CN105039646A - Processing method for SCR denitration catalyst - Google Patents
Processing method for SCR denitration catalyst Download PDFInfo
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- CN105039646A CN105039646A CN201510535971.0A CN201510535971A CN105039646A CN 105039646 A CN105039646 A CN 105039646A CN 201510535971 A CN201510535971 A CN 201510535971A CN 105039646 A CN105039646 A CN 105039646A
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Abstract
The invention discloses a processing method for an SCR denitration catalyst and belongs to the field of waste recycling. The processing method includes the steps that (1) molten iron and/or molten steel are/is prepared; (2) the SCR denitration catalyst is added to the molten iron and/or molten steel; (3) slag making is conducted, and the temperature of the molten iron and/or molten steel is maintained to be 1300-1800 DEG C; (4), furnace slag is poured out, constituents of the molten iron and/or molten steel are adjusted so as to meet the requirement for target constituents, and the molten iron and/or molten steel are/is poured into a mould. Molten iron prepared by melting waste steel and/or pig iron or molten iron prepared from an ironmaking device is used for transforming the vanadium element into stable and nontoxic calcium vanadate through slag making, and pollution of a waste SCR denitration catalyst to the environment is reduced; moreover, the molten iron can be used for manufacturing abrasion-resistant steel balls after being used for processing the SCR denitration catalyst. The processing cost is low, practicability is high and good economical benefits are achieved.
Description
Technical field
The invention belongs to nonferrous metals recycling field, more particularly, relate to a kind for the treatment of process of SCR denitration that is waste and old or that lost efficacy.
Background technology
Denitrating catalyst makes a general reference the catalyzer (Catalyst) be applied on power plant SCR (selectivecatalyticreduction) denitrating system, in SCR reaction, reductive agent is impelled optionally with the oxynitride in flue gas, the material of chemical reaction to occur at a certain temperature.Current SCR commercial catalyst is substantially all with TiO
2for base material, with V
2o
5for main active ingredient, with WO
3, MoO
3for anti-oxidant, antitoxinization auxiliary ingredients, catalyzer pattern can be divided into three kinds: board-like, honeycomb fashion and corrugated plate dst.
The wire netting that board-like catalyzer is pressed into stainless steel metal plate for base material, by TiO
2, V
2o
5deng mixture be attached on stainless (steel) wire, through compacting, after calcination, catalyst plates is assembled into catalyst module; Cellular catalyst is generally homogeneous catalysis, by TiO
2, V
2o
5, WO
3in mixture by a kind of ceramics extrusion equipment, making cross section is 150mm × 150mm, the catalyst element that length does not wait, and is then assembled into the standard module that cross section is about 2m × 1m; The manufacturing process of corrugated plate dst catalyzer is generally with the TiO strengthened with glass fibre
2for base material, by WO
3, V
2o
5isoreactivity composition is impregnated into the surface of catalyzer, improves catalyst activity, reduces SO to reach
2the object of oxidation ratio.
Selective catalytic reduction (SCR) denitration technology is the current topmost power plant stack gas denitration technology of China.According to statistics, before the end of the year 2015, the SCR that the whole nation completes implements engineering total will reach 5.7 hundred million kW.In the use procedure of catalyzer, the problems such as sintering of catalyst, basic metal are poisoning, ash content blocking, loss of active component all likely cause the infringement to catalyzer, finally cause catalyst failure.Along with the widespread use of SCR technique, waste and old SCR denitration will get more and more, and from 2014, every year by generation 1.2 ten thousand tons of discarded SCR denitration, and continue to increase.By 2018, this amount will reach 3.8 ten thousand tons, and keep stable.The catalyzer lost efficacy belongs to special article, if do not processed and arbitrarily bank up, will take a large amount of land resources.Meanwhile, the hazardous and noxious substances that catalyzer in use adsorbs, and in composition, contained heavy metal element etc. can enter physical environment, causes severe contamination to environment.A kind of waste is not only in the accumulation of a large amount of spent catalyst, and can bring serious environmental pollution.
The useless out of stock catalyst component of SCR of danger recycled, both can turn waste into wealth, change evil for benefit, a series of problem of environmental pollution can also be solved, thus bring considerable economic benefit and environmental benefit.Chinese Patent Application No. is 201410684143.9, and Shen Qing Publication day is the renovation process that the patent application document on April 1st, 2015 discloses a kind of SCR denitration that lost efficacy, and it comprises the following steps: (1) purges; (2) thermal treatment; (3) wash; (4) pickling: the mixing solutions SCR denitration after washing being placed in 10wt% sulfuric acid and 5wt% hydrofluoric acid, ultrasonic disperse 2h; (5) active regeneration: dry taking out after 2h in the active mixing solutions be immersed in through the SCR denitration of overpickling containing 5wt% ammonium paratungstate and 1wt% ammonium meta-vanadate, the renovation process of this invention can carry out comprehensive treating process to the catalyzer lost efficacy due to many reasons in actual production, improve the utilization ratio of SCR denitration, but finally can not solve waste and old SCR denitration reclaims problem.North China Electric Power University have developed a kind of method reclaiming Vanadium Pentoxide in FLAKES composition in waste and old SCR denitration, its Chinese Patent Application No. is 201410471988.X, Shen Qing Publication day is on December 10th, 2014, the method mainly utilizes the flow process of pickling alkali cleaning: utilize reductive agent that the pentavalent vanadium in catalyzer is reduced to more easily molten tetravalence vanadium first in an acidic solution, then again the tetravalence vanadium in acidic solution is oxidized to pentavalent vanadium with oxygenant, by the pH value of regulator solution, pentavalent vanadium is made fully to be hydrolyzed and to precipitate under certain condition, collecting precipitation can obtain highly purified Vanadium Pentoxide in FLAKES through calcination process.Although this method can reclaim high-purity Vanadium Pentoxide in FLAKES, complicated operation, processing cost is high and produce a large amount of waste water and not easily process, and can cause the problem of secondary pollution, not possess practicality.
Summary of the invention
1. the problem that will solve
The difficult problem of process is there is for existing waste and old SCR denitration, the invention provides a kind for the treatment of process of SCR denitration, SCR denitration is dissolved in molten iron, by slag making, harmful Vanadium Pentoxide in FLAKES is formed stable, nontoxic calcium vanadate (3CaOV
2o
5), reduce the pollution of waste and old SCR denitration to environment.In addition, molten iron can be used for manufacturing wear-resisting iron ball etc., makes full use of the stainless steel in the catalyzer of inefficacy, can not cause secondary pollution, practical.
2. technical scheme
In order to solve the problem, the technical solution adopted in the present invention is as follows:
A treatment process for SCR denitration, the steps include:
(1) molten iron and/or molten steel is prepared;
(2) SCR denitration is added molten iron and/or molten steel;
(3) carry out slag making, maintenance molten iron and/or liquid steel temperature are at 1300-1800 DEG C;
(4) poured out by slag, adjustment molten iron and/or molten steel composition, obtain iron and/or molten steel.
Preferably, described SCR denitration is waste and old Plate-type denitration catalyst, honeycomb type denitrification catalyst, corrugated denitrating catalyst containing Vanadium Pentoxide in FLAKES activeconstituents.
Preferably, in described step (3), maintenance molten iron and/or liquid steel temperature are at 1351 ~ 1499 DEG C or 1501 ~ 1599 DEG C or 1601 ~ 1699 DEG C or 1701 ~ 1799 DEG C.
Preferably, with electric arc furnace or intermediate frequency furnace, the pig iron and/or steel are fused into molten iron and/or molten steel in described step (1).
Preferably, prepare in described step (1) in molten iron and/or molten steel process add lime, Wingdale, containing SiO
2one or more in slag former are as slag former and be blown into oxygen.
Preferably, in described step (3) in slagging process when slag system illiquidity (illiquidity to take the form of slag stream motionless, cause last result be slag not out) time add dissolving agent.
Preferably, the dissolving agent added in slagging process in described step (3) is fluorite and/or the honeycomb type denitrification catalyst containing aluminium oxide active composition.
Preferably, FeO, CaO and SiO is contained in slag system in described step (4)
2, FeO, CaO and SiO
2mass ratio be (0 ~ 87): (11 ~ 69): (2 ~ 45).
Preferably, also MgO, TiO is contained in slag system in described step (4)
2, WO
3and V
2o
5.
Preferably, the iron obtained in step (4) and/or pouring molten steel are entered mould, after heat treatment obtain abrasion-proof steel ball or high carbon steel or other wear resistant alloys.
A kind for the treatment of process of Vanadium Pentoxide in FLAKES, above-mentioned treatment process is adopted to process Vanadium Pentoxide in FLAKES, difference is that the SCR denitration in claim 1 is replaced with Vanadium Pentoxide in FLAKES, make it to change into calcium vanadate stable in slag or alloying constituent, need Vanadium Pentoxide in FLAKES to be processed to be the waste and old or inefficacy SCR denitration containing Vanadium Pentoxide in FLAKES.
3. beneficial effect
Compared to prior art, beneficial effect of the present invention is:
(1), when process of the present invention contains the SCR denitration of Vanadium Pentoxide in FLAKES activeconstituents, appropriate lime, Wingdale, SiO is added
2in one or more carry out slag making as slag former, formed CaO-SiO
2-FeO slag system, ensures the CaO that there is enough free states in slag, and the V in Plate-type denitration catalyst
2o
5form calcium vanadate (3CaOV that is nontoxic, stable performance
2o
5);
(2) the present invention is carrying out in slagging process when slag is high alkalinity, and temperature is high, poor fluidity, therefore needs to add fluorite and/or the honeycomb type denitrification catalyst containing aluminium oxide active composition and/or other dissolving agents to strengthen the mobility of slag system;
(3) the present invention is to process molten iron in Vanadium Pentoxide in FLAKES process and/or molten steel for raw material, 430 stainless steels in Plate-type denitration catalyst can provide chromium metal, when target molten iron or molten steel are containing chromium, can reduce before skimming, improve the chromium content in molten iron;
(4) molten iron used in the present invention can obtain with steel scrap and/or pig iron fusing and/or from the molten iron of ironmaking equipment, take full advantage of waste and scrap, and do not have the problem of secondary pollution, economic worth can also be created while Vanadium Pentoxide in FLAKES in the waste and old denitrating catalyst of process, production cost is low, practical, good in economic efficiency.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
The present embodiment adopts 3 tons of electric arc furnace to prepare molten iron:
The 2500kg pig iron is added in electric arc furnace, and adds 125 kilograms of ferrosilicon, be heated to 1600 DEG C, in heat-processed, be blown into oxygen (object improves FeO mass content, facilitates slag making) and progressively add lime.In the pig iron, carbon content is 4.3%, and silicone content is 0.45%.After pig iron fine melt, add waste and old Plate-type denitration catalyst 300kg, Plate-type denitration catalyst is made up of carrier and catalyzer, wherein carrier is 430 stainless steels, the massfraction that carrier accounts for Plate-type denitration catalyst is 40% (120kg), surplus is catalyzer, and in carrier, Cr content is 16%; Catalyzer is by TiO
2, V
2o
5and WO
3composition, wherein TiO
2massfraction be 85% (153kg), V
2o
5massfraction be 5% (9kg), WO
3massfraction be 10% (18kg).
In slagging process, temperature is controlled at 1500 ~ 1700 DEG C.In heating and slagging process, add 960 kilograms, lime altogether, 130 kilograms, fluorite; Slag mainly consists of: the massfraction of FeO is 21%, SiO
2massfraction be the massfraction of 18%, CaO be 42%, all the other are CaF
2, MgO, TiO
2, V
2o
5.After slag making success, slag is poured out (the common 1850kg of the present embodiment deslagging, the form that Vanadium Pentoxide in FLAKES (in slag, content is 0.4%) is converted into calcium vanadate is present in slag), regulate hot metal composition, this experiment adds appropriate high carbon ferro-chrome, and (object improves the concentration of Cr in molten iron, by detecting hot metal composition, reach product composition standard), then balling-up of being cast by molten iron cools, obtain high-carbon low-chromium abrasion-proof steel ball 2200kg, wherein Cr content is 2.69%, and C content is 2.02%, packaging warehouse-in.
In the present embodiment, the addition of various material all obtains through material balance, carry out testing rear slag making i.e. success according to the requirement in the present embodiment, Vanadium Pentoxide in FLAKES now in slag system is exactly exist with calcium vanadate form, hot metal composition after slag making success also there occurs change, the compositions such as the Cr in Plate-type denitration catalyst fuse in molten iron, can obtain abrasion-proof steel ball again after balling-up of being cast by molten iron cooling through thermal treatment.
Embodiment 2
The present embodiment adopts 5 tons of electric arc furnace to prepare molten iron:
300kg steel scrap and the 4000kg pig iron are added in electric arc furnace, is heated to 1600 DEG C, in heat-processed, add 200 kilograms of ferrosilicon, be blown into oxygen, and add lime in batches.In the pig iron, carbon content is 4.3%, and silicone content is 0.45%.After steel scrap and pig iron fine melt, add waste and old Plate-type denitration catalyst 500kg, Plate-type denitration catalyst is made up of carrier and catalyzer, wherein carrier is 430 stainless steels, the massfraction that carrier accounts for Plate-type denitration catalyst is 40% (200kg), surplus is catalyzer, and in carrier, Cr content is 16%; Catalyzer is by TiO
2, V
2o
5and WO
3composition, wherein TiO
2massfraction be 85% (255kg), V
2o
5massfraction be 5% (15kg), WO
3massfraction be 10% (30kg).
Temperature controls, at 1600 ~ 1700 DEG C, to carry out slag making, adds 1600 kilograms, lime altogether, 280 kilograms, fluorite.When skimming, slag consists of: the massfraction of FeO is 20.5%, SiO
2massfraction be the massfraction of 19%, CaO be 37%, CaF
2content is 9.67%, and all the other are MgO, TiO
2, V
2o
5.After slag making success, slag is poured out (the common 2350kg of the present embodiment deslagging, the form that Vanadium Pentoxide in FLAKES (in slag, content is 0.32%) is converted into calcium vanadate is present in slag), regulate hot metal composition, this experiment adds appropriate high carbon ferro-chrome, and balling-up of then being cast by molten iron cools, obtain high-carbon low-chromium abrasion-proof steel ball 3540kg, wherein Cr content 2.25%, C content 2.17%, packaging warehouse-in.
Embodiment 3
The present embodiment adopts 10 tons of electric arc furnace to prepare molten iron:
1000kg steel scrap and the 9000kg pig iron are added in electric arc furnace, is heated to 1600 DEG C, in heat-processed, be blown into oxygen, and add No. 75 ferrosilicon (namely silicone content is 75%) and lime in batches.In the pig iron, carbon content is 4.3%, and silicone content is 0.45%.After steel scrap and pig iron fine melt, add waste and old denitrating catalyst 1200kg, denitrating catalyst is made up of carrier and catalyzer in batches, wherein carrier is 430 stainless steels, the massfraction that carrier accounts for denitrating catalyst is 40% (480kg), and surplus is catalyzer, and in carrier, Cr content is 16%; Catalyzer is by TiO
2, V
2o
5and WO
3composition, wherein TiO
2massfraction be 85% (612kg), V
2o
5massfraction be 5% (36kg), WO
3massfraction be 10% (72kg).
Temperature controls, at 1500 ~ 1700 DEG C, carry out slag making in batches and skim.Add 3200 kilograms, lime altogether, 520 kilograms, fluorite.Control slag when skimming to consist of: the massfraction of FeO is 20.8%, SiO
2massfraction be the massfraction of 21%, CaO be 39%, all the other are CaF
2, MgO, TiO
2, V
2o
5.The present embodiment deslagging is 5900kg altogether, the form that Vanadium Pentoxide in FLAKES (in slag, content is 0.38%) is converted into calcium vanadate is present in slag, regulate hot metal composition, this experiment adds appropriate high carbon ferro-chrome, then balling-up of being cast by molten iron cools, and obtains high-carbon low-chromium abrasion-proof steel ball 8500kg, wherein Cr content 1.89%, C content 2.37%, packaging warehouse-in.
Embodiment 4
The present embodiment adopts 1 ton of electric arc furnace to prepare molten iron:
800kg steel scrap is added in electric arc furnace, is heated to 1600 DEG C, in heat-processed, adds lime in batches.In the pig iron, carbon content is 4.3%, and silicone content is 0.45%.After steel scrap fine melt, add 50 kilograms of fluorites and waste and old denitrating catalyst 200kg, denitrating catalyst is made up of carrier and catalyzer, wherein carrier is 430 stainless steels, the massfraction that carrier accounts for denitrating catalyst is 40% (80kg), and surplus is catalyzer, and in carrier, Cr content is 16%; Catalyzer is by TiO
2, V
2o
5and WO
3composition, wherein TiO
2massfraction be 85% (102kg), V
2o
5massfraction be 5% (6kg), WO
3massfraction be 10% (12kg).
Temperature is controlled at 1500 ~ 1700 DEG C, add 400 kilograms, lime altogether, after slag making terminates, add the vanadium in proper amount of silicon Fe3+ reduction ferric oxide and slag.When skimming, slag consists of: SiO
2massfraction be the massfraction of 14%, CaO be 56%, all the other are CaF
2, MgO, TiO
2, V
2o
5.After slag making success, slag is clawed (the present embodiment is skimmed common 570kg, the form that Vanadium Pentoxide in FLAKES (in slag, content is 0.32%) is converted into calcium vanadate is present in slag), regulate hot metal composition, then balling-up of being cast by molten iron cools, obtain high-carbon steel ingot 780kg, C content is 1.75%, packaging warehouse-in.
Embodiment 5
The present embodiment adopts 10 tons of electric arc furnace to prepare molten iron:
4000kg steel scrap and the 4000kg pig iron and coal cinder are added in 10 tons of electric arc furnace, is heated to 1600 DEG C, in heat-processed, is blown into oxygen, and adds lime in batches.In the pig iron, carbon content is 4.3%, and silicone content is 0.45%.After steel scrap and pig iron fine melt, add waste and old corrugated denitrating catalyst 800kg, corrugated denitrating catalyst is made up of carrier and catalyzer, wherein carrier is glass fibre, the massfraction that carrier accounts for corrugated denitrating catalyst is 30% (150kg), surplus is catalyzer, and catalyzer is by TiO
2, V
2o
5and WO
3composition, wherein TiO
2massfraction be 85% (476kg), V
2o
5massfraction be 5% (28kg), WO
3massfraction be 10% (56kg).
Temperature controls, at 1600 ~ 1800 DEG C, to carry out slag making, adds 1750 kilograms, lime altogether, 300 kilograms, fluorite.When skimming, slag consists of: the massfraction of FeO is 4%, SiO
2massfraction be the massfraction of 16%, CaO be 47%, all the other are CaF
2, MgO, Na
2o, TiO
2, V
2o
5.After slag making success, slag is poured out (the common 2950kg of the present embodiment deslagging, the form that Vanadium Pentoxide in FLAKES (in slag, content is 0.52%) is converted into calcium vanadate is present in slag), regulate hot metal composition, then balling-up of being cast by molten iron cools, obtain high-carbon steel ingot 7500kg, wherein C content 2.6%, packaging warehouse-in.
Embodiment 6
The present embodiment adopts 1 ton of electric arc furnace to prepare molten iron:
800kg steel scrap and the 100kg pig iron are added in electric arc furnace, is heated to 1600 DEG C, in heat-processed, add 100 kilograms of coal cinders, and add lime and fluorite in batches.In the pig iron, carbon content is 4.3%, and silicone content is 0.45%.After steel scrap and pig iron fine melt, add waste and old corrugated denitrating catalyst 200 kilograms, corrugated denitrating catalyst is made up of carrier and catalyzer, wherein carrier is glass fibre, the massfraction that carrier accounts for corrugated denitrating catalyst is 30%, and surplus is catalyzer, and catalyzer is by TiO
2, V
2o
5and WO
3composition, wherein TiO
2massfraction be 85%, V
2o
5massfraction be 5%, WO
3massfraction be 10%.
Temperature controls, at 1500 ~ 1700 DEG C, to carry out slag making, adds 480 kilograms, lime altogether, 50 kilograms, fluorite and 10 kilograms of silicon carbide.When skimming, slag consists of: SiO
2massfraction be the massfraction of 16%, CaO be 58%, all the other are CaF
2, MgO, Na
2o, FeO, TiO
2, V
2o
5.After slag making success, slag is poured out (the common 650kg of the present embodiment deslagging, the form that Vanadium Pentoxide in FLAKES (in slag, content is 0.62%) is converted into calcium vanadate is present in slag), regulate hot metal composition, this experiment adds appropriate high carbon ferro-chrome, and balling-up of then being cast by molten iron cools, and obtains pig iron 840kg, C content 1.2%, packaging warehouse-in.
Embodiment 7
The present embodiment adopts 10 tons of electric arc furnace to prepare molten iron:
1000kg steel scrap and the 8000kg pig iron are added in electric arc furnace, is heated to 1600 DEG C, in heat-processed, add 20 kilograms of ferrosilicon, be blown into oxygen, and add lime in batches.In the pig iron, carbon content is 4.3%, and silicone content is 0.45%.After steel scrap and pig iron fine melt, add waste and old Plate-type denitration catalyst 1000kg, Plate-type denitration catalyst is made up of carrier and catalyzer, wherein carrier is 430 stainless steels, the massfraction that carrier accounts for Plate-type denitration catalyst is 40% (400kg), surplus is catalyzer, and in carrier, Cr content is 16%; Catalyzer is by TiO
2, V
2o
5and WO
3composition, wherein TiO
2massfraction be 85% (510kg), V
2o
5massfraction be 5% (30kg), WO
3massfraction be 10% (60kg).
Temperature controls, at 1300 ~ 1350 DEG C, to carry out slag making, adds 500 kilograms, lime altogether, 250 kilograms, fluorite.When skimming, slag consists of: the massfraction of FeO is 65%, SiO
2massfraction be the massfraction of 2%, CaO be 11%, all the other are CaF
2, MgO, TiO
2, V
2o
5.After slag making success, slag is poured out (the common 4190kg of the present embodiment deslagging, the form that Vanadium Pentoxide in FLAKES (in slag, content is 0.38%) is converted into calcium vanadate is present in slag), regulate hot metal composition, this experiment adds appropriate high carbon ferro-chrome, and balling-up of then being cast by molten iron cools, obtain high-carbon low-chromium abrasion-proof steel ball 6625kg, wherein Cr content 1.89%, C content 2.37%, packaging warehouse-in.
Embodiment 8
The present embodiment adopts 10 tons of electric arc furnace to prepare molten iron:
1000kg steel scrap and the 8000kg pig iron are added in electric arc furnace, is heated to 1600 DEG C, in heat-processed, add 900 kilograms of ferrosilicon, be blown into oxygen, and add lime in batches.In the pig iron, carbon content is 4.3%, and silicone content is 0.45%.After steel scrap and pig iron fine melt, add waste and old Plate-type denitration catalyst 1000kg, Plate-type denitration catalyst is made up of carrier and catalyzer, wherein carrier is 430 stainless steels, the massfraction that carrier accounts for Plate-type denitration catalyst is 40% (400kg), surplus is catalyzer, and in carrier, Cr content is 16%; Catalyzer is by TiO
2, V
2o
5and WO
3composition, wherein TiO
2massfraction be 85% (510kg), V
2o
5massfraction be 5% (30kg), WO
3massfraction be 10% (60kg).
Temperature controls, at 1701 ~ 1799 DEG C, to carry out slag making, adds 2200 kilograms, lime altogether, 280 kilograms, fluorite.When skimming, slag consists of: the massfraction of FeO is 15.7%, SiO
2massfraction be the massfraction of 14%, CaO be 45%, all the other are CaF
2, MgO, TiO
2, V
2o
5.After slag making success, slag is poured out (the common 4890kg of the present embodiment deslagging, the form that Vanadium Pentoxide in FLAKES (in slag, content is 0.38%) is converted into calcium vanadate is present in slag), regulate hot metal composition, this experiment adds appropriate high carbon ferro-chrome, and balling-up of then being cast by molten iron cools, obtain high-carbon low-chromium abrasion-proof steel ball 8490kg, wherein Cr content 1.89%, C content 2.37%, packaging warehouse-in.
Embodiment 9
The present embodiment adopts 5 tons of electric arc furnace to prepare molten iron:
300kg steel scrap and the 4000kg pig iron are added in electric arc furnace, is heated to 1600 DEG C, in heat-processed, add 50 kilograms of ferrosilicon, be blown into oxygen, and add lime in batches.In the pig iron, carbon content is 4.3%, and silicone content is 0.45%.After steel scrap and pig iron fine melt, add waste and old Plate-type denitration catalyst 500kg, Plate-type denitration catalyst is made up of carrier and catalyzer, wherein carrier is 430 stainless steels, the massfraction that carrier accounts for Plate-type denitration catalyst is 40% (200kg), surplus is catalyzer, and in carrier, Cr content is 16%; Catalyzer is by TiO
2, V
2o
5and WO
3composition, wherein TiO
2massfraction be 85% (255kg), V
2o
5massfraction be 5% (15kg), WO
3massfraction be 10% (30kg).
Temperature controls, at 1601 ~ 1699 DEG C, to carry out slag making, adds 400 kilograms, lime altogether, 260 kilograms, fluorite.When skimming, slag consists of: the massfraction of FeO is 56%, SiO
2massfraction be the massfraction of 5.5%, CaO be 18.5%, CaF
2content is 9.23%, and all the other are MgO, TiO
2, V
2o
5.After slag making success, slag is poured out (the common 2100kg of the present embodiment deslagging, the form that Vanadium Pentoxide in FLAKES (in slag, content is 0.32%) is converted into calcium vanadate is present in slag), regulate hot metal composition, this experiment adds appropriate high carbon ferro-chrome, and balling-up of then being cast by molten iron cools, obtain high-carbon low-chromium abrasion-proof steel ball 3640kg, wherein Cr content 2.25%, C content 2.17%, packaging warehouse-in.
Embodiment 10
The present embodiment adopts 3 tons of electric arc furnace to prepare molten iron:
Add in electric arc furnace by 1500kg steel scrap and the 1000kg pig iron, be heated to 1600 DEG C, in the pig iron, carbon content is 4.3%, and silicone content is 0.45%.After steel scrap and pig iron fine melt, add waste and old Plate-type denitration catalyst 500kg, Plate-type denitration catalyst is made up of carrier and catalyzer, wherein carrier is 430 stainless steels, the massfraction that carrier accounts for Plate-type denitration catalyst is 40% (200kg), surplus is catalyzer, and in carrier, Cr content is 16%; Catalyzer is by TiO
2, V
2o
5and WO
3composition, wherein TiO
2massfraction be 85% (255kg), V
2o
5massfraction be 5% (15kg), WO
3massfraction be 10% (30kg).
After Plate-type denitration catalyst fusing, temperature is controlled at 1501 ~ 1599 DEG C, carry out slag making, add lime 50kg, fluorite 200kg, waste and old honeycomb type denitrification catalyst 200kg, waste and old honeycomb type denitrification catalyst take pottery as carrier, and ceramic monolith accounts for 30% of total mass, SiO in carrier
2massfraction be the massfraction of 12.5%, CaO be 4.4%; Catalyzer accounts for 70% of honeycomb type denitrification catalyst total mass, TiO in catalyzer
2massfraction be 85%, V
2o
5massfraction be 5%, WO
3massfraction be 10%.
When skimming, slag consists of: the massfraction of FeO is 36%, SiO
2massfraction be the massfraction of 4%, CaO be 40%, all the other are MgO, TiO
2, V
2o
5, CaF
2.After slag making success, slag is poured out (the common 844kg of the present embodiment deslagging, the form that Vanadium Pentoxide in FLAKES (in slag, content is 0.62%) is converted into calcium vanadate is present in slag), regulate hot metal composition, this experiment adds appropriate high carbon ferro-chrome, and balling-up of then being cast by molten iron cools, obtain high-carbon low-chromium abrasion-proof steel ball 2475kg, wherein Cr content is 2.69%, and C content is 2.02%, packaging warehouse-in.
Embodiment 11
The present embodiment adopts 5 tons of electric arc furnace to prepare molten iron:
Add in electric arc furnace by 2500kg steel scrap and the 2300kg pig iron, be heated to 1600 DEG C, in the pig iron, carbon content is 4.3%, and silicone content is 0.45%.After steel scrap and pig iron fine melt, add waste and old Plate-type denitration catalyst 750kg, Plate-type denitration catalyst is made up of carrier and catalyzer, wherein carrier is 430 stainless steels, the massfraction that carrier accounts for Plate-type denitration catalyst is 40% (300kg), surplus is catalyzer, and in carrier, Cr content is 16%; Catalyzer is by TiO
2, V
2o
5and WO
3composition, wherein TiO
2massfraction be 85% (382.5kg), V
2o
5massfraction be 5% (22.5kg), WO
3massfraction be 10% (45kg).
After Plate-type denitration catalyst fusing, temperature is controlled at 1601 ~ 1699 DEG C, carry out slag making, add lime 100kg, bauxitic clay 100kg, waste and old cellular catalyst 100kg, waste and old cellular catalyst take pottery as carrier, and ceramic monolith accounts for 30% of total mass, SiO in carrier
2massfraction be the massfraction of 12.5%, CaO be 4.4%; Catalyzer accounts for 70% of honeycomb type denitrification catalyst total mass, TiO in catalyzer
2massfraction be 85%, V
2o
5massfraction be 5%, WO
3massfraction be 10%.
When skimming, slag consists of:: the massfraction of FeO is 28%, SiO
2massfraction be the massfraction of 8%, CaO be 44%, all the other are MgO, TiO
2, V
2o
5, CaF
2.After slag making success, slag is poured out (the common 1200kg of the present embodiment deslagging, the form that Vanadium Pentoxide in FLAKES (in slag, content is 0.53%) is converted into calcium vanadate is present in slag), regulate hot metal composition, this experiment adds appropriate high carbon ferro-chrome, and balling-up of then being cast by molten iron cools, obtain high-carbon low-chromium abrasion-proof steel ball 4975kg, wherein Cr content 2.25%, C content 2.17%, packaging warehouse-in.
Claims (10)
1. a treatment process for SCR denitration, the steps include:
(1) molten iron and/or molten steel is prepared;
(2) SCR denitration is added molten iron and/or molten steel;
(3) carry out slag making, maintenance molten iron and/or liquid steel temperature are at 1300-1800 DEG C;
(4) poured out by slag, adjustment molten iron and/or molten steel composition, obtain iron and/or molten steel.
2. the treatment process of a kind of SCR denitration according to claim 1, is characterized in that: described SCR denitration is Plate-type denitration catalyst, honeycomb type denitrification catalyst, corrugated denitrating catalyst containing Vanadium Pentoxide in FLAKES activeconstituents.
3. the treatment process of a kind of SCR denitration according to claim 1, is characterized in that: in described step (3), maintenance molten iron and/or liquid steel temperature are at 1351 ~ 1499 DEG C or 1501 ~ 1599 DEG C or 1601 ~ 1699 DEG C or 1701 ~ 1799 DEG C.
4. the treatment process of a kind of SCR denitration according to claim 1, is characterized in that: with electric arc furnace or intermediate frequency furnace, the pig iron and/or steel are fused into molten iron and/or molten steel in described step (1).
5. the treatment process of a kind of SCR denitration according to claim 4, is characterized in that: prepare in described step (1) in molten iron and/or molten steel process add lime, Wingdale, containing SiO
2one or more in slag former are as slag former and be blown into oxygen.
6. the treatment process of a kind of SCR denitration according to claim 1, it is characterized in that: in described step (3), in slagging process, add dissolving agent when slag system illiquidity, preferably add fluorite and/or the honeycomb type denitrification catalyst containing aluminium oxide active composition.
7. according to the treatment process of a kind of SCR denitration in claim 5-6 described in any one, it is characterized in that: in described step (4), in slag system, contain FeO, CaO and SiO
2, FeO, CaO and SiO
2mass ratio be (0 ~ 87): (11 ~ 69): (2 ~ 45).
8. the treatment process of a kind of SCR denitration according to claim 7, is characterized in that: also contain MgO, TiO in slag system in described step (4)
2, WO
3and V
2o
5.
9. the treatment process of a kind of SCR denitration according to claim 1, is characterized in that: the iron obtained in step (4) and/or pouring molten steel are entered mould, after heat treatment obtains abrasion-proof steel ball or high carbon steel or other wear resistant alloys.
10. the treatment process of a Vanadium Pentoxide in FLAKES, it is characterized in that: adopt treatment process according to claim 1 to process Vanadium Pentoxide in FLAKES, difference is that the SCR denitration in claim 1 is replaced with Vanadium Pentoxide in FLAKES, makes it to change into calcium vanadate stable in slag or alloying constituent.
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| CN105907950A (en) * | 2016-04-29 | 2016-08-31 | 浙江大学 | Treatment method for metallurgy sintering of abandoned SCR flue gas denitrification catalyst |
| CN105950873A (en) * | 2016-06-24 | 2016-09-21 | 浙江浙能催化剂技术有限公司 | Method for recycling vanadium, tungsten and titanium from waste SCR denitration catalyst |
| CN108677016A (en) * | 2018-05-18 | 2018-10-19 | 内蒙古科技大学 | A kind of preparation method of metallurgical titanium slag and ferrotitanium vanadium alloy containing waste denitration catalyst |
| CN109813738A (en) * | 2019-02-02 | 2019-05-28 | 大唐南京环保科技有限责任公司 | Eliminate the method that substrate influences the detection of denitrating catalyst chemical composition content |
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