CN102698737A - 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 PDFInfo
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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
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
Can discharge a large amount of blast furnace slags in the blast furnace ironmaking process, if do not carry out suitable treatment meeting land occupation, contaminated environment and cause the wasting of resources.Contain metal values such as titanium, silicon, aluminium, calcium in the blast furnace slag, can take suitable method separation and Extraction and be processed into chemical products, solve the problem of environmental pollution that it brings when rationally utilizing this trade waste resource.
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
CaO, SiO that high level is arranged in the blast furnace slag usually
2, Al
2O
3, thereby often be made into grain slag, slag rubble, expanded slag, mineral wool etc., as the raw material of cement, perhaps brickmaking, system sand, the construction material of paving the way etc.
(2) as industrial chemicals
Can be used for producing devitrified glass (CN 89105864.8), ceramic (CN00119612.X), refractory repairing mass (CN 200710202467.4) like titanium-containing blast furnace slag; Coagulant (CN 201010239034.8) etc.
(3) reclaim valuable metal such as Ti
The recovery of metal such as Ti has several different methods in the blast furnace slag; CN 201010216354.1 discloses a kind of method of comprehensive utilization of titanium-containing blast furnace slag; Adopt the salt acid treatment process; Recovery obtains rich titanium products, aluminium hydroxide, magnesia and calcium oxide, and this method can make full use of the 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 sulfur waste acid that utilizes sulfur waste acid to decompose titaniferous metallurgical slag, low concentration dissolves titanium dioxide; Diluted Ti solution extracts titanium article; Sulfur waste acid can be recycled in this process, helps environmental protection.
In addition; Titanium-containing blast furnace slag often is used as the preparation titanium white powder owing to its higher Ti content (about 20%); CN 86108511 discloses the method that a kind of titanium-containing blast furnace slag prepares titanium white powder; But the titanium white quality that this method is produced not is a pigment-level, can only be used for welding rod, enamel and metallurgy industry, and the scope of application is limited.CN200510021747.6 discloses and has a kind ofly produced the method for pigment-level titanium white powder and thick titanium white with titanium-containing blast furnace slag, and this method adopts sulfuric acid treatment titanium-containing blast furnace slag, through two sections mills soak, two sections hydrolysis and surface treatment obtain pigmentary titanium white powder.In addition, can also utilize titanium-containing blast furnace slag to produce ferro-silico-titanium through 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; With the titanium-containing blast furnace slag is raw material production synthetic rutile (CN 201110072575.0).
The above-mentioned various equal technical feasibility of patent that utilizes in the method, but mostly based on Ti and TiO
2Extraction, strict isolation of purified technology causes problems such as leaching process material consumption/energy consumption is big, cost is high, benefit is low, therefore, ineffective yet so far industrialization contains Ti blast furnace slag comprehensive utilization technique.
Nitrogen oxide is one of main air pollutants that cause a series of problems such as broken ring ball ecological environment such as acid rain, photochemical fog, also is emphasis and the difficult point in the present 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 restrictive index.Coal-fired flue gas denitration will be the major fields of state control thermal power plant pollutant emission during " 12 ".
Denitrating flue gas is meant the NO that has generated
XBe reduced to N
2Thereby, remove the NO in the flue gas
X, can be divided into wet method denitration and dry method denitration by administering technology.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 technology, and its principle is under catalyst action, NH
3Reductive NO and NO
2The desired temperature of reaction reduce and NH greatly
3Oxidation reaction take place hardly, thereby improved N
2Selectivity, reduced NH
3Consumption.Catalyst is the core of SCR technology.At present used commercial coal-fired plant flue gas denitrating catalyst is made up of vanadium, tungsten, titanyl compound usually, and titanium dioxide it is in great demand as the carrier of catalyst.
Because titanium-containing blast furnace slag has higher Ti content, this characteristic that therefore how to make full use of the 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 the SCR catalyst for denitrating flue gas.Titanium-containing blast furnace slag also contains elements such as a small amount of Mn, K except Ti, Ca, Si, Al, Mg, Fe; Produce in the technology of titanium dioxide in acidolysis-hydrolysis; Usually a small amount of plurality of impurities be can contain in the end product, the quality and the scope of application thereof that reclaim gained titanium dioxide influenced greatly.The employed Ti compound of preparation catalyst for denitrating flue gas (titanyl sulfate, skewness acid) has higher tolerance to various impurity components; The impurity component that has; Not only do not influence the denitrating catalyst activity like Mn, Fe and sulfate radical, also help the raising of catalyst activity and stability.
One of method for preparing the SCR catalyst for denitrating flue gas provided by the present invention comprises the steps:
(a) titanium-containing blast furnace slag is pulverized after, add sulfuric acid to wherein TiO
2Leach, get titanium liquid and filter residue after the filtration;
(b) under stirring condition, in step (a) gained titanium liquid, add the easy mistake type porous catalyst carrier that burns, selectivity adds alkali compounds and regulates pH, is hydrolyzed;
(c) material after step (b) hydrolysis obtains supported type metatitanic acid after filtering, wash, drying;
(d) load tungsten and vanadium on step (c) gained supported type metatitanic acid, roasting makes vanadium tungsten titanium SCR catalyst for denitrating flue gas then.
The schematic flow sheet of this method is seen Fig. 1.
Two of the method for preparing the SCR catalyst for denitrating flue gas provided by the present invention comprises the steps:
(a) titanium-containing blast furnace slag is pulverized after, add sulfuric acid to wherein TiO
2Leach, get titanium liquid and filter residue after the filtration;
(b) under stirring condition, in step (a) gained titanium liquid, add the easy mistake type porous catalyst carrier that burns, selectivity adds alkali compounds and regulates pH, is hydrolyzed, and adds tungsten source precursor in the hydrolytic process;
(c) material after step (b) hydrolysis obtains the supported type metatitanic acid of tungstenic after filtering, wash, drying;
(d) load vanadium source precursor on the supported type metatitanic acid of the tungstenic of step (c) gained promptly gets vanadium tungsten titanium SCR catalyst for denitrating flue gas after the roasting;
Or the supported type metatitanic acid of the tungstenic of step (c) gained is carried out roasting make the titanium tungsten powder, to the further load vanadium of titanium tungsten powder source precursor, roasting makes vanadium tungsten titanium SCR catalyst for denitrating flue gas then.
Three of the method for preparing the SCR catalyst for denitrating flue gas provided by the present invention comprises the steps:
(a) titanium-containing blast furnace slag is pulverized after, add sulfuric acid to wherein TiO
2Leach, get titanium liquid and filter residue after the filtration;
(b) under stirring condition, in step (a) gained titanium liquid, add the easy mistake type porous catalyst carrier that burns, selectivity adds alkali compounds and regulates pH, is hydrolyzed;
(c) material after step (b) hydrolysis obtains supported type metatitanic acid after filtering, wash, drying;
(d) load tungsten source precursor on the supported type metatitanic acid of step (c) gained, roasting gets the titanium tungsten powder then;
(e) load vanadium source precursor on the titanium tungsten powder of step (d) gained, roasting makes vanadium tungsten titanium SCR catalyst for denitrating flue gas then.
One of the object of the invention also is to provide a kind of preparation method of raw material titanium tungsten powder of SCR catalyst for denitrating flue gas, comprises the steps:
(a) titanium-containing blast furnace slag is pulverized after, add sulfuric acid to wherein TiO
2Leach, get titanium liquid and filter residue after the filtration;
(b) under stirring condition, in step (a) gained titanium liquid, add the easy mistake type porous catalyst carrier that burns, selectivity adds alkali compounds and regulates pH, is hydrolyzed;
(c) material after step (b) hydrolysis obtains supported type metatitanic acid after filtering, wash, drying;
(d) load tungsten source precursor on the supported type metatitanic acid of step (c) gained, roasting gets the titanium tungsten powder then.
The schematic flow sheet of this method is seen 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; The preparation coupling of hydrolysis and denitrating catalyst support material with titanyl sulfate---supported type metatitanic acid, and then through supported type metatitanic acid load vanadium tungsten active component is prepared denitrating catalyst raw material and powder denitrating catalyst.The higher value application that this method is not merely blast furnace slag provides a new way; Effectively reduce the production cost of catalyst for denitrating flue gas simultaneously as raw material with this trade waste; Help to alleviate the expensive situation of present domestic commerce denitrating catalyst, have important economic implications and social effect.
Through method provided by the present invention, the titanium on the one hand can the effective recycling blast furnace slag, and obtain high value-added product; This 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, and is significant to the Environmental Protection in China cause.
As optimal technical scheme, step (a) detailed process is: take by weighing the titanium-containing blast furnace slag after the pulverizing, by sulfuric acid (calculating with 100% sulfuric acid) quality: the blast furnace slag quality is 1 ~ 5: 1; For example 1: 1,2: 1,3: 1,4: 1,5: 1, preferred 1 ~ 3: 1, further preferred 2: 1; Add sulfuric acid, under heating and continuous the stirring, add blast furnace slag, fully stir, leach more than the 2h; Preferred 6 ~ 10h carries out centrifugal/isolated by filtration after the end, filter residue is with dilute sulfuric acid washing at least 2 times; Preferred 3 ~ 5 times, collect filtrating and obtain titanium liquid.Titanium-containing blast furnace slag after the pulverizing preferably is below 200 orders, so that blast furnace slag and sulfuric acid react fully.
Preferably, described titanium-containing blast furnace slag is TiO
2Content is the smelting iron and steel blast furnace slag more than 10%, and described heating-up temperature is 40 ~ 100 ℃, preferred 60 ~ 90 ℃, and further preferred 70 ~ 80 ℃.
Preferably, the easy burning mistake type porous catalyst carrier in the step (b) is one or more the mixture in active carbon, activated coke, semicoke, cellulose, the starch, preferred active carbon, activated coke, semicoke, further preferred active carbon; Being prone to burn mistake type porous catalyst carrier addition is TiO in the 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 preferred 20% ~ 50%.Easy burning mistake type porous catalyst carrier in this use is water insoluble, can be burnt under the high temperature and lose, and have certain dispersiveness and specific area, in order to increase the dispersiveness of final products.
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 the bicarbonate; Described alkali-metal hydroxide for example is NaOH, potassium hydroxide, lithium hydroxide etc.; Described alkali-metal carbonate or bicarbonate for example are 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; Said alkali compounds selectivity adds, and addition is so that the pH value of end reaction system is 0 ~ 4 to be standard, and for example 0.01,0.05,0.1,0.5,1,1.5,2,2.5,3,4 etc., further be preferably 0 ~ 3, be preferably 0 ~ 1 especially.But, and do not form insoluble compound with sulfuric acid reaction in the alkali compounds neutralisation of sulphuric acid of this use.
Preferably, the hydrolysis temperature described in the step (b) is 30 ℃ ~ 110 ℃, and hydrolysis time is 1h ~ 24h;
Preferably, described hydrolysis is hydrolysis at low temperatures earlier, and hydrolysis at high temperature obtains the metatitanic acid crystal then; Be hydrolyzed to 30 ~ 80 ℃ under the said low temperature, for example 30 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃ etc., further be preferably 30 ~ 60 ℃, be preferably 30 ~ 50 ℃ especially; The low temperature hydrolysis time is 1h ~ 12h, and for example 1h, 2h, 3h, 4h, 6h, 8h, 10h, 12h etc. further are preferably 1h ~ 8h, are preferably 2h ~ 4h especially; Be hydrolyzed to 80 ~ 110 ℃ under the said high temperature, for example 80 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃ etc., further be preferably 90 ~ 110 ℃, be preferably 95 ~ 105 ℃ especially; The pyrohydrolysis time is 2h ~ 24h, and for example 2h, 3h, 4h, 6h, 8h, 12h, 16h, 20h, 24h etc. further are preferably 4h ~ 12h, preferred especially 4h ~ 8h;
Preferably, described easy burning mistake type porous catalyst carrier and alkali compounds add at low thermophase.
As optimal technical scheme, the process of step (c) is: through filtering, use dilute sulfuric acid, water washing to neutral successively the material after step (b) hydrolysis, obtain supported type metatitanic acid after the oven dry down at 105 ~ 150 ℃.
As optimal technical scheme, in one of method on step (c) gained supported type metatitanic acid the method for load tungsten and vanadium be: with adding step (c) gained supported type metatitanic acid after the dissolving of tungsten source precursor, in 40 ~ 90 ℃ of water-baths; Preferred 40 ~ 80 ℃; Further preferred 60 ~ 80 ℃, keep 1h ~ 8h, preferred 2h ~ 6h; Behind further preferred 2h ~ 4h, dry the supported type metatitanic acid of tungstenic; With the supported type metatitanic acid that adds the tungstenic of gained after the dissolving of vanadium source precursor, in 40 ~ 90 ℃ of water-baths, for example 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ etc.; Preferred 40 ~ 80 ℃, further preferred 60 ~ 80 ℃, keep 1h ~ 8h; For example 1h, 2h, 2.5h, 3h, 4h, 5h, 6h, 7h etc.; Preferred 2h ~ 6h, behind further preferred 2h ~ 4h, oven dry.
As optimal technical scheme, method two on the supported type metatitanic acid of the tungstenic of step (c) gained the method for load vanadium source precursor be: with the supported type metatitanic acid that adds the tungstenic of step (c) gained after the dissolving of vanadium source precursor, in 40 ~ 90 ℃ of water-baths; For example 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ etc.; Preferred 40 ~ 80 ℃, further preferred 60 ~ 80 ℃, keep 1h ~ 8h; For example 1h, 2h, 2.5h, 3h, 4h, 5h, 6h, 7h etc.; Preferred 2h ~ 6h, behind further preferred 2h ~ 4h, oven dry.
As optimal technical scheme, method three on the supported type metatitanic acid of step (c) gained the method for load tungsten source precursor be: add step (c) gained supported type metatitanic acid with after the tungsten source precursor dissolving, in 40 ~ 90 ℃ of water-baths; For example 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ etc.; Preferred 40 ~ 80 ℃, further preferred 60 ~ 80 ℃, keep 1h ~ 8h; For example 1h, 2h, 2.5h, 3h, 4h, 5h, 6h, 7h etc.; Preferred 2h ~ 6h, behind further preferred 2h ~ 4h, oven dry;
Preferably, the method for load vanadium source precursor is on the titanium tungsten powder of step (d) gained: with adding in the titanium tungsten powder of step (d) gained after the dissolving of vanadium source precursor, in 40 ~ 90 ℃ of water-baths; For example 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ etc., preferred 40 ~ 80 ℃, further preferred 60 ~ 80 ℃; Keep 1h ~ 8h, for example 1h, 2h, 2.5h, 3h, 4h, 5h, 6h, 7h etc., preferably 2h ~ 6h; Behind further preferred 2h ~ 4h, oven dry.
As optimal technical scheme; Described tungsten source precursor is can be water-soluble or the tungsten compound of organic solvent; The mixture of one or more in preferred ammonium metatungstate, ethanol tungsten, para-tungstic acid, the ammonium paratungstate; Further preferred ammonium metatungstate, ethanol tungsten, load capacity are 1% ~ 10% (to press WO
3Meter), for example 1%, 2%, 3.5%, 4%, 5%, 7%, 8%, 10% etc., preferred 3% ~ 8% (presses WO
3Meter), further preferred 4% ~ 6% (press WO
3Meter);
Preferably, described vanadium source precursor is can be water-soluble or the vfanadium compound of organic solvent, the mixture of one or more in preferred vanadium oxalate, ammonium metavanadate, the vanadic sulfate, and preferred vanadium oxalate, ammonium metavanadate, load capacity is 0.5% ~ 5% (to press V
2O
5Meter), for example 0.6%, 0.8%, 1%, 2%, 2.5%, 4%, 5% etc., preferred 0.5% ~ 3% (presses V
2O
5Meter), further preferred 1% ~ 3% (press V
2O
5Meter);
Preferably, described sintering temperature is 400 ~ 800 ℃, preferred 400 ~ 700 ℃; Further preferred 500 ~ 600 ℃, for example 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 700 ℃ etc., roasting time is 1 ~ 6h; Preferred 2 ~ 5h, further preferred 3 ~ 4h, for example 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 metals such as contained Fe, Mn can be used as the reactive metal of denitrating flue gas in the blast furnace slag, is that the catalyst for denitrating flue gas that makes of raw material is active comparable with commercial catalysts 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.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Fig. 2 is the XRD spectra of gained titanium tungsten powder in the embodiment of the invention 1.
Fig. 3 is the XRD spectra of filter residue in the embodiment of the invention 1.
Fig. 4 is the XRD spectra of gained vanadium tungsten titanium catalyst in the embodiment of the invention 2.
Fig. 5 is the activity rating curve of gained vanadium tungsten titanium catalyst in the embodiment of the invention 2.
Fig. 6 is the activity rating curve of gained vanadium tungsten titanium catalyst in the embodiment of the invention 3.
Fig. 7 is the activity rating curve of gained vanadium tungsten titanium catalyst in the embodiment of the invention 4.
Fig. 8 is the anti-water activity curve of anti-sulphur of gained vanadium tungsten titanium catalyst in the embodiment of the invention 5.
The specific embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
The blast furnace slag main component of using in the embodiment of the 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 by weighing 20g and be crushed to the titanium-containing blast furnace slag below 200 orders; By sulfuric acid (calculating with 100% sulfuric acid) quality: the blast furnace slag quality is to add 20% dilute sulfuric acid at 2: 1; Under 80 ℃ of continuous stirring states, add blast furnace slag, fully stir, leach 8h, centrifugalize after the end; Filter residue washs 3 times with 10% dilute sulfuric acid, collects filtrating and is used for hydrolysis.(addition is TiO in the titanium-containing blast furnace slag in titanium liquid, to add active carbon
220% of quality, i.e. 0.64g), adding urea adjusting titanium liquid pH value is 0.5, adds ammonium metatungstate and (presses WO
3Load capacity 5%), keeps 4h, be warming up to 105 ℃ afterwards and keep 4h at 40 ℃.Reaction is filtered after finishing, and filter residue is washed till neutrality with deionized water in the back for several times with the dilute sulfuric acid washing, and drying then is warming up to 500 ℃ of roasting 4h, gets product titanium tungsten powder, wherein TiO
2The rate of recovery be 65%.TiO in the gained titanium tungsten powder
2Be anatase titanium dioxide, its XRD figure spectrum is shown in accompanying drawing 2; The XRD figure spectrum of filter residue is shown in accompanying drawing 3, and main component is CaSO
4And SiO
2
Take by weighing 20g and be crushed to the titanium-containing blast furnace slag below 200 orders; By sulfuric acid (calculating with 100% sulfuric acid) quality: the blast furnace slag quality is to add 20% dilute sulfuric acid at 2: 1; Under 80 ℃ of continuous stirring states, add blast furnace slag, fully stir leaching 8h, centrifugalize after the end; Filter residue washs 3 times with 10% dilute sulfuric acid, collects filtrating and is used for hydrolysis.(addition is TiO in the titanium-containing blast furnace slag in titanium liquid, to add active carbon
250% of quality, i.e. 1.6g), adding urea adjusting titanium liquid pH value is 0.5, keeps 2h at 40 ℃, is warming up to 110 ℃ afterwards and keeps 8h.Reaction finishes the back filters, and filter residue is washed till neutrality with deionized water in the back for several times with the dilute sulfuric acid washing, and drying obtains supported type metatitanic acid, wherein TiO
2The rate of recovery be 69%.Take by weighing ammonium metatungstate and (press WO
3Load capacity 5%) dissolving adds gained supported type metatitanic acid, places 60 ℃ of water-bath 3h, then in 80 ℃ of oven dry of baking oven, behind 500 ℃ of roasting 4h, obtains the titanium tungsten powder.Take by weighing ammonium metavanadate and (press V
2O
5Load capacity 2%) with the oxalic acid dissolving, add gained titanium tungsten powder, place 60 ℃ of water-bath 3h, then, behind 500 ℃ of roasting 4h, obtain vanadium tungsten titanium catalyst in 80 ℃ of oven dry of baking oven.The XRD figure spectrum of gained catalyst is shown in accompanying drawing 4.The activity rating curve is shown in accompanying drawing 5, and as can be seen from the figure present embodiment institute controlling catalyst all has favorable denitrification activity at 250 ~ 450 ℃.
Embodiment 3
Take by weighing 20g and be crushed to the titanium-containing blast furnace slag below 200 orders; By sulfuric acid (calculating with 100% sulfuric acid) quality: the blast furnace slag quality is to add 20% dilute sulfuric acid at 2: 1; Under 80 ℃ of continuous stirring states, add blast furnace slag, fully stir, leach 8h, centrifugalize after the end; Filter residue washs 3 times with 10% dilute sulfuric acid, collects filtrating and is used for hydrolysis.(addition is TiO in the titanium-containing blast furnace slag in titanium liquid, to add active carbon
220% of quality, i.e. 0.64g), adding urea adjusting titanium liquid pH value is 1.0, adds ammonium metatungstate and (presses WO
3Load capacity 5%), keeps 4h, be warming up to 105 ℃ afterwards and keep 8h at 40 ℃.Reaction finishes the back filters, and filter residue is washed till neutrality with deionized water in the back for several times with the dilute sulfuric acid washing, and drying obtains the supported type metatitanic acid of tungstenic, wherein TiO
2The rate of recovery be 72%.Take by weighing ammonium metavanadate and (press V
2O
5Load capacity 2%) with the oxalic acid dissolving, add the supported type metatitanic acid of gained tungstenic, place 60 ℃ of water-bath 3h, then, behind 500 ℃ of roasting 4h, obtain vanadium tungsten titanium catalyst in 80 ℃ of oven dry of baking oven.Gained activity of such catalysts appraisal curve is shown in accompanying drawing 6, and as can be seen from the figure present embodiment institute controlling catalyst all has favorable denitrification activity at 250 ~ 450 ℃.
Take by weighing 20g and be crushed to the titanium-containing blast furnace slag below 200 orders; By sulfuric acid (calculating with 100% sulfuric acid) quality: the blast furnace slag quality is to add 20% dilute sulfuric acid at 2: 1; Under 80 ℃ of continuous stirring states, add blast furnace slag, fully stir, leach 8h, centrifugalize after the end; Filter residue washs 3 times with 10% dilute sulfuric acid, collects filtrating and is used for hydrolysis.(addition is TiO in the titanium-containing blast furnace slag to the active carbon of adding 40% in titanium liquid
240% of quality, i.e. 1.28g), adding urea adjusting titanium liquid pH value is 1.0, keeps 2h at 60 ℃, is warming up to 105 ℃ afterwards and keeps 8h.Reaction is filtered after finishing, and filter residue is washed till neutrality with deionized water in the back for several times with the dilute sulfuric acid washing, and drying gets supported type metatitanic acid, wherein TiO
2The rate of recovery be 70%.Take by weighing ammonium metatungstate and (press WO
3Load capacity 5%) dissolving adds gained supported type metatitanic acid, places 60 ℃ of water-bath 3h, then in 80 ℃ of oven dry of baking oven.Take by weighing ammonium metavanadate and (press V
2O
5Load capacity 1%) with the oxalic acid dissolving, add the supported type metatitanic acid of gained tungstenic, place 60 ℃ of water-bath 3h, then, behind 500 ℃ of roasting 4h, obtain vanadium tungsten titanium catalyst in 80 ℃ of oven dry of baking oven.Gained activity of such catalysts appraisal curve is shown in accompanying drawing 7, and as can be seen from the figure present embodiment institute controlling catalyst all has favorable denitrification activity at 250 ~ 450 ℃.
Embodiment 5
Take by weighing 20g and be crushed to the titanium-containing blast furnace slag below 200 orders; By sulfuric acid (calculating with 100% sulfuric acid) quality: the blast furnace slag quality is to add 20% dilute sulfuric acid at 2: 1; Under 80 ℃ of continuous stirring states, add blast furnace slag, fully stir, leach 8h, centrifugalize after the end; Filter residue washs 3 times with 10% dilute sulfuric acid, collects filtrating and is used for hydrolysis.(addition is TiO in the titanium-containing blast furnace slag in titanium liquid, to add active carbon
220% of quality, i.e. 0.64g), adding urea adjusting titanium liquid pH value is 0.5, keeps 4h at 40 ℃, is warming up to 105 ℃ afterwards and keeps 8h.Reaction is filtered after finishing, and filter residue is washed till neutrality with deionized water in the back for several times with the dilute sulfuric acid washing, and drying gets supported type metatitanic acid.Take by weighing ammonium metatungstate and (press WO
3Load capacity 5%) dissolving adds gained supported type metatitanic acid, places 60 ℃ of water-bath 3h, in 80 ℃ of oven dry of baking oven, then is warming up to 500 ℃ of roasting 4h afterwards, gets product titanium tungsten powder, wherein TiO
2The rate of recovery be 68%.Take by weighing ammonium metavanadate and (press V
2O
52%) with the oxalic acid dissolving, add gained titanium tungsten powder, place 60 ℃ of water-bath 3h, then, behind 500 ℃ of roasting 4h, obtain vanadium tungsten titanium catalyst in 80 ℃ of oven dry of baking oven.The anti-water activity curve of the anti-sulphur of gained catalyst is shown in accompanying drawing 8, and as can be seen from the figure institute's controlling catalyst is good at 300 ℃ denitration activity and the anti-water stability of anti-sulphur.
The appreciation condition of vanadium tungsten titanium catalyst is in the embodiment of the invention: NO entrance concentration 600ppm, air speed 24000h-1, NH
3/ NO=0.8, O
2Content 3%.During the anti-water quality evaluation of anti-sulphur: temperature is 300 ℃, SO
2Be 2000ppm, H
2O is 5%.
Applicant's statement, the present invention explains detailed process flow of the present invention through the foregoing description, but the present invention is not limited to above-mentioned detailed process flow, does not mean that promptly the present invention must rely on above-mentioned detailed process flow and could implement.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the preparation method of a SCR catalyst for denitrating flue gas may further comprise the steps:
(a) titanium-containing blast furnace slag is pulverized after, add sulfuric acid to wherein TiO
2Leach, get titanium liquid and filter residue after the filtration;
(b) under stirring condition, in step (a) gained titanium liquid, add the easy mistake type porous catalyst carrier that burns, selectivity adds alkali compounds and regulates pH, is hydrolyzed;
(c) material after step (b) hydrolysis obtains supported type metatitanic acid after filtering, wash, drying;
(d) load tungsten and vanadium on step (c) gained supported type metatitanic acid, roasting makes vanadium tungsten titanium SCR catalyst for denitrating flue gas then.
2. the preparation method of a SCR catalyst for denitrating flue gas may further comprise the steps:
(a) titanium-containing blast furnace slag is pulverized after, add sulfuric acid to wherein TiO
2Leach, get titanium liquid and filter residue after the filtration;
(b) under stirring condition, in step (a) gained titanium liquid, add the easy mistake type porous catalyst carrier that burns, selectivity adds alkali compounds and regulates pH, is hydrolyzed, and adds tungsten source precursor in the hydrolytic process;
(c) material after step (b) hydrolysis obtains the supported type metatitanic acid of tungstenic after filtering, wash, drying;
(d) load vanadium source precursor on the supported type metatitanic acid of the tungstenic of step (c) gained promptly gets vanadium tungsten titanium SCR catalyst for denitrating flue gas after the roasting; Or,
The supported type metatitanic acid of the tungstenic of step (c) gained is carried out roasting make the titanium tungsten powder, to the further load vanadium of titanium tungsten powder source precursor, roasting makes vanadium tungsten titanium SCR catalyst for denitrating flue gas then.
3. the preparation method of a SCR catalyst for denitrating flue gas may further comprise the steps:
(a) titanium-containing blast furnace slag is pulverized after, add sulfuric acid to wherein TiO
2Leach, get titanium liquid and filter residue after the filtration;
(b) under stirring condition, in step (a) gained titanium liquid, add the easy mistake type porous catalyst carrier that burns, selectivity adds alkali compounds and regulates pH, is hydrolyzed;
(c) material after step (b) hydrolysis obtains supported type metatitanic acid after filtering, wash, drying;
(d) load tungsten source precursor on the supported type metatitanic acid of step (c) gained, roasting gets the titanium tungsten powder then;
(e) load vanadium source precursor on the titanium tungsten powder of step (d) gained, roasting makes vanadium tungsten titanium SCR catalyst for denitrating flue gas then.
4. the preparation method of the raw material titanium tungsten powder of a SCR catalyst for denitrating flue gas comprises the steps:
(a) titanium-containing blast furnace slag is pulverized after, add sulfuric acid to wherein TiO
2Leach, get titanium liquid and filter residue after the filtration;
(b) under stirring condition, in step (a) gained titanium liquid, add the easy mistake type porous catalyst carrier that burns, selectivity adds alkali compounds and regulates pH, is hydrolyzed;
(c) material after step (b) hydrolysis obtains supported type metatitanic acid after filtering, wash, drying;
(d) load tungsten source precursor on the supported type metatitanic acid of step (c) gained, roasting gets the titanium tungsten powder then.
5. like each described method of claim 1 ~ 4, it is characterized in that step (a) detailed process is: take by weighing the titanium-containing blast furnace slag after the pulverizing; By sulfuric acid (calculating with 100% sulfuric acid) quality: the blast furnace slag quality is 1 ~ 5: 1, preferred 1 ~ 3: 1, and further preferred 2: 1; Add sulfuric acid, under heating and continuous the stirring, add blast furnace slag, fully stir, leach more than the 2h; Preferred 6 ~ 10h carries out centrifugal/isolated by filtration after the end, filter residue is with dilute sulfuric acid washing at least 2 times; Preferred 3 ~ 5 times, collect filtrating and obtain titanium liquid;
Preferably, described titanium-containing blast furnace slag is TiO
2Content is the smelting iron and steel blast furnace slag more than 10%, and described heating-up temperature is 40 ~ 100 ℃, preferred 60 ~ 90 ℃, and further preferred 70 ~ 80 ℃.
Preferably, the easy burning mistake type porous catalyst carrier in the step (b) is one or more the mixture in active carbon, activated coke, semicoke, cellulose, the starch, preferred active carbon, activated coke, semicoke, further preferred active carbon; Being prone to burn mistake type porous catalyst carrier addition is TiO in the titanium-containing blast furnace slag
21% ~ 200% of quality is preferably 10% ~ 100%, and further preferred 20% ~ 50%;
Preferably, described alkali compounds is one or more in urea, ammoniacal liquor, carbonic hydroammonium, ammonium carbonate, alkali-metal hydroxide, alkali-metal carbonate or the bicarbonate; Said alkali compounds selectivity adds, and addition further is preferably 0 ~ 3 so that the pH value of end reaction system is 0 ~ 4 to be standard, is preferably 0 ~ 1 especially.
Preferably, the hydrolysis temperature described in the step (b) is 30 ℃ ~ 110 ℃, and hydrolysis time is 1h ~ 24h;
Preferably, described hydrolysis is hydrolysis at low temperatures earlier, and hydrolysis at high temperature obtains the metatitanic acid crystal then; Be hydrolyzed to 30 ~ 80 ℃ under the said low temperature, further be preferably 30 ~ 60 ℃, be preferably 30 ~ 50 ℃ especially; The low temperature hydrolysis time is 1h ~ 12h, further is preferably 1h ~ 8h, is preferably 2h ~ 4h especially; Be hydrolyzed to 80 ~ 110 ℃ under the said high temperature, further be preferably 90 ~ 110 ℃, be preferably 95 ~ 105 ℃ especially; The pyrohydrolysis time is 2h ~ 24h, further is preferably 4h ~ 12h, preferred especially 4h ~ 8h;
Preferably, described easy burning mistake type porous catalyst carrier and alkali compounds add at low thermophase.
6. like each described method of claim 1 ~ 4, it is characterized in that the process of step (c) is: through filtering, use dilute sulfuric acid, water washing successively the material after step (b) hydrolysis, obtain supported type metatitanic acid after the oven dry down at 105 ~ 150 ℃ to neutral.
7. the method for claim 1 is characterized in that, the method for load tungsten and vanadium is on step (c) gained supported type metatitanic acid: with adding step (c) gained supported type metatitanic acid after the dissolving of tungsten source precursor; In 40 ~ 90 ℃ of water-baths, preferred 40 ~ 80 ℃, further preferred 60 ~ 80 ℃; Keep 1h ~ 8h; Preferred 2h ~ 6h, behind further preferred 2h ~ 4h, dry the supported type metatitanic acid of tungstenic; With the supported type metatitanic acid that adds the tungstenic of gained after the dissolving of vanadium source precursor, in 40 ~ 90 ℃ of water-baths, preferred 40 ~ 80 ℃, further preferred 60 ~ 80 ℃, keep 1h ~ 8h, preferred 2h ~ 6h, behind further preferred 2h ~ 4h, oven dry.
8. method as claimed in claim 2 is characterized in that, the method for load vanadium source precursor is on the supported type metatitanic acid of the tungstenic of step (c) gained: with the supported type metatitanic acid that adds the tungstenic of step (c) gained after the dissolving of vanadium source precursor; In 40 ~ 90 ℃ of water-baths, preferred 40 ~ 80 ℃, further preferred 60 ~ 80 ℃; Keep 1h ~ 8h; Preferred 2h ~ 6h, behind further preferred 2h ~ 4h, oven dry.
9. method as claimed in claim 3 is characterized in that, the method for load tungsten source precursor is on the supported type metatitanic acid of step (c) gained: with adding step (c) gained supported type metatitanic acid after the dissolving of tungsten source precursor; In 40 ~ 90 ℃ of water-baths, preferred 40 ~ 80 ℃, further preferred 60 ~ 80 ℃; Keep 1h ~ 8h; Preferred 2h ~ 6h, behind further preferred 2h ~ 4h, oven dry;
Preferably, the method for load vanadium source precursor is on the titanium tungsten powder of step (d) gained: with adding in the titanium tungsten powder of step (d) gained after the dissolving of vanadium source precursor, in 40 ~ 90 ℃ of water-baths; Preferred 40 ~ 80 ℃; Further preferred 60 ~ 80 ℃, keep 1h ~ 8h, preferred 2h ~ 6h; Behind further preferred 2h ~ 4h, oven dry.
10. like each described method of claim 7 ~ 9; It is characterized in that; Described tungsten source precursor is can be water-soluble or the tungsten compound of organic solvent; The mixture of one or more in preferred ammonium metatungstate, ethanol tungsten, para-tungstic acid, the ammonium paratungstate, further preferred ammonium metatungstate, ethanol tungsten, load capacity is 1% ~ 10% (to press WO
3Meter), preferred 3% ~ 8% (presses WO
3Meter), further preferred 4% ~ 6% (press WO
3Meter);
Preferably, described vanadium source precursor is can be water-soluble or the vfanadium compound of organic solvent, the mixture of one or more in preferred vanadium oxalate, ammonium metavanadate, the vanadic sulfate, and preferred vanadium oxalate, ammonium metavanadate, load capacity is 0.5% ~ 5% (to press V
2O
5Meter), preferred 0.5% ~ 3% (presses V
2O
5Meter), further preferred 1% ~ 3% (press V
2O
5Meter);
Preferably, described sintering temperature is 400 ~ 800 ℃, and preferred 400 ~ 700 ℃, further preferred 500 ~ 600 ℃, roasting time is 1 ~ 6h, preferred 2 ~ 5h, further preferred 3 ~ 4h.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1353042A2 (en) * | 2002-04-10 | 2003-10-15 | Mitsubishi Heavy Industries, Ltd. | A gas turbine single plant modifying method, a catalyst re-using method and a re-produced catalyst |
| JP2004290754A (en) * | 2003-03-26 | 2004-10-21 | Mitsubishi Chemical Engineering Corp | Method for denitrificating exhaust gas of diesel engine |
| US20050054523A9 (en) * | 2003-03-14 | 2005-03-10 | Shigeru Nojima | Flue gas denitration catalyst and preparation process thereof |
| CN1746126A (en) * | 2005-08-02 | 2006-03-15 | 四川大学 | Production of titanium-enriched material by titanium-contained blast furnace slag blast furnace slag |
| CN1978325A (en) * | 2005-12-05 | 2007-06-13 | 西昌新钢业有限责任公司 | Method for producing titanium product from titanic slag for titanium white waste sulfuric acid treatment |
| CN101352681A (en) * | 2008-08-29 | 2009-01-28 | 浙江大学 | Low-temperature SCR catalyst using nitrogen-dopped activated carbon as carrier and preparation technique thereof |
| CN101396657A (en) * | 2008-10-23 | 2009-04-01 | 清华大学 | Denitration catalyst using titanium dioxide as raw material and preparation method thereof |
| CN102312102A (en) * | 2010-07-02 | 2012-01-11 | 成都理工大学 | Comprehensive utilization method for titanium-contained blast furnace slag |
| CN102319559A (en) * | 2011-06-03 | 2012-01-18 | 中国科学院过程工程研究所 | Surface deposition honeycomb flue gas denitration catalyst and preparation method thereof |
| CN102463110A (en) * | 2010-11-05 | 2012-05-23 | 中国科学院过程工程研究所 | Preparation method of denitration catalyst |
-
2012
- 2012-05-25 CN CN201210167211.5A patent/CN102698737B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1353042A2 (en) * | 2002-04-10 | 2003-10-15 | Mitsubishi Heavy Industries, Ltd. | A gas turbine single plant modifying method, a catalyst re-using method and a re-produced catalyst |
| US20050054523A9 (en) * | 2003-03-14 | 2005-03-10 | Shigeru Nojima | Flue gas denitration catalyst and preparation process thereof |
| JP2004290754A (en) * | 2003-03-26 | 2004-10-21 | Mitsubishi Chemical Engineering Corp | Method for denitrificating exhaust gas of diesel engine |
| CN1746126A (en) * | 2005-08-02 | 2006-03-15 | 四川大学 | Production of titanium-enriched material by titanium-contained blast furnace slag blast furnace slag |
| CN1978325A (en) * | 2005-12-05 | 2007-06-13 | 西昌新钢业有限责任公司 | Method for producing titanium product from titanic slag for titanium white waste sulfuric acid treatment |
| CN101352681A (en) * | 2008-08-29 | 2009-01-28 | 浙江大学 | Low-temperature SCR catalyst using nitrogen-dopped activated carbon as carrier and preparation technique thereof |
| CN101396657A (en) * | 2008-10-23 | 2009-04-01 | 清华大学 | Denitration catalyst using titanium dioxide as raw material and preparation method thereof |
| CN102312102A (en) * | 2010-07-02 | 2012-01-11 | 成都理工大学 | Comprehensive utilization method for titanium-contained blast furnace slag |
| CN102463110A (en) * | 2010-11-05 | 2012-05-23 | 中国科学院过程工程研究所 | Preparation method of denitration catalyst |
| CN102319559A (en) * | 2011-06-03 | 2012-01-18 | 中国科学院过程工程研究所 | Surface deposition honeycomb flue gas denitration catalyst and preparation method thereof |
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Application publication date: 20121003 Assignee: ANHUI WEIDA ENVIRONMENTAL PROTECTION TECHNOLOGY CO., LTD. Assignor: Institute of Process Engineering, Chinese Academy of Sciences Contract record no.: 2017340000025 Denomination of invention: 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 Granted publication date: 20141105 License type: Exclusive License Record date: 20170810 |
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