CN105498789A - Flexible glass fiber base catalyst used for VOCs catalytic combustion and preparing method and application thereof - Google Patents

Flexible glass fiber base catalyst used for VOCs catalytic combustion and preparing method and application thereof Download PDF

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CN105498789A
CN105498789A CN201510930190.1A CN201510930190A CN105498789A CN 105498789 A CN105498789 A CN 105498789A CN 201510930190 A CN201510930190 A CN 201510930190A CN 105498789 A CN105498789 A CN 105498789A
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glass fibre
catalyst
catalytic combustion
vocs
vocs catalytic
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CN105498789B (en
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陈英文
阚家伟
李兵
李林
何硕
沈树宝
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Nanjing Tech University
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Abstract

The invention provides a flexible glass fiber base catalyst used for VOCs catalytic combustion and a preparing method and application thereof. The catalyst has high activity, high heat stability and high mechanical performance, and is applied to the field of catalytic combustion for VOCs removal. A skeleton glass fiber of the catalyst is of a three-dimensional hole-like structure, and is high in porosity, and high in flexibility. When a catalytic combustion device operates, heat transfer is good, swelling coefficient is low, the catalyst is not sintered easily, and for some organic waste gas containing smoke, dust does not deposit on the surface of the catalyst easily.

Description

A kind of flexible fibreglass for VOCs catalytic combustion is catalyst based and its preparation method and application
Technical field
The present invention relates to a kind of catalyst material processing industrial organic exhaust gas, it is catalyst based and its preparation method and application to be specifically related to a kind of flexible fibreglass for VOCs catalytic combustion.
Background technology
The production process of Furniture manufacture, packages printing, petrochemical industry, automobile making and the industry such as spraying, electronics, all can discharge the volatile organic matters (Volatileorganiccompounds (VOCs)) such as benzene, dimethylbenzene, acetone, ethyl acetate, chlorobenzene.At present, volatile organic matter is a class atmosphere pollution, is also the main source forming photochemical fog and fine particle.This pollutant not only destroys the ecosystem, and destroys people's health five big systems, burst can be caused poisoning, the harm such as cause cancer.Therefore, administering VOCs is the important measures improving people's living environment and protecting ecology.
When the method for pre-treatment VOCs has the method such as absorption method, absorption process, condensation method, plasma method, burning, catalytic combustion, wherein catalytic combustion technology is one of the most cost-effective Treatment process.Under the use of catalyst, there is oxidation reaction in volatile organic matter at a lower temperature, generates carbon dioxide and water, release heat simultaneously.In addition, catalytic combustion technology almost can process all VOCs, compares direct burning, consumes energy low, reacts completely, and can not produce NO xsecondary pollution.
Glass fibre is a kind of Inorganic Non-metallic Materials of excellent performance, is also the widely used metal material alternative materials of every field, is mainly used in insulation, heat insulation, fire-resistant, encapsulant.In photochemical catalyst field, glass fibre also occasionally has application, patent (CN1962036A) is that carrier loaded nano titanium oxide is for active component photocatalysis to degrade organic matter with glass fibre, but have that active component bad dispersibility, specific area are less, life-span shorter point, but seldom relate in industrial organic exhaust gas process field.
Summary of the invention
the technical problem solved:the invention provides a kind of lighter in weight, install simple, cost is lower, the life-span longer flexible fibreglass for VOCs catalytic combustion is catalyst based and its preparation method and application.This catalyst has high activity, high thermal stability, high-mechanical property simultaneously, is applied in catalytic combustion and removes VOCs field.The skeleton glass fibre of catalyst of the present invention has three-dimensional cavernous structure, and porosity is higher, high flexible.When catalytic combustion system runs, better, the coefficient of expansion is low in heat transfer, not easily allows sintering of catalyst, and for the organic exhaust gas of part containing flue gas, dust is not easily deposited on catalyst surface.
technical scheme:a kind of preparation method of the glass fibre catalyst for VOCs catalytic combustion, step is: (1) glass fibre pretreatment: glass fibre soaks 1h in 10wt.% ~ 20wt.% hydrochloric acid, taking-up is washed to neutrality, then in distilled water, ultrasonic cleaning room temperature are dried, and 400 ~ 500 DEG C of roasting 2h obtain pretreated glass fibre in air atmosphere; Boehmite and cerous nitrate are mixed, wherein the atomic ratio of metal element A l:Ce is 2:(1 ~ 2), mixture adds in deionized water, and after fully stirring, nitric acid adjusts pH to 2 ~ 4, continues stirring 2 ~ 4h and obtains tie coat; (2) pretreated glass fibre is immersed tie coat, take out after 2h to be impregnated, with solution unnecessary inside air stream blowout glass fibre three-dimensional micropore, ageing 24h, then put into the oven dry of 80 ~ 105 DEG C, baking oven, put into Muffle furnace 450 ~ 550 DEG C of roasting 5h, obtain with Al 2o 3-CeO 2the glass fibre of coating; (3) be 1:1:1 according to La:M:Cu mol ratio, mixed by the nitrate of three kinds of non-noble metal j element, then join in deionized water, 60 DEG C of water-baths, and stir 1 ~ 2h, obtain uniform mixed liquor, described M is Mn, Co, Cr or Fe; (4) above-mentioned mixed liquor is through the effect of ion plating apparatus, injects with Al 2o 3-CeO 2the glass fibre duct of coating and surface, form one firmly diffusion coating, ageing 24h, 80 ~ 100Hz supersonic oscillations 2h, glass fibre catalyst after vibration is put into the oven dry of 100 ~ 110 DEG C, baking oven, finally put into Muffle furnace 450 ~ 550 DEG C of roasting 5h, namely obtain the glass fibre catalyst for VOCs catalytic combustion: LaMO 3/ CuCeO x/ Al 2o 3-CeO 2/ glass fibre catalyst.
Boehmite described in described step (1) and cerous nitrate mixed liquor, its metal element A l:Ce atomic ratio is 2:1.
Al described in described step (2) 2o 3-CeO 2content be 4.2 ~ 16.7%.
LaMO described in described step (4) 3content is 10wt.% ~ 20wt.%, CuCeO xcontent is 5wt.% ~ 10wt.%.
Ion plating described in described step (4) is activated reactive evaporation, and rifle voltage is 8000V, and rifle electric current is 0.5A.
Described glass fibre forms by mutually tangling between the glass fibre carpet veneer of filament diameter 5 ~ 10 μm and fiberglass-based cloth, and have three-dimensional micropore structure, its porosity is 70 ~ 90%, and thick is 1 ~ 5mm.
Above-mentioned preparation method's gained is used for the glass fibre catalyst of VOCs catalytic combustion.
For the application of the glass fibre catalyst of VOCs catalytic combustion, the beds of catalytic combustion system is put in the tiling of glass fibre catalyst, every block catalyst spacing 50 ~ 120mm, an air pressing operation, reaction temperature 175 ~ 300 DEG C, air speed is 10000 ~ 40000h -1, volatile organic matter volumetric concentration is 0.05% ~ 0.2%.
beneficial effect:1. catalyst carrier adopts glass fibre, and it has three-dimensional micropore structure, larger specific area, and air resistance is little, not easily dust stratification, cheap in addition, and convenient transportation is quick for installation.
2. tie coat adopts boehmite and cerous nitrate, support pores not only can be made to open, after coating, back pressure is substantially constant, and coating is combined with carrier very firmly, is convenient to subsequent ion and sputters to be combined with active component or to enter in active component lattice and cause lattice defect.
3. active constituent loading method is ion plating method, is plated to matrix surface at a high speed, is uniformly dispersed, in conjunction with very firm, part high-speed ion enters active component perovskite and solid solution lattice is inner, makes lattice produce defect, more oxy radical is provided, significantly reduces organic activation energy.
4. catalyst is all non-noble metal oxide, and resource is sufficient, cheap, is well suited for industrialization and uses.
Accompanying drawing explanation
Fig. 1 is catalyst preparing flow chart;
Fig. 2 is the reactivity figure of embodiment 1 pair of benzene;
Fig. 3 is the reactivity figure of embodiment 2 pairs of benzene;
Fig. 4 is the reactivity figure of embodiment 3 pairs of benzene;
Fig. 5 is the reactivity figure of embodiment 4 pairs of benzene;
Fig. 6 be equivalent responses Condition Example 5 with cordierite catalyst to the reactivity comparison diagram of benzene;
Fig. 7 is the stability diagram of embodiment 5 pairs of benzene.
Detailed description of the invention
With concrete case study on implementation, technical scheme of the present invention is described below, but protection scope of the present invention is not limited to this:
Embodiment 1:
(1) glass fibre is immersed completely in 10wt.% hydrochloric acid, soak 1h, take out be washed to neutrality, then put into the ultrasonic 10min of deionized water 80Hz, after drying in Muffle furnace 500 DEG C of roasting 5h.
(2) be that 2:1 mixes by boehmite (calculating by aluminium oxide), six water cerous nitrates by metal atomic ratio, be dissolved in 100mL distilled water, stir to dissolving completely, dropwise add red fuming nitric acid (RFNA) to pH=2, continue to stir 2h, then the glass fibre obtained in above-mentioned (1) is immersed in solution, after dipping 2h, take out and purge through high pressure air rifle, solution unnecessary inside blowout glass fibre three-dimensional micropore, ageing 24h, 80 DEG C of dryings, after to be dried in Muffle furnace 500 DEG C of roasting 5h.
(3) nitrate of lanthanum, chromium, copper is joined in 150mL distilled water according to metallic atom than the ratio of 1:1:1,60 DEG C of water-bath 1h, the Homogeneous phase mixing liquid obtained is through ion plating apparatus effect, be injected into containing cated glass fibre duct and surface, ion plating is activated reactive evaporation, rifle voltage is 8000V, rifle electric current is 0.5A, then 100Hz sonic oscillation 2h forms evenly firmly active layer, ageing 24h, 105 DEG C of dryings, put into Muffle furnace 500 DEG C of roasting 5h, namely obtain LaCrO after to be dried 3/ CuCeO x/ Al 2o 3-CeO 2/ glass fibre catalyst.
Getting above-mentioned catalyst and be placed in fixed reactor, take benzene as volatile organic matter, and the concentration of benzene is 7.8mg/L, and air speed is 15000h -1, adopt gas-chromatography on-line analysis, result shows: when 175 DEG C, 200 DEG C, 225 DEG C, 250 DEG C, 275 DEG C and 300 DEG C, the conversion ratio of benzene is respectively 6.84%, 20.35%, 56.49%, 79.73%, 91.68%, 100%, as Fig. 2.
Embodiment 2:
(1) glass fibre is immersed completely in 20wt.% hydrochloric acid, soak 1h, take out be washed to neutrality, then put into the ultrasonic 10min of deionized water 80Hz, after drying in Muffle furnace 500 DEG C of roasting 5h.
(2) be that 2:1 mixes by boehmite (calculating by aluminium oxide), six water cerous nitrates by metal atomic ratio, be dissolved in 100mL distilled water, stir to dissolving completely, dropwise add red fuming nitric acid (RFNA) to pH=2, continue to stir 2h, then the glass fibre obtained in above-mentioned (1) is immersed in solution, after dipping 2h, take out and purge through high pressure air rifle, solution unnecessary inside blowout glass fibre three-dimensional micropore, ageing 24h, 80 DEG C of dryings, after to be dried in Muffle furnace 500 DEG C of roasting 5h.
(3) nitrate of lanthanum, iron, copper is joined in 150mL distilled water according to metallic atom than the ratio of 1:1:1,60 DEG C of water-bath 1h, the Homogeneous phase mixing liquid obtained is through ion plating apparatus effect, be injected into containing cated glass fibre duct and surface, ion plating is activated reactive evaporation, rifle voltage is 8000V, rifle electric current is 0.5A, then 100Hz sonic oscillation 2h forms evenly firmly active layer, ageing 24h, 105 DEG C of dryings, put into Muffle furnace 500 DEG C of roasting 5h, namely obtain LaFeO after to be dried 3/ CuCeO x/ Al 2o 3-CeO 2/ glass fibre catalyst.
Getting above-mentioned catalyst and be placed in fixed reactor, take benzene as volatile organic matter, and the concentration of benzene is 7.8mg/L, and air speed is 15000h -1, adopt gas-chromatography on-line analysis, result shows: when 175 DEG C, 200 DEG C, 225 DEG C, 250 DEG C, 275 DEG C and 300 DEG C, the conversion ratio of benzene is respectively 8.03%, 21.36%, 58.89%, 82.07%, 94.53%, 100%, as Fig. 3.
Embodiment 3:
(1) glass fibre is immersed completely in 20wt.% hydrochloric acid, soak 1h, take out be washed to neutrality, then put into the ultrasonic 10min of deionized water 80Hz, after drying in Muffle furnace 500 DEG C of roasting 5h.
(2) be that 2:1 mixes by boehmite (calculating by aluminium oxide), six water cerous nitrates by metal atomic ratio, be dissolved in 100mL distilled water, stir to dissolving completely, dropwise add red fuming nitric acid (RFNA) to pH=2, continue to stir 2h, then the glass fibre obtained in above-mentioned (1) is immersed in solution, after dipping 2h, take out and purge through high pressure air rifle, solution unnecessary inside blowout glass fibre three-dimensional micropore, ageing 24h, 80 DEG C of dryings, after to be dried in Muffle furnace 500 DEG C of roasting 5h.
(3) nitrate of lanthanum, cobalt, copper is joined in 150mL distilled water according to metallic atom than the ratio of 1:1:1,60 DEG C of water-bath 1h, the Homogeneous phase mixing liquid obtained is through ion plating apparatus effect, be injected into containing cated glass fibre duct and surface, ion plating is activated reactive evaporation, rifle voltage is 8000V, rifle electric current is 0.5A, then 100Hz sonic oscillation 2h forms evenly firmly active layer, ageing 24h, 105 DEG C of dryings, put into Muffle furnace 500 DEG C of roasting 5h, namely obtain LaCoO after to be dried 3/ CuCeO x/ Al 2o 3-CeO 2/ glass fibre catalyst.
Getting above-mentioned catalyst and be placed in fixed reactor, take benzene as volatile organic matter, and the concentration of benzene is 7.8mg/L, and air speed is 15000h -1, adopt gas-chromatography on-line analysis, result shows: when 175 DEG C, 200 DEG C, 225 DEG C, 250 DEG C, 275 DEG C and 300 DEG C, the conversion ratio of benzene is respectively 8.32%, 24.18%, 61.87%, 83.75%, 96.74%, 100%, as Fig. 4.
Embodiment 4:
(1) glass fibre is immersed completely in 20wt.% hydrochloric acid, soak 1h, take out be washed to neutrality, then put into the ultrasonic 10min of deionized water 80Hz, after drying in Muffle furnace 500 DEG C of roasting 5h.
(2) be that 2:1 mixes by boehmite (calculating by aluminium oxide), six water cerous nitrates by metal atomic ratio, be dissolved in 100mL distilled water, stir to dissolving completely, dropwise add red fuming nitric acid (RFNA) to pH=2, continue to stir 2h, then the glass fibre obtained in above-mentioned (1) is immersed in solution, after dipping 2h, take out and purge through high pressure air rifle, solution unnecessary inside blowout glass fibre three-dimensional micropore, ageing 24h, 80 DEG C of dryings, after to be dried in Muffle furnace 500 DEG C of roasting 5h.
(3) nitrate of lanthanum, manganese, copper is joined in 150mL distilled water according to metallic atom than the ratio of 1:1:1,60 DEG C of water-bath 1h, the Homogeneous phase mixing liquid obtained is through ion plating apparatus effect, be injected into containing cated glass fibre duct and surface, purge surfaces externally and internally redundant solution, ion plating is activated reactive evaporation, rifle voltage is 8000V, rifle electric current is 0.5A, then 100Hz sonic oscillation 2h forms evenly firmly active layer, ageing 24h, 105 DEG C of dryings, put into Muffle furnace 500 DEG C of roasting 5h after to be dried, namely obtain LaMnO 3/ CuCeO x/ Al 2o 3-CeO 2/ glass fibre catalyst.
Getting above-mentioned catalyst and be placed in fixed reactor, take benzene as volatile organic matter, and the concentration of benzene is 7.8mg/L, and air speed is 15000h -1, adopt gas-chromatography on-line analysis, result shows: when 175 DEG C, 200 DEG C, 225 DEG C, 250 DEG C, 275 DEG C and 300 DEG C, the conversion ratio of benzene is respectively 10.56%, 23.41%, 64.92%, 86.54%, 98.81%, 100%.Compare above example, LaMnO 3/ CuCeO x/ Al 2o 3-CeO 2the activity of/glass fibre catalyst burning benzene is optimum, as Fig. 5.
Embodiment 5:
(1) glass fibre is immersed completely in 20wt.% hydrochloric acid, soak 1h, take out be washed to neutrality, then put into the ultrasonic 10min of deionized water 80Hz, after drying in Muffle furnace 500 DEG C of roasting 5h.
(2) be that 2:1 mixes by boehmite (calculating by aluminium oxide), six water cerous nitrates by metal atomic ratio, be dissolved in 100mL distilled water, stir to dissolving completely, dropwise add red fuming nitric acid (RFNA) to pH=3, continue to stir 2h, then the glass fibre obtained in above-mentioned (1) is immersed in solution, after dipping 2h, take out and purge through high pressure air rifle, solution unnecessary inside blowout glass fibre three-dimensional micropore, ageing 24h, 80 DEG C of dryings, after to be dried in Muffle furnace 530 DEG C of roasting 5h.
(3) lanthanum, manganese, copper nitrate are joined in 150mL distilled water according to metallic atom than the ratio of 1:1:1,60 DEG C of water-bath 1h, the Homogeneous phase mixing liquid obtained is through ion plating apparatus effect, be injected into containing cated glass fibre duct and surface, ion plating is activated reactive evaporation, rifle voltage is 8000V, rifle electric current is 0.5A, then 100Hz sonic oscillation 2h forms evenly firmly active layer, ageing 24h, 105 DEG C of dryings, put into Muffle furnace 530 DEG C of roasting 5h, namely obtain LaMnO after to be dried 3/ CuCeO x/ Al 2o 3-CeO 2/ glass fibre catalyst.
Getting above-mentioned catalyst and be placed in fixed reactor, take benzene as volatile organic matter, and the concentration of benzene is 7.8mg/L, and air speed is 20000h -1, adopt gas-chromatography on-line analysis, result shows: when 175 DEG C, 200 DEG C, 225 DEG C, 250 DEG C, 275 DEG C and 300 DEG C, the conversion ratio of benzene is respectively 10.75%, 28.29%, 70.63%, 88.45%, 98.28%, 100%.Under equivalent responses condition compared with cordierite catalyst catalytic combustion benzene, performance is better, as Fig. 6.In addition at constant 275 DEG C, continuous 32h tests the activity of its catalytic combustion benzene, and its stability is higher, as Fig. 7.
The substrate glass fibre single thread of catalyst of the present invention is unordered staggered interspersed, in omnidirectional three-dimensional micropore structure, porosity is high, specific area is large, and there is the feature of wear-resisting, corrosion-resistant, high temperature resistant, good restoration, there is not yet the relevant report of glass fibre for organic waste gas catalytic combustion catalyst carrier.Compared with the ceramic honeycomb catalyst of current catalytic combustion process VOCs, the glass fibre catalyst duct with three-dimensional micropore structure is intricate, organic exhaust gas by catalyst layer time due to turbulent flow and cross-flow reciprocation, interior microscopic can form complex flowfield, produce high-speed interface shear stress, substantially increase process mass transfer, enhance Temperature Distribution, thus improve the catalytic degradation efficiency of catalyst.Simultaneous temperature is evenly distributed, and to avoid catalyst local moment overheated and cause the FAQs such as sintering of catalyst inefficacy, extends the service life of catalyst.The catalyst based relative weight of flexible fibreglass is lighter, load compact, when organic gas is through beds, overall flexibility vibration is produced due to the impact of air-flow, solve the stifled bed problem that retain and produce of trickle finely ground particle substance at catalyst surface, maintain the high catalytic activity of catalyst surface.
Therefore the present invention is based on the good characteristic of glass fibre, carry out surface modification and microcellular structure optimization on this basis, and carried metal composite oxides and form the new catalyst being applicable to organic waste gas catalytic combustion, for the technical merit promoting China's VOCs treatment, there is important scientific meaning, also there is the extremely strong market competitiveness.Along with the continuous expansion of China's VOCs treatment industry size, its application market has a extensive future, and certainly leads to huge economic benefit and social influence.

Claims (8)

1., for a preparation method for the glass fibre catalyst of VOCs catalytic combustion, it is characterized in that step is:
(1) glass fibre pretreatment: glass fibre soaks 1h in 10wt.% ~ 20wt.% hydrochloric acid, takes out and is washed to neutrality, and then in distilled water, ultrasonic cleaning room temperature are dried, and 400 ~ 500 DEG C of roasting 2h obtain pretreated glass fibre in air atmosphere; Boehmite and cerous nitrate are mixed, wherein the atomic ratio of metal element A l:Ce is 2:(1 ~ 2), mixture adds in deionized water, and after fully stirring, nitric acid adjusts pH to 2 ~ 4, continues stirring 2 ~ 4h and obtains tie coat;
(2) pretreated glass fibre is immersed tie coat, take out after 2h to be impregnated, with solution unnecessary inside air stream blowout glass fibre three-dimensional micropore, ageing 24h, then put into the oven dry of 80 ~ 105 DEG C, baking oven, put into Muffle furnace 450 ~ 550 DEG C of roasting 5h, obtain with Al 2o 3-CeO 2the glass fibre of coating;
(3) be 1:1:1 according to La:M:Cu mol ratio, mixed by the nitrate of three kinds of non-noble metal j element, then join in deionized water, 60 DEG C of water-baths, and stir 1 ~ 2h, obtain uniform mixed liquor, described M is Mn, Co, Cr or Fe;
(4) above-mentioned mixed liquor is through the effect of ion plating apparatus, injects with Al 2o 3-CeO 2the glass fibre duct of coating and surface, form one firmly diffusion coating, ageing 24h, 80 ~ 100Hz supersonic oscillations 2h, glass fibre catalyst after vibration is put into the oven dry of 100 ~ 110 DEG C, baking oven, finally put into Muffle furnace 450 ~ 550 DEG C of roasting 5h, namely obtain the glass fibre catalyst for VOCs catalytic combustion: LaMO 3/ CuCeO x/ Al 2o 3-CeO 2/ glass fibre catalyst.
2. according to claim 1 for the preparation method of the glass fibre catalyst of VOCs catalytic combustion, it is characterized in that the boehmite described in described step (1) and cerous nitrate mixed liquor, its metal element A l:Ce atomic ratio is 2:1.
3., according to claim 1 for the preparation method of the glass fibre catalyst of VOCs catalytic combustion, it is characterized in that the Al described in described step (2) 2o 3-CeO 2content be 4.2 ~ 16.7%.
4., according to claim 1 for the preparation method of the glass fibre catalyst of VOCs catalytic combustion, it is characterized in that the LaMO described in described step (4) 3content is 10wt.% ~ 20wt.%, CuCeO xcontent is 5wt.% ~ 10wt.%.
5., according to claim 1 for the preparation method of the glass fibre catalyst of VOCs catalytic combustion, it is characterized in that the ion plating described in described step (4) is activated reactive evaporation, rifle voltage is 8000V, and rifle electric current is 0.5A.
6. according to claim 1 for the preparation method of the glass fibre catalyst of VOCs catalytic combustion, it is characterized in that described glass fibre forms by mutually tangling between the glass fibre carpet veneer of filament diameter 5 ~ 10 μm and fiberglass-based cloth, there is three-dimensional micropore structure, its porosity is 70 ~ 90%, and thick is 1 ~ 5mm.
7. the arbitrary described preparation method's gained of claim 1 ~ 6 is used for the glass fibre catalyst of VOCs catalytic combustion.
8. described in claim 7 for the application of the glass fibre catalyst of VOCs catalytic combustion, it is characterized in that the beds of catalytic combustion system is put in the tiling of glass fibre catalyst, every block catalyst spacing 50 ~ 120mm, an air pressing operation, reaction temperature 175 ~ 300 DEG C, air speed is 10000 ~ 40000h -1, volatile organic matter volumetric concentration is 0.05% ~ 0.2%.
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CN110252307A (en) * 2019-06-14 2019-09-20 南京工业大学 A kind of flat catalyst and preparation method thereof removing volatile organic waste gas

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