CN101559362B - Catalyst for removing dioxin in flue gas of garbage furnace and preparation method thereof - Google Patents

Abstract

The invention relates to a catalyst for removing dioxin in flue gas of a garbage furnace, which takes volcanic rock as a carrier and loads titanium dioxide (TiO2) and V2O5 on the carrier in turn, wherein the composition of the catalyst is the V2O5, and the TiO2 is the carrier for loading the V2O5. A method for preparing the catalyst comprises the following steps: firstly, loading the TiO2 on volcanic rock by adopting a sol-gel method or a sluggish precipitation method; and secondly, adopting a method of impregnation to load the V2O5 on the TiO2 carrier. The catalyst has the advantages that theporous volcanic rock is adopted as the carrier, so that the raw material is cheap and has larger specific surface area, and the catalytic capability is strengthened; the TiO2 is taken as the carrierof the catalyst and can well load the V2O5 catalyst, and simultaneously the TiO2 has obvious advantage in the aspect of resisting the intoxication of sulfur in the flue gas in the catalyst and shows high dioxin catalytic oxidative decomposition capacity in the temperature range of between 200 and 450 DEG C; and the preparation method is simple and easy, and has low manufacturing cost and wide application prospect.

Description

Be used for removing the Catalysts and its preparation method of flue gas of garbage furnace dioxin

(1) technical field

The present invention relates to the incineration treatment of garbage technology, specifically is a kind of Catalysts and its preparation method that is used for removing the flue gas of garbage furnace dioxin.

(2) background technology

Garbage burning processing method have subtract hold the loss of weight ratio big, handle big in batches, the cycle is short, innoxious and advantage such as resource, the proportion in waste disposal method is increasing in recent years.The shortcoming of incineration treatment of garbage is that incineration flue gas has the dioxin discharging, may cause the secondary pollution of air, and dioxin causes strange and carcinogenesis to human body.Dioxin is solid-state under standard state, and fusing point is 303～305 ℃, and the dioxin utmost point is insoluble in water and is dissolved in easily fat, discharges so it accumulates in vivo easily and is difficult to.

The dioxin source that discharges in waste incineration is as follows: the dioxin-like chemical that self contains in the rubbish; The presoma that rubbish forms in combustion process transforms as chlorobenzene, chlorophenol, polychlorostyrene aldehydes matter (PCBs); Little molecular carbon hydrogen compound forms polycyclic hydrocarbon compounds (PAH) by polymerization and cyclisation, the dioxin that these compounds and chlorine reaction form; At a lower temperature, the dioxin presoma forms dioxin under the flying dust catalytic action; Incinerator afterbody purification temperature under 200-300 ℃, the dioxin that HCl and simple substance chlorine generate with hydrocarbon reaction under the flying dust catalytic action.

The method of control dioxin mainly contains following: by the design of incinerator, increase the incineration temperature and the time of staying of flue gas under hot conditions; Utilize the adsorptivity of active carbon to absorb dioxin; The play of back-end ductwork gas is cold, shortens the time of staying of flue gas under 200～300 ℃; Spray into inhibitor to burner hearth; Catalytic oxidation decomposition etc.

At present every country all has strict discharge standard to the discharging of dioxin, is 0.1ngTEQ/Nm such as European Union to the discharge standard of dioxin ³, the dioxin standard of China is also by 1ngTEQ/Nm ³Bring up to 0.5ngTEQ/Nm ³From present technical Analysis, by the impossible emission problem that thoroughly solves dioxin of the design of incinerator, because can again synthesize dioxin on afterbody flying dust surface; Physical absorption also just takes place in charcoal absorption, and dioxin is not decomposed; And it is bigger by the method cost of the acute cold-peace spray of flue gas inhibitor.The catalytic oxidation decomposition technique is to utilize oxygen condition in the flue gas, and in about 300～400 ℃ temperature, dioxin is decomposed to form CO ₂And H ₂O steam, thus make dioxin innoxious completely.Catalytic oxidation decomposition technique energy consumption is low, is a kind of more potential method.

(3) summary of the invention

The objective of the invention is at above-mentioned existing problems, provide that a kind of specific area is big, the poisoning effect of sulphur is obvious in strong, the anti-flue gas of catalytic oxidation capacity of decomposition, the preparation method is simple and the Catalysts and its preparation method that is used for removing the flue gas of garbage furnace dioxin of low cost of manufacture.

Technical scheme of the present invention:

A kind of catalyst for removing dioxin from fume of garbage incinerator, take volcanic rock as carrier, priority carried titanium dioxide and V on this carrier ₂O ₅, wherein catalyst component is V ₂O ₅, TiO ₂Be supported V ₂O ₅Carrier.

The average diameter of particles of described volcanic rock is more than 0.8cm, and the porosity of volcanic rock is more than 60%.

TiO in the described catalyst ₂The percentage by weight that accounts for overall weight is 1%～15%, V ₂O ₅The percentage by weight that accounts for overall weight is 1%～6%.

A kind of described Preparation of catalysts method that is used for removing the flue gas of garbage furnace dioxin, step is as follows:

1) adopt sol-gel process with TiO ₂Load on the volcanic rock, promptly measure butyl titanate and absolute ethyl alcohol, its volume ratio is 1: 1.5～1: 3.5, and the mixing back is stirred to the magnetic stirring apparatus brute force and mixes, and forms yellow settled solution A, adds nitric acid and regulates pH≤3; With glacial acetic acid with analyze pure water and be configured to solution B, add nitric acid and regulate pH≤3 according to 1: 3～1: 10 volume ratio; Under intense agitation solution A is slowly splashed in the solution B, adding the volcanic rock particle then and soaking particle with solution is minimum standard, and the average diameter of particles of volcanic rock is more than 0.8cm, and the porosity of volcanic rock is more than 60%; In water-bath, heat evaporate to dryness; Volcanic rock particle after the load can be with TiO at 350 ℃～600 ℃ heat treatment 2h～6h of Muffle furnace ₂Load on the volcanic rock;

2) adopt infusion process with V ₂O ₅Load on TiO ₂On the carrier, namely according to V ₂O ₅Load capacity is that 1%～6% percentage by weight takes by weighing the predecessor ammonium metavanadate, is dissolved in the deionized water under heating water bath, and its mass percent concentration is≤5%, with the aforementioned TiO that loads on the volcanic rock ₂Carrier is immersed in this solution and floods, and dip time is 2h～24h, and oven dry is rear to be to calcine 2h～6h under 350 ℃～600 ℃ conditions in temperature, can make this catalyst.

A kind of described Preparation of catalysts method that is used for removing the flue gas of garbage furnace dioxin, step is as follows:

1) adopt sluggish precipitation with TiO ₂Load on the volcanic rock, be about to titanyl sulfate and urea and be configured as solution, both mol ratios are 1: 1～1: 4, in this solution, add the volcanic rock particle and soaked particle as minimum standard take solution, the average diameter of particles of volcanic rock is more than 0.8cm, and the porosity of volcanic rock is more than 60%; In closed system, be to react under 70 ℃～160 ℃ the condition in temperature, the reaction time is 1h～4h, cooling is by vacuum drying, again at 350 ℃～600 ℃ heat treatment 2h～6h of Muffle furnace, can be with TiO ₂Load on the volcanic rock;

2) adopt infusion process with V ₂O ₅Load on TiO ₂On the carrier, namely according to V ₂O ₅Load capacity is that 1%～6% percentage by weight takes by weighing the predecessor ammonium metavanadate, is dissolved in the deionized water under heating water bath, and its mass percent concentration is≤5%, with the aforementioned TiO that loads on the volcanic rock ₂Carrier is immersed in this solution and floods, and dip time is 2h～24h, and oven dry is rear to be to calcine 2h～6h under 350 ℃～600 ℃ conditions in temperature, can make this catalyst.

Advantage of the present invention is: the invention provides a kind of take volcanic rock as carrier loaded TiO ₂And V ₂O ₅The catalyst for preparing, its volcanic rock that adopts porous is carrier, raw material is cheap and have bigger specific area, and catalytic capability is strengthened; And TiO ₂As the carrier of catalyst, preferably supported V ₂O ₅Catalyst, TiO2 has clear superiority aspect the poisoning of the anti-sulfureous in flue gas of catalyst simultaneously, shows higher dioxin catalytic oxidation capacity of decomposition in 200 ℃～450 ℃ temperature ranges; Simple and the low cost of manufacture of this preparation method has broad application prospects.

(4) specific embodiment

Enumerate some examples of implementation explanation Preparation of catalysts methods below, but do not comprise all.The average diameter of particles of the volcanic rock that adopts among the embodiment is more than 0.8cm, and the porosity of volcanic rock is more than 60%.

Embodiment 1:

1) adopt sol-gel process with TiO ₂Load on the volcanic rock:

Measuring butyl titanate and absolute ethyl alcohol volume ratio is 1: 2, mixes the back and stirs and mix with magnetic stirring apparatus is powerful, forms yellow settled solution A, adds nitric acid and regulates pH≤3; Glacial acetic acid and ultra-pure water are configured to solution B according to 1: 8 volume ratio, add nitric acid and regulate pH≤3; Under vigorous stirring, solution A is slowly splashed in the solution B, put into the volcanic rock particle then and immerse solution fully; In water-bath, heat evaporate to dryness; Volcanic rock particle after the load gets final product at 400 ℃ of heat treatment 3h of Muffle furnace;

2) adopt infusion process with V ₂O ₅Load on TiO ₂On the carrier:

According to V ₂O ₅Load capacity is that 5% quantity takes by weighing predecessor ammonium metavanadate (NH ₄VO ₃), under heating water bath, being dissolved in the deionized water, its mass percent concentration is 5%, and the carrier of above-mentioned having (1) preparation is put into this solution and is flooded, and dip time is 24h; Be that calcining 3h gets final product under 400 ℃ the condition in temperature after the oven dry.

Detect to show that the catalyst of above-mentioned preparation is under 350 ℃, the flue gas condition of oxygen content 8%, the catalytic decomposition efficient of dioxin is up to 95%.

Embodiment 2:

1) adopt sluggish precipitation with TiO ₂Load on the volcanic rock:

Titanyl sulfate and urea are configured as solution, both mol ratios are 1: 3, adding the volcanic rock particle and soaked particle with solution in this solution is minimum standard, in closed system, be to react under 100 ℃ the condition in temperature, through supercooling, vacuum drying, get final product at 400 ℃ of heat treatment 3h of Muffle furnace again;

2) adopt infusion process with V ₂O ₅Load on TiO ₂On the carrier:

According to V ₂O ₅Load capacity is that 4% quantity takes by weighing predecessor ammonium metavanadate (NH ₄VO ₃), be dissolved in the deionized water under heating water bath, its mass percent concentration is 4%, having above-mentioned 1) carrier of preparation puts into this solution and floods, and dip time is 20h; Be that calcining 2h gets final product under 400 ℃ the condition in temperature after the oven dry.

Detect demonstration, the catalyst of above-mentioned preparation is at 420 ℃, and under the flue gas condition of oxygen content 5%, the catalytic decomposition efficient of dioxin is 90%%.

Embodiment 3:

1) adopt sol-gel process with TiO ₂Load on the volcanic rock:

Measuring butyl titanate and absolute ethyl alcohol volume ratio is 1: 2, with the magnetic stirring apparatus strong stirring and mix, forms yellow settled solution A, adds nitre acid for adjusting pH≤3; Glacial acetic acid and ultra-pure water dispose solution B according to 1: 6 volume ratio, and add nitre acid for adjusting pH≤3; Under vigorous stirring, solution A is slowly splashed in the solution B, then the volcanic rock particle is immersed in the solution; In water-bath, heat evaporate to dryness; Volcanic rock particle after the load gets final product at 550 ℃ of heat treatment 3h of Muffle furnace;

2) adopt infusion process with V ₂O ₅Load on TiO ₂On the carrier:

According to V ₂O ₅Load capacity is that 2% quantity takes by weighing predecessor ammonium metavanadate (NH ₄VO ₃), be dissolved in the deionized water under heating water bath, its mass percent concentration is 3%, having above-mentioned 1) carrier of preparation puts into this solution and floods, and dip time is 15h; Be that calcining 4h gets final product under 450 ℃ the condition in temperature after the oven dry.

Detect demonstration, the catalyst of above-mentioned preparation is at 350 ℃, and under the flue gas condition of oxygen content 5%, the catalytic decomposition efficient of dioxin is 85%.

Embodiment 4:

1) adopt sluggish precipitation with TiO ₂Load on the volcanic rock:

Titanyl sulfate and urea are configured as solution, both mol ratios are 1: 2, adding the volcanic rock particle and soaked particle with solution in this solution is minimum standard, in closed system, be to react under 90 ℃ the condition in temperature, through supercooling, vacuum drying, get final product at 450 ℃ of heat treatment 2h of Muffle furnace again;

2) adopt infusion process with V ₂O ₅Load on TiO ₂On the carrier:

According to V ₂O ₅Load capacity is that 3% quantity takes by weighing predecessor ammonium metavanadate (NH ₄VO ₃), be dissolved in the deionized water under heating water bath, its mass percent concentration is 2%, having above-mentioned 1) carrier of preparation puts into this solution and floods, and dip time is 15h; Be that calcining 5h gets final product under 450 ℃ the condition in temperature after the oven dry.

Detect demonstration, the catalyst of above-mentioned preparation is at 350 ℃, and under the flue gas condition of oxygen content 8%, the catalytic decomposition efficient of dioxin is 83%.

Claims (3)

1. catalyst of be used for removing dioxin from fume of garbage incinerator is characterized in that: take volcanic rock as carrier, and successively carried titanium dioxide and V on this carrier ₂O ₅, wherein catalyst component is V ₂O ₅, TiO ₂Be supported V ₂O ₅Carrier, the average diameter of particles of volcanic rock is more than 0.8cm, the porosity of volcanic rock is more than 60%, TiO in the catalyst ₂The percentage by weight that accounts for overall weight is 1%～15%, V ₂O ₅The percentage by weight that accounts for overall weight is 1%～6%.

2. Preparation of catalysts method that is used for removing the flue gas of garbage furnace dioxin according to claim 1 is characterized in that step is as follows:

1) adopt sol-gel process with TiO ₂Load on the volcanic rock, promptly measure butyl titanate and absolute ethyl alcohol, its volume ratio is 1: 1.5～1: 3.5, and the mixing back is stirred to the magnetic stirring apparatus brute force and mixes, and forms yellow settled solution A, adds nitric acid and regulates pH≤3; With glacial acetic acid with analyze pure water and be configured to solution B, add nitric acid and regulate pH≤3 according to 1: 3～1: 10 volume ratio; Under intense agitation solution A is slowly splashed in the solution B, adding the volcanic rock particle then and soaking particle with solution is minimum standard, and the average diameter of particles of volcanic rock is more than 0.8cm, and the porosity of volcanic rock is more than 60%; In water-bath, heat evaporate to dryness; Volcanic rock particle after the load can be with TiO at 350 ℃～600 ℃ heat treatment 2h～6h of Muffle furnace ₂Load on the volcanic rock;

2) adopt infusion process with V ₂O ₅Load on TiO ₂On the carrier, namely according to V ₂O ₅Load capacity is that 1%～6% percentage by weight takes by weighing the predecessor ammonium metavanadate, is dissolved in the deionized water under heating water bath, and its mass percent concentration is≤5%, with the aforementioned TiO that loads on the volcanic rock ₂Carrier is immersed in this solution and floods, and dip time is 2h～24h, and oven dry is rear to be to calcine 2h～6h under 350 ℃～600 ℃ conditions in temperature, can make this catalyst.

3. Preparation of catalysts method that is used for removing the flue gas of garbage furnace dioxin according to claim 1 is characterized in that step is as follows:

1) adopt sluggish precipitation with TiO ₂Load on the volcanic rock, be about to titanyl sulfate and urea and be configured as solution, both mol ratios are 1: 1～1: 4, in this solution, add the volcanic rock particle and soaked particle as minimum standard take solution, the average diameter of particles of volcanic rock is more than 0.8cm, and the porosity of volcanic rock is more than 60%; In closed system, be to react under 70 ℃～160 ℃ the condition in temperature, the reaction time is 1h～4h, cooling is by vacuum drying, again at 350 ℃～600 ℃ heat treatment 2h～6h of Muffle furnace, can be with TiO ₂Load on the volcanic rock;

2) adopt infusion process with V ₂O ₅Load on TiO ₂On the carrier, namely according to V ₂O ₅Load capacity is that 1%～6% percentage by weight takes by weighing the predecessor ammonium metavanadate, is dissolved in the deionized water under heating water bath, and its mass percent concentration is≤5%, with the aforementioned TiO that loads on the volcanic rock ₂Carrier is immersed in this solution and floods, and dip time is 2h～24h, and oven dry is rear to be to calcine 2h～6h under 350 ℃～600 ℃ conditions in temperature, can make this catalyst.