CN102060335A - Method for preparing ammonium ferrous sulfate from waste ferrous slag in sulfuric acid process titanium dioxide industry - Google Patents
Method for preparing ammonium ferrous sulfate from waste ferrous slag in sulfuric acid process titanium dioxide industry Download PDFInfo
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- CN102060335A CN102060335A CN 201010528662 CN201010528662A CN102060335A CN 102060335 A CN102060335 A CN 102060335A CN 201010528662 CN201010528662 CN 201010528662 CN 201010528662 A CN201010528662 A CN 201010528662A CN 102060335 A CN102060335 A CN 102060335A
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- sulfuric acid
- ferrous
- slag
- ammonium sulphate
- useless
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 56
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 title claims abstract description 55
- 239000002893 slag Substances 0.000 title claims abstract description 40
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002699 waste material Substances 0.000 title claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000004408 titanium dioxide Substances 0.000 title abstract description 6
- 229940010514 ammonium ferrous sulfate Drugs 0.000 title abstract 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 26
- 239000012452 mother liquor Substances 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 239000007790 solid phase Substances 0.000 claims abstract description 3
- 239000001038 titanium pigment Substances 0.000 claims description 23
- 239000006166 lysate Substances 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 230000003750 conditioning effect Effects 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- -1 industrial goods Substances 0.000 claims description 3
- 238000004176 ammonification Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000000243 solution Substances 0.000 abstract description 9
- 238000003756 stirring Methods 0.000 abstract description 7
- 239000011259 mixed solution Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004321 preservation Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 238000005516 engineering process Methods 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 9
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 235000010215 titanium dioxide Nutrition 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000001117 sulphuric acid Substances 0.000 description 6
- 235000011149 sulphuric acid Nutrition 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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Abstract
本发明公开了用硫酸法钛白粉行业废亚铁渣制备硫酸亚铁铵的方法，是将废亚铁渣与配比量的硫酸、氨反应，按以下步骤合成硫酸亚铁铵：将2份重量的硫酸含量为7.5～7.6wt％的溶解液泵入反应锅，启动搅拌机，加入1份重量的废亚铁渣后搅拌0.5～1.5h；加入氨，控制反应锅内液温不超过110℃，pH值不超过1.0，当pH值升高到0.5时，停止加氨，保温0.5～1.5h后得硫酸亚铁铵混合溶液；混合溶液经冷却结晶、分离纯化后固相硫酸亚铁铵，液相作为母液补加硫酸/水后作为溶解液循环利用。该工艺流程短，操作简便，设备投资少；主要原料为硫酸法钛白粉行业的废酸废亚铁渣，化废为宝；所得产品市场前景好，综合效益显著。The invention discloses a method for preparing ammonium ferrous sulfate by using waste ferrous slag in the titanium dioxide industry of the sulfuric acid method to prepare ferrous ammonium sulfate. Pump the dissolving solution with a sulfuric acid content of 7.5-7.6wt% by weight into the reaction pot, start the mixer, add 1 part by weight of waste ferrous slag and stir for 0.5-1.5 hours; add ammonia, and control the liquid temperature in the reaction pot not to exceed 110°C , the pH value does not exceed 1.0, when the pH value rises to 0.5, stop adding ammonia, and obtain a mixed solution of ferrous ammonium sulfate after 0.5 to 1.5 hours of heat preservation; the mixed solution is crystallized by cooling, separated and purified, and the solid-phase ammonium ferrous sulfate is obtained. The liquid phase is used as the mother liquor to add sulfuric acid/water and then recycled as the solution. The process is short, easy to operate, and low in equipment investment; the main raw material is waste acid waste ferrous slag in the sulfuric acid process titanium dioxide industry, turning waste into treasure; the obtained product has a good market prospect and significant comprehensive benefits.
Description
Technical field
The present invention relates to the preparation method of ferrous ammonium sulphate, be specifically related to prepare the method for ferrous ammonium sulphate with the useless ferrous slag of sulfuric acid method titanium pigment industry.
Background technology
A kind of double salt that ferrous ammonium sulphate is made up of moles such as ferrous sulfate and ammonium sulfate is commonly called as Mohr's salt, often with hexahydrate [(NH
4)
2SO
4FeSO
46H
2O] the form existence, it is reductive agent and a basic chemical industry raw material common in the analytical chemistry, is used to prepare ferrous ion standardized solution and quantitative analysis standard reagent, demarcates potassium permanganate and potassium bichromate solution; In agricultural, forestry, be used as iron fertilizer; Also Chang Zuowei Weak-acid cation promoting agent is as Biocidal algae-killing agent and polymerizing catalyst; All has vast market prospect in industries such as medicine, plating.
The traditional preparation process technology of ferrous ammonium sulphate (accompanying drawing 1): scrap iron (iron powder or iron plate) is after thermokalite oil removing impurity elimination and clear water are cleaned, drained, produce copperas solution earlier with the dilute sulphuric acid reaction, filtering and impurity removing, in filtrate, add ammonia sulfate crystal with the ferrous sulfate equimolar amount, stirring and dissolving, heating concentrates and makes high-concentration sulfuric acid ferrous ammonium mixing solutions, gets the finished product ferrous ammonium sulphate through crystallisation by cooling, separation and purification.Traditional process equipment is simple, raw material is clear, reduced investment, cost is transparent, its quality depends on the control of material purity and reaction process condition, easy to operate, production process only have small quantity of hydrogen, acid mist and alkaline degreasing impurity elimination waste water waste residue efflux, so this technology is used till today as classics always.
Titanium dioxide be a kind of be the important white inorganic pigment of main body composition with titanium dioxide, in coating, printing ink, rubber, papermaking and chemical fibre industry, be used as pigment, be used to make welding electrode, isolator and electroceramics in mechanical industry, also have a wide range of applications in industry such as sugared porcelain, metallurgy.At present, about 8,000,000 tons/year of global titanium dioxide aggregated capacity, the China's titanium ore resources is abundant, the raw material cheapness, is easy to get, and aggregated capacity surpasses 2,500,000 tons, and ultimate production has also reached 2,000,000 tons, and still with the annual growth rate fast development more than 10%.
Sulfuric acid process is the current topmost titanium white production method of China, and this method is based on periodical operation, and technology is ripe, equipment is simple, the raw material cheapness, is easy to get, but long flow path, the consumption of sulfuric acid and water is big, and spent acid, iron vitriol and useless ferrous slag the like waste are many, and environmental pollution is big.In order to reduce environmental pollution, traditional sulfuric acid process has been carried out many-sided improvement, as replacing ilmenite with solubility in acid titanium slag, ilmenite concentrate, utilizing technology by-product exhaust steam that spent acid is concentrated directly concentrated decrement or the like of recovery, hydrolysising mother liquid.According to preresearch estimates, surplus the annual by-product spent acid 800 of China's titanium white powder production industry ten thousand tons, nearly 3,000,000 tons of by-product iron vitriol, about 1,000,000 tons of the ferrous slag of by-product.Spent acid can be by concentrating means digestion such as recovery and other Chemicals of direct production, and the low-concentration waste acid that does not have recovery value in a large number also can carry out harmless treatment through simple neutralization; The channel of iron vitriol comprehensive utilization is a lot, as making water purification agent, iron pigment, agricultural chemicals, catalyzer, fertilizer, the blue or green orchid of titanium and fodder additives etc.;
It is the patent of CN101792187A that Chinese patent discloses the patent No. on August 4th, 2010, with the titanium white waste acid condensed slag is raw material, the processes such as acid, crystallisation by cooling, separation, commentaries on classics crystalline substance of falling by condensed slag are produced feed grade ferrous sulfate monohydrate, have realized the comprehensive utilization of sulfuric acid method titanium pigment by product spent acid condensed slag with high cost.Ferrous slag is a kind of khaki color, iron content height, big, the thick corrodibility mud of acidity, and its molecule constitutes FeSO
4XH
2SO
4YH
2O, x=0.5～0.6, y=0.9～1.2.It can't directly be used as iron vitriol, big to environmental hazard, so far do not find the gratifying approach that effectively utilizes yet, can only be as Hazardous wastes harmless treatment in addition, though or infiltration pyrite-based sulfuric acid production---these means have reached the purpose of decontamination substantially, the cost of paying extremely expensive (so many titanium dioxides enterprise all takes the environmental protection responsibility of means escapes oneself such as row steathily).
Summary of the invention
In order to improve the raw material mix of ferrous ammonium sulphate traditional preparation process technology, the useless ferrous slag of recycling sulfuric acid method titanium pigment industry (hereinafter to be referred as useless ferrous slag), the invention provides the method for preparing ferrous ammonium sulphate with the useless ferrous slag of sulfuric acid method titanium pigment industry, with useless ferrous slag is main raw material, with sulfuric acid, ammonia is reagent, make ferrous ammonium sulphate, make a silk purse out of a sow's ear, not only eliminated the environmental protection puzzlement of sulfuric acid method titanium pigment industry development, economize on resources, reduce cost, and started the new preparation process of ferrous ammonium sulphate, have important theoretical and be worth and realistic meaning.The present invention is achieved through the following technical solutions.
The method for preparing ferrous ammonium sulphate with the useless ferrous slag of sulfuric acid method titanium pigment industry, comprise the steps: that (1) is that the lysate of 7.5～7.6wt% pumps into reactor with the sulfuric acid content of 2 parts of weight, start stirrer, restir behind the useless ferrous slag of 1 part of weight of adding, when temperature no longer raises, when feed liquid has been converted into the tawny clear liquid, finish dissolving and hydrolysis; (2) add ammonia again, the liquid temperature is no more than 110 ℃ in the control reactor, and the pH value when the pH value is elevated to 0.5, shows that the dosage of ammonia is enough below 1.0, stops ammonification immediately, continues insulation reaction 0.5～1.5h, gets the ferrous ammonium sulphate mixing solutions; (3) mixing solutions solid phase after crystallisation by cooling, separation and purification is the ferrous ammonium sulphate product, and last liquid phase is as the mother liquor that can be recycled.
The above-mentioned method for preparing ferrous ammonium sulphate with the useless ferrous slag of sulfuric acid method titanium pigment industry, be used as lysate after in the conditioning groove, adding sulfuric acid/water behind the described mother liquor, pump into reactor and recycle, the additional amount of sulfuric acid/water so that in the lysate sulfuric acid content be 7.5～7.6wt%.
Above-mentionedly prepare the method for ferrous ammonium sulphate with the useless ferrous slag of sulfuric acid method titanium pigment industry, the described restir time of step (1) is 0.5～1.5h.
Above-mentionedly prepare the method for ferrous ammonium sulphate with the useless ferrous slag of sulfuric acid method titanium pigment industry, described useless ferrous slag is the hydrolysis of sulfuric acid method titanium pigment industry titanyl sulfate, separate metatitanic acid after mother liquor behind enrichment process, discharge, its molecule constitutes FeSO
4XH
2SO
4YH
2O, x=0.5～0.6, y=0.9～1.2.
Above-mentionedly prepare the method for ferrous ammonium sulphate with the useless ferrous slag of sulfuric acid method titanium pigment industry, described ammonia is one or both of liquefied ammonia, ammoniacal liquor.
Above-mentionedly prepare the method for ferrous ammonium sulphate with the useless ferrous slag of sulfuric acid method titanium pigment industry, described sulfuric acid, liquefied ammonia and ammoniacal liquor are one or more of chemical reagent, industrial goods, waste material of different grades.
Compared with prior art, the present invention has following advantage:
(1) useless ferrous slag is that the sulfuric acid method titanium pigment industry is difficult to primary pollution source of effectively utilizing and the main bottleneck that restricts industry development, important prerequisite and basic guarantee that it is the sulfuric acid method titanium pigment industry development that low-cost high-efficiency is eliminated its harm to ecotope beneficially.The present invention is the new channel that useless ferrous slag has been opened up a comprehensive utilization of resources, and it is made a silk purse out of a sow's ear, and makes the best use of everything, and will significantly improve sulfuric acid method titanium pigment industry cleaner production level, and will produce remarkable economical, social benefit.
(2) the present invention has thoroughly changed the raw material mix of ferrous ammonium sulphate traditional processing technology, with useless ferrous slag is main raw material, with sulfuric acid, ammonia (liquefied ammonia or ammoniacal liquor) is reagent, the scrap iron (iron powder or iron plate), dilute sulphuric acid and the ammonium sulfate that replace traditional processing technology, make the high-quality ferrous ammonium sulphate, further shorten and simplified technical process, started the new preparation process of ferrous ammonium sulphate.
(3) new preparation process of the ferrous ammonium sulphate of the present invention's proposition, not only raw material sources are recycled in the resource utilization of refuse, and there are not pollutents such as alkaline degreasing impurity elimination waste water, waste gas and waste residue to efflux mother liquid recycling, more green, the more environmental protection, more energy-conservation of technology itself.
(4) clean process at the scrap iron in the ferrous ammonium sulphate traditional processing technology (iron powder or iron plate) itself, thermokalite oil removing impurity elimination and clear water and may comprise impurity, the concentration and evaporation process also may cause defectives such as ferrous oxidation, ferrous ammonium sulphate preparation method of the present invention does not comprise fully that then these mainly cause general labourer's preface, the raw material that is adopted does not contain the detrimental impurity that influences quality of finished substantially yet, so the technology of the present invention more can be guaranteed the ferrous ammonium sulphate quality.
Description of drawings
Fig. 1 is the traditional preparation process process diagram of ferrous ammonium sulphate.
Fig. 2 is the technology of the present invention process flow diagram.
Embodiment
Below in conjunction with the embodiments enforcement of the present invention is described further.
Embodiment1
The dilute sulphuric acid that takes by weighing 500g concentration and be 7.6wt% is made lysate, pours the flat there-necked flask of 1000mL of band magnetic agitation into, slowly adds the useless ferrous slag of 250g under agitation condition, and 30min finishes dissolving and hydrolysis; Open the liquefied ammonia valve, slowly charge into ammonia, the liquid temperature is no more than 110 ℃ in the control reactor, and the pH value increases to 0.5 behind about 56min, fastens the liquefied ammonia valve, continues reaction 30min; Stirring, water-bath cooling, a large amount of light blue crystal grain are high-visible, and again with the ice-water bath cooling, the 30min post crystallization is finished when near room temperature; Utilize centrifugation apparatus to separate mother liquor and crystal grain, get the mother liquor about 313.4g ferrous ammonium sulphate and 460.0g.Add the 40g vitriol oil (95wt%) in the mother liquor and promptly can be used as lysate (amount to 500g) and recycle, finished product ferrous ammonium sulphate content reaches 95.76wt%, the content standard of far super ferrous ammonium sulphate industrial goods 90wt%.
Embodiment2
Take by weighing the lysate of 200g from embodiment 1, pour the flat there-necked flask of 500mL of band magnetic agitation into, slowly add the useless ferrous slag of 100g under agitation condition, 70min finishes dissolving and hydrolysis; Then the velocity flow with 5.00mL/min adds 28wt% analytical pure ammoniacal liquor, and the liquid temperature is no more than 110 ℃ in the control reactor, and the pH value increases to 0.5 behind about 10min, and termination of pumping immediately continues reaction 30min; Through water-bath, ice-water bath cooling, utilize centrifugation apparatus to separate mother liquor and crystal grain, get the mother liquor about 149.8g ferrous ammonium sulphate and 184g.Add the 16g vitriol oil in the mother liquor and promptly can be used as lysate and recycle, the ferrous ammonium sulphate effective content of finished product reaches 93.67wt%, surpasses the content standard of ferrous ammonium sulphate industrial goods 90wt%.
Embodiment3
Operation similarly to Example 2 just substitutes 28wt% analytical pure ammoniacal liquor with the 35wt% industrial ammonia, finally can get the mother liquor about 153.5g ferrous ammonium sulphate and 179.5g.Adding 20.5g concentration in the mother liquor and be 75% sulfur waste acid can recycle as lysate, and the ferrous ammonium sulphate effective content of finished product reaches 92.31wt%, surpasses the content standard of ferrous ammonium sulphate industrial goods 90wt%.
Embodiment4
The dilute sulphuric acid that takes by weighing 500kg concentration and be 7.6wt% is made lysate, pumps into the 1000L dissolving hydrolytic tank that band stirs, and starts stirrer, slowly adds the useless ferrous slag of 250kg, finishes and continues to stir 30min; Then open the liquefied ammonia valve, with the filling of the speed about 0.5kg/min liquefied ammonia, the liquid temperature is no more than 110 ℃ in the control reactor, and the pH value increases to 0.5 behind about 61min, closes the liquefied ammonia valve, continues reaction 30min; Mixed solution is put into crystallizer carry out crystallisation by cooling, separation and purification, get the mother liquor about 308.1kg ferrous ammonium sulphate and 460.3kg.Mother liquor enters the conditioning groove, add the 38.5kg industrial sulphuric acid (98～99wt%) and the 1.2L tap water, promptly can be used as lysate (amounting to 500kg) and recycle.The ferrous ammonium sulphate content 94.89wt% of finished product is above the specification of quality of ferrous ammonium sulphate industrial goods 90wt%.
Embodiment5
500kg lysate in the embodiment 4 conditioning grooves is pumped into the 1000L dissolving hydrolytic tank that band stirs, start stirrer, slowly add the useless ferrous slag of 250kg, finish and continue to stir 80min; Then open the liquefied ammonia valve, with the filling of the speed about 0.5kg/min liquefied ammonia, the liquid temperature is no more than 110 ℃ in the control reactor, and the pH value increases to 0.5 behind about 67min, closes the liquefied ammonia valve, continues reaction 30min; Mixed solution is put into crystallizer carry out crystallisation by cooling, separation and purification, get the mother liquor about 368.5kg ferrous ammonium sulphate and 416.7kg.Mother liquor enters the conditioning groove, adds 76kg sulfur waste acid (50wt%) and 7.3L tap water.The effective content 95.01wt% of finished product ferrous ammonium sulphate is above the specification of quality of ferrous ammonium sulphate industrial goods 90wt%.
Embodiment6
Operation similarly to Example 5, just substitute liquefied ammonia with the 35wt% industrial ammonia, finally can get the ferrous sulfate ammonium product of 375.4kg content 93.22wt% and the mother liquor about 461kg, mother liquor only need be added the 39kg industrial sulphuric acid at the conditioning groove, and (98～99wt%) get final product.
Claims (6)
1. the method for preparing ferrous ammonium sulphate with the useless ferrous slag of sulfuric acid method titanium pigment industry, it is characterized in that comprising the steps: that (1) is that the lysate of 7.5～7.6wt% pumps into reactor with the sulfuric acid content of 2 parts of weight, start stirrer, restir behind the useless ferrous slag of 1 part of weight of adding, when temperature no longer raises, when feed liquid has been converted into the tawny clear liquid, finish dissolving and hydrolysis; (2) add ammonia again, the liquid temperature is no more than 110 ℃ in the control reactor, and the pH value when the pH value is elevated to 0.5, stops ammonification below 1.0 immediately, continues insulation reaction 0.5～1.5h, gets the ferrous ammonium sulphate mixing solutions; (3) mixing solutions solid phase after crystallisation by cooling, separation and purification is the ferrous ammonium sulphate product, and last liquid phase is as the mother liquor that can be recycled.
2. the method for preparing ferrous ammonium sulphate with the useless ferrous slag of sulfuric acid method titanium pigment industry according to claim 1, it is characterized in that being used as lysate described mother liquor is added sulfuric acid/water in the conditioning groove after, pump into reactor and recycle, sulfuric acid content is 7.5～7.6wt% in the lysate.
3. according to claim 1ly prepare the method for ferrous ammonium sulphate, it is characterized in that the described restir time of step (1) is 0.5～1.5h with the useless ferrous slag of sulfuric acid method titanium pigment industry.
4. the method for preparing ferrous ammonium sulphate with the useless ferrous slag of sulfuric acid method titanium pigment industry according to claim 1, it is characterized in that described useless ferrous slag is that mother liquor is discharged behind enrichment process behind the hydrolysis of sulfuric acid method titanium pigment industry titanyl sulfate, the separation metatitanic acid, its molecule constitutes FeSO
4XH
2SO
4YH
2O, x=0.5～0.6, y=0.9～1.2.
5. according to claim 1ly prepare the method for ferrous ammonium sulphate, it is characterized in that described ammonia is one or both of liquefied ammonia, ammoniacal liquor with the useless ferrous slag of sulfuric acid method titanium pigment industry.
6. according to claim 5ly prepare the method for ferrous ammonium sulphate, it is characterized in that described sulfuric acid, liquefied ammonia and ammoniacal liquor are one or more of chemical reagent, industrial goods, waste material of different grades with the useless ferrous slag of sulfuric acid method titanium pigment industry.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102419321A (en) * | 2011-08-24 | 2012-04-18 | 同济大学 | Method for determining maximum value of ferrous ion impurity content |
| CN110586950A (en) * | 2019-10-14 | 2019-12-20 | 王敏 | Method for preparing 3D printing material by using titanium dioxide byproduct |
| CN111847520A (en) * | 2020-08-07 | 2020-10-30 | 攀枝花学院 | A kind of preparation method of ferrous ammonium sulfate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4058389A (en) * | 1974-12-20 | 1977-11-15 | Societa' Italiana Resine S.I.R. S.P.A. | Process for the preparation of fertilizers and soil modifiers |
| CN1200364A (en) * | 1997-05-22 | 1998-12-02 | 上海太平洋化工(集团)有限公司 | Method for preparing ferrous ammonium sulfate by using waste water from sulfuric acid method prodn. of titanium dioxide |
| US20050039508A1 (en) * | 2003-05-27 | 2005-02-24 | Burnham Jeffrey C. | Organic recycling with metal addition |
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2010
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4058389A (en) * | 1974-12-20 | 1977-11-15 | Societa' Italiana Resine S.I.R. S.P.A. | Process for the preparation of fertilizers and soil modifiers |
| CN1200364A (en) * | 1997-05-22 | 1998-12-02 | 上海太平洋化工(集团)有限公司 | Method for preparing ferrous ammonium sulfate by using waste water from sulfuric acid method prodn. of titanium dioxide |
| US20050039508A1 (en) * | 2003-05-27 | 2005-02-24 | Burnham Jeffrey C. | Organic recycling with metal addition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102419321A (en) * | 2011-08-24 | 2012-04-18 | 同济大学 | Method for determining maximum value of ferrous ion impurity content |
| CN102419321B (en) * | 2011-08-24 | 2013-11-13 | 同济大学 | Method for determining maximum value of ferrous ion impurity content |
| CN110586950A (en) * | 2019-10-14 | 2019-12-20 | 王敏 | Method for preparing 3D printing material by using titanium dioxide byproduct |
| CN111847520A (en) * | 2020-08-07 | 2020-10-30 | 攀枝花学院 | A kind of preparation method of ferrous ammonium sulfate |
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