Titanium slag recycles the method for titanium dioxide and recycles tungsten, titanium and vanadium from denitrating catalyst
Method
Technical field
The present invention relates to waste denitration catalyst recycling fields, and in particular to titanium slag recycle titanium dioxide method and from
The method that denitrating catalyst recycles tungsten, titanium and vanadium.
Background technique
Coal can discharge a large amount of nitrogen oxides (NO as China's main energy sources structure, burningx)。 NOxBe China most
One of main atmosphere pollution, therefore, China are directed to NOxIt is further severe to discharge the environmental legislation formulated.August 23 in 2014
Day, National Development and Reform Committee, Chinese Ministry of Environmental Protection, three ministries and commissions, National Energy Board, which combine, issues " coal electricity energy-saving and emission-reduction upgrading and transformation action plan
(2014~the year two thousand twenty) ", NO is proposed to coal unitxDischarge amount is lower than 50mg/Nm3Strict demand;China environmental protection phase
Prescribed specific is closed to require to the year two thousand twenty China NOxTotal emission volumn to be dropped on the basis of 2046.2 ten thousand tons of 2015 annual emissions
Low 15%.
The core of coal steam-electric plant smoke denitrification apparatus is denitrating catalyst, usually accounts for the 30-40% of initial investment.China's fire
Electric installed capacity is big, by thermoelectricity installed capacity in 2015 up to 9.33 hundred million kilowatts, the China the unit Yi Zhan coal for the denitrating flue gas that puts into operation
90% or more of motor pool-size.Denitrating catalyst General Life is 3 years or so, is had every year since 2015 a large amount of
Dead catalyst changes, and by 2018, the waste and old SCR denitration replaced every year was up to 25 ten thousand steres.Failure
Denitrating catalyst was classified as " hazardous waste " catalogue by country in 2014, if not being subject to processing appropriate, not only caused huge
Big waste, can also serious ground contamination environment.
Main component is titanium dioxide, tungstic acid, vanadic anhydride etc. in SCR denitration.For structural integrity
Waste and old denitrating catalyst, regenerated using physics and chemical method, activity can restore to the 90- of raw catelyst
100%.For damaged useless denitrating catalyst, it must be handled using the method for recycling and reusing, it is golden to extract vanadium, tungsten, titanium and molybdenum etc.
Belong to resource, turn waste into wealth, changes evil as benefit.Catalyst regeneration and recovery technology be restore catalyst activity, prolong the service life,
The effective way for reducing operating cost, reducing waste treatment.
CN102936049A discloses a kind of method that tungsten, titanium, vanadium are extracted from discarded SCR catalyst, comprising: 1) will
It is 100-200 mesh that discarded SCR catalyst, which is crushed to granularity, and it is 20-30% strong base solution that mass percent concentration, which is then added,
3-6h is reacted at 150-200 DEG C of temperature, is separated by filtration to obtain de- tungsten, the SCR catalyst of vanadium and sodium tungstate, sodium vanadate mixing
Solution, wherein the mass ratio of discarded SCR catalyst and highly basic is 10:3-6;2) first by strong acid and sodium tungstate and sodium vanadate solution
Mass ratio be 1:3-6, be made into mass percent concentration be 70-80% strong acid solution, then be added sodium tungstate, vanadium
In sour sodium mixed solution, 1-4h is reacted at 150-300 DEG C, it is molten to be separated by filtration to obtain tungstic acid solid and sodium salt, vanadic acid mixing
Liquid, then add ammonium hydroxide modulation pH value to be 7-8 in sodium salt, vanadic acid mixed solution, Precipitation is separated by filtration to obtain ammonium vanadate and ammonium
Salting liquid, ammonium salt solution concentration crystallisation by cooling obtain ammonium salt solid;3) SCR that sulfuric acid is pressed to the de- tungsten, vanadium that obtain with step 1) is urged
The mass ratio of agent is that 10-14:1 is made into the sulfuric acid solution that mass percent concentration is 90-98%, and de- tungsten, vanadium is then added
In SCR catalyst, 2-4h is reacted at 200-250 DEG C, is separated by filtration to obtain the solids such as titanyl sulfate solution and aluminium slag;4) in sulphur
In sour oxygen titanium solution by volume: water is added in 10-13, and in 80-100 DEG C of hydrolysis 1-2h, is separated by filtration metatitanic acid solid and to give up
Acid solution;5) ammonium vanadate, wolframic acid, the metatitanic acid obtained above step, carrying out calcining by existing technology can obtain respectively
Obtain vanadic anhydride, tungstic acid and titanium dioxide.This method thermokalite is reacted using acid hydrolyzation after titanium slag acidolysis system again
Titanyl sulfate is taken to hydrolyze generation metatitanic acid again.
The waste and old denitrating catalyst recovery technology of tradition mainly includes sodium or calcification baking, acidleach, alkali leaching etc..It is wherein hot
Alkali leaches recycling tungsten and vanadium recovery is high, and treatment temperature is low, and equipment requirement is simple etc., therefore has apparent superiority.But heat
Alkali reaction process has sodium titanate generation, and the titanium slag due to titanium dioxide to sodium hydroxide strong adsorption, after reaction leaching
Sodium oxide content is up to 16%, seriously constrains the application of titanium slag.Since sodium ion not only has ADSORPTION STATE in titanium slag, and
And have a large amount of compound states, being washed with water can not clean merely, be unable to get pure titanium dioxide.And titanium dioxide is in dead catalyst
Main component, therefore extract and have a large amount of titanium slags after tungsten and vanadium and generate, be the waste of resource if do not handled.
Summary of the invention
The purpose of the invention is to overcome the prior art to mix less with crystal phase using strong acid and product titanium dioxide yield
Miscellaneous, the not high problem of purity provides the method for titanium slag recycling titanium dioxide and recycles tungsten, titanium and vanadium from denitrating catalyst
Method.
To achieve the goals above, first aspect present invention provides a kind of method of titanium slag recycling titanium dioxide, comprising:
(1) titanium slag is mixed with ammonium salt solution and carries out ion exchange, and be separated by solid-liquid separation;
(2) solid that step (1) obtains is cleaned through water, and filters, dries and roasts, obtain titanium dioxide;
Wherein, the titanium slag is useless denitrating catalyst after thermokalite reacts and is extracted tungsten and vanadium, remaining residue.
Preferably, in step (1), the solid and liquid weight ratio (2-5) of the titanium slag and ammonium salt solution: 1.
Preferably, in step (1), ion exchange temperature is 40-90 DEG C, and the ion exchange time is 1-3h.
Preferably, in step (2), the solid is cleaned through water until the pH for cleaning the solution generated is 4.5-9.5.
Preferably, before step (1), the titanium slag is subjected to ultrasonic cleaning 2-3 times, the liquid of water and the titanium slag with water
Gu weight ratio is (2-5): 1.
Second aspect of the present invention provides a kind of method from denitrating catalyst recycling tungsten, titanium and vanadium, comprising:
(a) discarded denitrating catalyst is mixed with strong base solution and carries out thermokalite and react, and be separated by solid-liquid separation obtain titanium slag with
Mixed solution containing sodium tungstate, sodium vanadate;
(b) mixed solution and strong acid solution are subjected to acid liquid reaction, and are separated by filtration to obtain tungstic acid solid and vanadic acid
The vanadic acid solution is carried out precipitation reaction and ammonium vanadate is obtained by filtration by solution;
(c) titanium slag that step (a) obtains is obtained into titanium dioxide by method described in any one of claim 1-9
Titanium;
(d) tungstic acid solid and ammonium vanadate are subjected to calcining and respectively obtain tungstic acid and vanadic anhydride.
Through the above technical solutions, the beneficial effect that the present invention can obtain is:
(1) present invention reprocesses after spent catalyst in power plant is classified, can not regenerated catalyst by breakage
Titanium dioxide is prepared, it is easy to operate, the cost of disposal of dead catalyst is reduced, is provided for discarded SCR denitration recycling
New process route.
(2) the method for the present invention reaction condition is mild, does not need acidolysis, removal of impurities, hydrolytic process, compared to conventional method, work
Skill process is simple, wastewater flow rate is few, low energy consumption, has high economic benefit, social benefit and environmental benefit.
(3) the method for the present invention can recycle the titanium in spent catalyst as titanium dioxide, and titanium dioxide in recovery product
Content is high.Since ammonium salt easily decomposes, for the titanium dioxide crystal phase of acquisition based on single anatase titanium dioxide, purity is high does not generate solid
Waste.
Detailed description of the invention
Fig. 1 is the flow diagram for the method that waste denitration catalyst provided by the invention recycles tungsten, titanium and vanadium;
Fig. 2 is the temperature schedule curve roasted in method provided by the invention;
Fig. 3 is the ratio of the XRD diagram for the titanium dioxide that embodiment 1 obtains and the anatase titanium dioxide XRD spectra of standard
It is right;
Fig. 4 is the XRD diagram for the product that comparative example 1 obtains and the anatase titanium dioxide of standard and rutile titanium dioxide XRD spectra
Comparison.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value, these ranges herein
Or value should be understood as comprising the value close to these ranges or value.For numberical range, the endpoint value of each range it
Between, can be combined with each other between the endpoint value and individual point value of each range, and individually between point value and obtain one
Or multiple new numberical ranges, these numberical ranges should be considered as specific open herein.
First aspect present invention provides a kind of method of titanium slag recycling titanium dioxide, comprising:
(1) titanium slag is mixed with ammonium salt solution and carries out ion exchange, and be separated by solid-liquid separation;
(2) solid that step (1) obtains is cleaned through water, and filters, dries and roasts, obtain titanium dioxide;
Wherein, the titanium slag is useless denitrating catalyst after thermokalite reacts and is extracted tungsten and vanadium, remaining residue.
The present invention is reacted by ion exchange, the sodium ion in titanium slag component can be leached, can will be inclined in titanium slag
Sodium titanate is changed into metatitanic acid, and metatitanic acid through calcining can dehydration obtain titanium dioxide, and sodium ion is eliminated in product,
Improve the purity of titanium dioxide.And the use of strong acid can be effectively avoided, reduction contains without using strong acid during being somebody's turn to do
The processing of sour sewage.
According to the present invention, the titanium slag main component is meta-titanium perborate, is met using the ammonium salt solution and replaces the titanium
The sodium ion that slag contains.Preferably, in step (1), the solid and liquid weight ratio (2-5) of the titanium slag and ammonium salt solution: 1.
In accordance with the present invention it is preferred that the ammonium salt solution be ammonium sulfate, ammonium hydrogen carbonate, ammonium chloride, in ammonium nitrate extremely
A kind of few aqueous solution or the ammonium salt solution are the mixture of sulfuric acid and ammonium sulfate.
In accordance with the present invention it is preferred that in the ammonium salt solution, with NH4 +The ammonium salt concentration of meter is 5-15 weight %.
According to the present invention, the meta-titanium perborate that the ion exchange is sufficiently completed in titanium slag is changed into metatitanic acid, preferably
Ground, in step (1), ion exchange temperature is 40-90 DEG C, and the ion exchange time is 1-3h.
According to the present invention, separation of solid and liquid described in step (1) can be the product for obtaining the ion exchange and carry out
Filter, wherein isolated solid is metatitanic acid, solution of the liquid containing sodium ion.Step (2) is residual on removing solid for cleaning
The sodium ion stayed.Preferably, in step (2), the solid is cleaned through water until the pH for cleaning the solution generated is 4.5-
9.5。
In accordance with the present invention it is preferred that drying temperature is 100-120 DEG C, drying time 1-6h in step (2).
In accordance with the present invention it is preferred that maturing temperature is 550-850 DEG C, calcining time 2-5h in step (2).
In the present invention, the roasting can be Temperature Programmed Processes.Preferably, system is roasted are as follows: roasting system are as follows: from
Room temperature, which starts to be warming up to after 150 DEG C with the first heating rate of 2~5 DEG C/min, keeps the temperature 1h, then again with the of 2~5 DEG C/min
Two heating rates keep the temperature 2-5h after being warming up to 550-850 DEG C, then are naturally cooling to room temperature.Pure two can preferably be obtained
Titanium oxide.
According to the present invention, the titanium slag carries out titanium slag recycling titanium dioxide provided by the invention after preferably carrying out prerinse again
The method of titanium.Preferably, before step (1), the titanium slag is subjected to ultrasonic cleaning 2-3 times, the liquid of water and the titanium slag with water
Gu weight ratio is (2-5): 1.For removing the alkali for adsorbing entrainment on titanium slag.Wherein, ultrasonic cleaning can be using conventional side
Method is mainly able to achieve the alkali for effectively removing and adsorbing entrainment on titanium slag.The condition of ultrasonic cleaning can be conventional arrangement item
Part, details are not described herein.
Second aspect of the present invention provides a kind of method from denitrating catalyst recycling tungsten, titanium and vanadium, as shown in Fig. 1, packet
It includes:
(a) discarded denitrating catalyst is mixed with strong base solution and carries out thermokalite and react, and be separated by solid-liquid separation obtain titanium slag with
Mixed solution containing sodium tungstate, sodium vanadate;
(b) mixed solution and strong acid solution are subjected to acid liquid reaction, and are separated by filtration to obtain tungstic acid solid and vanadic acid
The vanadic acid solution is carried out precipitation reaction and ammonium vanadate is obtained by filtration by solution;
(c) method that the titanium slag for obtaining step (a) provides through the invention obtains titanium dioxide;
(d) tungstic acid solid and ammonium vanadate are subjected to calcining and respectively obtain tungstic acid and vanadic anhydride.
Method provided by the invention from denitrating catalyst recycling tungsten, titanium and vanadium, step (a) is to urge the denitration discarded
Agent first carries out thermokalite reaction treatment.Titanium slag obtained in it can pass through the application titanium slag recycling above-mentioned in step (c)
The method of titanium dioxide is handled;The obtained mixed solution containing tungsten, vanadium can be obtained by step (b) and (d)
Tungstic acid and vanadic anhydride, to realize that denitrating catalyst can recycle tungsten, titanium and vanadium, and the titanium dioxide wherein recycled
Titanium products can have high-purity.
In the present invention, it is preferable that the titanium slag is carried out prerinse before step (c), the liquid of generation can be through overrich
The thermokalite reaction of return step (a) after truncate alkali.Reduce the generation of secondary liquid waste.The prerinse is not as described above, exist
It repeats.
Step (a) (b) (d) may each be this field conventional technique measure, and details are not described herein.
The present invention will be described in detail by way of examples below.In following embodiment, obtained titanium dioxide product
Ingredient and material phase analysis can be carried out respectively by XRF and XRD analysis.
Embodiment 1
1) after crushing the denitrification catalyst module (affiliated power plant, Shenhua) of honeycomb failure, through thermokalite reaction and solid-liquid
Titanium slag is obtained after separation and prerinse, titanium slag be cleaned by ultrasonic 3 times with water, the solvent and solute weight ratio of water and titanium slag is 2:
1, cleaning returns to thermokalite reaction after generating the concentrated benefit alkali of liquid.
2) by the mixing of the sulfuric acid solution containing ammonium sulfate and 5 weight % that concentration is 5 weight % of the titanium slag after cleaning
The solid and liquid weight ratio of liquid progress ion exchange, titanium slag and mixed liquor is 2:1, and the ion exchange time is 2.5h, ion exchange temperature
It is 55 DEG C, stirring rate 350rpm is centrifuged after ion exchange, obtains solid product.
3) solid after centrifugation is cleaned with deionized water, until the pH value of solution that last cleaning generates is 4.53, knot
Shu Qingxi.
4) solid after cleaning is dry at 110 DEG C, time 6h.
5) solid after drying is roasted by the roasting system of Fig. 2, obtains final product.
Final product is subjected to ingredient and material phase analysis by XRF and XRD, the results are shown in Table 1.XRD is analysis shows that final produce
Object mainly contains anatase titanium dioxide, sees Fig. 3.
Embodiment 2
1) after crushing the denitrification catalyst module (affiliated power plant, Shenhua) of honeycomb failure, through thermokalite reaction and solid-liquid
Titanium slag is obtained after separation and prerinse, titanium slag be cleaned by ultrasonic 2 times with water, the solvent and solute weight ratio of water and titanium slag is 5:
1, cleaning returns to thermokalite reaction after generating the concentrated benefit alkali of liquid.
2) by (NH of 10 weight % of concentration of the titanium slag after cleaning4)2SO4Solution carries out ion exchange, titanium slag and solution
Solid and liquid weight be 5:1, the ion exchange time be 3h, ion exchange temperature be 40 DEG C, stirring rate 350rpm, ion is set
It is centrifuged after changing, obtains solid product.
3) solid after centrifugation is cleaned with deionized water, until the pH value of solution that last cleaning generates is 9.44, knot
Shu Qingxi.
4) solid after cleaning is dry at 120 DEG C, time 3h.
5) solid after drying is roasted by the roasting system of Fig. 2, obtains final product.
Final product is subjected to ingredient and material phase analysis by XRF and XRD, the results are shown in Table 1.XRD is analysis shows that final produce
Object mainly contains anatase titanium dioxide.
Embodiment 3
1) after crushing the denitrification catalyst module (affiliated power plant, Shenhua) of honeycomb failure, through thermokalite reaction and solid-liquid
Titanium slag is obtained after separation and prerinse, titanium slag be cleaned by ultrasonic 3 times with water, the solvent and solute weight ratio of water and titanium slag is 4:
1, cleaning returns to thermokalite reaction after generating the concentrated benefit alkali of liquid.
2) titanium slag after cleaning is subjected to ion exchange with the ammonium chloride solution of 10 weight % of concentration, titanium slag and solution
Solid and liquid weight is 4:1, and the ion exchange time is 1h, and ion exchange temperature is 90 DEG C, stirring rate 350rpm, ion exchange
After be centrifuged, obtain solid product.
3) solid after centrifugation is cleaned with deionized water, until the pH value of solution that last cleaning generates is 9.35, knot
Shu Qingxi.
4) solid after cleaning is dry at 100 DEG C, time 1h.
5) solid after drying is roasted by the roasting system of Fig. 2, obtains final product.
Final product is subjected to ingredient and material phase analysis by XRF and XRD, the results are shown in Table 1.XRD is analysis shows that final produce
Object mainly contains anatase titanium dioxide.
Embodiment 4
1) after crushing the denitrification catalyst module (affiliated power plant, Shenhua) of honeycomb failure, through thermokalite reaction and solid-liquid
Titanium slag is obtained after separation and prerinse, titanium slag be cleaned by ultrasonic 2 times with water, the solvent and solute weight ratio of water and titanium slag is 3:
1, cleaning returns to thermokalite reaction after generating the concentrated benefit alkali of liquid.
2) titanium slag after cleaning is subjected to ion exchange, titanium slag and solution with the ammonium bicarbonate soln of 10 weight % of concentration
Solid and liquid weight be 4:1, the ion exchange time be 2h, ion exchange temperature be 80 DEG C, stirring rate 350rpm, ion is set
It is centrifuged after changing, obtains solid product.
3) solid after centrifugation is cleaned with deionized water, until the pH value of solution that last cleaning generates is 9.13, knot
Shu Qingxi.
4) solid after cleaning is dry at 110 DEG C, time 4h.
5) solid after drying is roasted by the roasting system of Fig. 2, obtains final product.
Final product is subjected to ingredient and material phase analysis by XRF and XRD, the results are shown in Table 1.XRD is analysis shows that final produce
Object mainly contains anatase titanium dioxide.
Comparative example 1
1) after crushing the denitrification catalyst module (affiliated power plant, Shenhua) of honeycomb failure, through thermokalite reaction and solid-liquid
Titanium slag is obtained after separation and prerinse, titanium slag be cleaned by ultrasonic 3 times with water, the solvent and solute weight ratio of water and titanium slag is 4:
1, cleaning returns to thermokalite reaction after generating the concentrated benefit alkali of liquid.
2) by the sulfuric acid solution hybrid reaction of titanium slag and 90 weight % of concentration after cleaning, the solid-liquid weight of titanium slag and solution
Amount is 10:1, and hybrid reaction carries out 2h, stirring rate 350rpm at 250 DEG C;Product is separated by solid-liquid separation, sulphur is obtained
The solids such as sour oxygen titanium solution and aluminium slag;
3) water is added into titanyl sulfate solution, titanyl sulfate solution: the volume ratio of water is 1:13, in 100 DEG C of progress water
1h is solved, metatitanic acid solid and waste acid liquor is obtained by filtration.
4) metatitanic acid solid is roasted by the roasting system of Fig. 2, obtains final product.By final product by XRF and
XRD carries out ingredient and material phase analysis, the results are shown in Table 1.XRD analysis shows that final product predominantly contains anatase titanium dioxide and rutile
The mixture of type titanium dioxide, such as Fig. 4.
Table 1
Project |
Na2O/ weight % |
TiO2/ weight % |
Initial titanium slag |
14.6183 |
78.2449 |
Embodiment 1 |
0.0678 |
98.4886 |
Embodiment 2 |
1.8678 |
96.4886 |
Embodiment 3 |
0.8678 |
97.4886 |
Embodiment 4 |
2.3658 |
94.5783 |
Comparative example 1 |
2.8678 |
93.4886 |
It can be seen that embodiment 1-4 using method of the invention to thermokalite by the data of embodiment, comparative example and table 1
It reacts obtained titanium slag and carries out titanium dioxide recycling, sodium ion impurity can be effectively removed.The solid of recycling and initial titanium slag
It compares, can remove the sodium oxide molybdena of 80.37%-99.54%, and obtain content of titanium dioxide height in solid, it can be in 94 weights
% or more is measured, while obtained titanium dioxide mainly has single anatase titanium dioxide crystal phase, purity is more preferable.And the present invention provides
Method acid pickle is not discharged, be not present secondary pollution, make titanium slag processing and titanium dioxide recycling it is more environmentally friendly.
Comparative example 1 is the prior art, and content of titanium dioxide is low in obtained product and is the mixed of anatase titanium dioxide and rutile-type
Object phase is closed, purity is bad.There is the process route to generate spent acid discharge again, not environmentally.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited thereto.?
, can be with various simple variants of the technical solution of the present invention are made in range of the technology design of the invention, including each technology is special
Sign is combined with any other suitable method, these simple variants and combination equally should be considered as disclosed in this invention
Content all belongs to the scope of protection of the present invention.