CN104229906A - Method and equipment for preparing electroplating-grade nickel sulfate from nickel-containing wastewater produced in surface treatment process - Google Patents
Method and equipment for preparing electroplating-grade nickel sulfate from nickel-containing wastewater produced in surface treatment process Download PDFInfo
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Abstract
The invention discloses a method and equipment for preparing electroplating-grade nickel sulfate from nickel-containing wastewater produced in a surface treatment process, and belongs to the technical field of nickel-containing wastewater treatment process. The method is characterized by comprising the following steps: (1) collecting nickel-containing wastewater; (2) performing sedimentation and press filtration on nickel in the nickel-containing wastewater, and smashing nickel mud to obtain nickel slurry; (3) dissolving the nickel slurry into acid; (4) filtering a nickel sulfate solution; (5) removing impurities from the nickel sulfate solution for purification, and performing secondary filtration; (6) performing vacuum evaporative concentration, crystallization, filtration and centrifugal drying on the nickel sulfate solution to obtain nickel sulfate crystals. The invention aims to provide the method and the equipment which can reduce the waste of nickel resources, reduce potential hazard of nickel to the natural environment and realize recycling of the nickel resources and are used for preparing the electroplating-grade nickel sulfate from the nickel-containing wastewater produced in the surface treatment process. The method and the equipment are used for treating the nickel-containing wastewater.
Description
Technical field
The present invention relates to a kind of method preparing plating single nickel salt, more particularly, particularly relate to a kind of method that nickel-containing waste water utilizing surface treatment process to produce prepares plating level single nickel salt.The present invention also relates to a kind of specific equipment being applied to aforesaid method simultaneously.
Background technology
In the surface treatment course of processing, electronickelling and chemical sinking nickel are the two kinds of process of surface treatment often adopted, electronickelling mainly contains again several principal modes such as electroformed nickel, sub-nickel, half light nickel, light nickel, pearl nickel, and in this several plating form, nickel is mainly single nickel salt, a certain amount of nickelous chloride.Chemical nickel mainly contains alkali electroless nickel and acidic chemical nickel two class, and its main component is single nickel salt, reductive agent, complexing agent, stablizer etc.In electronickelling, nickel comparision contents is high, nickel content is generally at about 40-80g/L, in chemical nickel deposition solution, the content of nickel is relatively low, nickel content is approximately about 4-6g/L, in surface treatment, electronickelling application is more extensive, chemical nickel is mainly as functional surface process, and what these two kinds of techniques all can produce the lower Cleaning Wastewater of nickeliferous solubility and compare high content nickel on a small quantity scraps liquid and decoating liquid.
The treatment technology that the current nickel-containing waste water produced electronickelling and chemical sinking nickel process mainly adopts is first nickel-containing waste water and other heavy metal wastewater thereby mixed collection, then by adjusting PH to make the heavy metal in waste water generate precipitation, precipitation after generation becomes the mud containing heavy metal by press filtration, and this mud transfers to the enterprise of specific qualification carry out collecting and carry out safe handling.Because safe handling cost compare is high, often occur that bad enterprise stealthily arbitrarily abandons the mud containing heavy metal produced or directly the waste water containing heavy metal stolen row, cause great environmental hazard.Current Ye You smelting enterprise first carries out pyrometallurgical smelting the mud of cupric, nickel, obtain the hybrid metal of cupric, nickel, and then by other removal of impurities and separation circuit, obtain purer single metallic compound, the method not only complex process, energy consumption is high, also there is the risk of secondary pollution; Nickel is again a kind of important metals resources on earth, and deficienter in China, it is widely used in iron and steel, catalytic chemistry, surface treatment etc., and China every year all will from a large amount of nickel product of external import.
Summary of the invention
Last object of the present invention be to provide a kind of reduce nickel resources waste, reduce nickel to the potential hazard of physical environment, the nickel-containing waste water utilizing surface treatment process to produce realizing the recycle of nickel resources prepares the method for electroplating level single nickel salt.
After of the present invention, an object is to provide a kind of specific equipment for aforesaid method.
Last technical scheme of the present invention is achieved in that a kind of nickel-containing waste water utilizing surface treatment process to produce prepares the method for plating level single nickel salt, and the method comprises the steps: (1) collects separately the nickel-containing waste water produced in surface treatment process; (2) the nickel sedimentation in nickel-containing waste water is obtained the nickel mud solid of certain water ratio; (3) the nickel mud solid crushing of water content is become nickel mud; (4) nickel mud is pumped in dissolving vessel, under whipped state, adds the 98% technical grade vitriol oil dissolve, filter mazarine clarification nickel sulfate solution; (5) nickel sulfate solution is pumped in purifying tank, add oxygenant, sorbent material carries out edulcoration purification, filter after edulcoration purification; (6) vacuum evaporation is carried out by filtering the nickel sulfate solution obtained after edulcoration purification, be concentrated into nickel content when reaching 300-400g/L, stop evaporation, then lower the temperature, single nickel salt crystallization, finally the solution of sulfur acid nickel crystal is carried out filtering, centrifugal drying obtains nickel sulfate hexahydrate crystal.
The above-mentioned nickel-containing waste water utilizing surface treatment process to produce is prepared in the method for plating level single nickel salt, step (2) is specially: by one or more hybrid reactions in the alkali of nickel-containing waste water and solubility and/or soluble carbonate salt, after reaction, the pH value scope of solution is 8.3-10, obtain nickeliferous water-fast solid chemical compound, be separated by press filtration and obtain the nickel mud solid that water ratio is 70-90%.
The above-mentioned nickel-containing waste water utilizing surface treatment process to produce is prepared in the method for plating level single nickel salt, step (4) is specially: pump in dissolving vessel by nickel mud, under whipped state, add the 98% technical grade vitriol oil dissolve, add the 98% technical grade vitriol oil speed add 2-3ml/min for often liter of nickel mud; When solution PH is 5-6, stopping adds the 98% technical grade vitriol oil, continues to be stirred in solution to produce a large amount of foam, cleans out this foam, then filter in vacuum suction filtration tank with resistant to elevated temperatures spun yarn net, obtains mazarine clarification nickel sulfate solution.
The above-mentioned nickel-containing waste water utilizing surface treatment process to produce is prepared in the method for plating level single nickel salt, and step (5) described oxygenant is superoxide or hypochlorite or persulphate, and addition be often liter of solution interpolation 2-10g; Described sorbent material is that the specific surface areas such as molecular sieve are large, and adsorptive power is strong, the material of stable under acidic conditions; While adding sorbent material, regulator solution pH value is to 2-6.
The above-mentioned nickel-containing waste water utilizing surface treatment process to produce is prepared in the method for plating level single nickel salt, step (6) is specially: pump into vacuum evaporating pot by filtering the nickel sulfate solution obtained after edulcoration purification, be 2-4 by sulfuric acid regulation solution pH value, velocity of evaporation is the 20%-50% of evaporation starting soln amount per hour, when solution be concentrated into nickel content reach 300-400g/L time, stop evaporation, solution is proceeded to crystallizer. keep solution temperature 80-95 DEG C, continue stirred solution 15-30 minute, stir speed (S.S.) is 50-90r/min, by water quench, the flow 1-5l/min of water coolant, solution temperature in 1-2h is made slowly to drop to 50-65 DEG C, then water coolant is closed, tune stirring velocity is 30-40r/min, continue to lower the temperature with the speed of 0.5-1 DEG C/10min, start in solution to occur crystallization, when Tc drops to 33-45 DEG C, crystallization stops, obtain the solution of sulfur acid nickel crystal, ageing is carried out to nickel sulfate hexahydrate crystal, then sequentially vacuum filtration is carried out, centrifugal drying obtains nickel sulfate hexahydrate crystal.
The above-mentioned nickel-containing waste water utilizing surface treatment process to produce is prepared in the method for plating level single nickel salt, when starting to occur crystallization in described solution, improve agitator speed to 40-50r/min, increase is increased along with crystalline particle, solution colour becomes green by dark blue, agitator speed is reduced to 20-30r/min, until Tc drops to 33-45 DEG C.
After of the present invention, a technical scheme is achieved in that a kind of equipment of the nickel-containing waste water preparation plating level single nickel salt utilizing surface treatment process to produce, comprise the holding tank, setting tank and the pressure filter that sequentially connect, wherein said setting tank top pipeline is connected with the first container for storing liquid; Described pressure filter mud mouth sequentially pipeline is connected with the making beating tank of belt stirrer, dissolving vessel, the first filter vat, purifying tank, the second filter vat, vacuum evaporating pot, crystallizer and hay tank; Described first filter vat and the second filter vat are all connected with vacuum pump; Described dissolving vessel top pipeline is connected with sulphuric acid tank, and described purifying tank top pipeline is connected with the second container for storing liquid; Described vacuum evaporating pot upper pipeline is connected with sulfuric acid charging bucket.
In the equipment of the above-mentioned nickel-containing waste water utilizing surface treatment process to produce preparation plating level single nickel salt, the liquid outlet of described hay tank is connected on the pipeline between making beating tank and dissolving vessel by return line.
In the equipment of the above-mentioned nickel-containing waste water utilizing surface treatment process to produce preparation plating level single nickel salt, each pipeline is equipped with pump.
After the present invention adopts above-mentioned technique and structure, have the following advantages and effect relative to prior art:
(1) the present invention collects separately nickeliferous waste liquid, and the amount of bringing into of other impurity can be made greatly to reduce, for postorder purge process is simply effectively implemented to provide convenience.Carry out precipitation to nickel-containing waste water alkali or carbonate the Ni in waste water can be made to concentrate be precipitated out, the content of nickel in waste water and clear liquid reached meet the emission request of country, eliminate the potential hazard of nickel to physical environment.By precipitation, the volume of nickeliferous refuse is reduced greatly, achieve the minimizing of harmful waste, by pressure-filtering process, make the further decrement of harmful waste, recycling for postorder reduces larger evaporation concentration cost, improves the economic benefit of recycling.
(2) the nickel mud after press filtration, by the crushing effect of making beating tank, makes nickel mud particle become tiny especially, this not only make the nickel mud of postorder with during sulfuric acid reaction fast but also compare evenly abundant, nickel is farthest reclaimed.Be 5 ~ 6 by controlling the terminal pH value of nickel mud and sulfuric acid reaction, other impurity of major part in nickel mud is mainly existed and water fast in solid form.Some organism existed in nickel mud also can float at solution upper surface with form of foam, by with high temperature resistant spun yarn net, this foam overwhelming majority can be removed, fast filtering for postorder is separated and creates conditions, removing the mixing solutions after foam by filtering, obtaining the nickel sulfate solution of navy blue clarification.
(3) oxygenant that the oxidisability such as superoxide or hypochlorite is stronger is utilized, under certain pH value condition to nickel sulfate solution in the remaining further oxide treatment of the impurity with reductibility, add strong sorbent material and adsorption precipitation is carried out to the impurity in solution, by filtering, solution is made to obtain purifying further, the content of nickel and major impurity in analytical solution. through twice filtration, filtrate generally can reach specification of quality.If any exception, then carry out once special slagging-off, just can reach the specification of quality of plating level single nickel salt.
(4) filtrate conformed to quality requirements is pumped into vacuum evaporation tank, first adjust solution ph, by strictly controlling evaporative process, when in solution, nickel content reaches 300-400 grams per liter, stop solution evaporation, solution is proceeded to crystallizer, by implementing strict Crystallization Procedure, the final obtained nickel sulfate hexahydrate crystal meeting plating and require.
(5) adopt special equipment, make whole technical process realize continuous seepage, centre does not need to carry out transfer transport to material substantially, both saves manpower and materials, and in turn ensure that the quality of product.
Accompanying drawing explanation
Below in conjunction with the embodiment in accompanying drawing, the present invention is described in further detail, but do not form any limitation of the invention.
Fig. 1 is the structural representation of present device.
In figure: holding tank 1, setting tank 2, pressure filter 3, first container for storing liquid 4, making beating tank 5, dissolving vessel 6, first filter vat 7, purifying tank 8, second filter vat 9, vacuum evaporating pot 10, crystallizer 11, hay tank 12, vacuum pump 13, sulphuric acid tank 14, second container for storing liquid 15, sulfuric acid charging bucket 16, return line 17, pump 18.
Embodiment
Consult shown in Fig. 1, the equipment of a kind of nickel-containing waste water preparation plating level single nickel salt utilizing surface treatment process to produce of the present invention, comprise the holding tank 1, setting tank 2 and the pressure filter 3 that sequentially connect, setting tank 2 top pipeline is connected with the first container for storing liquid 4; Described pressure filter 3 mud mouth sequentially pipeline is connected with the making beating tank 5 of belt stirrer, dissolving vessel 6, first filter vat 7, purifying tank 8, second filter vat 9, vacuum evaporating pot 10, crystallizer 11 and hay tank 12; Described first filter vat 7 and the second filter vat 9 are all connected with vacuum pump 13; Described dissolving vessel 6 top pipeline is connected with sulphuric acid tank 14, and described purifying tank 8 top pipeline is connected with the second container for storing liquid 15; Described vacuum evaporating pot 10 upper pipeline is connected with sulfuric acid charging bucket 16.
For improving the cyclic utilization rate of raw material, to be connected to by return line 17 on the pipeline between making beating tank 5 and dissolving vessel 6 in the crystalline mother solution outlet of hay tank 12.Meanwhile, for realizing the automatically working of whole equipment, each pipeline is equipped with pump 18.Liquid circulation is between each device realized by pump 18.
A kind of nickel-containing waste water utilizing surface treatment process to produce of the present invention prepares the method for plating level single nickel salt, and the method comprises the steps:
(1) nickel-containing waste water produced in surface treatment process is collected separately;
(2) by one or more hybrid reactions in the alkali (sodium hydroxide, potassium hydroxide etc.) of nickel-containing waste water and solubility and/or soluble carbonate salt (sodium carbonate, salt of wormwood etc.), after reaction, the pH value scope of solution is 8.3-10, obtain nickeliferous water-fast solid chemical compound, be separated by press filtration and obtain the nickel mud solid that water ratio is 70-90%.By pressure-filtering process, make the further decrement of harmful waste, the recycling for postorder reduces larger evaporation concentration cost, improves the economic benefit of recycling.
(3) the nickel mud solid crushing of water content is become nickel mud; The granularity of nickel mud is more than 70 orders.
(4) nickel mud is pumped in dissolving vessel, under whipped state, adds the 98% technical grade vitriol oil dissolve, add the 98% technical grade vitriol oil speed add 2-3ml/min for often liter of nickel mud; When solution PH is 5-6, stopping adds the 98% technical grade vitriol oil, continues to be stirred in solution to produce a large amount of foam, cleans out this foam, then filter in vacuum suction filtration tank with resistant to elevated temperatures spun yarn net, obtains mazarine clarification nickel sulfate solution.
(5) nickel sulfate solution is pumped in purifying tank, add oxygenant, sorbent material carries out edulcoration purification, filter after edulcoration purification; Described oxygenant is superoxide or hypochlorite or persulphate, and addition is that often liter of solution adds 2-10g; Described sorbent material is that the specific surface areas such as molecular sieve are large, high adsorption capacity, the material of stable under acidic conditions; While adding sorbent material, regulator solution pH value is to 2-6.
(6) vacuum evaporating pot is pumped into by filtering the nickel sulfate solution obtained after edulcoration purification, be 2-4 by sulfuric acid regulation solution pH value, velocity of evaporation is the 20%-50% of evaporation starting soln amount per hour, when solution be concentrated into nickel content reach 300-400g/L time, stop evaporation, solution is proceeded to crystallizer. keep solution temperature 80-95 DEG C, continue stirred solution 15-30 minute, stir speed (S.S.) is 50-90r/min, cool with cold water, the flow of water coolant is 1-5l/min, solution temperature in 1-2h is made slowly to drop to 50-65 DEG C, then water coolant is closed, stirrer rotating speed is adjusted to be 30-40r/min, continue to lower the temperature with the speed of 0.5-1 DEG C/10min, when starting in solution to occur crystallization, improve agitator speed to 40-50r/min, increase is increased along with crystalline particle, solution colour becomes green by dark blue, agitator speed is reduced to 20-30r/min, when Tc drops to 33-45 DEG C, crystallization stops, obtain the solution of sulfur acid nickel crystal, ageing is carried out to nickel sulfate hexahydrate crystal, then sequentially vacuum filtration is carried out, centrifugal drying obtains nickel sulfate hexahydrate crystal.Mother liquor after filtration is returned in dissolving vessel by return line.
Embodiment 1
The nickel-containing waste water utilizing surface treatment process to produce prepares a method for plating level single nickel salt, and the method comprises the steps:
(1) holding tank is adopted to collect separately the nickel-containing waste water produced in surface treatment process;
(2) nickel-containing waste water is pumped in setting tank, the alkali lye of the solubility in the first container for storing liquid or carbonate solution are pumped in setting tank and carries out hybrid reaction, after reaction, the pH value scope of solution is 8.3-8.5, obtain nickeliferous water-fast solid chemical compound, be separated by pressure filter press filtration and obtain the nickel mud solid that water ratio is 70-90%.
(3) the nickel mud solid of water content is broken into nickel mud by the making beating tank of belt stirrer; The granularity of nickel mud is more than 70 orders.
(4) nickel mud is pumped in dissolving vessel, under whipped state, the 98% technical grade vitriol oil in sulphuric acid tank is added in dissolving vessel and dissolve, add the technical grade vitriol oil speed add 2ml/min for often liter of nickel mud; When solution PH is 5-6, stopping adds the technical grade vitriol oil, continues to be stirred in solution to produce a large amount of foam, this foam is cleaned out with resistant to elevated temperatures spun yarn net, again at vacuum suction filtration tank, namely filter with in the first filter vat of vacuum pump, obtain mazarine clarification nickel sulfate solution.
(5) nickel sulfate solution is pumped in purifying tank, the oxygenant in the second container for storing liquid, sorbent material are added in purifying tank and carries out edulcoration purification, by being with the second filter vat of vacuum pump to filter after edulcoration purification; Described oxygenant is superoxide or hypochlorite or persulphate, and addition is that often liter of solution adds 2g; Described sorbent material is molecular sieve; While adding sorbent material, regulator solution pH value is to 2-6.
(6) vacuum evaporating pot is pumped into by filtering the nickel sulfate solution obtained after edulcoration purification, sulfuric acid in sulfuric acid charging bucket being added regulator solution pH value in vacuum evaporating pot is 2-4, velocity of evaporation is the 20%-30% of evaporation starting soln amount per hour, when solution be concentrated into nickel content reach 300-350g/L time, stop evaporation, solution is proceeded to crystallizer, keep solution temperature 80-85 DEG C, continue stirred solution 15 minutes, stir speed (S.S.) is 50r/min, the flow of water coolant is 1l/min, solution temperature in 2h is made slowly to drop to 50-65 DEG C, then water coolant is closed, continue to lower the temperature with the speed of 0.5 DEG C/10min, when starting in solution to occur crystallization, improve agitator speed to 40r/min, increase is increased along with crystalline particle, solution colour becomes green by dark blue, agitator speed is reduced to 20r/min, when Tc is to 33-45 DEG C, crystallization stops, obtain the solution of sulfur acid nickel crystal, ageing is carried out to nickel sulfate hexahydrate crystal, then sequentially carry out hay tank and carry out vacuum filtration, carry out centrifugal drying by drier and obtain nickel sulfate hexahydrate crystal.Mother liquor after hay tank filters is returned in dissolving vessel by return line.
Embodiment 2
The nickel-containing waste water utilizing surface treatment process to produce prepares a method for plating level single nickel salt, and the method comprises the steps:
(1) holding tank is adopted to collect separately the nickel-containing waste water produced in surface treatment process;
(2) nickel-containing waste water is pumped in setting tank, soluble carbonate salt in first container for storing liquid is pumped in setting tank and carries out hybrid reaction, after reaction, the pH value scope of solution is 8.3-10, obtain nickeliferous water-fast solid chemical compound, be separated by pressure filter press filtration and obtain the nickel mud solid that water content is 70-90%.
(3) the nickel mud solid of water content is broken into nickel mud by the making beating tank of belt stirrer; The granularity of nickel mud is more than 70 orders.
(4) nickel mud is pumped in dissolving vessel, under whipped state, the 98% technical grade vitriol oil in sulphuric acid tank is added in dissolving vessel and dissolve, add the technical grade vitriol oil speed add 2.5ml/min for often liter of nickel mud; When solution PH is 5-6, stopping adds the technical grade vitriol oil, continues to be stirred in solution to produce a large amount of foam, this foam is cleaned out with resistant to elevated temperatures spun yarn net, again at vacuum suction filtration tank, namely filter with in the first filter vat of vacuum pump, obtain mazarine clarification nickel sulfate solution.
(5) nickel sulfate solution is pumped in purifying tank, the oxygenant in the second container for storing liquid, sorbent material are added in purifying tank and carries out edulcoration purification, by being with the second filter vat of vacuum pump to filter after edulcoration purification; Described oxygenant is superoxide or hypochlorite or persulphate, and addition is that often liter of solution adds 5g; Described sorbent material is molecular sieve; While adding sorbent material, regulator solution pH value is to 2-6.
(6) vacuum evaporating pot is pumped into by filtering the nickel sulfate solution obtained after edulcoration purification, sulfuric acid in sulfuric acid charging bucket being added regulator solution pH value in vacuum evaporating pot is 2-4, velocity of evaporation is the 30%-40% of evaporation starting soln amount per hour, when solution be concentrated into nickel content reach 320-380g/L time, stop evaporation, solution is proceeded to crystallizer, keep solution temperature 85-90 DEG C, continue stirred solution 20 minutes, stir speed (S.S.) is 70r/min, the flow of water coolant is 3l/min, solution temperature in 1.5h is made slowly to drop to 50-65 DEG C, then water coolant is closed, continue to lower the temperature with the speed of 0.8 DEG C/10min, when starting in solution to occur crystallization, improve agitator speed to 45r/min, increase is increased along with crystalline particle, solution colour becomes green by dark blue, agitator speed is reduced to 30r/min, when Tc is to 33-45 DEG C, crystallization stops, obtain the solution of sulfur acid nickel crystal, ageing is carried out to nickel sulfate hexahydrate crystal, then sequentially carry out hay tank and carry out vacuum filtration, carry out centrifugal drying by drier and obtain nickel sulfate hexahydrate crystal.Mother liquor after hay tank filters is returned in dissolving vessel by return line.
Embodiment 3
The nickel-containing waste water utilizing surface treatment process to produce prepares a method for plating level single nickel salt, and the method comprises the steps:
(1) holding tank is adopted to collect separately the nickel-containing waste water produced in surface treatment process;
(2) nickel-containing waste water is pumped in setting tank, the alkali of the solubility in the first container for storing liquid and the mixture of soluble carbonate salt are pumped in setting tank and carries out hybrid reaction, after reaction, the pH value scope of solution is 8.3-10, obtain nickeliferous water-fast solid chemical compound, be separated by pressure filter press filtration and obtain the nickel mud solid that water ratio is 70-90%.
(3) the nickel mud solid of water content is broken into nickel mud by the making beating tank of belt stirrer; The granularity of nickel mud is more than 70 orders.
(4) nickel mud is pumped in dissolving vessel, under whipped state, the 98% technical grade vitriol oil in sulphuric acid tank is added in dissolving vessel and dissolve, add the technical grade vitriol oil speed add 3ml/min for often liter of nickel mud; When solution PH is 5-6, stopping adds the technical grade vitriol oil, continues to be stirred in solution to produce a large amount of foam, this foam is cleaned out with resistant to elevated temperatures spun yarn net, again at vacuum suction filtration tank, namely filter with in the first filter vat of vacuum pump, obtain mazarine clarification nickel sulfate solution.
(5) nickel sulfate solution is pumped in purifying tank, the oxygenant in the second container for storing liquid, sorbent material are added in purifying tank and carries out edulcoration purification, by being with the second filter vat of vacuum pump to filter after edulcoration purification; Described oxygenant is superoxide or hypochlorite or persulphate, and addition is that often liter of solution adds 10g; Described sorbent material is molecular sieve; While adding sorbent material, regulator solution pH value is to 2-6.
(6) vacuum evaporating pot is pumped into by filtering the nickel sulfate solution obtained after edulcoration purification, sulfuric acid in sulfuric acid charging bucket being added regulator solution pH value in vacuum evaporating pot is 2-4, velocity of evaporation is the 40%-50% of evaporation starting soln amount per hour, when solution be concentrated into nickel content reach 350-400g/L time, stop evaporation, solution is proceeded to crystallizer, keep solution temperature 90-95 DEG C, continue stirred solution 30 minutes, stir speed (S.S.) is 90r/min, the flow of water coolant is 5l/min, solution temperature in 1h is made slowly to drop to 50-65 DEG C, then water coolant is closed, continue to lower the temperature with the speed of 1 DEG C/10min, when starting in solution to occur crystallization, improve agitator speed to 50r/min, increase is increased along with crystalline particle, solution colour becomes green by dark blue, agitator speed is reduced to 40r/min, when Tc is to 33-45 DEG C, crystallization stops, obtain the solution of sulfur acid nickel crystal, ageing is carried out to nickel sulfate hexahydrate crystal, then sequentially carry out hay tank and carry out vacuum filtration, carry out centrifugal drying by drier and obtain nickel sulfate hexahydrate crystal.Mother liquor after hay tank filters is returned in dissolving vessel by return line.
Experimental example
Utilize the nickel in Surface Processing Industry nickel-containing waste water to prepare a method for plating level single nickel salt, comprise the steps:
The nickeliferous waste liquid produced in surface treatment process is collected separately by I, precipitin reaction is carried out with water soluble alkali solution or soluble carbonate salt solution, must containing the nickel mud of certain moisture content by filter pressing, obtained nickel mud is carried out the obtained nickel mud of fragmentation in making beating tank, and this nickel mud (or nickel mud) chemical composition analytical results is as table 1 (getting 100 grams of wet mud is sample).
Table 1 nickel mud Main chemical component and content
II 2 liters of nickel mud load in the beaker of 3 liters, and 2 liters of nickel mud are about 2400g, add the 98% industrial vitriol oil with vigorous stirring by certain speed.The a large amount of heat release of period reaction system and have foam to produce.The nickel mud of 1 liter approximately will consume the vitriol oil of 80 milliliters, applies high temperature resistant gauze and constantly clear up a large amount of foams produced in beaker in reaction process.Stop when the PH of solution in beaker is between 5.0-6.0 adding sulfuric acid, continue stirred solution 20 minutes, survey solution ph, adjustment pH value of solution is between 5.0-6.0, and vacuum filtration, obtains mazarine clear filtrate.
Filtrate is placed in the beaker of 3 liters by III, under suitable pH value condition, adds the oxide solution of the strong oxidizing property of 4ml/l, stirring reaction 2hr, add 2g/L specific surface area large, high adsorption capacity, the zeolite that chemical property is more stable or molecular sieve etc., stir 1h, leave standstill 1h, solution for vacuum suction filtration, obtains the mazarine settled solution 2 liters be further purified, analyze the content of each composition in filtrate, data are in table 2.
Each component content in table 2 filtrate
Solution after purifying 2 liters loads in 3 liters of beakers by IV, and the pH value adjusting solution with sulfuric acid is about 3.0, evaporates solution with adjustable electric furnace, and velocity of evaporation can not be too fast, as Ni in solution
2+content when reaching more than 300g/L, stop heating by electric cooker, continue Temperature fall slowly, reduce solution stirring speed, when solution temperature drops to 50-65 DEG C, tune stirring velocity is 70r/min, continues Temperature fall, starts to separate out nickel sulfate hexahydrate crystal, when Tc drops to 33-45 DEG C, stop crystallization. but this crystal grain is partially thin, can obtain evenly, cubic macrobead crystal at 31-45 DEG C through ripening.In gained nickel sulfate hexahydrate crystal, the quality index of the content of nickel and major impurity and the single nickel salt of electroplating industry is in table 3.
The single nickel salt quality index that table 3 is obtained and electroplating industry single nickel salt quality index
The present invention utilizes the nickel preparation plating level single nickel salt product in the nickel-containing waste water produced in surface treatment process, greatly correct the comprehensive treating process method of disposal at present to such waste water, processing cost is not only made greatly to reduce, really achieve and turn waste into wealth, eliminate metallic nickel to the potential harm of environment.Even if compared to the pyrometallurgical smelting used at present and process for separating and purifying, technique also more simply, energy consumption is lower, secondary pollution risk is less.The present invention is beneficial to the recycling of resource.There is significant economic benefit, realize the Chemical Manufacture theory of green low-carbon simultaneously, meet the requirement of market development.
Above illustrated embodiment is better embodiment of the present invention, only be used for conveniently the present invention being described, not any pro forma restriction is done to the present invention, have in any art and usually know the knowledgeable, if do not depart from the present invention carry in the scope of technical characteristic, utilize the Equivalent embodiments that the done local of disclosed technology contents is changed or modified, and do not depart from technical characteristic content of the present invention, all still belong in the scope of the technology of the present invention feature.
Claims (9)
1. the nickel-containing waste water utilizing surface treatment process to produce prepares a method for plating level single nickel salt, it is characterized in that, the method comprises the steps: (1) collects separately the nickel-containing waste water produced in surface treatment process; (2) the nickel sedimentation in nickel-containing waste water is obtained the nickel mud solid of water content; (3) the nickel mud solid crushing of water content is become nickel mud; (4) nickel mud is pumped in dissolving vessel, under whipped state, adds the 98% technical grade vitriol oil dissolve, filter mazarine clarification nickel sulfate solution; (5) nickel sulfate solution is pumped in purifying tank, add oxygenant, sorbent material carries out edulcoration purification, filter after edulcoration purification; (6) vacuum evaporation is carried out by filtering the nickel sulfate solution obtained after edulcoration purification, be concentrated into nickel content when reaching 300-400g/L, stop evaporation, then lower the temperature, single nickel salt crystallization, finally the solution of sulfur acid nickel crystal is carried out filtering, centrifugal drying obtains nickel sulfate hexahydrate crystal.
2. the nickel-containing waste water utilizing surface treatment process to produce according to claim 1 prepares the method for plating level single nickel salt, it is characterized in that, step (2) is specially: by one or more hybrid reactions in the alkali of nickel-containing waste water and solubility and/or soluble carbonate salt, after reaction, the pH value scope of solution is 8.3-10, obtain nickeliferous water-fast solid chemical compound, be separated by press filtration and obtain the nickel mud solid that water ratio is 70-90%.
3. the nickel-containing waste water utilizing surface treatment process to produce according to claim 1 prepares the method for plating level single nickel salt, it is characterized in that, step (4) is specially: pump in dissolving vessel by nickel mud, under whipped state, add the 98% technical grade vitriol oil dissolve, add the 98% technical grade vitriol oil speed add 2-3ml/min for often liter of nickel mud; When solution PH is 5-6, stopping adds the 98% technical grade vitriol oil, continues to be stirred in solution to produce a large amount of foam, cleans out this foam, then filter in vacuum suction filtration tank with resistant to elevated temperatures spun yarn net, obtains mazarine clarification nickel sulfate solution.
4. the nickel-containing waste water utilizing surface treatment process to produce according to claim 1 prepares the method for plating level single nickel salt, it is characterized in that, step (5) described oxygenant is superoxide or hypochlorite or persulphate, and addition is that often liter of solution adds 2-10g; Described sorbent material is that the specific surface areas such as molecular sieve are large, and adsorptive power by force and material stable in acid condition; While adding sorbent material, regulator solution pH value is to 2-6.
5. the nickel-containing waste water utilizing surface treatment process to produce according to claim 1 prepares the method for plating level single nickel salt, it is characterized in that, step (6) is specially: pump into vacuum evaporating pot by filtering the nickel sulfate solution obtained after edulcoration purification, be 2-4 by sulfuric acid regulation solution pH value, velocity of evaporation is the 20%-50% of evaporation starting soln amount per hour, when solution be concentrated into nickel content reach 300-400g/L time, stop evaporation, solution is proceeded to crystallizer. keep solution temperature 80-95 DEG C, continue stirred solution 15-30 minute, stir speed (S.S.) is 50-90r/min, the flow of water coolant is 1-5l/min, solution temperature in 1-2h is made slowly to drop to 50-65 DEG C, stirring velocity is adjusted then to close water coolant to 30-40r/min, continue to lower the temperature with the speed of 0.5-1 DEG C/10min, start in solution to occur crystallization, when Tc drops to 33-45 DEG C, crystallization stops, obtain the solution of sulfur acid nickel crystal, ageing is carried out to nickel sulfate hexahydrate crystal, then sequentially vacuum filtration is carried out, centrifugal drying obtains nickel sulfate hexahydrate crystal.
6. the nickel-containing waste water utilizing surface treatment process to produce stated according to claim 5 prepares the method for plating level single nickel salt, it is characterized in that, when starting to occur crystallization in described solution, improve agitator speed to 40-50r/min, increase is increased along with crystalline particle, solution colour becomes green by dark blue, agitator speed is reduced to 20-30r/min, until Tc drops to 33-45 DEG C.
7. the equipment of the nickel-containing waste water preparation plating level single nickel salt utilizing surface treatment process to produce, comprise the holding tank (1), setting tank (2) and the pressure filter (3) that sequentially connect, it is characterized in that, described setting tank (2) top pipeline is connected with the first container for storing liquid (4); Described pressure filter (3) mud mouth sequentially pipeline is connected with the making beating tank (5) of belt stirrer, dissolving vessel (6), the first filter vat (7), purifying tank (8), the second filter vat (9), vacuum evaporating pot (10), crystallizer (11) and hay tank (12); Described first filter vat (7) and the second filter vat (9) are all connected with vacuum pump (13); Described dissolving vessel (6) top pipeline is connected with sulphuric acid tank (14), and described purifying tank (8) top pipeline is connected with the second container for storing liquid (15); Described vacuum evaporating pot (10) upper pipeline is connected with sulfuric acid charging bucket (16).
8. the equipment of the nickel-containing waste water preparation plating level single nickel salt utilizing surface treatment process to produce according to claim 7, it is characterized in that, the crystalline mother solution outlet of described hay tank (12) is connected on the pipeline between making beating tank (5) and dissolving vessel (6) by return line (17).
9. the equipment of the nickel-containing waste water preparation plating level single nickel salt utilizing surface treatment process to produce according to claim 7, is characterized in that, each pipeline is equipped with pump (18).
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| CN107827168A (en) * | 2017-11-17 | 2018-03-23 | 金川集团股份有限公司 | A kind of method for concentrating waste solution of copper electrolysis crystallization production crude nickle sulphate |
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| CN113184927A (en) * | 2021-04-29 | 2021-07-30 | 金川集团镍盐有限公司 | Method for producing nickel sulfate solution by using nickel powder |
| CN114573051A (en) * | 2022-03-21 | 2022-06-03 | 中山市中环环保废液回收有限公司 | Method for resource utilization of nickel-containing waste liquid |
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