CN1224723C - Processing method for industrial waste material - Google Patents
Processing method for industrial waste material Download PDFInfo
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- CN1224723C CN1224723C CNB031290027A CN03129002A CN1224723C CN 1224723 C CN1224723 C CN 1224723C CN B031290027 A CNB031290027 A CN B031290027A CN 03129002 A CN03129002 A CN 03129002A CN 1224723 C CN1224723 C CN 1224723C
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- aluminum
- weight part
- stripping
- industrial waste
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- 239000002440 industrial waste Substances 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title abstract description 26
- 238000003672 processing method Methods 0.000 title abstract 3
- 238000000034 method Methods 0.000 claims abstract description 52
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 51
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 37
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 20
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 9
- 238000003723 Smelting Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 239000002699 waste material Substances 0.000 claims abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims description 37
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 28
- 239000003518 caustics Substances 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 21
- 239000004411 aluminium Substances 0.000 claims description 21
- 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 description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 238000004090 dissolution Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 235000011089 carbon dioxide Nutrition 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 2
- 150000002366 halogen compounds Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 10
- 229910001648 diaspore Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 229910001570 bauxite Inorganic materials 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910001679 gibbsite Inorganic materials 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- FZFYOUJTOSBFPQ-UHFFFAOYSA-M dipotassium;hydroxide Chemical compound [OH-].[K+].[K+] FZFYOUJTOSBFPQ-UHFFFAOYSA-M 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 210000000582 semen Anatomy 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 pottery Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to a processing method of an industrial waste material which is the waste material in the smelting industry of aluminum and secondary aluminum, and the application industry of the aluminum and aluminum alloy, wherein the waste material comprises 60 to 90 weight portions of Al2O3, 0 to 20 weight portions of Al, 0 to 15 weight portions of SiO2 and 0 to 15 weight portions of impurities. The processing method orderly comprises the following procedures: (1) diffluence: a raw material is dissolved under the conditions that the diffluence temperature is from 70 to 220 DEG C, the caustic soda concentration is from 100 to 220 g/L, and the diffluence time is from 0.2 to 8 hours, and then a sodium aluminate solution is formed; (2) separation: liquid solid separation is carried out to dissolved slurry to obtain the sodium aluminate solution; (3) decomposition: aluminum hydroxide crystal seeds are added in the sodium aluminate solution for seed decomposition, or carbon dioxide is introduced in the sodium aluminate solution for carbonated decomposition to obtain aluminum hydroxide; (4) calcination: the aluminum hydroxide is calcined at the temperature of 500 to 1500 DEG C to obtain aluminum oxide. The method which is simpler than the existing method has the advantages of low cost and low energy consumption, and the method solves the environment pollution problem in the smelting industry of the aluminum and the secondary aluminum, and the application industry of the aluminum and the aluminum alloy.
Description
Technical field
The invention belongs to metallurgy and chemical technology field, relate to a kind of working method of the industrial waste of aluminium and secondary aluminum smelting industry and aluminium and aluminium alloy application industry.Specifically, the present invention relates to prepare sodium aluminate, aluminium hydroxide and method of alumina with described industrial waste.
Background technology
At present, in aluminum smelting technology, secondary aluminum smelting, aluminium and aluminium alloy application industry, produce a large amount of industrial wastes and waste residue, they are not utilized or reclaim, but be discharged in the physical environment, both wasted resource, again natural ecological environment has been caused severe contamination.
At present, most in the world factories are raw material with bauxite all when producing aluminium hydroxide and aluminum oxide, use gibbsite or boehmite type bauxite more than 80%, have only a few countries use diaspore type bauxites such as China.But diaspore type bauxite has following shortcoming:
(1) mineral structure of diaspore type bauxite belongs to extremely strong a kind of of chemical stability, is very difficult to stripping in producing alumina process.Gibbsite under 100 ℃ of left and right sides temperature, condition near normal pressure and lower caustic sodium concentration, stripping preferably.Temperature, 3Mpa for example＞200 just can reach close result of extraction under the grams per liter condition with upward pressure and higher caustic sodium concentration more than 240 ℃ and diaspore needs.
(2) impurity compositions such as higher silicon oxide, titanium oxide are often contained in the diaspore type ore deposit, and these compositions are the most deleterious impurity of alumina producing just.They increase the stripping difficulty of aluminum oxide; Increase the loss of aluminum oxide and caustic alkali; The equipment wall particularly heat transfer interface form and to scab etc.
(3) because the diaspore type mineral structure is much close, hard than San Shui Lv Shi Cause, increase the energy consumption and the expense of the broken mill of ore.
The bauxite reserves of China more than 95% are diaspore type, and present a small amount of gibbsite type mineral deposit of finding is all on the low side because of its grade, and unactual as yet exploitation utilizes.Based on the characteristics of China's bauxite resource, China's alumina producing technical sophistication, the flow process swelling is long, equipment is numerous and jumbled, processing condition are harsh, energy consumption and with high costs.Therefore, since the own aluminium industry of China, aluminum oxide does not satisfy the demand of electrolytic aluminum always and relies on import in a large number.The throughput of present domestic aluminum oxide can only satisfy 50% of domestic market demand.
Hence one can see that, both pressed at present the method for the industrial waste of recycling aluminium and secondary aluminum smelting, aluminium and aluminium alloy application industry, needs again a kind ofly can reduce the preparation aluminium hydroxide of technical difficulty and production cost and the novel method of aluminum oxide.
The content of invention
In view of present above-mentioned situation, the present inventor has studied a kind of industrial waste that utilizes and has prepared aluminium hydroxide and aluminum oxide, and its technology difficulty and production cost are lower than the novel method of the existing alumina producing of China.
The used raw material of the working method of industrial waste of the present invention is the waste material of aluminium and secondary aluminum smelting industry and aluminium and aluminium alloy application industry, and it comprises following composition:
Al
2O
3The 60-90 weight part
Al 0-20 weight part
SiO
2The 0-15 weight part
Described method may further comprise the steps successively:
(1) stripping: in digester, under the following conditions, above-mentioned industrial waste is dissolved with caustic solution, form sodium aluminate solution:
70--220 ℃ of stripping temperature,
Caustic sodium concentration 100-220 grams per liter is with Na
2The O meter,
Dissolution time 0.2-8 hour;
(2) separate: the stripping slurries are carried out liquid-solid separation, and the liquid that obtains is sodium aluminate solution.
In another embodiment of the inventive method, it comprises that also step (3) is a decomposition step, and it is to add aluminium hydroxide crystal seed to carry out seed and decompose in the sodium aluminate solution that obtains, or feeds carbonic acid gas and carry out carbonating and decompose, and obtains aluminium hydroxide;
In an embodiment of aforesaid method of the present invention, it also comprises step (3) step (4) afterwards, i.e. calcination steps, this step be the aluminium hydroxide that will obtain in the step (3) in 500-1500 ℃ of roasting temperature, obtain aluminum oxide.
In another embodiment of the inventive method, the digester in the stripping step is autoclave or canalization digester.
In another embodiment of the inventive method, the solvent temperature in the stripping step is 80-200 ℃.
In another embodiment of the inventive method, the caustic solution concentration in the stripping step is the 110-200 grams per liter.
In another embodiment of the inventive method, the dissolution time in the stripping step is 0.3-6 hour.
In another embodiment of the inventive method, described industrial waste also comprises the impurity that total amount is the 0-15 weight part, and the composition of described impurity comprises iron, calcium, magnesium, potassium, manganese, sodium, titanium, nickel, phosphorus, zinc, lead, mercury, nitrogen, sulfur oxide or halogen compounds etc.
Al in the used industrial waste of the inventive method
2O
3The preferred 65-90 weight part of content, more preferably 70-90 weight part.
Detailed description of the invention
The present invention utilizes industrial waste (hereinafter to be referred as AD material) to produce aluminium hydroxide and aluminum oxide, these industrial wastes comprise electrolytic aluminum, secondary aluminum recovery, aluminium and aluminium alloy smelting or moltenly join, oxide skin or slag that aluminium and commercial runs such as aluminium alloy casting or processing produce; Also comprise these waste residues slag for the treatment of processes generation again.AD material of the present invention is powdery, and fineness is below 60 orders, and composition as mentioned above.
The flow process of the inventive method is as described below.
(1) stripping
At first, AD material caustic solution stripping in digester.Preferred autoclave of digester or canalization digester.Following chemical reaction mainly takes place in process in leaching:
When containing oxidation of impurities calcium and magnesium oxide in the AD material, following reaction also takes place:
More than react the NaAl (OH) that generates
4Be the solution form, claim sodium aluminate solution.
The Na that generates
2OAl
2O
31.7SiO
2NH
2O, 3CaOAl
2O
3X SiO
2(6-2x) H
2O, 3MgOAl
2O
3X SiO
2(6-2x) H
2O then forms residue (being called red mud).
Stripping temperature in the stripping step is 70-220 ℃.If be lower than 70 ℃ then dissolution rate is too slow, under the identical situation of other conditions, Al
2O
3Solubility rate too low; The stripping temperature is higher than 220 ℃, then increases facility investment, production energy consumption and cost greatly.The preferred 80-200 of this solvent temperature ℃, more preferably 90-180 ℃.
Stripping pressure in the stripping step is the function of temperature and strength of solution.Temperature and concentration have determined that pressure has also just been determined.This pressure range is generally from normal pressure to 2.5MPa.Caustic solution concentration in the stripping step is the 100-220 grams per liter.If caustic sodium concentration is lower than 100 grams per liters, dissolution rate and solubility rate can not satisfy production requirement, and the sodium aluminate solution that obtains is extremely unstable, can resolve into aluminium hydroxide automatically.Like this, the decomposition in advance that sodium aluminate solution was taken place before follow-up separating impurity step can make product and separate impurities be difficult to carry out, thereby influence subsequent handling.Be higher than at caustic sodium concentration under the situation of 220 grams per liters, because in subsequent handling, caustic alkali recycles after through evaporation concentration, so its excessive concentration can increase the burden of circulating mother liquor evaporation concentration greatly.The preferred 110-200 grams per liter of caustic sodium concentration, more preferably 110-180 grams per liter.
Make the dissolving in the stripping step complete substantially, dissolution time is generally 0.2-8 hour, if less than 0.2 hour, does not then reach the solubility rate of hope; Dissolution time will reduce equipment capacity greatly greater than 8 hours.The preferred 0.3-6 of this dissolution time hour.
The solubility rate scope of the inventive method is the 25-95 weight part.Solubility rate is different and different according to material composition.
(2) separate
The above-mentioned stripping slurries that obtain from the stripping step are carried out liquid-solid separation, and separating device can adopt decanter type thickener, vacuum filter, separating centrifuge or various filtering equipment.Separating the liquid obtain is sodium aluminate concentrate solution, can direct marketing, and its composition is as follows:
Al
2O
3Content 100 grams per liters,
Na
2O content＞100 grams per liters,
Impurity SiO
2Content＜5 grams per liters,
Impurity F e
2O
3Content＜0.5 grams per liter.
It also can carry out the further processing of following operation.
The residue that separation is obtained washs with hot water more than 50 ℃, and the residue after the washing is red mud, is used to produce cement or material of construction.
(3) decompose
Add aluminium hydroxide crystal seed in the sodium aluminate concentrate solution that obtains and carry out the seed decomposition in above-mentioned steps, principal reaction is:
Added aluminium hydroxide crystal seed is a technical grade aluminium hydroxide, preferred product aluminium hydroxide obtained by the method for the present invention.Aluminium hydroxide preferably adds when the temperature of sodium aluminate concentrate solution reaches 70-75 ℃.Add-on is: the weight ratio of institute's aluminium hydroxide is 0.5-2.5 in institute's adding aluminum hydroxide and the seminal fluid.This weight ratio is called the seed ratio, and it is decided according to desired decomposition rate and rate of decomposition.If it is too slow that seed than＜0.5, then decomposes, if it＞2.5, then waste.
The decomposition of sodium aluminate solution also can be carried out like this: promptly, and by feeding CO
2Carrying out carbonating decomposes.Its reaction formula is as follows:
The carbonic acid gas that is adopted is the technical grade carbonic acid gas, and usage quantity is a stoichiometry.
This operation is carried out in the splitter of routine, for example the normal pressure decomposer of band stirring.
Then, will decompose slurries and carry out liquid-solid separation again, and with hot wash solid product aluminium hydroxide more than 50 ℃, used equipment is identical with the red mud separation washing.
Under the situation that aluminium hydroxide crystal seed decomposes, separating the liquid phase that obtains is NaOH solution, and it can return and reuse after additional part caustic alkali be with the requirement that reaches the used caustic solution of above-mentioned stripping, and promptly the caustic solution as stripping recycles.Such sodium hydroxide solution is called circulating mother liquor.
Under the situation that carbonating is decomposed, separating the liquid phase that obtains is Na
2CO
3, it also obtains sodium hydroxide solution through following causticization, returns use as circulating mother liquor:
The solid product aluminium hydroxide that obtains in this decomposition step can be used as technical grade product and sells, and its quality meets the requirement of GB4294-84, and composition is as shown in table 1 below, and each component content is all represented with weight part:
The composition of table 1 product aluminium hydroxide
| Grade | Chemical ingredients | ||||
| Al 2O 3Be not less than | Foreign matter content (being not more than) | ||||
| SiO 2 | Fe 2O 3 | Na 2O | Igloss | ||
| One-level | 64 | 0.03 | 0.03 | 0.45 | 35 |
| Secondary | 64 | 0.05 | 0.03 | 0.45 | 35 |
| Three grades | 63.5 | 0.10 | 0.05 | 0.50 | 35 |
Annotate: described " one-level, secondary, three grades " is the composition detection result according to product, and with production sharing
Each grade.
It also can stand the further processing of following operation, makes aluminum oxide.
(4) roasting
The product aluminium hydroxide that will from above-mentioned decomposition step, obtain in conventional stoving oven through 500～1500 ℃ of temperature roastings, obtain the product aluminum oxide, this product aluminum oxide quality meets the requirement of GB8178-87, and its chemical constitution is as shown in table 2 below, and each component content is all represented with weight part.
The composition of table 2 product aluminum oxide
| Grade | Chemical ingredients | ||||
| Al 2O 3Be not less than | Foreign matter content (being not more than) | ||||
| SiO 2 | Fe 2O 3 | Na 2O | Igloss | ||
| One-level | 98.6 | 0.02 | 0.03 | 0.55 | 0.8 |
| Secondary | 98.5 | 0.04 | 0.04 | 0.60 | 0.8 |
| Three grades | 98.4 | 0.06 | 0.04 | 0.65 | 0.8 |
| Level Four | 98.3 | 0.08 | 0.05 | 0.65 | 1.0 |
| Pyatyi | 98.2 | 0.10 | 0.05 | 0.70 | 1.0 |
Annotate: described " one-level, secondary, three grades, level Four and Pyatyi " is the composition detection result according to product,
And with each grade of production sharing.
Raw material that aluminium hydroxide made from the inventive method and aluminum oxide can be used for chemical industry, medicine, pottery, refractory materials and electrolytic aluminum etc.
The inventive method has the positively effect of the following aspects at least:
(1) the aluminum oxide major part in the AD material is an activated alumina, compares with diaspore, can stripping under lower temperature, pressure and caustic sodium concentration (diaspore:＞240 ℃,＞caustic sodium concentration of 200 grams per liters; The present invention: 70--220 ℃, 100-220 grams per liter, 0.2-8 hour), dissolution rate is also very fast.Not only simplify production unit and technology, reduce cost and energy consumption, and significantly reduce construction investment.
(2) aluminium in the AD material produces a large amount of heats during stripping, reduces production energy consumption; The recyclable utilization of hydrogen that generates.
(3) the AD material need not break the grinder preface, shortens flow process, simplified apparatus, reduces production costs and construction cost.
(4) AD expects the stripping of available lower concentration caustic solution, reduces circulating mother liquor evaporation concentration burden, simplified apparatus and reduction production energy consumption.
(5) These characteristics of AD material is that the construction of middle small scale aluminum oxide factory creates conditions, and can bring into play enthusiasm local and that private enterprise builds alumina producer, the demand pressure in alleviation aluminum oxide market.
(6) realize comprehensive utilization of resources, reduce industrial pollution.
Testing method
(1) solubility rate (η A)
The actual solubility rate of aluminum oxide (η A) promptly enters the Al of solution
2O
3Account for contained Al in the AD material
2O
3The weight percent of total amount.It is calculated as follows:
η A={[(A/S)
Material-(A/S)
Red mud]/(A/S)
Material} * 100%
In the formula: (A/S)
Material---the weight ratio of aluminum oxide and silicon oxide in the AD material,
(A/S)
Red mud---the weight ratio of aluminum oxide and silicon oxide in the red mud.
(2) sign of aluminium hydroxide and aluminum oxide product
The product aluminium hydroxide of being made by the inventive method and the sign of aluminum oxide are carried out like this: impurity SiO in test product aluminium hydroxide and the aluminum oxide
2, Fe
2O
3, Na
2The amount of O and igloss, surplus are Al
2O
3
Silicon oxide adopts GB 66103-86 molybdenum blue spectrophotometry to measure;
Ferric oxide adopts GB 66104-86 adjacent two assorted luxuriant and rich with fragrance spectrphotometric method for measuring;
Sodium oxide adopts GB 66105-86 flame spectrophotometric determination;
GB 66102-86 gravimetric determination is adopted in igloss;
Their content is expressed as weight part.
Embodiment
Embodiment 1
Used AD material is powdery, and fineness is crossed 60 mesh sieves, and its chemical constitution is as shown in table 3 below:
Table 3
| Composition | Content (weight part) |
| Aluminum oxide (Al 2O 3) | 72.5 |
| Aluminium (Al) | 10.0 |
| Silicon oxide (SiO 2) | 6.5 |
| Magnesium oxide (MgO) | 3.2 |
| Calcium oxide (CaO) | 1.2 |
| Titanium oxide (TiO 2) | 0.2 |
| Ferric oxide (Fe 2O 3) | 2.0 |
| Sodium oxide (Na 2O) | 1.5 |
| Potassium oxide (K 2O) | 0.6 |
| Other | 2.3 |
Above-mentioned raw materials is without broken mill, directly stripping in autoclave, 200 ℃ of stripping temperature, caustic sodium concentration 200 grams per liters, dissolution time 8 hours.The actual solubility rate 75% of aluminum oxide (contain aluminium and be converted to aluminum oxide).
The stripping slurries carry out liquid-solid separation through pressure filter, and the solid phase that obtains is a red mud, with hot wash more than 50 ℃, and discharging then.The liquid phase that obtains is a sodium aluminate concentrate solution.
In the normal pressure decomposer that band stirs, in the sodium aluminate concentrate solution that obtains, add technical grade aluminium hydroxide and carry out the seed decomposition as crystal seed, seed is than (promptly adding crystal seed Al (OH)
3Be converted into Al
2O
3Weight and seminal fluid in contained Al
2O
3The ratio of weight) be 1.5.70 ℃ of initial decomposition temperatures.
The slurries that decompose the back gained filter with vacuum filter, and the solid phase that obtains is a product aluminium hydroxide, with hot wash more than 50 ℃, adopts above-mentioned testing method to test then.Its each composition is measured as: SiO
20.055 weight part; Fe
2O
30.03 weight part; Na
2O 0.45 weight part; Igloss 34.8 weight parts; Al
2O
3Surplus.
The liquid phase that obtains is a sodium hydroxide solution, returns as mother liquor, recycles after the batching again.
With the product aluminium hydroxide that obtains in stoving oven in 1150 ℃ of roastings, the gained aluminum oxide is tested by above-mentioned method for testing and analyzing, its each composition is measured as: SiO
20.06 weight part; Fe
2O
30.03 weight part; Na
2O 0.55 weight part; Igloss 0.7 weight part; Al
2O
3Surplus.
Aluminum oxide per ton consumes 1.48 tons in AD material approximately.
Embodiment 2
Used AD expects with embodiment 1,70 ℃ of stripping temperature, caustic sodium concentration 100 grams per liters, dissolution time 0.5 hour.The actual solubility rate 25% of aluminum oxide (contain aluminium and be converted to aluminum oxide).Other processes and product quality analysis method are with embodiment 1
After tested, each composition of products therefrom aluminium hydroxide is: SiO
20.03 weight part; Fe
2O
30.025 weight part; Na
2O 0.40 weight part; Igloss 34.8 weight parts; Al
2O
3Surplus.
After tested, each composition of products therefrom aluminum oxide is: SiO
20.04 weight part; Fe
2O
30.03 weight part; Na
2O 0.50 weight part; Igloss 0.7 weight part; Al
2O
3Surplus.
Aluminum oxide per ton consumes 4.4 tons in AD material approximately.
Embodiment 3
Used AD material is with embodiment 1.140 ℃ of stripping temperature, caustic sodium concentration 160 grams per liters, dissolution time 4 hours.The actual solubility rate 64% of aluminum oxide (contain aluminium and be converted to aluminum oxide).Other processes and product analysis method are with embodiment 1.
After tested, each composition of products therefrom aluminium hydroxide is: SiO
20.03 weight part; Fe
2O
30.025 weight part; Na
2O 0.45 weight part; Igloss 34.8 weight parts; Al
2O
3Surplus.
After tested, each composition of products therefrom aluminum oxide is: SiO
20.04 weight part; Fe
2O
30.038 weight part; Na
2O 0.60 weight part; Igloss 0.7 weight part; Al
2O
3Surplus.
Aluminum oxide per ton consumes 1.8 tons in AD material approximately.
Embodiment 4
The chemical constitution of used AD material is as shown in table 4 below:
Table 4
| Composition | Content (weight part) |
| Aluminum oxide (Al 2O 3) | 69.7 |
| Aluminium (Al) | 7.5 |
| Silicon oxide (SiO 2) | 10.8 |
| Magnesium oxide (MgO) | 4.5 |
| Calcium oxide (CaO) | 1.5 |
| Titanium oxide (TiO 2) | 0.3 |
| Ferric oxide (Fe 2O 3) | 1.8 |
| Sodium oxide (Na 2O) | 1.7 |
| Potassium oxide (K 2O) | 0.5 |
| Other | 1.7 |
100 ℃ of stripping temperature, caustic sodium concentration 140 grams per liters, dissolution time 2 hours.The actual solubility rate 58% of aluminum oxide (contain aluminium and be converted to aluminum oxide).Other processes and product quality analysis method are with embodiment 1.
After tested, each composition of products therefrom aluminium hydroxide is: SiO
20.03 weight part; Fe
2O
30.025 weight part; Na
2O 0.45 weight part; Igloss 34.8 weight parts; Al
2O
3Surplus.
After tested, each composition of products therefrom aluminum oxide is: SiO
20.046 weight part; Fe
2O
30.038 weight part; Na
2O 0.60 weight part; Igloss 0.7 weight part; Al
2O
3Surplus.
Aluminum oxide per ton consumes 2.1 tons in AD material approximately.
Embodiment 5
Used AD material is with embodiment 4.
200 ℃ of stripping temperature, caustic sodium concentration 180 grams per liters, dissolution time 4 hours.The actual solubility rate 68% of aluminum oxide (contain aluminium and be converted to aluminum oxide).Other processes and product analysis method are with embodiment 1.
After tested, each composition of products therefrom aluminium hydroxide is: SiO
20.03 weight part; Fe
2O
30.025 weight part; Na
2O 0.40 weight part; Igloss 34.8 weight parts; Al
2O
3Surplus.
After tested, each composition of products therefrom aluminum oxide is: SiO
20.04 weight part; Fe
2O
30.03 weight part; Na
2O 0.55 weight part; Igloss 0.7 weight part; Al
2O
3Surplus.
Aluminum oxide per ton consumes 1.8 tons in AD material approximately.
Embodiment 6
Used AD material is with embodiment 4.
75 ℃ of stripping temperature, caustic sodium concentration 120 grams per liters, dissolution time 1 hour.The actual solubility rate 28% of aluminum oxide (contain aluminium and be converted to aluminum oxide).Other processes and product analysis method are with embodiment 1.
After tested, each composition of products therefrom aluminium hydroxide is: SiO
20.03 weight part; Fe
2O
30.025 weight part; Na
2O 0.40 weight part; Igloss 34.8 weight parts; Al
2O
3Surplus.
After tested, each composition of products therefrom aluminum oxide is: SiO
20.04 weight part; Fe
2O
30.035 weight part; Na
2O 0.55 weight part; Igloss 0.7 weight part; Al
2O
3Surplus.
Aluminum oxide per ton consumes 4.3 tons in AD material approximately.
Claims (10)
1. the working method of an industrial waste is characterized in that described industrial waste is the waste material of aluminium and secondary aluminum smelting industry and aluminium and aluminium alloy application industry, and it comprises following composition:
Al
2O
3The 60-90 weight part
Al 0-20 weight part
SiO
2The 0-15 weight part
Described method may further comprise the steps successively:
(1) stripping: in digester, under the following conditions, above-mentioned industrial waste is dissolved with caustic solution, form sodium aluminate solution:
70--220 ℃ of stripping temperature,
Caustic sodium concentration 100-220 grams per liter is with Na
2The O meter,
Dissolution time 0.2-8 hour;
(2) separate: the stripping slurries are carried out liquid-solid separation, and the liquid that obtains is sodium aluminate solution.
2. the method for claim 1, it is characterized in that described method comprises that also step (3) is a decomposition step, it is to add aluminium hydroxide crystal seed to carry out seed and decompose in the sodium aluminate solution that obtains, or feeds carbonic acid gas and carry out carbonating and decompose, and obtains aluminium hydroxide.
3. method as claimed in claim 2 is characterized in that described method comprises that also step (4) is a calcination steps, it be the aluminium hydroxide that will obtain in the step (3) in 500-1500 ℃ of roasting temperature, obtain aluminum oxide.
4. as each described method among the claim 1-3, it is characterized in that the digester in the described stripping step is autoclave or canalization digester.
5. as each described method among the claim 1-3, it is characterized in that the solvent temperature in the described stripping step is 80-200 ℃.
6. as each described method among the claim 1-3, it is characterized in that the caustic solution concentration in the described stripping step is the 110-200 grams per liter.
7. as each described method among the claim 1-3, it is characterized in that the dissolution time in the described stripping step is 0.3-6 hour.
8. as each described method among the claim 1-3, it is characterized in that described industrial waste also comprises the impurity that total amount is the 0-15 weight part, the composition of described impurity comprises iron, calcium, magnesium, potassium, manganese, sodium, titanium, nickel, phosphorus, zinc, lead, mercury, nitrogen, sulfur oxide or halogen compounds.
9. as each described method among the claim 1-3, it is characterized in that Al in the described industrial waste
2O
3Content be the 65-90 weight part.
10. as each described method among the claim 1-3, it is characterized in that Al in the described industrial waste
2O
3Content be the 70-90 weight part.
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|---|---|---|---|
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