CN103343236A - Method for recovering titanium, vanadium and tungsten from waste denitration catalyst - Google Patents
Method for recovering titanium, vanadium and tungsten from waste denitration catalyst Download PDFInfo
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- CN103343236A CN103343236A CN2013103152069A CN201310315206A CN103343236A CN 103343236 A CN103343236 A CN 103343236A CN 2013103152069 A CN2013103152069 A CN 2013103152069A CN 201310315206 A CN201310315206 A CN 201310315206A CN 103343236 A CN103343236 A CN 103343236A
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- vanadium
- tungsten
- denitrating catalyst
- titanium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to the technical field of catalyst recovery, and in particular relates to a method for recovering titanium, vanadium and tungsten from a waste denitration catalyst. The method disclosed by the invention comprises the following steps of: grinding the waste denitration catalyst, adding strong alkali, and performing a molten salt reaction; cooling to a room temperature, then adding deionized water to separate a titanium-containing solid from a tungsten-containing and vanadium-containing solution; and boiling the tungsten-containing and vanadium-containing solution to separate a vanadium-containing solid from tungsten-containing solution. The method disclosed by the invention is free from the discharge of the three wastes by adopting a closed-loop circulation mode, good in economic benefits and social benefits, convenient to operate, simple in process, and capable of recovering and reutilizing valuable elements of titanium, vanadium and tungsten from the waste denitration catalyst.
Description
Technical field
The present invention relates to the catalyst recovery technical field, be specifically related to a kind of method that from discarded denitrating catalyst, reclaims titanium, vanadium, tungsten.
Background technology
Along with country improves gradually to the requirement of thermal power plant's atmospheric polluting material ammonia nitrogen quantity discharged, the usage quantity of denitrating catalyst strengthens gradually, but at present the work-ing life of denitrating catalyst all about 3 years, and the denitrating catalyst use of can't regenerating.Be accompanied by " thermal power plant's atmosphere pollutants emission standards (exposure draft) " that in July, 2009, Chinese Ministry of Environmental Protection put into effect the denitration deadline is fixed on January 1st, 2015.Wherein, major area NOx quantity discharged reaches 200 milligrams/cubic metre, and non-major area then is 400 milligrams/cubic metre, and " thermal power plant's atmosphere pollutants emission standards (secondary exposure draft) " came into effect from January 1st, 2012.Its requirement, since on January 1st, 2012, all newly-built fired power generating unit NOx quantity dischargeds must not surpass the 100mg/ cubic meter.And from January 1st, 2014, require all thermoelectricitys of major area unit NOx quantity discharged that puts into operation to reach the 100mg/ cubic meter, non-major area unit reaches the 200mg/ cubic meter.Oxynitrides is faced with important mission as one of policy of China " 12 " pollution reduction.In thermal power plant's denitration technology, SCR(selective catalytic reduction) denitration technology relies on advantages such as its denitration rate height, selectivity are good, mature and reliable, is the mainstream technology of present coal-fired unit denitration.And the part of most critical is catalyzer in the SCR system, and its cost accounts for 30%～50% of denitrification apparatus gross investment usually.After country carries out mandatory limit row's policy, the potential demand amount will increase to annual 150000～20 ten thousand steres.The main component of SCR catalyzer is titanium dioxide, tungstic oxide, Vanadium Pentoxide in FLAKES etc., accounts for more than 95% of total amount.And catalyzer will be changed once in average per 3 years, became new solid waste, and how the catalyzer after the replacing is recycled, and just becomes a new problem.
Therefore, be necessary to seek an approach, solve the recycling of discarded denitrating catalyst, in addition recycling of the material that it is useful is turned waste into wealth.
Summary of the invention
The purpose of this invention is to provide a kind of method that reclaims titanium, vanadium, tungsten from discarded denitrating catalyst, technology is simple, and is easy to operate, do not have three waste discharge.
The method that reclaims titanium, vanadium, tungsten from discarded denitrating catalyst of the present invention is that discarded denitrating catalyst is ground, add highly basic and carry out the fused salt reaction, add deionized water behind the cool to room temperature with the solution separating of the solid of titaniferous and tungstenic, vanadium, the solution of tungstenic, vanadium will contain the solution separating of solid and the tungstenic of vanadium through boiling.
Described discarded denitrating catalyst grinds the back and sieves at 325 orders, and screen over-size is less than 5%.
Described highly basic is a kind of in sodium hydroxide or the potassium hydroxide.
The mass ratio of described discarded denitrating catalyst and highly basic is 1:1.4-1.7.
The temperature of reaction of described fused salt reaction is 395-555 ℃.
The reaction times of described fused salt reaction is 50-80min.
The quality of described deionized water is 3-6 times of discarded denitrating catalyst quality.
Stir 8-15min behind the described adding deionized water.
Described boiling temps is 95-105 ℃.
Described boiling time is 20-30min.
After discarded denitrating catalyst after described fused salt reaction refers to solid alkali and grinds evenly mixed according to a certain percentage, low-temperature heat was melted solid-state highly basic, and discarded denitrating catalyst reacts in the highly basic that melts, and generates the solid state powder reactant.
Described grinding adopts shredder to carry out, and shredder is a kind of in spectrum shredder, ball mill or the Raymond mill.
The method that from discarded denitrating catalyst, reclaims titanium, vanadium, tungsten of the present invention, concrete steps are as follows:
To discard denitrating catalyst and grind, and add highly basic and carry out the fused salt reaction, the reacting rear material cool to room temperature stirs behind the adding deionized water, adopts filter type to separate solid and liquid, and obtaining solid is sodium titanate, and filter liquide is vanadic acid sodium and sodium wolframate; Filtered liquid is by after boiling, and vanadic acid sodium becomes the sodium metavanadate of indissoluble, adopts solid-liquid separation with vanadium and tungsten Separation and Recovery.
For the first time solid-liquid separation is sodium titanate and the separating of vanadic acid sodium, sodium wolframate; Solid-liquid separation is separating of sodium wolframate and vanadic acid sodium for the second time, and the purpose of separation is that the form of the useful element in the discarded denitrating catalyst with compound reclaimed respectively.The main component of discarded denitrating catalyst is titanium, tungsten and vanadium, and in the sodium hydroxide frit reaction, the main chemical reactions of generation is:
TiO
2+2NaOH=Na
2TiO
3+H
2O
2Ti
3O
5+12NaOH+O
2＝6Na
2TiO
3+6H
2O
V
2O
5+6NaOH=2Na
3VO
4+3H
2O
2WO
3+4NaOH=2Na
2WO
4+2H
2O
Na
2TiO
3+H
2O=H
2TiO
3+2NaOH
Under boiled condition, vanadic acid sodium Na
3VO
4Generation is insoluble in the sodium metavanadate NaVO of water
3:
Na
3VO
4+H
2O＝NaVO
3+2NaOH
The sodium titanate that the present invention obtains reaches more than 90% by taking off the titanium dioxide titanium content that obtains behind the sodium, satisfies the specification of quality that pottery and welding electrode are used titanium dioxide.
The present invention compared with prior art has following beneficial effect:
The present invention adopts the closed cycle mode, does not have three waste discharge, has good economic benefit and social benefit.The present invention is easy to operate, and technology is simple, can be with valuable element titanium, tungsten, the vanadium recycling of discarding in the denitrating catalyst.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Be described further below in conjunction with the present invention of embodiment.
Embodiment 1
Discarded denitrating catalyst adopts the spectrum shredder to grind, sieve at 325 orders, screen over-size is less than 5%, and the discarded denitrating catalyst 100g after obtaining grinding adds 150g sodium hydroxide and carries out the fused salt reaction, the fused salt temperature of reaction is 500 ± 5 ℃, the fused salt reaction times is 60min, and the reacting rear material cool to room temperature added the 300g deionized water and stirring 10 minutes, adopt the sheet frame squeezing to separate solid and liquid, obtaining solid is that sodium titanate is (with TiO
2Meter) 91.70g, filter liquide is vanadic acid sodium and sodium wolframate; Filtered liquid be warmed up to 100 ℃ boil 20min after, vanadic acid sodium becomes the sodium metavanadate of indissoluble, adopts the sheet frame squeezing with vanadium and tungsten Separation and Recovery, obtains sodium metavanadate (with V
2O
5Meter) 2.37g, sodium wolframate is (with W
2O
3Meter) 4.85g.
Embodiment 2
Discarded denitrating catalyst adopts ball mill to grind, sieve at 325 orders, screen over-size is less than 5%, and the discarded denitrating catalyst 100g after obtaining grinding adds 140g potassium hydroxide and carries out the fused salt reaction, the fused salt temperature of reaction is 400 ± 5 ℃, the fused salt reaction times is 50min, and the reacting rear material cool to room temperature added the 400g deionized water and stirring 10 minutes, adopt the sheet frame squeezing to separate solid and liquid, obtaining solid is that sodium titanate is (with TiO
2Meter) 92.51g, filter liquide is vanadic acid sodium and sodium wolframate; Filtered liquid be warmed up to 95 ℃ boil 25min after, vanadic acid sodium becomes the sodium metavanadate of indissoluble, adopts the sheet frame squeezing with vanadium and tungsten Separation and Recovery, obtains sodium metavanadate (with V
2O
5Meter) 2.42g, sodium wolframate is (with W
2O
3Meter) 4.73g.
Embodiment 3
Discarded denitrating catalyst adopts Raymond mill to grind, sieve at 325 orders, screen over-size is less than 5%, and the discarded denitrating catalyst 100g after obtaining grinding adds 160g sodium hydroxide and carries out the fused salt reaction, the fused salt temperature of reaction is 550 ± 5 ℃, the fused salt reaction times is 70min, and the reacting rear material cool to room temperature added the 500g deionized water and stirring 9 minutes, adopt the sheet frame squeezing to separate solid and liquid, obtaining solid is that sodium titanate is (with TiO
2Meter) 91.91g, filter liquide is vanadic acid sodium and sodium wolframate; Filtered liquid be warmed up to 105 ℃ boil 30min after, vanadic acid sodium becomes the sodium metavanadate of indissoluble, adopts the sheet frame squeezing with vanadium and tungsten Separation and Recovery, obtains sodium metavanadate (with V
2O
5Meter) 2.41g, sodium wolframate is (with W
2O
3Meter) 4.65g.
Embodiment 4
Discarded denitrating catalyst adopts the spectrum shredder to grind, sieve at 325 orders, screen over-size is less than 5%, and the discarded denitrating catalyst 100g after obtaining grinding adds 170g sodium hydroxide and carries out the fused salt reaction, the fused salt temperature of reaction is 500 ± 5 ℃, the fused salt reaction times is 50min, and the reacting rear material cool to room temperature added the 600g deionized water and stirring 15 minutes, adopt the sheet frame squeezing to separate solid and liquid, obtaining solid is that sodium titanate is (with TiO
2Meter) 94.51g, filter liquide is vanadic acid sodium and sodium wolframate; Filtered liquid be warmed up to 100 ℃ boil 25min after, vanadic acid sodium becomes the sodium metavanadate of indissoluble, adopts the sheet frame squeezing with vanadium and tungsten Separation and Recovery, obtains sodium metavanadate (with V
2O
5Meter) 2.35g, sodium wolframate is (with W
2O
3Meter) 4.38g.
Embodiment 5
Discarded denitrating catalyst adopts ball mill to grind, sieve at 325 orders, screen over-size is less than 5%, and the discarded denitrating catalyst 100g after obtaining grinding adds 160g potassium hydroxide and carries out the fused salt reaction, the fused salt temperature of reaction is 450 ± 5 ℃, the fused salt reaction times is 80min, and the reacting rear material cool to room temperature added the 500g deionized water and stirring 8 minutes, adopt the sheet frame squeezing to separate solid and liquid, obtaining solid is that sodium titanate is (with TiO
2Meter) 93.12g, filter liquide is vanadic acid sodium and sodium wolframate; Filtered liquid be warmed up to 100 ℃ boil 30min after, vanadic acid sodium becomes the sodium metavanadate of indissoluble, adopts the sheet frame squeezing with vanadium and tungsten Separation and Recovery, obtains sodium metavanadate (with V
2O
5Meter) 2.23g, sodium wolframate is (with W
2O
3Meter) 4.37g.
The comprehensive recovery of table 1 embodiment 1-5
The recovering state of table 2 embodiment 1-5 (adopting the ICP plasma emission spectrometer to measure)
Table 3 embodiment 1-5 sodium titanate is taken off the content situation of titanium dioxide behind the sodium
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| TiO 2/% | 90.12 | 91.11 | 92.07 | 91.32 | 92.03 |
Claims (10)
1. method that from discarded denitrating catalyst, reclaims titanium, vanadium, tungsten, it is characterized in that discarding denitrating catalyst grinds, add highly basic and carry out the fused salt reaction, add deionized water behind the cool to room temperature with the solution separating of the solid of titaniferous and tungstenic, vanadium, the solution of tungstenic, vanadium will contain the solution separating of solid and the tungstenic of vanadium through boiling.
2. the method that reclaims titanium, vanadium, tungsten from discarded denitrating catalyst according to claim 1 is characterized in that described discarded denitrating catalyst grinds the back and sieves at 325 orders, and screen over-size is less than 5%.
3. the method that reclaims titanium, vanadium, tungsten from discarded denitrating catalyst according to claim 1 is characterized in that described highly basic is a kind of in sodium hydroxide or the potassium hydroxide.
4. the method that reclaims titanium, vanadium, tungsten from discarded denitrating catalyst according to claim 1 is characterized in that the mass ratio of described discarded denitrating catalyst and highly basic is 1:1.4-1.7.
5. the method that reclaims titanium, vanadium, tungsten from discarded denitrating catalyst according to claim 1 is characterized in that the temperature of reaction of described fused salt reaction is 395-555 ℃.
6. the method that reclaims titanium, vanadium, tungsten from discarded denitrating catalyst according to claim 1 is characterized in that the reaction times of described fused salt reaction is 50-80min.
7. the method that from discarded denitrating catalyst, reclaims titanium, vanadium, tungsten according to claim 1, the quality that it is characterized in that described deionized water be discarded denitrating catalyst quality 3-6 doubly.
8. the method that reclaims titanium, vanadium, tungsten from discarded denitrating catalyst according to claim 1 is characterized in that stirring 8-15min behind the described adding deionized water.
9. the method that reclaims titanium, vanadium, tungsten from discarded denitrating catalyst according to claim 1 is characterized in that described boiling temps is 95-105 ℃.
10. according to claim 1 or the 9 described methods that from discarded denitrating catalyst, reclaim titanium, vanadium, tungsten, it is characterized in that described boiling time is 20-30min.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104263946A (en) * | 2014-10-10 | 2015-01-07 | 武汉凯迪电力环保有限公司 | Method for recovering tungsten, vanadium and titanium from waste SCR (selective catalytic reduction) denitration catalyst |
| CN105709861A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Regeneration method of SCR denitration catalyst |
| CN105969991A (en) * | 2016-06-18 | 2016-09-28 | 浙江天蓝环保技术股份有限公司 | Method for extracting titanium, vanadium and tungsten metallic oxide from failed SCR catalyst |
| CN106884090A (en) * | 2017-01-15 | 2017-06-23 | 北京工业大学 | A kind of sub-molten salt method that vanadium tungsten titanium is reclaimed entirely in waste denitration catalyst |
| CN110015686A (en) * | 2018-01-08 | 2019-07-16 | 神华集团有限责任公司 | Titanium slag recycles the method for titanium dioxide and the method from denitrating catalyst recycling tungsten, titanium and vanadium |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105709863B (en) * | 2014-12-05 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of SCR regenerating flue gas denitrifying catalyst liquid and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995020434A1 (en) * | 1994-01-27 | 1995-08-03 | Engelhard Corporation | Process for recovering catalyst supports |
| CN101921916A (en) * | 2010-08-16 | 2010-12-22 | 华电电力科学研究院 | Method for recycling metal oxide from waste flue gas denitration catalyst |
| CN102557142A (en) * | 2012-02-16 | 2012-07-11 | 江苏万德电力环保有限公司 | Method for recovering tungsten trioxide and ammonium metavanadate from selective catalytic reduction (SCR) denitration catalyst |
-
2013
- 2013-07-24 CN CN201310315206.9A patent/CN103343236B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995020434A1 (en) * | 1994-01-27 | 1995-08-03 | Engelhard Corporation | Process for recovering catalyst supports |
| CN101921916A (en) * | 2010-08-16 | 2010-12-22 | 华电电力科学研究院 | Method for recycling metal oxide from waste flue gas denitration catalyst |
| CN102557142A (en) * | 2012-02-16 | 2012-07-11 | 江苏万德电力环保有限公司 | Method for recovering tungsten trioxide and ammonium metavanadate from selective catalytic reduction (SCR) denitration catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 张立等: "《SCR脱硝催化剂的再生与回收》", 《电站辅机》, vol. 33, no. 3, 30 September 2012 (2012-09-30) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104263946A (en) * | 2014-10-10 | 2015-01-07 | 武汉凯迪电力环保有限公司 | Method for recovering tungsten, vanadium and titanium from waste SCR (selective catalytic reduction) denitration catalyst |
| CN105709861A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Regeneration method of SCR denitration catalyst |
| CN105709861B (en) * | 2014-12-05 | 2018-07-03 | 中国石油化工股份有限公司 | A kind of regeneration method of SCR denitration |
| CN105969991A (en) * | 2016-06-18 | 2016-09-28 | 浙江天蓝环保技术股份有限公司 | Method for extracting titanium, vanadium and tungsten metallic oxide from failed SCR catalyst |
| CN106884090A (en) * | 2017-01-15 | 2017-06-23 | 北京工业大学 | A kind of sub-molten salt method that vanadium tungsten titanium is reclaimed entirely in waste denitration catalyst |
| CN106884090B (en) * | 2017-01-15 | 2018-06-01 | 北京工业大学 | A kind of sub-molten salt method that vanadium tungsten titanium recycles entirely in waste denitration catalyst |
| CN110015686A (en) * | 2018-01-08 | 2019-07-16 | 神华集团有限责任公司 | Titanium slag recycles the method for titanium dioxide and the method from denitrating catalyst recycling tungsten, titanium and vanadium |
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| CN103343236B (en) | 2014-08-13 |
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