CN106745230B - A method of separating and recovering titanium dioxide from discarded SCR denitration - Google Patents
A method of separating and recovering titanium dioxide from discarded SCR denitration Download PDFInfo
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- CN106745230B CN106745230B CN201710073413.6A CN201710073413A CN106745230B CN 106745230 B CN106745230 B CN 106745230B CN 201710073413 A CN201710073413 A CN 201710073413A CN 106745230 B CN106745230 B CN 106745230B
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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Abstract
The invention discloses one kind to separate and recover titanium dioxide method from discarded SCR denitration, the following steps are included: pretreated discarded SCR denitration powder is impregnated with lye, dipping method is level Four cross-flow or second level counter-current, filter cake after dipping obtains high-purity titania powder through washing, drying, calcining.The isolated titanium dioxide of method of the invention is rutile type titanium white, and for the rate of recovery up to 97%, material purity and crystal phase purity are all larger than 98%.Therefore, this technique has very high economic results in society, and industrialized implementation is higher.The present invention greatly reduces water consume and alkaline consumption by using adverse current or cross-flow operation, while reducing the dosage of drug added by subsequent technique, not only economized on resources but also highlighted economic benefit.The present invention is in operation without condition of high voltage, and operating procedure is simple.Reduce the requirement in actual industrial to equipment.
Description
Technical field
The present invention relates to environmental protection technology and circular economy field, in particular to one kind is divided from discarded SCR denitration
Method from recycling titanium dioxide.
Background technique
It is main energy sources in coal in China, the nitrogen oxides that burning generates not only will form acid rain, also result in chemistry
Smog endangers human health.In China's nitrogen oxide emission 70% from coal direct burning, and power industry is
The coal-fired rich and influential family in China, therefore thermal power plant is one of the main source of nitride (NOx) discharge.With Ecological Civilization Construction
It is included in the five in one layout of socialist construction, air pollution caused by fire coal increasingly causes the attention of government.
Selective catalytic reduction (referred to as: SCR method) is to apply technology most, that technology is more mature in the world at present,
It is considered to have higher denitration efficiency (up to 90%).SCR catalyst is generally with TiO2For carrier, with WO3、V2O5Etc. rare
Metal oxide is active constituent.Wherein WO3Content is in 2-10% or so, V2O5Content is greater than 0.5%, TiO2Content is greater than
70%, WO3、V2O5And TiO2Total content be often higher than 90%.Therefore, the TiO in SCR denitration is discarded2Isolated journey
Degree will directly affect the recycling of monolithic catalyst, while also directly affect the separation of other elements in catalyst.
It is useless to SCR method in " coal steam-electric plant smoke denitration engineering legislation-selective catalytic reduction " (HJ562-2010)
Denitrating catalyst defines harmless treatment mode, i.e., is filled after catalyst being crushed.But the useless denitrating catalyst crushing of SCR
After filled, on the one hand can occupy a large amount of land resource, increase the cost of enterprise；Another aspect catalyst is in use process
Adsorbed some poisonous and harmful substances and some metallic elements contained by itself can be entered due to various effects in the middle
To natural environment, especially water body, serious harm is brought to environment；The V that another further aspect SCR catalyst itself contains2O5、WO3With
TiO2It is all valuable resource, useless denitrating catalyst discarding causes various valuable metal resources contained therein to fail back
It receives and utilizes, will cause the huge waste of efficient resource.If the mode of separating-purifying can be taken to be recycled, not only can produce new
Profit growth point, also comply in " People's Republic of China's circular economy promotion law " in relation to recycle and recycling Industry Model
Requirement.Therefore, the recycling of denitrating catalyst, the research and development of innoxious process for treating and realization industrialized production have urgent society
It can demand.And TiO of the content up to 85% in SCR catalyst2Separation, more become isolated key.
Summary of the invention
Technical problem to be solved by the invention is to provide one kind to separate and recover titanium dioxide from discarded SCR denitration
The method of titanium.The major product rutile type titanium white that this method obtains, material purity and crystal phase purity are all larger than 98%.
The technical problem to be solved by the present invention is to what is be achieved through the following technical solutions:
One kind separating and recovering titanium dioxide method from discarded SCR denitration, comprising the following steps: after pretreatment
Discarded SCR denitration powder impregnated with lye, dipping method be level Four cross-flow or second level counter-current, dipping
Filter cake afterwards obtains high-purity titania powder through washing, drying, calcining.
Preferably, in above-mentioned technical proposal, specific steps are as follows:
1) it pre-processes: taking discarded SCR denitration, dedusting, broken, grinding obtain catalyst fines；
2) level Four cross-flow method dipping the following steps are included:
21) the catalyst fines soda-dip for obtaining step 1) is separated by solid-liquid separation after dipping, obtains filtrate and filter cake；
22) filter cake of step 21) is impregnated with aqueous slkali, is separated by solid-liquid separation after dipping, obtain filtrate and filter cake；
23) filter cake of step 22) is impregnated with aqueous slkali, is separated by solid-liquid separation after dipping, obtain filtrate and filter cake；
24) filter cake of step 23) is impregnated with aqueous slkali, is separated by solid-liquid separation after dipping, obtain filtrate and filter cake, which is
For titanium dioxide filter cake；
3) separate titanium dioxide: the filter cake that step 24) is obtained obtains titania powder through washing, drying, calcining.
Preferably, in above-mentioned technical proposal, specific steps are as follows:
1) it pre-processes: taking discarded SCR denitration, dedusting, broken, grinding obtain catalyst fines；
2) second level counter-current dipping the following steps are included:
21) catalyst fines obtained with soda-dip step 1) are separated by solid-liquid separation, obtain filtrate and filter cake；
22) filtrate that step 21) obtains is impregnated into the catalyst fines that a step 1) obtains again, is separated by solid-liquid separation, obtains
Filter cake and purpose filtrate；
23) lye is added into the filter cake that step 21) obtains to be impregnated, be separated by solid-liquid separation, obtain filtrate and purpose filter
Cake；
24) soda-dip is further added in the filter cake that step 22) obtains, is separated by solid-liquid separation, obtains filtrate and purpose filter cake, filtered
Liquid continues to repeat the operation of step 22)；
25) filtrate that step 23) obtains is impregnated into the catalyst fines that a step 1) obtains again, is separated by solid-liquid separation, must filter
Cake and purpose filtrate, filter cake continue to repeat the operation of step 23)；
26) operation to repeat the above steps；
3) separate titanium dioxide: the purpose filter cake that step 2) is obtained merges, and through washing, drying, calcining, obtains titanium dioxide
Titanium.
Preferably, in above-mentioned technical proposal, the catalyst fines of the step 1) are to be prepared by the following: will be discarded
It after SCR denitration dust removal process, is crushed, grinding, the SCR powder after grinding is screened through classifying screen, is classified grit number >=100
Mesh, screenings, that is, catalyst fines, oversize are mixed with broken discarded SCR denitration, are re-grind, and are sieved, weight
Multiple circulation.
Preferably, in above-mentioned technical proposal, the lye is sodium hydroxide solution, the potassium hydroxide solution of 10%-40%
Or both mixed solution.
Preferably, in above-mentioned technical proposal, the liquid-solid ratio of each step level Four cross-flow is (2-5): 1；Reaction temperature is
100-150 DEG C, the reaction time is 2-4 hours.
Preferably, in above-mentioned technical proposal, the liquid-solid ratio of each two stage countercurrent of step is (5-10): 1；Reaction temperature is
150-160 DEG C, the reaction time is 4-6 hours.
Preferably, in above-mentioned technical proposal, the washing specifically: washed filter cake twice, the liquid washed twice
Gu ratio is (5-10): 1, washing temperature is 40-60 DEG C, time 30-50min；The condition of calcining are as follows: 800 DEG C of calcinings 2 are small
When.
Preferably, in above-mentioned technical proposal, the titanium dioxide is rutile titanium dioxide, and purity purity and crystal phase are pure
Degree is all larger than 98%.
Preferably, in above-mentioned technical proposal, Collection and conservation filtrate, the separation for other compounds in catalyst.
Above-mentioned technical proposal of the present invention, has the following beneficial effects:
The isolated titanium dioxide of method of the invention is rutile type titanium white, and material purity and crystal phase purity are big
In 98%, the rate of recovery is up to 97%.Therefore, this technique has very high economic results in society, and industrialized implementation is higher.
The present invention greatly reduces water consume and alkaline consumption by using adverse current or cross-flow operation, while reducing added by subsequent technique
The dosage of drug, not only economized on resources but also highlighted economic benefit.
The present invention is in operation without condition of high voltage, and operating procedure is simple.It reduces in actual industrial and equipment is wanted
It asks.
Detailed description of the invention
Fig. 1 is level Four cross-flow operation schematic diagram according to the present invention.
Fig. 2 is second level counter-current operation schematic diagram according to the present invention.
Specific embodiment
Specific embodiments of the present invention are described in detail below, in order to further understand the present invention.
All experimental methods used are conventional method unless otherwise specified in following embodiment.
Material used in following embodiment, reagent etc. can be obtained through commercial channels unless otherwise specified.
Embodiment 1
1) it pre-processes: taking a certain amount of discarded SCR denitration, dedusting, broken, grinding sieve with 100 mesh sieve son, under sieve
Object is catalyst fines.Oversize is mixed with the broken discarded out of stock catalyst of SCR, is sieved again.
2) level Four cross-flow method impregnates:
21) the catalyst fines 10g for obtaining step 1) is impregnated with 10% sodium hydroxide solution 50ml, under the conditions of 150 DEG C
Oil bath 2h is separated by solid-liquid separation after dipping, obtains filtrate (filtrate a) and filter cake (filter cake a)；
22) by the filter cake of step 21), (10% sodium hydroxide solution 50ml of filter cake a) impregnates, oil bath under the conditions of 150 DEG C
2h is separated by solid-liquid separation after dipping, obtains filtrate (filtrate b) and filter cake (filter cake b)；
23) by the filter cake of step 22), (10% sodium hydroxide solution 50ml of filter cake b) impregnates, oil bath under the conditions of 150 DEG C
2h is separated by solid-liquid separation after dipping, obtains filtrate (filtrate c) and filter cake (filter cake c)；
24) by the filter cake of step 23), (10% sodium hydroxide solution 50ml of filter cake c) impregnates, oil bath under the conditions of 150 DEG C
2h is separated by solid-liquid separation after dipping, and obtaining filtrate, (filtrate d) and filter cake (filter cake 1), which is titanium dioxide filter cake.
3) it separates titanium dioxide: the filter cake (filter cake 1) that step 24) obtains being washed twice with 100ml water and (is used every time
Water 50ml), the time washed every time is 50min, and temperature is 40 DEG C, and water scouring water can be recycled.Filter cake after washing is put
In air dry oven, 120 DEG C of dry 1h.Filter cake after drying 800 DEG C of calcining 2h in Muffle furnace, obtain rutile-type titanium dioxide
Titanium valve.
It is detected by weight method, the isolated titanium dioxide 8.60g of the method for embodiment 1, purity is up to 99%.
Embodiment 2
1) it pre-processes: taking a certain amount of discarded SCR denitration, dedusting, broken, grinding sieve with 100 mesh sieve son, under sieve
Object is catalyst fines.Oversize is mixed with the broken discarded out of stock catalyst of SCR, is sieved again.
2) level Four cross-flow method impregnates:
21) the catalyst fines 10g for obtaining step 1) is impregnated with 40% potassium hydroxide solution 20ml, under the conditions of 100 DEG C
Oil bath 4h is separated by solid-liquid separation after dipping, obtains filtrate (filtrate a) and filter cake (filter cake a)；
22) by the filter cake of step 21), (40% potassium hydroxide solution 20ml of filter cake a) impregnates, oil bath under the conditions of 100 DEG C
4h is separated by solid-liquid separation after dipping, obtains filtrate (filtrate b) and filter cake (filter cake b)；
23) by the filter cake of step 22), (40% potassium hydroxide solution 20ml of filter cake b) impregnates, oil bath under the conditions of 100 DEG C
4h is separated by solid-liquid separation after dipping, obtains filtrate (filtrate c) and filter cake (filter cake c)；
24) by the filter cake of step 23), (40% sodium hydroxide solution 20ml of filter cake c) impregnates, oil bath under the conditions of 100 DEG C
4h is separated by solid-liquid separation after dipping, and obtaining filtrate, (filtrate d) and filter cake (filter cake 1), which is titanium dioxide filter cake.
3) it separates titanium dioxide: the filter cake (filter cake 1) that step 24) obtains being washed twice with 100ml water and (is used every time
Water 50ml), the time washed every time is 30min, and temperature is 60 DEG C, and water scouring water can be recycled.Filter cake after washing is put
In air dry oven, 120 DEG C of dry 1h.Filter cake after drying 800 DEG C of calcining 2h in Muffle furnace, obtain rutile-type titanium dioxide
Titanium valve.
It is detected by weight method, the isolated titanium dioxide 8.55g of the method for embodiment 2, purity is up to 99%.
Embodiment 3
1) it pre-processes: taking a certain amount of discarded SCR denitration, dedusting, broken, grinding sieve with 100 mesh sieve son, under sieve
Object is catalyst fines.Oversize is mixed with the broken discarded out of stock catalyst of SCR, is sieved again.
2) level Four cross-flow method impregnates:
21) the catalyst fines 10g for obtaining step 1) is impregnated with 25% potassium hydroxide solution 35ml, under the conditions of 125 DEG C
Oil bath 3h is separated by solid-liquid separation after dipping, obtains filtrate (filtrate a) and filter cake (filter cake a)；
22) by the filter cake of step 21), (25% potassium hydroxide solution 35ml of filter cake a) impregnates, oil bath under the conditions of 125 DEG C
3h is separated by solid-liquid separation after dipping, obtains filtrate (filtrate b) and filter cake (filter cake b)；
23) by the filter cake of step 22), (25% potassium hydroxide solution 35ml of filter cake b) impregnates, oil bath under the conditions of 125 DEG C
3h is separated by solid-liquid separation after dipping, obtains filtrate (filtrate c) and filter cake (filter cake c)；
24) by the filter cake of step 23) (25% sodium hydroxide solution 35ml of filter cake c) impregnates, oil bath 3h under the conditions of 25 DEG C,
It is separated by solid-liquid separation after dipping, obtaining filtrate, (filtrate d) and filter cake (filter cake 1), which is titanium dioxide filter cake.
3) it separates titanium dioxide: the filter cake (filter cake 1) that step 24) obtains being washed twice with 150ml water and (is used every time
Water 75ml), the time washed every time is 40min, and temperature is 50 DEG C, and water scouring water can be recycled.Filter cake after washing is put
In air dry oven, 120 DEG C of dry 1h.Filter cake after drying 800 DEG C of calcining 2h in Muffle furnace, obtain rutile-type titanium dioxide
Titanium valve.
It is detected by weight method, the isolated titanium dioxide 8.66g of the method for embodiment 3, purity is up to 99.4%.
Embodiment 4
1) it pre-processes: taking a certain amount of discarded SCR denitration, dedusting, broken, grinding sieve with 100 mesh sieve son, under sieve
Object is catalyst fines.Oversize is mixed with the broken discarded out of stock catalyst of SCR, is sieved again.
2) level Four cross-flow method impregnates:
21) 11% potassium hydroxide of the catalyst fines 10g for obtaining step 1) and sodium hydroxide solution (v:v=1:1)
40ml impregnates, oil bath 3h under the conditions of 125 DEG C, is separated by solid-liquid separation after dipping, obtains filtrate (filtrate a) and filter cake (filter cake a)；
22) by the filter cake of step 21), (11% potassium hydroxide of filter cake a) and sodium hydroxide solution (v:v=1:1) 40ml soak
Stain, oil bath 3h under the conditions of 130 DEG C are separated by solid-liquid separation after dipping, obtain filtrate (filtrate b) and filter cake (filter cake b)；
23) by the filter cake of step 22), (11% potassium hydroxide of filter cake b) and sodium hydroxide solution (v:v=1:1) 40ml soak
Stain, oil bath 3h under the conditions of 130 DEG C are separated by solid-liquid separation after dipping, obtain filtrate (filtrate c) and filter cake (filter cake c)；
24) by the filter cake of step 23), (11% potassium hydroxide of filter cake c) and sodium hydroxide solution (v:v=1:1) 40ml soak
Stain, oil bath 3h under the conditions of 130 DEG C are separated by solid-liquid separation after dipping, obtain filtrate (filtrate d) and filter cake (filter cake 1), the filter cake (filter cake
It 1) is titanium dioxide filter cake.
3) it separates titanium dioxide: the filter cake (filter cake 1) that step 24) obtains being washed twice with 150ml water and (is used every time
Water 75ml), the time washed every time is 40min, and temperature is 50 DEG C, and water scouring water can be recycled.Filter cake after washing is put
In air dry oven, 120 DEG C of dry 1h.Filter cake after drying 800 DEG C of calcining 2h in Muffle furnace, obtain rutile-type titanium dioxide
Titanium valve.
It is detected by weight method, the isolated titanium dioxide 8.63g of the method for embodiment 4, purity is up to 99.2%.
Embodiment 5
1) it pre-processes: taking a certain amount of discarded SCR denitration, dedusting, broken, grinding sieve with 100 mesh sieve son, under sieve
Object is catalyst fines.Oversize is mixed with the broken discarded out of stock catalyst of SCR, is sieved again.
2) second level counter-current impregnates:
21) with 10% potassium hydroxide solution 50ml impregnation steps 1) obtained catalyst fines 10g (screenings), 150
Oil bath 6h under the conditions of DEG C is separated by solid-liquid separation, and obtains filtrate (filtrate e) and filter cake (filter cake e)；
22) by filtrate that step 21) obtains, (catalyst fines that filtrate e) is obtained with step 1) of dipping again are (under sieve
Object), it is separated by solid-liquid separation, obtains filter cake (filter cake e) and purpose filtrate (filtrate 1)；
23) to filter cake that step 21) obtains (10% potassium hydroxide solution 50ml is added in filter cake e) to be impregnated,
Oil bath 6h under the conditions of 150 DEG C is separated by solid-liquid separation, and obtains filtrate (filtrate e) and purpose filter cake (filter cake 1)；
24) by filter cake that step 22) obtains, (the potassium hydroxide solution 50ml that filter cake e) is further added 10% soaks
Stain, oil bath 6h under the conditions of 150 DEG C are separated by solid-liquid separation, and obtaining filtrate, (filtrate e) and purpose filter cake (filter cake 1), filtrate continue to repeat step
22) operation；
25) by filtrate that step 23) obtains, (filtrate e) impregnates catalyst fines that a step 1) obtains (under sieve again
Object), it is separated by solid-liquid separation, obtaining filter cake, (filter cake e) and purpose filtrate (filtrate 1), filter cake continue to repeat the operation of step 23)；
26) operation to repeat the above steps.
3) it separates titanium dioxide: purpose filter cake (filter cake 1) obtained above being merged, is washed twice with 100ml water
(using water 50ml every time), the time washed every time are 50min, and temperature is 40 DEG C, and water scouring water can be recycled.After washing
Filter cake is placed in air dry oven, 120 DEG C of dry 1h.Filter cake after drying 800 DEG C of calcining 2h in Muffle furnace, obtain rutile-type
Titanium dioxide powder.
It is detected by weight method, the isolated titanium dioxide 8.62g of the method for embodiment 5, purity is up to 99%.
Embodiment 6
1) it pre-processes: taking a certain amount of discarded SCR denitration, dedusting, broken, grinding sieve with 100 mesh sieve son, under sieve
Object is catalyst fines.Oversize is mixed with the broken discarded out of stock catalyst of SCR, is sieved again.
2) second level counter-current impregnates:
21) with 40% sodium hydroxide solution 20ml impregnation steps 1) obtained catalyst fines 10g (screenings), 160
Oil bath 4h under the conditions of DEG C is separated by solid-liquid separation, and obtains filtrate (filtrate e) and filter cake (filter cake e)；
22) by filtrate that step 21) obtains, (catalyst fines that filtrate e) is obtained with step 1) of dipping again are (under sieve
Object), it is separated by solid-liquid separation, obtains filter cake (filter cake e) and purpose filtrate (filtrate 1)；
23) to filter cake that step 21) obtains (40% sodium hydroxide solution 20ml is added in filter cake e) to be impregnated,
Oil bath 4h under the conditions of 160 DEG C is separated by solid-liquid separation, and obtains filtrate (filtrate e) and purpose filter cake (filter cake 1)；
24) by filter cake that step 22) obtains, (the sodium hydroxide solution 20ml that filter cake e) is further added 40% soaks
Stain, oil bath 4h under the conditions of 160 DEG C are separated by solid-liquid separation, and obtaining filtrate, (filtrate e) and purpose filter cake (filter cake 1), filtrate continue to repeat step
22) operation；
25) by filtrate that step 23) obtains, (filtrate e) impregnates catalyst fines that a step 1) obtains (under sieve again
Object), it is separated by solid-liquid separation, obtaining filter cake, (filter cake e) and purpose filtrate (filtrate 1), filter cake continue to repeat the operation of step 23)；
26) operation to repeat the above steps.
3) it separates titanium dioxide: purpose filter cake (filter cake 1) obtained above being merged, is washed twice with 100ml water
(using water 50ml every time), the time washed every time are 30min, and temperature is 60 DEG C, and water scouring water can be recycled.After washing
Filter cake is placed in air dry oven, 120 DEG C of dry 1h.Filter cake after drying 800 DEG C of calcining 2h in Muffle furnace, obtain rutile-type
Titanium dioxide powder.
It is detected by weight method, the isolated titanium dioxide 8.53g of the method for embodiment 6, purity is up to 99%.
Embodiment 7
1) it pre-processes: taking a certain amount of discarded SCR denitration, dedusting, broken, grinding sieve with 100 mesh sieve son, under sieve
Object is catalyst fines.Oversize is mixed with the broken discarded out of stock catalyst of SCR, is sieved again.
2) second level counter-current impregnates:
21) with 11% sodium hydroxide solution 35ml impregnation steps 1) obtained catalyst fines 10g (screenings), 155
Oil bath 3h under the conditions of DEG C is separated by solid-liquid separation, and obtains filtrate (filtrate e) and filter cake (filter cake e)；
22) by filtrate that step 21) obtains, (catalyst fines that filtrate e) is obtained with step 1) of dipping again are (under sieve
Object), it is separated by solid-liquid separation, obtains filter cake (filter cake e) and purpose filtrate (filtrate 1)；
23) to filter cake that step 21) obtains (11% sodium hydroxide solution 35ml is added in filter cake e) to be impregnated,
Oil bath 3h under the conditions of 155 DEG C is separated by solid-liquid separation, and obtains filtrate (filtrate e) and purpose filter cake (filter cake 1)；
24) by filter cake that step 22) obtains, (the sodium hydroxide solution 35ml that filter cake e) is further added 11% soaks
Stain, oil bath 3h under the conditions of 155 DEG C are separated by solid-liquid separation, and obtaining filtrate, (filtrate e) and purpose filter cake (filter cake 1), filtrate continue to repeat step
22) operation；
25) by filtrate that step 23) obtains, (filtrate e) impregnates catalyst fines that a step 1) obtains (under sieve again
Object), it is separated by solid-liquid separation, obtaining filter cake, (filter cake e) and purpose filtrate (filtrate 1), filter cake continue to repeat the operation of step 23)；
26) operation to repeat the above steps.
3) it separates titanium dioxide: filter cake obtained above (filter cake 1) is merged, washed twice (every time with 150ml water
With water 75ml), the time washed every time is 40min, and temperature is 50 DEG C, and water scouring water can be recycled.By the filter cake after washing
It is placed in air dry oven, 120 DEG C of dry 1h.Filter cake after drying 800 DEG C of calcining 2h in Muffle furnace, obtain rutile-type dioxy
Change titanium valve.
It is detected by weight method, the isolated titanium dioxide 8.64g of the method for embodiment 7, purity is up to 99.2%.
Embodiment 8
1) it pre-processes: taking a certain amount of discarded SCR denitration, dedusting, broken, grinding sieve with 100 mesh sieve son, under sieve
Object is catalyst fines.Oversize is mixed with the broken discarded out of stock catalyst of SCR, is sieved again.
2) second level counter-current impregnates:
21) with 60% sodium hydroxide solution 35ml impregnation steps 1) obtained catalyst fines 10g (screenings), 90 DEG C
Under the conditions of oil bath 5h, be separated by solid-liquid separation, obtain filtrate (filtrate e) and filter cake (filter cake e)；
22) by filtrate that step 21) obtains, (catalyst fines that filtrate e) is obtained with step 1) of dipping again are (under sieve
Object), it is separated by solid-liquid separation, obtains filter cake (filter cake e) and purpose filtrate (filtrate 1)；
23) to filter cake that step 21) obtains (60% sodium hydroxide solution 35ml is added in filter cake e) to be impregnated,
Oil bath 5h under the conditions of 90 DEG C is separated by solid-liquid separation, and obtains filtrate (filtrate e) and purpose filter cake (filter cake 1)；
24) by filter cake that step 22) obtains, (the sodium hydroxide solution 35ml that filter cake e) is further added 60% soaks
Stain, oil bath 5h under the conditions of 90 DEG C are separated by solid-liquid separation, and obtaining filtrate, (filtrate e) and purpose filter cake (filter cake 1), filtrate continue to repeat step
22) operation；
25) by filtrate that step 23) obtains, (filtrate e) impregnates catalyst fines that a step 1) obtains (under sieve again
Object), it is separated by solid-liquid separation, obtaining filter cake, (filter cake e) and purpose filtrate (filtrate 1), filter cake continue to repeat the operation of step 23)；
26) operation to repeat the above steps.
3) it separates titanium dioxide: filter cake obtained above (filter cake 1) is merged, washed twice (every time with 150ml water
With water 75ml), the time washed every time is 40min, and temperature is 50 DEG C, and water scouring water can be recycled.By the filter cake after washing
It is placed in air dry oven, 120 DEG C of dry 1h.Filter cake after drying 800 DEG C of calcining 2h in Muffle furnace, obtain rutile-type dioxy
Change titanium valve.
It is detected by weight method, the isolated titanium dioxide 8.21g of the method for embodiment 8, purity is up to 93%.
Although the present invention is disclosed as above with embodiment, so it is not intended to limit the present invention, any those skilled in the art
Member, without departing from the spirit and scope of the present invention, can make a variety of different selections and modification, therefore protection model of the invention
It encloses and is limited by claims and its equivalents.
Claims (5)
1. one kind separates and recovers titanium dioxide method from discarded SCR denitration, which comprises the following steps:
By pretreated discarded SCR denitration powder soda-dip, dipping method is level Four cross-flow or second level counter-current, leaching
Solidliquid mixture after stain obtains high-purity titania powder through separation of solid and liquid, washing, drying, calcining；
Specific steps are as follows:
1) it pre-processes: taking discarded SCR denitration, dedusting, broken, grinding obtain catalyst fines；
2) level Four cross-flow method dipping the following steps are included:
21) the catalyst fines soda-dip for obtaining step 1) is separated by solid-liquid separation after dipping, obtains filtrate and filter cake；
22) filter cake of step 21) is impregnated with aqueous slkali, is separated by solid-liquid separation after dipping, obtain filtrate and filter cake；
23) filter cake of step 22) is impregnated with aqueous slkali, is separated by solid-liquid separation after dipping, obtain filtrate and filter cake；
24) filter cake of step 23) is impregnated with aqueous slkali, is separated by solid-liquid separation after dipping, obtain filtrate and filter cake, which is two
Titanium oxide filter cake；
3) separate titanium dioxide: the filter cake that step 24) is obtained obtains titania powder through washing, drying, calcining；
Or specific steps are as follows:
1) it pre-processes: taking discarded SCR denitration, dedusting, broken, grinding obtain catalyst fines；
2) second level counter-current dipping the following steps are included:
21) catalyst fines obtained with soda-dip step 1) are separated by solid-liquid separation, obtain filtrate and filter cake；
22) filtrate that step 21) obtains is impregnated into the catalyst fines that a step 1) obtains again, is separated by solid-liquid separation, obtains filter cake
With purpose filtrate；
23) lye is added into the filter cake that step 21) obtains to be impregnated, be separated by solid-liquid separation, obtain filtrate and purpose filter cake；
24) soda-dip is further added in the filter cake that step 22) obtains, is separated by solid-liquid separation, obtains filtrate and purpose filter cake, filtrate after
The continuous operation for repeating step 22)；
25) filtrate that step 23) obtains is impregnated into the catalyst fines that a step 1) obtains again, be separated by solid-liquid separation, obtain filter cake and
Purpose filtrate, filter cake continue to repeat the operation of step 23)；
26) operation to repeat the above steps；
3) separate titanium dioxide: the purpose filter cake that step 2) is obtained merges, and through washing, drying, calcining, obtains titanium dioxide；
The liquid-solid ratio of each step level Four cross-flow is (2-5) ml:1g；Reaction temperature is 100-150 DEG C, and the reaction time is that 2-4 is small
When；The liquid-solid ratio of each two stage countercurrent of step is (2-5) ml:1g；Reaction temperature is 150-160 DEG C, and the reaction time is that 4-6 is small
When.
2. according to claim 1 separate and recover titanium dioxide method from discarded SCR denitration, feature exists
In the catalyst fines of the step 1) are to be prepared by the following: after discarded SCR denitration dust removal process, breaking
Broken, grinding, the SCR powder after grinding are screened through classifying screen, classification grit number >=100 mesh, screenings, that is, catalyst fines, on sieve
Object is mixed with broken discarded SCR denitration, is re-grind, sieving, repetitive cycling.
3. according to claim 1 separate and recover titanium dioxide method from discarded SCR denitration, feature exists
In the lye is the mixed solution of the sodium hydroxide solution of 10%-40%, potassium hydroxide solution or both.
4. according to claim 1 separate and recover titanium dioxide method from discarded SCR denitration, feature exists
In the washing specifically: washed filter cake twice, the liquid-solid ratio washed twice is (5-10) ml:1g, washing temperature
It is 40-60 DEG C, time 30-50min；The condition of calcining are as follows: 800 DEG C are calcined 2 hours.
5. according to claim 1 separate and recover titanium dioxide method from discarded SCR denitration, feature exists
In the titanium dioxide is rutile titanium dioxide.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5440213A (en) * | 1977-09-06 | 1979-03-29 | Sakai Chem Ind Co Ltd | Separation method |
| CN102936039A (en) * | 2012-11-15 | 2013-02-20 | 攀枝花市晟天钛业有限公司 | Recovery process of honeycomb type selective catalytic reduction (SCR) waste catalyst containing tungsten, vanadium and titanium |
| CN105481007A (en) * | 2016-01-13 | 2016-04-13 | 江苏龙净科杰催化剂再生有限公司 | Recycling method of waste SCR (selective catalytic reduction) denitration catalyst |
| CN105714118A (en) * | 2016-03-01 | 2016-06-29 | 成都万里蓝环保科技有限公司 | Technology for extracting and recovering tungsten and vanadium from waste SCR catalyst |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5440213A (en) * | 1977-09-06 | 1979-03-29 | Sakai Chem Ind Co Ltd | Separation method |
| CN102936039A (en) * | 2012-11-15 | 2013-02-20 | 攀枝花市晟天钛业有限公司 | Recovery process of honeycomb type selective catalytic reduction (SCR) waste catalyst containing tungsten, vanadium and titanium |
| CN105481007A (en) * | 2016-01-13 | 2016-04-13 | 江苏龙净科杰催化剂再生有限公司 | Recycling method of waste SCR (selective catalytic reduction) denitration catalyst |
| CN105714118A (en) * | 2016-03-01 | 2016-06-29 | 成都万里蓝环保科技有限公司 | Technology for extracting and recovering tungsten and vanadium from waste SCR catalyst |
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