CN105618162B - A kind of recycling method of discarded vanadium tungsten titanium-based denitrating catalyst - Google Patents

A kind of recycling method of discarded vanadium tungsten titanium-based denitrating catalyst Download PDF

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CN105618162B
CN105618162B CN201610003453.9A CN201610003453A CN105618162B CN 105618162 B CN105618162 B CN 105618162B CN 201610003453 A CN201610003453 A CN 201610003453A CN 105618162 B CN105618162 B CN 105618162B
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catalyst
cleaning solution
cleaning
sodium
acid
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CN105618162A (en
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李春启
梅长松
王旭金
段世慈
冯巍
陈爱平
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Datang International Chemical Technology Research Institute Co Ltd
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    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
    • 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
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • B01J38/62—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids organic
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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Abstract

The present invention relates to a kind of recycling methods of discarded vanadium tungsten titanium-based denitrating catalyst, including：The first cleaning solution and the second cleaning solution is used to clean discarded vanadium tungsten titanium-based denitrating catalyst successively, dry and roasting.Alternatively, the method further includes：Reclaimed materials after roasting is crushed, the catalyst recycling powder of 500~2000 mesh is made and vanadium tungsten titanium-based denitrating catalyst is made in catalyst recycling powder.Waste catalyst has been carried out the cleaning of two steps by this method, eliminates the total poisonous and harmful component of dead catalyst.The method use two kinds of cleaning solutions, to ensure that reclaimed materials may be directly applied to prepare catalyst.The secondary use of waste flue gas denitration catalyst may be implemented in this method, realizes recycling for resource, reduces cost, energy saving, reduces environment protection treating difficulty, and comprehensive benefit is high.

Description

A kind of recycling method of discarded vanadium tungsten titanium-based denitrating catalyst
Technical field
The invention belongs to filed of flue gas purification, and returning in particular it relates to a kind of discarded vanadium tungsten titanium-based denitrating catalyst Receive reuse method.
Background technology
Selective catalytic reduction (Selective Catalytic Reduction, referred to as " SCR ") is the coal-fired electricity in China The method for the control discharged nitrous oxides that factory is most widely used, wherein SCR methods core the most is catalyst.It is the most frequently used at present Commercial SCR denitration be V2O5-WO3/TiO2It is (the out of stock catalyst of vanadium tungsten titanium-based), V2O5-WO3/TiO2Series catalysts exist In actual application, due to catalyst poisoning, duct blocking, abrasion etc., cause catalyst activity reduction and structure broken It is badly discarded, the service life of the catalyst is generally 2~4 years.According to statistics, domestic selective catalytic reduction reaction denitration catalysis Agent demand is about 300,000 m3/a.Largely discarded catalyst is will produce after 2~4 years as a result,.
What Chinese Ministry of Environmental Protection issued in 2014《About the notice for reinforcing waste flue gas denitration catalyst supervision》In clearly carry Go out, waste flue gas denitration catalyst, which is included in danger wastes, to be managed, it is desirable that improve its regeneration and utilize disposing capacity.Cause This, rationally using discarded catalyst for denitrating flue gas at current urgent problem.
If most passing through a series of physico-chemical process to the recoverying and utilizing method for discarding catalyst for denitrating flue gas at present Extract metal oxide therein.For example, Chinese patent application CN101921916A, entitled " to be catalyzed from waste flue gas denitration The breakage of discarded catalyst for denitrating flue gas is carried out high temperature roasting by the method that metal oxide is recycled in agent " after being mixed with sodium carbonate It burns, agglomerate filters after impregnating dissolving in the hot water, and sediment roasts after sulfuric acid treatment and obtains titanium dioxide.Filtrate is passed through It reconciles pH value and vanadium oxide, tungsten oxide is made respectively.Product purity made from the method is relatively low, it is difficult to the catalyst system of directly applying to It is standby.
For another example Chinese patent application CN103343236A, entitled " from waste denitration catalyst recovery Pd, vanadium, tungsten Method ", catalyst is ground, highly basic is added and carries out fused salt reaction, deionized water is added after cooling by the solid of titaniferous Detached with the solution of tungstenic, vanadium, tungstenic, vanadium solution the solution of solid and tungstenic containing vanadium is detached through boiling.End product For sodium titanate, sodium metavanadate and sodium tungstate.Product can not also directly apply to catalyst production.
Therefore, a kind of returning for vanadium tungsten titanium-based denitrating catalyst that reclaimed materials can be directly applied to catalyst production is developed Receiving method meets the growth requirement of current catalyst recycling.
Invention content
Therefore, the purpose of the present invention is to provide a kind of recycling methods of discarded vanadium tungsten titanium-based denitrating catalyst, should Method can be recycled discarded vanadium tungsten titanium-based denitrating catalyst, and reclaimed materials obtained may be directly applied to prepare Denitrating catalyst realizes that the closed loop of catalyst utilizes, reduces cost, economize on resources, be more advantageous to and avoid because of waste catalyst not It rationally utilizes and causes environmental pollution.
The purpose of the present invention is what is be achieved through the following technical solutions.
On the one hand, the present invention provides a kind of recycling method of discarded vanadium tungsten titanium-based denitrating catalyst, the sides Method includes the following steps：
(1) cleaning of vanadium tungsten titanium-based denitrating catalyst is discarded：Use the first cleaning solution and the second cleaning solution to discarded successively Vanadium tungsten titanium-based denitrating catalyst is cleaned, until di-iron trioxide (Fe in catalyst2O3), arsenic trioxide (As2O3), oxygen Change sodium (Na2) and potassium oxide (K O2O content) is below 0.001wt%, and phosphorus pentoxide (P2O5) content be less than 0.01wt%, wherein first cleaning solution include 0.01~5wt% sodium hydroxide and/or potassium hydroxide, 0.01~ The diethylene-triamine pentaacetic acid of the sodium carbonate of 5wt%, the sodium ethylene diamine tetracetate of 0.001~2wt%, 0.001~2wt% Sodium, the sodium nitrilo triacetate of 0~2wt%, the sodium citrate of 0.001~1wt%, the JFC of 0.001~1.5wt%, 0.001~ The water of the OP-10 of 1.5wt%, the peregal of 0.001~1.5wt%, the sodium pyrophosphate of 0.001~1wt% and surplus；With it is described Second cleaning solution includes oxalic acid, the 0~2wt% of the sulfuric acid of 0.01~15wt%, the citric acid of 0.01~2wt%, 0~2wt% Tartaric acid, the ethylenediamine tetra-acetic acid of 0.001~1wt%, the nitrilotriacetic acid of 0~0.5wt%, 0~2wt% diethylidene Pentaacetic acid, the JFC of 0.001~1.5wt%, the OP-10 of 0.001~1.5wt%, 0.001~1.5wt% peregal and The water of surplus；
(2) dry：The catalyst obtained to step (1) is dried；With
(3) it roasts：The catalyst that step (2) obtains is roasted at 300~600 DEG C, obtains reclaimed materials.
On the other hand, it the present invention provides a kind of recycling of discarded vanadium tungsten titanium-based denitrating catalyst and is prepared into being catalyzed The method of agent, the described method comprises the following steps：
(1) cleaning of vanadium tungsten titanium-based denitrating catalyst is discarded：Use the first cleaning solution and the second cleaning solution to discarded successively Vanadium tungsten titanium-based denitrating catalyst is cleaned, until di-iron trioxide (Fe in catalyst2O3), arsenic trioxide (As2O3), oxygen Change sodium (Na2) and potassium oxide (K O2O content) is below 0.001wt%, and phosphorus pentoxide (P2O5) content be less than 0.01wt%, wherein first cleaning solution include 0.01~5wt% sodium hydroxide and/or potassium hydroxide, 0.01~ The diethylene-triamine pentaacetic acid of the sodium carbonate of 5wt%, the sodium ethylene diamine tetracetate of 0.001~2wt%, 0.001~2wt% Sodium, the sodium nitrilo triacetate of 0~2wt%, the sodium citrate of 0.001~1wt%, the JFC of 0.001~1.5wt%, 0.001~ The water of the OP-10 of 1.5wt%, the peregal of 0.001~1.5wt%, the sodium pyrophosphate of 0.001~1wt% and surplus；With it is described Second cleaning solution includes oxalic acid, the 0~2wt% of the sulfuric acid of 0.01~15wt%, the citric acid of 0.01~2wt%, 0~2wt% Tartaric acid, the ethylenediamine tetra-acetic acid of 0.001~1wt%, the nitrilotriacetic acid of 0~0.5wt%, 0~2wt% diethylidene Pentaacetic acid, the JFC of 0.001~1.5wt%, the OP-10 of 0.001~1.5wt%, 0.001~1.5wt% peregal and The water of surplus；
(2) dry：The catalyst obtained to step (1) is dried；With
(3) it roasts：The catalyst that step (2) obtains is roasted at 300~600 DEG C, obtains reclaimed materials；
(4) it crushes：Reclaimed materials after roasting in step (3) is crushed, the catalyst recycling of 500~2000 mesh is made Powder；
(5) catalyst is prepared：Vanadium tungsten titanium-based denitrating catalyst is made in the catalyst recycling powder obtained in step (4).
According to method provided by the invention, in order to remove the dust in catalyst surface and duct, the method further includes： Before cleaning step, dedusting of negative pressure is carried out to discarded vanadium tungsten titanium-based denitrating catalyst first, it is preferable that the dedusting of negative pressure is It is carried out under the vacuum degree of 20~45kPa.
According to method provided by the invention, wherein sodium nitrilo triacetate in the first cleaning solution described in the step (1) Content is 0.001~2wt%；The content of the second cleaning solution mesoxalic acid is 0.01~2wt%, and the content of nitrilotriacetic acid is 0.001~0.5wt%'s and diethylene-triamine pentaacetic acid content is 0.001~2wt%.
In some embodiments, first cleaning solution include 0.5~5wt% sodium hydroxide and/or potassium hydroxide, Five second of diethylenetriamines of the sodium carbonate of 0.1~5wt%, the sodium ethylene diamine tetracetate of 0.01~1wt%, 0.05~1wt% Sour sodium, the sodium nitrilo triacetate of 0.001~0.1wt%, the sodium citrate of 0.01~1wt%, the JFC of 0.01~1wt%, 0.01 The water of the OP-10 of~1wt%, the peregal of 0.01~1wt%, the sodium pyrophosphate of 0.05~1wt% and surplus；And at some In preferred embodiment, first cleaning solution include 1~3wt% sodium hydroxide and/or potassium hydroxide and 0.5~ The sodium carbonate of 3wt%.
In some embodiments, second cleaning solution includes the lemon of the sulfuric acid of 0.5~15wt%, 0.01~2wt% Lemon acid, the oxalic acid of 0.01~1wt%, 0~2% tartaric acid, the ethylenediamine tetra-acetic acid of 0.01~1wt%, 0.01~0.5wt% Nitrilotriacetic acid, the diethylene-triamine pentaacetic acid of 0~1wt%, the JFC of 0.01~1wt%, 0.005~1wt% OP- 10, the water of the peregal of 0.01~1wt% and surplus；And in some preferred embodiments, the second cleaning solution packet The oxalic acid of the citric acid and 0.1~0.8wt% of sulfuric acid, 0.1~1wt% containing 0.5~5wt%.
According to method provided by the invention, wherein the first cleaning solution described in the step (1) and second cleaning The dosage of liquid is each independently 1.2~5L cleaning solutions per 0.001m3Catalyst, preferably 1.5~4L cleaning solutions are per 0.001m3 Catalyst.
According to method provided by the invention, wherein the cleaning operation in the step (1) includes：First by discarded vanadium tungsten Titanium-based denitrating catalyst impregnates such as 60~120min, ultrasonic cleaning or/and pressure pulse cleaning such as 15 in the first cleaning solution ~480min, preferably 30~240min, more preferable 60~120min；However again by discarded vanadium tungsten titanium-based denitrating catalyst second Impregnate such as 60~120min in cleaning solution, ultrasonic cleaning or/and pressure pulse cleaning such as 15~480min, preferably 30~ 240min, more preferable 60~120min.
According to method provided by the invention, the method further includes：In the first cleaning solution of use and the second cleaning solution to useless It abandons after vanadium tungsten titanium-based denitrating catalyst cleaned, deionized water cleaning is carried out to catalyst.
According to method provided by the invention, wherein using the first cleaning solution and the second cleaning solution to useless in the step (1) It is 10~90 DEG C to abandon the temperature that vanadium tungsten titanium-based denitrating catalyst is cleaned, preferably 20~60 DEG C, more preferably 30~60 DEG C.
According to method provided by the invention, wherein dry temperature is 60~200 DEG C in the step (2), preferably 80 ~120 DEG C, the time is 1~48h, preferably 2~30h.
According to method provided by the invention, wherein the temperature roasted in the step (3) is 300~500 DEG C, preferably 350~500 DEG C.
According to method provided by the invention, wherein the time roasted is 1~60h, preferably 2~30h.
According to method provided by the invention, wherein when preparing vanadium tungsten titanium-based denitrating catalyst using catalyst recycling powder, Catalyst recycling powder is can be used alone, can also the catalyst of acquisition be recycled to powder and is prepared by fresh denitrating catalyst Raw material is sufficiently mixed, to which production obtains molding denitrating catalyst.
The combination of JFC, OP-10, peregal and acid or alkali can be to blocking or covering catalysts in the cleaning solution of the present invention The dirts such as the silica in surface and duct, calcium sulfate are effectively removed.In addition, JFC, OP-10, peregal and acid or alkali Combination is under the collective effect of remaining component, it is possibility to have removes the poisoning substance such as arsenic, phosphorus in effect ground.
The recovery method of the SCR denitration of the present invention has the following advantages：
The priority effect of (1) two kind of cleaning solution (i.e. the first cleaning solution and the second cleaning solution) can effectively remove SCR denitration and urge The various dirts in agent surface (for example, silica, alchlor, calcium sulfate etc.) and multiple catalysts poisoning are (for example, alkalinity gold Category, phosphorus, heavy metal arsenic, chromium poisoning) substance；
(2) secondary use of waste denitration catalyst may be implemented in recovery method of the invention, and recovery utilization rate is high, is easy Quickly processing, saving is concentrated to prepare the use of the fresh feed of catalyst.Reduce dangerous solid waste discharge, realizes money Source recycles, and reduces cost, energy saving, and comprehensive benefit is high.
(3) the SCR denitration activity made from the method for the present invention is high, and stability is good.
Description of the drawings
Hereinafter, carry out the embodiment that the present invention will be described in detail in conjunction with attached drawing, wherein：
Fig. 1 is a kind of work of embodiment of the recycling method of the discarded vanadium tungsten titanium-based denitrating catalyst of the present invention Skill flow chart.
Fig. 2 is the SO used in the present invention3Concentration sampling analysis device schematic diagram；
Fig. 3 is the relational graph of catalyst run of the present invention and denitrification rate.
Specific implementation mode
The present invention is further described in detail With reference to embodiment, the embodiment provided is only for explaining The bright present invention, the range being not intended to be limiting of the invention.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, used equipment and raw material etc. It is commercially available or commonly uses in the art.
Embodiment 1
A kind of recycling method of discarded vanadium tungsten titanium-based denitrating catalyst, is as follows：
(1), 0.001m is taken3Run more than the inactivation honeycomb type catalyst of 150mm × 150mm × 1100mm of 24000h V2O5-WO3/TiO2Series catalysts carry out dedusting of negative pressure by negative-pressure vacuum equipment, in fully erased catalyst surface and duct Dust.
(2), the first cleaning solution and the second cleaning solution are prepared：The formula of first cleaning solution is：1% sodium hydroxide, 0.5% Sodium carbonate, 0.05% sodium ethylene diamine tetracetate, 0.05% diethylenetriaminepentaacetic acid sodium, 0.03% citric acid The deionized water of sodium, 1% JFC, 0.01% OP-10,0.01% peregal, 0.05% sodium pyrophosphate and surplus；With The formula of second cleaning solution is：3% sulfuric acid, 0.5% citric acid, 0.1% tartaric acid, 0.01% ethylenediamine tetrem Acid, 0.01% JFC, 0.005% OP-10,1% peregal and the deionized water of surplus.First is prepared by above-mentioned formula With the second cleaning solution, 2h is stirred after each material mixing.
(3), cleaning catalyst：First, the first cleaning solution prepared by 2.5L steps (2) is put into supersonic wave cleaning machine and is added Heat is put into the catalyst after ash disposal made from step (1) in supersonic wave cleaning machine to 40 DEG C and impregnates 2h, is cleaned by ultrasonic 1h；So Afterwards, the first cleaning solution is emptied, the second cleaning solution for injecting 2.5L is warming up to 40 DEG C, impregnates 1h, is cleaned by ultrasonic 1h；Finally, will Catalyst, which is put into deionized water, is cleaned by ultrasonic 0.5h.
(4), analysis detection：Catalyst after being cleaned to step (3) carries out elemental analysis, if three oxidation two in catalyst Iron (Fe2O3), arsenic trioxide (As2O3), sodium oxide molybdena (Na2) and potassium oxide (K O2O content) is below 0.001wt%, and five Aoxidize two phosphorus (P2O5) content be less than 0.01wt%, then it is up to standard, carry out next step operation, conversely, then repeat step (3).
(5), it is dried：Processing is dried in the catalyst up to standard of detection in step (4), drying temperature is 120 DEG C, Drying time is 10h.
(6), calcination process：Catalyst after will be dry in step (5), which is put into roaster, to be roasted, and is recycled Material, wherein calcination temperature is 450 DEG C, roasting time 10h.
(7), pulverization process：Reclaimed materials after roasting in step (6) is crushed to 1200 mesh, catalyst is obtained and recycles powder Material.
(8), catalyst preparation：By the denitrating catalyst system that the recycling powder and 700g that are obtained in 300g steps (7) are fresh Standby raw material (wherein, 591g titanium dioxide, 36g ammonium paratungstates, 8g ammonium metavanadates, 35g methylcellulose and 30g glass fibres) into Row is sufficiently mixed, and molding denitrating catalyst is obtained using catalysis former (the vertical sleeping extruder of LWJ70 type vacuum) production.
Embodiment 2
A kind of recycling method of discarded vanadium tungsten titanium-based denitrating catalyst, is as follows：
(1), 0.001m is taken3Run more than the inactivation honeycomb type catalyst of 150mm × 150mm × 1100mm of 24000h V2O5-WO3/TiO2Series catalysts carry out dedusting of negative pressure by negative-pressure vacuum equipment, in fully erased catalyst surface and duct Dust.
(2), the first cleaning solution and the second cleaning solution are prepared：The formula of first cleaning solution is：1% sodium hydroxide, 1% Potassium hydroxide, 1% sodium carbonate, 0.05% sodium ethylene diamine tetracetate, 0.1% diethylenetriaminepentaacetic acid sodium, 0.05% sodium nitrilo triacetate, 0.1% sodium citrate, 0.1% JFC, 1% OP-10,0.1% peregal, 0.1% sodium pyrophosphate and the deionized water of surplus；It is with the second cleaning formula of liquid：1% sulfuric acid, 1% citric acid, 1% Oxalic acid, 0.5% tartaric acid, 0.02% ethylenediamine tetra-acetic acid, 0.1% nitrilotriacetic acid, 0.02% diethylidene Pentaacetic acid, 1% JFC, 0.1% OP-10,0.5% peregal and the deionized water of surplus.It is prepared by above-mentioned formula First and second cleaning solutions stir 1h after each material mixing.
(3), cleaning catalyst：First, the first cleaning solution prepared by 1.5L steps (2) is put into supersonic wave cleaning machine and is added Catalyst after ash disposal in step (1) is put into supersonic wave cleaning machine to 30 DEG C and impregnates 1h by heat, is cleaned by ultrasonic 2h；Then, will First cleaning solution empties, and the second cleaning solution for injecting 1.5L is warming up to 30 DEG C, impregnates 1h, is cleaned by ultrasonic 2h；Finally, by catalyst It is put into deionized water and is cleaned by ultrasonic 1h.
(4), analysis detection：Catalyst after being cleaned to step (3) carries out elemental analysis, if three oxidation two in catalyst Iron (Fe2O3), arsenic trioxide (As2O3), sodium oxide molybdena (Na2) and potassium oxide (K O2O content) is below 0.001wt%, and five Aoxidize two phosphorus (P2O5) content be less than 0.01wt%, then it is up to standard, carry out next step operation, conversely, then repeat step (3).
(5), it is dried：Processing is dried by catalyst up to standard is detected through step (4), drying temperature is 140 DEG C, Drying time is 5h.
(6), calcination process：Catalyst after will be dry in step (5), which is put into roaster, to be roasted, and is recycled Material, wherein calcination temperature is 500 DEG C, roasting time 8h.
(7), pulverization process：Reclaimed materials after roasting in step (6) is crushed to 800 mesh, catalyst is obtained and recycles powder.
(8), catalyst preparation：By the denitrating catalyst system that the recycling powder and 800g that are obtained in 200g steps (7) are fresh Standby raw material (wherein, 645g titanium dioxide, 45g ammonium paratungstates, 10g ammonium metavanadates, 45g methylcellulose and glass fibre 55g) It is sufficiently mixed, molding denitrating catalyst is obtained using catalysis former (the vertical sleeping extruder of LWJ70 type vacuum) production.
Embodiment 3
A kind of recycling method of discarded vanadium tungsten titanium-based denitrating catalyst, is as follows：
(1), 0.003m is taken3Run more than the inactivation honeycomb type catalyst of 150mm × 150mm × 1100mm of 24000h V2O5-WO3/TiO2Series catalysts carry out dedusting of negative pressure by negative-pressure vacuum equipment, in fully erased catalyst surface and duct Dust.
(2), the first cleaning solution and the second cleaning solution are prepared：The formula of first cleaning solution is：1% sodium hydroxide, 1% Potassium hydroxide, 1% sodium carbonate, 0.05% sodium ethylene diamine tetracetate, 0.1% diethylenetriaminepentaacetic acid sodium, 0.05% sodium nitrilo triacetate, 0.1% sodium citrate, 0.1% JFC, 0.1% OP-10,1% peregal, 0.1% sodium pyrophosphate and the deionized water of surplus；Second, which cleans formula of liquid, is：5% sulfuric acid, 1% citric acid, 0.02% Ethylenediamine tetra-acetic acid, 0.1% nitrilotriacetic acid, 0.02% diethylene-triamine pentaacetic acid, 0.1% JFC, 1% OP-10,0.5% peregal and the deionized water of surplus.Cleaning solution is prepared by above-mentioned formula, 1h is stirred after each material mixing.
(3), cleaning catalyst：First, the first cleaning solution prepared by 12L steps (2) is put into supersonic wave cleaning machine and is added Catalyst after ash disposal in step (1) is put into supersonic wave cleaning machine to 50 DEG C and impregnates 1h by heat, is cleaned by ultrasonic 2h；Then, will First cleaning solution empties, and the second cleaning solution for injecting 12L is warming up to 50 DEG C, impregnates 1h, is cleaned by ultrasonic 2h；Finally, by catalyst It is put into deionized water and is cleaned by ultrasonic 2h.
(4), analysis detection：Catalyst after being cleaned to step (3) carries out elemental analysis, if three oxidation two in catalyst Iron (Fe2O3), arsenic trioxide (As2O3), sodium oxide molybdena (Na2) and potassium oxide (K O2O content) is below 0.001wt%, and five Aoxidize two phosphorus (P2O5) content be less than 0.01wt%, then it is up to standard, carry out next step operation, conversely, then repeat step (3).
(5), it is dried：Processing is dried by catalyst up to standard is detected through step (4), drying temperature is 120 DEG C, Drying time is 8h.
(6), calcination process：Catalyst after will be dry in step (5), which is put into roaster, to be roasted, and is recycled Material, calcination temperature are 500 DEG C, roasting time 5h.
(7), pulverization process：Reclaimed materials after roasting in step (6) is crushed to 1000 mesh, catalyst is obtained and recycles powder Material.
(8), catalyst preparation：By the recycling powder and 500g that obtain in 500g steps (7) (wherein, 395g titanium dioxide, 27g ammonium paratungstates, 6g ammonium metavanadates, 32g methylcellulose and glass fibre 40g) it is sufficiently mixed, it is set using catalysis molding Standby (the vertical sleeping extruder of LWJ70 type vacuum) production obtains molding denitrating catalyst.
Embodiment 4
A kind of recycling method of discarded vanadium tungsten titanium-based denitrating catalyst, is as follows：
(1), 0.003m is taken3Run more than the inactivation honeycomb type catalyst of 150mm × 150mm × 1100mm of 24000h V2O5-WO3/TiO2Series catalysts carry out dedusting of negative pressure by negative-pressure vacuum equipment, in fully erased catalyst surface and duct Dust.
(2), the first cleaning solution and the second cleaning solution are prepared：The formula of first cleaning solution is：2% sodium hydroxide, 1% carbon Sour sodium, 0.2% sodium ethylene diamine tetracetate, 0.1% diethylenetriaminepentaacetic acid sodium, 0.1% sodium nitrilo triacetate, 0.2% sodium citrate, 0.1% JFC, 0.1% OP-10,0.1% peregal, 1% sodium pyrophosphate and surplus go from Sub- water；Second, which cleans formula of liquid, is：3% sulfuric acid, 1% citric acid, 0.5% ethylenediamine tetra-acetic acid, 0.1% nitrilo three Acetic acid, 1% diethylene-triamine pentaacetic acid, 0.1% JFC, 0.1% OP-10,0.5% peregal and surplus are gone Ionized water.Cleaning solution is prepared by above-mentioned formula, 40min is stirred after each material mixing.
(3), cleaning catalyst：First, the first cleaning solution prepared by 8L steps (2) is put into supersonic wave cleaning machine and is heated To 60 DEG C, the catalyst in step (1) after ash disposal, which is put into supersonic wave cleaning machine, impregnates 2h, is cleaned by ultrasonic 2h；Then, by first Clear cleaning solution empties, and the second cleaning solution for injecting 8L is warming up to 60 DEG C, impregnates 2h, is cleaned by ultrasonic 2h；Finally, catalyst is put into It is cleaned by ultrasonic 1h in deionized water.
(4), analysis detection：Catalyst after being cleaned to step (3) carries out elemental analysis, if three oxidation two in catalyst Iron (Fe2O3), arsenic trioxide (As2O3), sodium oxide molybdena (Na2) and potassium oxide (K O2O content) is below 0.001wt%, and five Aoxidize two phosphorus (P2O5) content be less than 0.01wt%, then it is up to standard, carry out next step operation, conversely, then repeat step (3).
(5), it is dried：Processing is dried by catalyst up to standard is detected through step (4), drying temperature is 130 DEG C, Drying time is 8h.
(6), calcination process：Catalyst after will be dry in step (5), which is put into roaster, to be roasted, and is recycled Material, calcination temperature are 500 DEG C, roasting time 20h.
(7), pulverization process：Reclaimed materials after roasting in step (6) is crushed to 1200 mesh, catalyst is obtained and recycles powder Material.
(8), catalyst preparation：It prepared by the fresh denitrating catalyst of the powder and 400g that are obtained in 600g steps (7) former It is abundant to expect that (338.5g titanium dioxide, 22g ammonium paratungstates, 4.5g ammonium metavanadates, 25g methylcellulose, 10g glass fibres) carries out Mixing obtains molding denitrating catalyst using catalysis former (the vertical sleeping extruder of LWJ70 type vacuum) production.
Embodiment 5
A kind of recycling method of discarded vanadium tungsten titanium-based denitrating catalyst, is as follows：
(1), 0.02m is taken3Run more than the inactivation honeycomb type catalyst of 150mm × 150mm × 1100mm of 24000h V2O5-WO3/TiO2Series catalysts carry out dedusting of negative pressure by negative-pressure vacuum equipment, in fully erased catalyst surface and duct Dust.
(2), the first cleaning solution and the second cleaning solution are prepared：The formula of first cleaning solution is：2% sodium hydroxide, 1% carbon Sour sodium, 0.15% sodium ethylene diamine tetracetate, 0.2% diethylenetriaminepentaacetic acid sodium, 1% sodium citrate, 0.01% JFC, 0.01% OP-10,0.01% peregal, 0.05% sodium pyrophosphate and surplus deionized water；With the second cleaning Formula of liquid is：2.5% sulfuric acid, 0.5% citric acid, 0.5% tartaric acid, 0.5% nitrilotriacetic acid, 0.1% second Ethylenediamine tetraacetic acid (EDTA), 0.1% JFC, 0.2% OP-10,0.2% peregal and the deionized water of surplus.By above-mentioned formula system For cleaning solution, 1h is stirred after each material mixing.
(3), cleaning catalyst：First, the first cleaning solution prepared by 40L steps (2) is put into supersonic wave cleaning machine and is added Heat is put into the catalyst of ash disposal in step (1) in supersonic wave cleaning machine to 40 DEG C and impregnates 1h, is cleaned by ultrasonic 2h；Then, by One clear cleaning solution empties, and the second cleaning solution for injecting 60L is warming up to 40 DEG C, impregnates 1h, is cleaned by ultrasonic 3h；Finally, by catalyst It is put into deionized water and is cleaned by ultrasonic 2h.
(4), analysis detection：Catalyst after being cleaned to step (3) carries out elemental analysis, if three oxidation two in catalyst Iron (Fe2O3), arsenic trioxide (As2O3), sodium oxide molybdena (Na2) and potassium oxide (K O2O content) is below 0.001wt%, and five Aoxidize two phosphorus (P2O5) content be less than 0.01wt%, then it is up to standard, carry out next step operation, conversely, then repeat step (3).
(5), it is dried：Processing is dried by catalyst up to standard is detected through step (4), drying temperature is 120 DEG C, Drying time is 8h.
(6), calcination process：Catalyst after will be dry in step (5), which is put into roaster, to be roasted, and is recycled Material, calcination temperature are 500 DEG C, roasting time 15h.
(7), pulverization process：Reclaimed materials after roasting in step (6) is crushed to 800 mesh, catalyst is obtained and recycles powder.
(8), catalyst preparation：By the powder and 7000g that are obtained in 2000g steps (7), (6021g titanium dioxide, 365g are secondary Ammonium tungstate, 74g ammonium metavanadates, 300g methylcellulose, 240g glass fibres) it is sufficiently mixed, use catalysis former (the vertical sleeping extruder of LWJ70 type vacuum) production obtains molding denitrating catalyst.
Embodiment 6
A kind of recycling method of discarded vanadium tungsten titanium-based denitrating catalyst, is as follows：
(1), 0.001m is taken3Run more than the inactivation honeycomb type catalyst of 150mm × 150mm × 1100mm of 24000h V2O5-WO3/TiO2Series catalysts carry out dedusting of negative pressure by negative-pressure vacuum equipment, in fully erased catalyst surface and duct Dust.
(2), the first cleaning solution and the second cleaning solution are prepared：The formula of first cleaning solution is：5% sodium hydroxide, 0.1% Sodium carbonate, 1% sodium ethylene diamine tetracetate, 0.05% diethylenetriaminepentaacetic acid sodium, 0.03% sodium citrate, The deionized water of 0.01% JFC, 0.01% OP-10,0.01% peregal, 0.05% sodium pyrophosphate and surplus；With The formula of second cleaning solution is：0.5% sulfuric acid, 2% citric acid, 2% tartaric acid, 0.5% ethylenediamine tetra-acetic acid, 0.01% JFC, 0.01% OP-10,0.01% peregal and the deionized water of surplus.The first He is prepared by above-mentioned formula Second cleaning solution stirs 2h after each material mixing.
(3), cleaning catalyst：First, the first cleaning solution prepared by 3L steps (2) is put into supersonic wave cleaning machine and is heated To 40 DEG C, the catalyst after ash disposal made from step (1) is put into supersonic wave cleaning machine and impregnates 2h, is cleaned by ultrasonic 1h；Then, First cleaning solution is emptied, the second cleaning solution for injecting 3L is warming up to 40 DEG C, impregnates 1h, is cleaned by ultrasonic 1h；Finally, by catalyst It is put into deionized water and is cleaned by ultrasonic 0.5h.
(4), analysis detection：Catalyst after being cleaned to step (3) carries out elemental analysis, if three oxidation two in catalyst Iron (Fe2O3), arsenic trioxide (As2O3), sodium oxide molybdena (Na2) and potassium oxide (K O2O content) is below 0.001wt%, and five Aoxidize two phosphorus (P2O5) content be less than 0.01wt%, then it is up to standard, carry out next step operation, conversely, then repeat step (3).
(5), it is dried：Processing is dried in the catalyst up to standard of detection in step (4), drying temperature is 120 DEG C, Drying time is 10h.
(6), calcination process：Catalyst after will be dry in step (5), which is put into roaster, to be roasted, and is recycled Material, wherein calcination temperature is 450 DEG C, roasting time 10h.
(7), pulverization process：Reclaimed materials after roasting in step (6) is crushed to 1200 mesh, catalyst is obtained and recycles powder Material.
(8), catalyst preparation：By the denitrating catalyst system that the recycling powder and 700g that are obtained in 500g steps (7) are fresh Standby raw material (wherein, 591g titanium dioxide, 36g ammonium paratungstates, 8g ammonium metavanadates, 35g methylcellulose and 30g glass fibres) into Row is sufficiently mixed, and molding denitrating catalyst is obtained using catalysis former (the vertical sleeping extruder of LWJ70 type vacuum) production.
Embodiment 7
A kind of recycling method of discarded vanadium tungsten titanium-based denitrating catalyst, is as follows：
(1), 0.001m is taken3Run more than the inactivation honeycomb type catalyst of 150mm × 150mm × 1100mm of 24000h V2O5-WO3/TiO2Series catalysts carry out dedusting of negative pressure by negative-pressure vacuum equipment, in fully erased catalyst surface and duct Dust.
(2), the first cleaning solution and the second cleaning solution are prepared：The formula of first cleaning solution is：0.5% sodium hydroxide, 5% Sodium carbonate, 0.01% sodium ethylene diamine tetracetate, 1% diethylenetriaminepentaacetic acid sodium, 0.01% sodium citrate, The deionized water of 0.01% JFC, 0.01% OP-10,0.01% peregal, 0.05% sodium pyrophosphate and surplus；With The formula of second cleaning solution is：15% sulfuric acid, 1% ethylenediamine tetra-acetic acid, 0.01% JFC, 0.01% OP-10, 0.01% peregal and the deionized water of surplus.The first and second cleaning solutions are prepared by above-mentioned formula, are stirred after each material mixing Mix 2h.
(3), cleaning catalyst：First, the first cleaning solution prepared by 2.5L steps (2) is put into supersonic wave cleaning machine and is added Heat is put into the catalyst after ash disposal made from step (1) in supersonic wave cleaning machine to 30 DEG C and impregnates 1h, is cleaned by ultrasonic 1.5h； Then, the first cleaning solution is emptied, the second cleaning solution for injecting 2.5L is warming up to 25 DEG C, impregnates 1h, is cleaned by ultrasonic 1h；Finally, Catalyst is put into deionized water and is cleaned by ultrasonic 0.5h.
(4), analysis detection：Catalyst after being cleaned to step (3) carries out elemental analysis, if three oxidation two in catalyst Iron (Fe2O3), arsenic trioxide (As2O3), sodium oxide molybdena (Na2) and potassium oxide (K O2O content) is below 0.001wt%, and five Aoxidize two phosphorus (P2O5) content be less than 0.01wt%, then it is up to standard, carry out next step operation, conversely, then repeat step (3).
(5), it is dried：Processing is dried in the catalyst up to standard of detection in step (4), drying temperature is 120 DEG C, Drying time is 10h.
(6), calcination process：Catalyst after will be dry in step (5), which is put into roaster, to be roasted, and is recycled Material, wherein calcination temperature is 450 DEG C, roasting time 10h.
(7), pulverization process：Reclaimed materials after roasting in step (6) is crushed to 1200 mesh, catalyst is obtained and recycles powder Material.
(8), catalyst preparation：By the denitrating catalyst system that the recycling powder and 700g that are obtained in 250g steps (7) are fresh Standby raw material (wherein, 591g titanium dioxide, 36g ammonium paratungstates, 8g ammonium metavanadates, 35g methylcellulose and 30g glass fibres) into Row is sufficiently mixed, and molding denitrating catalyst is obtained using catalysis former (the vertical sleeping extruder of LWJ70 type vacuum) production.
Embodiment 8
A kind of recycling method of discarded vanadium tungsten titanium-based denitrating catalyst, is as follows：
(1), 0.001m is taken3Run more than the inactivation honeycomb type catalyst of 150mm × 150mm × 1100mm of 24000h V2O5-WO3/TiO2Series catalysts carry out dedusting of negative pressure by negative-pressure vacuum equipment, in fully erased catalyst surface and duct Dust.
(2), the first cleaning solution and the second cleaning solution are prepared：The formula of first cleaning solution is：2% sodium hydroxide, 2% Sodium carbonate, 0.01% sodium ethylene diamine tetracetate, 0.05% diethylenetriaminepentaacetic acid sodium, 0.05% nitrilotriacetic acid Sodium, 0.03% sodium citrate, 0.01% JFC, 0.01% OP-10,0.01% peregal, 0.05% sodium pyrophosphate With the deionized water of surplus；Formula with the second cleaning solution is：3% sulfuric acid, 1% citric acid, 1% tartaric acid, 0.5% Ethylenediamine tetra-acetic acid, 0.01% diethylenetriaminepentaacetic acid sodium, 0.01% sodium nitrilo triacetate, 0.01% JFC, The deionized water of 0.01% OP-10,0.01% peregal and surplus.The first and second cleaning solutions are prepared by above-mentioned formula, 2h is stirred after each material mixing.
(3), cleaning catalyst：First, the first cleaning solution prepared by 3L steps (2) is put into supersonic wave cleaning machine and is heated To 40 DEG C, the catalyst after ash disposal made from step (1) is put into supersonic wave cleaning machine and impregnates 2h, is cleaned by ultrasonic 1h；Then, First cleaning solution is emptied, the second cleaning solution for injecting 3L is warming up to 40 DEG C, impregnates 1h, is cleaned by ultrasonic 1h；Finally, by catalyst It is put into deionized water and is cleaned by ultrasonic 0.5h.
(4), analysis detection：Catalyst after being cleaned to step (3) carries out elemental analysis, if three oxidation two in catalyst Iron (Fe2O3), arsenic trioxide (As2O3), sodium oxide molybdena (Na2) and potassium oxide (K O2O content) is below 0.001wt%, and five Aoxidize two phosphorus (P2O5) content be less than 0.01wt%, then it is up to standard, carry out next step operation, conversely, then repeat step (3).
(5), it is dried：Processing is dried in the catalyst up to standard of detection in step (4), drying temperature is 120 DEG C, Drying time is 10h.
(6), calcination process：Catalyst after will be dry in step (5), which is put into roaster, to be roasted, and is recycled Material, wherein calcination temperature is 450 DEG C, roasting time 10h.
(7), pulverization process：Reclaimed materials after roasting in step (6) is crushed to 1200 mesh, catalyst is obtained and recycles powder Material.
(8), catalyst preparation：The recycling powder obtained in 500g steps (7) is used into catalysis former (LWJ70 types The vertical sleeping extruder of vacuum) production obtains molding denitrating catalyst.
Embodiment 9
Using the catalyst of the preparation of Examples 1 to 8 and completely by the catalyst progress catalyst work of fresh feed preparation Property comparison, and test the oxidation rate of sulfur dioxide of catalyst.
1. test method
Catalyst is evaluated in 316L stainless steel fixed bed reactors.Reactor apparatus with catalyst inside loads basket, Load basket apparatus with catalyst inside.To prevent flue gas short-circuit, the gap between catalyst and filling basket, between filling basket and reaction tube It is sealed with silica wool.It is respectively provided with thermocouple in Catalyst packing basket upper and lower part, with the temperature of test reactor, is used N4440 type WEST precision temperature controllers control temperature of reactor.
Experiment uses steel cylinder gas simulative power plant flue gas.Its composition is respectively：N2、O2、CO2、H2O (gaseous state), 5 volume %NO+ N2, 5 volume %SO2+N2.Since NO accounts for NO in typical flue gasx95% or more, NO of volume2Influence very little, can ignore, institute In test NO to be used to replace NOx.Wherein, with volume fraction, the ingredient of experimental condition flue gas is as follows：200ppmNO, 200ppmNH3、800ppmSO2, 3.9%O2, 13.5%CO2, 12.5%H2O and aequum N2, air speed control is in 4500h-1Left and right, Reaction temperature is controlled at 350 DEG C.
Each gas component enters preheating mixer after mass flowmenter control metering；Deionized water is by U.S. ELDEX Steam is added after being vaporized into preheating mixer in brand P-81 type micro-precision metering pumps；5 volume %NH of reducing agent3+N2In ammonia It is added before mixer.
NO, SO in flue gas2、O2Concentration is using the silent winged generation that on-line continuous flue gas analyzer detection of match.SO3Concentration is using beautiful Environmental Protection Administration of state M8 method manual samplings are analyzed, with reference to Fig. 2, specially：SO in flue gas is absorbed by isopropanol3, exhaust gas volumn is recorded, By thorium indicator titrimetry is carried out with barium chloride.
2. denitrification rate
Denitrification rate is calculated according to formula (I), the results are shown in Table 1.
In formula (I)：
η is catalyst denitrification rate, %；
[NOx]inFor reactor inlet NOxVolumetric concentration, ppm；
[NOx]outFor reactor outlet NOxVolumetric concentration, ppm.
3. catalyst activity：
Catalyst activity is calculated according to formula (II), and calculates the mixing of the catalyst and Examples 1 to 5 of fresh feed preparation The catalyst activity that catalyst prepared by material is prepared relative to fresh feed, that is, relative activity (K/Ko), wherein Ko are fresh original The activity for expecting the catalyst prepared, the results are shown in Table 1.
In formula (II)：
K is catalyst activity, m/h；
Q is flue gas flow, m3/h；
V is catalyst volume, m3；
ApFor catalyst geometry specific surface area, m2/m3；
η is catalyst denitrification rate, %；
MR is ammonia nitrogen molar ratio.
4.SO2/SO3Oxygenation efficiency
Catalyst activity is calculated by formula (III), the results are shown in Table 1.
In formula (III)：
K2/3For SO2Oxygenation efficiency, %；
[SO3]inFor reactor inlet SO3Volumetric concentration, ppm；
[SO3]outFor reactor outlet SO3Volumetric concentration, ppm；
[SO2]inFor reactor inlet SO2Volumetric concentration, ppm.
1 catalyst performance test result of table
Catalyst sample Denitrification rate (%) Relative activity (K/Ko) SO2/SO3Oxygenation efficiency (%)
Fresh catalyst 95.0 - 0.82
Embodiment 1 95.2 1.01 0.80
Embodiment 2 94.5 0.97 0.76
Embodiment 3 93.8 0.93 0.77
Embodiment 4 94.4 0.96 0.80
Embodiment 5 95.8 1.06 0.81
Embodiment 6 94.3 0.95 0.72
Embodiment 7 96.1 1.08 0.61
Embodiment 8 94.1 0.94 0.87
As it can be seen from table 1 the results show that the present invention can be good with denitration performance using catalyst prepared by reclaimed materials.
Fig. 3 shows that the catalyst 3000h life assessment result figures prepared in embodiment 1, the catalyst are examined 3000h's Denitrification rate in the time is examined to stablize 95% or so.Catalyst stability of the present invention is good as a result,.

Claims (26)

1. a kind of recycling method of discarded vanadium tungsten titanium-based denitrating catalyst, the described method comprises the following steps：
(1) cleaning of vanadium tungsten titanium-based denitrating catalyst is discarded：Use the first cleaning solution and the second cleaning solution to discarding vanadium tungsten successively Titanium-based denitrating catalyst is cleaned, up to the content of di-iron trioxide, arsenic trioxide, sodium oxide molybdena and potassium oxide in catalyst It is below 0.001wt%, and the content of phosphorus pentoxide is less than 0.01wt%, wherein first cleaning solution includes 0.01~ The ethylenediamine tetra-acetic acid of the sodium hydroxide and/or potassium hydroxide of 5wt%, the sodium carbonate of 0.01~5wt%, 0.001~2wt% The lemon of sodium, the diethylenetriaminepentaacetic acid sodium of 0.001~2wt%, the sodium nitrilo triacetate of 0~2wt%, 0.001~1wt% Lemon acid sodium, the JFC of 0.001~1.5wt%, the OP-10 of 0.001~1.5wt%, the peregal of 0.001~1.5wt%, 0.001 The water of~1wt% sodium pyrophosphates and surplus；Include sulfuric acid, the 0.01~2wt% of 0.01~15wt% with second cleaning solution Citric acid, the oxalic acid of 0~2wt%, the tartaric acid of 0~2wt%, the ethylenediamine tetra-acetic acid of 0.001~1wt%, 0~ The nitrilotriacetic acid of 0.5wt%, the diethylene-triamine pentaacetic acid of 0~2wt%, the JFC of 0.001~1.5wt%, 0.001~ The water of the OP-10 of 1.5wt%, the peregal of 0.001~1.5wt% and surplus；
(2) dry：The catalyst obtained to step (1) is dried；
(3) it roasts：The catalyst that step (2) obtains is roasted at 300-600 DEG C, obtains reclaimed materials.
2. a kind of recycling method of discarded vanadium tungsten titanium-based denitrating catalyst, the described method comprises the following steps：
(1) cleaning of vanadium tungsten titanium-based denitrating catalyst is discarded：Use the first cleaning solution and the second cleaning solution to discarding vanadium tungsten successively Titanium-based denitrating catalyst is cleaned, up to the content of di-iron trioxide, arsenic trioxide, sodium oxide molybdena and potassium oxide in catalyst It is below 0.001wt%, and the content of phosphorus pentoxide is less than 0.01wt%, wherein first cleaning solution includes 0.01~ The ethylenediamine tetra-acetic acid of the sodium hydroxide and/or potassium hydroxide of 5wt%, the sodium carbonate of 0.01~5wt%, 0.001~2wt% The lemon of sodium, the diethylenetriaminepentaacetic acid sodium of 0.001~2wt%, the sodium nitrilo triacetate of 0~2wt%, 0.001~1wt% Lemon acid sodium, the JFC of 0.001~1.5wt%, the OP-10 of 0.001~1.5wt%, the peregal of 0.001~1.5wt%, 0.001 The sodium pyrophosphate of~1wt% and the water of surplus；With second cleaning solution include 0.01~15wt% sulfuric acid, 0.01~ The citric acid of 2wt%, the oxalic acid of 0~2wt%, the tartaric acid of 0~2wt%, the ethylenediamine tetra-acetic acid of 0.001~1wt%, 0~ The nitrilotriacetic acid of 0.5wt%, the diethylene-triamine pentaacetic acid of 0~2wt%, the JFC of 0.001~1.5wt%, 0.001~ The water of the OP-10 of 1.5wt%, the peregal of 0.001~1.5wt% and surplus；
(2) dry：The catalyst obtained to step (1) is dried；With
(3) it roasts：The catalyst that step (2) obtains is roasted at 300-600 DEG C, obtains reclaimed materials；
(4) it crushes：Reclaimed materials after roasting in step (3) is crushed, the catalyst that 500-2000 mesh is made recycles powder； With
(5) catalyst is prepared：Vanadium tungsten titanium-based denitrating catalyst is made in the catalyst recycling powder obtained in step (4).
3. method according to claim 1 or 2, wherein the method further includes：Before cleaning step, first to useless It abandons vanadium tungsten titanium-based denitrating catalyst and carries out dedusting of negative pressure.
4. according to the method described in claim 3, wherein, the dedusting of negative pressure is carried out under the vacuum degree of 20~45kPa.
5. method according to claim 1 or 2, wherein nitrilotriacetic acid in the first cleaning solution described in the step (1) The content of sodium is 0.001~2wt%；The content of the second cleaning solution mesoxalic acid is 0.01~2wt%, and nitrilotriacetic acid contains For 0.001~0.5wt%'s and diethylene-triamine pentaacetic acid, content is 0.001~2wt% to amount.
6. method according to claim 1 or 2, wherein first cleaning solution includes the sodium hydroxide of 0.5~5wt% And/or the two of the sodium carbonate of potassium hydroxide, 0.1~5wt%, the sodium ethylene diamine tetracetate of 0.01~1wt%, 0.05~1wt% Ethylenetriamine pentacetic acid sodium, the sodium nitrilo triacetate of 0.001~0.1wt%, the sodium citrate of 0.01~1wt%, 0.01~ The JFC of 1wt%, the OP-10 of 0.01~1wt%, the peregal of 0.01~1wt%, the sodium pyrophosphate of 0.05~1wt% and surplus Water.
7. according to the method described in claim 6, wherein, first cleaning solution include 1~3wt% sodium hydroxide and/or The sodium carbonate of potassium hydroxide and 0.5~3wt%.
8. method according to claim 1 or 2, wherein sulfuric acid of second cleaning solution comprising 0.5~15wt%, The ethylenediamine tetrem of the citric acid of 0.01~2wt%, the oxalic acid of 0.01~1wt%, 0~2% tartaric acid, 0.01~1wt% Acid, the nitrilotriacetic acid of 0.01~0.5wt%, the diethylene-triamine pentaacetic acid of 0~1wt%, 0.01~1wt% JFC, The water of the OP-10 of 0.005~1wt%, the peregal of 0.01~1wt% and surplus.
9. according to the method described in claim 8, wherein, second cleaning solution include the sulfuric acid of 0.5~5wt%, 0.1~ The citric acid of 1wt% and the oxalic acid of 0.1~0.8wt%.
10. method according to claim 1 or 2, wherein the first cleaning solution and described second described in the step (1) The dosage of cleaning solution is each independently 1.2~5L cleaning solutions per 0.001m3Catalyst.
11. method according to claim 1 or 2, wherein the first cleaning solution and described second described in the step (1) The dosage of cleaning solution is each independently 1.5~4L cleaning solutions per 0.001m3Catalyst.
12. method according to claim 1 or 2, wherein the cleaning operation in the step (1) includes：It will discard first Vanadium tungsten titanium-based denitrating catalyst impregnates 60~120min in the first cleaning solution, and ultrasonic cleaning or/and pressure pulse cleaning 15~ 480min；However discarded vanadium tungsten titanium-based denitrating catalyst is impregnated into 60~120min, ultrasonic cleaning in the second cleaning solution again Or/and 15~480min of pressure pulse cleaning.
13. according to the method for claim 12, wherein the discarded vanadium tungsten titanium-based denitrating catalyst is in the first cleaning solution The time of ultrasonic cleaning or/and pressure pulse cleaning is 30~240min.
14. according to the method for claim 12, wherein the discarded vanadium tungsten titanium-based denitrating catalyst is in the first cleaning solution The time of ultrasonic cleaning or/and pressure pulse cleaning is 60~120min.
15. according to the method for claim 12, wherein the discarded vanadium tungsten titanium-based denitrating catalyst is in the second cleaning solution The time of ultrasonic cleaning or/and pressure pulse cleaning is 30~240min.
16. according to the method for claim 12, wherein the discarded vanadium tungsten titanium-based denitrating catalyst is in the second cleaning solution The time of ultrasonic cleaning or/and pressure pulse cleaning is 60~120min.
17. according to the method for claim 12, wherein the method further includes：Clear using the first cleaning solution and second After washing lotion cleans discarded vanadium tungsten titanium-based denitrating catalyst, deionized water cleaning is carried out to catalyst.
18. method according to claim 1 or 2, wherein using the first cleaning solution and the second cleaning in the step (1) Liquid is 10~90 DEG C to discarding the temperature that vanadium tungsten titanium-based denitrating catalyst is cleaned.
19. method according to claim 1 or 2, wherein using the first cleaning solution and the second cleaning in the step (1) Liquid is 20~60 DEG C to discarding the temperature that vanadium tungsten titanium-based denitrating catalyst is cleaned.
20. method according to claim 1 or 2, wherein using the first cleaning solution and the second cleaning in the step (1) Liquid is 30~60 DEG C to discarding the temperature that vanadium tungsten titanium-based denitrating catalyst is cleaned.
21. method according to claim 1 or 2, wherein dry temperature described in the step (2) is 60~200 DEG C, the time is 1~48h.
22. method according to claim 1 or 2, wherein dry temperature described in the step (2) is 80~120 DEG C, the time is 2~30h.
23. method according to claim 1 or 2, wherein the temperature roasted in the step (3) is 300~500 DEG C.
24. method according to claim 1 or 2, wherein the temperature roasted in the step (3) is 350~500 DEG C.
25. method according to claim 1 or 2, wherein roasting time is 1~60h in the step (3).
26. method according to claim 1 or 2, wherein roasting time is 2~30h in the step (3).
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