CN107876050A - A kind of catalyst for purifying organic waste gas and preparation method thereof - Google Patents
A kind of catalyst for purifying organic waste gas and preparation method thereof Download PDFInfo
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- CN107876050A CN107876050A CN201711137119.3A CN201711137119A CN107876050A CN 107876050 A CN107876050 A CN 107876050A CN 201711137119 A CN201711137119 A CN 201711137119A CN 107876050 A CN107876050 A CN 107876050A
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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
- B01J23/63—Platinum group metals 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0232—Coating by pulverisation
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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
Abstract
The present invention relates to a kind of catalyst for purifying organic waste gas and preparation method thereof, using cordierite honeycomb ceramic as main carrier, aluminum oxide, silica, cerium oxide, zirconium oxide is Second support, precious metals pd, Pt, Rh is as active component, aluminum oxide in every liter of catalyst, silica, cerium oxide, the gross mass content of zirconium oxide is 20~80g/L, precious metals pd, Pt, Rh gross mass is 0.6~2.0g/L, Pd, Pt, Rh mass ratio is 1: 0.1~9: 0.1~1, three steps of preparation process point, first step coating alumina, alumina sol, silica, second step coats cerium oxide, zirconium oxide, 3rd step impregnates Pd, Pt, the Rh aqueous solution, catalyst is prepared after drying and calcining respectively；The present invention has the features such as simple production process, catalyst activity is high, service life is long.
Description
Technical field
The present invention relates to a kind of catalyst for purifying organic waste gas and preparation method thereof, particularly suitable for volatile organic waste gas
The purification treatment of pollution, belongs to catalyst technical field.
Background technology
At present, contain in the waste gas of the industry such as petrochemical industry, printing, application, spray painting, medication chemistry, making sheet, shoemaking discharge
The volatile organic matters such as alkanes, aromatic hydrocarbons, alkene, halogenated hydrocarbons, esters, aldehydes, alcohols, ketone, its concentration more than one timing,
In a short time people can be made to feel headache, Nausea and vomiting, limbs fatigue, occur that twitch, stupor, memory subtract when serious
Phenomena such as moving back, it can also damage liver, kidney, brain and the nervous system of people, it is therefore necessary to adopt an effective measure and it is controlled
Reason, can be discharged into air.It is right at present with increasingly strict and environmental law enforcement dynamics the progressively reinforcement of Environmental Protection in China discharge standard
Received significant attention in the improvement of volatile organic matter, the improvement of volatile organic matter is the emphasis neck of current environmental protection regulation
Domain.
At present, administer the method for volatile organic waste gas mainly have condensation absorption method, absorption method, heating power burning method (including
Accumulation of heat burning method), catalytic oxidation (including heat-storage catalytic method), low temperature plasma method, ultraviolet light solution etc..Condense absorption method
Directly to condense waste gas or by being condensed after sorbing material Adsorption Concentration, condensate liquid through separating and recovering valuable organic matter,
It is suitable for handling high-concentration organic waste gas, but equipment investment is big, its operating cost is higher.Absorption method is adsorbed with activated carbon etc.
Material absorbs organic matter and then be desorbed again the technology of processing, and the technology is typically only suitable for the net of the higher organic matter of boiling point
Change and administer, and total purification efficiency is poor.Heating power burning method (including accumulation of heat burning method) refers to organic exhaust gas 700~850
Burnt under DEG C high temperature, the combustible in waste gas changes into carbon dioxide and vapor, and its shortcoming is that fuel cost is big, reaction easily production
Raw N0x is He bioxin, causes secondary pollution, and larger potential safety hazard be present.Catalytic oxidation (including heat-storage catalytic method)
Refer in the presence of catalyst, the catalysis oxidation at 250~400 DEG C of the organic exhaust gas in tail gas changes into carbon dioxide, water
Steam etc., the technology purification efficiency is high, and reaction temperature is than heating power burning method Di Ji Baidu, and application field is wider, and shortcoming is catalysis
Agent is expensive and easy poisoning, equipment investment are larger.Low temperature plasma method is utilized caused by during dielectric barrier discharge
Produced inside plasma and be rich in high chemically active particle, such as electronics, ion, free radical and excited state molecule, with giving up
Polluter reaction in gas, is eventually converted into low molecular compound, CO2And H2The materials such as O, so as to reach the mesh of purification waste gas
's.Similar with plasma, ultraviolet light solution is using ultraviolet beam irradiation waste gas containing VOCs, the structure of VOCs molecules, is made
Degraded is transformed into low molecular compound, CO2And H2O etc., while high energy ultraviolet can also excite ambient oxygen partial to produce trip
From oxygen, and then ozone is formed, carry out collaboration decomposition-oxidation reaction using UV ultraviolet beams and Pre-Ozonation on Organic Matter, realize gas
The purification of body.
Catalytic oxidation cleaning organic waste gas due to organic matter purification efficiency it is high, it is simple to operate and stably, non-secondary pollution
The advantages that, increasingly paid close attention to by user, application is also more and more wider.
The catalyst of organic waste-gas purification is presently used for, mainly there is pellet type catalyst and the major class of honeycombed catalyst two.
Typically using aluminum oxide as carrier, load Pd, Pt, Cu, Mn isoreactivity component is prepared pellet type catalyst；Honeycombed catalyst
Typically using cordierite honeycomb ceramic or regular Metal Substrate honeycomb as carrier, Supported alumina, co-catalyst and active component Pd,
Pt, Rh, Cu, Mn etc. are prepared.
Alumina particle is used to prepare catalyst for carrier, its advantage is that manufacture craft is simple, and general need to be aluminum oxide
Carrier impregnation waits into active component solution and can be prepared by catalyst through high-temperature calcination after adsorption saturation, shortcoming is to make
Cause loss of active component completely because active component solution is typically not easy absorption in journey, and pellet type catalyst was using
Easy to wear crush causes activity decrease in journey.In order to overcome this problem, honeycomb support receives the extensive concern of industry, in
State patent CN103240083A discloses a kind of system of the monoblock type Pd catalyst for purifying industrial organic waste gas catalytic purification
Preparation Method, the catalyst coat at twice, coat cerium zirconium sosoloid, La on cordierite carrier for the first time2O3、Nb(OH)5, intend
Boehmite adhesive, second coating cerium zirconium sosoloid, La2O3, boehmite adhesive, absolute ethyl alcohol and H2PdCl6,
Its defect is that active component is easily covered the activity for influenceing catalyst by oxides such as cerium zirconiums.Chinese patent CN103831104A is disclosed
A kind of monoblock type Pd-Pt catalyst for purifying industrial organic waste gas and preparation method thereof, the catalyst coats in three times,
First step coating cerium-rich mischmetal oxide, intend the thin aluminium stone adhesive of water, acidic silicasol, second step load KOH, the 3rd step
Impregnate H2PdCl6、H2PtCl6The aqueous solution, the amount containing Pd-Pt is 0.3g in every liter of catalyst, which overcomes the scattered of noble metal
Problem, but because its active component content is low, have impact on the activity and service life of catalyst.
The content of the invention
The technical problem to be solved in the present invention is the deficiency for existing catalyst for purifying organic waste gas and preparation method thereof,
Catalyst for purifying organic waste gas of a kind of simple production process, activity height, service life length and preparation method thereof is provided.
The present invention is using cordierite honeycomb ceramic as main carrier, coating alumina, silica, cerium oxide, zirconium oxide the
Two carriers, precious metals pd, Pt, Rh are active component, aluminum oxide in every liter of catalyst, silica, cerium oxide, zirconium oxide it is total
Mass content is 20~80g/L, and precious metals pd, Pt, Rh gross mass are 0.6~2.0g/L, and Pd, Pt, Rh mass ratio are 1:
0.1~9: 0.1~1.
The preparation method of the present invention, three steps of preparation process point, the first step are molten aluminum oxide, the aluminum oxide calculated by aluminum oxide
Glue, silica and water stir for 1: 0.05~0.3: 0.1~1: 4~6 solution prepared in mass ratio, solution ball milling
After 2 hours, it is adjusted to pH=2.0~2.5 with nitric acid and solution A is prepared, solution A is then coated on cordierite honeycomb ceramic,
After blowing away duct and the unnecessary solution of carrier outer wall, dried 1 hour through 120 DEG C, be warming up to 550 DEG C and calcine 2 hours, taken after cooling
Go out；Second step in mass ratio stirs cerium oxide, zirconium oxide and water for 1: 0.1~1: 40 solution prepared, solution ball
Mill is adjusted to pH=2.0~2.5 with nitric acid and B solution is prepared, then applied on the carrier that the first step is prepared after 2 hours
B solution is covered, after blowing away duct and the unnecessary solution of carrier outer wall, is dried 1 hour through 120 DEG C, 550 DEG C is warming up to and calcines 2 hours,
Taken out after cooling；The C solution that 3rd step is in mass ratio prepared palladium nitrate solution, platinum nitrate solution, rhodium nitrate solution and water, is stirred
After mixing uniformly, it is adjusted to pH=2.0~2.5 with nitric acid and C solution is prepared, the carrier impregnation that second step is prepared is molten to C
In liquid, after blowing away duct and the unnecessary solution of carrier outer wall, dried 1 hour through 120 DEG C, be warming up to 550 DEG C and calcine 2 hours, it is cold
But take out afterwards, that is, catalyst is prepared.
The preparation method of above-mentioned a kind of catalyst for purifying organic waste gas, it is characterised in that aoxidized in the alumina sol
The mass content of aluminium is 9.8~10.2%.
A kind of catalyst for purifying organic waste gas provided by the present invention and preparation method thereof, the advantage is that：Preparation technology
Simply, catalyst activity height, service life length, the catalytic purification particularly suitable for organic exhaust gas are administered.
Embodiment
Embodiment 1
Weigh aluminum oxide, the alumina sol, silica and the water that are calculated by aluminum oxide are 1: 0.1: 0.1: 4 in mass ratio
The aluminum oxide (450g) of calculating, alumina sol (450g, wherein Al2O3Mass ratio be 10%, with Al2O3It is calculated as 45g),
Silica (45g), water (1800g) are poured into blending tank, after being stirred with agitator, solution are circulated with ball mill and polished
After 2 hours, it is adjusted to pH=2.0~2.5 with nitric acid and solution A is made.It is 1: 1: 40 in mass ratio to weigh cerium oxide, zirconium oxide and water
Cerium oxide (50g), zirconium oxide (50g), the water (2000g) of calculating are poured into blending tank, after being stirred with agitator, solution
After ball mill circulation polishing 2 hours, it is adjusted to pH=2.0~2.5 with nitric acid and B solution is made.Weigh palladium nitrate solution (60g, with
Pd counts 9g), platinum nitrate solution (30g, the 3g in terms of Pt), rhodium nitrate solution (9g, the 0.9g in terms of rhodium), water (1901g) pour into mixing
PH=2.0.~2.5 are adjusted to nitric acid C solution is made in tank, after stirring.
10 liters of cordierite honeycomb ceramic carriers are taken, its appearance and size is 100 × 100 × 50mm, and the number of openings is 200
Hole/in2, with 0.1MPa compressed air purging carrier, to remove the powder on surface and dust, purging is standby after 10 minutes.The
One step is impregnated into the cordierite honeycomb ceramic after dedusting in solution A, and duct and carrier outer wall are blown away with compressed air after taking-up
Unnecessary solution, dried 1 hour through 120 DEG C, be warming up to 550 DEG C and calcine 2 hours, taken out after cooling；Then prepared in the first step
B solution is coated on the carrier formed, it is small through 120 DEG C of drying 1 after blowing away duct and the unnecessary solution of carrier outer wall with compressed air
When, it is warming up to 550 DEG C and calcines 2 hours, is taken out after cooling；Then carrier impregnation second step being prepared is blown into C solution
After removing duct and the unnecessary solution of carrier outer wall, dried 1 hour through 120 DEG C, be warming up to 550 DEG C and calcine 2 hours, taken after cooling
Go out, that is, catalyst is prepared.Remaining A, B, C solution and obtained catalyst in blending tank are weighed respectively, are calculated
Aluminum oxide, silica, cerium oxide, the gross mass content of zirconium oxide are 33g in every liter of catalyst, and Pd, Pt, Rh gross mass are
1.03g, Pd, Pt, Rh mass ratio are 1: 0.33: 0.1.Respectively mould is used as by the use of the gaseous mixture of benzene, ethyl acetate, methane and air
Intend gas, in air speed 20000h-1, the performance of catalyst has been investigated, catalyst activity evaluation result is shown in Table 1.
Embodiment 2
With the same preparation method of embodiment 1, institute's difference aluminum oxide, titanium dioxide in every liter of catalyst in preparation
Silicon, cerium oxide, the gross mass content of zirconium oxide are 50g, and catalyst activity appreciation condition is same as Example 1, catalyst activity
Evaluation result is shown in Table 2.
Embodiment 3
With the same preparation method of embodiment 1, institute's difference in every liter of catalyst in preparation Pd, Pt, Rh it is total
Quality is 1.92g, and Pd, Pt mass ratio are 1: 0.2: 0.1, and catalyst activity appreciation condition is same as Example 1, and catalyst is lived
Property evaluation result is shown in Table 3.
As can be seen here, catalyst of the invention is urged for the organic exhaust gas high conversion rate of simulation, excellent catalytic effect, embodiment 3
Change performance and be better than other two, the present invention has the characteristics that technique is simple, the catalyst activity of preparation is high.
Claims (3)
- A kind of 1. catalyst for purifying organic waste gas, it is characterised in that：The catalyst is using cordierite honeycomb ceramic as main carrier, coating Aluminum oxide, silica, cerium oxide, zirconium oxide are Second support, and precious metals pd, Pt, Rh are active component, in every liter of catalyst Aluminum oxide, silica, cerium oxide, the gross mass content of zirconium oxide are 20~80g/L, and precious metals pd, Pt, Rh gross mass are 0.6~2.0g/L, Pd, Pt, Rh mass ratio are 1: 0.1~9: 0.1~1.
- A kind of 2. preparation method of catalyst for purifying organic waste gas according to claim 1, it is characterised in that：Preparation process Point three steps, alumina sol, silica and the water that the first step calculates aluminum oxide, by aluminum oxide in mass ratio for 1: 0.05~ 0.3: 0.1~1: 4~6 solution prepared stir, and after solution ball milling 2 hours, are adjusted to pH=2.0~2.5 with nitric acid and make It is standby to obtain solution A, solution A is then coated on cordierite honeycomb ceramic, after blowing away duct and the unnecessary solution of carrier outer wall, warp 120 DEG C dry 1 hour, are warming up to 550 DEG C and calcine 2 hours, are taken out after cooling；Cerium oxide, zirconium oxide and water are pressed matter by second step After solution ball milling 2 hours, pH=2.0~2.5 are adjusted to nitric acid than being stirred for 1: 0.1~1: 40 solution prepared for amount B solution is prepared, then coats B solution on the carrier that the first step is prepared, blows away duct and carrier outer wall is unnecessary After solution, dried 1 hour through 120 DEG C, be warming up to 550 DEG C and calcine 2 hours, taken out after cooling；3rd step is palladium nitrate solution, nitre The C solution that sour platinum solution, rhodium nitrate solution and water are prepared in mass ratio, after stirring, pH=2.0~2.5 are adjusted to nitric acid C solution is prepared, the carrier impregnation that second step is prepared blows away duct and unnecessary molten of carrier outer wall into C solution After liquid, dried 1 hour through 120 DEG C, be warming up to 550 DEG C and calcine 2 hours, taken out after cooling, that is, catalyst is prepared.
- A kind of 3. preparation method of catalyst for purifying organic waste gas according to claim 2, it is characterised in that the oxidation The mass content of aluminum oxide is 9.8~10.2% in Alumina gel.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110773159A (en) * | 2019-10-31 | 2020-02-11 | 中自环保科技股份有限公司 | Preparation process of Pt/Pd/Rh oxidation catalyst and catalyst prepared by same |
| CN114029056A (en) * | 2021-12-24 | 2022-02-11 | 安徽元琛环保科技股份有限公司 | Volatile organic compound treatment catalyst, preparation method and application thereof |
| CN114602503A (en) * | 2022-03-27 | 2022-06-10 | 山东亮剑环保新材料有限公司 | Spherical particle VOCs catalyst and preparation method thereof |
| CN114669296A (en) * | 2022-04-28 | 2022-06-28 | 杭州森发环保科技有限公司 | Blocky Ru-Pt organic waste gas purification catalyst and preparation method thereof |
| CN115155576A (en) * | 2022-07-22 | 2022-10-11 | 山东亮剑环保新材料有限公司 | Preparation method of monolithic metal substrate precious metal catalytic module |
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| CN115155576A (en) * | 2022-07-22 | 2022-10-11 | 山东亮剑环保新材料有限公司 | Preparation method of monolithic metal substrate precious metal catalytic module |
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Application publication date: 20180406 |