CN106046413A - Microwave automatic cracking reaction device for waste rubber - Google Patents

Abstract

The invention relates to a microwave automatic cracking reaction device for waste rubber. The microwave automatic cracking reaction device comprises a control unit, a reducing agent supply unit, a catalytic reduction unit, a particulate trapping unit and temperature sensors. The catalytic reduction unit and the particulate trapping unit are connected through a communicating pipeline, and a branch is arranged on the communicating pipeline and is connected with the reducing agent supply unit. The control unit controls the particulate trapping unit, the reducing agent supply unit, the catalytic reduction unit and the temperature sensors. The catalytic reduction unit comprises multiple cylindrical catalytic reduction devices capable of rotating around a rotating shaft, multiple catalytic reduction channels are formed in each catalytic reduction device in the length direction at intervals and include a high-temperature catalytic reduction channel, a medium-temperature catalytic reduction channel and a low-temperature catalytic reduction channel, and a movable pressure reduction buffering structure is arranged between the catalytic reduction devices in pairs. Different catalysts are switched according to the temperature of waste gas, and the catalytic efficiency is maximized.

Description

Waste old microwave automatic cracking reaction device

Technical field

The present invention relates to rubber recycling field, particularly relate to waste old microwave automatic cracking reaction device.

Background technology

In correlation technique, waste rubber cracking technology is a most emerging solid refuse treatment technology, domestic factory Polytype cracking apparatus that family produces all installs emission-control equipment, and this is substantial amounts of owing to producing during rubber cracking By-product, such as harmful gass such as dust, nitrogen oxides and sulfur dioxide.These noxious gas emissions, can serious shadow in air Ring the health of the mankind, may interfere with the growth of plant, thus cause the severe contamination of earth environment.But, in correlation technique, base All there is equipment cost and put into the shortcomings such as big, pollutant removing efficiency is low in this.

Summary of the invention

For the problems referred to above, the exhaust-gas treatment removing effect produced during present invention aim to address waste rubber cracking The technical problem that rate is low.

For solving above-mentioned technical problem, the technical solution used in the present invention is waste old microwave automatic cracking reaction dress Put, including exhaust-gas treatment part, described exhaust-gas treatment part include control unit, reducing agent feeding unit, catalytic reduction unit, Micro particle catching unit and temperature sensor, described catalytic reduction unit is connected by connecting pipe with described micro particle catching unit, And described connecting pipe is provided with branch road and connects described reducing agent feeding unit.Described control unit controls micro particle catching list respectively Unit, reducing agent feeding unit, catalytic reduction unit and temperature sensor.Described catalytic reduction unit is located in described temperature sensor Air inlet one end.

Described catalytic reduction unit includes rotary shaft, air inlet pipe and the exhaustor of connection air inlet pipe.Described rotary shaft edge Air inlet pipe, the direction, axis of exhaustor extend across air inlet pipe and exhaustor, and the two ends of described rotary shaft connect motor, Described motor can drive rotary shaft to rotate.Multiple cylindrical urging that can rotate it is arranged in sequence with around rotary shaft in described rotary shaft Changing restorer, the inside of described catalysis restorer is interval with multiple catalysis reduction passage along its length, and described recall is also Former passage is divided into high-temperature catalytic reduction passage, middle temperature catalysis reduction passage and low-temperature catalyzed reduction passage.Described high-temperature catalytic It is provided with spiral helicine high-temperature catalytic metallic carrier in reduction passage, is provided with spiral helicine in described middle temperature catalysis reduction passage Middle temperature catalytic metal support, is provided with spiral helicine low-temperature catalyzed metallic carrier in described low-temperature catalyzed reduction passage.Described height Temperature catalysis reduction passage, middle temperature catalysis reduction passage and the arrangement of low-temperature catalyzed reduction passage regularity.

Being additionally provided with opening and closing disc in described catalysis restorer, described opening and closing disc is positioned at one end of catalysis reduction channel inlet.Institute The surface stating opening and closing disc is provided with the through hole of regular arrangement, rotary opening closing dish, the high temperature on described through-hole alignment catalysis restorer Catalysis reduction passage, middle temperature catalysis reduction passage or low-temperature catalyzed reduction passage, cover remaining two kinds catalysis reduction passages, waste gas Enter this catalysis reduction passage by through hole and carry out the catalytic reduction reaction of correspondence.

One end of described catalysis restorer air inlet is provided with movable pressure-reducing cushioning structure, during described pressure-reducing cushioning structure is Empty cylinder or discoid, the outer surface of described pressure-reducing cushioning structure is interval with multiple opening, and each opening is inserted with can Movable barrier sheet, when opening and closing disc needs to rotate when, described barrier sheet enters pressure-reducing cushioning structure and ties in pressure-reducing cushioning Structure is internally formed waste gas interception structure, and waste gas need to could enter posterior catalysis also through the cavity of multiple adjacent barrier sheets composition Prototype, thus temporary reduction exhaust gas pressure so that posterior opening and closing disc can be with smooth rotation, it is to avoid exhaust gas leakage occurs.? After opening and closing disc complete rotate after, described barrier sheet detaches, waste gas recover original pressure, be rapidly introduced into posterior catalysis also Former passage.

When burning under the influence of various factors, the temperature of waste gas discharge is different, and different catalyst optimal processing temperature Degree difference, therefore arranges three kinds of different catalyst of operating temperature and reduces in passage in catalysis, cooperate with opening and closing disc, work as temperature After degree sensor detects EGT, according to its temperature, rotary opening closing dish so that the through-hole alignment in opening and closing disc adapts to this temperature The catalysis reduction passage of degree scope, covers remaining two kinds catalysis reduction passages, and waste gas is by the efficiency that matches with its temperature The catalysis reduction passage of bigization, thus realize the maximization of exhaust treatment efficiency and effect.

Described high-temperature catalytic metallic carrier works under 400～600 DEG C of environment, and described middle temperature catalytic metal support is 250 ～work under 400 DEG C of environment, described low-temperature catalyzed metallic carrier works under 150～250 DEG C of environment.

Described high-temperature catalytic metallic carrier includes being loaded with WO₃/TiO₂The metallic carrier of catalyst, WO₃/TiO₂Catalyst It is carried on through the following steps on metallic carrier: (1) carries out alkali cleaning and removes surface and oil contaminant metallic carrier, and soda-wash solution composition is Water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser light Speckle radius is 2.25 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short-pulse laser irradiate clean after metal Carrier surface so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation blast, forms microetch hole, wherein The microetch hole gross area accounts for the 60% of the metal carrier surface gross area；(3) metallic carrier after step (2) processes is in 900 DEG C Roasting 5h so that it is surface forms oxide-film；(4) use sol-gel process in the surface-coated glass ceramics of described metallic carrier Coating, composition is mol ratio SiO₂: Al₂O₃=5:1；(5) butyl titanate, acetic acid and ethanol 1:8:5 in molar ratio stirring is obtained Solution A, ammonium paratungstate is dissolved in oxalic acid solution and obtains solution B, solution B is quantitatively adding in A, is stirred vigorously and obtains 25wt.% WO₃/TiO₂Catalyst colloidal sol, is immersed in 25wt.%WO by the metallic carrier of coating glass ceramic coating₃/TiO₂Catalyst colloidal sol Middle 30min, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C, roasting at 500 DEG C 5h, obtains loading 25wt.%WO₃WO₃/TiO₂The high-temperature catalytic metallic carrier of catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more WO₃/TiO₂Catalyst.When microetch hole, the gross area accounts for the 60% of the metal carrier surface gross area Time, under 400～600 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through laser ablation The catalytic efficiency of high-temperature catalytic metallic carrier improves 35%.

At a temperature of 400～550 DEG C, the catalysis activity with temperature of high-temperature catalytic metallic carrier raises and strengthens, NOx conversion Rate is above 80%, more than 92% when 500 DEG C, downward trend occurs, but NOx still has when 600 DEG C after temperature is higher than 500 DEG C The conversion ratio of 65%.

Described middle temperature catalytic metal support includes being loaded with CeO₂/W₂₅The metallic carrier of Ti catalyst, CeO₂/W₂₅Ti is catalyzed Agent is carried on metallic carrier through the following steps: (1) carries out alkali cleaning and removes surface and oil contaminant, soda-wash solution composition metallic carrier For water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser Spot radius is 2.25 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short-pulse laser irradiate clean after gold Belong to carrier surface so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation blast, form microetch hole, its The middle microetch hole gross area accounts for the 60% of the metal carrier surface gross area；(3) metallic carrier after step (2) processes is in cleaning After metallic carrier roasting 5h in 900 DEG C so that it is surface formed oxide-film；(4) sol-gel process is used to carry at described metal The surface-coated glass ceramic coating of body, composition is mol ratio SiO₂: Al₂O₃=5:1；(5) by butyl titanate, acetic acid and ethanol 1:8:5 stirring in molar ratio obtains solution A, and ammonium paratungstate is dissolved in oxalic acid solution and obtains solution B；(6) solution B is quantitatively adding In A, being stirred vigorously and obtain colloidal sol, room temperature is placed and is obtained 110 DEG C of drying in thermostatic drying chamber after xerogel, then roasting at 600 DEG C Burn 4h, obtain WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst；(7) by quantitative Ce (NO₃)₃·6H₂O is dissolved in water and obtains To cerous nitrate solution, then by WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst is immersed, and obtains after 1h is stirred at room temperature CeO to load 10wt.%Ce₂/W₂₅Ti catalyst colloidal sol, is immersed in CeO by the metallic carrier of coating glass ceramic coating₂/ W₂₅1h in Ti catalyst colloidal sol, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C, then at Roasting 5h at 500 DEG C, obtains being loaded with CeO₂/W₂₅The middle temperature catalytic metal support of Ti catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more CeO₂/W₂₅Ti catalyst.When microetch hole, the gross area accounts for the metal carrier surface gross area When 60%, under 250～400 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through laser incising The catalytic efficiency of the high-temperature catalytic metallic carrier of erosion improves 30%.

At a temperature of 250～300 DEG C, the catalysis activity with temperature of middle temperature catalytic metal support raises and strengthens, NOx conversion Rate is above 60%, and at a temperature of 250～300 DEG C, conversion rate of NOx reaches the highest, close to 80%, after temperature is higher than 400 DEG C The catalysis activity of middle temperature catalytic metal support reduces rapidly.

Described low-temperature catalyzed metallic carrier includes being loaded with Cr₂O₃-SO₄ ^2-/TiO₂The metallic carrier of catalyst, Cr₂O₃- SO₄ ^2-/TiO₂Catalyst is carried on metallic carrier through the following steps: (1) carries out alkali cleaning and removes surface oil metallic carrier Dirt, soda-wash solution composition is water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser facula radius are 2.25 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short pulse impulse Light irradiates the metal carrier surface after cleaning so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation are quick-fried Fried, form microetch hole, wherein the microetch hole gross area accounts for the 60% of the metal carrier surface gross area；(3) after step (2) processes Metallic carrier metallic carrier roasting 5h in 900 DEG C after cleaning so that it is surface forms oxide-film；(4) colloidal sol-solidifying is used Glue method is at the surface-coated glass ceramic coating of described metallic carrier, and composition is mol ratio SiO₂: Al₂O₃=5:1；(5) by metatitanic acid Butyl ester, acetic acid and ethanol 1:8:5 in molar ratio stirring obtain solution A, ammonium paratungstate be dissolved in the sulfuric acid solution of 70% obtain molten Liquid B, is quantitatively adding solution B in A, and wherein sulfate radical is SO with the mol ratio of titanium dioxide₄ ^2-: TiO₂=1:4；(6) by solution B is quantitatively adding in A, is stirred vigorously and obtains colloidal sol, and room temperature is placed and obtained 110 DEG C of drying in thermostatic drying chamber after xerogel, then At 600 DEG C, roasting 4h, obtains WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst；(7) by quantitative Cr (NO₃)₃·9H₂O It is dissolved in water and obtains chromium nitrate solution, then by WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst is immersed, and room temperature is stirred Cr is obtained after mixing 1h₂O₃-SO₄ ^2-/TiO₂Catalyst colloidal sol, is immersed in Cr by the metallic carrier of coating glass ceramic coating₂O₃- SO₄ ^2-/TiO₂1h in catalyst colloidal sol, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C Dry, roasting 5h at 500 DEG C, obtain being loaded with Cr₂O₃-SO₄ ^2-/TiO₂The metallic carrier of catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more Cr₂O₃-SO₄ ^2-/TiO₂Catalyst.When microetch hole, the gross area accounts for the total face of metal carrier surface When long-pending 60%, under 150～250 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through too drastic The catalytic efficiency of the high-temperature catalytic metallic carrier of photoengraving improves 32%.

The low-temperature catalyzed metallic carrier of load 10wt.%Ce is when 150～250 DEG C, and conversion rate of NOx is along with the increase of temperature And gradually rise, close to 100%.In 175～250 DEG C of temperature ranges, conversion rate of NOx is all more than 80%.

Compared to using single catalyst, the NOx ratio discharge used after the catalytic conversion system of the present invention in waste gas from 12.192g/kW h drops to 2.579g/kW h, and treatment effect significantly promotes.

Described micro particle catching unit includes housing and polylith micro particle catching metallic carrier, described micro particle catching metallic carrier warp Cross the following step to process: taking quantitative chromic nitrate, cobalt nitrate and citric acid and be dissolved in deionized water, wherein chromium ion divides with citric acid Sub-mol ratio is 1:1.5, and chromium ion concentration is 0.2mol/L.Micro particle catching metallic carrier it is applied in after 80 DEG C of complex reaction 5h On, described micro particle catching metallic carrier obtains final products after 600 DEG C of roasting 5h.In order to carry high catalytic activity further, Catalyst surface has supported and has accounted for the precious metals pt that catalyst quality mark is 0.5%.After described final products cut into elongate Mutually overlap joint forms metal gauze, and described metal gauze is vertically connected with the metal wire mesh filter forming intensive porous.

Described housing includes shell body and inner housing, and described inner housing is wrapped up at described shell body interval so that shell body with Form vacuum layer between inner housing, keep the temperature of metal wire mesh filter, promote its passive combustive regeneration, reduce micro particle catching Exhaust back pressure in device.Described inner housing is divided into expansion, filtration fraction and constriction, and described expansion connects air inlet Pipe, described constriction connects exhaustor, and the external diameter of the constriction of wherein said inner housing with exhaustor external diameter diameter ratio is 2.5～4, the angle of described inner housing expansion is 80 °～100 °.

In particle trapper, the uniformity of flow velocity and particle concentration determines the height of particle trapper inner filtration body utilization rate Low, filter regeneration cycle and the length in filtering bodies service life, in the actual application of particle trapper, particle trapper Exhaust parameter (exhaust entrance speed) and structural parameters (angle of flare, diameter than) are to velocity flow profile and particle concentration distributions Uniformity has very important impact.

In the case of inlet flow rate (inlet velocity and inlet-duct area) is identical, diameter flows through enlarged portion than little inner housing Timesharing, speed reduces less, and the eddy current effect of generation is less, almost without, but, less diameter ratio can make microgranule catch In storage, exhaust flow rate is higher, exhaust flow rate skewness, thus micro-in particle trapper during causing actual filtration Grain concentrates at the central axis of metal wire mesh filter, increases the weight of the load at metal wire mesh filter central axis.Work as diameter Than when being 2～4, the VELOCITY DISTRIBUTION in each cross section of particle trapper is more uniform, thus in metal wire mesh filter, particle deposition divides Cloth is the most uniform.Now in the case of same charge flow rate, particle trapper arresting efficiency is 96%.

The angle of flare is the least, and the mistake from air inlet pipe to expansion gets over smooth-going, and the angle of flare is the biggest, the most easily produces eddy current District, and vortex is the most close to central axis, therefore, selecting the angle of flare is 80 °～100 °, now in the feelings of same charge flow rate Under condition, particle trapper arresting efficiency is 95%.

Described reducing agent feeding unit includes solid urea holding vessel, metering rotor and the heat resolve pipe being sequentially connected with Road, described solid urea holding vessel internal memory is placed with urea powder, and its lower surface is formed slopely the cone structure with opening.Described Metering rotor is cylindric, and its outer surface is interval with the pit accommodating urea powder.The cental axial position of described metering rotor Connect actuating device, drive metering rotor to rotate relative to solid urea holding vessel.The outer surface interval bag of described metering rotor Being wrapped with the seal bootr being fixed on described solid urea holding vessel, described seal bootr is directed at the opening part of described cone structure and is provided with Through hole, described seal bootr is directed at described heat resolve pipeline and is again provided with through hole, rotates metering rotor, solid urea holding vessel Interior urea powder enters in pit, is rotated further metering rotor, and the pit equipped with urea powder turns to be directed at described heating Decomposing the through hole of pipeline, urea powder drops, and waste gas blows urea powder and enters heat resolve pipeline, described heat resolve pipe Road is tortuous to be folded in microwave launcher, and urea powder decomposes generation ammonia through microwave launcher under the effect of microwave Gas and Carbimide., the steam in waste gas can make Carbimide. decompose, thus produce ammonia.

As preferably, described pit is the hemispherical of a diameter of 5mm.

Accompanying drawing explanation

Utilize accompanying drawing that invention is described further, but the embodiment in accompanying drawing do not constitute any limitation of the invention, For those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to obtain it according to the following drawings Its accompanying drawing.

Fig. 1 is the structural representation of the present invention.

Fig. 2 is the structural representation of pressure-reducing cushioning structure of the present invention.

Fig. 3 is the structural representation at another visual angle of pressure-reducing cushioning structure of the present invention.

Fig. 4 is the structural representation enlarged drawing of reducing agent feeding unit of the present invention.

Reference: 1, motor, 2, rotary shaft, 3, catalytic reduction unit, 4, air inlet pipe, 5, temperature sensor, 6, opening and closing Dish, 7, catalysis restorer, 8, pressure-reducing cushioning structure, 9, exhaustor, 10, micro particle catching unit, 11, shell body, 12, inner housing, 13, metal wire mesh filter, 14, reducing agent feeding unit, 15, microwave launcher, 16, heat resolve pipeline, 17, close Cover, 18, metering rotor, 19, solid urea holding vessel, 20, barrier sheet.

Detailed description of the invention

The invention will be further described with the following Examples.

Embodiment one

Refering to Fig. 1, waste old microwave automatic cracking reaction device, including exhaust-gas treatment part, described exhaust-gas treatment portion Divide and include control unit, reducing agent feeding unit 14, catalytic reduction unit 3, micro particle catching unit 10 and temperature sensor 5, institute State catalytic reduction unit 3 to be connected by connecting pipe with described micro particle catching unit 10, and described connecting pipe is provided with branch road Connect described reducing agent feeding unit 14.Described control unit control respectively micro particle catching unit 10, reducing agent feeding unit 14, Catalytic reduction unit 3 and temperature sensor 5.Described catalytic reduction unit 3 air inlet one end is located in described temperature sensor 5.

Described catalytic reduction unit 3 includes rotary shaft 2, air inlet pipe 4 and the exhaustor 9 of connection air inlet pipe 4.Described rotation Axle 2 extends across air inlet pipe 4 and exhaustor 9, the two ends of described rotary shaft 2 along the direction, axis of air inlet pipe 4, exhaustor 9 Connecting has motor 1, described motor 1 that rotary shaft 2 can be driven to rotate.Be arranged in sequence with in described rotary shaft 2 multiple can be around rotary shaft 2 The cylindrical catalysis restorer 7 rotated, the inside of described catalysis restorer 7 is interval with multiple catalysis also along its length Former passage, described recall reduction passage is divided into high-temperature catalytic reduction passage, middle temperature catalysis reduction passage and low-temperature catalyzed reduction Passage.Being provided with spiral helicine high-temperature catalytic metallic carrier in described high-temperature catalytic reduction passage, the catalysis reduction of described middle temperature is logical It is provided with spiral helicine middle temperature catalytic metal support in road, is provided with spiral helicine low temperature in described low-temperature catalyzed reduction passage and urges Change metallic carrier.Described high-temperature catalytic reduction passage, middle temperature catalysis reduction passage and low-temperature catalyzed reduction passage regularity row Cloth.

Being additionally provided with opening and closing disc 6 in described catalysis restorer 7, described opening and closing disc 6 is positioned at one end of catalysis reduction channel inlet. The surface of described opening and closing disc 6 is provided with the through hole of regular arrangement, and rotary opening closing dish 6, on described through-hole alignment catalysis restorer 7 High-temperature catalytic reduction passage, middle temperature catalysis reduction passage or low-temperature catalyzed reduction passage, cover remaining two kinds catalysis reduction passages, Waste gas enters this catalysis reduction passage by through hole and carries out the catalytic reduction reaction of correspondence.

One end of described catalysis restorer 7 air inlet is provided with movable pressure-reducing cushioning structure 8, refering to Fig. 2 and Fig. 3, described Pressure-reducing cushioning structure 8 is the cylinder of hollow or discoid, and the outer surface of described pressure-reducing cushioning structure 8 is interval with multiple opening Mouthful, each opening is inserted with mobilizable barrier sheet 20, when opening and closing disc 6 needs to rotate when, described barrier sheet 20 enters and subtracts Pressure buffer structure 8 is also internally formed waste gas interception structure in pressure-reducing cushioning structure 8, and waste gas need to be through multiple adjacent barrier sheets 20 groups The cavity become could enter posterior catalysis restorer 7, thus temporary reduction exhaust gas pressure so that posterior opening and closing disc 6 can With smooth rotation, it is to avoid exhaust gas leakage occurs.After posterior opening and closing disc 6 completes to rotate, described barrier sheet 20 detaches, and waste gas recovers Original pressure, is rapidly introduced into posterior catalysis reduction passage.

When burning under the influence of various factors, the temperature of waste gas discharge is different, and different catalyst optimal processing temperature Degree difference, therefore arranges three kinds of different catalyst of operating temperature and reduces in passage in catalysis, cooperate with opening and closing disc 6, when After temperature sensor 5 detects EGT, according to its temperature, rotary opening closing dish 6 so that the through-hole alignment in opening and closing disc 6 is fitted Should the catalysis reduction passage of temperature range, cover remaining two kinds catalysis reduction passages, waste gas is by matching with its temperature Efficiency maximized catalysis reduction passage, thus realize the maximization of exhaust treatment efficiency and effect.

Described high-temperature catalytic metallic carrier works under 400～600 DEG C of environment, and described middle temperature catalytic metal support is 250 ～work under 400 DEG C of environment, described low-temperature catalyzed metallic carrier works under 150～250 DEG C of environment.

Described high-temperature catalytic metallic carrier includes being loaded with WO₃/TiO₂The metallic carrier of catalyst, WO₃/TiO₂Catalyst It is carried on through the following steps on metallic carrier: (1) carries out alkali cleaning and removes surface and oil contaminant metallic carrier, and soda-wash solution composition is Water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser light Speckle radius is 2.25 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short-pulse laser irradiate clean after metal Carrier surface so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation blast, forms microetch hole, wherein The microetch hole gross area accounts for the 60% of the metal carrier surface gross area；(3) metallic carrier after step (2) processes is in 900 DEG C Roasting 5h so that it is surface forms oxide-film；(4) use sol-gel process in the surface-coated glass ceramics of described metallic carrier Coating, composition is mol ratio SiO₂: Al₂O₃=5:1；(5) butyl titanate, acetic acid and ethanol 1:8:5 in molar ratio stirring is obtained Solution A, ammonium paratungstate is dissolved in oxalic acid solution and obtains solution B, solution B is quantitatively adding in A, is stirred vigorously and obtains 25wt.% WO₃/TiO₂Catalyst colloidal sol, is immersed in 25wt.%WO by the metallic carrier of coating glass ceramic coating₃/TiO₂Catalyst colloidal sol Middle 30min, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C, roasting at 500 DEG C 5h, obtains loading 25wt.%WO₃WO₃/TiO₂The high-temperature catalytic metallic carrier of catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more WO₃/TiO₂Catalyst.When microetch hole, the gross area accounts for the 60% of the metal carrier surface gross area Time, under 400～600 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through laser ablation The catalytic efficiency of high-temperature catalytic metallic carrier improves 35%.

At a temperature of 400～550 DEG C, the catalysis activity with temperature of high-temperature catalytic metallic carrier raises and strengthens, NOx conversion Rate is above 80%, more than 92% when 500 DEG C, downward trend occurs, but NOx still has when 600 DEG C after temperature is higher than 500 DEG C The conversion ratio of 65%.

Described middle temperature catalytic metal support includes being loaded with CeO₂/W₂₅The metallic carrier of Ti catalyst, CeO₂/W₂₅Ti is catalyzed Agent is carried on metallic carrier through the following steps: (1) carries out alkali cleaning and removes surface and oil contaminant, soda-wash solution composition metallic carrier For water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser Spot radius is 2.25 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short-pulse laser irradiate clean after gold Belong to carrier surface so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation blast, form microetch hole, its The middle microetch hole gross area accounts for the 60% of the metal carrier surface gross area；(3) metallic carrier after step (2) processes is in cleaning After metallic carrier roasting 5h in 900 DEG C so that it is surface formed oxide-film；(4) sol-gel process is used to carry at described metal The surface-coated glass ceramic coating of body, composition is mol ratio SiO₂: Al₂O₃=5:1；(5) by butyl titanate, acetic acid and ethanol 1:8:5 stirring in molar ratio obtains solution A, and ammonium paratungstate is dissolved in oxalic acid solution and obtains solution B；(6) solution B is quantitatively adding In A, being stirred vigorously and obtain colloidal sol, room temperature is placed and is obtained 110 DEG C of drying in thermostatic drying chamber after xerogel, then roasting at 600 DEG C Burn 4h, obtain WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst；(7) by quantitative Ce (NO₃)₃·6H₂O is dissolved in water and obtains To cerous nitrate solution, then by WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst is immersed, and obtains after 1h is stirred at room temperature CeO to load 10wt.%Ce₂/W₂₅Ti catalyst colloidal sol, is immersed in CeO by the metallic carrier of coating glass ceramic coating₂/ W₂₅1h in Ti catalyst colloidal sol, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C, then at Roasting 5h at 500 DEG C, obtains being loaded with CeO₂/W₂₅The middle temperature catalytic metal support of Ti catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more CeO₂/W₂₅Ti catalyst.When microetch hole, the gross area accounts for the metal carrier surface gross area When 60%, under 250～400 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through laser incising The catalytic efficiency of the high-temperature catalytic metallic carrier of erosion improves 30%.

At a temperature of 250～300 DEG C, the catalysis activity with temperature of middle temperature catalytic metal support raises and strengthens, NOx conversion Rate is above 60%, and at a temperature of 250～300 DEG C, conversion rate of NOx reaches the highest, close to 80%, after temperature is higher than 400 DEG C The catalysis activity of middle temperature catalytic metal support reduces rapidly.

Described low-temperature catalyzed metallic carrier includes being loaded with Cr₂O₃-SO₄ ^2-/TiO₂The metallic carrier of catalyst, Cr₂O₃- SO₄ ^2-/TiO₂Catalyst is carried on metallic carrier through the following steps: (1) carries out alkali cleaning and removes surface oil metallic carrier Dirt, soda-wash solution composition is water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser facula radius are 2.25 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short pulse impulse Light irradiates the metal carrier surface after cleaning so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation are quick-fried Fried, form microetch hole, wherein the microetch hole gross area accounts for the 60% of the metal carrier surface gross area；(3) after step (2) processes Metallic carrier metallic carrier roasting 5h in 900 DEG C after cleaning so that it is surface forms oxide-film；(4) colloidal sol-solidifying is used Glue method is at the surface-coated glass ceramic coating of described metallic carrier, and composition is mol ratio SiO₂: Al₂O₃=5:1；(5) by metatitanic acid Butyl ester, acetic acid and ethanol 1:8:5 in molar ratio stirring obtain solution A, ammonium paratungstate be dissolved in the sulfuric acid solution of 70% obtain molten Liquid B, is quantitatively adding solution B in A, and wherein sulfate radical is SO with the mol ratio of titanium dioxide₄ ^2-: TiO₂=1:4；(6) by solution B is quantitatively adding in A, is stirred vigorously and obtains colloidal sol, and room temperature is placed and obtained 110 DEG C of drying in thermostatic drying chamber after xerogel, then At 600 DEG C, roasting 4h, obtains WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst；(7) by quantitative Cr (NO₃)₃·9H₂O It is dissolved in water and obtains chromium nitrate solution, then by WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst is immersed, and room temperature is stirred Cr is obtained after mixing 1h₂O₃-SO₄ ^2-/TiO₂Catalyst colloidal sol, is immersed in Cr by the metallic carrier of coating glass ceramic coating₂O₃- SO₄ ^2-/TiO₂1h in catalyst colloidal sol, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C Dry, roasting 5h at 500 DEG C, obtain being loaded with Cr₂O₃-SO₄ ^2-/TiO₂The metallic carrier of catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more Cr₂O₃-SO₄ ^2-/TiO₂Catalyst.When microetch hole, the gross area accounts for the total face of metal carrier surface When long-pending 60%, under 150～250 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through too drastic The catalytic efficiency of the high-temperature catalytic metallic carrier of photoengraving improves 32%.

The low-temperature catalyzed metallic carrier of load 10wt.%Ce is when 150～250 DEG C, and conversion rate of NOx is along with the increase of temperature And gradually rise, close to 100%.In 175～250 DEG C of temperature ranges, conversion rate of NOx is all more than 80%.

Compared to using single catalyst, the NOx ratio discharge used after the catalytic conversion system of the present invention in waste gas from 12.192g/kW h drops to 2.579g/kW h, and treatment effect significantly promotes.

Described micro particle catching unit 10 includes housing and polylith micro particle catching metallic carrier, described micro particle catching metallic carrier Process through the following step: take quantitative chromic nitrate, cobalt nitrate and citric acid and be dissolved in deionized water, wherein chromium ion and citric acid Molecule mol ratio is 1:1.5, and chromium ion concentration is 0.2mol/L.It is applied on metallic carrier after 80 DEG C of complex reaction 5h, institute State micro particle catching metallic carrier and obtain final products after 600 DEG C of roasting 5h.In order to carry high catalytic activity further, at catalyst Surface has supported and has accounted for the precious metals pt that catalyst quality mark is 0.5%.Described final products cut into phase lap after elongate Connecing formation metal gauze, described metal gauze is vertically connected with the metal wire mesh filter 13 forming intensive porous.

Described housing includes that shell body 11 and inner housing 12, described shell body 11 interval wrap up described inner housing 12 so that Form vacuum layer between shell body 11 and inner housing 12, keep the temperature of metal wire mesh filter 13, promote that it passively burns again Raw, reduce the exhaust back pressure in particle trapper.Described inner housing 12 is divided into expansion, filtration fraction and constriction, institute Stating expansion and connect air inlet pipe, described constriction connects exhaustor, the external diameter of the constriction of wherein said inner housing 12 Being 2.5～4 with exhaustor external diameter diameter ratio, the angle of described inner housing 12 expansion is 80 °～100 °.

In particle trapper, the uniformity of flow velocity and particle concentration determines the height of particle trapper inner filtration body utilization rate Low, filter regeneration cycle and the length in filtering bodies service life, in the actual application of particle trapper, particle trapper Exhaust parameter (exhaust entrance speed) and structural parameters (angle of flare, diameter than) are to velocity flow profile and particle concentration distributions Uniformity has very important impact.

In the case of inlet flow rate (inlet velocity and inlet-duct area) is identical, diameter flows through expansion than little inner housing 12 During part, speed reduces less, and the eddy current effect of generation is less, almost without, but, less diameter ratio can make microgranule In catcher, exhaust flow rate is higher, exhaust flow rate skewness, thus during causing actual filtration in particle trapper Collection of particles, at the central axis of metal wire mesh filter 13, increases the weight of the load at metal wire mesh filter 13 central axis. When diameter ratio is 2～4, the VELOCITY DISTRIBUTION in each cross section of particle trapper is more uniform, thus micro-in metal wire mesh filter 13 Grain deposition distribution is the most uniform.Now in the case of same charge flow rate, particle trapper arresting efficiency is 96%.

The angle of flare is the least, and the mistake from air inlet pipe to expansion gets over smooth-going, and the angle of flare is the biggest, the most easily produces eddy current District, and vortex is the most close to central axis, therefore, selecting the angle of flare is 80 °～100 °, now in the feelings of same charge flow rate Under condition, particle trapper arresting efficiency is 95%.

Refering to Fig. 4, described reducing agent feeding unit 14 includes solid urea holding vessel 19, the metering rotor 18 being sequentially connected with With heat resolve pipeline 16, described solid urea holding vessel 19 internal memory is placed with urea powder, and its lower surface is formed slopely with opening The cone structure of mouth.Described metering rotor 18 is cylindric, and its outer surface is interval with the pit accommodating urea powder.Described meter The cental axial position of amount rotor 18 connects actuating device, drives metering rotor 18 to rotate relative to solid urea holding vessel 19.Institute The outer surface interval stating metering rotor 18 is enclosed with the seal bootr 17 being fixed on described solid urea holding vessel 19, described closing The opening part of the cover 17 described cone structure of alignment is provided with through hole, and described seal bootr 17 is directed at described heat resolve pipeline 16 same Being provided with through hole, rotate metering rotor 18, the urea powder in solid urea holding vessel 19 enters in pit, is rotated further metering and turns Son 18, the pit equipped with urea powder turns to be directed at the through hole of described heat resolve pipeline 16, and urea powder drops, waste gas Blowing urea powder and enter heat resolve pipeline 16, described heat resolve pipeline 16 is tortuous to be folded in microwave launcher 15, Urea powder decomposes generation ammonia and Carbimide., the steam in waste gas when microwave launcher 15 under the effect of microwave Carbimide. can be made to decompose, thus produce ammonia.

In being embodied as, described pit is the hemispherical of a diameter of 5mm.

Embodiment two

Refering to Fig. 1, waste old microwave automatic cracking reaction device, including exhaust-gas treatment part, described exhaust-gas treatment portion Divide and include control unit, reducing agent feeding unit 14, catalytic reduction unit 3, micro particle catching unit 10 and temperature sensor 5, institute State catalytic reduction unit 3 to be connected by connecting pipe with described micro particle catching unit 10, and described connecting pipe is provided with branch road Connect described reducing agent feeding unit 14.Described control unit control respectively micro particle catching unit 10, reducing agent feeding unit 14, Catalytic reduction unit 3 and temperature sensor 5.Described catalytic reduction unit 3 air inlet one end is located in described temperature sensor 5.

Described catalytic reduction unit 3 includes rotary shaft 2, air inlet pipe 4 and the exhaustor 9 of connection air inlet pipe 4.Described rotation Axle 2 extends across air inlet pipe 4 and exhaustor 9, the two ends of described rotary shaft 2 along the direction, axis of air inlet pipe 4, exhaustor 9 Connecting has motor 1, described motor 1 that rotary shaft 2 can be driven to rotate.Be arranged in sequence with in described rotary shaft 2 multiple can be around rotary shaft 2 The cylindrical catalysis restorer 7 rotated, the inside of described catalysis restorer 7 is interval with multiple catalysis also along its length Former passage, described recall reduction passage is divided into high-temperature catalytic reduction passage, middle temperature catalysis reduction passage and low-temperature catalyzed reduction Passage.Being provided with spiral helicine high-temperature catalytic metallic carrier in described high-temperature catalytic reduction passage, the catalysis reduction of described middle temperature is logical It is provided with spiral helicine middle temperature catalytic metal support in road, is provided with spiral helicine low temperature in described low-temperature catalyzed reduction passage and urges Change metallic carrier.Described high-temperature catalytic reduction passage, middle temperature catalysis reduction passage and low-temperature catalyzed reduction passage regularity row Cloth.

Being additionally provided with opening and closing disc 6 in described catalysis restorer 7, described opening and closing disc 6 is positioned at one end of catalysis reduction channel inlet. The surface of described opening and closing disc 6 is provided with the through hole of regular arrangement, and rotary opening closing dish 6, on described through-hole alignment catalysis restorer 7 High-temperature catalytic reduction passage, middle temperature catalysis reduction passage or low-temperature catalyzed reduction passage, cover remaining two kinds catalysis reduction passages, Waste gas enters this catalysis reduction passage by through hole and carries out the catalytic reduction reaction of correspondence.

One end of described catalysis restorer 7 air inlet is provided with movable pressure-reducing cushioning structure 8, refering to Fig. 2 and Fig. 3, described Pressure-reducing cushioning structure 8 is the cylinder of hollow or discoid, and the outer surface of described pressure-reducing cushioning structure 8 is interval with multiple opening Mouthful, each opening is inserted with mobilizable barrier sheet 20, when opening and closing disc 6 needs to rotate when, described barrier sheet 20 enters and subtracts Pressure buffer structure 8 is also internally formed waste gas interception structure in pressure-reducing cushioning structure 8, and waste gas need to be through multiple adjacent barrier sheets 20 groups The cavity become could enter posterior catalysis restorer 7, thus temporary reduction exhaust gas pressure so that posterior opening and closing disc 6 can With smooth rotation, it is to avoid exhaust gas leakage occurs.After posterior opening and closing disc 6 completes to rotate, described barrier sheet 20 detaches, and waste gas recovers Original pressure, is rapidly introduced into posterior catalysis reduction passage.

When burning under the influence of various factors, the temperature of waste gas discharge is different, and different catalyst optimal processing temperature Degree difference, therefore arranges three kinds of different catalyst of operating temperature and reduces in passage in catalysis, cooperate with opening and closing disc 6, when After temperature sensor 5 detects EGT, according to its temperature, rotary opening closing dish 6 so that the through-hole alignment in opening and closing disc 6 is fitted Should the catalysis reduction passage of temperature range, cover remaining two kinds catalysis reduction passages, waste gas is by matching with its temperature Efficiency maximized catalysis reduction passage, thus realize the maximization of exhaust treatment efficiency and effect.

Described high-temperature catalytic metallic carrier works under 400～600 DEG C of environment, and described middle temperature catalytic metal support is 250 ～work under 400 DEG C of environment, described low-temperature catalyzed metallic carrier works under 150～250 DEG C of environment.

Described high-temperature catalytic metallic carrier includes being loaded with WO₃/TiO₂The metallic carrier of catalyst, WO₃/TiO₂Catalyst It is carried on through the following steps on metallic carrier: (1) carries out alkali cleaning and removes surface and oil contaminant metallic carrier, and soda-wash solution composition is Water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser light Speckle radius is 2.35 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short-pulse laser irradiate clean after metal Carrier surface so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation blast, forms microetch hole, wherein The microetch hole gross area accounts for the 65% of the metal carrier surface gross area；(3) metallic carrier after step (2) processes is in 900 DEG C Roasting 5h so that it is surface forms oxide-film；(4) use sol-gel process in the surface-coated glass ceramics of described metallic carrier Coating, composition is mol ratio SiO₂: Al₂O₃=5:1；(5) butyl titanate, acetic acid and ethanol 1:8:5 in molar ratio stirring is obtained Solution A, ammonium paratungstate is dissolved in oxalic acid solution and obtains solution B, solution B is quantitatively adding in A, is stirred vigorously and obtains 25wt.% WO₃/TiO₂Catalyst colloidal sol, is immersed in 25wt.%WO by the metallic carrier of coating glass ceramic coating₃/TiO₂Catalyst colloidal sol Middle 30min, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C, roasting at 550 DEG C 5h, obtains loading 25wt.%WO₃WO₃/TiO₂The high-temperature catalytic metallic carrier of catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more WO₃/TiO₂Catalyst.When microetch hole, the gross area accounts for the 65% of the metal carrier surface gross area Time, under 400～600 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through laser ablation The catalytic efficiency of high-temperature catalytic metallic carrier improves 36%.

At a temperature of 400～550 DEG C, the catalysis activity with temperature of high-temperature catalytic metallic carrier raises and strengthens, NOx conversion Rate is above 80%, more than 92% when 500 DEG C, downward trend occurs, but NOx still has when 600 DEG C after temperature is higher than 500 DEG C The conversion ratio of 65%.

Described middle temperature catalytic metal support includes being loaded with CeO₂/W₂₅The metallic carrier of Ti catalyst, CeO₂/W₂₅Ti is catalyzed Agent is carried on metallic carrier through the following steps: (1) carries out alkali cleaning and removes surface and oil contaminant, soda-wash solution composition metallic carrier For water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser Spot radius is 2.35 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short-pulse laser irradiate clean after gold Belong to carrier surface so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation blast, form microetch hole, its The middle microetch hole gross area accounts for the 65% of the metal carrier surface gross area；(3) metallic carrier after step (2) processes is in cleaning After metallic carrier roasting 5h in 900 DEG C so that it is surface formed oxide-film；(4) sol-gel process is used to carry at described metal The surface-coated glass ceramic coating of body, composition is mol ratio SiO₂: Al₂O₃=5:1；(5) by butyl titanate, acetic acid and ethanol 1:8:5 stirring in molar ratio obtains solution A, and ammonium paratungstate is dissolved in oxalic acid solution and obtains solution B；(6) solution B is quantitatively adding In A, being stirred vigorously and obtain colloidal sol, room temperature is placed and is obtained 110 DEG C of drying in thermostatic drying chamber after xerogel, then roasting at 600 DEG C Burn 4h, obtain WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst；(7) by quantitative Ce (NO₃)₃·6H₂O is dissolved in water and obtains To cerous nitrate solution, then by WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst is immersed, and obtains after 1h is stirred at room temperature CeO to load 10wt.%Ce₂/W₂₅Ti catalyst colloidal sol, is immersed in CeO by the metallic carrier of coating glass ceramic coating₂/ W₂₅1h in Ti catalyst colloidal sol, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C, then at Roasting 5h at 550 DEG C, obtains being loaded with CeO₂/W₂₅The middle temperature catalytic metal support of Ti catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more CeO₂/W₂₅Ti catalyst.When microetch hole, the gross area accounts for the metal carrier surface gross area When 60%, under 250～400 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through laser incising The catalytic efficiency of the high-temperature catalytic metallic carrier of erosion improves 29%.

At a temperature of 250～300 DEG C, the catalysis activity with temperature of middle temperature catalytic metal support raises and strengthens, NOx conversion Rate is above 60%, and at a temperature of 250～300 DEG C, conversion rate of NOx reaches the highest, close to 80%, after temperature is higher than 400 DEG C The catalysis activity of middle temperature catalytic metal support reduces rapidly.

Described low-temperature catalyzed metallic carrier includes being loaded with Cr₂O₃-SO₄ ^2-/TiO₂The metallic carrier of catalyst, Cr₂O₃- SO₄ ^2-/TiO₂Catalyst is carried on metallic carrier through the following steps: (1) carries out alkali cleaning and removes surface oil metallic carrier Dirt, soda-wash solution composition is water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser facula radius are 2.35 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short pulse impulse Light irradiates the metal carrier surface after cleaning so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation are quick-fried Fried, form microetch hole, wherein the microetch hole gross area accounts for the 65% of the metal carrier surface gross area；(3) after step (2) processes Metallic carrier metallic carrier roasting 5h in 900 DEG C after cleaning so that it is surface forms oxide-film；(4) colloidal sol-solidifying is used Glue method is at the surface-coated glass ceramic coating of described metallic carrier, and composition is mol ratio SiO₂: Al₂O₃=5:1；(5) by metatitanic acid Butyl ester, acetic acid and ethanol 1:8:5 in molar ratio stirring obtain solution A, ammonium paratungstate be dissolved in the sulfuric acid solution of 70% obtain molten Liquid B, is quantitatively adding solution B in A, and wherein sulfate radical is SO with the mol ratio of titanium dioxide₄ ^2-: TiO₂=1:4；(6) by solution B is quantitatively adding in A, is stirred vigorously and obtains colloidal sol, and room temperature is placed and obtained 110 DEG C of drying in thermostatic drying chamber after xerogel, then At 600 DEG C, roasting 4h, obtains WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst；(7) by quantitative Cr (NO₃)₃·9H₂O It is dissolved in water and obtains chromium nitrate solution, then by WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst is immersed, and room temperature is stirred Cr is obtained after mixing 1h₂O₃-SO₄ ^2-/TiO₂Catalyst colloidal sol, is immersed in Cr by the metallic carrier of coating glass ceramic coating₂O₃- SO₄ ^2-/TiO₂1h in catalyst colloidal sol, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C Dry, roasting 5h at 550 DEG C, obtain being loaded with Cr₂O₃-SO₄ ^2-/TiO₂The metallic carrier of catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more Cr₂O₃-SO₄ ^2-/TiO₂Catalyst.When microetch hole, the gross area accounts for the total face of metal carrier surface When long-pending 65%, under 150～250 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through too drastic The catalytic efficiency of the high-temperature catalytic metallic carrier of photoengraving improves 32%.

The low-temperature catalyzed metallic carrier of load 10wt.%Ce is when 150～250 DEG C, and conversion rate of NOx is along with the increase of temperature And gradually rise, close to 100%.In 175～250 DEG C of temperature ranges, conversion rate of NOx is all more than 80%.

Compared to using single catalyst, the NOx ratio discharge used after the catalytic conversion system of the present invention in waste gas from 12.192g/kW h drops to 1.985g/kW h, and treatment effect significantly promotes.

Described micro particle catching unit 10 includes housing and polylith micro particle catching metallic carrier, described micro particle catching metallic carrier Process through the following step: take quantitative chromic nitrate, cobalt nitrate and citric acid and be dissolved in deionized water, wherein chromium ion and citric acid Molecule mol ratio is 1:1.5, and chromium ion concentration is 0.2mol/L.After 80 DEG C of complex reaction 5h, it is applied in micro particle catching metal carry On body, described micro particle catching metallic carrier obtains final products after 600 DEG C of roasting 5h.In order to carry high catalytic activity further, Support at catalyst surface and accounted for the precious metals pt that catalyst quality mark is 0.5%.Described final products cut into elongate Rear mutually overlap joint forms metal gauze, and described metal gauze is vertically connected with the metal wire mesh filter 13 forming intensive porous.

Described housing includes that shell body 11 and inner housing 12, described shell body 11 interval wrap up described inner housing 12 so that Form vacuum layer between shell body 11 and inner housing 12, keep the temperature of metal wire mesh filter 13, promote that it passively burns again Raw, reduce the exhaust back pressure in particle trapper.Described inner housing 12 is divided into expansion, filtration fraction and constriction, institute Stating expansion and connect air inlet pipe, described constriction connects exhaustor, the external diameter of the constriction of wherein said inner housing 12 Being 2.5～4 with exhaustor external diameter diameter ratio, the angle of described inner housing 12 expansion is 80 °～100 °.

In particle trapper, the uniformity of flow velocity and particle concentration determines the height of particle trapper inner filtration body utilization rate Low, filter regeneration cycle and the length in filtering bodies service life, in the actual application of particle trapper, particle trapper Exhaust parameter (exhaust entrance speed) and structural parameters (angle of flare, diameter than) are to velocity flow profile and particle concentration distributions Uniformity has very important impact.

In the case of inlet flow rate (inlet velocity and inlet-duct area) is identical, diameter flows through expansion than little inner housing 12 During part, speed reduces less, and the eddy current effect of generation is less, almost without, but, less diameter ratio can make microgranule In catcher, exhaust flow rate is higher, exhaust flow rate skewness, thus during causing actual filtration in particle trapper Collection of particles, at the central axis of metal wire mesh filter 13, increases the weight of the load at metal wire mesh filter 13 central axis. When diameter ratio is 2～4, the VELOCITY DISTRIBUTION in each cross section of particle trapper is more uniform, thus micro-in metal wire mesh filter 13 Grain deposition distribution is the most uniform.Now in the case of same charge flow rate, particle trapper arresting efficiency is 96%.

The angle of flare is the least, and the mistake from air inlet pipe to expansion gets over smooth-going, and the angle of flare is the biggest, the most easily produces eddy current District, and vortex is the most close to central axis, therefore, selecting the angle of flare is 80 °～100 °, now in the feelings of same charge flow rate Under condition, particle trapper arresting efficiency is 95%.

Refering to Fig. 4, described reducing agent feeding unit 14 includes solid urea holding vessel 19, the metering rotor 18 being sequentially connected with With heat resolve pipeline 16, described solid urea holding vessel 19 internal memory is placed with urea powder, and its lower surface is formed slopely with opening The cone structure of mouth.Described metering rotor 18 is cylindric, and its outer surface is interval with the pit accommodating urea powder.Described meter The cental axial position of amount rotor 18 connects actuating device, drives metering rotor 18 to rotate relative to solid urea holding vessel 19.Institute The outer surface interval stating metering rotor 18 is enclosed with the seal bootr 17 being fixed on described solid urea holding vessel 19, described closing The opening part of the cover 17 described cone structure of alignment is provided with through hole, and described seal bootr 17 is directed at described heat resolve pipeline 16 same Being provided with through hole, rotate metering rotor 18, the urea powder in solid urea holding vessel 19 enters in pit, is rotated further metering and turns Son 18, the pit equipped with urea powder turns to be directed at the through hole of described heat resolve pipeline 16, and urea powder drops, waste gas Blowing urea powder and enter heat resolve pipeline 16, described heat resolve pipeline 16 is tortuous to be folded in microwave launcher 15, Urea powder decomposes generation ammonia and Carbimide., the steam in waste gas when microwave launcher 15 under the effect of microwave Carbimide. can be made to decompose, thus produce ammonia.

In being embodied as, described pit is the hemispherical of a diameter of 5mm.

Embodiment three

Refering to Fig. 1, waste old microwave automatic cracking reaction device, including exhaust-gas treatment part, described exhaust-gas treatment portion Divide and include control unit, reducing agent feeding unit 14, catalytic reduction unit 3, micro particle catching unit 10 and temperature sensor 5, institute State catalytic reduction unit 3 to be connected by connecting pipe with described micro particle catching unit 10, and described connecting pipe is provided with branch road Connect described reducing agent feeding unit 14.Described control unit control respectively micro particle catching unit 10, reducing agent feeding unit 14, Catalytic reduction unit 3 and temperature sensor 5.Described catalytic reduction unit 3 air inlet one end is located in described temperature sensor 5.

Described catalytic reduction unit 3 includes rotary shaft 2, air inlet pipe 4 and the exhaustor 9 of connection air inlet pipe 4.Described rotation Axle 2 extends across air inlet pipe 4 and exhaustor 9, the two ends of described rotary shaft 2 along the direction, axis of air inlet pipe 4, exhaustor 9 Connecting has motor 1, described motor 1 that rotary shaft 2 can be driven to rotate.Be arranged in sequence with in described rotary shaft 2 multiple can be around rotary shaft 2 The cylindrical catalysis restorer 7 rotated, the inside of described catalysis restorer 7 is interval with multiple catalysis also along its length Former passage, described recall reduction passage is divided into high-temperature catalytic reduction passage, middle temperature catalysis reduction passage and low-temperature catalyzed reduction Passage.Being provided with spiral helicine high-temperature catalytic metallic carrier in described high-temperature catalytic reduction passage, the catalysis reduction of described middle temperature is logical It is provided with spiral helicine middle temperature catalytic metal support in road, is provided with spiral helicine low temperature in described low-temperature catalyzed reduction passage and urges Change metallic carrier.Described high-temperature catalytic reduction passage, middle temperature catalysis reduction passage and low-temperature catalyzed reduction passage regularity row Cloth.

Being additionally provided with opening and closing disc 6 in described catalysis restorer 7, described opening and closing disc 6 is positioned at one end of catalysis reduction channel inlet. The surface of described opening and closing disc 6 is provided with the through hole of regular arrangement, and rotary opening closing dish 6, on described through-hole alignment catalysis restorer 7 High-temperature catalytic reduction passage, middle temperature catalysis reduction passage or low-temperature catalyzed reduction passage, cover remaining two kinds catalysis reduction passages, Waste gas enters this catalysis reduction passage by through hole and carries out the catalytic reduction reaction of correspondence.

One end of described catalysis restorer 7 air inlet is provided with movable pressure-reducing cushioning structure 8, refering to Fig. 2 and Fig. 3, described Pressure-reducing cushioning structure 8 is the cylinder of hollow or discoid, and the outer surface of described pressure-reducing cushioning structure 8 is interval with multiple opening Mouthful, each opening is inserted with mobilizable barrier sheet 20, when opening and closing disc 6 needs to rotate when, described barrier sheet 20 enters and subtracts Pressure buffer structure 8 is also internally formed waste gas interception structure in pressure-reducing cushioning structure 8, and waste gas need to be through multiple adjacent barrier sheets 20 groups The cavity become could enter posterior catalysis restorer 7, thus temporary reduction exhaust gas pressure so that posterior opening and closing disc 6 can With smooth rotation, it is to avoid exhaust gas leakage occurs.After posterior opening and closing disc 6 completes to rotate, described barrier sheet 20 detaches, and waste gas recovers Original pressure, is rapidly introduced into posterior catalysis reduction passage.

When burning under the influence of various factors, the temperature of waste gas discharge is different, and different catalyst optimal processing temperature Degree difference, therefore arranges three kinds of different catalyst of operating temperature and reduces in passage in catalysis, cooperate with opening and closing disc 6, when After temperature sensor 5 detects EGT, according to its temperature, rotary opening closing dish 6 so that the through-hole alignment in opening and closing disc 6 is fitted Should the catalysis reduction passage of temperature range, cover remaining two kinds catalysis reduction passages, waste gas is by matching with its temperature Efficiency maximized catalysis reduction passage, thus realize the maximization of exhaust treatment efficiency and effect.

Described high-temperature catalytic metallic carrier works under 400～600 DEG C of environment, and described middle temperature catalytic metal support is 250 ～work under 400 DEG C of environment, described low-temperature catalyzed metallic carrier works under 150～250 DEG C of environment.

Described high-temperature catalytic metallic carrier includes being loaded with WO₃/TiO₂The metallic carrier of catalyst, WO₃/TiO₂Catalyst It is carried on through the following steps on metallic carrier: (1) carries out alkali cleaning and removes surface and oil contaminant metallic carrier, and soda-wash solution composition is Water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser light Speckle radius is 2.40 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short-pulse laser irradiate clean after metal Carrier surface so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation blast, forms microetch hole, wherein The microetch hole gross area accounts for the 70% of the metal carrier surface gross area；(3) metallic carrier after step (2) processes is in 900 DEG C Roasting 5h so that it is surface forms oxide-film；(4) use sol-gel process in the surface-coated glass ceramics of described metallic carrier Coating, composition is mol ratio SiO₂: Al₂O₃=5:1；(5) butyl titanate, acetic acid and ethanol 1:8:5 in molar ratio stirring is obtained Solution A, ammonium paratungstate is dissolved in oxalic acid solution and obtains solution B, solution B is quantitatively adding in A, is stirred vigorously and obtains 25wt.% WO₃/TiO₂Catalyst colloidal sol, is immersed in 25wt.%WO by the metallic carrier of coating glass ceramic coating₃/TiO₂Catalyst colloidal sol Middle 30min, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C, roasting at 500 DEG C 6h, obtains loading 25wt.%WO₃WO₃/TiO₂The high-temperature catalytic metallic carrier of catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more WO₃/TiO₂Catalyst.When microetch hole, the gross area accounts for the 70% of the metal carrier surface gross area Time, under 400～600 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through laser ablation The catalytic efficiency of high-temperature catalytic metallic carrier improves 34%.

At a temperature of 400～550 DEG C, the catalysis activity with temperature of high-temperature catalytic metallic carrier raises and strengthens, NOx conversion Rate is above 80%, more than 92% when 500 DEG C, downward trend occurs, but NOx still has when 600 DEG C after temperature is higher than 500 DEG C The conversion ratio of 65%.

Described middle temperature catalytic metal support includes being loaded with CeO₂/W₂₅The metallic carrier of Ti catalyst, CeO₂/W₂₅Ti is catalyzed Agent is carried on metallic carrier through the following steps: (1) carries out alkali cleaning and removes surface and oil contaminant, soda-wash solution composition metallic carrier For water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser Spot radius is 2.40 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short-pulse laser irradiate clean after gold Belong to carrier surface so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation blast, form microetch hole, its The middle microetch hole gross area accounts for the 70% of the metal carrier surface gross area；(3) metallic carrier after step (2) processes is in cleaning After metallic carrier roasting 5h in 900 DEG C so that it is surface formed oxide-film；(4) sol-gel process is used to carry at described metal The surface-coated glass ceramic coating of body, composition is mol ratio SiO₂: Al₂O₃=5:1；(5) by butyl titanate, acetic acid and ethanol 1:8:5 stirring in molar ratio obtains solution A, and ammonium paratungstate is dissolved in oxalic acid solution and obtains solution B；(6) solution B is quantitatively adding In A, being stirred vigorously and obtain colloidal sol, room temperature is placed and is obtained 110 DEG C of drying in thermostatic drying chamber after xerogel, then roasting at 600 DEG C Burn 4h, obtain WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst；(7) by quantitative Ce (NO₃)₃·6H₂O is dissolved in water and obtains To cerous nitrate solution, then by WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst is immersed, and obtains after 1h is stirred at room temperature CeO to load 10wt.%Ce₂/W₂₅Ti catalyst colloidal sol, is immersed in CeO by the metallic carrier of coating glass ceramic coating₂/ W₂₅1h in Ti catalyst colloidal sol, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C, then at Roasting 6h at 500 DEG C, obtains being loaded with CeO₂/W₂₅The middle temperature catalytic metal support of Ti catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more CeO₂/W₂₅Ti catalyst.When microetch hole, the gross area accounts for the metal carrier surface gross area When 70%, under 250～400 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through laser incising The catalytic efficiency of the high-temperature catalytic metallic carrier of erosion improves 32%.

At a temperature of 250～300 DEG C, the catalysis activity with temperature of middle temperature catalytic metal support raises and strengthens, NOx conversion Rate is above 60%, and at a temperature of 250～300 DEG C, conversion rate of NOx reaches the highest, close to 80%, after temperature is higher than 400 DEG C The catalysis activity of middle temperature catalytic metal support reduces rapidly.

Described low-temperature catalyzed metallic carrier includes being loaded with Cr₂O₃-SO₄ ^2-/TiO₂The metallic carrier of catalyst, Cr₂O₃- SO₄ ^2-/TiO₂Catalyst is carried on metallic carrier through the following steps: (1) carries out alkali cleaning and removes surface oil metallic carrier Dirt, soda-wash solution composition is water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser facula radius are 2.40 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short pulse impulse Light irradiates the metal carrier surface after cleaning so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation are quick-fried Fried, form microetch hole, wherein the microetch hole gross area accounts for the 70% of the metal carrier surface gross area；(3) after step (2) processes Metallic carrier metallic carrier roasting 5h in 900 DEG C after cleaning so that it is surface forms oxide-film；(4) colloidal sol-solidifying is used Glue method is at the surface-coated glass ceramic coating of described metallic carrier, and composition is mol ratio SiO₂: Al₂O₃=5:1；(5) by metatitanic acid Butyl ester, acetic acid and ethanol 1:8:5 in molar ratio stirring obtain solution A, ammonium paratungstate be dissolved in the sulfuric acid solution of 70% obtain molten Liquid B, is quantitatively adding solution B in A, and wherein sulfate radical is SO with the mol ratio of titanium dioxide₄ ^2-: TiO₂=1:4；(6) by solution B is quantitatively adding in A, is stirred vigorously and obtains colloidal sol, and room temperature is placed and obtained 110 DEG C of drying in thermostatic drying chamber after xerogel, then At 600 DEG C, roasting 4h, obtains WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst；(7) by quantitative Cr (NO₃)₃·9H₂O It is dissolved in water and obtains chromium nitrate solution, then by WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst is immersed, and room temperature is stirred Cr is obtained after mixing 1h₂O₃-SO₄ ^2-/TiO₂Catalyst colloidal sol, is immersed in Cr by the metallic carrier of coating glass ceramic coating₂O₃- SO₄ ^2-/TiO₂1h in catalyst colloidal sol, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C Dry, roasting 6h at 500 DEG C, obtain being loaded with Cr₂O₃-SO₄ ^2-/TiO₂The metallic carrier of catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more Cr₂O₃-SO₄ ^2-/TiO₂Catalyst.When microetch hole, the gross area accounts for the total face of metal carrier surface When long-pending 70%, under 150～250 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through too drastic The catalytic efficiency of the high-temperature catalytic metallic carrier of photoengraving improves 31%.

The low-temperature catalyzed metallic carrier of load 10wt.%Ce is when 150～250 DEG C, and conversion rate of NOx is along with the increase of temperature And gradually rise, close to 100%.In 175～250 DEG C of temperature ranges, conversion rate of NOx is all more than 80%.

Compared to using single catalyst, the NOx ratio discharge used after the catalytic conversion system of the present invention in waste gas from 12.192g/kW h drops to 2.174g/kW h, and treatment effect significantly promotes.

Described micro particle catching unit 10 includes housing and polylith micro particle catching metallic carrier, described micro particle catching metallic carrier Process through the following step: take quantitative chromic nitrate, cobalt nitrate and citric acid and be dissolved in deionized water, wherein chromium ion and citric acid Molecule mol ratio is 1:1.5, and chromium ion concentration is 0.2mol/L.After 80 DEG C of complex reaction 5h, it is applied in micro particle catching metal carry On body, described micro particle catching metallic carrier obtains final products after 600 DEG C of roasting 5h.In order to carry high catalytic activity further, Support at catalyst surface and accounted for the precious metals pt that catalyst quality mark is 0.5%.Described final products cut into elongate Rear mutually overlap joint forms metal gauze, and described metal gauze is vertically connected with the metal wire mesh filter 13 forming intensive porous.

Described housing includes that shell body 11 and inner housing 12, described shell body 11 interval wrap up described inner housing 12 so that Form vacuum layer between shell body 11 and inner housing 12, keep the temperature of metal wire mesh filter 13, promote that it passively burns again Raw, reduce the exhaust back pressure in particle trapper.Described inner housing 12 is divided into expansion, filtration fraction and constriction, institute Stating expansion and connect air inlet pipe, described constriction connects exhaustor, the external diameter of the constriction of wherein said inner housing 12 Being 2.5～4 with exhaustor external diameter diameter ratio, the angle of described inner housing 12 expansion is 80 °～100 °.

In particle trapper, the uniformity of flow velocity and particle concentration determines the height of particle trapper inner filtration body utilization rate Low, filter regeneration cycle and the length in filtering bodies service life, in the actual application of particle trapper, particle trapper Exhaust parameter (exhaust entrance speed) and structural parameters (angle of flare, diameter than) are to velocity flow profile and particle concentration distributions Uniformity has very important impact.

In the case of inlet flow rate (inlet velocity and inlet-duct area) is identical, diameter flows through expansion than little inner housing 12 During part, speed reduces less, and the eddy current effect of generation is less, almost without, but, less diameter ratio can make microgranule In catcher, exhaust flow rate is higher, exhaust flow rate skewness, thus during causing actual filtration in particle trapper Collection of particles, at the central axis of metal wire mesh filter 13, increases the weight of the load at metal wire mesh filter 13 central axis. When diameter ratio is 2～4, the VELOCITY DISTRIBUTION in each cross section of particle trapper is more uniform, thus micro-in metal wire mesh filter 13 Grain deposition distribution is the most uniform.Now in the case of same charge flow rate, particle trapper arresting efficiency is 96%.

The angle of flare is the least, and the mistake from air inlet pipe to expansion gets over smooth-going, and the angle of flare is the biggest, the most easily produces eddy current District, and vortex is the most close to central axis, therefore, selecting the angle of flare is 80 °～100 °, now in the feelings of same charge flow rate Under condition, particle trapper arresting efficiency is 95%.

Refering to Fig. 4, described reducing agent feeding unit 14 includes solid urea holding vessel 19, the metering rotor 18 being sequentially connected with With heat resolve pipeline 16, described solid urea holding vessel 19 internal memory is placed with urea powder, and its lower surface is formed slopely with opening The cone structure of mouth.Described metering rotor 18 is cylindric, and its outer surface is interval with the pit accommodating urea powder.Described meter The cental axial position of amount rotor 18 connects actuating device, drives metering rotor 18 to rotate relative to solid urea holding vessel 19.Institute The outer surface interval stating metering rotor 18 is enclosed with the seal bootr 17 being fixed on described solid urea holding vessel 19, described closing The opening part of the cover 17 described cone structure of alignment is provided with through hole, and described seal bootr 17 is directed at described heat resolve pipeline 16 same Being provided with through hole, rotate metering rotor 18, the urea powder in solid urea holding vessel 19 enters in pit, is rotated further metering and turns Son 18, the pit equipped with urea powder turns to be directed at the through hole of described heat resolve pipeline 16, and urea powder drops, waste gas Blowing urea powder and enter heat resolve pipeline 16, described heat resolve pipeline 16 is tortuous to be folded in microwave launcher 15, Urea powder decomposes generation ammonia and Carbimide., the steam in waste gas when microwave launcher 15 under the effect of microwave Carbimide. can be made to decompose, thus produce ammonia.

In being embodied as, described pit is the hemispherical of a diameter of 5mm.

Embodiment four

Refering to Fig. 1, waste old microwave automatic cracking reaction device, including exhaust-gas treatment part, described exhaust-gas treatment portion Divide and include control unit, reducing agent feeding unit 14, catalytic reduction unit 3, micro particle catching unit 10 and temperature sensor 5, institute State catalytic reduction unit 3 to be connected by connecting pipe with described micro particle catching unit 10, and described connecting pipe is provided with branch road Connect described reducing agent feeding unit 14.Described control unit control respectively micro particle catching unit 10, reducing agent feeding unit 14, Catalytic reduction unit 3 and temperature sensor 5.Described catalytic reduction unit 3 air inlet one end is located in described temperature sensor 5.

Described catalytic reduction unit 3 includes rotary shaft 2, air inlet pipe 4 and the exhaustor 9 of connection air inlet pipe 4.Described rotation Axle 2 extends across air inlet pipe 4 and exhaustor 9, the two ends of described rotary shaft 2 along the direction, axis of air inlet pipe 4, exhaustor 9 Connecting has motor 1, described motor 1 that rotary shaft 2 can be driven to rotate.Be arranged in sequence with in described rotary shaft 2 multiple can be around rotary shaft 2 The cylindrical catalysis restorer 7 rotated, the inside of described catalysis restorer 7 is interval with multiple catalysis also along its length Former passage, described recall reduction passage is divided into high-temperature catalytic reduction passage, middle temperature catalysis reduction passage and low-temperature catalyzed reduction Passage.Being provided with spiral helicine high-temperature catalytic metallic carrier in described high-temperature catalytic reduction passage, the catalysis reduction of described middle temperature is logical It is provided with spiral helicine middle temperature catalytic metal support in road, is provided with spiral helicine low temperature in described low-temperature catalyzed reduction passage and urges Change metallic carrier.Described high-temperature catalytic reduction passage, middle temperature catalysis reduction passage and low-temperature catalyzed reduction passage regularity row Cloth.

Being additionally provided with opening and closing disc 6 in described catalysis restorer 7, described opening and closing disc 6 is positioned at one end of catalysis reduction channel inlet. The surface of described opening and closing disc 6 is provided with the through hole of regular arrangement, and rotary opening closing dish 6, on described through-hole alignment catalysis restorer 7 High-temperature catalytic reduction passage, middle temperature catalysis reduction passage or low-temperature catalyzed reduction passage, cover remaining two kinds catalysis reduction passages, Waste gas enters this catalysis reduction passage by through hole and carries out the catalytic reduction reaction of correspondence.

One end of described catalysis restorer 7 air inlet is provided with movable pressure-reducing cushioning structure 8, refering to Fig. 2 and Fig. 3, described Pressure-reducing cushioning structure 8 is the cylinder of hollow or discoid, and the outer surface of described pressure-reducing cushioning structure 8 is interval with multiple opening Mouthful, each opening is inserted with mobilizable barrier sheet 20, when opening and closing disc 6 needs to rotate when, described barrier sheet 20 enters and subtracts Pressure buffer structure 8 is also internally formed waste gas interception structure in pressure-reducing cushioning structure 8, and waste gas need to be through multiple adjacent barrier sheets 20 groups The cavity become could enter posterior catalysis restorer 7, thus temporary reduction exhaust gas pressure so that posterior opening and closing disc 6 can With smooth rotation, it is to avoid exhaust gas leakage occurs.After posterior opening and closing disc 6 completes to rotate, described barrier sheet 20 detaches, and waste gas recovers Original pressure, is rapidly introduced into posterior catalysis reduction passage.

When burning under the influence of various factors, the temperature of waste gas discharge is different, and different catalyst optimal processing temperature Degree difference, therefore arranges three kinds of different catalyst of operating temperature and reduces in passage in catalysis, cooperate with opening and closing disc 6, when After temperature sensor 5 detects EGT, according to its temperature, rotary opening closing dish 6 so that the through-hole alignment in opening and closing disc 6 is fitted Should the catalysis reduction passage of temperature range, cover remaining two kinds catalysis reduction passages, waste gas is by matching with its temperature Efficiency maximized catalysis reduction passage, thus realize the maximization of exhaust treatment efficiency and effect.

Described high-temperature catalytic metallic carrier works under 400～600 DEG C of environment, and described middle temperature catalytic metal support is 250 ～work under 400 DEG C of environment, described low-temperature catalyzed metallic carrier works under 150～250 DEG C of environment.

Described high-temperature catalytic metallic carrier includes being loaded with WO₃/TiO₂The metallic carrier of catalyst, WO₃/TiO₂Catalyst It is carried on through the following steps on metallic carrier: (1) carries out alkali cleaning and removes surface and oil contaminant metallic carrier, and soda-wash solution composition is Water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser light Speckle radius is 2.45 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short-pulse laser irradiate clean after metal Carrier surface so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation blast, forms microetch hole, wherein The microetch hole gross area accounts for the 75% of the metal carrier surface gross area；(3) metallic carrier after step (2) processes is in 900 DEG C Roasting 5h so that it is surface forms oxide-film；(4) use sol-gel process in the surface-coated glass ceramics of described metallic carrier Coating, composition is mol ratio SiO₂: Al₂O₃=5:1；(5) butyl titanate, acetic acid and ethanol 1:8:5 in molar ratio stirring is obtained Solution A, ammonium paratungstate is dissolved in oxalic acid solution and obtains solution B, solution B is quantitatively adding in A, is stirred vigorously and obtains 25wt.% WO₃/TiO₂Catalyst colloidal sol, is immersed in 25wt.%WO by the metallic carrier of coating glass ceramic coating₃/TiO₂Catalyst colloidal sol Middle 30min, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C, roasting at 550 DEG C 6h, obtains loading 25wt.%WO₃WO₃/TiO₂The high-temperature catalytic metallic carrier of catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more WO₃/TiO₂Catalyst.When microetch hole, the gross area accounts for the 75% of the metal carrier surface gross area Time, under 400～600 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through laser ablation The catalytic efficiency of high-temperature catalytic metallic carrier improves 33%.

At a temperature of 400～550 DEG C, the catalysis activity with temperature of high-temperature catalytic metallic carrier raises and strengthens, NOx conversion Rate is above 80%, more than 92% when 500 DEG C, downward trend occurs, but NOx still has when 600 DEG C after temperature is higher than 500 DEG C The conversion ratio of 65%.

Described middle temperature catalytic metal support includes being loaded with CeO₂/W₂₅The metallic carrier of Ti catalyst, CeO₂/W₂₅Ti is catalyzed Agent is carried on metallic carrier through the following steps: (1) carries out alkali cleaning and removes surface and oil contaminant, soda-wash solution composition metallic carrier For water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser Spot radius is 2.45 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short-pulse laser irradiate clean after gold Belong to carrier surface so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation blast, form microetch hole, its The middle microetch hole gross area accounts for the 75% of the metal carrier surface gross area；(3) metallic carrier after step (2) processes is in cleaning After metallic carrier roasting 5h in 900 DEG C so that it is surface formed oxide-film；(4) sol-gel process is used to carry at described metal The surface-coated glass ceramic coating of body, composition is mol ratio SiO₂: Al₂O₃=5:1；(5) by butyl titanate, acetic acid and ethanol 1:8:5 stirring in molar ratio obtains solution A, and ammonium paratungstate is dissolved in oxalic acid solution and obtains solution B；(6) solution B is quantitatively adding In A, being stirred vigorously and obtain colloidal sol, room temperature is placed and is obtained 110 DEG C of drying in thermostatic drying chamber after xerogel, then roasting at 600 DEG C Burn 4h, obtain WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst；(7) by quantitative Ce (NO₃)₃·6H₂O is dissolved in water and obtains To cerous nitrate solution, then by WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst is immersed, and obtains after 1h is stirred at room temperature CeO to load 10wt.%Ce₂/W₂₅Ti catalyst colloidal sol, is immersed in CeO by the metallic carrier of coating glass ceramic coating₂/ W₂₅1h in Ti catalyst colloidal sol, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C, then at Roasting 6h at 550 DEG C, obtains being loaded with CeO₂/W₂₅The middle temperature catalytic metal support of Ti catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more CeO₂/W₂₅Ti catalyst.When microetch hole, the gross area accounts for the metal carrier surface gross area When 60%, under 250～400 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through laser incising The catalytic efficiency of the high-temperature catalytic metallic carrier of erosion improves 30%.

At a temperature of 250～300 DEG C, the catalysis activity with temperature of middle temperature catalytic metal support raises and strengthens, NOx conversion Rate is above 60%, and at a temperature of 250～300 DEG C, conversion rate of NOx reaches the highest, close to 80%, after temperature is higher than 400 DEG C The catalysis activity of middle temperature catalytic metal support reduces rapidly.

Described low-temperature catalyzed metallic carrier includes being loaded with Cr₂O₃-SO₄ ^2-/TiO₂The metallic carrier Cr of catalyst₂O₃- SO₄ ^2-/TiO₂Catalyst is carried on metallic carrier through the following steps: (1) carries out alkali cleaning and removes surface oil metallic carrier Dirt, soda-wash solution composition is water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser facula radius are 2.45 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short pulse impulse Light irradiates the metal carrier surface after cleaning so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation are quick-fried Fried, form microetch hole, wherein the microetch hole gross area accounts for the 75% of the metal carrier surface gross area；(3) after step (2) processes Metallic carrier metallic carrier roasting 5h in 900 DEG C after cleaning so that it is surface forms oxide-film；(4) colloidal sol-solidifying is used Glue method is at the surface-coated glass ceramic coating of described metallic carrier, and composition is mol ratio SiO₂: Al₂O₃=5:1；(5) by metatitanic acid Butyl ester, acetic acid and ethanol 1:8:5 in molar ratio stirring obtain solution A, ammonium paratungstate be dissolved in the sulfuric acid solution of 70% obtain molten Liquid B, is quantitatively adding solution B in A, and wherein sulfate radical is SO with the mol ratio of titanium dioxide₄ ^2-: TiO₂=1:4；(6) by solution B is quantitatively adding in A, is stirred vigorously and obtains colloidal sol, and room temperature is placed and obtained 110 DEG C of drying in thermostatic drying chamber after xerogel, then At 600 DEG C, roasting 4h, obtains WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst；(7) by quantitative Cr (NO₃)₃·9H₂O It is dissolved in water and obtains chromium nitrate solution, then by WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst is immersed, and room temperature is stirred Cr is obtained after mixing 1h₂O₃-SO₄ ^2-/TiO₂Catalyst colloidal sol, is immersed in Cr by the metallic carrier of coating glass ceramic coating₂O₃- SO₄ ^2-/TiO₂1h in catalyst colloidal sol, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C Dry, roasting 6h at 550 DEG C, obtain being loaded with Cr₂O₃-SO₄ ^2-/TiO₂The metallic carrier of catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more Cr₂O₃-SO₄ ^2-/TiO₂Catalyst.When microetch hole, the gross area accounts for the total face of metal carrier surface When long-pending 75%, under 150～250 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through too drastic The catalytic efficiency of the high-temperature catalytic metallic carrier of photoengraving improves 29%.

The low-temperature catalyzed metallic carrier of load 10wt.%Ce is when 150～250 DEG C, and conversion rate of NOx is along with the increase of temperature And gradually rise, close to 100%.In 175～250 DEG C of temperature ranges, conversion rate of NOx is all more than 80%.

Compared to using single catalyst, the NOx ratio discharge used after the catalytic conversion system of the present invention in waste gas from 12.192g/kW h drops to 2.063g/kW h, and treatment effect significantly promotes.

Described micro particle catching unit 10 includes housing and polylith micro particle catching metallic carrier, described micro particle catching metallic carrier Process through the following step: take quantitative chromic nitrate, cobalt nitrate and citric acid and be dissolved in deionized water, wherein chromium ion and citric acid Molecule mol ratio is 1:1.5, and chromium ion concentration is 0.2mol/L.After 80 DEG C of complex reaction 5h, it is applied in micro particle catching metal carry On body, described micro particle catching metallic carrier obtains final products after 600 DEG C of roasting 5h.In order to carry high catalytic activity further, Support at catalyst surface and accounted for the precious metals pt that catalyst quality mark is 0.5%.Described final products cut into elongate Rear mutually overlap joint forms metal gauze, and described metal gauze is vertically connected with the metal wire mesh filter 13 forming intensive porous

Described housing includes that shell body 11 and inner housing 12, described shell body 11 interval wrap up described inner housing 12 so that Form vacuum layer between shell body 11 and inner housing 12, keep the temperature of metal wire mesh filter 13, promote that it passively burns again Raw, reduce the exhaust back pressure in particle trapper.Described inner housing 12 is divided into expansion, filtration fraction and constriction, institute Stating expansion and connect air inlet pipe, described constriction connects exhaustor, the external diameter of the constriction of wherein said inner housing 12 Being 2.5～4 with exhaustor external diameter diameter ratio, the angle of described inner housing 12 expansion is 80 °～100 °.

In particle trapper, the uniformity of flow velocity and particle concentration determines the height of particle trapper inner filtration body utilization rate Low, filter regeneration cycle and the length in filtering bodies service life, in the actual application of particle trapper, particle trapper Exhaust parameter (exhaust entrance speed) and structural parameters (angle of flare, diameter than) are to velocity flow profile and particle concentration distributions Uniformity has very important impact.

In the case of inlet flow rate (inlet velocity and inlet-duct area) is identical, diameter flows through expansion than little inner housing 12 During part, speed reduces less, and the eddy current effect of generation is less, almost without, but, less diameter ratio can make microgranule In catcher, exhaust flow rate is higher, exhaust flow rate skewness, thus during causing actual filtration in particle trapper Collection of particles, at the central axis of metal wire mesh filter 13, increases the weight of the load at metal wire mesh filter 13 central axis. When diameter ratio is 2～4, the VELOCITY DISTRIBUTION in each cross section of particle trapper is more uniform, thus micro-in metal wire mesh filter 13 Grain deposition distribution is the most uniform.Now in the case of same charge flow rate, particle trapper arresting efficiency is 96%.

The angle of flare is the least, and the mistake from air inlet pipe to expansion gets over smooth-going, and the angle of flare is the biggest, the most easily produces eddy current District, and vortex is the most close to central axis, therefore, selecting the angle of flare is 80 °～100 °, now in the feelings of same charge flow rate Under condition, particle trapper arresting efficiency is 95%.

Refering to Fig. 4, described reducing agent feeding unit 14 includes solid urea holding vessel 19, the metering rotor 18 being sequentially connected with With heat resolve pipeline 16, described solid urea holding vessel 19 internal memory is placed with urea powder, and its lower surface is formed slopely with opening The cone structure of mouth.Described metering rotor 18 is cylindric, and its outer surface is interval with the pit accommodating urea powder.Described meter The cental axial position of amount rotor 18 connects actuating device, drives metering rotor 18 to rotate relative to solid urea holding vessel 19.Institute The outer surface interval stating metering rotor 18 is enclosed with the seal bootr 17 being fixed on described solid urea holding vessel 19, described closing The opening part of the cover 17 described cone structure of alignment is provided with through hole, and described seal bootr 17 is directed at described heat resolve pipeline 16 same Being provided with through hole, rotate metering rotor 18, the urea powder in solid urea holding vessel 19 enters in pit, is rotated further metering and turns Son 18, the pit equipped with urea powder turns to be directed at the through hole of described heat resolve pipeline 16, and urea powder drops, waste gas Blowing urea powder and enter heat resolve pipeline 16, described heat resolve pipeline 16 is tortuous to be folded in microwave launcher 15, Urea powder decomposes generation ammonia and Carbimide., the steam in waste gas when microwave launcher 15 under the effect of microwave Carbimide. can be made to decompose, thus produce ammonia.

In being embodied as, described pit is the hemispherical of a diameter of 5mm.

Embodiment five

Refering to Fig. 1, waste old microwave automatic cracking reaction device, including exhaust-gas treatment part, described exhaust-gas treatment portion Divide and include control unit, reducing agent feeding unit 14, catalytic reduction unit 3, micro particle catching unit 10 and temperature sensor 5, institute State catalytic reduction unit 3 to be connected by connecting pipe with described micro particle catching unit 10, and described connecting pipe is provided with branch road Connect described reducing agent feeding unit 14.Described control unit control respectively micro particle catching unit 10, reducing agent feeding unit 14, Catalytic reduction unit 3 and temperature sensor 5.Described catalytic reduction unit 3 air inlet one end is located in described temperature sensor 5.

Described catalytic reduction unit 3 includes rotary shaft 2, air inlet pipe 4 and the exhaustor 9 of connection air inlet pipe 4.Described rotation Axle 2 extends across air inlet pipe 4 and exhaustor 9, the two ends of described rotary shaft 2 along the direction, axis of air inlet pipe 4, exhaustor 9 Connecting has motor 1, described motor 1 that rotary shaft 2 can be driven to rotate.Be arranged in sequence with in described rotary shaft 2 multiple can be around rotary shaft 2 The cylindrical catalysis restorer 7 rotated, the inside of described catalysis restorer 7 is interval with multiple catalysis also along its length Former passage, described recall reduction passage is divided into high-temperature catalytic reduction passage, middle temperature catalysis reduction passage and low-temperature catalyzed reduction Passage.Being provided with spiral helicine high-temperature catalytic metallic carrier in described high-temperature catalytic reduction passage, the catalysis reduction of described middle temperature is logical It is provided with spiral helicine middle temperature catalytic metal support in road, is provided with spiral helicine low temperature in described low-temperature catalyzed reduction passage and urges Change metallic carrier.Described high-temperature catalytic reduction passage, middle temperature catalysis reduction passage and low-temperature catalyzed reduction passage regularity row Cloth.

Being additionally provided with opening and closing disc 6 in described catalysis restorer 7, described opening and closing disc 6 is positioned at one end of catalysis reduction channel inlet. The surface of described opening and closing disc 6 is provided with the through hole of regular arrangement, and rotary opening closing dish 6, on described through-hole alignment catalysis restorer 7 High-temperature catalytic reduction passage, middle temperature catalysis reduction passage or low-temperature catalyzed reduction passage, cover remaining two kinds catalysis reduction passages, Waste gas enters this catalysis reduction passage by through hole and carries out the catalytic reduction reaction of correspondence.

One end of described catalysis restorer 7 air inlet is provided with movable pressure-reducing cushioning structure 8, refering to Fig. 2 and Fig. 3, described Pressure-reducing cushioning structure 8 is the cylinder of hollow or discoid, and the outer surface of described pressure-reducing cushioning structure 8 is interval with multiple opening Mouthful, each opening is inserted with mobilizable barrier sheet 20, when opening and closing disc 6 needs to rotate when, described barrier sheet 20 enters and subtracts Pressure buffer structure 8 is also internally formed waste gas interception structure in pressure-reducing cushioning structure 8, and waste gas need to be through multiple adjacent barrier sheets 20 groups The cavity become could enter posterior catalysis restorer 7, thus temporary reduction exhaust gas pressure so that posterior opening and closing disc 6 can With smooth rotation, it is to avoid exhaust gas leakage occurs.After posterior opening and closing disc 6 completes to rotate, described barrier sheet 20 detaches, and waste gas recovers Original pressure, is rapidly introduced into posterior catalysis reduction passage.

When burning under the influence of various factors, the temperature of waste gas discharge is different, and different catalyst optimal processing temperature Degree difference, therefore arranges three kinds of different catalyst of operating temperature and reduces in passage in catalysis, cooperate with opening and closing disc 6, when After temperature sensor 5 detects EGT, according to its temperature, rotary opening closing dish 6 so that the through-hole alignment in opening and closing disc 6 is fitted Should the catalysis reduction passage of temperature range, cover remaining two kinds catalysis reduction passages, waste gas is by matching with its temperature Efficiency maximized catalysis reduction passage, thus realize the maximization of exhaust treatment efficiency and effect.

Described high-temperature catalytic metallic carrier works under 400～600 DEG C of environment, and described middle temperature catalytic metal support is 250 ～work under 400 DEG C of environment, described low-temperature catalyzed metallic carrier works under 150～250 DEG C of environment.

Described high-temperature catalytic metallic carrier includes being loaded with WO₃/TiO₂The metallic carrier of catalyst, WO₃/TiO₂Catalyst It is carried on through the following steps on metallic carrier: (1) carries out alkali cleaning and removes surface and oil contaminant metallic carrier, and soda-wash solution composition is Water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser light Speckle radius is 2.50 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short-pulse laser irradiate clean after metal Carrier surface so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation blast, forms microetch hole, wherein The microetch hole gross area accounts for the 80% of the metal carrier surface gross area；(3) metallic carrier after step (2) processes is in 900 DEG C Roasting 5h so that it is surface forms oxide-film；(4) use sol-gel process in the surface-coated glass ceramics of described metallic carrier Coating, composition is mol ratio SiO₂: Al₂O₃=5:1；(5) butyl titanate, acetic acid and ethanol 1:8:5 in molar ratio stirring is obtained Solution A, ammonium paratungstate is dissolved in oxalic acid solution and obtains solution B, solution B is quantitatively adding in A, is stirred vigorously and obtains 25wt.% WO₃/TiO₂Catalyst colloidal sol, is immersed in 25wt.%WO by the metallic carrier of coating glass ceramic coating₃/TiO₂Catalyst colloidal sol Middle 30min, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C, roasting at 600 DEG C 5h, obtains loading 25wt.%WO₃WO₃/TiO₂The high-temperature catalytic metallic carrier of catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more WO₃/TiO₂Catalyst.When microetch hole, the gross area accounts for the 80% of the metal carrier surface gross area Time, under 400～600 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through laser ablation The catalytic efficiency of high-temperature catalytic metallic carrier improves 32%.

At a temperature of 400～550 DEG C, the catalysis activity with temperature of high-temperature catalytic metallic carrier raises and strengthens, NOx conversion Rate is above 80%, more than 92% when 500 DEG C, downward trend occurs, but NOx still has when 600 DEG C after temperature is higher than 500 DEG C The conversion ratio of 65%.

Described middle temperature catalytic metal support includes being loaded with CeO₂/W₂₅The metallic carrier of Ti catalyst, CeO₂/W₂₅Ti is catalyzed Agent is carried on metallic carrier through the following steps: (1) carries out alkali cleaning and removes surface and oil contaminant, soda-wash solution composition metallic carrier For water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser Spot radius is 2.50 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short-pulse laser irradiate clean after gold Belong to carrier surface so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation blast, form microetch hole, its The middle microetch hole gross area accounts for the 80% of the metal carrier surface gross area；(3) metallic carrier after step (2) processes is in cleaning After metallic carrier roasting 5h in 900 DEG C so that it is surface formed oxide-film；(4) sol-gel process is used to carry at described metal The surface-coated glass ceramic coating of body, composition is mol ratio SiO₂: Al₂O₃=5:1；(5) by butyl titanate, acetic acid and ethanol 1:8:5 stirring in molar ratio obtains solution A, and ammonium paratungstate is dissolved in oxalic acid solution and obtains solution B；(6) solution B is quantitatively adding In A, being stirred vigorously and obtain colloidal sol, room temperature is placed and is obtained 110 DEG C of drying in thermostatic drying chamber after xerogel, then roasting at 600 DEG C Burn 4h, obtain WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst；(7) by quantitative Ce (NO₃)₃·6H₂O is dissolved in water and obtains To cerous nitrate solution, then by WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst is immersed, and obtains after 1h is stirred at room temperature CeO to load 10wt.%Ce₂/W₂₅Ti catalyst colloidal sol, is immersed in CeO by the metallic carrier of coating glass ceramic coating₂/ W₂₅1h in Ti catalyst colloidal sol, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C, then at Roasting 5h at 600 DEG C, obtains being loaded with CeO₂/W₂₅The middle temperature catalytic metal support of Ti catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more CeO₂/W₂₅Ti catalyst.When microetch hole, the gross area accounts for the metal carrier surface gross area When 60%, under 250～400 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through laser incising The catalytic efficiency of the high-temperature catalytic metallic carrier of erosion improves 32%.

At a temperature of 250～300 DEG C, the catalysis activity with temperature of middle temperature catalytic metal support raises and strengthens, NOx conversion Rate is above 60%, and at a temperature of 250～300 DEG C, conversion rate of NOx reaches the highest, close to 80%, after temperature is higher than 400 DEG C The catalysis activity of middle temperature catalytic metal support reduces rapidly.

Described low-temperature catalyzed metallic carrier includes being loaded with Cr₂O₃-SO₄ ^2-/TiO₂The metallic carrier of catalyst, Cr₂O₃- SO₄ ^2-/TiO₂Catalyst is carried on metallic carrier through the following steps: (1) carries out alkali cleaning and removes surface oil metallic carrier Dirt, soda-wash solution composition is water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser facula radius are 2.50 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short pulse impulse Light irradiates the metal carrier surface after cleaning so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation are quick-fried Fried, form microetch hole, wherein the microetch hole gross area accounts for the 80% of the metal carrier surface gross area；(3) after step (2) processes Metallic carrier metallic carrier roasting 5h in 900 DEG C after cleaning so that it is surface forms oxide-film；(4) colloidal sol-solidifying is used Glue method is at the surface-coated glass ceramic coating of described metallic carrier, and composition is mol ratio SiO₂: Al₂O₃=5:1；(5) by metatitanic acid Butyl ester, acetic acid and ethanol 1:8:5 in molar ratio stirring obtain solution A, ammonium paratungstate be dissolved in the sulfuric acid solution of 70% obtain molten Liquid B, is quantitatively adding solution B in A, and wherein sulfate radical is SO with the mol ratio of titanium dioxide₄ ^2-: TiO₂=1:4；(6) by solution B is quantitatively adding in A, is stirred vigorously and obtains colloidal sol, and room temperature is placed and obtained 110 DEG C of drying in thermostatic drying chamber after xerogel, then At 600 DEG C, roasting 4h, obtains WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst；(7) by quantitative Cr (NO₃)₃·9H₂O It is dissolved in water and obtains chromium nitrate solution, then by WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst is immersed, and room temperature is stirred Cr is obtained after mixing 1h₂O₃-SO₄ ^2-/TiO₂Catalyst colloidal sol, is immersed in Cr by the metallic carrier of coating glass ceramic coating₂O₃- SO₄ ^2-/TiO₂1h in catalyst colloidal sol, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C Dry, roasting 5h at 600 DEG C, obtain being loaded with Cr₂O₃-SO₄ ^2-/TiO₂The metallic carrier of catalyst.

The microetch hole of metal carrier surface can greatly increase the total surface area of metallic carrier, exposes bigger surface area shape Become oxide-film, thus load more Cr₂O₃-SO₄ ^2-/TiO₂Catalyst.When microetch hole, the gross area accounts for the total face of metal carrier surface When long-pending 80%, under 150～250 DEG C of environment, through the high-temperature catalytic metallic carrier of laser ablation compared to not through too drastic The catalytic efficiency of the high-temperature catalytic metallic carrier of photoengraving improves 28%.

The low-temperature catalyzed metallic carrier of load 10wt.%Ce is when 150～250 DEG C, and conversion rate of NOx is along with the increase of temperature And gradually rise, close to 100%.In 175～250 DEG C of temperature ranges, conversion rate of NOx is all more than 80%.

Compared to using single catalyst, the NOx ratio discharge used after the catalytic conversion system of the present invention in waste gas from 12.192g/kW h drops to 2.089g/kW h, and treatment effect significantly promotes.

Described micro particle catching unit 10 includes housing and polylith micro particle catching metallic carrier, described micro particle catching metallic carrier Process through the following step: take quantitative chromic nitrate, cobalt nitrate and citric acid and be dissolved in deionized water, wherein chromium ion and citric acid Molecule mol ratio is 1:1.5, and chromium ion concentration is 0.2mol/L.After 80 DEG C of complex reaction 5h, it is applied in micro particle catching metal carry On body, described micro particle catching metallic carrier obtains final products after 600 DEG C of roasting 5h.In order to carry high catalytic activity further, Support at catalyst surface and accounted for the precious metals pt that catalyst quality mark is 0.5%.Described final products cut into elongate Rear mutually overlap joint forms metal gauze, and described metal gauze is vertically connected with the metal wire mesh filter 13 forming intensive porous.

Described housing includes that shell body 11 and inner housing 12, described shell body 11 interval wrap up described inner housing 12 so that Form vacuum layer between shell body 11 and inner housing 12, keep the temperature of metal wire mesh filter 13, promote that it passively burns again Raw, reduce the exhaust back pressure in particle trapper.Described inner housing 12 is divided into expansion, filtration fraction and constriction, institute Stating expansion and connect air inlet pipe, described constriction connects exhaustor, the external diameter of the constriction of wherein said inner housing 12 Being 2.5～4 with exhaustor external diameter diameter ratio, the angle of described inner housing 12 expansion is 80 °～100 °.

In particle trapper, the uniformity of flow velocity and particle concentration determines the height of particle trapper inner filtration body utilization rate Low, filter regeneration cycle and the length in filtering bodies service life, in the actual application of particle trapper, particle trapper Exhaust parameter (exhaust entrance speed) and structural parameters (angle of flare, diameter than) are to velocity flow profile and particle concentration distributions Uniformity has very important impact.

In the case of inlet flow rate (inlet velocity and inlet-duct area) is identical, diameter flows through expansion than little inner housing 12 During part, speed reduces less, and the eddy current effect of generation is less, almost without, but, less diameter ratio can make microgranule In catcher, exhaust flow rate is higher, exhaust flow rate skewness, thus during causing actual filtration in particle trapper Collection of particles, at the central axis of metal wire mesh filter 13, increases the weight of the load at metal wire mesh filter 13 central axis. When diameter ratio is 2～4, the VELOCITY DISTRIBUTION in each cross section of particle trapper is more uniform, thus micro-in metal wire mesh filter 13 Grain deposition distribution is the most uniform.Now in the case of same charge flow rate, particle trapper arresting efficiency is 96%.

The angle of flare is the least, and the mistake from air inlet pipe to expansion gets over smooth-going, and the angle of flare is the biggest, the most easily produces eddy current District, and vortex is the most close to central axis, therefore, selecting the angle of flare is 80 °～100 °, now in the feelings of same charge flow rate Under condition, particle trapper arresting efficiency is 95%.

Refering to Fig. 4, described reducing agent feeding unit 14 includes solid urea holding vessel 19, the metering rotor 18 being sequentially connected with With heat resolve pipeline 16, described solid urea holding vessel 19 internal memory is placed with urea powder, and its lower surface is formed slopely with opening The cone structure of mouth.Described metering rotor 18 is cylindric, and its outer surface is interval with the pit accommodating urea powder.Described meter The cental axial position of amount rotor 18 connects actuating device, drives metering rotor 18 to rotate relative to solid urea holding vessel 19.Institute The outer surface interval stating metering rotor 18 is enclosed with the seal bootr 17 being fixed on described solid urea holding vessel 19, described closing The opening part of the cover 17 described cone structure of alignment is provided with through hole, and described seal bootr 17 is directed at described heat resolve pipeline 16 same Being provided with through hole, rotate metering rotor 18, the urea powder in solid urea holding vessel 19 enters in pit, is rotated further metering and turns Son 18, the pit equipped with urea powder turns to be directed at the through hole of described heat resolve pipeline 16, and urea powder drops, waste gas Blowing urea powder and enter heat resolve pipeline 16, described heat resolve pipeline 16 is tortuous to be folded in microwave launcher 15, Urea powder decomposes generation ammonia and Carbimide., the steam in waste gas when microwave launcher 15 under the effect of microwave Carbimide. can be made to decompose, thus produce ammonia.

In being embodied as, described pit is the hemispherical of a diameter of 5mm.

Last it should be noted that, above example is only in order to illustrate technical scheme, rather than the present invention is protected Protecting the restriction of scope, although having made to explain to the present invention with reference to preferred embodiment, those of ordinary skill in the art should Work as understanding, technical scheme can be modified or equivalent, without deviating from the reality of technical solution of the present invention Matter and scope.

Claims (5)

1. waste old microwave automatic cracking reaction device, it is characterised in that include control unit, reducing agent feeding unit, urge Changing reduction unit, micro particle catching unit and temperature sensor, described catalytic reduction unit and described micro particle catching unit are by even Thread a pipe connection, and described connecting pipe is provided with branch road and connects described reducing agent feeding unit；Described control unit is controlled respectively Micro particle catching unit processed, reducing agent feeding unit, catalytic reduction unit and temperature sensor；Described temperature sensor is located at described Catalytic reduction unit air inlet one end；Described catalytic reduction unit includes rotary shaft, air inlet pipe and the exhaustor of connection air inlet pipe, Described rotary shaft extends across air inlet pipe and exhaustor, the two of described rotary shaft along the direction, axis of air inlet pipe, exhaustor End connection has motor；Multiple cylindrical catalysis restorer that can rotate, institute it is arranged in sequence with around rotary shaft in described rotary shaft The inside stating catalysis restorer is interval with multiple catalysis reduction passage along its length, and described recall reduction passage is divided into height Temperature catalysis reduction passage, middle temperature catalysis reduction passage and low-temperature catalyzed reduction passage；Set in described high-temperature catalytic reduction passage It is equipped with spiral helicine high-temperature catalytic metallic carrier, in described middle temperature catalysis reduction passage, is provided with spiral helicine middle temperature catalytic metal Carrier, is provided with spiral helicine low-temperature catalyzed metallic carrier in described low-temperature catalyzed reduction passage, the reduction of described high-temperature catalytic is logical Road, middle temperature catalysis reduction passage and the arrangement of low-temperature catalyzed reduction passage regularity；

Being additionally provided with opening and closing disc in described catalysis restorer, described opening and closing disc is positioned at one end of catalysis reduction channel inlet；Described open The surface closing dish is provided with the through hole of regular arrangement, rotary opening closing dish, the high-temperature catalytic on described through-hole alignment catalysis restorer Reduction passage, middle temperature catalysis reduction passage or low-temperature catalyzed reduction passage, cover remaining two kinds catalysis reduction passages, and waste gas passes through Through hole enters this catalysis reduction passage and carries out the catalytic reduction reaction of correspondence；

One end of described catalysis restorer air inlet is provided with movable pressure-reducing cushioning structure, and described pressure-reducing cushioning structure is hollow Cylindrical or discoid, the outer surface of described pressure-reducing cushioning structure is interval with multiple opening, each opening is inserted with movable Barrier sheet, when opening and closing disc needs to rotate when, described barrier sheet enters pressure-reducing cushioning structure in pressure-reducing cushioning structure Portion forms waste gas interception structure；

Described high-temperature catalytic metallic carrier works under 400～600 DEG C of environment, and described middle temperature catalytic metal support is 250～400 Working under DEG C environment, described low-temperature catalyzed metallic carrier works under 150～250 DEG C of environment；

Described high-temperature catalytic metallic carrier includes being loaded with WO₃/TiO₂The metallic carrier of catalyst, WO₃/TiO₂Under catalyst passes through Row step is carried on metallic carrier: (1) carries out alkali cleaning and removes surface and oil contaminant metallic carrier, and soda-wash solution composition is water: ammonia Water: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser facula half Footpath is 2.25 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short-pulse laser irradiate clean after metallic carrier Surface so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation blast, forms microetch hole, wherein microetch The hole gross area accounts for the 60% of the metal carrier surface gross area；(3) the metallic carrier roasting in 900 DEG C after step (2) processes 5h so that it is surface forms oxide-film；(4) employing sol-gel process is at the surface-coated glass ceramic coating of described metallic carrier, Composition is mol ratio SiO₂: Al₂O₃=5:1；(5) butyl titanate, acetic acid and ethanol 1:8:5 in molar ratio stirring is obtained solution A, ammonium paratungstate is dissolved in oxalic acid solution and obtains solution B, solution B is quantitatively adding in A, is stirred vigorously and obtains 25wt.%WO₃/ TiO₂Catalyst colloidal sol, is immersed in 25wt.%WO by the metallic carrier of coating glass ceramic coating₃/TiO₂In catalyst colloidal sol 30min, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C, roasting at 500 DEG C 5h, obtains loading 25wt.%WO₃WO₃/TiO₂The high-temperature catalytic metallic carrier of catalyst；

Described middle temperature catalytic metal support includes being loaded with CeO₂/W₂₅The metallic carrier of Ti catalyst, CeO₂/W₂₅Ti catalyst leads to Cross the following step to be carried on metallic carrier: (1) carries out alkali cleaning and removes surface and oil contaminant metallic carrier, and soda-wash solution composition is Water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilizing wavelength for 532nm, pulse width is 500ps～50ns, laser light Speckle radius is 2.25 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short-pulse laser irradiate clean after metal Carrier surface so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation blast, forms microetch hole, wherein The microetch hole gross area accounts for the 60% of the metal carrier surface gross area；(3) metallic carrier after step (2) processes will be after cleaning Metallic carrier roasting 5h in 900 DEG C so that it is surface formed oxide-film；(4) use sol-gel process at described metallic carrier Surface-coated glass ceramic coating, composition is mol ratio SiO₂: Al₂O₃=5:1；(5) butyl titanate, acetic acid and ethanol are pressed The stirring of mol ratio 1:8:5 obtains solution A, and ammonium paratungstate is dissolved in oxalic acid solution and obtains solution B；(6) solution B is quantitatively adding A In, it being stirred vigorously and obtain colloidal sol, room temperature is placed and is obtained 110 DEG C of drying in thermostatic drying chamber after xerogel, then roasting at 600 DEG C 4h, obtains WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst；(7) by quantitative Ce (NO₃)₃·6H₂O is dissolved in water and obtains Cerous nitrate solution, then by WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst is immersed, and obtains after 1h is stirred at room temperature The CeO of load 10wt.%Ce₂/W₂₅Ti catalyst colloidal sol, is immersed in CeO by the metallic carrier of coating glass ceramic coating₂/ W₂₅1h in Ti catalyst colloidal sol, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C, then at Roasting 5h at 500 DEG C, obtains being loaded with CeO₂/W₂₅The middle temperature catalytic metal support of Ti catalyst；

Described low-temperature catalyzed metallic carrier includes being loaded with Cr₂O₃-SO₄ ^2-/TiO₂The metallic carrier of catalyst, Cr₂O₃-SO₄ ^2-/ TiO₂Catalyst is carried on metallic carrier through the following steps: (1) carries out alkali cleaning and removes surface and oil contaminant, alkali cleaning metallic carrier Solution composition is water: ammonia: hydrogen peroxide=5:1:1 (volume ratio)；(2) utilize wavelength for 532nm, pulse width be 500ps～ 50ns, laser facula radius are 2.25 μm, and energy density scope is 4 × 10⁷～12 × 10⁸W/cm²Short-pulse laser irradiate clear Metal carrier surface after washing so that the metal carrier surface local heating after cleaning, melted, vaporization and phase transformation blast, is formed Microetch is cheated, and wherein the microetch hole gross area accounts for the 60% of the metal carrier surface gross area；(3) metal after step (2) processes carries Body metallic carrier roasting 5h in 900 DEG C after cleaning so that it is surface forms oxide-film；(4) sol-gel process is used to exist The surface-coated glass ceramic coating of described metallic carrier, composition is mol ratio SiO₂: Al₂O₃=5:1；(5) by butyl titanate, Acetic acid and ethanol 1:8:5 in molar ratio stirring obtains solution A, and ammonium paratungstate is dissolved in the sulfuric acid solution of 70% and obtains solution B, will Solution B is quantitatively adding in A, and wherein sulfate radical is SO with the mol ratio of titanium dioxide₄ ^2-: TiO₂=1:4；(6) solution B is quantitative Adding in A, be stirred vigorously and obtain colloidal sol, room temperature is placed and is obtained 110 DEG C of drying in thermostatic drying chamber after xerogel, then at 600 DEG C Lower roasting 4h, obtains WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst；(7) by quantitative Cr (NO₃)₃·9H₂O is dissolved in Water obtains chromium nitrate solution, then by WO₃Weight/mass percentage composition is the WO of 25%₃/TiO₂Catalyst is immersed, and 1h is stirred at room temperature After obtain Cr₂O₃-SO₄ ^2-/TiO₂Catalyst colloidal sol, is immersed in Cr by the metallic carrier of coating glass ceramic coating₂O₃-SO₄ ^2-/ TiO₂1h in catalyst colloidal sol, then slowly lifts out, and dry at room temperature over night is placed in baking oven and dries at 60 DEG C, then at Roasting 5h at 500 DEG C, obtains being loaded with Cr₂O₃-SO₄ ^2-/TiO₂The metallic carrier of catalyst.

Waste old microwave the most according to claim 1 automatic cracking reaction device, it is characterised in that described micro particle catching Unit includes housing and polylith micro particle catching metallic carrier, and described micro particle catching metallic carrier processes through the following step: it is fixed to take Measuring chromic nitrate, cobalt nitrate and citric acid are dissolved in deionized water, and wherein chromium ion and citric acid molecule mol ratio are 1:1.5, chromium Ion concentration is 0.2mol/L；It is applied in after 80 DEG C of complex reaction 5h on micro particle catching metallic carrier, described micro particle catching gold Belong to carrier and obtain final products after 600 DEG C of roasting 5h；After described final products cut into elongate, mutually overlap joint forms metal Silk screen, described metal gauze is vertically connected with the metal wire mesh filter forming intensive porous；Described housing includes shell body and interior Housing, described shell body interval is wrapped up described inner housing, is formed vacuum layer between shell body and inner housing；Described inner housing is divided into Expansion, filtration fraction and constriction, described expansion connects air inlet pipe, and described constriction connects exhaustor, its Described in the external diameter of constriction of inner housing be 2.5～4 with exhaustor external diameter diameter ratio, the angle of described inner housing expansion Degree is 80 °～100 °.

Waste old microwave the most according to claim 2 automatic cracking reaction device, it is characterised in that described metallic carrier Surface is supported with and accounts for the precious metals pt that catalyst quality mark is 0.5%.

Waste old microwave the most according to claim 1 and 2 automatic cracking reaction device, it is characterised in that described reduction Agent feeding unit includes solid urea holding vessel, metering rotor and the heat resolve pipeline being sequentially connected with, and described solid urea stores up Depositing tank internal memory and be placed with urea powder, its lower surface is formed slopely the cone structure with opening；Described metering rotor is cylindric, Its outer surface is interval with the pit accommodating urea powder；The cental axial position of described metering rotor connects actuating device, drives Metering rotor rotates relative to solid urea holding vessel；The outer surface interval of described metering rotor is enclosed with is fixed on described solid Seal bootr on urea storage tank, described seal bootr is directed at the opening part of described cone structure and is provided with through hole, described seal bootr pair Being again provided with through hole at accurate described heat resolve pipeline, rotate metering rotor, the urea powder in solid urea holding vessel enters In pit, being rotated further metering rotor, the pit equipped with urea powder turns to be directed at the through hole of described heat resolve pipeline； Described heat resolve pipeline is tortuous to be folded in microwave launcher.

Waste old microwave the most according to claim 4 automatic cracking reaction device, it is characterised in that described pit is straight Footpath is the hemispherical of 5mm.