CN105036803A - Method for preparing gilvous occlusion pigment from cadmium-containing waste acid solution generated in acid pickling process - Google Patents
Method for preparing gilvous occlusion pigment from cadmium-containing waste acid solution generated in acid pickling process Download PDFInfo
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Abstract
The invention discloses a method for preparing a gilvous occlusion pigment from cadmium-containing waste acid solution generated in an acid pickling process. Cadmium-containing wastewater generated in the acid pickling process is directly utilized to produce a zirconium silicate microcrystal occluded cadmium sulfide pigment, and zinc ions are doped by virtue of introduction of zinc sulfate to form a cadmium sulfide and zinc sulfide solid solution color former which is used for producing the zirconium silicate microcrystal occluded zinc cadmium sulfide pigment. According to the invention, zirconium oxychloride, zinc sulfate and waste acid solution containing cadmium and selenium generated in the acid pickling process as well as sodium hydroxide and sodium sulphide are subjected to chemical coprecipitation reaction in a reaction kettle, filter-pressed and washed, and dried; and then the above reaction product is evenly mixed with a mineralizer and white carbon black according to a certain ratio and calcined at a high temperature, and the calcined product is acidized, ball-milled, filter-pressed, washed and dried to obtain the zirconium silicate occluded cadmium sulfide yellow pigment or zirconium silicate occluded zinc cadmium sulfide gilvous occlusion pigment product. The gilvous occlusion pigment can replace praseodymium yellow pigment for use.
Description
Technical field
The present invention relates to a kind of ceramic decoration material process for making that is painted and pigment, refer in particular to a kind of cadmium spent acid solution that contains of acid soak operation in the production of zirconium silicate parcel Cadmium Sulfide colorant that utilizes directly to recycle, regenerative ratio zirconium silicate parcel yellow ultramarine, and introduce doping zine ion by zinc sulfate, produce the parcel true yellow pigment of zirconium silicate crystallite parcel Cadmium Sulfide zinc, to replace praseodymium yellow, reach the processing method that form and aspect and color development ability are all better than traditional praseodymium yellow pigments.Belong to ceramic pigment (pigment) manufacture technology field.
background technology:
In zirconium silicate parcel Cadmium Sulfide colorant (namely wrapping up yellow) is produced, because chromogenic reagent Cadmium Sulfide is complete not by zirconium silicate crystal parcel, must by acid soak operation by the Cadmium Sulfide soaking and washing that do not wrap out, pure to ensure the color development of colorant.
The Cadmium Sulfide soaked out is present in spent acid solution with Cadmium Sulphate, and the cadmium in waste acid recovery liquid is the needs of the needs economized in raw materials, environment protection especially.
To the treatment process of acid soak containing cadmium waste liquid, normally with the first neutralizing treatment spent acid solution of alkali, regulate pH value, produce precipitation, and precipitated and isolated recycling.Such treatment process utilization ratio is not high, and cost recovery is high, easily causes great pollution to environment.
In zirconium silicate parcel Cadmium Sulfide series colorant (parcel yellow) is produced, because chromogenic reagent Cadmium Sulfide is complete not by zirconium silicate crystal parcel, must by acid soak operation by the Cadmium Sulfide soaking and washing that do not wrap out, pure to ensure the color development of colorant.But in acid soak operation, the Cadmium Sulfide soaked out is present in spent acid solution with Cadmium Sulphate, if directly discharge will cause the pollution of environment, so the cadmium in waste acid recovery liquid is the needs of the needs economized in raw materials, environment protection especially.
At present, to acid soak containing Cadmium treated method, normally with the first neutralizing treatment spent acid solution of alkali, regulate pH value, produce carbon cadmium precipitation or other cadmium compound precipitates, and precipitated and isolated to reclaim, such treatment process recovery utilization rate is not high, cost recovery is high, easily causes great pollution to environment.Therefore, existing acid soak is containing the large headache be processed into administer environmental pollution in occlusion pigment production now of cadmium waste liquid.
Do not find that there is the patent literature constructed with the present invention by patent retrieval, related to the present invention mainly containing is following:
1, the patent No. is CN201310262241, the patent of invention that name is called " leaching the system of the automatic recovery acetic acid waste liquid from pottery ", which disclose a kind of system of the automatic recovery acetic acid from pottery leaching waste liquid, be provided with liquid level sensor and temperature sensor in the cavity of the liquid storage tank of its storage heat abstractor, liquid storage tank is connected with powered heating apparatus by pipeline.The entrance of the recycle pump of powered heating apparatus connects liquid storage tank, and outlet is connected with refrigerating unit.The water cooler of refrigerating unit is connected with reaction main frame; Be provided with pond for recovering liquid level sensor in the pure Acetic Acid-Water pond for recovering of collection device, pure liquid pipe one termination water cooler, the other end inserts and connects in pure Acetic Acid-Water pond for recovering.Control device comprises main control PLC, frequency transformer, sensor, rly.; Recycle pump is connected with main control PLC by frequency transformer, and each sensor is connected with main control PLC respectively, and native system adopts PLC to control, effectively isolate plumbous and cadmium heavy metal ion, obtain the acetum that can be reused for ceramic immersion, reduce environmental pollution, realize resource reclaim recycling.
2, the patent No. is CN201220558204, what name was called " ceramic product soaks spent acid solution treatment system "
utility modelpatent, which discloses a kind of ceramic product and soaks spent acid solution treatment system.Existing ceramic product detection soaks spent acid solution after the immersion completing pottery, directly enters lower water, and the acetic acid pH value of this 4%, about 2.5, belongs to acid stronger waste liquid, can to environmental concerns.Should
utility modeladopt two water tank compositions, communicating pipe is arranged at the top between two tanks, and water tank A bottom is provided with vent pipe, and water tank B top has to soak detects spent acid solution receiving tube, between two water tanks, acidproof vacuum primingpump is housed.Utilize two water tanks can as collection, in and spent acid solution, make it to discharge again when reaching environmental protection standard pH6-9.
3, the patent No. is CN201210552862, and the patent of invention that name is called " a kind of method of the purifying and cadmium removing from nickel and cobalt solution containing cadmium ", which discloses a kind of method of the purifying and cadmium removing from nickel and cobalt solution containing cadmium.Although it is effective that traditional extraction method removes cadmium, except cadmium is thorough, extraction progression is many, extraction line length; Although it is short, easy and simple to handle that single resin removes cadmium flow process, running cost is low, and metal yield is high, is suitable only for chloride system.The invention is characterized in, select cadmium concentration to be less than the nickel and cobalt solution of 0.1g/L, first the cadmium in nickel and cobalt solution is enriched in cobalt liquor or washing lotion by solvent extraction and goes, make the concentration of cadmium reach 0.1-1.0g/L; Then adopt resin anion(R.A) by the cadmium removing in cobalt liquor or washing lotion, make Cd<0.001g/L, Ni/Cd and Co/Cd all reaches 50000-100000:1.
4, the patent No. is CN201110319352, and the patent of invention that name is called " a kind for the treatment of process of cadmium wastewater ", which discloses a kind for the treatment of process of cadmium wastewater.Its method steps is: (1) is prepared into milk sap by pore forming material, organic solvent, auxiliary agent.Its volume ratio is respectively: pore forming material 1% ~ 5%, auxiliary agent 15% ~ 25%, organic solvent 70% ~ 80%; (2) immobilized on carrier for the above-mentioned milk sap be prepared from; (3) material of above-mentioned preparation is joined in cadmium wastewater, with acid adjustment pH to 3.0 ~ 6.5, carry out stir process with the rotating speed of 100 ~ 450r/min; (4) leave standstill 2 ~ 10min, emulsion floats, and the emulsion of floating, through high-voltage electric field breakdown of emulsion, realizes the recovery of heavy metal cadmium, and the oil phase of gained can return circulation system breast in the newborn device of system; Water outlet can be lower than
countryfirst discharge standard.
5, the patent No. is CN201110279875, name is called the patent of invention of " a kind for the treatment of process of cadmium wastewater ", which disclose a kind for the treatment of process of cadmium wastewater, it comprises the steps: (1), make described cadmium wastewater generate CdS and precipitation separation; (2), the waste water after described precipitation separation is carried out negatively charged ion and cationic exchange process.Waste water after method process of the present invention, its cadmium goes out water-content and controls at below 0.03mg/L, far below
countryemission standard, whole process has accomplished the efficient recovery to cadmium.Though coagulation of the present invention has related to the CdS precipitator method, but sulphur is recycled by ion exchange column in second-stage treatment, therefore do not introduce this contaminative ion of sulphur in water outlet, precipitation process does not adopt any flocculation agent simultaneously, and after making process, cadmium precipitation dewatered solid is convenient to recycle.
Though what these patents above-mentioned had has related to ceramic product soak spent acid solution process, but not to how recycling acid soak containing cadmium, selenium spent acid solution, although other patent has related to the recycling of cadmium goods selenium, but be not the process to ceramic pickling liquor, directly can not be used for processing ceramic product and soak spent acid solution, if by technological improvement, find a kind of new processing method, the waste water of acid bubble process is directly utilized and produces zirconium silicate crystallite parcel cadmium sulfoselenide colorant, waste water treatment and reclamation cost can be reduced, again can cadmium in recycling acid soak waste water and selenium, farthest reduce the pollution to environment simultaneously, this is that this area needs to solve, and there is the technical problem of very high value.
Summary of the invention
Object of the present invention is exactly according to containing the deficiency existing for the process of cadmium spent acid solution with the acid soak in the production of zirconium silicate parcel Cadmium Sulfide colorant at present, there is provided a kind of utilize zirconium silicate wrap up Cadmium Sulfide colorant produce in acid soak operation produce containing cadmium spent acid solution, directly recycle the production method that regenerative ratio zirconium silicate wraps up yellow ultramarine; It is large containing the intractability existing for cadmium spent acid solution that the method effectively can solve the acid soak in producing with zirconium silicate parcel Cadmium Sulfide colorant, environment had to the problem of pollution.
According to foregoing invention object, technical scheme proposed by the invention is: one utilizes acid soak to contain cadmium spent acid solution preparation parcel yellow ultramarine method, directly utilizes regenerative ratio zirconium silicate crystallite to wrap up Cadmium Sulfide colorant the cadmium wastewater of acid bubble process; Introduce doping zine ion by zinc sulfate, form Cadmium Sulfide, zinc sulphide sosoloid chromogenic reagent, produce the parcel true yellow pigment of zirconium silicate crystallite parcel Cadmium Sulfide zinc.
Further, described directly utilizes production zirconium silicate crystallite parcel Cadmium Sulfide colorant to be, after utilizing chemical process to carry out comprehensive treating process containing cadmium spent acid solution acid soak, be directly used in the true yellow produced and produce zirconium silicate crystallite parcel Cadmium Sulfide zinc by the cadmium wastewater of acid bubble process
look lookmaterial
Further, it is described that to utilize chemical process to carry out comprehensive treating process containing cadmium spent acid solution acid soak be that the alkaline mixed solution that utilize basic zirconium chloride and zinc sulfate and acid soak to contain acidic mixed solution that cadmium spent acid solution prepares and sodium hydroxide and sodium sulphite are prepared carries out coprecipitation reaction in reactor, after having reacted, carry out press filtration washing, dry; Again by dried feed and mineralizer, white carbon black is by 100: (35 ~ 40): (5 ~ 12) mix, and through high-temperature calcination, calcinate is acidified, ball milling, press filtration, washing, obtain the parcel true yellow of zirconium silicate parcel zinc-cadmium sulfide after oven dry
look lookmaterial product.
Further, the preparation of described basic zirconium chloride, cadmium and zinc sulfate acidic mixed solution be first add in mixer acid soak containing drop into again after cadmium spent acid solution basic zirconium chloride and zinc sulfate be made into basic zirconium chloride, zinc sulfate containing zirconium, cadmium, zincic acid mixing solutions.
Further, described basic zirconium chloride quality is volume according to spent acid solution and concentration of cadmium ions, calculates the total amount of cadmium, then presses the mol ratio 1 of cadmium in basic zirconium chloride and spent acid solution: (0.15 ~ 0.52), calculate the quality of basic zirconium chloride.
Further, the quality of described zinc sulfate is according to cadmium: the mol ratio 1 of zinc: (0.165 ~ 0.65), calculates the quality of zinc sulfate.
Further, the mass concentration containing zirconium in described acidic mixed solution is: (10 ~ 50) g/L.
Further, determine according to the volume of spent acid solution and concentration of cadmium ions containing the mass concentration of zirconium in described acidic mixed solution, when spent acid solution concentration of cadmium ions is very low, Cadmium Sulphate can be dropped in spent acid solution, to change concentration of cadmium ions in spent acid solution, thus change the mass concentration containing zirconium in acidic mixed solution.
Further, the described sodium hydroxide of preparation that adds water, the preparation of sodium sulphite alkaline mixed solution are after adding water in a kettle., drop into sodium hydroxide; After adding water in mixer again, dropping into sodium sulphite and be made into mass concentration 20-30% solution, after clarification, join reactor, being made into alkaline mixed solution by stirring.
Further, the quality of the sodium hydroxide of described input is according to basic zirconium chloride amount, by the mol ratio 1: 2 of basic zirconium chloride and sodium hydroxide, calculate sodium hydroxide quality, and add the hydrogen ion concentration according to got spent acid solution volume V and spent acid solution, according in and pH value for 6 ~ 7 calculate in and spent acid needed for sodium hydroxide quality.
Further, the sodium sulphite quality of described input is the total amount according to cadmium, zinc in acidic mixed solution, and the mol ratio 1 by cadmium, zinc and sodium sulphite: (1.10 ~ 1.70), calculates the quality of sodium sulphite.
Further, described mineralizer refers to lithium fluoride, Quilonum Retard, Neutral ammonium fluoride, Sodium Silicofluoride.Lithium fluoride can add by single component, and also can add with Neutral ammonium fluoride, the many components of Sodium Silicofluoride, Quilonum Retard can only add with Neutral ammonium fluoride, the many components of Sodium Silicofluoride.
Further, in described alkaline mixed solution containing sodium hydroxide mass concentration be: (30 ~ 50) g/L.
Further, described utilize basic zirconium chloride, sodium hydroxide and sodium sulphite process containing cadmium spent acid solution acid soak, comprise the steps:
1, the acid solution separating clarifying wrapped up by zirconium silicate in Cadmium Sulfide colorant acid soak production process is collected in homogenizing storage tank, carries out quantitative chemical analysis, detect cadmium (Ccd in spent acid solution to spent acid solution in storage tank
2+), selenium (Cse), hydrogen (C
h +) ionic concn;
2, the clarification spent acid solution getting certain volume amount V puts into batching agitation vat A, according to volume V and the concentration of cadmium ions of spent acid solution, calculates the total amount of cadmium in mixer A.Mol ratio 1 by cadmium in basic zirconium chloride and spent acid solution: (0.15 ~ 0.52) calculates the mass M 1 of basic zirconium chloride;
3, measure according to basic zirconium chloride M1, by basic zirconium chloride and sodium hydroxide mol ratio 1: 2, calculate sodium hydroxide mass M 2, in calculating according to the hydrogen ion concentration of got spent acid solution volume V and spent acid solution and sodium hydroxide mass M 3 needed for spent acid;
When 4, doing yellow: in Mix and dosing bucket A during spent acid solution, add the A1 solution that basic zirconium chloride M1 is made into basic zirconium chloride and cadmium; Do gilvous: in Mix and dosing bucket A during spent acid solution, add the A2 solution that basic zirconium chloride M1 and zinc sulfate are made into basic zirconium chloride, cadmium and zinc sulfate zinc, in the mass concentration of A1, A2 solution, the concentration of zirconium exists: (10 ~ 50) g/L;
5, according to the total amount of cadmium, zinc in mixer A, the mol ratio 1 by cadmium, zinc and sodium sulphite: (1.10 ~ 1.70), calculates the mass M 4 of sodium sulphite;
6, M2+M3+M4 is added water be dissolved in synthesis reaction vessel, be made into the B solution of quality naoh concentration (30 ~ 50) g/L;
7, stir synthesis reaction vessel B solution, solution A is added to reactor simultaneously and reacts, when control pH value is about 7 ~ 9, complete reaction;
8, after having reacted, press filtration washing is carried out, dry.Be dried to water ratio and be less than 2%, dried feed is pulverized, cross sieve on the 320th ~ 400, again by dried material and mineralizer, white carbon black is by 100: (35 ~ 40): (5 ~ 12) mix, 1000 DEG C ~ 1100 DEG C calcinings, calcinate is acidified, ball milling, press filtration, washing, obtain the occlusion pigment product of zirconium silicate parcel Cadmium Sulfide or parcel zinc-cadmium sulfide after oven dry.
The invention has the advantages that:
The present invention utilizes basic zirconium chloride, sodium hydroxide, zinc sulfate and sodium sulphite to carry out comprehensive treating process to acid soak containing cadmium spent acid solution, in being produced by zirconium silicate occlusion pigment, in acidified waste water, heavy metal cadmium carries out recycle, the rate of recovery of cadmium reaches maximization, reduce material cost, greatly reduce the pollution to environment; Meanwhile, introduce doping zine ion by zinc sulfate, form Cadmium Sulfide, zinc sulphide sosoloid chromogenic reagent, produce the parcel true yellow pigment of zirconium silicate crystallite parcel Cadmium Sulfide zinc.
Before the present invention, the process of the acidified waste water in producing occlusion pigment is mostly: take neutralization reaction to generate precipitation, and by precipitation agent and flocculation agent, solid-liquid diversion is carried out in the press filtration of cadmium selenium precipitation, make discharged wastewater met the national standard, the mud of precipitation transfers the recovery of environmental protection company after drying and processes, and this treatment process, can cause secondary pollution to environment, increase process waste water, useless solid treatment cost.Even if take the extracting method cadmium in acidified waste water being carried out to cadmium, extract cadmium and be re-used as starting material and use, also inevitably increase cost recovery and recovery utilization rate is low, also can cause secondary pollution simultaneously.Waste acid water in acidizing process is directly carried out recycling, and its utilization ratio is not only high, and the greatly possible pollution reduced environment.
Accompanying drawing explanation
fig. 1for technical process of the present invention
figure.
Embodiment
Below in conjunction with embodiment and
accompanying drawingthe present invention will be further described.
Embodiment 1-9
A kind of acid soak is containing cadmium, the direct recoverying and utilizing method of selenium spent acid solution, and in utilizing basic zirconium chloride, sodium hydroxide, zinc sulfate and sodium sulphite to produce occlusion pigment, acid soak processes containing cadmium, selenium spent acid solution; Basic zirconium chloride and zinc sulfate and acid soak are mixed with acidic mixed solution containing cadmium, selenium spent acid solution, after adding water with sodium hydroxide and sodium sulphite be mixed with alkaline mixed solution according to aequum again, again acidic mixed solution is joined in alkaline mixed solution, after stirring generation co-precipitation chemical reaction, carry out press filtration washing, dry, mix with mineralizer and white carbon black again, again through calcining, and calcinate is acidified, ball milling, press filtration, washing, obtain zirconium silicate parcel cadmium sulfoselenide occlusion pigment product after oven dry.
Concrete fabrication processing as
accompanying drawing 1shown in.Step is as follows:
1, first the spent acid of zirconium silicate occlusion pigment production technique acidizing process is collected in spent acid storage tank, in tank, leaves standstill homogenizing clarification;
2, clarify spent acid in absorption waste acid pot, detect concentration, the hydrionic concentration of cadmium in spent acid;
3, in mixer A, put into the spent acid of determined volume V, calculate the cadmium content in mixer: V*C
cd* 112.411;
4, in mixer A, add basic zirconium chloride and zinc sulfate, make basic zirconium chloride ZrOCl in mixer
2the mol ratio 1: 0.15 ~ 0.52 of cadmium Cd in 8HO and spent acid solution; Cadmium: the mol ratio 1: 0.165 ~ 0.65 of zinc.
5, in synthesis reaction vessel B, add NaOH, make ZrOCl in the amount=A bucket of NaOH in mixer
2c in 8HO quality × 25%+A bucket
h+× V × 40, in B bucket, mass concentration adjustment is 5 ~ 10%, adds sodium sulphite, make Na in mixer in mixer C
2quality × 69.6% × (1 ~ 1.1) of cadmium in S quality=A bucket, adjustment Na
2s mass concentration, about 25%, is added to reactor B after clarification;
6, stir synthesis reaction vessel B, rotating speed, at 60 ~ 80r/mim, adds A bucket solution and completes series reaction, when reaching terminal pH value about 7 ~ 9, continues to maintain stirring two hours;
7, after having reacted, carry out press filtration, rinsing, drying, be dried to water ratio and be less than 2%;
8, dried material was pulverized sieve on the 320th ~ 400;
9, in dried material: white carbon black: mineralizer :=100: (35 ~ 40): the ratio mixing homogenizing of (5 ~ 12), calcine at 950 DEG C ~ 1100 DEG C, in calcinate: water: sulfuric acid: nitric acid=100: (13 ~ 25): (15 ~ 21): after the ratio of (16 ~ 25) first soaks 2 ~ 48 hours in acidifying ball mill, ball milling 0.5 ~ 1.5 hour, makes ball milling fineness reach: D
90it is 10 ~ 25 microns;
10, after ball milling, ball milling material is carried out rinsing, after drying, become final product.
In process of the test, get the spent acid solution in production.Detect: cadmium volumetric molar concentration: 0.04708mol/L; Hydrogen ion concentration: 0.8469mol/L, press
figurethe test of table technological process draws one group of 9 case, and the yellow wrapper that the test adding equivalent in same foundation glaze respectively obtains contrasts, and through grinding glaze, glaze spraying sample preparation plate, fires, detected result at 1180 DEG C
as table 1
(
table 1)
In test research and development, all Adjustment Tests was carried out to various raw-material proportioning, therefrom optimized
in tablecase.From
in tablecan find out that No. 1 sample color development is true yellow; 2, No. 3 sample color development polarizations are yellow; 4,5, No. 6 become gilvous, than the Huang of praseodymium yellow
look lookpurer mutually, color development ability is stronger; 7,8, No. 9 start to partially green phase change.
Can be found out by above-described embodiment, the present invention relates to one utilizes acid soak to contain cadmium, selenium spent acid solution preparation parcel yellow ultramarine method, it is characterized in that: the cadmium wastewater of acid bubble process is directly utilized and produces zirconium silicate crystallite parcel Cadmium Sulfide colorant, doping zine ion is introduced by zinc sulfate, form Cadmium Sulfide, zinc sulphide sosoloid chromogenic reagent, produce the parcel true yellow pigment of zirconium silicate crystallite parcel Cadmium Sulfide zinc.
Further, described directly utilizes production zirconium silicate crystallite parcel Cadmium Sulfide colorant to be after utilizing chemical process to carry out comprehensive treating process containing cadmium spent acid solution acid soak by the cadmium wastewater of acid bubble process, be directly used in produce and produce zirconium silicate crystallite parcel cadmium sulfoselenide colorant and parcel true yellow
look lookmaterial.
Further, it is described that to utilize chemical process to carry out comprehensive treating process containing cadmium spent acid solution acid soak be that the alkaline mixed solution that utilize basic zirconium chloride and zinc sulfate and acid soak to contain acidic mixed solution that cadmium spent acid solution prepares and sodium hydroxide and sodium sulphite are prepared carries out coprecipitation reaction in reactor, after having reacted, carry out press filtration washing, dry; Again in dried material: white carbon black: mineralizer: the ratio of=100: 35 ~ 40: 5 ~ 12 mixing homogenizing, through high-temperature calcination, calcinate is acidified, ball milling, press filtration, washing, obtain zirconium silicate parcel sulfuration cadmium yellow after oven dry
look lookthe parcel true yellow of material or parcel zinc-cadmium sulfide
look lookmaterial product.
Further, described basic zirconium chloride, sodium hydroxide and solution of zinc sulfate first basic zirconium chloride are made into basic zirconium chloride, cadmium and zinc sulfate acidic mixed solution with acid soak containing cadmium spent acid solution together with zinc sulfate.
Further, the basic zirconium chloride quality in described acidic mixed solution is volume according to spent acid solution and concentration of cadmium ions, calculates the total amount of cadmium, then presses the mol ratio 1: 0.15 ~ 0.52 of cadmium in basic zirconium chloride and spent acid solution, calculate the quality of basic zirconium chloride.
Further, the quality of the described zinc sulfate in described acidic mixed solution is according to cadmium: the mol ratio 1: 0.165 ~ 0.65 of zinc, calculates the quality of zinc sulfate.
Further, the mass concentration containing zirconium in described acidic mixed solution is 10 ~ 50g/L; Determine according to the volume of spent acid solution and concentration of cadmium ions containing the mass concentration of zirconium in described acidic mixed solution, when spent acid solution concentration of cadmium ions is very low, Cadmium Sulphate can be dropped in spent acid solution, to change concentration of cadmium ions in spent acid solution, thus change the mass concentration containing zirconium in acidic mixed solution.
Further, the described described sodium hydroxide of preparation that adds water, the preparation of sodium sulphite alkaline mixed solution are after adding water in a kettle., drop into sodium hydroxide; After adding water in mixer again, dropping into sodium sulphite and be made into mass concentration 20-30% solution, after clarification, join reactor, being made into alkaline mixed solution by stirring.
Further, the quality of the sodium hydroxide of described input is according to basic zirconium chloride amount, by the mol ratio 1: 2 of basic zirconium chloride and sodium hydroxide, calculate sodium hydroxide quality, and add the hydrogen ion concentration according to got spent acid solution volume V and spent acid solution, according in and pH value for 6 ~ 7 calculate in and spent acid needed for sodium hydroxide quality; Containing sodium hydroxide mass concentration in described alkaline mixed solution is 30 ~ 50g/L.
Further, the sodium sulphite quality of described input is the total amount according to cadmium, zinc in acidic mixed solution, by the mol ratio 1: 1.10 ~ 1.70 of cadmium, zinc and sodium sulphite, calculates the quality of sodium sulphite.
Further, described mineralizer refers to lithium fluoride, Quilonum Retard, Neutral ammonium fluoride, Sodium Silicofluoride.Lithium fluoride can add by single component, and also can add with Neutral ammonium fluoride, the many components of Sodium Silicofluoride, Quilonum Retard can only add with Neutral ammonium fluoride, the many components of Sodium Silicofluoride.
Above-mentioned listed embodiment, just combines
accompanying drawingclear, complete description is carried out to technical scheme of the present invention; Obviously, described embodiment is only a part of embodiment of the present invention, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments all obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention has the advantages that: the present invention utilizes basic zirconium chloride, sodium hydroxide, zinc sulfate and sodium sulphite to carry out comprehensive treating process to acid soak containing cadmium spent acid solution, in being produced by zirconium silicate occlusion pigment, in acidified waste water, heavy metal cadmium carries out recycle, the rate of recovery of cadmium reaches maximization, reduce material cost, greatly reduce the pollution to environment.Simultaneously, doping zine ion is introduced by zinc sulfate, form Cadmium Sulfide, zinc sulphide sosoloid chromogenic reagent, produce the parcel true yellow pigment of zirconium silicate crystallite parcel Cadmium Sulfide zinc, parcel true yellow pigment can replace praseodymium yellow to use, stronger than the color development ability of praseodymium yellow one times, and the production of parcel true yellow pigment will alleviate the demand of praseodymium yellow production to praseodymium, when praseodymium price goes up day by day, parcel gilvous pigment will have better cost advantage and quality-advantage.
Before the present invention, the process of the acidified waste water in producing occlusion pigment is mostly: take neutralization reaction to generate precipitation, and by precipitation agent and flocculation agent, solid-liquid diversion is carried out in the press filtration of cadmium selenium precipitation, make discharged wastewater met the national standard, the mud of precipitation transfers the recovery of environmental protection company after drying and processes, and this treatment process, can cause secondary pollution to environment, increase process waste water, useless solid treatment cost.Even if take the extracting method cadmium in acidified waste water being carried out to cadmium, extract cadmium and be re-used as starting material and use, also inevitably increase cost recovery and recovery utilization rate is low, also can cause secondary pollution simultaneously.Waste acid water in acidizing process is directly carried out recycling, and its utilization ratio is not only high, and the greatly possible pollution reduced environment.
Claims (10)
1. one kind utilizes acid soak to contain cadmium, selenium spent acid solution preparation parcel yellow ultramarine method, it is characterized in that: the cadmium wastewater of acid bubble process is directly utilized and produces zirconium silicate crystallite parcel Cadmium Sulfide colorant, doping zine ion is introduced by zinc sulfate, form Cadmium Sulfide, zinc sulphide sosoloid chromogenic reagent, produce the parcel true yellow pigment of zirconium silicate crystallite parcel Cadmium Sulfide zinc.
2. utilize acid soak to contain cadmium spent acid solution preparation parcel yellow ultramarine method as claimed in claim 1, it is characterized in that: it is after utilizing chemical process to carry out comprehensive treating process containing cadmium spent acid solution acid soak that zirconium silicate crystallite parcel Cadmium Sulfide colorant is produced in described directly being utilized by the cadmium wastewater of acid bubble process, be directly used in produce and produce zirconium silicate crystallite parcel cadmium sulfoselenide colorant and parcel gilvous colorant.
3. utilize acid soak to contain cadmium spent acid solution preparation parcel yellow ultramarine method as claimed in claim 2, it is characterized in that: described to utilize chemical process to carry out comprehensive treating process containing cadmium spent acid solution acid soak be that the alkaline mixed solution that utilize basic zirconium chloride and zinc sulfate and acid soak to contain acidic mixed solution that cadmium spent acid solution prepares and sodium hydroxide and sodium sulphite are prepared carries out coprecipitation reaction in reactor, after having reacted, carry out press filtration washing, dry; Again in dried material: white carbon black: mineralizer: the ratio mixing homogenizing of=100: 35 ~ 40: 5 ~ 12, through high-temperature calcination, calcinate is acidified, ball milling, press filtration, washing, obtain the parcel gilvous colorant product of the yellow colorant of zirconium silicate parcel Cadmium Sulfide or parcel zinc-cadmium sulfide after oven dry.
4. utilize acid soak to contain cadmium spent acid solution preparation parcel yellow ultramarine method as claimed in claim 3, it is characterized in that: described basic zirconium chloride, sodium hydroxide and solution of zinc sulfate first basic zirconium chloride are made into basic zirconium chloride, cadmium and zinc sulfate acidic mixed solution with acid soak containing cadmium spent acid solution together with zinc sulfate.
5. utilize acid soak to contain cadmium spent acid solution preparation parcel yellow ultramarine method as claimed in claim 4, it is characterized in that: the basic zirconium chloride quality in described acidic mixed solution is volume according to spent acid solution and concentration of cadmium ions, calculate the total amount of cadmium, then press the mol ratio 1: 0.15 ~ 0.52 of cadmium in basic zirconium chloride and spent acid solution, calculate the quality of basic zirconium chloride.
6. utilize acid soak to contain cadmium spent acid solution preparation parcel yellow ultramarine method as claimed in claim 4, it is characterized in that: the quality of the described zinc sulfate in described acidic mixed solution is according to cadmium: the mol ratio 1: 0.165 ~ 0.65 of zinc, calculates the quality of zinc sulfate.
7. utilize acid soak to contain cadmium spent acid solution preparation parcel yellow ultramarine method as claimed in claim 4, it is characterized in that: the mass concentration containing zirconium in described acidic mixed solution is 10 ~ 50g/L; Determine according to the volume of spent acid solution and concentration of cadmium ions containing the mass concentration of zirconium in described acidic mixed solution, when spent acid solution concentration of cadmium ions is very low, Cadmium Sulphate can be dropped in spent acid solution, to change concentration of cadmium ions in spent acid solution, thus change the mass concentration containing zirconium in acidic mixed solution; The described sodium hydroxide of preparation that adds water, the preparation of sodium sulphite alkaline mixed solution are after adding water in a kettle., drop into sodium hydroxide; After adding water in mixer again, dropping into sodium sulphite and be made into mass concentration 20-30% solution, after clarification, join reactor, being made into alkaline mixed solution by stirring.
8. utilize acid soak to contain cadmium spent acid solution preparation parcel yellow ultramarine method as claimed in claim 3, it is characterized in that: the quality of the sodium hydroxide of described input is according to basic zirconium chloride amount, by the mol ratio 1: 2 of basic zirconium chloride and sodium hydroxide, calculate sodium hydroxide quality, and add the hydrogen ion concentration according to got spent acid solution volume V and spent acid solution, according in and pH value for 6 ~ 7 calculate in and spent acid needed for sodium hydroxide quality; Containing sodium hydroxide mass concentration in described alkaline mixed solution is 30 ~ 50g/L.
9. utilize acid soak to contain cadmium spent acid solution preparation parcel yellow ultramarine method as claimed in claim 3, it is characterized in that: the sodium sulphite quality of described input is the total amount according to cadmium, zinc in acidic mixed solution, by the mol ratio 1: 1.10 ~ 1.70 of cadmium, zinc and sodium sulphite, calculate the quality of sodium sulphite.
10. utilize acid soak to contain cadmium, selenium spent acid solution preparation parcel yellow ultramarine method as claimed in claim 1, it is characterized in that: described utilize basic zirconium chloride, zinc sulfate and sodium hydroxide, sodium sulphite processes containing cadmium spent acid solution acid soak, comprise the steps:
1) the acid solution separating clarifying wrapped up by zirconium silicate in cadmium sulfoselenide colorant acid soak production process is collected in homogenizing storage tank, quantitative chemical analysis is carried out to spent acid solution in storage tank, detects cadmium in spent acid solution (Ccd), selenium (Cse), hydrogen (CH+) ionic concn;
2) the clarification spent acid solution getting certain volume amount V puts into batching agitation vat A, according to volume V and the concentration of cadmium ions of spent acid solution, calculates the total amount of cadmium in mixer A; The mass M 1 of basic zirconium chloride is calculated by the mol ratio 1: 0.15 ~ 0.52 of cadmium in basic zirconium chloride and spent acid solution;
3) measure according to basic zirconium chloride M1, by basic zirconium chloride and sodium hydroxide mol ratio 1: 2, calculate sodium hydroxide mass M 2, in calculating according to the hydrogen ion concentration of got spent acid solution volume V and spent acid solution and sodium hydroxide mass M 3 needed for spent acid;
4), when doing yellow: in Mix and dosing bucket A during spent acid solution, the A1 solution that basic zirconium chloride M1 is made into basic zirconium chloride and cadmium is added; Do gilvous: in Mix and dosing bucket A during spent acid solution, add the A2 solution that basic zirconium chloride M1 and zinc sulfate are made into basic zirconium chloride, cadmium and zinc sulfate zinc, in the mass concentration of A1, A2 solution, the concentration of zirconium is at 10 ~ 50g/L;
5) according to the total amount of cadmium in mixer A, by the mol ratio 1: 1.10 ~ 1.70 of cadmium and sodium sulphite, the mass M 4 of sodium sulphite is calculated;
6) M2+M3+M4 is added water be dissolved in synthesis reaction vessel, be made into the B solution of quality naoh concentration 30 ~ 50g/L;
7) stir synthesis reaction vessel B solution, solution A is added to reactor simultaneously and reacts, when control pH value is about 7 ~ 9, complete reaction;
8), after having reacted, press filtration washing is carried out, dry; Be dried to water ratio and be less than 2%, dried feed is pulverized, cross sieve on the 320th ~ 400, in dried material: white carbon black: mineralizer: the ratio mixing homogenizing of=100: 35 ~ 40: 5 ~ 12,950 DEG C ~ 1100 DEG C calcinings, calcinate is acidified, ball milling, press filtration, washing step, obtain after oven dry zirconium silicate parcel Cadmium Sulfide or parcel zinc-cadmium sulfide occlusion pigment product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107500807A (en) * | 2017-09-30 | 2017-12-22 | 江西金环颜料有限公司 | A kind of preparation method of high temperature resistant green ceramic pigment |
| CN110204927A (en) * | 2019-06-14 | 2019-09-06 | 佛山市华意陶瓷颜料有限公司 | A kind of ash ceramic pigment color and preparation method thereof |
| CN112111178A (en) * | 2020-08-21 | 2020-12-22 | 佛山市华意陶瓷颜料有限公司 | Low-temperature lemon yellow pigment and preparation method and application thereof |
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| CN103145451A (en) * | 2013-03-29 | 2013-06-12 | 佛山市南海万兴材料科技有限公司 | Zirconium silicate coated cadmium yellow ceramic pigment and preparation method thereof |
| CN103159505A (en) * | 2013-03-29 | 2013-06-19 | 佛山市南海万兴材料科技有限公司 | Process for preparing zirconium-cadmium-selenium series colorant from recycled cadmium-containing wastewater |
| CN103523757A (en) * | 2013-10-31 | 2014-01-22 | 佛山市南海万兴材料科技有限公司 | A processing process for extracting selenium from waste acid water containing cadmium selenium |
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| CN103145451A (en) * | 2013-03-29 | 2013-06-12 | 佛山市南海万兴材料科技有限公司 | Zirconium silicate coated cadmium yellow ceramic pigment and preparation method thereof |
| CN103159505A (en) * | 2013-03-29 | 2013-06-19 | 佛山市南海万兴材料科技有限公司 | Process for preparing zirconium-cadmium-selenium series colorant from recycled cadmium-containing wastewater |
| CN103523757A (en) * | 2013-10-31 | 2014-01-22 | 佛山市南海万兴材料科技有限公司 | A processing process for extracting selenium from waste acid water containing cadmium selenium |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107500807A (en) * | 2017-09-30 | 2017-12-22 | 江西金环颜料有限公司 | A kind of preparation method of high temperature resistant green ceramic pigment |
| CN110204927A (en) * | 2019-06-14 | 2019-09-06 | 佛山市华意陶瓷颜料有限公司 | A kind of ash ceramic pigment color and preparation method thereof |
| CN112111178A (en) * | 2020-08-21 | 2020-12-22 | 佛山市华意陶瓷颜料有限公司 | Low-temperature lemon yellow pigment and preparation method and application thereof |
| CN112111178B (en) * | 2020-08-21 | 2021-09-28 | 佛山市华意陶瓷颜料有限公司 | Low-temperature lemon yellow pigment and preparation method and application thereof |
| CN115246710A (en) * | 2022-07-12 | 2022-10-28 | 佛山市三水区康立泰无机合成材料有限公司 | Antibacterial powder for glaze and preparation method thereof |
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