CN102698737B - Method for preparing selective catalytic reduction SCR flue gas denitration catalyst and method for preparing raw material titanium-tungsten powder of SCR flue gas denitration catalyst - Google Patents

Method for preparing selective catalytic reduction SCR flue gas denitration catalyst and method for preparing raw material titanium-tungsten powder of SCR flue gas denitration catalyst Download PDF

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CN102698737B
CN102698737B CN201210167211.5A CN201210167211A CN102698737B CN 102698737 B CN102698737 B CN 102698737B CN 201210167211 A CN201210167211 A CN 201210167211A CN 102698737 B CN102698737 B CN 102698737B
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titanium
blast furnace
sulfuric acid
furnace slag
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CN102698737A (en
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杨娟
余剑
许光文
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Institute of Process Engineering of CAS
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Abstract

The invention relates to a method for preparing a selective catalytic reduction SCR flue gas denitration catalyst and a method for preparing a raw material titanium-tungsten powder of the SCR flue gas denitration catalyst. The method for preparing the SCR flue gas denitration catalyst comprises the followings: smashing titanium-bearing blast furnace slag, leaching TiO2 in the smashed titanium-bearing blast furnace slag with dilute sulphuric acid, filtering and separating the mixture to obtain residues and titanium solution, adding a porous catalyst carrier which is easy to be burnt off into the titanium solution and hydrolyzing the mixture; filtering, washing and drying the hydrolyzed product to obtain a carrier supported metatitanic acid, and further loading tungsten and vanadium on the metatitanic acid, and baking the obtained product to obtain a vanadium-tungsten-titanium SCR denitration catalyst. The method not only effectively utilizes valuable elements in blast furnace slag, solves the problems that the titanium dioxide product is extracted, separated and purified difficultly from the blast furnace slag, and the quality of the product cannot meet the standard easily, and also greatly reduces the production cost of the vanadium-tungsten-titanium SCR denitration catalyst and has a broad application prospect.

Description

The preparation method of a kind of SCR catalyst for denitrating flue gas and raw material titanium tungsten powder thereof
Technical field
The present invention relates to the preparation method of a kind of SCR catalyst for denitrating flue gas and raw material titanium tungsten powder thereof, relate in particular to a kind of method of utilizing titanium-containing blast furnace slag to prepare SCR denitrating catalyst and raw material titanium tungsten powder thereof.
Background technology
In blast furnace ironmaking process, can discharge a large amount of blast furnace slags, if do not carry out suitable treatment meeting land occupation, contaminated environment and cause the wasting of resources.In blast furnace slag, contain the metal values such as titanium, silicon, aluminium, calcium, can take suitable method separation and Extraction and be processed into chemical products, when rationally utilizing this trade waste resource, solve the problem of environmental pollution that it brings.
The TiO of titanium-containing blast furnace slag 2grade is higher, has very high recycling and is worth.The recycling of titanium-containing blast furnace slag mainly comprises the following aspects at present:
(1) as construction material
In blast furnace slag, conventionally there are CaO, the SiO of high level 2, Al 2o 3, thereby be often made into grain slag, slag rubble, expanded slag, mineral wool etc., as the raw material of cement, or brickmaking, sand processed, the construction material of paving the way etc.
(2) as industrial chemicals
As titanium-containing blast furnace slag can be used for producing devitrified glass (CN 89105864.8), ceramic (CN00119612.X), refractory repairing mass (CN 200710202467.4); Coagulant (CN 201010239034.8) etc.
(3) reclaim the valuable metals such as Ti
In blast furnace slag, the recovery of the metal such as Ti has several different methods, CN 201010216354.1 discloses a kind of method of comprehensive utilization of titanium-containing blast furnace slag, adopt salt acid treatment process, recovery obtains rich titanium products, aluminium hydroxide, magnesia and calcium oxide, the method can make full use of blast furnace slag resource, and byproduct is abundant.CN200510125682.X discloses a kind of method of utilizing producing titanium product from titanic slag for titanium white waste sulfuric acid treatment; the Waste Sulfuric Acid that utilizes Waste Sulfuric Acid to decompose titaniferous metallurgical slag, low concentration dissolves titanium dioxide; diluted Ti solution extracts titanium article; in this process, Waste Sulfuric Acid can be recycled, and is conducive to environmental protection.
In addition, titanium-containing blast furnace slag is prepared titanium dioxide because its higher Ti content (20% left and right) is often used as, CN 86108511 discloses a kind of method that titanium-containing blast furnace slag is prepared titanium dioxide, but the titanium white quality that the method is produced not is pigment-level, can only be used for welding rod, enamel and metallurgy industry, the scope of application is limited.CN200510021747.6 discloses a kind of method of producing pigment-level titanium dioxide and thick titanium white with titanium-containing blast furnace slag, and the method adopts sulfuric acid treatment titanium-containing blast furnace slag, through two sections of mills soak, two sections of hydrolysis and surface treatment obtain pigmentary titanium dioxide.In addition, can also utilize titanium-containing blast furnace slag to produce ferro-silico-titanium by silicothermic reduction and smelting technique; Adopt high-temperature selective carbonization and cryogenic selective chlorination to produce TiCl 4(CN 87107488.5); Directly prepare Ti by titanium-containing blast furnace slag 5si 3superalloy powder (CN 201010023113.5); Prepare solid-state calcium sulfur magnesium iron nitrogen silicon composite fertilizer from titanium (CN 200710012164.6) with titanium-containing blast furnace slag; Produce synthetic rutile (CN 201110072575.0) taking titanium-containing blast furnace slag as raw material.
The above-mentioned various equal technical feasibility of patent utilizing in method, but mostly based on Ti and TiO 2extraction, require strict isolation of purified technique, cause the problems such as leaching process material consumption/energy consumption is large, cost is high, benefit is low, therefore, so far not yet effective industrialization containing Ti Comprehensive Utilization Technology of Blast Furnace Slag.
Nitrogen oxide is one of main air pollutants that cause the series of problems such as the broken ring ball ecological environment such as acid rain, photochemical fog, is also the Focal point and difficult point in current atmospheric environment protection.In " 12 " planning outline that NPC and CPPCC in 2011 passes through, the reduction of discharging of nitrogen oxide is put into the binding indicator.Coal-fired flue gas denitration will be the major fields of state control thermal power plant pollutant emission during " 12 ".
Denitrating flue gas refers to the NO having generated xbe reduced to N 2thereby, remove the NO in flue gas x, can be divided into wet denitration and dry method denitration by administering technique.Mainly comprise: sour absorption process, alkali absorb method, selective catalytic reduction, non-selective catalytic reduction, absorption method, gas ions activation method etc.Selective catalytic reduction is called for short SCR technique, and its principle is under catalyst action, NH 3reductive NO and NO 2the desired temperature of reaction greatly reduce, and NH 3oxidation reaction occur hardly, thereby improved N 2selective, reduced NH 3consumption.Catalyst is the core of SCR technique.At present business coal-fired plant flue gas denitrating catalyst used is made up of vanadium, tungsten, titanyl compound conventionally, and titanium dioxide as the carrier of catalyst, it is in great demand.
Because titanium-containing blast furnace slag has higher Ti content, this characteristic that therefore how to make full use of titaniferous blast furnace also becomes a problem of people's research.
Summary of the invention
The object of the present invention is to provide three kinds of distinct methods that utilize titanium-containing blast furnace slag to prepare SCR catalyst for denitrating flue gas.Titanium-containing blast furnace slag also contains the elements such as a small amount of Mn, K except Ti, Ca, Si, Al, Mg, Fe; produce in the technique of titanium dioxide in acidolysis-hydrolysis; in end product, conventionally can contain a small amount of plurality of impurities, greatly affect the quality and the scope of application thereof that reclaim gained titanium dioxide.Prepare the Ti compound (titanyl sulfate, skewness acid) that catalyst for denitrating flue gas uses various impurity components are had to higher tolerance, some impurity components, as Mn, Fe and sulfate radical not only do not affect denitrating catalyst activity, also help the raising of catalyst activity and stability.
One of method of preparing SCR catalyst for denitrating flue gas provided by the present invention, comprises the steps:
(a) after titanium-containing blast furnace slag is pulverized, add sulfuric acid to TiO wherein 2leach, after filtration, obtain titanium liquid and filter residue;
(b) under stirring condition, in step (a) gained titanium liquid, add Easy LOI type porous catalyst carrier, selectively add alkali compounds to regulate pH, be hydrolyzed;
(c) material after step (b) hydrolysis after filtration, washing, obtain carrier supported type metatitanic acid after drying;
(d) load tungsten and vanadium on step (c) gained carrier supported type metatitanic acid, then roasting makes vanadium tungsten titanium SCR catalyst for denitrating flue gas.
The schematic flow sheet of the method is shown in Fig. 1.
Two of the method for preparing SCR catalyst for denitrating flue gas provided by the present invention, comprises the steps:
(a) after titanium-containing blast furnace slag is pulverized, add sulfuric acid to TiO wherein 2leach, after filtration, obtain titanium liquid and filter residue;
(b) under stirring condition, in step (a) gained titanium liquid, add Easy LOI type porous catalyst carrier, selectively add alkali compounds to regulate pH, be hydrolyzed, in hydrolytic process, add tungsten source precursor;
(c) material after step (b) hydrolysis after filtration, washing, obtain the carrier supported type metatitanic acid of tungstenic after drying;
(d) load vanadium source precursor on the carrier supported type metatitanic acid of the tungstenic of step (c) gained, obtains vanadium tungsten titanium SCR catalyst for denitrating flue gas after roasting;
Or the carrier supported type metatitanic acid of tungstenic to step (c) gained carries out roasting and make titanium tungsten powder, to the further load vanadium of titanium tungsten powder source precursor, then roasting makes vanadium tungsten titanium SCR catalyst for denitrating flue gas.
Three of the method for preparing SCR catalyst for denitrating flue gas provided by the present invention, comprises the steps:
(a) after titanium-containing blast furnace slag is pulverized, add sulfuric acid to TiO wherein 2leach, after filtration, obtain titanium liquid and filter residue;
(b) under stirring condition, in step (a) gained titanium liquid, add Easy LOI type porous catalyst carrier, selectively add alkali compounds to regulate pH, be hydrolyzed;
(c) material after step (b) hydrolysis after filtration, washing, obtain carrier supported type metatitanic acid after drying;
(d) load tungsten source precursor on the carrier supported type metatitanic acid of step (c) gained, then roasting obtains titanium tungsten powder;
(e) load vanadium source precursor on the titanium tungsten powder of step (d) gained, then roasting makes vanadium tungsten titanium SCR catalyst for denitrating flue gas.
One of object of the present invention is also the preparation method of the raw material titanium tungsten powder that a kind of SCR catalyst for denitrating flue gas is provided, and comprises the steps:
(a) after titanium-containing blast furnace slag is pulverized, add sulfuric acid to TiO wherein 2leach, after filtration, obtain titanium liquid and filter residue;
(b) under stirring condition, in step (a) gained titanium liquid, add Easy LOI type porous catalyst carrier, selectively add alkali compounds to regulate pH, be hydrolyzed;
(c) material after step (b) hydrolysis after filtration, washing, obtain carrier supported type metatitanic acid after drying;
(d) load tungsten source precursor on the carrier supported type metatitanic acid of step (c) gained, then roasting obtains titanium tungsten powder.
The schematic flow sheet of the method is shown in Fig. 1.
The present invention proposes to utilize titanium-containing blast furnace slag to prepare the method for denitrating flue gas SCR catalyst, do not require the isolation of purified of strict titanium slag leaching liquid, by the hydrolysis of titanyl sulfate and denitration catalyst carrier raw material---the preparation coupling of carrier supported type metatitanic acid, and then by carrier supported type metatitanic acid load vanadium tungsten active component is prepared to denitrating catalyst raw material and powder denitrating catalyst.The method is not only for the higher value application of blast furnace slag provides a new way, effectively reduce the production cost of catalyst for denitrating flue gas simultaneously using this trade waste as raw material, contribute to alleviate the expensive situation of current domestic commerce denitrating catalyst, there is important economic implications and social effect.
By method provided by the present invention, the titanium on the one hand can effective recycling blast furnace slag, and obtain high value-added product; The method can solve the environmental problem that blast furnace slag brings on the other hand, reduces the production cost of SCR catalyst for denitrating flue gas, significant to Environmental Protection in China cause.
As optimal technical scheme, step (a) detailed process is: take the titanium-containing blast furnace slag after pulverizing, by sulfuric acid (taking 100% sulfuric acid calculate) quality: blast furnace slag quality is as 1 ~ 5: 1, for example 1: 1,2: 1,3: 1,4: 1,5: 1, preferably 1 ~ 3: 1, further preferably 2: 1, add sulfuric acid, add blast furnace slag in heating and under constantly stirring, fully stir, more than leaching 2h, preferably 6 ~ 10h, after end, carry out centrifugal/isolated by filtration, dilute sulfuric acid washing at least 2 times for filter residue, preferably 3 ~ 5 times, collects filtrate and obtains titanium liquid.Titanium-containing blast furnace slag after pulverizing is preferably below 200 orders, so that blast furnace slag reacts fully with sulfuric acid.
Preferably, described titanium-containing blast furnace slag is TiO 2content is more than 10% smelting iron and steel blast furnace slag, and described heating-up temperature is 40 ~ 100 DEG C, preferably 60 ~ 90 DEG C, and further preferably 70 ~ 80 DEG C.
Preferably, the Easy LOI type porous catalyst carrier in step (b) is one or more the mixture in active carbon, activated coke, semicoke, cellulose, starch, preferably active carbon, activated coke, semicoke, further preferred active carbon; Easy LOI type porous catalyst carrier addition is TiO in titanium-containing blast furnace slag 21% ~ 200% of quality, for example 1%, 5%, 10%, 20%, 50%, 100%, 150%, 200% etc., be preferably 10% ~ 100%, further preferably 20% ~ 50%.Easy LOI type porous catalyst carrier is water insoluble as used herein, can be burnt and lose, and have certain dispersiveness and specific area, in order to increase the dispersiveness of final products under high temperature.
Preferably, described alkali compounds is one or more the mixture in urea, ammoniacal liquor, carbonic hydroammonium, ammonium carbonate, alkali-metal hydroxide, alkali-metal carbonate or bicarbonate, described alkali-metal hydroxide is for example NaOH, potassium hydroxide, lithium hydroxide etc., described alkali-metal carbonate or bicarbonate are for example sodium carbonate, sodium acid carbonate, potash, saleratus etc., the preferred urea of described alkali compounds, ammoniacal liquor, carbonic hydroammonium, ammonium carbonate, further preferred urea, ammoniacal liquor; Described alkali compounds selectively adds, and addition is so that the pH value of end reaction system is 0 ~ 4 for standard, and for example 0.01,0.05,0.1,0.5,1,1.5,2,2.5,3,4 etc., more preferably 0 ~ 3, be particularly preferably 0 ~ 1.Alkali compounds can neutralisation of sulphuric acid as used herein, and does not form insoluble compound with sulfuric acid reaction.
Preferably, the hydrolysis temperature described in step (b) is 30 DEG C ~ 110 DEG C, and hydrolysis time is 1h ~ 24h;
Preferably, described hydrolysis is first hydrolysis at low temperatures, and then at high temperature hydrolysis obtains metatitanic acid crystal; Under described low temperature, be hydrolyzed to 30 ~ 80 DEG C, for example 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 80 DEG C etc., more preferably 30 ~ 60 DEG C, be particularly preferably 30 ~ 50 DEG C; The low temperature hydrolysis time is 1h ~ 12h, such as 1h, 2h, 3h, 4h, 6h, 8h, 10h, 12h etc., and more preferably 1h ~ 8h, is particularly preferably 2h ~ 4h; Under described high temperature, be hydrolyzed to 80 ~ 110 DEG C, for example 80 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C etc., more preferably 90 ~ 110 DEG C, be particularly preferably 95 ~ 105 DEG C; The pyrohydrolysis time is 2h ~ 24h, such as 2h, 3h, 4h, 6h, 8h, 12h, 16h, 20h, 24h etc., more preferably 4h ~ 12h, particularly preferably 4h ~ 8h;
Preferably, described Easy LOI type porous catalyst carrier and alkali compounds add at low thermophase.
As optimal technical scheme, the process of step (c) is: by the material after step (b) hydrolysis after filtration, use successively dilute sulfuric acid, water washing to neutral, after drying, obtain carrier supported type metatitanic acid at 105 ~ 150 DEG C.
As optimal technical scheme, in one of method, on step (c) gained carrier supported type metatitanic acid, the method for load tungsten and vanadium is: after will tungsten source precursor dissolving, add step (c) gained carrier supported type metatitanic acid, in 40 ~ 90 DEG C of water-baths, preferably 40 ~ 80 DEG C, further preferably 60 ~ 80 DEG C, maintain 1h ~ 8h, preferably 2h ~ 6h, further preferably after 2h ~ 4h, dry to obtain the carrier supported type metatitanic acid of tungstenic; After being dissolved, vanadium source precursor adds the carrier supported type metatitanic acid of the tungstenic of gained, in 40 ~ 90 DEG C of water-baths, for example 40 DEG C, 45 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C etc., preferably 40 ~ 80 DEG C, further preferably 60 ~ 80 DEG C, maintain 1h ~ 8h, such as 1h, 2h, 2.5h, 3h, 4h, 5h, 6h, 7h etc., preferably 2h ~ 6h, after further preferred 2h ~ 4h, dries.
As optimal technical scheme, method two on the carrier supported type metatitanic acid of the tungstenic of step (c) gained the method for load vanadium source precursor be: the carrier supported type metatitanic acid that adds the tungstenic of step (c) gained after vanadium source precursor is dissolved, in 40 ~ 90 DEG C of water-baths, for example 40 DEG C, 45 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C etc., preferably 40 ~ 80 DEG C, further preferably 60 ~ 80 DEG C, maintain 1h ~ 8h, such as 1h, 2h, 2.5h, 3h, 4h, 5h, 6h, 7h etc., preferably 2h ~ 6h, after further preferred 2h ~ 4h, dry.
As optimal technical scheme, method three on the carrier supported type metatitanic acid of step (c) gained the method for load tungsten source precursor be: after will tungsten source precursor dissolving, add step (c) gained carrier supported type metatitanic acid, in 40 ~ 90 DEG C of water-baths, for example 40 DEG C, 45 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C etc., preferably 40 ~ 80 DEG C, further preferably 60 ~ 80 DEG C, maintain 1h ~ 8h, such as 1h, 2h, 2.5h, 3h, 4h, 5h, 6h, 7h etc., preferably 2h ~ 6h, after further preferred 2h ~ 4h, dry;
Preferably, on the titanium tungsten powder of step (d) gained, the method for load vanadium source precursor is: after vanadium source precursor is dissolved, add in the titanium tungsten powder of step (d) gained, in 40 ~ 90 DEG C of water-baths, for example 40 DEG C, 45 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C etc., preferably 40 ~ 80 DEG C, further preferably 60 ~ 80 DEG C, maintain 1h ~ 8h, such as 1h, 2h, 2.5h, 3h, 4h, 5h, 6h, 7h etc., preferably 2h ~ 6h, after further preferred 2h ~ 4h, dry.
As optimal technical scheme, described tungsten source precursor is can be water-soluble or the tungsten compound of organic solvent, the preferably mixture of one or more in ammonium metatungstate, ethanol tungsten, para-tungstic acid, ammonium paratungstate, further preferred ammonium metatungstate, ethanol tungsten, load capacity is that 1% ~ 10%(is by WO 3meter), for example 1%, 2%, 3.5%, 4%, 5%, 7%, 8%, 10% etc., preferably 3% ~ 8%(presses WO 3meter), further preferably 4% ~ 6%(presses WO 3meter);
Preferably, described vanadium source precursor is can be water-soluble or the vfanadium compound of organic solvent, the preferably mixture of one or more in vanadium oxalate, ammonium metavanadate, vanadic sulfate, and preferably vanadium oxalate, ammonium metavanadate, load capacity is that 0.5% ~ 5%(is by V 2o 5meter), for example 0.6%, 0.8%, 1%, 2%, 2.5%, 4%, 5% etc., preferably 0.5% ~ 3%(presses V 2o 5meter), further preferably 1% ~ 3%(presses V 2o 5meter);
Preferably, described sintering temperature is 400 ~ 800 DEG C, preferably 400 ~ 700 DEG C, further preferably 500 ~ 600 DEG C, for example 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 700 DEG C etc., roasting time is 1 ~ 6h, preferably 2 ~ 5h, further preferably 3 ~ 4h, such as 1h, 2h, 3h, 4h, 6h etc.
Titanium-containing blast furnace slag recoverying and utilizing method provided by the invention, utilizes the denitrating flue gas V-W-Ti catalyst of trade waste production high added value, has realized resource, the higher value application of titanium-containing blast furnace slag.
The method of the invention process is simple, does not need removal of impurities, and in blast furnace slag, the contained metal such as Fe, Mn can be used as the active metal of denitrating flue gas, is that the raw material fume denitration catalyst activity and the commercial catalysts that make are comparable by titanium-containing blast furnace slag; Method of the present invention has reduced the production cost of catalyst for denitrating flue gas, for titanium-containing blast furnace slag provides a new approach that utilizes, has broad application prospects.
Brief description of the drawings
Fig. 1 is process flow diagram of the present invention.
Fig. 2 is the XRD spectra of gained titanium tungsten powder in the embodiment of the present invention 1.
Fig. 3 is the XRD spectra of filter residue in the embodiment of the present invention 1.
Fig. 4 is the XRD spectra of gained vanadium tungsten titanium catalyst in the embodiment of the present invention 2.
Fig. 5 is the activity rating curve of gained vanadium tungsten titanium catalyst in the embodiment of the present invention 2.
Fig. 6 is the activity rating curve of gained vanadium tungsten titanium catalyst in the embodiment of the present invention 3.
Fig. 7 is the activity rating curve of gained vanadium tungsten titanium catalyst in the embodiment of the present invention 4.
Fig. 8 is the anti-sulphur water resistant activity curve of gained vanadium tungsten titanium catalyst in the embodiment of the present invention 5.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
The blast furnace slag main component using in the embodiment of the present invention is: CaO 26.7%, SiO 223.9%, TiO 216%, Al 2o 312.2%, MgO 7.8%, Fe 2o 32.3%, SO 31.6%, Mn, K etc. 9.5%.
Embodiment 1
Take 20g and be crushed to the titanium-containing blast furnace slag below 200 orders, by sulfuric acid (taking 100% sulfuric acid calculate) quality: blast furnace slag quality added 20% dilute sulfuric acid as 2: 1, under 80 DEG C of continuous stirring states, add blast furnace slag, fully stir, leach 8h, after end, carry out centrifugation, filter residue washs 3 times with 10% dilute sulfuric acid, collects filtrate for hydrolysis.To adding active carbon in titanium liquid, (addition is TiO in titanium-containing blast furnace slag 220% of quality, i.e. 0.64g), adding urea adjusting titanium liquid pH value is 0.5, adds ammonium metatungstate (by WO 3load capacity 5%), maintain 4h at 40 DEG C, be warming up to afterwards 105 DEG C and maintain 4h.Reaction finishes rear filtration, and filter residue is with being washed till neutrality by deionized water after dilute sulfuric acid washing for several times, dry, is then warming up to 500 DEG C of roasting 4h, obtains product titanium tungsten powder, wherein TiO 2the rate of recovery be 65%.TiO in gained titanium tungsten powder 2for anatase titanium dioxide, its XRD collection of illustrative plates as shown in Figure 2; As shown in Figure 3, main component is CaSO to the XRD collection of illustrative plates of filter residue 4and SiO 2.
Embodiment 2
Take 20g and be crushed to the titanium-containing blast furnace slag below 200 orders, by sulfuric acid (taking 100% sulfuric acid calculate) quality: blast furnace slag quality added 20% dilute sulfuric acid as 2: 1, under 80 DEG C of continuous stirring states, add blast furnace slag, fully stir leaching 8h, after end, carry out centrifugation, filter residue washs 3 times with 10% dilute sulfuric acid, collects filtrate for hydrolysis.To adding active carbon in titanium liquid, (addition is TiO in titanium-containing blast furnace slag 250% of quality, i.e. 1.6g), adding urea adjusting titanium liquid pH value is 0.5, maintains 2h at 40 DEG C, is warming up to afterwards 110 DEG C and maintains 8h.Reaction finishes rear filtration, and filter residue is with being washed till neutrality by deionized water after dilute sulfuric acid washing for several times, dry, obtains carrier supported type metatitanic acid, wherein TiO 2the rate of recovery be 69%.Take ammonium metatungstate (by WO 3load capacity 5%) dissolve, add gained carrier supported type metatitanic acid, be placed in 60 DEG C of water-bath 3h, then, in 80 DEG C of oven dry of baking oven, after 500 DEG C of roasting 4h, obtain titanium tungsten powder.Take ammonium metavanadate (by V 2o 5load capacity 2%) with oxalic acid dissolving, add gained titanium tungsten powder, be placed in 60 DEG C of water-bath 3h, then, in 80 DEG C of oven dry of baking oven, after 500 DEG C of roasting 4h, obtain vanadium tungsten titanium catalyst.The XRD collection of illustrative plates of gained catalyst as shown in Figure 4.As shown in Figure 5, as can be seen from the figure the present embodiment institute controlling catalyst all has good denitration activity at 250 ~ 450 DEG C to activity rating curve.
Embodiment 3
Take 20g and be crushed to the titanium-containing blast furnace slag below 200 orders, by sulfuric acid (taking 100% sulfuric acid calculate) quality: blast furnace slag quality added 20% dilute sulfuric acid as 2: 1, under 80 DEG C of continuous stirring states, add blast furnace slag, fully stir, leach 8h, after end, carry out centrifugation, filter residue washs 3 times with 10% dilute sulfuric acid, collects filtrate for hydrolysis.To adding active carbon in titanium liquid, (addition is TiO in titanium-containing blast furnace slag 220% of quality, i.e. 0.64g), adding urea adjusting titanium liquid pH value is 1.0, adds ammonium metatungstate (by WO 3load capacity 5%), maintain 4h at 40 DEG C, be warming up to afterwards 105 DEG C and maintain 8h.Reaction finishes rear filtration, and filter residue is with being washed till neutrality by deionized water after dilute sulfuric acid washing for several times, dry, obtains the carrier supported type metatitanic acid of tungstenic, wherein TiO 2the rate of recovery be 72%.Take ammonium metavanadate (by V 2o 5load capacity 2%) dissolve with oxalic acid, add the carrier supported type metatitanic acid of gained tungstenic, be placed in 60 DEG C of water-bath 3h, then, in 80 DEG C of oven dry of baking oven, after 500 DEG C of roasting 4h, obtain vanadium tungsten titanium catalyst.As shown in Figure 6, as can be seen from the figure the present embodiment institute controlling catalyst all has good denitration activity at 250 ~ 450 DEG C to the activity rating curve of gained catalyst.
Embodiment 4
Take 20g and be crushed to the titanium-containing blast furnace slag below 200 orders, by sulfuric acid (taking 100% sulfuric acid calculate) quality: blast furnace slag quality added 20% dilute sulfuric acid as 2: 1, under 80 DEG C of continuous stirring states, add blast furnace slag, fully stir, leach 8h, after end, carry out centrifugation, filter residue washs 3 times with 10% dilute sulfuric acid, collects filtrate for hydrolysis.To the active carbon that adds 40% in titanium liquid, (addition is TiO in titanium-containing blast furnace slag 240% of quality, i.e. 1.28g), adding urea adjusting titanium liquid pH value is 1.0, maintains 2h at 60 DEG C, is warming up to afterwards 105 DEG C and maintains 8h.Reaction finishes rear filtration, and filter residue is with being washed till neutrality by deionized water after dilute sulfuric acid washing for several times, dry, obtains carrier supported type metatitanic acid, wherein TiO 2the rate of recovery be 70%.Take ammonium metatungstate (by WO 3load capacity 5%) dissolve, add gained carrier supported type metatitanic acid, be placed in 60 DEG C of water-bath 3h, then in 80 DEG C of oven dry of baking oven.Take ammonium metavanadate (by V 2o 5load capacity 1%) dissolve with oxalic acid, add the carrier supported type metatitanic acid of gained tungstenic, be placed in 60 DEG C of water-bath 3h, then, in 80 DEG C of oven dry of baking oven, after 500 DEG C of roasting 4h, obtain vanadium tungsten titanium catalyst.As shown in Figure 7, as can be seen from the figure the present embodiment institute controlling catalyst all has good denitration activity at 250 ~ 450 DEG C to the activity rating curve of gained catalyst.
Embodiment 5
Take 20g and be crushed to the titanium-containing blast furnace slag below 200 orders, by sulfuric acid (taking 100% sulfuric acid calculate) quality: blast furnace slag quality added 20% dilute sulfuric acid as 2: 1, under 80 DEG C of continuous stirring states, add blast furnace slag, fully stir, leach 8h, after end, carry out centrifugation, filter residue washs 3 times with 10% dilute sulfuric acid, collects filtrate for hydrolysis.To adding active carbon in titanium liquid, (addition is TiO in titanium-containing blast furnace slag 220% of quality, i.e. 0.64g), adding urea adjusting titanium liquid pH value is 0.5, maintains 4h at 40 DEG C, is warming up to afterwards 105 DEG C and maintains 8h.Reaction finishes rear filtration, and filter residue is with being washed till neutrality by deionized water after dilute sulfuric acid washing for several times, dry, obtains carrier supported type metatitanic acid.Take ammonium metatungstate (by WO 3load capacity 5%) dissolve, add gained carrier supported type metatitanic acid, be placed in 60 DEG C of water-bath 3h, in 80 DEG C of oven dry of baking oven, be then warming up to 500 DEG C of roasting 4h afterwards, obtain product titanium tungsten powder, wherein TiO 2the rate of recovery be 68%.Take ammonium metavanadate (by V 2o 52%) dissolve with oxalic acid, add gained titanium tungsten powder, be placed in 60 DEG C of water-bath 3h, then, in 80 DEG C of oven dry of baking oven, after 500 DEG C of roasting 4h, obtain vanadium tungsten titanium catalyst.As shown in Figure 8, as can be seen from the figure institute's controlling catalyst has good stability denitration activity and the anti-sulphur water resistant of 300 DEG C the anti-sulphur water resistant activity curve of gained catalyst.
In the embodiment of the present invention, the appreciation condition of vanadium tungsten titanium catalyst is: NO entrance concentration 600ppm, air speed 24000h-1, NH 3/ NO=0.8, O 2content 3%.When anti-sulphur water resistant is evaluated: temperature is 300 DEG C, SO 2for 2000ppm, H 2o is 5%.
Applicant's statement, the present invention illustrates detailed process flow of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process flow, does not mean that the present invention must rely on above-mentioned detailed process flow and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope.

Claims (67)

1. a preparation method for SCR catalyst for denitrating flue gas, comprises the following steps:
(a) after titanium-containing blast furnace slag is pulverized, add sulfuric acid to TiO wherein 2leach, after filtration, obtain titanium liquid and filter residue;
(b) under stirring condition, in step (a) gained titanium liquid, add Easy LOI type porous catalyst carrier, selectively add alkali compounds to regulate pH to 0-4, be hydrolyzed;
(c) material after step (b) hydrolysis after filtration, washing, obtain carrier supported type metatitanic acid after drying;
(d) load tungsten and vanadium on step (c) gained carrier supported type metatitanic acid, then roasting makes vanadium tungsten titanium SCR catalyst for denitrating flue gas;
Wherein, step (a) is by sulfuric acid quality: blast furnace slag quality is 1～5:1, and more than leaching 2h, wherein sulfuric acid calculates with 100% sulfuric acid.
2. a preparation method for SCR catalyst for denitrating flue gas, comprises the following steps:
(a) after titanium-containing blast furnace slag is pulverized, add sulfuric acid to TiO wherein 2leach, after filtration, obtain titanium liquid and filter residue;
(b) under stirring condition, in step (a) gained titanium liquid, add Easy LOI type porous catalyst carrier, selectively add alkali compounds to regulate pH to 0-4, be hydrolyzed, in hydrolytic process, add tungsten source precursor;
(c) material after step (b) hydrolysis after filtration, washing, obtain the carrier supported type metatitanic acid of tungstenic after drying;
(d) load vanadium source precursor on the carrier supported type metatitanic acid of the tungstenic of step (c) gained, obtains vanadium tungsten titanium SCR catalyst for denitrating flue gas after roasting; Or,
The carrier supported type metatitanic acid of the tungstenic to step (c) gained carries out roasting and makes titanium tungsten powder, and to the further load vanadium of titanium tungsten powder source precursor, then roasting makes vanadium tungsten titanium SCR catalyst for denitrating flue gas;
Wherein, step (a) is by sulfuric acid quality: blast furnace slag quality is 1～5:1, and more than leaching 2h, wherein sulfuric acid calculates with 100% sulfuric acid.
3. a preparation method for SCR catalyst for denitrating flue gas, comprises the following steps:
(a) after titanium-containing blast furnace slag is pulverized, add sulfuric acid to TiO wherein 2leach, after filtration, obtain titanium liquid and filter residue;
(b) under stirring condition, in step (a) gained titanium liquid, add Easy LOI type porous catalyst carrier, selectively add alkali compounds to regulate pH to 0-4, be hydrolyzed;
(c) material after step (b) hydrolysis after filtration, washing, obtain carrier supported type metatitanic acid after drying;
(d) load tungsten source precursor on the carrier supported type metatitanic acid of step (c) gained, then roasting obtains titanium tungsten powder;
(e) load vanadium source precursor on the titanium tungsten powder of step (d) gained, then roasting makes vanadium tungsten titanium SCR catalyst for denitrating flue gas;
Wherein, step (a) is by sulfuric acid quality: blast furnace slag quality is 1～5:1, and more than leaching 2h, wherein sulfuric acid calculates with 100% sulfuric acid.
4. a preparation method for the raw material titanium tungsten powder of SCR catalyst for denitrating flue gas, comprises the steps:
(a) after titanium-containing blast furnace slag is pulverized, add sulfuric acid to TiO wherein 2leach, after filtration, obtain titanium liquid and filter residue;
(b) under stirring condition, in step (a) gained titanium liquid, add Easy LOI type porous catalyst carrier, selectively add alkali compounds to regulate pH to 0-4, be hydrolyzed;
(c) material after step (b) hydrolysis after filtration, washing, obtain carrier supported type metatitanic acid after drying;
(d) load tungsten source precursor on the carrier supported type metatitanic acid of step (c) gained, then roasting obtains titanium tungsten powder;
Wherein, step (a) is by sulfuric acid quality: blast furnace slag quality is 1～5:1, and more than leaching 2h, wherein sulfuric acid calculates with 100% sulfuric acid.
5. the method as described in claim 1～4 any one, it is characterized in that, step (a) detailed process is: take the titanium-containing blast furnace slag after pulverizing, by sulfuric acid quality: blast furnace slag quality is 1～5:1, and wherein sulfuric acid calculates with 100% sulfuric acid, add sulfuric acid, add blast furnace slag in heating and under constantly stirring, fully stir, more than leaching 2h, after finishing, carry out centrifugal/isolated by filtration, dilute sulfuric acid washing at least 2 times for filter residue, collects filtrate and obtains titanium liquid.
6. method as claimed in claim 5, is characterized in that, described titanium-containing blast furnace slag, by sulfuric acid quality: blast furnace slag quality is 1～3:1, and wherein sulfuric acid calculates with 100% sulfuric acid.
7. method as claimed in claim 5, is characterized in that, described titanium-containing blast furnace slag, by sulfuric acid quality: blast furnace slag quality is 2:1, and wherein sulfuric acid calculates with 100% sulfuric acid.
8. method as claimed in claim 5, is characterized in that, the time of described leaching is 6～10h.
9. method as claimed in claim 5, is characterized in that, dilute sulfuric acid washing 3～5 times for filter residue.
10. method as claimed in claim 5, is characterized in that, described titanium-containing blast furnace slag is TiO 2content is more than 10% smelting iron and steel blast furnace slag, and described heating-up temperature is 40～100 DEG C.
11. methods as claimed in claim 5, is characterized in that, described heating-up temperature is 60～90 DEG C.
12. methods as claimed in claim 5, is characterized in that, described heating-up temperature is 70～80 DEG C.
13. methods as described in claim 1～4 any one, is characterized in that, the Easy LOI type porous catalyst carrier in step (b) is one or more the mixture in active carbon, activated coke, semicoke, cellulose, starch; Easy LOI type porous catalyst carrier addition is TiO in titanium-containing blast furnace slag 21%～200% of quality.
14. methods as claimed in claim 13, is characterized in that, the Easy LOI type porous catalyst carrier in step (b) is active carbon, activated coke, semicoke.
15. methods as claimed in claim 13, is characterized in that, the Easy LOI type porous catalyst carrier in step (b) is active carbon.
16. methods as claimed in claim 13, is characterized in that, Easy LOI type porous catalyst carrier addition is TiO in titanium-containing blast furnace slag 210%～100% of quality.
17. methods as claimed in claim 13, is characterized in that, Easy LOI type porous catalyst carrier addition is TiO in titanium-containing blast furnace slag 220%～50% of quality.
18. methods as described in claim 1～4 any one, it is characterized in that, the alkali compounds described in step (b) is one or more in urea, ammoniacal liquor, carbonic hydroammonium, ammonium carbonate, alkali-metal hydroxide, alkali-metal carbonate or bicarbonate; Described alkali compounds selectively adds, and addition is so that the pH value of end reaction system is 0～4 for standard.
19. methods as claimed in claim 18, is characterized in that, the pH value of described end reaction system is 0～3.
20. methods as claimed in claim 18, is characterized in that, the pH value of described end reaction system is 0～1.
21. methods as described in claim 1～4 any one, is characterized in that, the hydrolysis temperature described in step (b) is 30 DEG C～110 DEG C, and hydrolysis time is 1h～24h.
22. methods as described in claim 1～4 any one, is characterized in that, described hydrolysis is first hydrolysis at low temperatures, and then at high temperature hydrolysis obtains metatitanic acid crystal; Under described low temperature, be hydrolyzed to 30～80 DEG C; The low temperature hydrolysis time is 1h～12h; Under described high temperature, be hydrolyzed to 80～110 DEG C; The pyrohydrolysis time is 2h～24h.
23. methods as claimed in claim 22, is characterized in that, are hydrolyzed to 30～60 DEG C under described low temperature.
24. methods as claimed in claim 22, is characterized in that, are hydrolyzed to 30～50 DEG C under described low temperature.
25. methods as claimed in claim 22, is characterized in that, the described low temperature hydrolysis time is 1h～8h.
26. methods as claimed in claim 22, is characterized in that, the described low temperature hydrolysis time is 2h～4h.
27. methods as claimed in claim 22, is characterized in that, are hydrolyzed to 90～110 DEG C under described high temperature.
28. methods as claimed in claim 22, is characterized in that, are hydrolyzed to 95～105 DEG C under described high temperature.
29. methods as claimed in claim 22, is characterized in that, under described high temperature, hydrolysis time is 4h～12h.
30. methods as claimed in claim 22, is characterized in that, under described high temperature, hydrolysis time is 4h～8h.
31. methods as claimed in claim 22, is characterized in that, described Easy LOI type porous catalyst carrier and alkali compounds add at low thermophase.
32. methods as described in claim 1～4 any one, it is characterized in that, the process of step (c) is: by the material after step (b) hydrolysis after filtration, use successively dilute sulfuric acid, water washing to neutral, after drying, obtain carrier supported type metatitanic acid at 105～150 DEG C.
33. the method for claim 1, it is characterized in that, on step (c) gained carrier supported type metatitanic acid, the method for load tungsten and vanadium is: after tungsten source precursor is dissolved, add step (c) gained carrier supported type metatitanic acid, in 40～90 DEG C of water-baths, maintain after 1h～8h, dry to obtain the carrier supported type metatitanic acid of tungstenic; The carrier supported type metatitanic acid that adds the tungstenic of gained after vanadium source precursor is dissolved, in 40～90 DEG C of water-baths, maintains after 1h～8h, dries.
34. methods as claimed in claim 33, is characterized in that, the temperature of described water-bath is 40～80 DEG C.
35. methods as claimed in claim 33, is characterized in that, the temperature of described water-bath is 60～80 DEG C.
36. methods as claimed in claim 33, is characterized in that, the time maintaining in water-bath is 2h～6h.
37. methods as claimed in claim 33, is characterized in that, the time maintaining in water-bath is 2h～4h.
38. methods as claimed in claim 2, it is characterized in that, on the carrier supported type metatitanic acid of the tungstenic of step (c) gained, the method for load vanadium source precursor is: the carrier supported type metatitanic acid that adds the tungstenic of step (c) gained after vanadium source precursor is dissolved, in 40～90 DEG C of water-baths, maintain after 1h～8h, dry.
39. methods as claimed in claim 38, is characterized in that, the temperature of described water-bath is 40～80 DEG C.
40. methods as claimed in claim 38, is characterized in that, the temperature of described water-bath is 60～80 DEG C.
41. methods as claimed in claim 38, is characterized in that, the time maintaining in water-bath is 2h～6h.
42. methods as claimed in claim 38, is characterized in that, the time maintaining in water-bath is 2h～4h.
43. methods as claimed in claim 3, it is characterized in that, on the carrier supported type metatitanic acid of step (c) gained, the method for load tungsten source precursor is: after tungsten source precursor is dissolved, add step (c) gained carrier supported type metatitanic acid, in 40～90 DEG C of water-baths, maintain after 1h～8h, dry.
44. methods as claimed in claim 43, is characterized in that, the temperature of described water-bath is 40～80 DEG C.
45. methods as claimed in claim 43, is characterized in that, the temperature of described water-bath is 60～80 DEG C.
46. methods as claimed in claim 43, is characterized in that, the time maintaining in water-bath is 2h～6h.
47. methods as claimed in claim 43, is characterized in that, the time maintaining in water-bath is 2h～4h.
48. methods as claimed in claim 3, it is characterized in that, on the titanium tungsten powder of step (d) gained, the method for load vanadium source precursor is: after vanadium source precursor is dissolved, add in the titanium tungsten powder of step (d) gained, in 40～90 DEG C of water-baths, maintain after 1h～8h, dry.
49. methods as claimed in claim 48, is characterized in that, the temperature of described water-bath is 40～80 DEG C.
50. methods as claimed in claim 48, is characterized in that, the temperature of described water-bath is 60～80 DEG C.
51. methods as claimed in claim 48, is characterized in that, the time maintaining in water-bath is 2h～6h.
52. methods as claimed in claim 48, is characterized in that, the time maintaining in water-bath is 2h～4h.
53. methods as described in claim 33～52 any one, is characterized in that, described tungsten source precursor is can be water-soluble or the tungsten compound of organic solvent, and load capacity is 1%～10%, by WO 3meter.
54. methods as claimed in claim 53, is characterized in that, described tungsten source precursor is one or more the mixture in ammonium metatungstate, ethanol tungsten, para-tungstic acid, ammonium paratungstate.
55. methods as claimed in claim 53, is characterized in that, described tungsten source precursor is ammonium metatungstate, ethanol tungsten.
56. methods as claimed in claim 53, is characterized in that, described load capacity is 3%～8%, by WO 3meter.
57. methods as claimed in claim 53, is characterized in that, described load capacity is 4%～6%, by WO 3meter.
58. methods as described in claim 33～52 any one, is characterized in that, described vanadium source precursor is can be water-soluble or the vfanadium compound of organic solvent, and load capacity is 0.5%～5%, by V 2o 5meter.
59. methods as claimed in claim 58, is characterized in that, described vanadium source precursor is one or more the mixture in vanadium oxalate, ammonium metavanadate, vanadic sulfate.
60. methods as claimed in claim 58, is characterized in that, described vanadium source precursor is vanadium oxalate, ammonium metavanadate.
61. methods as claimed in claim 58, is characterized in that, described load capacity is 0.5%～3%, by V 2o 5meter.
62. methods as claimed in claim 58, is characterized in that, described load capacity is 1%～3%, by V 2o 5meter.
63. methods as described in claim 1～4 any one, is characterized in that, described sintering temperature is 400～800 DEG C, and roasting time is 1～6h.
64. methods as described in claim 63, is characterized in that, described sintering temperature is 400～700 DEG C.
65. methods as described in claim 63, is characterized in that, described sintering temperature is 500～600 DEG C.
66. methods as described in claim 63, is characterized in that, described roasting time is 2～5h.
67. methods as described in claim 63, is characterized in that, described roasting time is 3～4h.
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