CN106076351A - One is used for administering industry stationary source organic exhaust gas catalyst and preparation method thereof - Google Patents
One is used for administering industry stationary source organic exhaust gas catalyst and preparation method thereof Download PDFInfo
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- CN106076351A CN106076351A CN201610420679.9A CN201610420679A CN106076351A CN 106076351 A CN106076351 A CN 106076351A CN 201610420679 A CN201610420679 A CN 201610420679A CN 106076351 A CN106076351 A CN 106076351A
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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
- B01J23/83—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 rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/40—Mixed oxides
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The present invention relates to a kind of for administering industry stationary source organic exhaust gas catalyst and preparation method thereof, belong to technical field of atmospheric pollution control.The method mainly uses one or more oxides of Pt/Ag/Cu/Fe/Rh/Pd/Co/Ni/Mn/Ce to be active component, using ceramic honey comb, ZSM 5 or SBA 15 as carrier, preparing organic exhaust gas catalyst, this catalyst performance is good, can be 255 DEG C of removal efficiency realizing toluene is up to 99%；310 DEG C of removal efficiency realized ethylene 99%.With similar catalyst first than, to toluene 99% removal efficiency temperature reduce about 30 DEG C, to ethylene remove temperature reduce about 60 DEG C；And this catalyst preparation process is simple, raw material sources is extensive, cheap, is suitable for industrialized production application.
Description
Technical field
The present invention relates to a kind of for administering industry stationary source organic exhaust gas catalyst and preparation method thereof, belong to air dirty
Dye Treatment process field.
Background technology
Industry industry involved by stationary source organic exhaust gas is numerous, and pollutant kind is various, composition complexity.Through be commonly encountered
Classes of compounds has the organic compound such as hydro carbons, ketone, esters, alcohols, phenols, aldehydes, amine, nitrile (cyanogen) class, the most mostly
Toxic, serious harm health；Light then stimulate eyes and respiratory system, heavy then be poisoned；Some can dash forward in carcinogenic, teratogenesis, cause
Become.Some is if these widely known organic compound such as formaldehyde, benzene,toluene,xylene, vinyl chloride, polycyclic aromatic hydrocarbon are to human body
Healthy extremely harmful.In addition some has destruction to ozone layer such as Chlorofluorocarbons (CFCs) and HCFC, is paid close attention to by the world, and
Prohibit the use of.Therefore solve to control its discharge focus that always researchers are paid close attention to.
Administer at present the end-of-pipe control technology of industry stationary source organic exhaust gas and be broadly divided into two big classes: be i.e. recovery technology and pin
Ruin technology.Recovery technology is the method by physics, changes temperature, pressure or uses selective absorbent and permoselective membrane
The method carrying out concentration and separation organic pollution etc. method.Destruction technology is by chemistry or biochemical reaction, with heat, light, catalyst
Or the method that organic compound is transformed into the nonhazardous micromolecular compound such as carbon dioxide and water by microorganism etc..Catalysis burning
Method is used widely because having the advantages such as running cost is relatively low, removing pollutant scope is wide, effect is thorough.
The noble metals such as the many employings of Production by Catalytic Combustion Process, platinum, rhodium are as catalyst, but this kind of catalyst is expensive, instead
Should be temperature required the highest, medium-sized and small enterprises are difficult to bear the investment of its costliness and running cost；And catalyst is easily poisoned, hinder
The spread of this technology uses.
Summary of the invention
In order to reduce production cost and the reaction temperature of catalyst, promoting the anti-poisoning performance of catalyst, the present invention provides
A kind of improvement industry stationary source organic exhaust gas catalyst and preparation method thereof, preparation method includes that infusion process, mixing method, ion are handed over
Change method and solid-phase sequencing etc..
The technical scheme is that
A kind of catalyst for administering industry stationary source organic exhaust gas, using ceramic honey comb, ZSM-5 or SBA-15 as the
One carrier, coats one layer of γ-Al at its inner surfaces of pores2O3Coating as Second support, and with Pt, Ag, Cu, Fe, Rh, Pd,
One or more in the oxide of Co, Ni, Mn, Ce are as active component；Second support account for the first carrier quality 1～
14%；Active component content accounts for the 1～4.4% of the first carrier quality.
Further, described γ-Al2O3Coating is by γ-Al2O3Type activated alumina is configured to after Alumina gel at honeycomb
On ceramic monolith, coating forms.
Further, the total load amount of described active component is 10～30g/L.
The above-mentioned catalyst for administering industry stationary source organic exhaust gas, comprises the steps:
(1) first Vehicle element；Ceramic honey comb, ZSM-5 or SBA-15 be impregnated in 10-150 in nitric acid or distilled water
Minute, electric stirring 10-150 minute；Then 80-200 DEG C dry 1-8 hour；
(2)γ-Al2O3Colloidal sol is prepared；By γ-Al2O3Type activated alumina and distilled water mix to be completely dispersed,
Electric stirring 10-150 minute；γ-Al2O3Type activated alumina accounts for the 1.5-20% of dispersion liquid quality；
(3) impregnation liquid preparation；By one or more the nitrate of Pt, Ag, Cu, Fe, Rh, Pd, Co, Ni, Mn, Ce
It is configured to solution；
(4)γ-Al2O3Coating；By step (1) gained the first carrier impregnation in step (2) gained γ-Al2O3In colloidal sol
Take out after 0.5-6 hour, γ-Al2O3The volume ratio of colloidal sol and the first carrier is 0.1～0.6, and 200-700 DEG C of roasting 5-15 is little
Time；
(5) activating oxide load, coats γ-Al by step (4) gained2O3The first carrier impregnation in step (3) gained
Impregnation liquid took out after 10-180 minute, 100-700 DEG C of roasting 1-15 hour, obtain final products, be i.e. used for administering Industrial Solid
Determine the catalyst of source organic exhaust gas.
Further, the rotating speed of electric stirring is 10-200 rev/min.
In research and heuristic process, inventor surprisingly finds, due to γ-Al2O3The difference of coating and active metal is joined
Ratio, the catalyst of gained produces significant difference in final performance, also creates different adaptabilities, the most simultaneously
Proportioning could decompose the organic exhaust gas such as toluene, ethylene effectively.
The beneficial effects of the present invention is:
(1) gained catalyst performance of the present invention is good, can be 255 DEG C of removal efficiency realized toluene 99%；310 DEG C of realities
The now removal efficiency to ethylene 99%.With similar catalyst first than, to toluene 99% removal efficiency temperature reduce about 30 DEG C, to second
Alkene is removed temperature and is reduced about 60 DEG C；
(2) production process technology of the present invention is simple, facilitates industrialized production；
(3) raw material sources of the present invention is wide, and price is low, significantly reduces the production cost of catalyst.
Accompanying drawing explanation
Fig. 1 is coating γ-Al2O3Ceramic honey comb graph of pore diameter distribution.
Fig. 2 is embodiment 5 test result figure.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further details, but the present invention is not limited to this.
Embodiment 1
(1) ceramic honey comb pretreatment: being immersed in by ceramic honey comb in distilled water 1 hour, electric stirring 30 minutes, rotating speed is
30 revs/min；Be placed on the oven drying 2 hours that temperature is 150 DEG C.
(2)γ-Al2O3Colloidal sol is prepared: by commercially available 20g γ-Al2O3Type activated alumina adds in 150ml distilled water,
Constant temperature 60 DEG C stirs to being completely dispersed, and electric stirring 30 minutes, rotating speed is 60 revs/min.
(3) impregnation liquid preparation: mix to be completely dissolved by copper nitrate, cerous nitrate and distilled water 1:2:5 in mass ratio.
(4)γ-Al2O3Coating；Ceramic honey comb in step (1) is immersed in the γ-Al in step (2)2O3In colloidal sol 1
Taking out after hour, roasting 6 hours, temperature is 450 DEG C.
(5) active component load: the ceramic honey comb of step (4) is immersed in the impregnation liquid of step (3) and takes after 2 hours
Going out, roasting 6 hours, temperature is 450 DEG C.
Catalyst performance illustrates: is placed in reactor by above-mentioned catalyst, when being passed through 100ppm toluene, is 300 in temperature
DEG C time, removal effect reaches 94%, and air speed is 10000hr-1；When being passed through 100ppm ethylene, when 300 DEG C, removal efficiency is 15%,
Air speed is 5000hr-1。
Embodiment 2
(1) ceramic honey comb pretreatment: being immersed in by ceramic honey comb in distilled water 1 hour, electric stirring 30 minutes, rotating speed is
30 revs/min；Be placed on the oven drying 2 hours that temperature is 150 DEG C.
(2)γ-Al2O3Colloidal sol is prepared: by commercially available 20g γ-Al2O3Type activated alumina adds in 150ml distilled water,
Constant temperature 60 DEG C stirs to being completely dispersed, and electric stirring 30 minutes, rotating speed is 60 revs/min.
(3) impregnation liquid preparation: by copper nitrate, cobalt nitrate and cerous nitrate and the distilled water mix and blend of 2:1:4:10 in mass ratio
To being completely dissolved.
(4)γ-Al2O3Coating；Ceramic honey comb in step (1) is immersed in the γ-Al in step (2)2O3In colloidal sol 1
Taking out after hour, roasting 6 hours, temperature is 450 DEG C.
(5) active component load: the ceramic honey comb of step (4) is immersed in the impregnation liquid of step (3) and takes after 2 hours
Going out, roasting 6 hours, temperature is 450 DEG C.
Catalyst performance illustrates: is placed in reactor by above-mentioned catalyst, when being passed through 100ppm toluene, is 290 in temperature
DEG C time, removal effect reaches 99%, and air speed is 10000hr-1；When being passed through 100ppm ethylene, when 300 DEG C, removal efficiency is 46%,
Air speed is 5000hr-1。
Embodiment 3
(1) ceramic honey comb pretreatment: being immersed in by ceramic honey comb in distilled water 1 hour, electric stirring 30 minutes, rotating speed is
30 revs/min；Be placed on the oven drying 2 hours that temperature is 150 DEG C.
(2)γ-Al2O3Colloidal sol is prepared: by commercially available 20g γ-Al2O3Type activated alumina adds in 150ml distilled water,
Constant temperature 60 DEG C stirs to being completely dispersed, and electric stirring 30 minutes, rotating speed is 60 revs/min.
(3) impregnation liquid preparation: by copper nitrate, nickel nitrate, cerous nitrate and the distilled water mix and blend of 2:1:4:10 in mass ratio
To being completely dissolved.
(4)γ-Al2O3Coating；Ceramic honey comb in step (1) is immersed in the γ-Al in step (2)2O3In colloidal sol 1
Taking out after hour, roasting 6 hours, temperature is 450 DEG C.
(5) active component load: the ceramic honey comb of step (4) is immersed in the impregnation liquid of step (3) and takes after 2 hours
Going out, roasting 6 hours, temperature is 450 DEG C.
Catalyst performance illustrates: is placed in reactor by above-mentioned catalyst, when being passed through 100ppm toluene, is 280 in temperature
DEG C time, removal effect reaches 99%, and air speed is 10000hr-1；When being passed through 100ppm ethylene, when 300 DEG C, removal efficiency is 69%,
Air speed is 5000hr-1。
Embodiment 4:
(1) ceramic honey comb pretreatment: being immersed in by ceramic honey comb in distilled water 1 hour, electric stirring 30 minutes, rotating speed is
30 revs/min；Be placed on the oven drying 2 hours that temperature is 150 DEG C.
(2)γ-Al2O3Colloidal sol is prepared: by commercially available 20g γ-Al2O3Type activated alumina adds in 150ml distilled water,
Constant temperature 60 DEG C stirs to being completely dispersed, and electric stirring 30 minutes, rotating speed is 60 revs/min.
(3) impregnation liquid preparation: by copper nitrate, cobalt nitrate, nickel nitrate, cerous nitrate and distilled water 2:1:1:4:10 in mass ratio
Mix to be completely dissolved.
(4)γ-Al2O3Coating；Ceramic honey comb in step (1) is immersed in the γ-Al in step (2)2O3In colloidal sol 1
Taking out after hour, roasting 6 hours, temperature is 450 DEG C.
(5) active component load: the ceramic honey comb of step (4) is immersed in the impregnation liquid of step (3) and takes after 2 hours
Going out, roasting 6 hours, temperature is 450 DEG C.
Catalyst performance illustrates: is placed in reactor by above-mentioned catalyst, when being passed through 100ppm toluene, is 270 in temperature
DEG C time, removal effect reaches 99%, and air speed is 10000hr-1；When being passed through 100ppm ethylene, when 300 DEG C, removal efficiency is 93%,
Air speed is 5000hr-1。
Embodiment 5:
(1) ceramic honey comb pretreatment: being immersed in by ceramic honey comb in distilled water 1 hour, electric stirring 30 minutes, rotating speed is
30 revs/min；Be placed on the oven drying 2 hours that temperature is 150 DEG C.
(2)γ-Al2O3Colloidal sol is prepared: by commercially available 20g γ-Al2O3Type activated alumina adds in 150ml distilled water,
Constant temperature 60 DEG C stirs to being completely dispersed, and electric stirring 30 minutes, rotating speed is 60 revs/min.
(3) impregnation liquid preparation: by silver nitrate, copper nitrate, cobalt nitrate, nickel nitrate, cerous nitrate and distilled water in mass ratio 1:
2:1:1:4:10 mixes to be completely dissolved.
(4)γ-Al2O3Coating；Ceramic honey comb in step (1) is immersed in the γ-Al in step (2)2O3In colloidal sol 1
Taking out after hour, roasting 6 hours, temperature is 450 DEG C.
(5) active component load: the ceramic honey comb of step (4) is immersed in the impregnation liquid of step (3) and takes after 2 hours
Going out, roasting 6 hours, temperature is 450 DEG C.
Catalyst performance illustrates: is placed in reactor by above-mentioned catalyst, when being passed through 100ppm toluene, is 255 in temperature
DEG C time, removal effect reaches 99%, and air speed is 10000hr-1；When being passed through 100ppm ethylene, when 310 DEG C, removal efficiency is 99%,
Air speed is 5000hr-1。
Claims (5)
1. one kind for administering the catalyst of industry stationary source organic exhaust gas, it is characterised in that with ceramic honey comb, ZSM-5 or
SBA-15, as the first carrier, coats one layer of γ-Al at its inner surfaces of pores2O3Coating as Second support, and with Pt, Ag,
One or more in the oxide of Cu, Fe, Rh, Pd, Co, Ni, Mn, Ce are as active component；Second support accounts for first
The 1～14% of carrier quality；Active component content accounts for the 1～4.4% of the first carrier quality.
Catalyst for administering industry stationary source organic exhaust gas the most according to claim 1, it is characterised in that described
γ-Al2O3Coating is by γ-Al2O3Type activated alumina coats on honeycomb ceramic carrier after being configured to Alumina gel and forms.
Catalyst for administering industry stationary source organic exhaust gas the most according to claim 1, it is characterised in that described
The total load amount of active component is 10～30g/L.
4. the preparation method of the catalyst for administering industry stationary source organic exhaust gas described in any one of claims 1 to 3, its
It is characterised by, comprises the steps:
(1) first Vehicle element；Ceramic honey comb, ZSM-5 or SBA-15 be impregnated in nitric acid or distilled water 10-150 minute,
Electric stirring 10-150 minute；Then 80-200 DEG C dry 1-8 hour；
(2)γ-Al2O3Colloidal sol is prepared；By γ-Al2O3Type activated alumina and distilled water mix to be completely dispersed, electric mixing
Mix 10-150 minute；γ-Al2O3Type activated alumina accounts for the 1.5-20% of dispersion liquid quality；
(3) impregnation liquid preparation；One or more the nitrate of Pt, Ag, Cu, Fe, Rh, Pd, Co, Ni, Mn, Ce is prepared
Become solution；
(4)γ-Al2O3Coating；By step (1) gained the first carrier impregnation in step (2) gained γ-Al2O3In colloidal sol, 0.5-6 is little
Take out time after, γ-Al2O3The volume ratio of colloidal sol and the first carrier is 0.1～0.6,200-700 DEG C of roasting 5-15 hour；
(5) activating oxide load, coats γ-Al by step (4) gained2O3The first carrier impregnation step (3) gained impregnate
Liquid took out after 10-180 minute, 100-700 DEG C of roasting 1-15 hour, obtain final products, be i.e. used for administering industry stationary source
The catalyst of organic exhaust gas.
The preparation method of the catalyst for administering industry stationary source organic exhaust gas the most according to claim 4, its feature
Being, the rotating speed of electric stirring is 10-200 rev/min.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107497472A (en) * | 2017-07-25 | 2017-12-22 | 上海纳米技术及应用国家工程研究中心有限公司 | For VOCsThe load type palladium catalyst of low-temperature catalyzed elimination |
| CN108187483A (en) * | 2018-01-26 | 2018-06-22 | 常州大学 | A kind of naphthalene tail-gas deep treating column |
| CN108940352A (en) * | 2018-08-23 | 2018-12-07 | 南京大学 | Loading type Pd O/Al2O3/SBA-15 bifunctional catalyst and its preparation method and application |
| CN109261147A (en) * | 2018-10-24 | 2019-01-25 | 无锡威孚环保催化剂有限公司 | A kind of Pt-Pd single coating catalyst and preparation method thereof handling benezene material |
| CN112108154A (en) * | 2020-10-16 | 2020-12-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Ozone sensitive formaldehyde removal catalyst and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107497472A (en) * | 2017-07-25 | 2017-12-22 | 上海纳米技术及应用国家工程研究中心有限公司 | For VOCsThe load type palladium catalyst of low-temperature catalyzed elimination |
| CN108187483A (en) * | 2018-01-26 | 2018-06-22 | 常州大学 | A kind of naphthalene tail-gas deep treating column |
| CN108940352A (en) * | 2018-08-23 | 2018-12-07 | 南京大学 | Loading type Pd O/Al2O3/SBA-15 bifunctional catalyst and its preparation method and application |
| CN109261147A (en) * | 2018-10-24 | 2019-01-25 | 无锡威孚环保催化剂有限公司 | A kind of Pt-Pd single coating catalyst and preparation method thereof handling benezene material |
| CN112108154A (en) * | 2020-10-16 | 2020-12-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Ozone sensitive formaldehyde removal catalyst and preparation method and application thereof |
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Application publication date: 20161109 |