CN101054629A - Method of treating sodium-silicon slag by chlorination method - Google Patents
Method of treating sodium-silicon slag by chlorination method Download PDFInfo
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- CN101054629A CN101054629A CNA2007100157633A CN200710015763A CN101054629A CN 101054629 A CN101054629 A CN 101054629A CN A2007100157633 A CNA2007100157633 A CN A2007100157633A CN 200710015763 A CN200710015763 A CN 200710015763A CN 101054629 A CN101054629 A CN 101054629A
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- Prior art keywords
- sodium
- slag
- chlorination
- white residue
- silicon
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- 238000000034 method Methods 0.000 title claims abstract description 101
- 239000002893 slag Substances 0.000 title claims abstract description 56
- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 47
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical compound [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 title claims description 20
- 239000011734 sodium Substances 0.000 claims abstract description 68
- 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 claims abstract description 63
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 63
- 238000005406 washing Methods 0.000 claims abstract description 36
- 239000000460 chlorine Substances 0.000 claims abstract description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000012545 processing Methods 0.000 claims abstract description 9
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 7
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 6
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000004568 cement Substances 0.000 claims abstract description 4
- 230000002829 reductive effect Effects 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 238000011282 treatment Methods 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 33
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 5
- 230000001698 pyrogenic effect Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 238000005245 sintering Methods 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 239000003513 alkali Substances 0.000 description 10
- 238000004131 Bayer process Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 229910001570 bauxite Inorganic materials 0.000 description 4
- 239000003518 caustics Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 208000012639 Balance disease Diseases 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001238 wet grinding Methods 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
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The present invention relates to a process for processing sodium white slime through chlorin-ation routeand belongs to the field of non-ferro metals pyrogenic process chlorine metallurgy.Said method comprises the following steps:(1) adding a reducing reagent to sodium white slime, and adding them continuouly to a fluidized bed chlorination furnace to perform a chloridization process to realize a section of selection chloridization of sodium in sodium white slime;(2) washing the chloridized slag with water to get a sodium chloride solution to realize separation of sodium elementand get rinshing slag at the same time;(3) after being washed again and dryed, the rinshing slag being added to a high temperature furnace for a calcinationto get mullite; (4)condensating and separating the chloridized tail gas through a condensatorto get aluminum chloride and silicon tetrachloride solution respectively, wherein the chloridized slags are washed using water and then preserved for making cement. By dealing with waste slags to obtain useful components, the present invention reduces the manufacturing cost of aluminum oxide.
Description
Technical field
The present invention relates to a kind of method of method for the treatment of sodium-silicon slag by chlorination, handle waste residue, obtain useful component, belong to non-ferrous metal pyrogenic process dchlorine metallurgy field.
Background technology
Hydrated aluminum silicate [Na
2O.Al
2O
3.xSiO
2(6-2x) H
2O] be the sodium white residue, the reaction product of most important silicon mine when being alkaline process processing bauxite.The key that alkaline process is produced aluminum oxide is that aluminium, silicon separate, and in the process of Bayer process high pressure stripping diaspore, nearly all silicon mine all is active at home, will and mainly enter red mud with sodium white residue form with the sodium aluminate solution reaction mostly; In the process for desiliconizing crude liquid obtained by sinter process, the SiO more than 90%
2Also from solution, separate out with the form of sodium white residue.Contain a large amount of alkali and aluminum oxide in the sodium white residue, and the quantity of slag (when the medium grade ore of Bayer process high pressure stripping ore deposit and in the process for desiliconizing crude liquid obtained by sinter process, reaches 1000kg/t-Al respectively greatly approximately in producing
2O
3And 200kg/t-Al
2O
3).
Adopt white residue to produce cement, because the too high (K of white residue alkali content
2O+Na
2O generally is higher than 5%), therefore have to reduce white residue proportioning in the raw material, make a large amount of white residues not utilize.In order to reclaim alkali and the aluminium in the white residue, alumina producing factory generally adopts mixed combining method, as sintering process sodium white residue and Bayer process red mud are returned the wet-milling burden process, carry out sintering after the adjustment of process slip together with ore, this traditional white residue is batching later, though reclaimed certain aluminum oxide and sodium oxide, also made a large amount of SiO
2Come back in the flow process, it accounts for total more than 17% of silicon amount in the sintering process.When batching in order to make SiO
2In sintering process, form 2CaO.SiO
2, need allocate a large amount of calcium oxide into, thereby reduce the content of aluminum oxide in the grog greatly and improved the grog reduced ratio; Owing to red mud and sodium white residue are brought a large amount of attached liquid (water ratio reaches as high as 50%) into and needed to guarantee its water ratio for the flowability that guarantees charge pulp, cause steaming in the chamotte kiln increase of the water yield, cause the invalid circulation of aluminum oxide, sodium oxide simultaneously, the sodium aluminate in the attached liquid is through expensive grog sintering circuit; Water, vapour, soda balance difficulty, the production stability variation.Existing sodium white residue aluminium silicon isolation technique is alumina producing energy consumption and the high major cause of cost.Therefore, need seek cost-effective method for the processing of sodium white residue and seem very urgent.
The content of the silicon-dioxide in the sodium white residue is higher, USSR (Union of Soviet Socialist Republics), and the novel process of wet processing sodium white residue is being studied always by Hungary and China, has proposed such as methods such as high pressure aquation method and hydrothermal methods.
High pressure aquation method is to use high density (325g/L-500g/L), high a down at high temperature (280-300 ℃)
k(ie in solution Na
2O
K/ Al
2O
3Molecular ratio) solution-treated obtains a after the stripping
kSodium aluminate solution for 12-14.Silicon oxide is stayed in the slag with the form of calcium silicate hydrate, and aluminum oxide enters solution with the form of sodium aluminate, reaches the isolating purpose of aluminium silicon.The sodium white residue mixes with lime and circulating mother liquor, and stripping under high pressure obtains the aluminate slurries, separates and a body refuse washing, and the body refuse after the washing is handled under high pressure in sig water, just can obtain sodium aluminate solution.This method has been avoided high-temperature sintering process, Al
2O
3Leaching yield about 70%, the leaching yield of alkali reaches 97-98%, the alkali that obtains is caustic alkali.
The research department of USSR (Union of Soviet Socialist Republics) has carried out technological economics evaluation to the scheme of multiple high pressure aquation method, and the effect in these schemes processing nepheline ore deposits is better than soda-lime sintering process certainly.Because their energy consumption is far below sintering process; And need not the required high-grade fuel of sintering.Amount of lime can be saved half.High pressure aquation method can comprehensively reclaim aluminum oxide and sodium oxide wherein, Na in the waste
2O content＜1%, A/S are less than 0.5, but this method has a lot of shortcomings: the concentration of sodium aluminate solution fluid is big, caustic ratio is high; The Recycling Mother Solution amount is big; Leaching condition is very harsh, requires the equipment can high temperature resistant and high pressure, at high temperature handles high a
k, high-alkalinity solution will increase investment with lining nickel equipment.The alkali lye a that the aquation method obtains
kGreater than 10, be difficult to get back in the Bayer process system Al in the dissolution fluid
2O
3Further reclaim very difficult.High pressure aquation method does not obtain industrial application so far.
Hydrothermal method adopts the loose slightly condition of higher pressure aquation method, uses a
kBe that about 4.0 solution is handled, the rate of recovery of alkali can reach 80-90%, and the alumina recovery rate is low, has only 10-20%, and the alumina silica ratio after the processing is still greater than 1.Contain a large amount of [OH in this method stripping temperature height and the dissolution fluid
-], easy etching reactor.This test was once done by Shenyang magnalium designing institute, and in order to solve the problem of caustic corrosion, they have designed the titanium alloy reactor especially, but [the Cl in the dissolution fluid
-] same etching reactor, chlorion mainly is to be brought into by bauxite, liquid caustic soda and service water etc., presses when boiling and enters flow process with ionic species.As seen, this method also be have circumscribed.Because technology and economic dispatch aspect, two kinds of methods all are difficult to industrial application.
Except high pressure aquation method and hydrothermal method, also having a kind of method is exactly the residue that reclaims in the yellow soda ash system after the dealkalize for the recovery of sodium white residue.This method is that residue was used certain density Na after the dealkalize of sodium white residue was handled in autoclave under the certain reaction condition
2CO
3Solution-treated, the slag after the processing carries out secondary treatment with caustic solution.This method can reclaim alkali wherein, and the rate of recovery reaches 90%, also can reclaim certain aluminum oxide, but the rate of recovery of aluminum oxide is lower, and the A/S in the waste is greater than 0.7.This method does not need high temperature high pressure process, does not have special requirement for equipment, but this method flow is longer, and primary treatment can not reach the purpose that reclaims aluminum oxide, and there are many uncertain factors in this method in addition.
Summary of the invention
The object of the present invention is to provide a kind of method of method for the treatment of sodium-silicon slag by chlorination, handle waste residue, obtain useful component, reduce manufacturing cost of aluminum oxide.
The method of method for the treatment of sodium-silicon slag by chlorination of the present invention, step is as follows:
(1) in the sodium white residue, adds reductive agent, join continuously and carry out chlorination in the boiling chloridizing furnace, realize one section selective chlorination of sodium element in the sodium white residue;
(2) chloride slag is washed and is obtained sodium chloride solution, realizes the separation of sodium element, obtains washing slag simultaneously;
(3) join roasting in the High Temperature Furnaces Heating Apparatus after will washing slag secondary washing oven dry, obtain mullite;
(4) chlorinated exhaust obtains aluminum chloride and silicon tetrachloride solution respectively through the condensation separation of condenser, and the washing chloride slag retains and is used for cement baking.
Can adopt an above-mentioned step to handle, also can adopt two step treatment processs, after the oven dry of washing slag, add reductive agent once more, join continuously and carry out chlorination in the boiling chloridizing furnace, realize two sections selective chlorinations of silicon, aluminium element in the sodium white residue.
Among the present invention:
Reductive agent is a carbon material, and as Graphite Powder 99, coke powder etc., the granularity of carbon dust (d50) is controlled to be: 20-200um, be preferably 40-140um, and sodium white residue and reductive agent mass ratio are: 15-20: 2-4 is preferably 10: 1.Wherein the sodium white residue is the oven dry material.
One section chlorination temperature is 400-550 ℃, is preferably 450-550 ℃, and time of chlorinating control 10-20min is preferably 12-17min, and the chlorine dominant discharge is a 0.1-0.5kg/min.kg sodium white residue, preferred 0.1-0.25kg/min.kg sodium white residue.
Adopt distilled water normal temperature washing chloride slag in tank, liquid-solid ratio control 4-5: 1, filtration washing obtains sodium chloride solution.
The washing slag adds the tank washing once more, liquid-solid ratio control 9-10: 1, and washed twice is to PH=7, join roasting in the High Temperature Furnaces Heating Apparatus after the oven dry, 1500-2000 ℃ of maturing temperature control, preferred 1800-1950 ℃, time control 1.5-2.0 hour obtains alumina content greater than 40% mullite.
In the secondary chlorination:
The granularity of carbon dust (d50) is controlled to be: 20-200um, be preferably 40-80um, and sodium white residue and reductive agent mass ratio are 6-12: 1-3, are preferably 7: 1.
Time of chlorinating control 10-25min is preferably 15-20min, and the chlorine dominant discharge is a 0.2-1.0kg/min.kg washing slag, preferred 0.3-0.45kg/min.kg washing slag.
Chlorination temperature is 700-1000 ℃, more preferably 750-900 ℃.
Chlorination of the present invention can adopt single stage method to handle:
The sodium white residue is the oven dry material, and reductive agent is a carbon material, and as Graphite Powder 99, coke powder etc., the granularity of carbon dust (d50) is controlled to be: 20-200um, be preferably 40-140um, and sodium white residue and reductive agent mass ratio are: 5-20: 1-4 is preferably 5: 1.
Chlorination temperature 700-1000 ℃ technology is preferably 750-900 ℃, and time of chlorinating control 10-30min is preferably 15-25min, and the chlorine dominant discharge is a 0.1-0.7kg/min.kg sodium white residue, preferred 0.2-0.55kg/min.kg sodium white residue.
30-70 ℃ of the condensing temperature control of silicon tetrachloride solution, 120-200 ℃ of the condensing temperature control of liquor alumini chloridi.
The inventive method has following characteristics:
(1) raw materials for production are product desiliconizing crude liquid obtained in the alumina producing flow process, utilize according to this method, have extended industrial chain, have reduced the alumina producing link, cut down the consumption of energy, and have reduced alumina production cost.
(2) adopt pyrogenic process chlorating way to handle the sodium white residue, realized the selective chlorination of element in the sodium white residue, and realized effective separation.
(3) processing parameter is controlled easily, and the element effective rate of utilization can reach more than 95%.
(4) the Technology flow process can make up, and produces alumina content greater than 40% mullite.
(5) production cost is low, and resultant purity height, primary product are the chlorinated solution of silicon, aluminium, sodium, and the resultant market capacity is big, has established and has applied the basis.
(6) alkali recovery is greater than 99%, and the alumina recovery rate is produced simultaneously and adopted short flow process greater than 95%, realizes that the sodium aluminium silicon in the sodium white residue separates available then similar flow process individual curing Bayer process red mud and the sodium white residue in the sintering process.
(7) not only can make Bayer process can directly handle medium grade alumyte, solve the day by day exhausted contradiction of higher-grade bauxite (alumina silica ratio is greater than 10), and can make sintering process system only handle bauxite, make sintering system realize energy-conservation significantly and consumption reduction, this helps bringing into play to greatest extent the throughput of sintering process and Bayer process two big systems, optimization production flow process.
(8) realize the serialization operation, be convenient to carry out large industrialized production.
(9) help reducing and sneak into red mud because of the sodium white residue and deposit pollution environment.
Embodiment
The invention will be further described below in conjunction with performance.
Embodiment 1
The method of method for the treatment of sodium-silicon slag by chlorination of the present invention, step is as follows:
(1) oven dry sodium white residue 100g, reductive agent is a coke powder, granularity (d50)=100um, sodium white residue and reductive agent mass ratio 10: 1.Chlorination temperature 460-540 ℃, time of chlorinating 15min, the chlorine dominant discharge is a 0.2kg/min.kg sodium white residue.
(2) control liquid-solid ratio 5 adopts distilled water normal temperature washing chloride slag in tank, and filtration washing obtains sodium chloride solution 60ml.
(3) in the washing slag of step (2) is added the tank washing once more, liquid-solid ratio control 10, washed twice joins roasting in the High Temperature Furnaces Heating Apparatus to PH=7 after the oven dry, 1900 ℃ of maturing temperatures, time: 1.5 hours, obtain the mullite 40g of alumina content 43%.
Embodiment 2
The method of method for the treatment of sodium-silicon slag by chlorination of the present invention, step is as follows:
(1) oven dry sodium white residue 100g, reductive agent is a Graphite Powder 99, and granularity (d50) is 80um, and sodium white residue and reductive agent mass ratio are 10: 1.Chlorination temperature is 450-540 ℃, and time of chlorinating is 14min, and the chlorine dominant discharge is a 0.2kg/min.kg sodium white residue.
(2) with embodiment 1
(3) the washing slag that (2) are obtained adds granularity (d50) 60um of carbon powder of reducing agent once more, and sodium white residue and reductive agent mass ratio are 7: 1, and chlorination temperature 760-850 ℃, time of chlorinating is 18min, and the chlorine dominant discharge is a 0.4kg/min.kg washing slag.
(4) during the chlorinated exhaust condensation, 52 ℃ of the condensation point temperature of silicon tetrachloride solution obtain 15ml, and 180 ℃ of the condensing temperature controls of liquor alumini chloridi obtain 10ml.
(5) 3g. is retained in the chloride slag washing
Embodiment 3
The method of method for the treatment of sodium-silicon slag by chlorination of the present invention, step is as follows:
(1) oven dry sodium white residue 100g, reductive agent is a Graphite Powder 99, granularity (d50) is: 80um, sodium white residue and reductive agent mass ratio are 5: 1.Chlorination temperature 780-850 ℃, time of chlorinating is 20min, and the chlorine dominant discharge is a 0.45kg/min.kg sodium white residue.
(2) during the chlorinated exhaust condensation, 50 ℃ of the condensation point temperature of silicon tetrachloride solution obtain 15ml, and 180 ℃ of the condensing temperature controls of liquor alumini chloridi obtain 10ml.
(3) control liquid-solid ratio 5 adopts distilled water normal temperature washing chloride slag in tank, and filtration washing obtains sodium chloride solution 60ml.The washing chloride slag is retained 3g.
Embodiment 4
The method of method for the treatment of sodium-silicon slag by chlorination of the present invention, step is as follows:
(1) embodiment 3 simultaneously, different is chlorination temperature 800-950 ℃, and time of chlorinating is 150min, and the chlorine dominant discharge is a 0.3kg/min.kg sodium white residue.
(2) embodiment 3 simultaneously.
(3) embodiment 3 simultaneously, the washing chloride slag is retained 2.9g.
Embodiment 5
The method of method for the treatment of sodium-silicon slag by chlorination of the present invention, step is as follows:
(1) embodiment 2 simultaneously, different is that sodium white residue and reductive agent mass ratio are 15: 4.Chlorination temperature is 400-500 ℃, and time of chlorinating is 20min, and the chlorine dominant discharge is a 0.5kg/min.kg sodium white residue.
(2) with embodiment 1
(3) the washing slag that (2) are obtained adds granularity (d50) 200um of carbon powder of reducing agent once more, and sodium white residue and reductive agent mass ratio are 12: 3, and chlorination temperature 850-990 ℃, time of chlorinating is 10min, and the chlorine dominant discharge is a 0.9kg/min.kg washing slag.
(4) embodiment 2 simultaneously
(5) 3g is retained in the chloride slag washing.
Claims (10)
1, a kind of method of method for the treatment of sodium-silicon slag by chlorination is characterized in that step is as follows:
(1) in the sodium white residue, adds reductive agent, join continuously and carry out chlorination in the boiling chloridizing furnace, realize one section selective chlorination of sodium element in the sodium white residue;
(2) chloride slag is washed and is obtained sodium chloride solution, realizes the separation of sodium element, obtains washing slag simultaneously;
(3) join roasting in the High Temperature Furnaces Heating Apparatus after will washing slag secondary washing oven dry, obtain mullite;
(4) chlorinated exhaust obtains aluminum chloride and silicon tetrachloride solution respectively through the condensation separation of condenser, and the washing chloride slag retains and is used for cement baking.
2, the method for method for the treatment of sodium-silicon slag by chlorination according to claim 1, it is characterized in that washing slag oven dry after, add reductive agent once more, join continuously and carry out chlorination in the boiling chloridizing furnace, realize two sections selective chlorinations of silicon, aluminium element in the sodium white residue.
3, the method for method for the treatment of sodium-silicon slag by chlorination according to claim 1 is characterized in that reductive agent is a carbon dust, and powder particles control d50 is: 20-200um, sodium white residue and reductive agent mass ratio are: 15-20: 2-4.
4, the method for method for the treatment of sodium-silicon slag by chlorination according to claim 1 is characterized in that chlorination temperature is 400-550 ℃, time of chlorinating 10-20min, and the chlorine dominant discharge is a 0.1-0.5kg/min.kg sodium white residue.
5, the method for method for the treatment of sodium-silicon slag by chlorination according to claim 1 is characterized in that chloride slag uses distilled water wash at normal temperatures, liquid-solid ratio control 4-5: 1, and filtration washing obtains sodium chloride solution.
6, the method for method for the treatment of sodium-silicon slag by chlorination according to claim 5 is characterized in that washing slag and washs once more, liquid-solid ratio control 9-10: 1, washed twice is to PH=7, join roasting in the High Temperature Furnaces Heating Apparatus after the oven dry, 1500-2000 ℃ of maturing temperature control, time control 1.5-2.0 hour.
7, the method for method for the treatment of sodium-silicon slag by chlorination according to claim 2, the granularity that it is characterized in that secondary chlorating carbon dust is d50=20-200um, sodium white residue and reductive agent mass ratio are 6-12: 1-3.
8, the method for method for the treatment of sodium-silicon slag by chlorination according to claim 7 is characterized in that secondary chlorating chlorination temperature is 700-1000 ℃, and time of chlorinating is 10-25min, and the chlorine dominant discharge is a 0.2-1.0kg/min.kg washing slag.
9, the method for method for the treatment of sodium-silicon slag by chlorination according to claim 1, it is characterized in that the processing of chlorination employing single stage method, sodium white residue and reductive agent mass ratio are 5-20: 1-4, time of chlorinating control 10-30min, the chlorine dominant discharge is a 0.1-0.7kg/min.kg sodium white residue, chlorination temperature 700-1000 ℃.
10,, it is characterized in that the condensing temperature of silicon tetrachloride solution is controlled 30-70 ℃, 120-200 ℃ of the condensing temperature control of liquor alumini chloridi according to the method for the described method for the treatment of sodium-silicon slag by chlorination of the arbitrary claim of claim 1-9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101629238B (en) * | 2009-07-30 | 2012-04-18 | 浙江华友钴业股份有限公司 | Residue washing method in cobalt hydrometallurgy industry |
| CN102923747A (en) * | 2012-11-28 | 2013-02-13 | 东北大学 | Method for producing aluminum chloride, silicon chloride and ferric chloride by utilizing coal gangue |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101629238B (en) * | 2009-07-30 | 2012-04-18 | 浙江华友钴业股份有限公司 | Residue washing method in cobalt hydrometallurgy industry |
| CN102923747A (en) * | 2012-11-28 | 2013-02-13 | 东北大学 | Method for producing aluminum chloride, silicon chloride and ferric chloride by utilizing coal gangue |
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