CN105797577A - Process and catalyst for catalytically reducing NOX by using methane - Google Patents

Process and catalyst for catalytically reducing NOX by using methane Download PDF

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Publication number
CN105797577A
CN105797577A CN201610268637.8A CN201610268637A CN105797577A CN 105797577 A CN105797577 A CN 105797577A CN 201610268637 A CN201610268637 A CN 201610268637A CN 105797577 A CN105797577 A CN 105797577A
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catalyst
oxide
gas
board
passed
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CN105797577B (en
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陆强
马帅
董长青
仇志超
蔺卓玮
唐昊
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North China Electric Power University
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North China Electric Power University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/76—Gas phase processes, e.g. by using aerosols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

Abstract

The invention relates to the field of industrial catalysis and environmental governance, in particular to a process and catalyst for catalytically reducing nitrogen oxide (NOx) by using methane. A tail gas from a fuel gas/oil burning boiler flows through the bottom of a catalytic reduction reactor, and enters a catalyst layer after being fully mixed with supplied methane to complete a catalytic reduction reaction under the action of a plate-type catalyst to realize the removal of the nitrogen oxide. The flow direction of flue gas is regulated and controlled by a switching valve and a flue gas baffle, and the timely oxidation and regeneration of a deactivated catalyst are ensured by the supplementation of an appropriate amount of oxygen. The plate-type catalyst is obtained by mixing, rolling and coating, pleating, drying and calcinating nanoscale gamma-Al2O3 as a carrier, copper oxide as an active ingredient, and one or more of yttrium oxide, praseodymium oxide, magnesium oxide, or lanthanum oxide as metal additives. The catalyst provided by the invention has relatively high catalytic activity, thermal stability and mechanical strength.

Description

A kind of methyl hydride catalyzed reduction NOxTechnique and catalyst
Technical field
The present invention relates to Industrial Catalysis and field of environmental improvement, be specifically related to a kind of methyl hydride catalyzed reduction NOxWork Skill and catalyst.
Background technology
NOxIt is one of the major pollutants of serious harm human health, is mainly derived from power plant, heating boiler cigarette Gas and vehicle exhaust.The whole world enters the NO of air every yearxTotal amount reaches 30,000,000 tons, and still in sustainable growth. Nitrogen oxides can produce acid rain, photochemical fog and damage the ozone layer, and not only causes ecological environment sternly The pollution of weight, but also threaten the life and health of the mankind.Therefore, the discharge reducing nitrogen oxides has important Meaning.
NOxRemoving sulfuldioxide huge number, be broadly divided into dry and wet.Wherein dry method includes contact catalysis Method (catalytic decomposition, catalysis reduction and catalytic adsorption) and on-catalytic method (acceleration electronics decomposition method, absorption method and Absorption process)；Wet method includes acid absorption, complexed absorption, oxidative absorption and oxidoreduction absorption process.Develop Purified treatment NO with applicationxMethod, the overwhelming majority belongs to dry method, and wherein SCR denitration technique is current The Dry denitration technology that the whole world is widely used, has the advantages such as efficiency height, technology maturation.(201410056783.5) In disclose a kind of SCR flue-gas denitration process, NOxRemoval efficiency reach more than 80%.
NH under oxidizing atmosphere3Selective catalysis reduction NOxAchieve industrialization in the country that industry is flourishing, but Due to ammonia process selective catalysis reduction NOxThere is corrosion and blocking and the fortune of the storage of ammonia, transport, pipeline Row cost is high, easily cause secondary pollution problems, it is therefore necessary to explore one without ammonia as reducing agent NO in removing flue gasxMethod.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that one utilizes methane as reducing agent removing NO in flue gasxTechnique and catalyst.
As a kind of technical scheme, the invention provides a kind of methyl hydride catalyzed reduction NOxProcess technology scheme, Placing the board-like catalyst of upper and lower two-layer in catalytic reduction reactor, wherein the board-like catalyst in upper strata is auxiliary catalysis Agent, the board-like catalyst of lower floor is major catalyst, with dividing plate board-like for described lower floor catalyst is divided into left and right also Discharge Zhi Zuo district catalyst and right district catalyst, connect switching valve and gas baffle below dividing plate, and regulation is cut Changing valve can make gas baffle close switching between described dividing plate left field and right side area；In dividing plate left field With output left gas pipeline and Top right gas pipeline on the catalytic reduction reactor wall of right side area respectively；Work Will be containing NO when makingxBoiler smoke be passed through from the bottom of catalytic reduction reactor, by reacted flue gas from urging The top exit changing reduction reactor is discharged, and work process includes two kinds of mode of operations:
Mode of operation one: regulation switching valve makes gas baffle enclosed baffle right side area, the boiler smoke air-flow being passed through Through untight left district catalyst, in left gas pipeline, it is passed through methane gas simultaneously and completes in left field Denitration reaction, unreacted methane gas completely continues fully oxidized generation titanium dioxide in the board-like catalyst in upper strata Carbon and water；In Top right gas pipeline, it is passed through air simultaneously, keeps the board-like catalyst of lower floor of this side to be in oxidation State, and air enters the board-like catalyst in upper strata, it is provided that the air needed for methane oxidation；Mode of operation two: Regulation switching valve makes gas baffle enclosed baffle left field, and the boiler smoke being passed through flows through untight right district and urges Agent, being passed through methane gas in Top right gas pipeline completes denitration reaction in right side area simultaneously, and on a left side It is passed through air in the gas piping of side；Circulation uses mode of operation one and mode of operation two to carry out the continuous of boiler smoke Denitration reaction, switches to another kind when the board-like catalyst activity of the lower floor of denitration reaction region starts to reduce Mode of operation.
As another technical scheme, the invention provides one and utilize methane as NO in reducing agent removing flue gasx Catalyst, it is characterised in that: described catalyst includes that active component, metal promoter, carrier and molding help Agent and rustless steel web plate, wherein, described active component is copper oxide, metal promoter be praseodymium oxide, yittrium oxide, One or more in magnesium oxide or lanthana, carrier is γ type aluminium oxide, and described shaping assistant is also γ type oxygen Change aluminum.
Preferably, catalyst components percentage by weight is: copper oxide is 0.5-10%, metal oxide auxiliary agent It is 85-95% for 0.1-5%, γ type aluminium oxide.
The preparation method of above-mentioned catalyst, comprises the steps:
(1) Gerhardite of 15-300 weight portion, the magnesium nitrate of 2-180 weight portion or six hydrations are weighed One or more in praseodymium nitrate or six nitric hydrate yttriums or lanthanum nitrate hexahydrate, the γ type of 800-900 weight portion Alumina support；Water absorption rate according to carrier calculates water requirement, Gerhardite and auxiliary agent presoma is divided It is not configured to saline solution, uses equi-volume impregnating that the saline solution configured is added sequentially to γ type carrying alumina In body, and carry out in a mixer mixing and stirring；
(2) boehmite of 10-50 weight portion, the organic binder bond of 5-15 weight portion are joined step (1) carry out in the batch mixing obtained in mixing and stirring, obtain catalyst mastic；
(3) the catalyst mastic after mix homogeneously in step (2) is placed on rustless steel web plate, is coated with through roll-in Cover, crimped, shear, be dried and roasting after can obtain flat CH4-SCR catalyst.
Preferably, the organic binder bond in described step (2) is carboxymethyl cellulose, methylcellulose, gathers The combination of one or more in vinyl alcohol or polyethylene glycol oxide.
Preferably, being dried as oven drying in described step (3), baking temperature is 105 DEG C, drying time For 2-24h.
Preferably, the sintering temperature in described step (3) is 500-900 DEG C, and roasting time is 2-8h.
The invention have the benefit that
The present invention realizes NO in flue gas with methane for reducing agentxReduction, thus the NO in efficient removal flue gasx Gas.Heretofore described copper-based catalysts has higher, wider temperature window, is particularly well-suited to combustion gas The denitrating flue gas of/oil burning boiler.Catalyst is after running after a while, and the active component in catalyst is the highest The methane reduction of concentration and cause being catalyzed activity reduction.In order to solve this problem, under the present invention utilizes dividing plate to incite somebody to action Layer catalyst is divided into two parts.System is during putting into operation, and the only catalyst of half is in flue gas environment In, additionally half catalyst is then in oxidation resting state.When the catalyst activity being in flue gas side reduces, By adjusting switching valve, flue gas is imported the catalyst side of resting state, flue gas so can be made constant Be purified；Meanwhile, supply air to the side of decaying catalyst, make the work being reduced in catalyst Property component obtains fully oxidized, completes the regeneration to catalyst.Therefore, without inciting somebody to action during whole service The catalyst of inactivation is fetched into its exterior and regenerates, it is achieved that denitrating flue gas regenerates with catalyst and synchronization carries out Purpose, substantially increase operational efficiency.
The present invention uses nanoscale γ type aluminium oxide as carrier, has the spy that specific surface area is big and heat stability is high Point.CuO/γ-Al2O3There is good CH4-SCR performance, the present invention, on the basis of this catalyst, is doped with One or more in yittrium oxide, praseodymium oxide, magnesium oxide or lanthana, as coagent, can be greatly improved The activity of catalyst and N2Selectivity.Further, under excess oxygen, catalyst of the present invention is to methane There is excellent catalytic oxidation performance.Methane gas unnecessary in flue gas is when flowing through overlying catalyst, by completely Oxidation generates carbon dioxide and water, does not haves methane gas escape and cause secondary dirty in the most whole denitrating technique The problems such as dye.Additionally, by introducing boehmite as shaping assistant, prepared Plate-type denitration catalyst There is higher mechanical strength and longer service life.
Accompanying drawing explanation
Fig. 1 is the structural representation of the present invention
Wherein:
1: catalytic reduction reactor；2: the board-like catalyst in upper strata；3: the board-like catalyst of lower floor；3-1: left district Catalyst；3-2: right district catalyst；4: dividing plate；5: switching valve；6: gas baffle；7: gas piping； 7-1: left gas pipeline；7-2: Top right gas pipeline；S1: mode of operation one；S2: mode of operation two.
Detailed description of the invention
The invention provides a kind of NO utilized methane as in reducing agent removing flue gasxTechnique and catalyst, Below in conjunction with detailed description of the invention, the present invention will be further described.
The technique used in each embodiment is identical, as shown in Figure 1.
Being placed with the board-like catalyst of upper and lower two-layer in catalytic reduction reactor 1, wherein the board-like catalyst in upper strata 2 is Cocatalyst, the board-like catalyst of lower floor 3 is major catalyst, is separated into by dividing plate and lays respectively at arranged on left and right sides Left district catalyst 3-1 and right district catalyst 3-2, connect below dividing plate 4 and have switching valve 5 and gas baffle 6, Gas baffle 6 is controlled, it is ensured that flue gas the most only flows through in the board-like catalyst of lower floor 3 by regulation switching valve 5 Left district catalyst 3-1 or right district catalyst 3-2；Between the board-like catalyst of lower floor 3 and gas baffle 6 Gas piping 7, respectively left gas pipeline 7-1 and right side gas is offered on the wall of catalytic reduction reactor Body pipeline 7-2, methane or air all can be passed through in catalytic reduction reactor by two gas pipings.
This catalytic reduction reactor has two mode of operations.At mode of operation one S1, containing NOxBoiler smoke Gas is passed through from the bottom of catalytic reduction reactor, flows through left district catalyst, is passed through in left gas pipeline simultaneously Methane gas, completes denitration reaction；Unreacted methane gas completely continues in the board-like catalyst in upper strata abundant Oxidation generates carbon dioxide and water, and reacted flue gas is discharged from the top exit of catalytic reduction reactor.With this Meanwhile, in Top right gas pipeline, it is passed through air, keeps right district catalyst to be in the state of oxidation, and air enters Enter the board-like catalyst in upper strata, it is provided that the air needed for methane oxidation.When left district catalyst activity starts to reduce, Switch to mode of operation two S2, control gas baffle by regulation switching valve, make boiler smoke flow through the catalysis of right district Agent, changes ventilating methane by Top right gas pipeline simultaneously, and left gas pipeline is changed blowing air.Use above-mentioned work Pattern one and the circulation of mode of operation two, can realize the continuous denitration reaction of boiler smoke.
Embodiment 1
Use above-mentioned technique, described board-like CH4-SCR denitration, its preparation process includes following step Rapid:
(1) weigh the six nitric hydrate praseodymiums of the Gerhardite of 1000g, 180g, be dissolved in respectively In the deionized water of 3500mL, respectively it is configured to saline solution；Use the saline solution that equi-volume impregnating will configure It is added sequentially in the γ type alumina support of 6000g, and carries out in a mixer mixing and stirring；
(2) carboxymethyl cellulose of the boehmite of 300g, 100g is joined in step (1) obtain Batch mixing in carry out mixing and stirring, obtain catalyst mastic；
(3) the catalyst mastic after mix homogeneously in step (2) is placed on rustless steel web plate, is coated with through roll-in Cover, crimped, shearing, can obtain after 105 DEG C of dry 2h of air dry oven, 800 DEG C of roasting 5h of Muffle furnace flat Board-like CH4-SCR catalyst.It is 5% that catalyst components percentage by weight is respectively as follows: copper oxide, praseodymium oxide Being 1%, γ type aluminium oxide is 94%.
Simulated flue gas condition is used the performance of this denitrating catalyst to be evaluated, with CH4For reducing agent, typical case Under flue gas operating mode: NO is 700mg/m3, CH4For 3700mg/m3, O2It is 1% (v/v), H2O is 8% (v/v), N2For Balance Air, air speed is 5000h-1, reaction temperature be denitration efficiency when 550 DEG C be 98.2%, The removal efficiency of methane is 99.8%.
Embodiment 2
Use the device identical with embodiment 1 structure, described board-like CH4-SCR denitration, its system Standby process comprises the following steps:
(1) weigh the six nitric hydrate yttriums of the Gerhardite of 1610g, 1800g, be dissolved in respectively In the deionized water of 5000mL, respectively it is configured to saline solution；Use the saline solution that equi-volume impregnating will configure It is added sequentially in the γ type alumina support of 9000g, and carries out in a mixer mixing and stirring；
(2) methylcellulose of the boehmite of 450g, 150g joined step (1) obtains Carry out in batch mixing mixing and stirring, obtain catalyst mastic；
(3) the catalyst mastic after mix homogeneously in step (2) is placed on rustless steel web plate, is coated with through roll-in Cover, crimped, shearing, can obtain after 105 DEG C of dry 4h of air dry oven, 850 DEG C of roasting 6h of Muffle furnace flat Board-like catalyst.It is 5% that catalyst components percentage by weight is respectively as follows: copper oxide, and yittrium oxide is 5%, γ Type aluminium oxide is 90%.
Simulated flue gas condition is used the performance of this denitrating catalyst to be evaluated, with CH4For reducing agent, typical case Under flue gas operating mode: NO is 700mg/m3, CH4For 3700mg/m3, O2It is 1% (v/v), H2O is 8% (v/v), N2For Balance Air, air speed is 5000h-1, reaction temperature be denitration efficiency when 600 DEG C be 96%, The removal efficiency of methane is 100%.
Embodiment 3
Use the device identical with embodiment 1 structure, described board-like CH4-SCR denitration, its system Standby process comprises the following steps:
(1) weigh the magnesium nitrate of the Gerhardite of 970g, 1180g, be dissolved in 3100mL respectively Deionized water in, be respectively configured to saline solution；Equi-volume impregnating is used to be added successively by the saline solution configured Enter in the γ type alumina support of 5400g, and carry out in a mixer mixing and stirring；
(2) polyvinyl alcohol of the boehmite of 270g, 90g is joined the batch mixing obtained in step (1) In carry out mixing and stirring, obtain catalyst mastic；
(3) the catalyst mastic after mix homogeneously in step (2) is placed on rustless steel web plate, is coated with through roll-in Cover, crimped, shearing, obtain flat board after 105 DEG C of dry 10h of air dry oven, 800 DEG C of roasting 5h of Muffle furnace Formula denitrating catalyst.It is 5% that catalyst components percentage by weight is respectively as follows: copper oxide, and magnesium oxide is 5%, γ type aluminium oxide is 90%.
Simulated flue gas condition is used the performance of this denitrating catalyst to be evaluated, with CH4For reducing agent, typical case Under flue gas operating mode: NO is 700mg/m3, CH4For 7300mg/m3, O2It is 2% (v/v), H2O is 8% (v/v), N2For Balance Air, air speed is 5000h-1, reaction temperature be denitration efficiency when 700 DEG C be 95%, The removal efficiency of methane is 99.8%.
Embodiment 4
Use the device identical with embodiment 1 structure, described board-like CH4-SCR denitration, its system Standby process comprises the following steps:
(1) weigh the lanthanum nitrate hexahydrate of the Gerhardite of 540g, 470g, be dissolved in respectively In the deionized water of 1700mL, respectively it is configured to saline solution；Use the saline solution that equi-volume impregnating will configure It is added sequentially in the γ type alumina support of 3000g, and carries out in a mixer mixing and stirring；
(2) polyethylene glycol oxide of the boehmite of 150g, 50g is joined obtain in step (1) mixed Carry out in material mixing and stirring, obtain catalyst mastic；
(3) the catalyst mastic after mix homogeneously in step (2) is placed on rustless steel web plate, is coated with through roll-in Cover, crimped, shearing, can obtain after 105 DEG C of dry 12h of air dry oven, 900 DEG C of roasting 6h of Muffle furnace Flat catalyst.It is 5% that catalyst components percentage by weight is respectively as follows: copper oxide, and lanthana is 5%, γ type aluminium oxide is 90%.
Simulated flue gas condition is used the performance of this denitrating catalyst to be evaluated, with CH4For reducing agent, typical case Under flue gas operating mode: NO is 700mg/m3, CH4For 3700mg/m3, O2It is 1% (v/v), H2O is 8% (v/v), N2For Balance Air, air speed is 5000h-1, reaction temperature be denitration efficiency when 550 DEG C be 98%, The removal efficiency of methane is 99.8%.
Embodiment 5
Use the device identical with embodiment 1 structure, described board-like CH4-SCR denitration, its system Standby process comprises the following steps:
(1) the six nitric hydrate praseodymiums of the Gerhardite of 1000g, 180g are weighed, the six hydration nitre of 980g Acid yttrium, is dissolved in respectively in the deionized water of 2220mL, is respectively configured to saline solution；Use incipient impregnation The saline solution configured is added sequentially in the γ type alumina support of 6000g by method, and carries out in a mixer Mixing and stirring；
(2) methylcellulose of the boehmite of 270g, the carboxymethyl cellulose of 80g, 50g is added Carry out mixing and stirring in the batch mixing obtained in step (1), obtain catalyst mastic；
(3) the catalyst mastic after mix homogeneously in step (2) is placed on rustless steel web plate, is coated with through roll-in Cover, crimped, shearing, can obtain after 105 DEG C of dry 3h of air dry oven, 800 DEG C of roasting 6h of Muffle furnace flat Board-like CH4-SCR catalyst.It is 5% that catalyst components percentage by weight is respectively as follows: copper oxide, praseodymium oxide Being 1%, yittrium oxide is 4%, and γ type aluminium oxide is 90%.
Simulated flue gas condition is used the performance of this denitrating catalyst to be evaluated, with CH4For reducing agent, typical case Under flue gas operating mode: NO is 700mg/m3, CH4For 3700mg/m3, O2It is 1% (v/v), H2O is 8% (v/v), N2For Balance Air, air speed is 5000h-1, reaction temperature be denitration efficiency when 550 DEG C be 98.7%, The removal efficiency of methane is 100%.
Embodiment 6
Use the device identical with embodiment 1 structure, described board-like CH4-SCR denitration, its system Standby process comprises the following steps:
(1) magnesium nitrate of the Gerhardite of 970g, 240g is weighed, the lanthanum nitrate hexahydrate of 680g, It is dissolved in respectively in the deionized water of 2030mL, is respectively configured to saline solution；Equi-volume impregnating is used to join The saline solution put is added sequentially in the γ type alumina support of 5400g, and in a mixer carry out mixing with Stirring；
(2) polyvinyl alcohol of the boehmite of 270g, 90g is joined the batch mixing obtained in step (1) In carry out mixing and stirring, obtain catalyst mastic；
(3) the catalyst mastic after mix homogeneously in step (2) is placed on rustless steel web plate, is coated with through roll-in Cover, crimped, shearing, obtain flat board after 105 DEG C of dry 10h of air dry oven, 800 DEG C of roasting 5h of Muffle furnace Formula denitrating catalyst.It is 5% that catalyst components percentage by weight is respectively as follows: copper oxide, and magnesium oxide is 1%, Lanthana is 4%, and γ type aluminium oxide is 90%.
Simulated flue gas condition is used the performance of this denitrating catalyst to be evaluated, with CH4For reducing agent, typical case Under flue gas operating mode: NO is 700mg/m3, CH4For 7300mg/m3, O2It is 2% (v/v), H2O is 8% (v/v), N2For Balance Air, air speed is 5000h-1, reaction temperature be denitration efficiency when 650 DEG C be 97.7%, The removal efficiency of methane is 100%.
Embodiment 7
Use the device identical with embodiment 1 structure, described board-like CH4-SCR denitration, its system Standby process comprises the following steps:
(1) the six nitric hydrate praseodymiums of the Gerhardite of 1000g, 180g are weighed, the six hydration nitre of 490g Acid yttrium, the magnesium nitrate of 530g, it is dissolved in respectively in the deionized water of 1700mL, is respectively configured to saline solution； Equi-volume impregnating is used to be added sequentially in the γ type alumina support of 6000g by the saline solution configured, and Carry out in a mixer mixing and stirring；
(2) carboxymethyl cellulose of the boehmite of 330g, 70g joined step (1) obtains Carry out in batch mixing mixing and stirring, obtain catalyst mastic；
(3) the catalyst mastic after mix homogeneously in step (2) is placed on rustless steel web plate, is coated with through roll-in Cover, crimped, shearing, can obtain after 105 DEG C of dry 3h of air dry oven, 800 DEG C of roasting 6h of Muffle furnace flat Board-like CH4-SCR catalyst.Catalyst components percentage by weight is respectively as follows: copper oxide 5%, and praseodymium oxide is 1%, yittrium oxide is 2%, and magnesium oxide is 2%, and γ type aluminium oxide is 90%.
Simulated flue gas condition is used the performance of this denitrating catalyst to be evaluated, with CH4For reducing agent, typical case Under flue gas operating mode: NO is 700mg/m3, CH4For 3700mg/m3, O2It is 1% (v/v), H2O is 8% (v/v), N2For Balance Air, air speed is 5000h-1, reaction temperature be denitration efficiency when 550 DEG C be 98.8%, The removal efficiency of methane is 100%.
Should be understood that the above-described embodiment technology only for the explanation present invention is conceived and feature, its object is to for ability Field technique personnel understand present disclosure and implement according to this, and not detailed description of the invention is exhaustive, can not be with This limits the scope of the invention.All modify according to technical scheme or equivalent, and Without departing from objective and the scope of technical solution of the present invention, it all should be contained in the middle of scope of the presently claimed invention.

Claims (8)

1. a methyl hydride catalyzed reduction NOxTechnique, it is characterised in that comprise the following steps:
The board-like catalyst of upper and lower two-layer, the wherein board-like catalyst in upper strata (2) is placed in catalytic reduction reactor (1) For cocatalyst, the board-like catalyst of lower floor (3) is major catalyst, with dividing plate (4) by board-like for described lower floor catalysis Agent (3) is divided into left and right left district catalyst (3-1) placed side by side and right district catalyst (3-2), under dividing plate (4) Side connects switching valve (5) and gas baffle (6), and regulation switching valve (5) can make gas baffle (6) close described dividing plate (4) switch between left field and right side area；At dividing plate (4) left field and the catalytic reduction reaction of right side area Left gas pipeline (7-1) and Top right gas pipeline (7-2) is outputed respectively on device (1) wall；
Will be containing NO during workxBoiler smoke be passed through from the bottom of catalytic reduction reactor (1), will reaction after Flue gas discharge from the top exit of catalytic reduction reactor (1), work process includes two kinds of mode of operations:
Mode of operation one: regulation switching valve (5) makes gas baffle (6) enclosed baffle (4) right side area, the pot being passed through Kiln gas flows through untight left district catalyst (3-1), is passed through methane gas in left gas pipeline (7-1) simultaneously In left field, complete denitration reaction, and be passed through air in Top right gas pipeline (7-2)；
Mode of operation two: regulation switching valve (5) makes gas baffle (6) enclosed baffle (4) left field, the pot being passed through Kiln gas flows through untight right district catalyst (3-2), is passed through methane gas in Top right gas pipeline (7-2) simultaneously In right side area, complete denitration reaction, and be passed through air in left gas pipeline (7-1)；
Circulation uses mode of operation one and mode of operation two to carry out the continuous denitration reaction of boiler smoke, when denitration is anti- Lower floor's board-like catalyst (3) activity answering region switches to another kind of mode of operation when starting to reduce.
Technique the most according to claim 1, it is characterised in that: described flue-gas temperature is 350-800 DEG C.
3. it has been used for the board-like catalyst of technique described in claim 1, it is characterised in that: described catalyst Including active component, metal promoter, carrier, shaping assistant and rustless steel web plate, wherein said active component is Copper oxide, metal promoter is one or more in yittrium oxide, praseodymium oxide, magnesium oxide or lanthana, and carrier is γ type aluminium oxide, described shaping assistant is also γ type aluminium oxide.
Catalyst the most according to claim 3, it is characterised in that: each composition weight hundred in described catalyst Proportion by subtraction is: copper oxide is 0.5-10%, metal oxide auxiliary agent be 0.1-5%, γ type aluminium oxide be 85-95%.
Catalyst the most according to claim 3, its preparation method comprises the steps:
1. the Gerhardite of 15-300 weight portion, the magnesium nitrate of 2-180 weight portion or six nitric hydrates are weighed One or more in praseodymium or six nitric hydrate yttriums or lanthanum nitrate hexahydrate, the γ type oxidation of 800-900 weight portion Alumina supporter；Water absorption rate according to carrier calculates water requirement, Gerhardite and auxiliary agent presoma is respectively configured Become saline solution, use equi-volume impregnating to be added sequentially to by the saline solution configured in γ type alumina support, And carry out in a mixer mixing and stirring；
2. the boehmite of 10-50 weight portion, the organic binder bond of 5-15 weight portion are joined step 1. in Carry out in the batch mixing obtained mixing and stirring, obtain catalyst mastic；
3. the catalyst mastic after step 2. middle mix homogeneously is placed on rustless steel web plate, through roll coated, pressure Pleat, shear, be dried and roasting after can obtain flat CH4-SCR catalyst.
The preparation method of catalyst the most according to claim 5, it is characterised in that: described step 2. in Organic binder bond is the one in carboxymethyl cellulose, methylcellulose, polyvinyl alcohol or polyethylene glycol oxide or several The combination planted.
The preparation method of catalyst the most according to claim 5, it is characterised in that: described step 3. in Being dried as oven drying, baking temperature is 105 DEG C, and drying time is 2-24h.
The preparation method of catalyst the most according to claim 5, it is characterised in that: described step 3. in Sintering temperature is 500-900 DEG C, and roasting time is 2-8h.
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