CN103553138B - 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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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 field 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, magnesium sulfate, calcium sulfate, magnesium sulfate, calcium sulfate substep separation, condensing crystal, purification and wastewater recycling method.
Background technology
Electrolytic manganese enterprise is in qualified manganese sulfate electrolyte producing process, and vanadium chemical enterprise is produced in the process of vanadium oxide at calcification baking, mostly can produce the high-salt wastewater of sulfur acid manganese, magnesium sulfate, 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 removes problem, and enterprise all can solve.For the separation of manganous sulfate, magnesium sulfate, calcium sulfate, the treating method of current most enterprise is, first with milk of lime by manganous sulfate, magnesium sulfate, calcium sulfate coprecipitation out, waste water is outer again to be arranged or manages reuse, because the manganous sulfate, magnesium sulfate, the calcium sulfate that are precipitated out cannot be separated, not only waste resource, and the waste water after process is also difficult to reach emission standard.Ye You enterprise carries out the way of manganous sulfate electrolysis after proposing deliming, but because in waste water, magnesium sulfate content is higher, considerably increase 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, have lost quite a few manganous sulfate, and the calcium separated in the lump, magnesium has also wasted.Along with the enforcement of environmental protection and energy-conservation new standard, and the increasing of supervision, this kind of waste water is difficult to qualified discharge, and especially resource cannot fully utilize.For this reason, try to explore new treatment process, under the prerequisite meeting 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 other similar heavy metal distill enterprises, be badly in need of a kind of technological treatment, by the manganous sulfate in waste water, magnesium sulfate, the comprehensive extraction and application of calcium sulfate, can realize comprehensive utilization of resources and wastewater zero discharge; Invest rather moderate simultaneously, and realize as far as possible running positive income.
Summary of the invention
The object of this invention is to provide manganous sulfate in a kind of high-salt wastewater, magnesium sulfate, calcium sulfate be separated, concentrated, the method for comprehensive utilization of purifying, make waste water can meet national requirements for environmental protection completely after treatment, and realize comprehensive utilization of resources, thus turn waste into wealth, the final raising quality of production, promotes Social and economic benef@.
For achieving the above object, the technical solution used in the present invention is: the method for comprehensive utilization that in a kind of high-salt wastewater, manganous sulfate, magnesium sulfate, calcium sulfate are separated, concentrate, purify: comprise the steps:
(1) high-salt wastewater mother liquor enters airtight wastewater equalization pond, and temperature remains on 50 ~ 60 DEG C, and first in waste water, quantitatively add ammoniacal liquor or liquefied ammonia, waste water ph is adjusted to 10 ~ 10.5, and manganese, magnesium are with Mn (OH)
2with Mg (OH)
2form precipitate; Keep precipitation endpoint pH 8 ~ 8.5, device is by Mn (OH) after filtration
2with Mg (OH)
2filtered while hot out; The Mn (OH) simultaneously will filtered out
2with Mg (OH)
2mixing slag 50 ~ 60 DEG C of hot water wash, and wash rear secondary filtration and centrifuge dehydration, to remove impurity calcium ion and ammonium sulfate;
(2) Mn (OH) after secondary filtration
2with Mg (OH)
2confined reaction tank squeezed into rapidly by mixing slag slurry, add water, the sulfuric acid of 75% is added retort through means for feeding acid simultaneously, at the uniform velocity stir, generate manganous sulfate, Adlerika, control ph 4 ~ 4.2, and after keeping reaction in tank in solution manganous sulfate, the common content mass concentration of magnesium sulfate 25 ~ 30%; Solution enters metre filter, and calcium sulfate will be separated out further;
(3) solution after reaction in (2) being filtered by first step manganous sulfate vaporizer 140 ~ 145 DEG C of evaporation concentration to magnesium sulfate close to saturated, a large amount of manganese sulfate monohydrate crystallization, Quick spin dehydration under high temperature; Wash the crystal after centrifugation with the steam condensate of 140 ~ 145 DEG C, after washing, recentrifuge is separated, and obtains manganese sulfate monohydrate finished product after drying again; Supernatant liquor after separation and high-temperature wash, be separated after remaining liquid, enter magnesium sulfate low-temperature evaporation crystal system, at 55 ~ 65 DEG C of negative pressure evaporations to manganous sulfate close to saturated, a large amount of six water magnesium sulfate crystallizations, dewatered by centrifuge, after drying, obtain six water magnesium sulfate finished products;
(4) mother liquor after magnesium sulfate centrifugation in (3) is squeezed into second stage manganous sulfate vaporizer, at 140 ~ 145 DEG C of temperature again evaporation concentration to magnesium sulfate close to saturated, a large amount of manganese sulfate monohydrate crystallization, Quick spin dehydration under high temperature; Wash the crystal after centrifugation with the steam condensate of 140 ~ 145 DEG C, after washing, recentrifuge is separated, and obtains manganese sulfate monohydrate finished product after drying again; Supernatant liquor after separation enters the magnesium sulfate low-temperature evaporation crystal system in (3), at 55 ~ 65 DEG C of negative pressure evaporations to manganous sulfate close to saturated, a large amount of six water magnesium sulfate crystallizations, are dewatered by centrifuge, obtain six water magnesium sulfate finished products after drying;
(5) mother liquor after magnesium sulfate centrifugation in (4) is returned to second stage manganous sulfate vaporizer circulating and evaporating crystallization;
(6) by remaining liquid, the filter residue in (2) after twice filtration in (1), washing, 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 Control pond overflows from (6) enters airtight No. three equalizing tanks, still containing a small amount of calcium sulfate and calcium hydroxide in waste water, Xiang Chizhong adds 1.3 ~ 1.8 kilograms of sodium carbonate by every side's waste water, the calcium carbonate precipitated carries out centrifuge dehydration, become calcium carbonate finished product, enter deamination system after remaining liquid filters further, the slag slurry of filtering returns the centrifuge dehydration of calcium carbonate centrifuge dehydration system, obtains calcium carbonate finished product;
(8) mother liquor after the deliming (7) obtained, filtration, enter ammonia steaming system and carry out deamination process, after ammonia nitrogen removal to below 15mg/L, waste water is as process water reuse or directly discharge;
(9) ammonia removing 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 adjust ph.
Principal feature of the present invention is: first the manganous sulfate in waste water, magnesium sulfate are jointly separated with the form of manganous hydroxide, magnesium hydroxide, calcium sulfate is stayed in waste water; Then the manganous hydroxide separated, magnesium hydroxide are added sulfuric acid extracting sulfuric acid manganese, Adlerika, and adopt the way of stage evaporation crystallization to realize being separated, produce manganese sulfate monohydrate and six water magnesium sulfates; The waste water isolating manganous hydroxide and magnesium hydroxide first adds milk of lime adjust ph, by calcium sulfate precipitation out, produces terra alba after press filtration; Finally by isolate manganous sulfate, magnesium sulfate, calcium sulfate ammonia-containing water take the way removal of ammonia and nitrogen of ammonia still process, and the ammonia nitrogen removed is produced the strong aqua of more than 15%, uses at present treatment system internal recycle; Steam thermal energy repeatedly utilizes simultaneously, and energy-saving effect is obvious.Waste water after process reaches emission standard, can arrange outward or reuse enterprises, the manganous sulfate in waste water, magnesium sulfate, calcium sulfate are all recycled, the recycling economy target of round Realization wastewater zero discharge, solid waste complete utilization.Present method investment is lower, invests clean return rate more than 15% year, and the waste water comprehensive treating process that can be used for similar technological process utilizes.
Accompanying drawing explanation
Fig. 1 is present invention process schema.
Embodiment
Present invention process flow process is shown in accompanying drawing 1
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 DEG C, and first in waste water, quantitatively add ammoniacal liquor or liquefied ammonia, waste water ph is adjusted to 10 ~ 10.5, and manganese, magnesium are with Mn (OH)
2with Mg (OH)
2form precipitate; Keep precipitation endpoint pH 8 ~ 8.5, device is by Mn (OH) after filtration
2with Mg (OH)
2filtered while hot out, water ratio 40%; The Mn (OH) simultaneously will filtered out
2with Mg (OH)
2mixing slag 280g, 50 ~ 60 DEG C of hot water wash, and wash rear secondary filtration and centrifuge dehydration, to remove impurity calcium ion and ammonium sulfate; Secondary filtration also counts heavy 298g, water ratio 8% after dehydration, 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 mixes slag slurry and squeezes into rapidly confined reaction tank, add 50 ~ 60 DEG C of hot water 1275g, the sulfuric acid of 75% is quantitatively added retort through means for feeding acid simultaneously, stirrer is established at the uniform velocity to stir in tank, promote that Mn (OH) 2, Mg (OH) 2 and sulfuric acid fully react, generate manganous sulfate, Adlerika, to keep after reaction in tank in solution manganous sulfate, the common content mass concentration of magnesium sulfate 25 ~ 30%, control ph 4 ~ 4.2; Also containing the calcium sulfate impurity of minute quantity in solution, according to the common-ion effcet of calcium sulfate and manganous sulfate, magnesium sulfate, solution enters metre filter, and calcium sulfate will be separated out further; After filtration, solution weight 2005g;
(3) solution after reaction in (2) being filtered by first step manganous sulfate vaporizer 140 ~ 145 DEG C of evaporation concentration to magnesium sulfate close to saturated, because at this temperature, manganous sulfate solubleness only has about 30% of magnesium sulfate solubleness, a large amount of manganese sulfate monohydrate crystallization, Quick spin dehydration under high temperature; For improving purity, then wash the crystal after centrifugation with the steam condensate 100g of 140 ~ 145 DEG C, after washing, recentrifuge is separated, and obtains manganese sulfate monohydrate finished product after drying, the heavy 358g of meter, purity 99.3%.Liquid more than supernatant liquor after separation and high-temperature wash, enter magnesium sulfate low-temperature evaporation crystal system, at 55 ~ 65 DEG C of negative pressure evaporations to manganous sulfate close to saturated, due to more than three times that magnesium sulfate quality in now solution is manganous sulfate, and at this temperature, the solubleness of the two is close, a large amount of six water magnesium sulfate crystallizations, dewatered by centrifuge, six water magnesium sulfate finished products are obtained, the heavy 65.5g of meter, purity 96.2% after drying;
(4) mother liquor after magnesium sulfate centrifugation in (3) is squeezed into second stage manganous sulfate vaporizer, at 140 ~ 145 DEG C of temperature, evaporation concentration is to magnesium sulfate close to saturated again, and make a large amount of manganese sulfate monohydrate crystallization, under high temperature, Quick spin dewaters; For improving purity, then wash the crystal after centrifugation with the steam condensate of 140 ~ 145 DEG C, after washing, recentrifuge is separated, and obtains manganese sulfate monohydrate finished product after drying, the heavy 20.5g of meter, purity 99.2%.Liquid more than supernatant liquor after separation and high-temperature wash, enter the magnesium sulfate low-temperature evaporation crystal system in (3), at 55 ~ 65 DEG C of negative pressure evaporations to manganous sulfate close to saturated, a large amount of six water magnesium sulfate crystallizations, dewatered by centrifuge, six water magnesium sulfate finished products are obtained, the heavy 20.6g of meter, purity 96.5% after drying;
(5) mother liquor after magnesium sulfate centrifugation in (4) is returned to second stage manganous sulfate vaporizer circulating and evaporating crystallization.(3)-(4) evaporative crystallization of two circulations, 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 magnesium sulfate 82.89g, the rate of recovery (accounting for the ratio of magnesium sulfate total amount 100.3g in waste water) 82.6%.Continue circulating and evaporating, manganous sulfate, the magnesium sulfate rate of recovery are all close to 100%, and manganous sulfate purity is stabilized in more than 99%, and magnesium sulfate purity is stabilized in more than 96%.
(6) by remaining liquid, the filter residue in (2) after twice filtration in (1), washing, 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 Control pond overflows from (6) enters airtight No. three equalizing tanks, still containing a small amount of calcium sulfate and calcium hydroxide in waste water, for ensureing equipment non-scaling in subsequent disposal, 1.6 kilograms of sodium carbonate must be added by removing a part of calcium ion: Xiang Chizhong by every side's waste water, the calcium sulfate dissolved in water and calcium hydroxide are removed 40%, the calcium carbonate precipitated carries out centrifuge dehydration, becomes precipitated chalk finished product; Enter deamination system after remaining liquid filters further, the slag slurry of filtering returns 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) obtained, filtration, enters ammonia steaming system and carries out deamination process.Waste water is squeezed into ammonia still and is carried the liquid distributor heating up in a steamer layer top by fresh feed pump, after the even cloth liquid of liquid distributor, passes through to carry and heats up in a steamer a layer filler natural flow; Waste water up to standard at the bottom of tower is squeezed into the ammonia secondary steam that contains that the outer vaporizer of tower and ammonia still steam and is carried out indirect heat exchange, is reentered flash distillation in ammonia still by the hot wastewater heated, and the secondary steam of generation is as the thermal source of air lift ammonia still process and stripping medium.Secondary steam heats up in a steamer a layer filler upwards flow by carrying from bottom to top, and contact with waste water is reverse between filler, free ammonia constantly shifts from waste water in steam.According to relative volatility principle during vapor liquid equilibrium, waste water more walks downward, and ammonia nitrogen parsing removes more thorough.When arriving at the bottom of tower, waste water is parsed, and its ammonia-nitrogen content reaches 13mg/L.Waste water up to standard is got in tower, with enter tower wastewater heat exchange after as process water reuse or directly discharge.
(9) ammonia that ammonia still removes prepares ammoniacal liquor.Constantly the ammonia in waste water is absorbed in the process that steam in ammonia still flows from bottom to top, 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, and for improving ammonia concn, the rectification layer adopting the mode of backflow weak ammonia to be returned to ammonia still top carries out circulation ammonia still process.The ammonia be not condensed enters ammonia absorption tower by vacuum system, by the mass ratio of water, ammonia 6:1 toward spray technology water in ammonia absorption tower, carries out cyclic absorption to ammonia.Because of ammonia meeting heat release in water-soluble process, the rising of absorption liquid temperature can have an impact to the concentration of obtained ammoniacal liquor, lowers the temperature so arrange condenser on absorption tower to absorption liquid, carries out under making ammonia absorption maintain the low-temperature condition of 45 ~ 50 DEG C.After ammonia concn reaches 15%, be back to use wastewater equalization pond in (1), for adjust ph.
So far, the manganous sulfate in waste water, magnesium sulfate, calcium sulfate are all separated and reclaim, and waste water realizes reuse, and the ammoniacal liquor added utilizes at 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 exotic high temperature high pressure, and the heat of magnesium sulfate low-temperature evaporation crystal system is by the first step, second stage manganous sulfate vaporizer, and the secondary steam produced during solution evaporation provides; After secondary steam more than needed mixes with steam in outer next life, 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 solution remaining after high temperature evaporation, to save process energy consumption; System itself is without feed enrichment problem.
Claims (1)
1. the method for comprehensive utilization that in high-salt wastewater, manganous sulfate, magnesium sulfate, calcium sulfate are separated, concentrate, purify, is characterized in that: comprise the steps:
(1) high-salt wastewater mother liquor enters airtight wastewater equalization pond, and temperature remains on 50 ~ 60 DEG C, and first in waste water, quantitatively add ammoniacal liquor or liquefied ammonia, waste water ph is adjusted to 10 ~ 10.5, and manganese, magnesium are with Mn (OH)
2with Mg (OH)
2form precipitate; Keep precipitation endpoint pH 8 ~ 8.5, device is by Mn (OH) after filtration
2with Mg (OH)
2filtered while hot out; The Mn (OH) simultaneously will filtered out
2with Mg (OH)
2mixing slag 50 ~ 60 DEG C of hot water wash, and wash rear secondary filtration and centrifuge dehydration, to remove impurity calcium ion and ammonium sulfate;
(2) Mn (OH) after secondary filtration
2with Mg (OH)
2confined reaction tank squeezed into rapidly by mixing slag slurry, add water, the sulfuric acid of 75% is added retort through means for feeding acid simultaneously, at the uniform velocity stir, generate manganous sulfate, Adlerika, control ph 4 ~ 4.2, and after keeping reaction in tank in solution manganous sulfate, the common content mass concentration of magnesium sulfate 25 ~ 30%; Solution enters metre filter, and calcium sulfate will be separated out further;
(3) solution after reaction in (2) being filtered by first step manganous sulfate vaporizer 140 ~ 145 DEG C of evaporation concentration to magnesium sulfate close to saturated, a large amount of manganese sulfate monohydrate crystallization, Quick spin dehydration under high temperature; Wash the crystal after centrifugation with the steam condensate of 140 ~ 145 DEG C, after washing, recentrifuge is separated, and obtains manganese sulfate monohydrate finished product after drying again; Supernatant liquor after separation and high-temperature wash, be separated after remaining liquid, enter magnesium sulfate low-temperature evaporation crystal system, at 55 ~ 65 DEG C of negative pressure evaporations to manganous sulfate close to saturated, a large amount of six water magnesium sulfate crystallizations, dewatered by centrifuge, after drying, obtain six water magnesium sulfate finished products;
(4) mother liquor after magnesium sulfate centrifugation in (3) is squeezed into second stage manganous sulfate vaporizer, at 140 ~ 145 DEG C of temperature again evaporation concentration to magnesium sulfate close to saturated, a large amount of manganese sulfate monohydrate crystallization, Quick spin dehydration under high temperature; Wash the crystal after centrifugation with the steam condensate of 140 ~ 145 DEG C, after washing, recentrifuge is separated, and obtains manganese sulfate monohydrate finished product after drying again; Supernatant liquor after separation enters the magnesium sulfate low-temperature evaporation crystal system in (3), at 55 ~ 65 DEG C of negative pressure evaporations to manganous sulfate close to saturated, a large amount of six water magnesium sulfate crystallizations, are dewatered by centrifuge, obtain six water magnesium sulfate finished products after drying;
(5) mother liquor after magnesium sulfate centrifugation in (4) is returned to second stage manganous sulfate vaporizer circulating and evaporating crystallization;
(6) by remaining liquid, the filter residue in (2) after twice filtration in (1), washing, airtight Secondary Control pond 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 Control pond overflows from (6) enters airtight No. three equalizing tanks, still containing a small amount of calcium sulfate and calcium hydroxide in waste water, Xiang Chizhong adds 1.3 ~ 1.8 kilograms of sodium carbonate by every side's waste water, the calcium carbonate precipitated carries out centrifuge dehydration, become calcium carbonate finished product, enter deamination system after remaining liquid filters further, the slag slurry of filtering returns the centrifuge dehydration of calcium carbonate centrifuge dehydration system, obtains calcium carbonate finished product;
(8) mother liquor after the deliming (7) obtained, filtration, enter ammonia steaming system and carry out deamination process, after ammonia nitrogen removal to below 15mg/L, waste water is as process water reuse or directly discharge;
(9) ammonia removing 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 adjust ph.
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