CN106480310A - Method for removing alkali metal from metallurgical dust and mud - Google Patents
Method for removing alkali metal from metallurgical dust and mud Download PDFInfo
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- CN106480310A CN106480310A CN201510548302.7A CN201510548302A CN106480310A CN 106480310 A CN106480310 A CN 106480310A CN 201510548302 A CN201510548302 A CN 201510548302A CN 106480310 A CN106480310 A CN 106480310A
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- Prior art keywords
- mud
- alkali metal
- zinc
- solid waste
- iron
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 32
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 32
- 239000000428 dust Substances 0.000 title claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 53
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 18
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 239000002910 solid waste Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 33
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000001110 calcium chloride Substances 0.000 claims description 16
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 15
- 239000010802 sludge Substances 0.000 claims description 15
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 13
- 239000000920 calcium hydroxide Substances 0.000 claims description 13
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 13
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 235000013980 iron oxide Nutrition 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003546 flue gas Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011343 solid material Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 238000004939 coking Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 2
- 238000001465 metallisation Methods 0.000 abstract description 14
- 239000011734 sodium Substances 0.000 abstract description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011591 potassium Substances 0.000 abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 4
- 238000011946 reduction process Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 20
- 238000005453 pelletization Methods 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 239000008188 pellet Substances 0.000 description 7
- 150000001339 alkali metal compounds Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229910020451 K2SiO3 Inorganic materials 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001408630 Chloroclystis Species 0.000 description 1
- 241000254158 Lampyridae Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Inorganic materials [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000009491 slugging Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a method for removing alkali metal in metallurgical dust and mud, which has short process flow, is simple and easy to implement, and completely uses mature equipment of metallurgical enterprises; the method for removing alkali metals from metallurgical dust and mud is implemented in a horizontal moving bed reduction process, and is carried out for 20 min-40 min under the roasting temperature condition of 1100-1300 ℃, so that the metallized iron material with the metallization rate of more than 70 percent can be obtained, the removal rate of alkali metals of potassium and sodium reaches more than 90 percent, and the removal rate of zinc also reaches more than 96 percent.
Description
Technical field
The invention belongs to technical field of ferrous metallurgy, relate generally to a kind of metallurgical dust sludge and remove alkali-metal method.
Background technology
Traditional iron and steel enterprise all can produce substantial amounts of dirt mud solid waste in operations such as ironmaking, steel-making and steel rolling, accounts for total output of steel
More than 10%.Often contain a large amount of ferrum in these dirt mud and there is very high recovery value, returning sintering as dispensing is still mesh
Front topmost way of recycling, such as " method that a kind of ion dust mud contaning of CN102492833A is applied to sinter " etc., also have and join
Enter the mode that pelletizing is reclaimed, for example " CN200410040020.8 steel-smelting sewage sludge starches the method for pelletizing production pelletizing "
Deng, but there are a lot of problems in such method, because the physical parameter of dirt pug is larger with breeze materials variance, to sintering or pelletizing
Production and technical indication and product quality impact are larger;Often contain more alkali metal (K, Na), zinc (Zn) in dirt pug simultaneously
Deng harmful element, directly return raw material and a large amount of enrichments in blast furnace for the harmful element, impact blast furnace stable smooth operation and safety will be led to long
Longevity, therefore be extremely limited using the dirt mud amount that such method recycles, enterprise can only be stored up using a large amount of places, if dealing with improperly,
Not only caused the wasting of resources but also easily environment had been impacted.Therefore, how dirt mud solid wastes recycling more effectively to be reclaimed profit
With becoming an important topic of iron and steel enterprise.
As long as it is true that the harmful elements such as the alkali metal in dirt pug, zinc can effectively be removed, it recycles approach will very
Extensively.Presently, there are some treatment technologies for iron and steel enterprise's dirt mud dezincification, for example " CN101386913 rotary hearth furnace processes and contains
The method that zinc powder dirt reclaims zinc oxide ", " CN104073649A iron content zinc powder dirt recycle technique ", " CN101092664 contains zinc
The processing method of electric furnace dust ", is substantially and allocates the reducing agents such as coal into and make carbonaceous pelletizing, and then passes through rotary hearth furnace, shaft furnace etc.
Be reduced into metallized pellet, after zinc reduction, enter flue gas, above-mentioned process dirt mud patent have in common that universal just for removing zinc,
And actually all containing alkali metal and zinc in iron and steel enterprise's number of types of dirt mud solid waste simultaneously, the alkali metal in some dirt pugs contains
Amount is even above zinc, but because the reduction temperature ratio of zinc compound is relatively low, usual dezincification is relatively easy, and alkali metal compound is (such as
Alkali silicate) reduction temperature is generally higher, and relative difficulty is wanted in removing, ultimately results in alkali metal and still resides in metal in a large number
Change in raw material.In addition the patent such as " a kind of zinc-iron-containing dust of CN101818264A, processing method of mud " discloses and utilizes high temperature
Sludge pellet is reduced fusing by molten iron, makes reduced iron enter molten iron, and zinc enters flue gas, and other impurity enter the processing method of slag,
But the dirt mud treating capacity of the method is limited, otherwise may impact hot metal composition and temperature, simultaneously this method generally add firefly for slugging
Stone composition, the commonly used tank lining that easily causes corrodes.
To sum up, due to containing the harmful elements such as more alkali metal, zinc in dirt mud solid waste material, its recycling is extremely restricted,
The also many removings just for zinc of some treatment technologies that presently, there are or method, and how to realize alkali-metal efficient removal to entering one
It is great that step improves its recycling horizontal terms.
Technical scheme
The technical problem to be solved is to provide a kind of alkali-metal method in removing metallurgical dust sludge, to realize at 1100 DEG C
Under the conditions of~1300 DEG C, alkali metal in efficient removal iron and steel enterprise dirt mud solid waste material, thus be greatly improved metallurgical dust sludge resource
Using level.
For solving the above problems, the technical scheme is that:
1. in a kind of removing metallurgical dust sludge alkali-metal method it is characterised in that comprising the following steps:
(1). the chemical composition according to different metallurgical dust sludge carries out dispensing, and its composition includes dirt mud solid waste Glass Batch Quality percentage
Ratio for 85%~95%, binding agent mass percent 0%~5%, slaked lime mass percent 0%~10%, remaining is additive;
Control TFe >=40%, carbon content meets (C/O)=1.1~1.5 with the oxygen element total content mol ratio of iron oxides, zinc oxide,
CaO and SiO2Mass percent [CaO]/[SiO of composition2]=1.0~2.0, alkali metal (K, Na) and Cl elemental mole ratios
Meet (K+Na)/Cl=0.5~1.0;Described dirt mud solid waste batch includes blast furnace dedusting ash, gas mud, sintering dust separation ash, converter
Dedusting ash, revolving furnace mud, iron scale, iron oxide red, coking, dust removing ash in two or more;Described binding agent be starch or
One of other organic binder bonds;Described additive includes one of industrial calcium chloride, industrial hex-ammoniate;
(2). carry out reasonable dispensing according to each material chemical analysis, first will be fully broken to dirt mud solid waste batch, slaked lime solid material
Broken roll, then put it into and in batch mixer, carry out mixed once;Desired amount of additive and binding agent are added to the water simultaneously
It is made into aqueous solution, inject aqueous solution after solid material mix homogeneously and carry out secondary mixing;By final mixing after mix homogeneously
Material is sent in ball press, is pressed into 10mm~30mm agglomerate, standby after agglomerate drying to biodiversity percentage composition≤3%;
(3). using horizontal moving bed reducing process, dirt walk block is processed under the conditions of 1100 DEG C~1300 DEG C sintering temperatures
20min~40min, obtains the iron charge that metallizes after high temperature reduction roasting, and alkali metal enters flue gas removing in a chloride-form, with
When zinc also reduced removing in the lump.
The consumption of described slaked lime is according to CaO and SiO in described dirt mud solid waste batch2The mass percent of composition determines, if
Described CaO and SiO2Mass percent [CaO]/[SiO of composition2] be less than 1.0, then adding appropriate slaked lime makes [CaO]/[SiO2]
=1.0~2.0, otherwise need not add.
The CaCl of described industrial calcium chloride2Weight/mass percentage composition >=90%, the MgCl of described industrial hex-ammoniate2Weight/mass percentage composition
>=45%.
Described moving bed reducing process includes rotary hearth furnace process or the similar technique of other principle.
The dirt mud solid waste material by reasonably combined iron and steel enterprise for the present invention, makes high ferro dirt mud complementary with high carbon dust mud element, fully profit
The carbon itself being rich in dirt mud is it is not necessary to more additionally with addition of reducing agent, be pressed into pelletizing, further under the auxiliary of a small amount of binding agent
Carry out subsequent treatment in conjunction with pyrogenic process direct-reduction technique, can the harmful element such as efficient removal alkali metal, and obtain metallization iron charge,
Thus its recycling level is greatly improved.
In order that the metallization iron charge obtaining after processing reaches certain taste, dirt mud batch TFe content to be properly increased, simultaneously
Take into account rationally a large amount of adapteds of dirt pug, substantially control the balance that can meet in TFe >=40% from the aspect of two.
Pass through to control carbon-to-oxygen ratio (C/O) simultaneously, make to join that carbon is suitably excessive in pelletizing, the reducing atmosphere of such pelletizing bed of material and temperature
Degree is readily obtained guarantee, and test shows under the range of condition of (C/O)=1.1~1.5, and iron oxides and zinc impregnation in sludge pellet of the present invention is closed
Thing can sufficiently be reduced.
In dirt mud solid waste material, removing zinc is reduced directly relatively easily by pyrogenic process, because reduction started temperature all phases of zinc compound
To relatively low, be will also realize that by calculation of thermodynamics, ferrite (the ZnO Fe of zinc2O3), silicate (2ZnO SiO2), oxygen
Compound (ZnO) etc. and C direct reduction reactor can occur below at 1000 DEG C substantially, much studied and also indicated that and will realize
The more thoroughly removing of zinc is relatively easy, and the reduction relative difficulty of alkali metal K, Na compound is many, such as silicate (K2SiO3、
Na2SiO3), carbonate (K2CO3、Na2CO3) etc., its direct-reduction is temperature required higher, and the especially reduction of silicate needs
The high temperature wanting 1600 DEG C about just starts to react, and therefore removes alkali metal relative difficulty by high temperature reduction.And the present invention is due to adopting
With chloride additive so as to remove the easy, in CaCl of change2Or MgCl2In the presence of, alkali metal compound can be with
Its generation displacement reaction generates corresponding alkali metal chloride, and reaction is as follows (with K compound, CaCl2As a example):
K2SiO3+ C=2K+CO+SiO2→K2SiO3+CaCl2=2KCl+CaSiO3
K2CO3+ 2C=2K+3CO → K2CO3+CaCl2=2KCl+3CaCO3
Thermodynamically the reaction Gibbs free energy of the latter is negative value always, and is easy to wave under alkali metal chloride hot conditionss
Send out, add quick flow of flue gas purification, make the thermodynamics and kineticses condition of reaction all ideal, so that alkali is golden
Belonging to also being capable of efficient removal.In order to ensure the abundant of reaction, the consumption of agent is accordingly suitably excessively added, research shows in alkali metal
Under conditions of meeting (K+Na)/Cl=0.5~1.0 with Cl elemental mole ratios, optimal dealkalize effect can be obtained.
Test finds further, can play facilitation to the removing of alkali metal and zinc under a certain amount of CaO existence condition,
Think that the compounds such as zinc ferrite, zinc silicate, alkali silicate can occur correlated response further with CaO, make
The reduction reaction of these compounds or displacement reaction temperature have the trend reducing further, therefore properly increase basicity to removing alkali
Metal and zinc are all favourable, control basicity in [CaO]/[SiO2Removal efficiency highest during]=1.0~2.0 scope.And in major part dirt mud
Natural alkalinity all higher, essentially without additionally condition can be met with addition of material containing CaO, when need on a small quantity with addition of when,
Consider that slaked lime fully digests, have certain colloidal nature simultaneously concurrently, therefore select not using limestone with addition of slaked lime.
Sludge pellet of the present invention is used in horizontal moving bed class reducing process processing, can achieve alkali-metal efficient removal,
The final metallization iron charge obtaining degree of metalization more than 70%, potassium, soda metal removal rate reach more than 90%.
Beneficial effects of the present invention:
1. the dirt mud solid waste material by reasonably combined iron and steel enterprise for the inventive method, can make full use of the carbon being wherein rich in,
Metallization iron charge product need not finally be obtained again additionally with addition of reducing agent, pass through in addition to add appropriate additive and adjust suitably
Basicity, makes the alkali metal compound of difficult reduction be replaced into volatile chloride removing, thus realizing the height to dirt mud solid waste material
Effect dealkalize is processed, and its recycling level is greatly improved.
2. the inventive method process flow is short, simple and easy to do, all using smelter mature equipment;Using present invention removing
The alkali-metal method of metallurgical dust sludge, implements, in horizontal moving bed reducing process under the conditions of 1100 DEG C~1300 DEG C sintering temperatures
Process 20min~40min, the metallization iron charge that degree of metalization is more than 70% can be obtained, potassium, soda metal removal rate reach 90%
More than, zinc removal efficiency also reaches more than 96% simultaneously.
Brief description
Fig. 1 is the inventive method schematic flow sheet.
Specific embodiment
Illustrate with reference to specific embodiment:
Embodiment 1
Dirt mud solid waste batch uses revolving furnace mud, blast furnace gas mud, blast furnace dedusting ash, blast furnace dust, iron scale, according to
Its chemical composition carries out reasonably combined, controls TFe >=40% of dirt mud solid waste batch, control simultaneously carbon content and iron oxides,
The oxygen element total content mol ratio of zinc oxide meets (C/O)=1.1, obtains dirt mud batch composition as shown in table 1.According to dirt
It is [CaO]/[SiO that mud solid waste batch detection composition calculates basicity2]=1.55, can not be with addition of slaked lime in the present embodiment.
The present embodiment uses industrial chlorinations calcium additive (CaCl2Content 92%), according to the alkali metal of dirt mud solid waste batch
Learn component molar ratio [(K+Na)/Cl]=0.5~1.0, can be calculated 100g dirt mud solid waste batch needs with addition of 2.7g~5.4g
CaCl2, converting as industrial calcium chloride is 2.9~5.9g.
By above-mentioned dirt mud solid waste Glass Batch Quality percentage ratio 90%, industrial calcium chloride mass percent 5%, starch quality percentage ratio
5% gets the raw materials ready.First roll fully broken for the solid materials such as dirt mud solid waste batch, then put it in batch mixer and carry out once
Mixing;Desired amount of industrial calcium chloride and starch are added in suitable quantity of water simultaneously and be made into aqueous solution, treat solid material mix homogeneously
Inject aqueous solution afterwards and carry out secondary mixing, after mix homogeneously send into final mixed material in ball press, be pressed into
10mm~30mm agglomerate, after agglomerate drying to moisture≤3%, described sludge pellet is used in rotary hearth furnace process, in roasting
Reduction roasting 40min at 1150 DEG C of temperature, joins under carbon effect, iron oxides and zinc oxide are all reduced sufficiently in excess,
And the alkali metal compound of hardly possible reduction is also replaced into volatile chloride, under quick flow of flue gas purification, volatilization
Zinc and alkali metal chloride are constantly taken away by flue gas, thus realizing efficient removal, analyze after testing, finally obtain degree of metalization
81.2% metallization iron charge, and the removal efficiency of potassium is 92.4%, and sodium removal efficiency is 90.5%, and zinc removal efficiency also reaches simultaneously
97.5%.
Table 1 dirt mud solid waste batch chemical composition %
TFe | FeO | C | SiO2 | CaO | K2O | Na2O | Zn |
45.13 | 31.78 | 16.16 | 4.37 | 6.76 | 1.35 | 0.62 | 2.31 |
Embodiment 2
According to embodiment 1 same steps, dirt mud solid waste batch uses blast furnace dedusting ash, gas mud, sintering dust separation ash, converter
Dedusting ash, revolving furnace mud, iron scale, iron oxide red, coking, dust removing ash, carry out according to its chemical composition reasonably combined, control dirt mud
TFe >=40% of solid waste batch, controls carbon content full with the oxygen element total content mol ratio of iron oxides, zinc oxide simultaneously
Foot (C/O)=1.5.Detect that composition calculates basicity [CaO]/[SiO according to dirt mud solid waste batch2]=0.92, passes through in the present embodiment to join
Plus 0.5g~7.2g slaked lime can adjust basicity and reach 1.0~2.0 scopes.
The present embodiment uses industrial chlorinations magnesium additive (MgCl2Content 45%), according to the alkali metal of dirt mud solid waste batch
Learn component molar ratio [(K+Na)/Cl]=0.5~1.0, can be calculated 100g dirt mud solid waste batch needs with addition of 3.1g~6.2g
MgCl2, convert and need with addition of 6.9g~13.8g for industrial hex-ammoniate.
By above-mentioned dirt mud solid waste Glass Batch Quality percentage ratio 86%, slaked lime mass percent 4%, industrial hex-ammoniate percent mass
Get the raw materials ready than 10%.First the solid materials such as dirt mud solid waste batch, slaked lime are carried out crushing and roll, then put it into batch mixing
Carry out mixed once in machine;Desired amount of industrial hex-ammoniate is added in suitable quantity of water simultaneously and be made into additive solution, treat solidss
Inject additive aqueous solution after material mix homogeneously and carry out secondary mixing, after mix homogeneously, final mixed material is sent into ball press
In, it is pressed into 10mm~30mm pelletizing, after pelletizing drying to moisture≤3%, described sludge pellet is used for car-type reduction
In furnace technology, reduction roasting 20min at 1300 DEG C of sintering temperature, joins under carbon effect, iron oxides and zinc oxygen in excess
Compound is all reduced sufficiently, and the alkali metal compound of difficult reduction is also replaced into volatile chloride, in quick flow of flue gas
Under purification, the zinc of volatilization and alkali metal chloride are constantly taken away by flue gas, thus realizing efficient removal, analyze after testing,
The final metallization iron charge obtaining degree of metalization 93.2%, and the removal efficiency of potassium is 95.1%, and the removal efficiency of sodium is 92.0%,
The removal efficiency of zinc reaches 99.2% simultaneously.
Embodiment 3
According to embodiment 1 same steps, dirt mud solid waste batch uses blast furnace dedusting ash, revolving furnace mud, is entered according to its chemical composition
Row is reasonably combined, controls TFe >=40% of dirt mud solid waste batch, controls carbon content and iron oxides, zinc oxide simultaneously
Oxygen element total content mol ratio meets (C/O)=1.3.Detect that composition calculates basicity according to dirt mud solid waste batch
[CaO]/[SiO2]=1.38, can not be with addition of slaked lime in the present embodiment.
Using industrial calcium chloride (CaCl in the present embodiment2Content 90%) additive, according to the alkali metal of dirt mud solid waste batch
Chemical composition mol ratio [(K+Na)/Cl]=0.5~1.0, can be calculated 100g dirt mud solid waste batch needs with addition of 3.4g~6.8g's
CaCl2, converting as industrial calcium chloride is 3.8g~7.6g.
By above-mentioned dirt mud solid waste Glass Batch Quality percentage ratio 94%, industrial calcium chloride mass percent 4.5%, polyacrylamide
(PAM) mass percent 1.5% is got the raw materials ready.First the solid materials such as dirt mud solid waste batch are carried out crushing and roll, then by it
Put into and in batch mixer, carry out mixed once;Simultaneously water-soluble by being made in desired amount of industrial calcium chloride and PAM addition suitable quantity of water
Liquid, injects aqueous solution after solid material mix homogeneously and carries out secondary mixing, after mix homogeneously send into final mixed material
In ball press, it is pressed into 10mm~30mm pelletizing, after pelletizing drying to moisture≤3%, described sludge pellet is used for turning bottom
In furnace technology, reduction roasting 30min at 1250 DEG C of sintering temperature, joins under carbon effect, iron oxides and zinc oxygen in excess
Compound is all reduced sufficiently, and the alkali metal compound of difficult reduction is also replaced into volatile chloride, in quick flow of flue gas
Under purification, the zinc of volatilization and alkali metal chloride are constantly taken away by flue gas, thus realizing efficient removal, analyze after testing,
The final metallization iron charge obtaining degree of metalization 73.9%, and the removal efficiency of potassium is 93.1%, and the removal efficiency of sodium is 90.3%,
The removal efficiency of zinc also reaches 97.2% simultaneously.
Claims (1)
1. in a kind of removing metallurgical dust sludge alkali-metal method it is characterised in that comprising the following steps:
(1). the chemical composition according to different metallurgical dust sludge carries out dispensing, and its composition includes dirt mud solid waste Glass Batch Quality percentage
Ratio for 85%~95%, binding agent mass percent 0%~5%, slaked lime mass percent 0%~10%, remaining is additive;
Control TFe >=40%, carbon content meets (C/O)=1.1~1.5 with the oxygen element total content mol ratio of iron oxides, zinc oxide,
CaO and SiO2Mass percent [CaO]/[SiO of composition2]=1.0~2.0, alkali metal (K, Na) and Cl elemental mole ratios
Meet (K+Na)/Cl=0.5~1.0;Described dirt mud solid waste batch includes blast furnace dedusting ash, gas mud, sintering dust separation ash, converter
Dedusting ash, revolving furnace mud, iron scale, iron oxide red, coking, dust removing ash in two or more;Described binding agent be starch or
One of other organic binder bonds;Described additive includes one of industrial calcium chloride, industrial hex-ammoniate;
(2). carry out reasonable dispensing according to each material chemical analysis, first will be fully broken to dirt mud solid waste batch, slaked lime solid material
Broken roll, then put it into and in batch mixer, carry out mixed once;Desired amount of additive and binding agent are added to the water simultaneously
It is made into aqueous solution, inject aqueous solution after solid material mix homogeneously and carry out secondary mixing;By final mixing after mix homogeneously
Material is sent in ball press, is pressed into 10mm~30mm agglomerate, standby after agglomerate drying to biodiversity percentage composition≤3%;
(3). using horizontal moving bed reducing process, dirt walk block is processed under the conditions of 1100 DEG C~1300 DEG C sintering temperatures
20min~40min, obtains the iron charge that metallizes after high temperature reduction roasting, and alkali metal enters flue gas removing in a chloride-form, with
When zinc also reduced removing in the lump.
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