CN102580731B - Gamma-aluminum oxide globular catalyst for purifying waste gas of volatile compounds and preparation method for catalyst - Google Patents
Gamma-aluminum oxide globular catalyst for purifying waste gas of volatile compounds and preparation method for catalyst Download PDFInfo
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Abstract
The invention relates to a gamma-aluminum oxide globular catalyst for purifying waste gas of volatile compounds and a preparation method for the catalyst, and belongs to the technical field of the purification of industrial waste gas by a catalytic combustion method. The gamma-aluminum oxide globular catalyst is prepared by using low-cost aluminum oxide globules as a carrier, one or a mixture of more of aluminum oxide, cerium oxide, gallium oxide, a cerium zirconium solid solution and the like as a coating and Pd as an active ingredient through pretreatment, the preparation of coating slurry, impregnation and aftertreatment. The globular catalyst prepared by the method is wide in application range and low in air resistance, and volatile organic compounds (VOCs) and the surface of the catalyst are contacted for a long time. According to the globular catalyst, the gamma-aluminum oxide globule carrier is used as a framework, and the slurry is high in adhesion; the temperature of a catalyst bed is reduced by the air resistance among the gamma-aluminum oxide globules and heat transfer; and rare-earth nitrate and/or organic acid are/is used as a dispersing agent of the noble metal active ingredient in the process of preparing the catalyst, so that the stability of the catalyst is improved greatly, and the service life of the catalyst is prolonged.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst of purifying volatile organic compound waste gas, be specifically related to a kind of coccoid Catalysts and its preparation method of gama-alumina of purifying volatile compound exhaust air, belong to the technical field of catalytic combustion method purifying industrial waste gases.
Background technology
VOC (Volatile Organic Compounds, be called for short VOCs) refer to that boiling point is at 50～260 ℃, under room temperature, saturated vapour pressure surpasses the volatile organic compound of 133.3Pa, petrochemical industry, pharmacy, print, spray paint, the major pollutants in the industry discharging waste gas such as motor vehicle, shoemaking, comprise hydro carbons, aldehydes, ketone, halogenated hydrocarbons, aromatic hydrocarbon, polycyclic aromatic hydrocarbons (PAH) etc.Such organic compounds often is accompanied by peculiar smell, stench distributes in air, it is the polluter of harmful health, eye, nose, respiratory tract to the people have spread effect, to internal organ and nervous system generation adverse effects such as the heart, lung, livers, even cause acute and slow poisoning, can carcinogenic, mutagenesis, even enter water body, cause water to pollute.Under certain condition, VOCs can with atmosphere in NO
2reaction generates O
3, make O in the atmosphere of low latitude
3concentration raises, and forms photochemical fog, is detrimental to health and causes crop production reduction.
The domestic and international VOCs groundwater pollution control of bibliographical information mainly contains burning method, absorption method, condensation method, corona method, catalytic combustion, photochemical catalytic oxidation, membrane separation process and bioanalysis etc. at present, wherein some has realized the business application, and some is also under test.The VOCs catalytic combustion technology is one of most widely used processing method in industrial production in recent years, and meets the economy of production.
In purification and the using energy source link of waste gas, catalyst plays conclusive effect.At present this type of catalyst is for honeycomb-like cordierite or metal material are carrier, then one or both and part transition metal oxide in carried noble metal Pt, Pd.This kind of method, the problem such as not only have that gas is shorter in the catalyst surface time of staying, the heat conductivility of honeycomb-like cordierite and metallic carrier is poor, and also catalyst is difficult for better its catalytic performance of performance under high-speed, low temperature.Thereby the addition that can cause more utilizing noble metal solves low temperature, the high-speed activity problems of catalyst, this can bring cost pressure to enterprise.
Summary of the invention
The purpose of this invention is to provide a kind ofly utilize that scope is wide, vapour lock is little, VOCs and catalyst surface time of contact long novel processing volatile organic compound from waste gas coccoid catalyst.It is skeleton that this catalyst be take gama-alumina bead carrier, and slurries have tack preferably.Carrier beads is filled in pipeline, utilizes the Interglobular vapour lock of gama-alumina, the transfer of heat reduces reaction bed temperature; Scribble on gama-alumina bead surface the gallium oxide that Pd in load, used rare earth nitrades and/or the organic acid dispersant as the noble metal active component in catalyst preparation process, improved greatly the stability of catalyst, extended the life-span of catalyst.
Technical scheme of the present invention: the coccoid catalyst of the gama-alumina of purifying volatile compound exhaust air, its coating by gama-alumina bead and coating forms, and contains gama-alumina, cerium zirconium eutectic, the soluble-salt of cerium and the soluble-salt of gallium in coating.
The preparation method of the coccoid catalyst of gama-alumina of purifying volatile compound exhaust air, step is by weight:
(1) pretreatment: selecting gama-alumina bead carrier is skeleton, pretreatment in air, and 450～550 ℃ of calcining 4～6h, make the activation of surperficial duct;
(2) preparation of coating slurries: get 3～4 parts of gama-aluminas, 1～2 part of cerium zirconium eutectic, the soluble-salt of cerium is by 0.5～1.5 part of cerium, the soluble-salt of gallium, by 1～3 part of gallium, joins in 4～8 parts of deionized waters, after agitator stirs, join ball milling in ball mill, the control granularity is D90,90% of amounts of particles is less than 20 microns, obtains slurries; In slurries, solid content is 20%～50%;
Add 0.5～20mol/L palladium nitrate or palladium bichloride, the concentration that is adjusted to palladium in slurries is 0.3～0.5g/L, makes the coating slurries;
(3) dipping: in the coating slurries that will prepare in step (2) through the pretreated gama-alumina bead of step (1) carrier impregnation, fully take out after dipping;
(4) post processing: the gama-alumina bead of step (3) gained is dried to 30～60min under 100～300 ℃, then repeating step (3), until be coated to every liter of coating levels on gama-alumina bead carrier, be 10～50g, then, at 400 ℃～600 ℃ roasting 1～5min, be purified the coccoid catalyst of gama-alumina of volatile compound waste gas.
The soluble-salt of described cerium is cerous nitrate.The soluble-salt of described gallium is gallium nitrate.
The Pd that contains 0.03～12g on the coccoid catalyst of the gama-alumina of every liter of purifying volatile compound exhaust air.
In described cerium zirconium eutectic, cerium and zirconium mol ratio are 3: 1.
Beneficial effect of the present invention: coccoid catalyst prepared by the present invention utilizes that scope is wide, vapour lock is little, VOCs and catalyst surface long time of contact.It is skeleton that this catalyst be take gama-alumina bead carrier, and slurries have tack preferably; Carrier beads is filled in pipeline, utilizes the Interglobular vapour lock of gama-alumina, the transfer of heat reduces reaction bed temperature; Scribble on gama-alumina bead surface the gallium oxide that Pd in load, used rare earth nitrades and/or the organic acid dispersant as the noble metal active component in catalyst preparation process, improved greatly the stability of catalyst, extended the life-span of catalyst.
The specific embodiment
Below in conjunction with example, the invention will be further described.
The gama-alumina bead adopted in embodiment is purchased from the following Refractory Co., ltd of Zibo side dragon, cerium zirconium eutectic is purchased from Yixing City three match superfine powder Co., Ltds, cerous nitrate is purchased from Nanjing Xi Nuo Chemical Industry Science Co., Ltd, and gallium nitrate is purchased from Shanghai Long John metal material Co., Ltd.
Activity test method
Test condition: chromatographic column, ST-30-2, detector (FID) temperature: 105 ℃; Post case temperature: 120 ℃; Before post, press: 0.1Mpa; Input mode: six-way valve sample introduction (band 1mL quantity tube)
Atmospheric condition: benzene: 200ppm, toluene: 320ppm, acetone: 200ppm, Balance Air: air.
The conversion ratio of waste gas under the test different temperatures.
Embodiment 1
The coccoid catalyst A 1 of gama-alumina for preparing the purifying volatile compound exhaust air:
Selecting gama-alumina bead carrier is skeleton, gama-alumina content>=92% wherein, and particle diameter is 5～6mm, specific surface>=170m
2/ g, density 0.65g/ml, with stainless steel plain net cloth parcel, re-use the thin tied silk binding of Cr20Ni30 firmly, and in the air atmosphere of 500 ℃, pretreatment is 5 hours.
Remove ionized water 6000g, nine nitric hydrate gallium 2000g, aluminium oxide 3500g, cerium zirconium compound oxide (cerium and zirconium mol ratio are 3: 1) 1240 grams, 800 gram cerous nitrates, stir, and dissolves fully to nitrate, uses ball mill by slurries ball milling particle diameter D
90be less than 20 microns, drip the palladium nitrate solution that contains the 183g palladium containing weighing in the process stirred, be diluted to 625g; Make the coating slurries;
Above-mentioned pretreated alumina globule carrier impregnation, in these slurries, is stopped 3 seconds, with the speed proposition of per second 30mm.
The gama-alumina bead that applies slurries is dried to 60min under 150 ℃, then repetitive coatings is until the coating amount reaches 10g/L, containing precious metal palladium 0.423g/L, then at 600 ℃ of roasting 1min, be purified the coccoid catalyst of gama-alumina of volatile compound waste gas.
Catalyst activity is estimated with the bed temperature test result in Table 1.
Embodiment 2
The coccoid catalyst A 2 of gama-alumina for preparing the purifying volatile compound exhaust air:
Concrete preparation method is substantially the same manner as Example 1, and difference is that the coating amount reaches 20g/L.Catalyst activity is estimated with the bed temperature test result in Table 1.
Embodiment 3
The coccoid catalyst A 3 of gama-alumina for preparing the purifying volatile compound exhaust air:
Concrete preparation method is substantially the same manner as Example 1, and difference is that the coating amount reaches 35g/L.Catalyst activity is estimated with the bed temperature test result in Table 1.
Embodiment 4
The coccoid catalyst A 4 of gama-alumina for preparing the purifying volatile compound exhaust air:
Concrete preparation method is substantially the same manner as Example 1, and difference is that the coating amount reaches 50g/L.Catalyst activity is estimated with the bed temperature test result in Table 1.
Table 1
Claims (4)
1. the preparation method of the coccoid catalyst of gama-alumina of purifying volatile compound exhaust air, it is characterized in that: its coating by gama-alumina bead and coating forms, and contains gama-alumina, cerium zirconium eutectic, the soluble-salt of cerium and the soluble-salt of gallium in coating;
The preparation method of the coccoid catalyst of gama-alumina of described purifying volatile compound exhaust air, step is by weight:
(1) pretreatment: selecting gama-alumina bead carrier is skeleton, pretreatment in air, and 450 ~ 550 ℃ of calcining 4 ~ 6h, make the activation of surperficial duct;
(2) preparation of coating slurries: get 3 ~ 4 parts of gama-aluminas, 1 ~ 2 part of cerium zirconium eutectic, the soluble-salt of cerium is by 0.5 ~ 1.5 part of cerium, and the soluble-salt of gallium, by 1 ~ 3 part of gallium, joins in 4 ~ 8 parts of deionized waters, after agitator stirs, join ball milling in ball mill, the control granularity is D90,90% of amounts of particles, be less than 20 microns, obtain slurries; In slurries, solid content is 20% ~ 50%;
Add 0.5 ~ 20mol/L palladium nitrate or palladium bichloride, the concentration that is adjusted to palladium in slurries is 0.3 ~ 0.5g/L, makes the coating slurries;
(3) dipping: in the coating slurries that will prepare in step (2) through the pretreated gama-alumina bead of step (1) carrier impregnation, fully take out after dipping;
(4) post processing: the gama-alumina bead of step (3) gained is dried to 30 ~ 60min under 100 ~ 300 ℃, then repeating step (3), until be coated to every liter of coating levels on gama-alumina bead carrier, be 10 ~ 50g, then, at 400 ℃ ~ 600 ℃ roasting 1 ~ 5min, be purified the coccoid catalyst of gama-alumina of volatile compound waste gas;
The Pd that contains 0.03 ~ 12g on the coccoid catalyst of the gama-alumina of every liter of purifying volatile compound exhaust air.
2. the preparation method of the coccoid catalyst of gama-alumina of purifying volatile compound exhaust air according to claim 1, it is characterized in that: the soluble-salt of described cerium is cerous nitrate.
3. the preparation method of the coccoid catalyst of gama-alumina of purifying volatile compound exhaust air according to claim 1, it is characterized in that: the soluble-salt of described gallium is gallium nitrate.
4. the preparation method of the coccoid catalyst of gama-alumina of purifying volatile compound exhaust air according to claim 1, it is characterized in that: in described cerium zirconium eutectic, cerium and zirconium mol ratio are 3:1.
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| CN107970921A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of catalyst with catalysis organic exhaust gas combustion function and its preparation method and application and the method for catalysis organic exhaust gas burning |
| CN106824174A (en) * | 2017-03-22 | 2017-06-13 | 无锡威孚环保催化剂有限公司 | A kind of coccoid catalyst of high-efficient purification nitrogen oxides and preparation method thereof |
| WO2022158270A1 (en) * | 2021-01-21 | 2022-07-28 | 株式会社キャタラー | Particles for exhaust gas purification catalyst |
| CN115212878A (en) * | 2022-07-06 | 2022-10-21 | 四川大学 | Method for preparing high-performance Pd-Ga2O3 catalyst by recycling waste palladium catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5312608A (en) * | 1990-10-31 | 1994-05-17 | Idemitsu Kosan Company Limited | Exhaust gas purifying catalyst and an exhaust gas purifying method using the catalyst |
| CN101711268A (en) * | 2007-04-05 | 2010-05-19 | 纳米X有限公司 | Coating material having a catalytic activity and use of said coating material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5312608A (en) * | 1990-10-31 | 1994-05-17 | Idemitsu Kosan Company Limited | Exhaust gas purifying catalyst and an exhaust gas purifying method using the catalyst |
| CN101711268A (en) * | 2007-04-05 | 2010-05-19 | 纳米X有限公司 | Coating material having a catalytic activity and use of said coating material |
Non-Patent Citations (2)
| Title |
|---|
| 杨莉等.汽车尾气三效催化净化技术研究.《武汉科技学院学报》.2001,第15卷(第1期),第54-57页. |
| 汽车尾气三效催化净化技术研究;杨莉等;《武汉科技学院学报》;20010228;第15卷(第1期);第54-57页 * |
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