CN106337133B - The recovery method of titanium vanadium tungsten in a kind of useless SCR denitration - Google Patents
The recovery method of titanium vanadium tungsten in a kind of useless SCR denitration Download PDFInfo
- Publication number
- CN106337133B CN106337133B CN201610867480.0A CN201610867480A CN106337133B CN 106337133 B CN106337133 B CN 106337133B CN 201610867480 A CN201610867480 A CN 201610867480A CN 106337133 B CN106337133 B CN 106337133B
- Authority
- CN
- China
- Prior art keywords
- raw material
- mixture
- scr denitration
- useless scr
- tungsten
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000011084 recovery Methods 0.000 title claims abstract description 35
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 title claims abstract description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 29
- 239000010937 tungsten Substances 0.000 claims abstract description 29
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 29
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910000805 Pig iron Inorganic materials 0.000 claims abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 59
- 239000002994 raw material Substances 0.000 claims description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000002893 slag Substances 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 19
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 239000012141 concentrate Substances 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000002817 coal dust Substances 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- MRHSJWPXCLEHNI-UHFFFAOYSA-N [Ti].[V].[Fe] Chemical compound [Ti].[V].[Fe] MRHSJWPXCLEHNI-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 10
- 230000008859 change Effects 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 6
- 150000004706 metal oxides Chemical class 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000001698 pyrogenic effect Effects 0.000 abstract description 5
- 238000005275 alloying Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 14
- 238000009740 moulding (composite fabrication) Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000000292 calcium oxide Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- NWJUARNXABNMDW-UHFFFAOYSA-N tungsten vanadium Chemical compound [W]=[V] NWJUARNXABNMDW-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 229910001349 ledeburite Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical class O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
- C22B34/225—Obtaining vanadium from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
- C22B34/365—Obtaining tungsten from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Catalysts (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention provides a kind of recovery methods of titanium vanadium tungsten in useless SCR denitration, belong to catalyst recovery technology field, useless SCR denitration is recycled different from wet-dry change technique, it employs pyrogenic process to recycle the metal oxide in useless SCR catalyst directly in the form of alloying, has the following advantages：1) it is directly recycled using iron member carbothermic method, saves complicated operation, technological process is simple, settles at one go；2) equipment is simple, recycles useless SCR denitration technique compared with wet-dry change, cost, low energy consumption；3) pig iron of tungsten containing vanadium is directly obtained, reduces subsequent job step；4) farthest reduce the pollution to environment.
Description
Technical field
The present invention relates to waste catalyst recovery technical field, titanium vanadium tungsten in more particularly to a kind of useless SCR denitration
Recovery method.
Background technology
Useless SCR denitration is the solid waste in Flue Gas Denitrification Engineering, using it is most be titania based V2O5-
WO3(MoO3)/TiO2Catalyst series contain a large amount of TiO2、V2O5、WO3Valuable metals oxide is waited, they are all valuable
Resource.The service life of domestic SCR denitration is usually 3 years, according to the arrangement of denitrating catalyst " 2+1 ", in advance
Meter was since 2016, the domestic useless SCR catalyst that will generate 3.8 ten thousand t/a, so being recycled to useless SCR denitration
Using being very important, its utility value can be improved, avoids TiO2With the waste of Prospects of Rare Metal Vanadium tungsten, and also have one
Fixed social benefit and environmental benefit.
At present, the recovery process for SCR denitration of giving up is broadly divided into two kinds of dry and wet.Dry method, i.e. alkali roast work
Skill, as CN105274341A discloses a kind of recovery method of out of stock catalyst：Alkali (Na is added in by proportioning2CO3) co-grinding afterwards
Uniformly, the powder mixture obtained carries out high-temperature roasting, and gained sodium vanadate, sodium tungstate are soluble easily in water.Wet method include alkaline process and
Two kinds of acid system, acid system, the scheme as disclosed in CN103130265A：Utilize TiO2Titanium and vanadium tungsten are detached with strong sulfuric acid response；Alkaline process,
The scheme as disclosed in CN104071832A, CN103526031A：It is anti-using the metal oxide in useless SCR denitration and alkali
Should, generate vanadate and tungstates soluble easily in water, and TiO2The various alkali metal titanates that generation is reacted with alkali are almost insoluble
Yu Shui, then separation is achieved the purpose that by filtering technique.There are many ways to detaching vanadium tungsten, common method is to use NH4Cl sinks
Vanadium, anhydrous CaCl2Heavy tungsten.The recovery process of above-mentioned useless SCR denitration has the following disadvantages：1) consumption of acid or alkali
Greatly；2) technological process too complex；3) dry method is to equipment requirement height, and high energy consumption, water extraction efficiency is low, and treatment effect is bad.
Invention content
In view of this, present invention aims at the recovery methods for providing titanium vanadium tungsten in a kind of useless SCR denitration, use
Pyrogenic process recycles the metal oxide in useless SCR catalyst directly in the form of alloying, and recovery process is simple, cost, energy consumption
It is low, the pig iron of tungsten containing vanadium can be directly obtained, reduces subsequent job step.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
The recovery method of titanium vanadium tungsten, comprises the steps of in a kind of useless SCR denitration：
(1) useless SCR denitration, ferriferous raw material, carbon raw material, binding agent and calcic raw material are mixed, is mixed
Material；
(2) the mixture granulating and forming for obtaining the step (1), obtains spherical material；
(3) the spherical material for obtaining the step (2) roasts, and obtains the pig iron of tungsten containing vanadium and titanium slag.
Preferably, the mass ratio for the SCR denitration, ferriferous raw material and carbon raw material of giving up in the step (1) is 100:
80~850:3~400；The quality of the binding agent is the 15~25% of mixture gross mass, and the quality of the calcic raw material is
The 7.0~15% of mixture gross mass.
Preferably, the ferriferous raw material in the step (1) includes sefstromite concentrate, Fe2O3、Fe3O4With one kind in iron powder
Or several mixture；The mass content of iron is 50~100% in the ferriferous raw material.
Preferably, the carbon raw material in the step (1) includes the mixed of one or more of coal dust, coke powder and graphite powder
Object is closed, the mass content of fixed carbon is more than 80% in the carbon raw material.
Preferably, the mass content of fixed carbon is 85~99% in the carbon raw material in the step (1).
Preferably, the binding agent in the step (1) includes one or both of polyvinyl alcohol and carboxymethyl cellulose
Mixture.
Preferably, the calcic raw material in the step (1) includes the mixture of one or more of calcium oxide and calcium salt.
Preferably, the useless SCR denitration in the step (1) is the powder raw material of 200~400 mesh, comprising following
The component of mass content：80~85% TiO2, 1~5% V2O5, 5~10% WO3, 2~5% SiO2。
Preferably, in the step (2) pressure of granulating and forming for 5~15MPa, time of the granulating and forming for 20~
60s。
Preferably, the temperature roasted in the step (3) is 1500~1650 DEG C, and the time of the roasting is 1~3h.
The present invention provides a kind of recovery methods of titanium vanadium tungsten in useless SCR denitration, are returned different from wet-dry change technique
Useless SCR denitration is received, pyrogenic process is employed and returns the metal oxide in useless SCR catalyst directly in the form of alloying
It receives, has the following advantages：1) it is directly recycled using iron member carbothermic method, saves complicated operation, technological process is simple, a step
In place；2) equipment is simple, recycles useless SCR denitration technique compared with wet-dry change, cost, low energy consumption；3) it directly obtains containing vanadium
The tungsten pig iron reduces subsequent job step；4) farthest reduce the pollution to environment.
Description of the drawings
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the recovery method process flow chart of titanium vanadium tungsten in the useless SCR denitration of the present invention.
Specific embodiment
The present invention provides a kind of recovery methods of titanium vanadium tungsten in useless SCR denitration, comprise the steps of：
(1) useless SCR denitration, ferriferous raw material, carbon raw material, binding agent and calcic raw material are mixed, is mixed
Material；
(2) the mixture granulating and forming for obtaining the step (1), obtains spherical material；
(3) the spherical material for obtaining the step (2) roasts, and obtains the pig iron of tungsten containing vanadium and titanium slag.
The present invention restriction special to the type of the useless SCR denitration and source is recycled the non-SCR after denitration and is urged
Agent.The present invention preferably pulverizes and sieves the useless SCR denitration that recycling obtains, and obtains granularity as 200~400 purposes
Powder raw material, then carry out the recycling of titanium vanadium tungsten；In the present invention, the useless SCR denitration preferably comprises following quality and contains
The component of amount：80~85% TiO2, 1~5% V2O5, 5~10% WO3, 2~5% SiO2, more preferably 81~84%
TiO2, 2~4% V2O5, 6~9% WO3, 3~4% SiO2, most preferably 82~83% TiO2, 2.5~3.5%
V2O5, 7.5~8.5% WO3, 3.4~3.6% SiO2。
The present invention mixes useless SCR denitration, ferriferous raw material, carbon raw material, binding agent and calcic raw material, is mixed
Close material.In the present invention, the ferriferous raw material preferably comprises sefstromite concentrate, Fe2O3、Fe3O4One or more of with iron powder
Mixture, the mixture is preferably the mixture of two kinds of ferriferous raw materials, more preferably sefstromite concentrate and Fe2O3Mixing
Object, the mixture of sefstromite concentrate and iron powder, Fe3O4With the mixture of iron powder.In the present invention, it is former to irony each in mixture
There is no limit those skilled in the art can select the mixing of the ferriferous raw material of arbitrary mass ratio to the mass ratio of material according to actual needs
Object；In the present invention, do not have to the source of the ferriferous raw material it is any specifically limited, using city well known to those skilled in the art
Sell commodity；
In the present invention, the mass content of iron is preferably 50~100% in the ferriferous raw material, more preferably 70~
90%, most preferably 80~85%.
In the present invention, the carbon raw material includes the mixture of one or more of coal dust, coke powder and graphite powder, institute
State the mixture that mixture is preferably two kinds of carbon raw materials, the more preferably mixture of coal dust and graphite powder, coke powder and graphite powder
Mixture.In the present invention, to the mass ratio of carbon raw material each in mixture, there is no limit those skilled in the art can basis
Actual needs selects the mixture of the carbon raw material of arbitrary mass ratio；In the present invention, do not have to the source of the carbon raw material
It is any specifically limited, using commercial goods well known to those skilled in the art；
In the present invention, the mass content of fixed carbon is preferably greater than 80% in the carbon raw material, more preferably 85~
99%, most preferably 90~95%.
In the present invention, the binding agent includes the mixing of one or both of polyvinyl alcohol and carboxymethyl cellulose
Object, to the mass ratio of binding agent each in mixture, there is no limit those skilled in the art can select arbitrary matter according to actual needs
Measure the mixture of the binding agent of ratio.
In the present invention, the calcic raw material includes the mixture of one or more of calcium oxide and calcium salt, the calcium
Salt is preferably calcirm-fluoride, calcium carbonate, calcium chloride, and the mixture is preferably the mixture of two kinds of calcic raw materials, more preferably oxygen
The mixture of the mixture of change calcium and calcirm-fluoride, calcium oxide and calcium carbonate.In the present invention, to calcic raw material each in mixture
There is no limit those skilled in the art can select the mixture of the calcic raw material of arbitrary mass ratio to mass ratio according to actual needs.
In the present invention, the granularity of the binding agent and calcic raw material is preferably independently 200~500 mesh, more preferably
250~400 mesh, most preferably 300~350 mesh.
The present invention does not have the source of the binding agent and calcic raw material any special limitation, using people in the art
Commercially available technical grade commodity known to member.
In the present invention, the mass ratio of the useless SCR denitration, ferriferous raw material and carbon raw material is preferably 100:80
~850:3~400, more preferably 100:120~650:20~350, most preferably 100:400~500:150~250；It is described
The quality of binding agent is preferably the 15~25% of mixture gross mass, more preferably 18~23%, most preferably 20~22%；Institute
The quality for stating calcic raw material is preferably the 7.0~15% of mixture gross mass, more preferably 9~12%, most preferably 10~
11%.
After obtaining mixture, mixture granulating and forming is obtained spherical material by the present invention.The present invention is to the granulating and forming
Method there is no special limitation, using the technical solution of granulation well known to those skilled in the art.In the present invention, institute
The pressure for stating granulating and forming is preferably 5~15MPa, more preferably 7~13MPa, most preferably 8~10MPa；The granulating and forming
Time be preferably 20~60s.
In the present invention, the equipment used the granulating and forming does not have any special restriction, using art technology
Granulating and forming equipment known to personnel, it is preferable to use hand hydraulic tablet press machine granulating and formings in embodiments of the present invention.
In the present invention, the diameter of the spherical material is preferably 15~40mm, more preferably 20~35mm, most preferably
25~30mm.
After obtaining spherical material, the present invention roasts the spherical material, obtains the pig iron of tungsten containing vanadium and titanium slag.In the roasting
Before burning, preferably the spherical material is dried by the present invention.The present invention does not have the mode of the drying any special limit
It is fixed, using the technical solution of drying well known to those skilled in the art；In the present invention, it is preferred to by the way of drying,
The temperature of the drying is preferably 100~130 DEG C, more preferably 110~125 DEG C, most preferably 115~120 DEG C, the drying
Time be preferably 1~5h, more preferably 2~4h, most preferably 3~3.5h.
In the present invention, the temperature of the roasting is preferably 1500~1650 DEG C, more preferably 1550~1600 DEG C, optimal
It is selected as 1570~1580 DEG C；It being kept the temperature under the calcination temperature, the time of the heat preservation is preferably 1~3h, more preferably 1.5~
2.5h, most preferably 1.8~2.2h.
In the present invention, there is no any special restriction to the environment of the roasting, it is ripe using those skilled in the art institute
The baking modes known.
In the present invention, there is no any special restriction to the mode of the roasting, using known to those skilled in the art
Baking modes.Preferably roasted in crucible in embodiments of the present invention, the crucible can be specially graphite crucible,
One kind in corundum crucible.
After the roasting, the present invention preferably cools down the material after roasting, obtains the pig iron of tungsten containing vanadium and titanium slag.Specifically,
Material after the roasting is cooled to room temperature by the present invention.
The pig iron of tungsten containing vanadium and the isolated pig iron of tungsten containing vanadium of titanium slag and titanium slag will be preferably obtained in the present invention, and to containing vanadium
The tungsten pig iron carries out chemical composition and Metallographic Analysis, and the chemical composition of titanium slag is analyzed.
Fig. 1 is the recovery method process flow chart of titanium vanadium tungsten in the useless SCR denitration of the present invention, and useless SCR denitration is urged
Agent, ferriferous raw material, carbon raw material, binding agent and the mixing of calcic raw material, obtain mixture, mixture obtains after granulating and forming
Spherical material, then obtained spherical material is roasted, obtain the pig iron of tungsten containing vanadium and titanium slag.
The present invention provides a kind of recovery methods of titanium vanadium tungsten in useless SCR denitration, are returned different from wet-dry change technique
Useless SCR denitration is received, pyrogenic process is employed and returns the metal oxide in useless SCR catalyst directly in the form of alloying
It receives, has the following advantages：1) it is directly recycled using iron member carbothermic method, saves complicated operation, technological process is simple, a step
In place；2) equipment is simple, recycles useless SCR denitration technique compared with wet-dry change, cost, low energy consumption；3) it directly obtains containing vanadium
The tungsten pig iron reduces subsequent job step, and the rate of recovery of vanadium>80%, the rate of recovery of tungsten>60%；4) farthest reduce
Pollution to environment.
The recovery method of titanium vanadium tungsten in useless SCR denitration provided by the invention is carried out with reference to embodiment detailed
Explanation, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) useless SCR denitration 100g is taken, wherein 1.50g containing v element, 5.50g containing wolfram element, Fe2O3Powder
933.6g, coke powder 315.0g add in polyvinyl alcohol adhesive 229.7g, calcium oxide 121.7g after mixing；
(2) by after mixture is sufficiently mixed in (1) step, using hand hydraulic tablet press machine pressure ball, each ball during pressure ball
Group demoulds after about 20s is kept under the pressure of 5MPa；
(3) the spherical material obtained in (2) step is put into drying equipment, is taken out after drying 1h at 100 DEG C；
(4) spherical material dried in (3) step is put into black-fead crucible, after high temperature resistance furnace is raised to 1550 DEG C
Crucible is put into stove, taking out protection after heat preservation 1h is cooled to room temperature；
(5) slag gold in (4) step is directly separated, the pig iron of tungsten containing vanadium weight 700.8g, titanium slag weight 228.6g.What is prepared contains vanadium
The main chemical compositions of the tungsten pig iron are shown in Table 1, and the main chemical compositions of titanium slag are shown in Table 2.Vanadium can be calculated by the data of table 1
The rate of recovery is 61.8%, and the rate of recovery of tungsten is 38.7%.By to containing vanadium tungsten pig iron Metallographic Analysis, being organized as ledeburite, pearly-lustre
Body or ferrite.
The main chemical compositions (wt.%) of 1 pig iron of tungsten containing vanadium of table
| V | W | Si | Fe | Ti |
| 0.132 | 0.304 | 0.067 | 90.43 | 0.007 |
The main chemical compositions (wt.%) of 2 titanium slag of table
| TiO2 | FeO | V2O5 | MgO | CaO | SiO2 | WO3 |
| 37.15 | 11.20 | 1.026 | 2.849 | 53.20 | 1.34 | 1.86 |
Embodiment 2
(1) useless SCR denitration 10g is taken, wherein 0.2g containing v element, 0.60g containing wolfram element, Fe3O4Powder 45.0g,
Iron powder 60g, coke powder 16.88g, graphite powder 10.0g, CaO18.0g add in PVA binding agents 26.72g after mixing；
(2) after the raw material that binding agent is added in (1) step is sufficiently mixed, hand hydraulic tablet press machine pressure ball, pressure are used
Each pelletizing demoulds after about 60s is kept under the pressure of 15MPa during ball；
(3) the spherical material obtained in (2) step is put into drying equipment, is taken out after drying 5h at 130 DEG C；
(4) spherical material dried in (3) step is put into black-fead crucible, after high temperature resistance furnace is raised to 1650 DEG C
Crucible is put into stove, taking out protection after heat preservation 3h is cooled to room temperature；
(5) slag gold in (4) step is directly separated, the pig iron of tungsten containing vanadium weight 93.09g, titanium slag weight 29.67g.What is prepared contains vanadium
The main chemical compositions of the tungsten pig iron are shown in Table 3, and the main chemical compositions of titanium slag are shown in Table 4.Vanadium can be calculated by the data of table 3
The rate of recovery is 78.2%, and the rate of recovery of tungsten is 50.3%.By to containing vanadium tungsten pig iron Metallographic Analysis, being organized as ledeburite and pearly-lustre
Body.
The main chemical compositions (wt.%) of 3 pig iron of tungsten containing vanadium of table
| V | W | Si | Fe | Ti |
| 0.168 | 0.324 | 1.405 | 92.15 | 0.756 |
The main chemical compositions (wt.%) of 4 titanium slag of table
| TiO2 | FeO | V2O5 | MgO | CaO | SiO2 | WO3 |
| 27.64 | 29.49 | 0.64 | 2.56 | 50.67 | 3.05 | 1.25 |
Embodiment 3
(1) useless SCR denitration 10g is taken, wherein 0.50g containing v element, 1.00g containing wolfram element, sefstromite concentrate
35.0g Fe2O3Powder 95.0g, coal dust 30.0g, graphite powder 5.0g, CaO26.0g add in carboxymethyl cellulose and glue after mixing
Tie agent 39.2g；
(2) after the raw material that binding agent is added in (1) step is sufficiently mixed, hand hydraulic tablet press machine pressure ball, pressure are used
Each pelletizing demoulds after about 30s is kept under the pressure of 10MPa during ball；
(3) the spherical material obtained in (2) step is put into drying equipment, is taken out after drying 4h at 125 DEG C；
(4) spherical material dried in (3) step is put into black-fead crucible, after high temperature resistance furnace is raised to 1580 DEG C
Crucible is put into stove, taking out protection after heat preservation 2.5h is cooled to room temperature；
(5) slag gold in (4) step is directly separated, the pig iron of tungsten containing vanadium weight 88.3g, titanium slag weight 45.97g.What is prepared contains vanadium
The main chemical compositions of the tungsten pig iron are shown in Table 5, and the main chemical compositions of titanium slag are shown in Table 6.Vanadium can be calculated by the data of table 5
The rate of recovery is 80.4%, and the rate of recovery of tungsten is 68.8%.By to containing vanadium tungsten pig iron Metallographic Analysis, being organized as ledeburite and pearly-lustre
Body.
The main chemical compositions (wt.%) of 5 pig iron of tungsten containing vanadium of table
| V | W | Si | Fe | Ti |
| 0.455 | 0.779 | 1.021 | 91.37 | 0.865 |
The main chemical compositions (wt.%) of 6 titanium slag of table
| TiO2 | FeO | V2O5 | MgO | CaO | SiO2 | WO3 |
| 17.83 | 11.02 | 0.37 | 2.89 | 56.45 | 3.741 | 0.85 |
As seen from the above embodiment, in useless SCR denitration provided by the invention titanium vanadium tungsten recovery method, be different from
The useless SCR denitration of wet-dry change technique recycling, employs pyrogenic process by the metal oxide in useless SCR catalyst directly with alloy
The form recycling of change, is directly recycled using iron member carbothermic method, saves complicated operation, and technological process is simple, settles at one go,
Equipment is simple, recycles useless SCR denitration technique compared with wet-dry change, cost, low energy consumption, directly obtains the pig iron of tungsten containing vanadium, subtracts
Few subsequent job step, and the rate of recovery of vanadium is up to 80.4%, the rate of recovery of tungsten has reached 68.8%.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (6)
1. the recovery method of titanium vanadium tungsten in a kind of useless SCR denitration, which is characterized in that comprise the steps of：
(1) useless SCR denitration, ferriferous raw material, carbon raw material, binding agent and calcic raw material are mixed, obtains mixture, institute
State mixture of the binding agent for one or both of polyvinyl alcohol and carboxymethyl cellulose；The useless SCR denitration, iron
The mass ratio of matter raw material and carbon raw material is 100:80~850:3~400；
The quality of the binding agent is the 15~25% of mixture gross mass, and the quality of the calcic raw material is mixture gross mass
7.0~15%；
The useless SCR denitration is the powder raw material of 200~400 mesh, includes the component of following mass content：80~85%
TiO2, 1~5% V2O5, 5~10% WO3, 2~5% SiO2；
(2) the mixture granulating and forming for obtaining the step (1), obtains spherical material；
(3) the spherical material for obtaining the step (2) roasts, and obtains the pig iron of tungsten containing vanadium and titanium slag, the temperature of the roasting is
1500~1650 DEG C, the time of the roasting is 1~3h.
2. recovery method according to claim 1, which is characterized in that the ferriferous raw material in the step (1) includes vanadium titanium
Iron ore concentrate, Fe2O3、Fe3O4With the mixture of one or more of iron powder；
The mass content of iron is 50~100% in the ferriferous raw material.
3. recovery method according to claim 1, which is characterized in that carbon raw material in the step (1) include coal dust,
The mixture of one or more of coke powder and graphite powder, the mass content of fixed carbon is more than 80% in the carbon raw material.
4. recovery method according to claim 3, which is characterized in that fixed carbon in the carbon raw material in the step (1)
Mass content be 85~99%.
5. recovery method according to claim 1, which is characterized in that the calcic raw material in the step (1) includes oxidation
The mixture of one or more of calcium and calcium salt.
6. recovery method according to claim 1, which is characterized in that in the step (2) pressure of granulating and forming for 5~
15MPa, the time of the granulating and forming is 20~60s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610867480.0A CN106337133B (en) | 2016-09-30 | 2016-09-30 | The recovery method of titanium vanadium tungsten in a kind of useless SCR denitration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610867480.0A CN106337133B (en) | 2016-09-30 | 2016-09-30 | The recovery method of titanium vanadium tungsten in a kind of useless SCR denitration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106337133A CN106337133A (en) | 2017-01-18 |
| CN106337133B true CN106337133B (en) | 2018-06-29 |
Family
ID=57839609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610867480.0A Active CN106337133B (en) | 2016-09-30 | 2016-09-30 | The recovery method of titanium vanadium tungsten in a kind of useless SCR denitration |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106337133B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107354325B (en) * | 2017-07-07 | 2018-12-18 | 攀枝花学院 | A method of γ-TiAl-base alloy is prepared using useless SCR denitration as raw material |
| CN108677016B (en) * | 2018-05-18 | 2019-12-27 | 内蒙古科技大学 | Preparation method of metallurgical titanium slag and iron-titanium-vanadium alloy containing waste denitration catalyst |
| CN110193364A (en) * | 2019-06-04 | 2019-09-03 | 河北惠尔信新材料有限公司 | A kind of discarded SCR catalyst recycling technique |
| CN113005287B (en) * | 2021-02-26 | 2023-04-07 | 安徽工业大学 | Blast furnace pellet capable of being used for treating failure SCR denitration catalyst and preparation method thereof |
| CN113025812B (en) * | 2021-02-26 | 2023-05-12 | 安徽工业大学 | Pellet, preparation method thereof and molten iron |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1603439A (en) * | 2004-11-15 | 2005-04-06 | 四川川投峨眉铁合金（集团）有限责任公司 | Production method for extracting nickel by pyrogenic process |
| CN105886771A (en) * | 2015-01-26 | 2016-08-24 | 昆明冶金高等专科学校 | Method for efficiently collecting platinum group metals through mixing reduction smelting of iron powder and iron ores |
| CN105950873A (en) * | 2016-06-24 | 2016-09-21 | 浙江浙能催化剂技术有限公司 | Method for recycling vanadium, tungsten and titanium from waste SCR denitration catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962079B (en) * | 2012-11-27 | 2014-06-25 | 南京工业大学 | Regeneration method for waste vanadium-titanium-based SCR (Selective Catalytic Reduction) flue gas denitrification catalyst |
| CN105063360B (en) * | 2015-08-14 | 2018-02-27 | 神雾科技集团股份有限公司 | Handle the method and system of low titanium material |
-
2016
- 2016-09-30 CN CN201610867480.0A patent/CN106337133B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1603439A (en) * | 2004-11-15 | 2005-04-06 | 四川川投峨眉铁合金（集团）有限责任公司 | Production method for extracting nickel by pyrogenic process |
| CN105886771A (en) * | 2015-01-26 | 2016-08-24 | 昆明冶金高等专科学校 | Method for efficiently collecting platinum group metals through mixing reduction smelting of iron powder and iron ores |
| CN105950873A (en) * | 2016-06-24 | 2016-09-21 | 浙江浙能催化剂技术有限公司 | Method for recycling vanadium, tungsten and titanium from waste SCR denitration catalyst |
Non-Patent Citations (1)
| Title |
|---|
| V-W-Ti 基脱硝催化剂资源化回收;李冬芳等;《环境工程》;20151231;第33卷;335-338，397 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106337133A (en) | 2017-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106337133B (en) | The recovery method of titanium vanadium tungsten in a kind of useless SCR denitration | |
| CN102698737B (en) | 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 | |
| CN107090551B (en) | A kind of method of the direct vanadium extraction of vanadium titano-magnetite | |
| KR101281579B1 (en) | Method of leaching valuable metal in spent catalyst of denitrification using roasting water leaching | |
| CN102127654B (en) | Method for decomposing chromium-containing vanadium slag by using sodium hydroxide molten salt | |
| CN102071321B (en) | Method for extracting vanadium and chromium from vanadium-containing steel slag by high-alkalinity potassium hydroxide | |
| CN107299223B (en) | A kind of compound alkaline-leaching and vanadium extraction method of bone coal and its system | |
| CN105274341A (en) | Method for leaching metallic vanadium and metallic tungsten in waste selective catalytic reduction (SCR) denitration catalyst | |
| CN102337396A (en) | Iron-smelting metallized pellets prepared by utilizing metallurgical dust and mud and production method thereof | |
| CN106536765A (en) | Method for producing pellets and method for producing iron-nickel alloy | |
| CN115193877A (en) | Method for comprehensively utilizing aluminum ash resources | |
| CN107254584A (en) | The method of roasting and separation method of chromium vanadium titanium octahedral iron ore | |
| CN110218837A (en) | A kind of method of recycling harmlessness disposing aluminium ash | |
| CN104745826B (en) | It is a kind of to implement the method for carrying chromium by the way that chromium slag is carried out into sodium pellet roasting | |
| CN107287453A (en) | A kind of method of v-bearing steel slag ion exchange method vanadium extraction | |
| CN110317958A (en) | Alkaline oxygenated pelletizing and the method for vanadium extraction are smelted iron in a kind of preparation of vanadium iron material | |
| CN107523691B (en) | A method of extracting valuable metal from industrial produced wastes | |
| CN107416904A (en) | A kind of method for reclaiming component materials in waste and old SCR denitration | |
| CN105349778B (en) | Clean production method for recycling yellow phosphorus, iron oxide red or precious metal from ferrophosphorus | |
| CN106756050B (en) | The method that conbustion synthesis recycles waste denitration catalyst | |
| CN109943708A (en) | A kind of technique using rotary kiln production secondary zinc oxide | |
| CN106319230B (en) | A kind of Dry recovery is given up the method for Titanium vanadium tungsten in SCR catalyst | |
| CN105803190A (en) | Method for preparing cold-bonded pellets of low water content by using dry method electrostatic precipitator dust of converter gas | |
| CN108893600A (en) | A kind of method of troilite production iron acid pellet | |
| CN108085505A (en) | A kind of method of valuable component titanium high efficiency extraction in titanium-containing blast furnace slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201202 Address after: Room 202, building 5, Bailian innovation and Technology Industrial Park, 16 Xiaguang Avenue, Xingtang sub district office, Linquan County, Fuyang City, Anhui Province Patentee after: Fuyang Keyou Testing Technology Co.,Ltd. Address before: 617000 Airport Road, Panzhihua, Sichuan, No. 10 Patentee before: PANZHIHUA University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220217 Address after: 413599 Gaoming Industrial Park, Anhua Economic Development Zone, Yiyang City, Hunan Province Patentee after: HUNAN JINDIAO ENERGY TECHNOLOGY Co.,Ltd. Address before: 236400 Room 202, building 5, Bailian Innovation Technology Industrial Park, No. 16, Xiaguang Avenue, Xingtang sub district office, Linquan County, Fuyang City, Anhui Province Patentee before: Fuyang Keyou Testing Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A method for recovering titanium vanadium tungsten from waste SCR denitrification catalyst Granted publication date: 20180629 Pledgee: China Co. truction Bank Corp Yiyang branch Pledgor: HUNAN JINDIAO ENERGY TECHNOLOGY Co.,Ltd. Registration number: Y2024980009894 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |