wherein, TiO2And Al2O3Mass ratio be 4: 1, and TiO2For Detitanium-ore-type TiO2, Al2O3With the compound β in γ type part
Based on type crystal phase is constituted；And auxiliary agent includes C4H6MnO4·4H2O、Ce(NO3)·6H2O and Nd (NO3)3Three kinds of mixtures, three
Between mass ratio be 1: 1: 1；Furthermore reinforcing agent is the mixture of conch meal and magnesia, and the matter of conch meal and magnesia
Amount is than being 1: 1.7.Secondly, ammonium metavanadate activity liquid is mixed by ammonium metavanadate and oxalic acid, and the matter of ammonium metavanadate and oxalic acid
Amount is than being 1: 2.And ruthenium trichloride living solution is mixed to prepare by ruthenium trichloride and deionized water, and ruthenium trichloride and deionized water
Mass ratio be 1: 10；
Meanwhile the preparation method of conch meal: the sodium sulfite buffer solution that 50ml pH is 8.0 is first prepared, with 1ml Qula
It is logical to be used as surfactant, and use the alkali protease that mass ratio is 1: 1: 1, the group synthase of papain and trypsase
5g is catalyzed；By sodium sulfite buffer solution, Qula is logical and group synthase three is mixed to get enzyme solution；Shell is soaked in enzyme solution
In, control constant temperature shaker temperature is 50 DEG C, is hydrolyzed 2 hours under conditions of revolving speed 300r/min；Later, by grinding shells at average
The conch meal that granularity is 10 μm.Wherein, the preparation of sodium sulfite buffer solution is the prior art, and is not the core of the application
Content, because without being developed in details herein.
Embodiment five,
A kind of preparation method of the catalyst with core-casing structure of high-efficient purification burning waste gas, it is characterised in that: include the following steps,
Step 1: weighing TiO2And Al2O3Mixed carrier 85kg, glass fibre 6kg, wood pulp 3kg, ammonium metavanadate activity liquid
5kg, ammonium paratungstate 8kg, ruthenium trichloride living solution 4kg, auxiliary agent 4kg, tristerin 2kg, reinforcing agent 3kg and deionization
Water 22kg；
Step 2: the mixed carrier of 35kg, the glass fibre of 3kg, 0.5kg tristerin and 4kg ammonium paratungstate are carried out
It is dry-mixed, 10kg deionized water is added later, is further continued for mixing until uniformly, obtaining just mixing；
Step 3: by the wood pulp of 2kg, 1kg auxiliary agent, 1kg reinforcing agent, 1kg ammonium metavanadate activity liquid and 2kg ruthenium trichloride activity liquid
It is mixed with the first mixing in step 1, obtains pug one；
Step 4: remaining material is mixed according to step 2 and step 3, pug two is obtained；
Step 5: pug one and pug two are distinguished aging 6 hours, several cores are made in pug one later, and be put in 80 DEG C
It is 1 hour dry in drying box, obtain solidification pug one；
Step 6: pug two is all uniformly coated on each surface for solidifying pug one, and it is coated with the solidification of pug two
Pug one is placed in drying 1 hour in 80 DEG C of drying boxes, obtains semi-finished product；
Step 7: carrying out asbestos cladding to semi-finished product, is sent later as being sintered 3 hours at 500 DEG C in sintering furnace, obtain finished product
Catalyst.
Wherein, TiO2And Al2O3Mass ratio be 4: 1, and TiO2For Detitanium-ore-type TiO2, Al2O3With the compound β in γ type part
Based on type crystal phase is constituted；And auxiliary agent includes C4H6MnO4·4H2O、Ce(NO3)·6H2O and Nd (NO3)3Three kinds of mixtures, thirdly
Kind mass ratio is 1: 1: 1；Furthermore reinforcing agent is the mixture of conch meal and magnesia, and the mass ratio of conch meal and magnesia
It is 1: 1.7.Secondly, ammonium metavanadate activity liquid is mixed by ammonium metavanadate and oxalic acid, and the mass ratio of ammonium metavanadate and oxalic acid
It is 1: 2.And ruthenium trichloride living solution is mixed to prepare by ruthenium trichloride and deionized water, and the matter of ruthenium trichloride and deionized water
Amount is than being 1: 10.
Meanwhile the preparation method of conch meal: the sodium sulfite buffer solution that 50ml pH is 8.0 is first prepared, with 1ml Qula
It is logical to be used as surfactant, and use the alkali protease that mass ratio is 1: 1: 1, the group synthase of papain and trypsase
5g is catalyzed；By sodium sulfite buffer solution, Qula is logical and group synthase three is mixed to get enzyme solution；Shell is soaked in enzyme solution
In, control constant temperature shaker temperature is 50 DEG C, is hydrolyzed 2 hours under conditions of revolving speed 300r/min；Later, by grinding shells at average
The conch meal that granularity is 10 μm.Wherein, the preparation of sodium sulfite buffer solution is the prior art, and is not the core of the application
Content, because without being developed in details herein.
According to the testing standard of such as following table one, embodiment one to embodiment five is tested:
Table one
Result shown in table two that test result is as follows:
Table two
It can be seen that catalyst with core-casing structure disclosed in the present application for combustion by the experimental result of embodiment one to embodiment two
Burn NO in flue gasx、Hg0And the cooperation-removal of VOCs etc. has good effect, and its production method is relatively simple, is appropriate for
Large-scale production.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the scope of the claims of invention.
Claims (9)
1. a kind of catalyst with core-casing structure of high-efficient purification burning waste gas, which is characterized in that according to the mass fraction, raw material packet
It includes,
2. a kind of catalyst with core-casing structure of high-efficient purification burning waste gas according to claim 1, it is characterised in that: TiO2
And Al2O3Mass ratio be 4: 1, the TiO2For Detitanium-ore-type TiO2, Al2O3Based on being constituted with the compound β type crystal phase in γ type part.
3. a kind of catalyst with core-casing structure of high-efficient purification burning waste gas according to claim 1, it is characterised in that: described
Auxiliary agent includes C4H6MnO4·4H2O、Ce(NO3)·6H2O、Nd(NO3)3In two or three of mixture.
4. a kind of catalyst with core-casing structure of high-efficient purification burning waste gas according to claim 1, it is characterised in that: described
Reinforcing agent is the mixture of conch meal and magnesia, and the mass ratio of conch meal and magnesia is 1: 1.7.
5. a kind of catalyst with core-casing structure of high-efficient purification burning waste gas according to claim 4, it is characterised in that: described
Conch meal is by by the mixed enzyme solution containing alkali protease, papain and trypsase, treated that shell is made.
6. a kind of catalyst with core-casing structure of high-efficient purification burning waste gas according to claim 1, it is characterised in that: described
Ammonium metavanadate activity liquid is mixed by ammonium metavanadate and oxalic acid, and the mass ratio of ammonium metavanadate and oxalic acid is 1: 2.
7. a kind of catalyst with core-casing structure of high-efficient purification burning waste gas according to claim 1, it is characterised in that: described
Ruthenium trichloride living solution is mixed to prepare by ruthenium trichloride and deionized water, and ruthenium trichloride and the mass ratio of deionized water are 1:
10。
8. a kind of core-shell structure of high-efficient purification burning waste gas as described in any one of claim 1 to 7 claim is urged
The preparation method of agent, it is characterised in that: include the following steps,
Step 1: according to the mass fraction, by 35~45 parts of TiO2And Al2O3Mixed carrier, 2~3 parts of glass fibre, 0.5
~1.5 parts of tristerins and 3~5 parts of ammonium paratungstates progress are dry-mixed, and 10~12 parts of deionized waters are added later, are further continued for mixing
It closes until uniformly, obtaining just mixing；
Step 2: by 1~2 part of wood pulp, 1~2 part of auxiliary agent, 0.5~1 part of reinforcing agent, 1~2 part of ammonium metavanadate activity liquid and 1~
2 parts of ruthenium trichloride activity liquid are mixed with the first mixing in step 1, obtain pug one；
Step 3: remaining whole materials are mixed according to step 1 and step 2, pug two is obtained；
Step 4: pug one is placed under normal temperature state aging 6~8 hours, several spherical cores are made in pug one later, and
It is dried, obtains semi-finished product；
Step 5: pug two is all uniformly coated on the surface of semi-finished product, and the semi-finished product for being coated with pug two are done
It is dry；
Step 6: transferring them to and being sintered in sintering furnace when the water content of semi-finished product is 15%, finished product catalysis is obtained
Agent.
9. a kind of preparation method of the catalyst with core-casing structure of high-efficient purification burning waste gas according to claim 8, feature exist
In: before sintering, in two outer cladding asbestos of pug.
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