CN103553138A - Comprehensive utilization method for separating, concentrating and purifying manganese sulfate, magnesium sulfate and calcium sulfate in high-salt waste water - Google Patents
Comprehensive utilization method for separating, concentrating and purifying manganese sulfate, magnesium sulfate and calcium sulfate in high-salt waste water Download PDFInfo
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- CN103553138A CN103553138A CN201310539000.4A CN201310539000A CN103553138A CN 103553138 A CN103553138 A CN 103553138A CN 201310539000 A CN201310539000 A CN 201310539000A CN 103553138 A CN103553138 A CN 103553138A
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- sulfate
- waste water
- calcium
- manganese
- sal epsom
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 80
- 239000002351 wastewater Substances 0.000 title claims abstract description 69
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- 235000019341 magnesium sulphate Nutrition 0.000 title claims abstract description 17
- 229910052943 magnesium sulfate Inorganic materials 0.000 title claims abstract description 16
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title claims description 45
- 235000011132 calcium sulphate Nutrition 0.000 title abstract description 33
- 229940099596 manganese sulfate Drugs 0.000 title abstract 3
- 239000011702 manganese sulphate Substances 0.000 title abstract 3
- 235000007079 manganese sulphate Nutrition 0.000 title abstract 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 83
- 238000001914 filtration Methods 0.000 claims abstract description 33
- 238000001704 evaporation Methods 0.000 claims abstract description 27
- 230000008020 evaporation Effects 0.000 claims abstract description 23
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000012452 mother liquor Substances 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 230000018044 dehydration Effects 0.000 claims description 26
- 238000006297 dehydration reaction Methods 0.000 claims description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- 239000011777 magnesium Substances 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 18
- 239000011572 manganese Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 15
- 239000006200 vaporizer Substances 0.000 claims description 14
- 238000013459 approach Methods 0.000 claims description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- 230000009615 deamination Effects 0.000 claims description 7
- 238000006481 deamination reaction Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 5
- 229910001424 calcium ion Inorganic materials 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 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 5
- 239000000203 mixture Substances 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 abstract description 6
- 239000000347 magnesium hydroxide Substances 0.000 abstract description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 abstract description 6
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 abstract description 6
- 239000001175 calcium sulphate Substances 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract 1
- 235000011941 Tilia x europaea Nutrition 0.000 abstract 1
- 239000004571 lime Substances 0.000 abstract 1
- 229910001425 magnesium ion Inorganic materials 0.000 abstract 1
- 229910001437 manganese ion Inorganic materials 0.000 abstract 1
- 239000008267 milk Substances 0.000 abstract 1
- 210000004080 milk Anatomy 0.000 abstract 1
- 235000013336 milk Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- KNLQKHUBPCXPQD-UHFFFAOYSA-N manganese;sulfuric acid Chemical compound [Mn].OS(O)(=O)=O KNLQKHUBPCXPQD-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
The invention relates to a comprehensive utilization method for separating, concentrating and purifying manganese sulfate, magnesium sulfate and calcium sulfate in high-salt waste water. The method is characterized by comprising the following steps of maintaining the temperature of mother liquor of waste water at 50DEG C to 60DEG C, utilizing ammonia water or liquid ammonia to adjust the pH value of the waste water to 10 to 1.5, collecting separating manganese ions and magnesium ions in the waste water in a form of manganese hydroxide and magnesium hydroxide, adding sulfuric acid into the separated manganese hydroxide and magnesium hydroxide to prepare a manganese sulfate solution and a magnesium sulfate solution, and adopting a segmented evaporation crystallization method to realize the separation to produce manganese sulfate monohydrate and magnesium sulfate hexahydrate; adding lime milk into the waste water after the manganese hydroxide and magnesium hydroxide are separated to adjust the pH value, crystallizing calcium sulfate, precipitating the calcium sulfate, and press filtering the calcium sulfate to produce calcium sulphate dehydrate. After being treated by utilizing the method, the waste water can reach the emission standard and can be externally discharged or recycled by the enterprise, and solid wastes in the waste water can be completely recycled. The investment is low, and the annual net investment return rate is more than 15 percent.
Description
Technical field
The invention belongs to wastewater treatment production field in the chemical fields such as manganese work, vanadium chemical industry and metallurgy industry heavy metal distill, be specifically related to manganous sulfate in the high-salt wastewater of sulfur acid manganese, sal epsom, calcium sulfate, sal epsom, calcium sulfate substep separation, condensing crystal, purification and wastewater recycling method.
Background technology
Electrolytic manganese enterprise produces in process at qualified manganous sulfate electrolytic solution, and vanadium chemical enterprise is in the process of calcification baking production vanadium oxide, mostly can produce the high-salt wastewater of sulfur acid manganese, sal epsom, calcium sulfate, wherein Mn
2+content is at 10-20g/L, Mg
2+content is at 1-3g/L, Ca
2+content, at 0.5-1.5g/L, also contains the heavy metal ion of denier simultaneously.Beavy metal impurity is removed problem, and enterprise all can solve.Separation for manganous sulfate, sal epsom, calcium sulfate, the treating method of current most enterprises is, first with milk of lime by manganous sulfate, sal epsom, calcium sulfate coprecipitation out, waste water arranges or manages reuse more outward, because the manganous sulfate being precipitated out, sal epsom, calcium sulfate cannot be separated, not only wasted resource, and the waste water after processing is also difficult to reach emission standard.Ye You enterprise proposes the way of carrying out manganous sulfate electrolysis after deliming, but because sal epsom content in waste water is higher, greatly increased electrolytic power consumption, manganous sulfate concentration is too low simultaneously, do not reach the concentration requirement of qualified electrolytic solution far away, moreover also have a large amount of calcium ions to exist, therefore cannot walk logical, and with high costs, lose more than gain.Also some manganous sulfate manufacturing enterprise, although calcium, magnesium are removed from manganous sulfate, has lost quite a few manganous sulfate, and the calcium of separating in the lump, magnesium have also wasted.Along with the enforcement of environmental protection and energy-conservation new standard, and the increasing of supervision, this class waste water is difficult to qualified discharge, especially resource and cannot fully utilizes.For this reason, try to explore new treatment process, meeting under the prerequisite of national environmental standard, realize the target of comprehensive utilization of resources, become the important and eager task of above-mentioned enterprise and scientific research institution.
Therefore, manganese work, vanadium chemical industry and similarly other heavy metal distill enterprises, be badly in need of a kind of technological treatment, can, by the manganous sulfate in waste water, sal epsom, the comprehensive extraction and application of calcium sulfate, realize comprehensive utilization of resources and wastewater zero discharge; Investment is simultaneously relatively moderate, and realizes as far as possible the positive income of operation.
Summary of the invention
The object of this invention is to provide the method for comprehensive utilization that manganous sulfate in a kind of high-salt wastewater, sal epsom, calcium sulfate are separated, concentrated, purify, make waste water can meet national requirements for environmental protection completely after treatment, and realize comprehensive utilization of resources, thereby turn waste into wealth, the final quality of production that improves, promotes society and economic benefit.
For achieving the above object, the technical solution used in the present invention is: the method for comprehensive utilization that manganous sulfate in a kind of high-salt wastewater, sal epsom, calcium sulfate be separated, concentrated, purify: comprise the steps:
(1) high-salt wastewater mother liquor enters airtight wastewater equalization pond, and temperature remains on 50～60 ℃, first in waste water, quantitatively adds ammoniacal liquor or liquefied ammonia, and waste water ph is adjusted to 10～10.5, and manganese, magnesium are with Mn (OH)
2and Mg (OH)
2form precipitate; Keep precipitation endpoint pH 8～8.5, install after filtration by Mn (OH)
2and Mg (OH)
2filtered while hot out; Simultaneously by the Mn filtering out (OH)
2and Mg (OH)
2mix slag and wash with 50～60 ℃ of hot water, secondary filtration centrifuge dehydration after washing, to remove impurity calcium ion and ammonium sulfate;
(2) Mn after secondary filtration (OH)
2and Mg (OH)
2mix slag slurry and squeeze into rapidly confined reaction tank, add water, 75% sulfuric acid is added to retort through acid adding device simultaneously, at the uniform velocity stir, generate manganous sulfate, Adlerika, control pH value 4～4.2, and keep after reaction in the interior solution of tank manganous sulfate, the common content mass concentration of sal epsom 25～30%; Solution enters strainer and filters, and calcium sulfate will further be separated out;
(3) solution after reaction in (2) is filtered by first step manganous sulfate vaporizer, at 140～145 ℃ of evaporation concentration to sal epsom, approach saturated, a large amount of manganese sulfate monohydrate crystallizations, rapid centrifuge dehydration under high temperature; With the steam condensate of 140～145 ℃, the crystal after to centrifugation washs again, and after washing, recentrifuge is separated, obtains manganese sulfate monohydrate finished product after dry; Supernatant liquor after separation and high-temperature wash, the remaining liquid after separated, enter sal epsom low-temperature evaporation crystal system, at 55～65 ℃ of negative pressure evaporation to manganous sulfates, approach saturated, a large amount of six water magnesium sulfate crystallizations, by whizzer centrifuge dehydration, after being dried, obtain six water magnesium sulfate finished products;
(4) mother liquor after sal epsom centrifugation in (3) is squeezed into second stage manganous sulfate vaporizer, at 140～145 ℃ of temperature again evaporation concentration to sal epsom approach saturated, a large amount of manganese sulfate monohydrate crystallizations, rapid centrifuge dehydration under high temperature; With the steam condensate of 140～145 ℃, the crystal after to centrifugation washs again, and after washing, recentrifuge is separated, obtains manganese sulfate monohydrate finished product after dry; Supernatant liquor after separation enters the sal epsom low-temperature evaporation crystal system in (3), approaches saturatedly at 55～65 ℃ of negative pressure evaporation to manganous sulfates, and a large amount of six water magnesium sulfate crystallizations, by whizzer centrifuge dehydration, obtain six water magnesium sulfate finished products after dry;
(5) mother liquor after sal epsom centrifugation in (4) is returned to second stage manganous sulfate vaporizer circulating and evaporating crystallization;
(6) by the remaining liquid after twice filtration in (1), washing, the filter residue in (2), airtight second homogenate equalizing tank is squeezed in unification, by adder-subtractor, liquid milk of lime is added, pH value is adjusted to 11.5～12, stirrer at the uniform velocity stirs, terra alba is separated out in a large number, becomes terra alba finished product after pressure filter press filtration;
(7) supernatant liquor that secondary equalizing tank overflows from (6) enters airtight No. three equalizing tanks, in waste water, still contain a small amount of calcium sulfate and calcium hydroxide, Xiang Chizhong adds 1.3～1.8 kilograms of sodium carbonate by every side's waste water, the calcium carbonate precipitating carries out centrifuge dehydration, become calcium carbonate finished product, remaining liquid enters deamination system after further filtering, and the slag slurry of filtering returns to the centrifuge dehydration of calcium carbonate centrifuge dehydration system, obtains calcium carbonate finished product;
(8) deliming (7) being obtained, the mother liquor after filtering, enter ammonia steaming system and carry out deamination processing, and by ammonia nitrogen removal, to after 15mg/L below, waste water is as process water reuse or directly discharge;
(9) ammonia that removes out in (8) is absorbed by ammonia absorber, produce the ammoniacal liquor that concentration is greater than 15%, be back to use wastewater equalization pond in (1), for regulating pH value.
Principal feature of the present invention is: first the manganous sulfate in waste water, sal epsom are separated jointly with the form of manganous hydroxide, magnesium hydroxide, calcium sulfate is stayed in waste water; Then the manganous hydroxide of separating, magnesium hydroxide are added to sulfuric acid extracting sulfuric acid manganese, Adlerika, and adopt the way of stage evaporation crystallization to realize separation, produce manganese sulfate monohydrate and six water magnesium sulfates; The waste water of isolating manganous hydroxide and magnesium hydroxide first adds milk of lime and regulates pH value, by calcium sulfate precipitation out, produces terra alba after press filtration; Finally the ammonia-containing water of isolating manganous sulfate, sal epsom, calcium sulfate is taked to the way removal of ammonia and nitrogen of ammonia still process, and the ammonia nitrogen removing is produced to more than 15% strong aqua, at this treatment system internal recycle, use; Steam thermal energy repeatedly utilizes simultaneously, and energy-saving effect is obvious.Waste water after processing reaches emission standard, can arrange outward or reuse enterprises, and the manganous sulfate in waste water, sal epsom, calcium sulfate are all recycled, round Realization the recycling economy target of wastewater zero discharge, solid waste complete utilization.Present method investment is lower, and year clean return rate of investment more than 15%, can be used for the waste water comprehensive treating process utilization of similar technological process.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Accompanying drawing 1 is shown in technical process of the present invention
The main water-quality guideline table of high-salt wastewater after removing heavy metals
(1) high-salt wastewater mother liquor enters airtight wastewater equalization pond, and temperature remains on 50～60 ℃, first in waste water, quantitatively adds ammoniacal liquor or liquefied ammonia, and waste water ph is adjusted to 10～10.5, and manganese, magnesium are with Mn (OH)
2and Mg (OH)
2form precipitate; Keep precipitation endpoint pH 8～8.5, install after filtration by Mn (OH)
2and Mg (OH)
2filtered while hot out, water ratio 40%; Simultaneously by the Mn filtering out (OH)
2and Mg (OH)
2mix slag 280g, 50～60 ℃ of hot water wash, and secondary filtration centrifuge dehydration after washing, to remove impurity calcium ion and ammonium sulfate; The heavy 298g of meter after secondary filtration dehydration, water ratio 8%, calcium sulphate content accounts for 0.02% of butt weight; Ammonium sulfate accounts for 0.24%;
(2) Mn (OH) 2 after secondary filtration dehydration and Mg (OH) 2 mixing slag slurries are squeezed into rapidly confined reaction tank, add 50～60 ℃ of hot water 1275g, 75% sulfuric acid is quantitatively added to retort through acid adding device simultaneously, in tank, establishing stirrer at the uniform velocity stirs, promote Mn (OH) 2, Mg (OH) 2 and sulfuric acid fully to react, generate manganous sulfate, Adlerika, keep manganous sulfate, the common content mass concentration of sal epsom in the interior solution of the rear tank of reaction 25～30%, to control pH value 4～4.2; The calcium sulfate impurity that also contains minute quantity in solution, according to the common-ion effcet of calcium sulfate and manganous sulfate, sal epsom, solution enters strainer and filters, and calcium sulfate will further be separated out; After filtration, solution weight 2005g;
(3) solution after reaction filtration in (2) is approached saturated by first step manganous sulfate vaporizer at 140～145 ℃ of evaporation concentration to sal epsom, because manganous sulfate solubleness at this temperature only has 30% left and right of sal epsom solubleness, a large amount of manganese sulfate monohydrate crystallizations, centrifuge dehydration rapidly under high temperature; For improving purity, then the crystal after to centrifugation washs with the steam condensate 100g of 140～145 ℃, and after washing, recentrifuge is separated, obtains manganese sulfate monohydrate finished product after dry, and meter weighs 358g, purity 99.3%.The remaining liquid of supernatant liquor after separation and high-temperature wash, enter sal epsom low-temperature evaporation crystal system, at 55～65 ℃ of negative pressure evaporation to manganous sulfates, approach saturated, because sal epsom quality in solution is now the more than three times of manganous sulfate, and at this temperature, the solubleness of the two approaches, a large amount of six water magnesium sulfate crystallizations, by whizzer centrifuge dehydration, after dry, obtain six water magnesium sulfate finished products, the heavy 65.5g of meter, purity 96.2%;
(4) mother liquor after sal epsom centrifugation in (3) is squeezed into second stage manganous sulfate vaporizer, at 140～145 ℃ of temperature, evaporation concentration to sal epsom approaches saturatedly again, makes a large amount of manganese sulfate monohydrate crystallizations, rapid centrifuge dehydration under high temperature; For improving purity, then the crystal after to centrifugation washs with the steam condensate of 140～145 ℃, and after washing, recentrifuge is separated, obtains manganese sulfate monohydrate finished product after dry, and meter weighs 20.5g, purity 99.2%.The remaining liquid of supernatant liquor after separation and high-temperature wash, enter the sal epsom low-temperature evaporation crystal system in (3), at 55～65 ℃ of negative pressure evaporation to manganous sulfates, approach saturated, a large amount of six water magnesium sulfate crystallizations, by whizzer centrifuge dehydration, after dry, obtain six water magnesium sulfate finished products, the heavy 20.6g of meter, purity 96.5%;
(5) mother liquor after sal epsom centrifugation in (4) is returned to second stage manganous sulfate vaporizer circulating and evaporating crystallization.(3) evaporative crystallization of two circulations-(4), reclaim manganese sulfate monohydrate contents on dry basis 378.5g(358+20.5), average purity 99.29% ((358*99.3%+20.5*99.2)/(358+20.5)), amount to pure manganous sulfate 375.83g, the rate of recovery (accounting for the ratio of manganous sulfate total amount 398g in waste water) 94.4%; Reclaim six water magnesium sulfate contents on dry basis 86.1g(65.5+20.6), average purity 96.27%, amounts to pure sal epsom 82.89g, the rate of recovery (accounting for the ratio of sal epsom total amount 100.3g in waste water) 82.6%.Continue circulating and evaporating, manganous sulfate, the sal epsom rate of recovery all approach 100%, and manganous sulfate purity is stabilized in more than 99%, and sal epsom purity is stabilized in more than 96%.
(6) by the remaining liquid after twice filtration in (1), washing, the filter residue in (2), airtight second homogenate equalizing tank is squeezed in unification, by adder-subtractor, liquid milk of lime is quantitatively added, stirrer at the uniform velocity stirs, pH value is adjusted to 11.5～12, and terra alba is separated out in a large number, becomes terra alba finished product after pressure filter press filtration, the heavy 832g of terra alba meter, water ratio 10%; Calcium sulfate (not containing crystal water) butt weight 592g, purity 99%, the rate of recovery (account for the ratio of calcium sulfate total amount 626g in waste water, this calcium sulfate total amount comprises because adding the newly-generated calcium sulfate of milk of lime) 94.5%;
(7) supernatant liquor that secondary equalizing tank overflows from (6) enters airtight No. three equalizing tanks, in waste water, still contain a small amount of calcium sulfate and calcium hydroxide, for guaranteeing equipment non-scaling in subsequent disposal, must remove a part of calcium ion: Xiang Chizhong and add 1.6 kilograms of sodium carbonate by every side's waste water, the calcium sulfate dissolving in water and calcium hydroxide are removed to 40%, the calcium carbonate precipitating carries out centrifuge dehydration, becomes precipitated chalk finished product; Remaining liquid enters deamination system after further filtering, and the slag slurry of filtering returns to the centrifuge dehydration of calcium carbonate centrifuge dehydration system, obtains calcium carbonate finished product; Calcium carbonate finished product, amounts to heavy 16.8g, water ratio 10%;
(8) mother liquor after the deliming (7) being obtained, filtration, enters ammonia steaming system and carries out deamination processing.Fresh feed pump is squeezed into ammonia still by waste water and is carried the liquid distributor that heats up in a steamer layer top, after the even cloth liquid of liquid distributor, heats up in a steamer a layer filler natural flow from top to bottom by carrying; At the bottom of tower, waste water up to standard is squeezed into the outer vaporizer of tower and containing ammonia secondary steam, is carried out indirect heat exchange with ammonia still steams, and heated hot wastewater reenters the interior flash distillation of ammonia still, and the secondary steam of generation is as the gentle matter of recommending of thermal source of air lift ammonia still process.Secondary steam heats up in a steamer layer filler and upwards flows by carrying from bottom to top, and with waste water reverse contact between filler, free ammonia constantly shifts from waste water in steam.Relative volatility principle during according to vapor liquid equilibrium, waste water more walks downward, and ammonia nitrogen parsing removes more thorough.In the time of at the bottom of arrival tower, waste water is parsed, and its ammonia-nitrogen content reaches 13mg/L.Waste water up to standard is got in tower, and enters after tower wastewater heat exchange as process water reuse or directly discharge.
(9) ammonia that ammonia still removes is prepared ammoniacal liquor.In steam in the ammonia still process mobile from bottom to top, constantly the ammonia in waste water is absorbed, more up walk himself ammonia level also higher, until discharge from tower top.Should containing ammonia secondary steam after vapour compressor increasing temperature and pressure, enter the outer vaporizer shell side of tower, self is condensed into weak ammonia, is to improve ammonia concn, the rectifying layer that adopts the mode that refluxes that weak ammonia is returned to the ammonia still top ammonia still process that circulates.The ammonia not being condensed enters ammonia absorption tower by vacuum system, and the mass ratio of pressing water, ammonia 6:1 is toward spray technology water in ammonia absorption tower, to the ammonia absorption that circulates.Because of ammonia meeting heat release in water-soluble process, absorption liquid temperature rising meeting exerts an influence to making the concentration of ammoniacal liquor, so condenser is set on absorption tower, absorption liquid is lowered the temperature, and ammonia is absorbed under the low-temperature condition that maintains 45～50 ℃ and carry out.After ammonia concn reaches 15%, be back to use wastewater equalization pond in (1), for regulating pH value.
So far, the manganous sulfate in waste water, sal epsom, calcium sulfate is separated and recovery all, and waste water is realized reuse, and the ammoniacal liquor adding is in the utilization of system internal recycle.
Major equipment of the present invention and facility comprise: vaporizer, preheater, recycle pump, vacuum pump, crystallizer, thickener, whizzer, stirrer, filtration unit, moisture eliminator, container for storing liquid, equalizing tank, ammonia still, ammonia absorber etc.In the present invention, the first step, second stage manganous sulfate vaporizer heat are provided by the raw steam of external High Temperature High Pressure, and the heat of sal epsom low-temperature evaporation crystal system is in the first step, second stage manganous sulfate vaporizer, and the secondary steam producing during solution evaporation provides; Secondary steam more than needed is with after outer next life, steam mixed, as the origin of heat of ammonia still deamination; Steam condensate is used for high-temperature wash and waste water heats, solution preheating water; Remaining manganous sulfate, Adlerika after low temperature crystallization, carry out indirect heat exchange with remaining solution after high temperature evaporation, to save process energy consumption; System itself is without material enrichment problem.
Claims (1)
1. separated, concentrated, the method for comprehensive utilization of purifying of manganous sulfate in high-salt wastewater, sal epsom, calcium sulfate, is characterized in that: comprise the steps:
(1) high-salt wastewater mother liquor enters airtight wastewater equalization pond, and temperature remains on 50～60 ℃, first in waste water, quantitatively adds ammoniacal liquor or liquefied ammonia, and waste water ph is adjusted to 10～10.5, and manganese, magnesium are with Mn (OH)
2and Mg (OH)
2form precipitate; Keep precipitation endpoint pH 8～8.5, install after filtration by Mn (OH)
2and Mg (OH)
2filtered while hot out; Simultaneously by the Mn filtering out (OH)
2and Mg (OH)
2mix slag and wash with 50～60 ℃ of hot water, secondary filtration centrifuge dehydration after washing, to remove impurity calcium ion and ammonium sulfate;
(2) Mn after secondary filtration (OH)
2and Mg (OH)
2mix slag slurry and squeeze into rapidly confined reaction tank, add water, 75% sulfuric acid is added to retort through acid adding device simultaneously, at the uniform velocity stir, generate manganous sulfate, Adlerika, control pH value 4～4.2, and keep after reaction in the interior solution of tank manganous sulfate, the common content mass concentration of sal epsom 25～30%; Solution enters strainer and filters, and calcium sulfate will further be separated out;
(3) solution after reaction in (2) is filtered by first step manganous sulfate vaporizer, at 140～145 ℃ of evaporation concentration to sal epsom, approach saturated, a large amount of manganese sulfate monohydrate crystallizations, rapid centrifuge dehydration under high temperature; With the steam condensate of 140～145 ℃, the crystal after to centrifugation washs again, and after washing, recentrifuge is separated, obtains manganese sulfate monohydrate finished product after dry; Supernatant liquor after separation and high-temperature wash, the remaining liquid after separated, enter sal epsom low-temperature evaporation crystal system, at 55～65 ℃ of negative pressure evaporation to manganous sulfates, approach saturated, a large amount of six water magnesium sulfate crystallizations, by whizzer centrifuge dehydration, after being dried, obtain six water magnesium sulfate finished products;
(4) mother liquor after sal epsom centrifugation in (3) is squeezed into second stage manganous sulfate vaporizer, at 140～145 ℃ of temperature again evaporation concentration to sal epsom approach saturated, a large amount of manganese sulfate monohydrate crystallizations, rapid centrifuge dehydration under high temperature; With the steam condensate of 140～145 ℃, the crystal after to centrifugation washs again, and after washing, recentrifuge is separated, obtains manganese sulfate monohydrate finished product after dry; Supernatant liquor after separation enters the sal epsom low-temperature evaporation crystal system in (3), approaches saturatedly at 55～65 ℃ of negative pressure evaporation to manganous sulfates, and a large amount of six water magnesium sulfate crystallizations, by whizzer centrifuge dehydration, obtain six water magnesium sulfate finished products after dry;
(5) mother liquor after sal epsom centrifugation in (4) is returned to second stage manganous sulfate vaporizer circulating and evaporating crystallization;
(6) by the remaining liquid after twice filtration in (1), washing, the filter residue in (2), airtight secondary equalizing tank is squeezed in unification, by adder-subtractor, liquid milk of lime is added, pH value is adjusted to 11.5～12, stirrer at the uniform velocity stirs, terra alba is separated out in a large number, becomes terra alba finished product after pressure filter press filtration;
(7) supernatant liquor that secondary equalizing tank overflows from (6) enters airtight No. three equalizing tanks, in waste water, still contain a small amount of calcium sulfate and calcium hydroxide, Xiang Chizhong adds 1.3～1.8 kilograms of sodium carbonate by every side's waste water, the calcium carbonate precipitating carries out centrifuge dehydration, become calcium carbonate finished product, remaining liquid enters deamination system after further filtering, and the slag slurry of filtering returns to the centrifuge dehydration of calcium carbonate centrifuge dehydration system, obtains calcium carbonate finished product;
(8) deliming (7) being obtained, the mother liquor after filtering, enter ammonia steaming system and carry out deamination processing, and by ammonia nitrogen removal, to after 15mg/L below, waste water is as process water reuse or directly discharge;
(9) ammonia that removes out in (8) is absorbed by ammonia absorber, produce the ammoniacal liquor that concentration is greater than 15%, be back to use wastewater equalization pond in (1), for regulating pH value.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0567373A1 (en) * | 1992-04-24 | 1993-10-27 | Socadour | Fluid hydrated ferrous sulfate and process for fluidizing polyhydrated metallic sulfates |
| CN102115245A (en) * | 2010-12-30 | 2011-07-06 | 何云 | Method for preparing chloride and magnesium sulfate mixed product and calcium sulfate with manganese-containing waste liquid |
| CN102249262A (en) * | 2011-04-29 | 2011-11-23 | 史永军 | Concentration and cold-precipitation separation method of sodium sulfate and ammonium sulfate from vanadium-precipitation mother liquor high-salt wastewater |
| CN102260001A (en) * | 2011-07-22 | 2011-11-30 | 内蒙古介电电泳应用技术研究院 | Process for treating and recycling rare-earth wastewater containing magnesium sulfate, ammonium sulfate and sulfuric acid |
| US20120316340A1 (en) * | 2009-11-26 | 2012-12-13 | Universite Montpellier 2 Sciences Et Techniques | Use of metal-accumulating plants for the preparation of catalysts that can be used in chemical reactions |
| CN103241887A (en) * | 2013-05-27 | 2013-08-14 | 兰州节能环保工程有限责任公司 | Method and device for treating and recycling high salinity wastewater |
-
2013
- 2013-11-01 CN CN201310539000.4A patent/CN103553138B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0567373A1 (en) * | 1992-04-24 | 1993-10-27 | Socadour | Fluid hydrated ferrous sulfate and process for fluidizing polyhydrated metallic sulfates |
| US20120316340A1 (en) * | 2009-11-26 | 2012-12-13 | Universite Montpellier 2 Sciences Et Techniques | Use of metal-accumulating plants for the preparation of catalysts that can be used in chemical reactions |
| CN102115245A (en) * | 2010-12-30 | 2011-07-06 | 何云 | Method for preparing chloride and magnesium sulfate mixed product and calcium sulfate with manganese-containing waste liquid |
| CN102249262A (en) * | 2011-04-29 | 2011-11-23 | 史永军 | Concentration and cold-precipitation separation method of sodium sulfate and ammonium sulfate from vanadium-precipitation mother liquor high-salt wastewater |
| CN102260001A (en) * | 2011-07-22 | 2011-11-30 | 内蒙古介电电泳应用技术研究院 | Process for treating and recycling rare-earth wastewater containing magnesium sulfate, ammonium sulfate and sulfuric acid |
| CN103241887A (en) * | 2013-05-27 | 2013-08-14 | 兰州节能环保工程有限责任公司 | Method and device for treating and recycling high salinity wastewater |
Non-Patent Citations (2)
| Title |
|---|
| 晁雷等: "高盐废水处理工艺技术研究进展", 《安徽农业科学》 * |
| 李福勤等: "高盐废水制取高纯水工艺研究", 《水处理技术》 * |
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