CN103588235B - Method for producing polyaluminium sulfate by using red mud slag - Google Patents
Method for producing polyaluminium sulfate by using red mud slag Download PDFInfo
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- CN103588235B CN103588235B CN201310575974.8A CN201310575974A CN103588235B CN 103588235 B CN103588235 B CN 103588235B CN 201310575974 A CN201310575974 A CN 201310575974A CN 103588235 B CN103588235 B CN 103588235B
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- red mud
- slag
- iron
- polyaluminium sulfate
- sulfate
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- 239000002893 slag Substances 0.000 title claims abstract description 67
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 89
- 238000000034 method Methods 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052742 iron Inorganic materials 0.000 claims abstract description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 238000011084 recovery Methods 0.000 claims abstract description 16
- 238000000605 extraction Methods 0.000 claims abstract description 14
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000000920 calcium hydroxide Substances 0.000 claims description 19
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 18
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000005987 sulfurization reaction Methods 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 230000005070 ripening Effects 0.000 claims description 7
- 229910000805 Pig iron Inorganic materials 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 5
- 241001062472 Stokellia anisodon Species 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 239000000571 coke Substances 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 238000010079 rubber tapping Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 4
- 238000004131 Bayer process Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical group OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 230000000717 retained effect Effects 0.000 claims description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- 229960002167 sodium tartrate Drugs 0.000 claims description 2
- 235000011004 sodium tartrates Nutrition 0.000 claims description 2
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 2
- 238000013517 stratification Methods 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 239000010936 titanium Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052719 titanium Inorganic materials 0.000 abstract description 10
- -1 rare earth Chemical class 0.000 abstract description 9
- 230000007062 hydrolysis Effects 0.000 abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 8
- 239000002910 solid waste Substances 0.000 abstract description 8
- 239000000839 emulsion Substances 0.000 abstract description 6
- 238000002386 leaching Methods 0.000 abstract description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 3
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 3
- 239000004571 lime Substances 0.000 abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000008267 milk Substances 0.000 abstract 2
- 210000004080 milk Anatomy 0.000 abstract 2
- 235000013336 milk Nutrition 0.000 abstract 2
- 238000003825 pressing Methods 0.000 abstract 2
- 230000032683 aging Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 18
- 239000000284 extract Substances 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 239000004411 aluminium Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000003311 flocculating effect Effects 0.000 description 8
- 229940037003 alum Drugs 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910001710 laterite Inorganic materials 0.000 description 1
- 239000011504 laterite Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Treatment Of Sludge (AREA)
Abstract
The invention provides a method for producing polyaluminium sulfate by using a red mud slag. The method comprises the following steps: iron in the red mud is recovered, wherein the red mud is a solid waste produced in the production of aluminium oxide, the slag is blended with concentrated sulfuric acid after the recovery of iron to conduct sulfurizing roasting, then water leaching is implemented to obtain an aluminum sulfate solution containing rare metals like rare earth, the rare metal slag is extracted through extraction, the raffinate is added into lime milk to conduct an alkalized polymerization reaction, the pH value and the temperature of the raffinate are controlled, the impurities like titanium and iron are separated through hydrolysis, a stabilizing agent is added at the low basicity, then lime milk is added to conduct an emulsion reaction, the solution is subjected to filter pressing when the basicity reaches a preset value, the filter residue is a titanium-rich slag, the liquid subjected to the filter-pressing is put into an aging vat and aged to obtain a high-concentration polyaluminium sulfate product. The method has the advantages of simple process and feasible operation, the comprehensive utilization of the red mud is achieved, the correlative charge for the stockpiling of the red mud is reduced, and meanwhile, the influence caused by the stockpiling of the red mud to the environment and the accident potential are also eliminated.
Description
Technical field
The present invention relates to field of metallurgy, be specifically related to a kind ofly from ore, extract the method reclaiming aluminium in the waste red mud slag of aluminum oxide.
Background technology
In aluminum ore Bayer process alumina producing, carry out stripping after bauxite and lime, circulation alkali liquor mixer mill make qualified ore pulp, under high temperature, High Pressure, the aluminum oxide in ore enters solution, and its insolubles is red mud.After stripping, ore pulp is through dilution, after sedimentation solid-liquid separation, and the underflow red mud slurry of generation is outer row after three counter flow washings, the attached alkali of filtered and recycled.Produce l ton aluminum oxide and can produce 1.1 ~ 1.5 tons of red muds, along with the fast development of aluminum oxide industry in recent years, nearly 100,000,000 tons of the aluminum oxide output that the whole world is annual, only China's aluminum oxide output of 2012 just reaches 4,214 ten thousand tons, red mud quantity discharged about 5000 ~ 6,000 ten thousand tons.Red muds a large amount of is in the world that the method adopting ocean disposal and land to store up is disposed at present, and China mostly adopts the method such as level land plateau, lowland filling to the process of red mud, occupies a large amount of soil.The red mud produced is middle strong basicity, because stacking red mud, certain pollution can be caused to underground water, surrounding resident domestic water and farm crop are subject to certain impact, particularly 2010, after there occurs Hungary's red mud dam break pollution Danube accident, cause the whole world showing great attention to red mud problem especially.Therefore red mud store up management difficulty and environmental risk is increasing, the simultaneously stacking of red mud can spend a large amount of handling chargess, stockyard construction and maintenance cost, and therefore alumina laterite has a strong impact on and governs ecotope.
Along with China is to the pay attention to day by day of environmental issue, the research in recent years about red mud comprehensive utilization becomes focus again.There is valency rare metal kind many in red mud, as iron, aluminium, rare metal, rare earth etc., its Fe in red mud
2o
3content can reach more than 38%, Al
2o
3: 16 ~ 18%.The comprehensive utilizating research of red mud mainly comprises two aspects: one is extract the useful component in red mud, reclaims valuable metal; Two is that entirety is used using red mud as general raw mineral materials.Due to red mud processing cost problem, many research on utilization achievements about red mud, also non-Industry Promotion.
At present, from red mud, in prior art, reclaim the method for aluminium, mainly adopt the method for hydrochloric acid acidleach, pass through comparatively high temps, after the mode of Leaching in Hydrochloric Acid leaches under such as 70 DEG C of heated conditions, after removing titanium slag, calcium slag, rare earth, be finally separated and obtain aluminium, such as Chinese document, Wang Keqin, Wanghao, Li Shenghu work, title " Leaching in Hydrochloric Acid red mud reclaims the research of aluminium ", the technology described in " non-ferrous metal (Smelting Part) " the 7th phase 16-18 page in 2012.The method can reclaim aluminium with the higher rate of recovery.But the method exists step complexity, reclaim composition single, the throw out be separated in its process is purified cumbersome, is unfavorable for the recycling of other compositions.
Prior art processes route is comparatively complicated, and treatment process bothers, and mostly be specially for the recovery of one or two kind of element, overall availability is low, and other compositions in red mud are discarded more, still has relatively large waste residue and discharges.Further, prior art does not directly utilize red mud to produce the method for polyaluminium sulfate.Therefore, find a kind of technique more simple, rate of recovery product purity is high, and the method that other elements in red mud also can reclaim aluminium in the red mud of effective recycling very has realistic meaning.
Current polyaluminium sulfate is applied in drinking-water water source purifying is produced more, and for operation of flocculating, the coagulation effect of polymerize aluminum chloride is better, and the colority of water after process is substantially constant, but in tap water, understands aluminium residual, toxigenous problem.
Summary of the invention
The object of this invention is to provide a kind of method that red mud slag produces polyaluminium sulfate, this process simplify operational path, in red mud, each useful component comprehensive reutilization rate is high, overcomes the defect of prior art.
Red mud slag of the present invention produces the method for polyaluminium sulfate, comprises the following steps:
A, to extract from ore after alumina producing waste red mud carry out recovery ferro element, make the content of ferro element be down to 1%-8%;
B, to mix with the vitriol oil reclaiming the slag after ferro element, carrying out sulfurization roasting;
C, the mixture after roasting is carried out water logging, obtain main containing rare metal vitriol, Tai-Ace S 150 and titanyl sulfate metal-salt mixing solutions after filtering;
D, utilize mixed extractant to extract metal-salt mixing solutions, remove organic phase filter residue, retain raffinate solution;
E, alkalization polyreaction is carried out to raffinate solution: limit is stirred and added milk of lime in surplus solution, control solution temperature 60-80 DEG C, when basicity is 15-25%, add stablizer, continue again to add milk of lime until basicity is greater than 40%, solution is carried out press filtration, removing filter residue, liquid after press filtration puts into ripening tank slaking 20-40 hour, obtains polyaluminum sulfate aluminum solutions.
The method extracting aluminum oxide in described steps A from ore is Bayer process, soda-lime sintering process or Bayer-sintering integrated process.The tailings that these methods obtain after preparing aluminum oxide is red mud.
Described steps A is that the pig iron is produced in high temperature reduction melting from the method for recovering iron from red mud element.As the patent of applicant, title: " a kind of method reclaiming iron from alumina producing waste red mud ", the patent No.: the technology recorded in " 201310006001.2 ".
The raw ferriferous method of described high temperature reduction melting is:
First red mud is removed most of moisture content through super-dry, be the 12-25% of its gross weight to red mud water content, this is had to necessarily moisture red mud and carries out ball processed, the heat of reduction furnace exhaust combustion is utilized to dry red mud ball subsequently, then dry red mud ball, coke, Wingdale, rhombspar are mixed in the ratio of 25-40:15-20:2-3:1-2, add in reduction furnace and smelt iron, be separated by scum and obtain iron and slag.
When the pig iron is produced in described high temperature reduction melting, the hot blast temperature of reduction furnace ironmaking is 900 ~ 1100 DEG C, and blast 220mmHg, smelting temperature 1550 ~ 1600 DEG C in stove, tapping temperature is higher than 1400 DEG C.
Adopt high temperature reduction melting direct production pig iron technology, iron recovery can reach more than 98%, and in slag, iron level is very low.
In described step B, the weight proportion of slag and the vitriol oil is 1:1-2, and roasting time is 1-2 hour, and by the high heat release of the vitriol oil and metal reaction, the temperature of sulfurization roasting can reach more than 400 DEG C, and reaction is fast, leaching effect is good.
In described step C during water logging, the weight proportion of water and mixture is 2-5:1, water logging 1-2 hour.
In described step D, the method that rare metal slag is extracted in extraction is:
Mixed extractant solvent is extracted with P2O4, mixed solvent is extracted with metal-salt mixed liquor volume than the ratio for 1:8 ~ 15 according to P2O4, P2O4 being extracted mixed solvent adds in metal-salt mixing solutions, stratification after stirring, rare metal vitriol enters organic phase, Tai-Ace S 150, titanyl sulfate and other metal ions are retained in raffinate, isolate raffinate solution for standby.
In described step e, alkalization polyreaction is by slowly adding milk of lime, solution pH value control 2.5-4, control temperature 65-75 DEG C, and the basicity before finally filtering controls as 40%-50%.
The definition of basicity: the equivalent percent ((OH)/(Al) × 100 (%)) of OH and Al in poly aluminium chloride molecule.
When extracting mixed extractant solvent with P2O4, after P2O4 extraction mixed solvent mixes with metal-salt mixing solutions, organic phase and raffinate solution phase can be divided into, organic phase can also be carried out extraction process and be extracted titanium and rich scandium scraps, its process is: by sodium hydroxide solution back extraction organic phase, obtain back extraction slag, with dissolving with hydrochloric acid back extraction slag, regulator solution pH value, heating hydrolysis is except titanium; Then use TBP, namely tributyl phosphate carries out second time extraction, uses sodium hydroxide solution back extraction, obtains the rich scraps that scandium content is higher.
In described step e, stablizer is tartrate and/or sodium tartrate.
The chemical reaction of alum recovery of the present invention is:
3H
2SO
4+ Al
2O
3= Al
2（SO
4）
3+3H
2O
nAl
2(SO
4)
3·14H
2O+(n×m/2)Ca(OH)
2+xH
2O = [Al
2(OH)m(SO
4)
3-m/2]n+( n×m/2)CaSO
4↓+yH
20
Wherein 1≤m≤5, n≤10.
Positively effect of the present invention:
1, the present invention using the solid waste red mud of alumina producing smelt iron after slag as raw material, aluminium is reclaimed and is polymerized, produce polyaluminium sulfate, the rate of recovery can reach more than 85%, the product polyaluminium sulfate solution quality obtained is good, on flocculating property or on dosage, all there is larger superiority than traditional Tai-Ace S 150, and there is the broader use range to former water pH value.Meanwhile, because iron content is very low, be more suitable for the application of the industry such as high-quality papermaking.
2, material mainly directly mixes with the vitriol oil and carries out chemical reaction by sulfurization roasting, this reaction is thermopositive reaction, produce a large amount of heat, temperature of reaction is raised, more than 400 DEG C can be reached, play the effect of roasting, relative to the extract technology of prior art, be characterized in that speed of response is fast, leaching effect good, reaction completeness is high, only need within 1-2 hour, just can react completely, and the slag after sulfurization roasting, water logging, main component is calcium sulfate, can be used for producing gypsum or cement additire, can not outer row be carried out, environment is not affected.The amount of integrated solid waste decreases 20 ~ 30%.
3, existing iron recovery technology mainly adopts the method for magnetic separation, directly from recovering iron from red mud concentrate, iron recovery is about 20%, very not thorough, contriver finds after deliberation, if utilize slag high Fe contained like this to carry out sulfuric acid baking according to method of the present invention, then water logging, extraction is carried out to metal-salt mixing solutions and extracts rare metal slag, surplus solution adds milk of lime and carries out alkalization polyreaction, the polyaluminum sulfate aluminum solutions prepared after getting rid of Ti-enriched slag, because the content of iron ion is too high, the iron ion of unavoidable meeting doped portion in last solution, affect the purity of polyaluminium sulfate, therefore, the method cannot be carried out according to technique of the present invention after reclaiming iron.In addition, if in polyaluminium sulfate all there there is no any iron ions, also be unfavorable for ensuring safety with water, because if there is no iron ion, have aluminum ion after polyaluminium sulfate process water and pollute, increase the toxicity of water, if containing a small amount of iron composition, the coagulation performance of polymerize aluminum chloride, its molysite during process water, not only can be kept can also to degrade Organic substance in water, increase water quality, there is advantages such as reducing water toxicity.Contriver, after lot of experiment validation, show that in red mud, iron level will control at 1%-8%, the purity of the polyaluminium sulfate that guarantee extracts, promotes technique effect during its post-processed water simultaneously.
4, containing a lot of valuable element in the raw material blast furnace slag in the present invention, filtrate after sulfurization roasting, water logging extracts rare metal slag by extraction, Ti-enriched slag is separated out in hydrolysis, a large amount of valuable elements is made to obtain enrichment, reach industrial grade, for comprehensive utilization creates favourable condition further.
5, the present invention have technique simple, operate easy, accomplished the comprehensive utilization of red mud, decreased the associated cost of red mud pilling, also eliminated impact and accident potential that red mud pilling brings to environment simultaneously.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that the present invention's red mud slag produces polyaluminium sulfate
Fig. 2 is PAS and the PAC processing drinking water effect that the embodiment of the present invention provides
embodiment
As shown in Figure 1, the solid waste red mud of alumina producing is through reclaiming iron, slag after recovery iron is mixed with the vitriol oil and carries out sulfurization roasting, after being gone out by water logging, obtain the alum liquor containing rare metals such as rare earths, rare metal slag is extracted by extraction, the alum liquor of raffinate is heated, add milk of lime and carry out alkalization polyreaction, control pH value and the temperature of solution, the impurity such as titanium and iron is separated out in hydrolysis, and when low basicity, add stablizer, continue to add milk of lime again and carry out emulsion reaction, after basicity reaches preset value, solution is carried out press filtration, filter residue is Ti-enriched slag, liquid after press filtration is put into ripening tank slaking and is high density polyaluminium sulfate product.The addition of milk of lime can calculate according to the amount of aluminium in slag, controls basicity, thus controls the amount adding milk of lime.
Below in conjunction with embodiment, present method is further illustrated
Embodiment 1
Iron-holder 8% in slag after the solid waste red mud recovery iron of alumina producing, slag mixes with the vitriol oil and carries out sulfurization roasting, the weight of slag and the vitriol oil is 1:2, roasting 2 hours, then add the water of 3 times, water logging 1.5 hours, filter, metal-salt mixing solutions P2O4 after water logging being filtered extracts mixed solvent and extracts, P2O4 extracts mixed solvent with metal-salt mixed liquor volume than being 1:8, and rare metal slag is extracted in extraction, the alum liquor composition Al of raffinate
2o
335.24g/L, TiO
218.02g/L, Na
2o 23.1g/L, Fe
2o
38.72g/L, Sc
2o
30.32mg/L, adds milk of lime and carries out alkalization polyreaction, controls the pH value 2.5 of solution, temperature 60 C, titanium and iron are separated out in hydrolysis, when detecting basicity 20%, add stablizer, continue to add milk of lime and carry out emulsion reaction, after basicity reaches 40%, solution is carried out press filtration, filter residue is Ti-enriched slag, liquid after press filtration puts into ripening tank slaking 30 hours, obtains alumina content 10.7%, the polyaluminium sulfate product of basicity 53.4%.
Embodiment 2
Iron-holder 5% in slag after the solid waste red mud recovery iron of alumina producing, slag mixes with the vitriol oil and carries out sulfurization roasting, the weight of slag and the vitriol oil is 1:1, roasting 1 hour, then the water of 2 times is added, water logging 2 hours, filters, and the metal-salt mixing solutions P2O4 after water logging being filtered extracts mixed solvent and extracts, P2O4 extracts mixed solvent with metal-salt mixed liquor volume than being 1:10, the alum liquor composition Al of raffinate
2o
347.26g/L, TiO
210.58g/L, Na
2o 10.60g/L, Fe
2o
35.15g/L, Sc
2o
30.65mg/L, is heated to 75 DEG C and adds milk of lime and carry out alkalization polyreaction, controls the pH value 2.5 ~ 3.0 of solution, stir 1h hydrolysis and separate out titanium and iron, when detection basicity reaches 15%, add stablizer, continue to add milk of lime and carry out emulsion reaction, after basicity reaches 45%, solution is carried out press filtration, and filter residue is Ti-enriched slag, and the liquid after press filtration puts into ripening tank slaking 20 hours, obtain alumina content 13.3%, the polyaluminium sulfate product of basicity 52.4%.
Embodiment 3
First red mud is removed most of moisture content through super-dry, be red mud water content be 12% of gross weight, this is had to necessarily moisture red mud and carries out ball processed, the heat of reduction furnace exhaust combustion is utilized to dry red mud ball subsequently, then dry red mud ball, coke, Wingdale, rhombspar are mixed in the ratio of 25:15:2:1, add in reduction furnace and smelt iron, be separated by scum and obtain iron and slag.Slag adds in reduction furnace smelts iron, and the hot blast temperature of reduction furnace ironmaking is 900 ~ 1000 DEG C, blast 220mmHg, smelting temperature 1550 ~ 1600 DEG C in stove, and tapping temperature, higher than 1400 DEG C, is separated by scum and obtains iron and slag; Iron-holder 3% in slag after the solid waste red mud recovery iron of alumina producing, slag mixes with the vitriol oil and carries out sulfurization roasting, the weight of slag and the vitriol oil is 1:1.5, roasting 1.5 hours, then the water of 5 times is added, water logging 1 hour, filters, and the metal-salt mixing solutions P2O4 after water logging being filtered extracts mixed solvent and extracts, P2O4 extracts mixed solvent with metal-salt mixed liquor volume than being 1:12, the alum liquor composition Al of raffinate
2o
332.16g/L, TiO
218.65g/L, Na
2o 19.75g/L, Fe
2o
37.94g/L, Sc
2o
30.70mg/L, is heated to 80 DEG C and adds milk of lime and carry out alkalization polyreaction, controls the pH value 3.5 of solution, stir 1h hydrolysis and separate out titanium and iron, when detection basicity reaches 25%, add stablizer, continue to add milk of lime and carry out emulsion reaction, after basicity reaches 50%, solution is carried out press filtration, and filter residue is Ti-enriched slag, and the liquid after press filtration puts into ripening tank slaking 40 hours, obtain alumina content 10.1%, the polyaluminium sulfate product of basicity 43.9%.
Embodiment 4
First red mud is removed most of moisture content through super-dry, be red mud water content be 20% of gross weight, this is had to necessarily moisture red mud and carries out ball processed, the heat of reduction furnace exhaust combustion is utilized to dry red mud ball subsequently, then dry red mud ball, coke, Wingdale, rhombspar are mixed in the ratio of 40:20:3:2, add in reduction furnace and smelt iron, be separated by scum and obtain iron and slag.The hot blast temperature of reduction furnace ironmaking is 1000 ~ 1100 DEG C, blast 220mmHg, smelting temperature 1550 ~ 1600 DEG C in stove, and tapping temperature, higher than 1400 DEG C, is separated by scum and obtains iron and slag; Iron-holder 1% in slag after the solid waste red mud recovery iron of alumina producing, slag mixes with the vitriol oil and carries out sulfurization roasting, the weight of slag and the vitriol oil is 1:1.8, roasting 1.6 hours, then the water of 4 times is added, water logging 1 hour, filters, and the metal-salt mixing solutions P2O4 after water logging being filtered extracts mixed solvent and extracts, P2O4 extracts mixed solvent with metal-salt mixed liquor volume than being 1:15, the alum liquor composition Al of raffinate
2o
330.36g/L, TiO
217.62g/L, Na
2o 18.70g/L, Fe
2o
37.65g/L, Sc
2o
30.80mg/L, is heated to 65 DEG C and adds milk of lime and carry out alkalization polyreaction, controls the pH value 4 of solution, stir 1h hydrolysis and separate out titanium and iron, when detection basicity reaches 25%, add stablizer, continue to add milk of lime and carry out emulsion reaction, after basicity reaches 50%, solution is carried out press filtration, and filter residue is Ti-enriched slag, and the liquid after press filtration puts into ripening tank slaking 32 hours, obtain alumina content 12.3%, the polyaluminium sulfate product of basicity 47.9%.
Embodiment 5
The river of Qu Liangzumou water factory, each group establishes 5 1000ml reactors, and the turbidity of this river is 20.08NTU.First group is added this waterworks of different amounts technical grade polymerize aluminum chloride (PAC) at present, the polyaluminium sulfate (PAS) of second group of interpolation embodiment of the present invention 2, compares the effect of the polyaluminium sulfate process river of technical grade polymerize aluminum chloride and the embodiment of the present invention 2.Can be found out by design sketch 1, river turbidity all diminishes along with the consumption increase of the polyaluminium sulfate of polymerize aluminum chloride and the embodiment of the present invention 2, and when consumption is 30mg/L, river turbidity is respectively 1.3NTU and 1.67NTU, when consumption is 50mg/L, the river turbidity basic simlarity after process.In this flow process of purifying river water, require that the turbidity of process river is lower than 2NTU, therefore, these two kinds of chemicals treatment rivers can reach cleanup standard, but containing a small amount of iron in the polyaluminium sulfate of the embodiment of the present invention 2, be the water purification agent with Polyferric Sulfate class character, after wherethrough reason, can avoid or reduce the aluminium toxicity and secondary pollution problem that bring through simple polymerisation aluminum chloride process river.PAS and PAC processing drinking water effect is shown in Fig. 1.
Embodiment 6
The polyaluminium sulfate dosage of development is made comparisons on the impact of its flocculating property investigate the relation of dosage and flocculating effect by being adopted the polyaluminium sulfate (PAS) of the embodiment of the present invention 4 and traditional Tai-Ace S 150 wadding (AS), the solidifying agent situation of polymerize aluminum chloride (PAC), and the turbidity that the results are shown in Table the former water of 1(process is 18.6NTU):
As can be seen from Table 1, when identical dosage, the flocculating effect of the polyaluminium sulfate of the embodiment of the present invention 4 is better than traditional Tai-Ace S 150 greatly, suitable with polyaluminium aluminum ratio flocculating effect, when dosage reaches 20mg/L, raw water turbidity reaches 2.1NTU, and flocculating effect is fine.
By showing its performance study, polyaluminium sulfate is all having larger superiority than traditional Tai-Ace S 150 on flocculating property or on dosage, under the same conditions, the turbidity removal effect of polyaluminium sulfate is obviously better than Tai-Ace S 150, slightly better than polymerize aluminum chloride.
Claims (10)
1. produce a method for polyaluminium sulfate with red mud slag, it is characterized in that comprising the following steps:
A, to extract from ore after alumina producing waste red mud carry out recovery ferro element, make the content of ferro element be down to 1%-8%;
B, to mix with the vitriol oil reclaiming the slag after ferro element, carrying out sulfurization roasting;
C, the mixture after roasting is carried out water logging, obtain main containing rare metal vitriol, Tai-Ace S 150 and titanyl sulfate metal-salt mixing solutions after filtering;
D, utilize mixed extractant to extract metal-salt mixing solutions, remove organic phase filter residue, retain raffinate solution;
E, alkalization polyreaction is carried out to raffinate solution: limit is stirred and added milk of lime in surplus solution, control solution temperature 60-80 DEG C, when basicity is 15-25%, add stablizer, continue again to add milk of lime until basicity reaches more than 40%, solution is carried out press filtration, removing filter residue, liquid after press filtration puts into ripening tank slaking 20-40 hour, obtains polyaluminum sulfate aluminum solutions.
2. method of producing polyaluminium sulfate with red mud slag as claimed in claim 1, is characterized in that: the method extracting aluminum oxide in described steps A from ore is Bayer process, soda-lime sintering process or Bayer-sintering integrated process.
3. method of producing polyaluminium sulfate with red mud slag as claimed in claim 1, is characterized in that: described steps A is that the pig iron is produced in high temperature reduction melting from the method for recovering iron from red mud element.
4. method of producing polyaluminium sulfate with red mud slag as claimed in claim 3, is characterized in that, the raw ferriferous method of described high temperature reduction melting is:
First red mud is removed most of moisture content through super-dry, be the 12-25% of its gross weight to red mud water content, this is had to necessarily moisture red mud and carries out ball processed, the heat of reduction furnace exhaust combustion is utilized to dry red mud ball subsequently, then dry red mud ball, coke, Wingdale, rhombspar are mixed in the ratio of 25-40:15-20:2-3:1-2, add in reduction furnace and smelt iron, be separated by scum and obtain iron and slag.
5. method of producing polyaluminium sulfate with red mud slag as claimed in claim 4, it is characterized in that: when the pig iron is produced in described high temperature reduction melting, the hot blast temperature of reduction furnace ironmaking is 900 ~ 1100 DEG C, blast 220mmHg, smelting temperature 1550 ~ 1600 DEG C in stove, tapping temperature is higher than 1400 DEG C.
6. method of producing polyaluminium sulfate with red mud slag as claimed in claim 1, it is characterized in that: in described step B, the weight proportion of slag and the vitriol oil is 1:1-2, and roasting time is 1-2 hour.
7. method of producing polyaluminium sulfate with red mud slag as claimed in claim 1, it is characterized in that: in described step C during water logging, the weight proportion of water and mixture is 2-5:1, water logging 1-2 hour.
8. method of producing polyaluminium sulfate with red mud slag as claimed in claim 1, is characterized in that, in described step D, the method that rare metal slag is extracted in extraction is:
Mixed extractant solvent is extracted with P2O4, mixed solvent is extracted with metal-salt mixed liquor volume than the ratio for 1:8 ~ 15 according to P2O4, P2O4 being extracted mixed solvent adds in metal-salt mixing solutions, stratification after stirring, rare metal vitriol enters organic phase, Tai-Ace S 150, titanyl sulfate and other metal ions are retained in raffinate, isolate raffinate solution for standby.
9. method of producing polyaluminium sulfate with red mud slag as claimed in claim 1, it is characterized in that: in described step e, alkalization polyreaction is by slowly adding milk of lime, solution pH value control 2.5-4, control temperature 65-75 DEG C, the basicity before finally filtering controls as 40%-50%.
10. method of producing polyaluminium sulfate with red mud slag as claimed in claim 1, it is characterized in that: in described step e, stablizer is tartrate and/or sodium tartrate.
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| CN104445441B (en) * | 2014-11-14 | 2016-01-06 | 河南省煤气（集团）有限责任公司 | A kind of method utilizing the industrial waste sulfuric acid of purification acetylene gas generation and red mud to produce polyaluminium sulfate ferrous solution |
| CN106590689B (en) * | 2016-12-26 | 2018-06-19 | 荆门市格林美新材料有限公司 | The method that magnalium prepares composite flame-retardant agent is recycled from different sludge |
| CN106745142B (en) * | 2017-01-19 | 2018-01-26 | 济南大学 | A kind of extracting process for preparing high-purity aluminium chloride |
| CN107140718A (en) * | 2017-05-09 | 2017-09-08 | 辽宁科技大学 | A kind of utilize couples the method that external field treatment red mud prepares iron aluminium flocculating agent |
| CN109019651A (en) * | 2018-09-30 | 2018-12-18 | 上海高桥大同净水材料有限公司 | A kind of production method of the high-purity poly aluminium sulfate of liquid |
| CA3134962A1 (en) * | 2019-03-27 | 2020-10-01 | The Governing Council Of The University Of Toronto | Methods for recovering a target metal from iron or steel slag using at least one of a carbothermic reduction process and a pyro-hydrometallurgical process |
| CN110639930B (en) * | 2019-09-17 | 2020-07-31 | 昆明理工大学 | Recycling treatment process for roasting red mud by using activated carbon adsorbent for removing benzene and heavy hydrocarbon substances in failure |
| CN110639929B (en) * | 2019-09-17 | 2020-07-31 | 昆明理工大学 | Recycling treatment process for roasting red mud by using spent desulfurization activated carbon adsorbent |
| CN114438335B (en) * | 2021-12-29 | 2024-02-09 | 绵阳师范学院 | Treatment method of titanium-containing blast furnace slag |
| CN114873900B (en) * | 2022-05-31 | 2023-10-03 | 湖南平安环保股份有限公司 | Advanced dewatering treatment process for comprehensively utilizing red mud in municipal sludge conditioning |
| CN115057650B (en) * | 2022-06-27 | 2023-01-24 | 安徽海螺材料科技股份有限公司 | Chlorine ion permeation resistant fluoride-free alkali-free liquid accelerator and preparation method thereof |
| CN116177779B (en) * | 2022-12-09 | 2024-04-19 | 四川大学 | Recycling method of titanium white wastewater |
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