CN105036803B - A kind of method that parcel gilvous pigment is prepared using acid soak acid pickle containing cadmium - Google Patents
A kind of method that parcel gilvous pigment is prepared using acid soak acid pickle containing cadmium Download PDFInfo
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Abstract
One kind prepares parcel yellow uitramarine method using acid soak acid pickle containing cadmium, by acid bubble processing cadmium wastewater directly using produce zirconium silicate crystallite parcel cadmium sulfide colorant, doping zinc ion is introduced by zinc sulfate, form cadmium sulfide, zinc sulphide solid solution colour former, the parcel true yellow pigment of production zirconium silicate crystallite parcel cadmium zinc sulfide.The present invention carries out chemical coprecipitation reaction containing cadmium, the same sodium hydroxide of selenium acid pickle, vulcanized sodium using basic zirconium chloride, zinc sulfate and acid soak in reactor, after the completion of reaction, carries out pressure filtration washing, dries；Be well mixed by a certain percentage with mineralizer, white carbon again, by high-temperature calcination, calcined product is acidified, ball milling, press filtration, washing step, obtained after drying zirconium silicate parcel cadmium sulfide yellow uitramarine or wrap up zinc-cadmium sulfide parcel gilvous pigment material product.Wrapping up gilvous pigment can replace praseodymium yellow pigments to use.
Description
Technical field
The present invention relates to a kind of coloring of ceramic decoration material and the process for making of pigment, a kind of profit is referred in particular to
Directly recycled with the acid pickle containing cadmium of acid soak process in zirconium silicate parcel cadmium sulfide colorant production, reproduction zirconium silicate bag
Yellow uitramarine is wrapped up in, and doping zinc ion, the parcel true yellow face of production zirconium silicate crystallite parcel cadmium zinc sulfide are introduced by zinc sulfate
Material, to substitute praseodymium yellow, reaches form and aspect and color development ability is better than the process of traditional praseodymium yellow pigments.Belong to ceramic pigment（Pigment）
Manufacture technology field.
Background technology：
Cadmium sulfide colorant is wrapped up in zirconium silicate（Wrap up yellow）In production, because colour former cadmium sulfide is by zirconium silicate crystal
Parcel is not complete enough, it is necessary to is come out the cadmium sulfide soaking and washing not wrapped by acid soak process, to ensure the hair of colorant
Colour purity is just.
Soak out the cadmium sulfide come with cadmium sulfate to be present in acid pickle, the cadmium in waste acid recovery liquid, be both saving raw material
Needs, even more environmental protection needs.
To the processing method of acid soak waste liquid containing cadmium, typically with alkali elder generation neutralisation treatment acid pickle, pH value is adjusted, it is heavy to produce
Form sediment, and precipitated and separate recycling.Such processing method utilization rate is not high, and cost recovery is high, and environment is held
Easily cause great pollution.
Cadmium sulfide series colorant is wrapped up in zirconium silicate（Wrap up yellow）In production, because colour former cadmium sulfide is brilliant by zirconium silicate
Body parcel is not complete enough, it is necessary to is come out the cadmium sulfide soaking and washing not wrapped by acid soak process, to ensure colorant
Color development is pure.But in acid soak process, soak out the cadmium sulfide come and be present in cadmium sulfate in acid pickle, if directly discharged
The pollution of environment will be caused, so the cadmium in waste acid recovery liquid is both the needs of the needs, even more environmental protection of saving raw material.
At present, to acid soak method containing Cadmium treated, typically with alkali elder generation neutralisation treatment acid pickle, pH value is adjusted, produces carbon
Cadmium precipitates or other cadmium compound precipitates, and is precipitated and separate recovery, and such processing method recovery utilization rate is not
Height, cost recovery is high, and great pollution is easily caused to environment.Therefore, existing acid soak waste liquid containing cadmium be processed into order to
The current big headache for administering environmental pollution in occlusion pigment production.
By patent retrieval and do not find there be the patent literature constructed with the present invention, related to the present invention is main
Have following：
1st, Patent No. CN201310262241, entitled " system that automatic recovery of acetic acid in waste liquid is leached from ceramics "
Patent of invention, which disclose a kind of system that automatic recovery of acetic acid in waste liquid is leached from ceramics, its storage radiating dress
Liquid level sensor and temperature sensor are installed, liquid storage tank is connected by pipeline and powered heating apparatus in the cavity for the liquid storage tank put
Connect.The entrance of the circulating pump of powered heating apparatus connects liquid storage tank, and outlet is connected with cooling device.The cooler of cooling device with it is anti-
Main frame is answered to connect；Recovery pond liquid level sensor, the pure termination of liquid pipe one cooling are installed in the pure Acetic Acid-Water recovery pond of collection device
Device, other end insertion are connect in pure Acetic Acid-Water recovery pond.Control device includes main control PLC, frequency converter, sensor, relay；Follow
Ring pump is connected by frequency converter with main control PLC, and each sensor is connected with main control PLC respectively, and the system is controlled using PLC, effectively
Lead and cadmium heavy metal ion are isolated, obtains being reused for the acetum of ceramic immersion, reduces environmental pollution, realize resource
Recycling.
2nd, Patent No. CN201220558204, the practicality of entitled " ceramic product immersion spent acid liquid treating system " are new
Type patent, it which disclose a kind of ceramic product immersion spent acid liquid treating system.Existing ceramic product detection is useless with immersion
Acid solution is directly discharged into lower water after the immersion of pottery is completed, this 4% acetic acid pH value 2.5 or so, belong to it is acid compared with
Strong waste liquid, can be to environmental concerns.The utility model is formed using two water tanks, and connection is arranged at the top between two tanks
Pipe, water tank A bottoms are provided with discharge pipe, and there is immersion detection acid pickle reception pipe on water tank B tops, had between two water tanks equipped with acidproof
Self priming pump.It can be discharged again when making up to environmental protection standard pH6-9 as collecting, neutralizing acid pickle by the use of two water tanks.
3rd, Patent No. CN201210552862, entitled " a kind of method of the purifying and cadmium removing from nickel and cobalt solution containing cadmium "
Patent of invention, it which disclose a kind of method of the purifying and cadmium removing from nickel and cobalt solution containing cadmium.Although traditional extraction method removes cadmium effect
Good, except cadmium is thorough, but extraction series is more, extracts line length；Although single resin is short, easy to operate except cadmium flow, operating cost
It is low, metal high income, but it is suitable only for chloride system.The invention is characterised by, 0.1g/L nickel cobalt is less than from cadmium concentration
Solution, first the cadmium in nickel and cobalt solution is enriched in cobalt liquor or washing lotion by solvent extraction, the concentration of cadmium is reached 0.1-
1.0g/L；Then the cadmium in cobalt liquor or washing lotion is removed using resin anion (R.A.), makes Cd<0.001g/L, Ni/Cd and Co/Cd
Reach 50000-100000：1.
4th, Patent No. CN201110319352, the patent of invention of entitled " a kind of processing method of cadmium wastewater " should
Patent discloses a kind of processing method of cadmium wastewater.Its method and step is：（1）It is prepared into by foaming agent, organic solvent, auxiliary agent
Emulsion.Its volume ratio is respectively：Foaming agent 1%~5%, auxiliary agent 15%~25%, organic solvent 70%~80%；（2）
The above-mentioned emulsion being prepared is immobilized on carrier；（3）The material of above-mentioned preparation is added in cadmium wastewater, adjusted with acid
PH to 3.0~6.5, it is stirred with 100~450r/min rotating speed；（4）2~10min is stood, emulsion floats, and floats
Emulsion be demulsified through high voltage electric field, realize the recovery of heavy metal cadmium, the oil phase of gained can return to circulation system breast in the newborn device of system；Water outlet
National grade one discharge standard can be less than.
5th, Patent No. CN201110279875, the patent of invention of entitled " a kind of processing method of cadmium wastewater " should
Patent discloses a kind of processing method of cadmium wastewater, and it comprises the following steps：(1), make the cadmium wastewater generation CdS and divide
From precipitation；(2) waste water after the precipitation and separation, is subjected to anion and cation exchange treatment.By the side of the invention
Waste water after method processing, its cadmium go out water content and controlled in below 0.03mg/L, and far below discharging standards, whole process is accomplished
Effective recovery to cadmium.Though the invention coagulation has been related to the CdS precipitation method, sulphur is handed over by ion in two stage treatment
Post recycling is changed, therefore does not introduce this contaminative ion of sulphur in water outlet, while precipitation process does not use any flocculant, makes
Cadmium precipitation dewatered solid is easy to recycle after processing.
Though these above-mentioned patent some have been related to ceramic product immersion acid pickle processing, not to how to reclaim profit
With acid soak containing cadmium, selenium acid pickle, although other patents have been related to the recycling of cadmium goods selenium, but are not to ceramic acidleach
The processing of liquid, it can not be used directly to handle ceramic product immersion acid pickle, if can find a kind of new by technological improvement
Process, acid is steeped to the waste water handled directly using zirconium silicate crystallite parcel cadmium sulfoselenide colorant is produced, waste water can be reduced
Cost recovery is handled, cadmium and selenium in and can recycling acid soak waste water, while farthest reduce to environment
Pollution, this is that this area needs to solve, and with the technical problem of very high value.
The content of the invention
The purpose of the present invention is exactly according at present with the acid soak spent acid containing cadmium in zirconium silicate parcel cadmium sulfide colorant production
The existing deficiency of liquid processing, there is provided one kind contains cadmium using caused by acid soak process in zirconium silicate parcel cadmium sulfide colorant production
Acid pickle, directly recycle the production method of reproduction zirconium silicate parcel yellow uitramarine；This method can be solved effectively with silicon
The intractability present in acid soak acid pickle containing cadmium in sour zirconium parcel cadmium sulfide colorant production is big, has pollution to ask environment
Topic.
According to foregoing invention purpose, technical scheme proposed by the invention is：One kind utilizes acid soak acid pickle system containing cadmium
Standby parcel yellow uitramarine method, the cadmium wastewater that acid is steeped to processing directly utilize reproduction zirconium silicate crystallite parcel cadmium sulfide color
Material；Doping zinc ion is introduced by zinc sulfate, forms cadmium sulfide, zinc sulphide solid solution colour former, production zirconium silicate crystallite parcel
The parcel true yellow pigment of cadmium zinc sulfide.
Further, it is described by acid steep processing cadmium wastewater directly using produce zirconium silicate crystallite parcel cadmium sulfide color
Material is after acid soak acid pickle containing cadmium is carried out into integrated treatment using chemical method, is directly used in and produces production zirconium silicate crystallite bag
Wrap up in the gilvous colorant of cadmium zinc sulfide
Further, it is described by acid soak acid pickle containing cadmium using chemical method carry out integrated treatment be to utilize oxychloride
The alkalescence that zirconium and zinc sulfate are prepared with the acidic mixed solution that acid soak acid pickle containing cadmium is prepared with sodium hydroxide and vulcanized sodium is mixed
Close solution and coprecipitation reaction is carried out in reactor, after the completion of reaction, carry out pressure filtration washing, dry；Again by dried feed and mineralising
Agent, white carbon press 100:（35~40）∶（5~12）Mixing, by high-temperature calcination, calcined product is acidified, ball milling, press filtration, water
Wash, dry after obtain zirconium silicate parcel zinc-cadmium sulfide parcel gilvous colorant product.
Further, the preparation of described basic zirconium chloride, cadmium and zinc sulfate acidic mixed solution is first added in mixer
Enter to put into after acid soak acid pickle containing cadmium basic zirconium chloride again and zinc sulfate be made into basic zirconium chloride, zinc sulfate containing zirconium, cadmium, zincic acid
Mixed solution.
Further, described basic zirconium chloride quality is the volume and concentration of cadmium ions according to acid pickle, calculates cadmium
Total amount, then by the mol ratio 1 of cadmium in basic zirconium chloride and acid pickle:（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 ）, calculate
The quality of zinc sulfate.
Further, the mass concentration containing zirconium is in described acidic mixed solution：(10~50)g/L.
Further, the mass concentration containing zirconium is the volume and cadmium ion according to acid pickle in described acidic mixed solution
What concentration determined, when acid pickle concentration of cadmium ions is very low, cadmium sulfate can be put into acid pickle, to change cadmium in acid pickle
Ion concentration, so as to change the mass concentration containing zirconium in acidic mixed solution.
Further, the preparation of sodium hydroxide, vulcanized sodium alkaline mixed solution described plus that water is prepared is in reactor
In plus water after, put into sodium hydroxide；Again in mixer plus after water, input vulcanized sodium is made into mass concentration 20-30% solution, passes through
Reactor is added to after crossing clarification, alkaline mixed solution is made into by stirring.
Further, the quality of the sodium hydroxide of described input is according to basic zirconium chloride amount, by basic zirconium chloride and hydrogen-oxygen
Change the mol ratio 1: 2 of sodium, calculate sodium hydroxide quality, and plus the hydrogen ion according to taken acid pickle volume V and acid pickle
Concentration, sodium hydroxide quality needed for neutralization spent acid is calculated for 6 ~ 7 according to pH value is neutralized.
Further, the vulcanized sodium quality of described input be according to the total amount of cadmium, zinc in acidic mixed solution, by cadmium,
The mol ratio 1 of zinc and vulcanized sodium:（1.10~1.70）, calculate the quality of vulcanized sodium.
Further, described mineralizer refers to lithium fluoride, lithium carbonate, ammonium fluoride, prodan.Lithium fluoride can be with single group
Part adds, and can also be added with ammonium fluoride, the more components of prodan, and lithium carbonate can only add with ammonium fluoride, the more components of prodan.
Further, mass concentration containing sodium hydroxide is in described alkaline mixed solution：(30~50)g/L.
Further, it is described using basic zirconium chloride, sodium hydroxide and vulcanized sodium to acid soak acid pickle containing cadmium at
Reason, comprises the following steps：
1st, the acid solution separating clarifying wrapped up zirconium silicate in cadmium sulfide colorant acid soak production process is collected in homogenizing storage tank
In, quantitative chemical analysis is carried out to acid pickle in storage tank, detects cadmium in acid pickle（Ccd2+）, selenium（Cse）, hydrogen（CH +）Ion
Concentration；
2nd, take certain volume amount V clarification acid pickle to be put into dispensing agitator A, according to the volume V of acid pickle and cadmium from
Sub- concentration, calculate the total amount of cadmium in mixer A.By the mol ratio 1 of cadmium in basic zirconium chloride and acid pickle:（0.15~0.52）Meter
Calculate the mass M 1 of basic zirconium chloride；
3rd, according to basic zirconium chloride M1 amounts, by basic zirconium chloride and sodium hydroxide mol ratio 1: 2, sodium hydroxide quality is calculated
M2, sodium hydroxide mass M 3 needed for neutralizing spent acid is calculated according to taken acid pickle volume V and acid pickle hydrogen ion concentration；
When the 4th, doing yellow：In Mix and dosing bucket A during acid pickle, the A1 that basic zirconium chloride M1 is made into basic zirconium chloride and cadmium is added
Solution；Do gilvous：In Mix and dosing bucket A during acid pickle, add basic zirconium chloride M1 and zinc sulfate be made into basic zirconium chloride, cadmium and
The A2 solution of zinc sulfate zinc, the concentration of zirconium exists in the mass concentration of A1, A2 solution：(10~50)g/L；
5th, according to the total amount of cadmium, zinc in mixer A, by the mol ratio 1 of cadmium, zinc and vulcanized sodium:（1.10~1.70）, calculate
Go out the mass M 4 of vulcanized sodium；
6th, M2+M3+M4 is added water-soluble in synthesis reaction vessel, being made into quality naoh concentration（30~50）G/L B solution；
7th, synthesis reaction vessel B solution is stirred, while solution A is added to reactor and reacted, it is 7 ~ 9 or so to control pH value
When, complete reaction；
8th, after the completion of reacting, pressure filtration washing is carried out, is dried.Moisture content is dried to less than 2%, dried feed is crushed, crosses 320
Sieve within 1, then dried material and mineralizer, white carbon pressed 100:（35~40）∶（5~12）Mixing, 1000 DEG C~1100
DEG C calcining, calcined product is acidified, ball milling, press filtration, washing, zirconium silicate parcel cadmium sulfide or parcel zinc sulphide is obtained after drying
The occlusion pigment product of cadmium.
The advantage of the invention is that：
The present invention is integrated using basic zirconium chloride, sodium hydroxide, zinc sulfate and vulcanized sodium to acid soak acid pickle containing cadmium
Processing, heavy metal cadmium is recycled in acidified waste water during zirconium silicate occlusion pigment is produced, and the rate of recovery of cadmium reaches maximum
Change, reduce the cost of raw material, greatly reduce the pollution to environment；Meanwhile doping zinc ion, shape are introduced by zinc sulfate
Into cadmium sulfide, zinc sulphide solid solution colour former, the parcel true yellow pigment of production zirconium silicate crystallite parcel cadmium zinc sulfide.
Before the present invention, the processing of the acidified waste water in being produced to occlusion pigment is mostly：Neutralization reaction is taken to generate
Precipitation, and cadmium selenium is precipitated by press filtration by precipitating reagent and flocculant and carries out solid-liquid diversion, make discharged wastewater met the national standard, the sludge of precipitation
Environmental protection company recovery is transferred after drying to be handled, this processing method, secondary pollution, increase processing can be caused to environment
Waste water, give up solid treatment cost.The extracting method that cadmium is carried out to the cadmium in acidified waste water is even taken, extraction cadmium is re-used as original
Materials'use, also inevitably increase cost recovery and recovery utilization rate is low, while will also result in secondary pollution.Will acidifying
Waste acid water in process directly carries out recycling, and its utilization rate is not only high, and greatly possible reduces to environment
Pollution.
Brief description of the drawings
Fig. 1 is the process chart of the present invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention will be further described.
Embodiment 1-9
A kind of acid soak utilizes basic zirconium chloride, sodium hydroxide, zinc sulfate containing cadmium, the direct recoverying and utilizing method of selenium acid pickle
Acid soak is handled containing cadmium, selenium acid pickle in being produced with vulcanized sodium to occlusion pigment；By basic zirconium chloride and zinc sulfate and acidleach
Bubble is configured to acidic mixed solution, then adds water to be configured to alkali according to aequum with sodium hydroxide and vulcanized sodium containing cadmium, selenium acid pickle
Property mixed solution after, then acidic mixed solution is added in alkaline mixed solution, passes through to stir co-precipitation chemical reaction occurs
Afterwards, pressure filtration washing is carried out, is dried, then is well mixed with mineralizer and white carbon, then by calcining, and by calcined product through peracid
Zirconium silicate parcel cadmium sulfoselenide occlusion pigment product is obtained after change, ball milling, press filtration, washing, drying.
Specific fabrication processing is as shown in Figure 1.Step is as follows：
1st, first the spent acid of zirconium silicate occlusion pigment production technology acidizing process is collected in spent acid storage tank, stood in tank
Homogenizing clarification；
2nd, draw and spent acid is clarified in waste acid pot, detect concentration, the hydrionic concentration of cadmium in spent acid；
3rd, determined volume V spent acid is put into mixer A, calculates the cadmium content in mixer：V*Ccd*112.411；
4th, basic zirconium chloride and zinc sulfate are added in mixer A, makes basic zirconium chloride ZrOCl in mixer28HO and spent acid
Cadmium Cd mol ratio 1: 0.15~0.52 in liquid；Cadmium: the mol ratio 1: 0.165 ~ 0.65 of zinc.
5th, NaOH is added in synthesis reaction vessel B, makes ZrOCl in amount=A buckets of NaOH in mixer28HO mass × 25%
C in+A bucketsH+Mass concentration adjustment adds vulcanized sodium in mixer C, makes mixer 5~10% in × V × 40, B bucket
Middle Na2Quality × 69.6% of cadmium in S mass=A buckets ×（1~1.1）, adjust Na2S mass concentrations are added to after 25% or so, clarification
Reactor B；
6th, synthesis reaction vessel B is stirred, rotating speed is completed series reaction, reached eventually in 60~80r/mim, addition A buckets solution
During point pH value 7 ~ 9 or so, stirring two hours is continued to；
7th, after the completion of reacting, press filtration, rinsing, drying are carried out, is dried to moisture content less than 2%；
8th, dried material crushed 320~400 and sieves；
9th, by dried material: white carbon: mineralizer :=100:（35~40）∶（5~12）Ratio mixing homogenizing, 950
DEG C~1100 DEG C at calcine, by calcined product: water: sulfuric acid: nitric acid=100: (13 ~ 25):（15~21) ∶(16~25）Ratio
Example ball milling 0.5~1.5 hour, reaches ball milling fineness after being acidified and first soaking 2 ~ 48 hours in ball mill：D90For 10 ~ 25 microns；
10th, ball milling material is rinsed after ball milling, into finished product after drying.
During experiment, the acid pickle in production is taken.Detect：Cadmium molar concentration：0.04708mol/L；Hydrogen ion is dense
Degree：0.8469mol/L, one group of 9 case is drawn by the experiment of chart technical process, adds equivalent respectively in same foundation glaze
The obtained yellow wrapper of experiment contrasted, by grinding glaze, glaze spraying sample preparation plate, fired at 1180 DEG C, detection knot
Fruit such as table 1：
（Table 1）
Adjustment Tests were all carried out to the proportioning of various raw material in experiment research and development, therefrom preferably go out case in table.From table
In it can be seen that No. 1 sample color development be in true yellow；2nd, No. 3 sample color development polarization yellow；4th, 5, No. 6 into gilvous, than the yellow of praseodymium yellow
Form and aspect are purer, and color development ability is stronger；7th, 8, No. 9 start to partially green phase change.
It can be seen from above-described embodiment that prepare parcel containing cadmium, selenium acid pickle using acid soak the present invention relates to one kind
Yellow uitramarine method, it is characterised in that：By acid bubble processing cadmium wastewater directly using produce zirconium silicate crystallite parcel cadmium sulfide
Colorant, doping zinc ion is introduced by zinc sulfate, cadmium sulfide, zinc sulphide solid solution colour former is formed, produces zirconium silicate crystallite bag
Wrap up in the parcel true yellow pigment of cadmium zinc sulfide.
Further, it is described by acid steep processing cadmium wastewater directly using produce zirconium silicate crystallite parcel cadmium sulfide color
Material is after acid soak acid pickle containing cadmium is carried out into integrated treatment using chemical method, is directly used in and produces production zirconium silicate crystallite bag
Wrap up in cadmium sulfoselenide colorant and parcel gilvous colorant.
Further, it is described by acid soak acid pickle containing cadmium using chemical method carry out integrated treatment be to utilize oxychloride
The alkalescence that zirconium and zinc sulfate are prepared with the acidic mixed solution that acid soak acid pickle containing cadmium is prepared with sodium hydroxide and vulcanized sodium is mixed
Close solution and coprecipitation reaction is carried out in reactor, after the completion of reaction, carry out pressure filtration washing, dry；Dried material: hard charcoal is pressed again
It is black: mineralizer :=100: 35 ~ 40: 5~12 ratio mixing homogenizing, by high-temperature calcination, calcined product is acidified, ball milling,
Zirconium silicate parcel cadmium sulfide yellow colorant is obtained after press filtration, washing, drying or wraps up the parcel gilvous colorant production of zinc-cadmium sulfide
Product.
Further, described basic zirconium chloride, sodium hydroxide and solution of zinc sulfate are first by basic zirconium chloride and zinc sulfate one
Rise and be made into basic zirconium chloride, cadmium and zinc sulfate acidic mixed solution with acid soak acid pickle containing cadmium.
Further, the basic zirconium chloride quality in described acidic mixed solution is the volume and cadmium ion according to acid pickle
Concentration, the total amount of cadmium is calculated, then by the mol ratio 1: 0.15~0.52 of cadmium in basic zirconium chloride and acid pickle, calculate chlorine oxygen
Change the quality of zirconium.
Further, the quality of the described zinc sulfate in described acidic mixed solution is according to cadmium: the mol ratio 1 of zinc
: 0.165 ~ 0.65, calculate the quality of zinc sulfate.
Further, the mass concentration containing zirconium is 10 ~ 50g/L in described acidic mixed solution；Described acidic mixed
The mass concentration containing zirconium determines according to the volume and concentration of cadmium ions of acid pickle in solution, when acid pickle concentration of cadmium ions is very low
When, cadmium sulfate can be put into acid pickle, to change concentration of cadmium ions in acid pickle, is contained so as to change in acidic mixed solution
The mass concentration of zirconium.
Further, described described plus sodium hydroxide, vulcanized sodium alkaline mixed solution that water is prepared preparation be
In reactor plus after water, sodium hydroxide is put into；Again in mixer plus after water, it is molten that input vulcanized sodium is made into mass concentration 20-30%
Liquid, reactor is added to after clarification, alkaline mixed solution is made into by stirring.
Further, the quality of the sodium hydroxide of described input is according to basic zirconium chloride amount, by basic zirconium chloride and hydrogen-oxygen
Change the mol ratio 1: 2 of sodium, calculate sodium hydroxide quality, and plus the hydrogen ion according to taken acid pickle volume V and acid pickle
Concentration, sodium hydroxide quality needed for neutralization spent acid is calculated for 6 ~ 7 according to pH value is neutralized；It is hydrogeneous in described alkaline mixed solution
Sodium oxide molybdena mass concentration is 30 ~ 50g/L.
Further, the vulcanized sodium quality of described input be according to the total amount of cadmium, zinc in acidic mixed solution, by cadmium,
The mol ratio 1: 1.10 ~ 1.70 of zinc and vulcanized sodium, calculate the quality of vulcanized sodium.
Further, described mineralizer refers to lithium fluoride, lithium carbonate, ammonium fluoride, prodan.Lithium fluoride can be with single
Component adds, and can also be added with ammonium fluoride, the more components of prodan, lithium carbonate can only be with ammonium fluoride, the more components of prodan
Add.
Above-mentioned listed embodiment, simply carries out clear, complete description to technical scheme with reference to accompanying drawing；It is aobvious
So, described embodiment is only the part of the embodiment of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, all other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
The advantage of the invention is that：The present invention is contained using basic zirconium chloride, sodium hydroxide, zinc sulfate and vulcanized sodium to acid soak
Cadmium acid pickle carries out integrated treatment, and heavy metal cadmium is recycled in acidified waste water during zirconium silicate occlusion pigment is produced, cadmium
The rate of recovery reach maximization, reduce the cost of raw material, greatly reduce the pollution to environment.Meanwhile pass through zinc sulfate
Doping zinc ion is introduced, forms cadmium sulfide, zinc sulphide solid solution colour former, the parcel of production zirconium silicate crystallite parcel cadmium zinc sulfide
True yellow pigment, parcel true yellow pigment can replace praseodymium yellow to use, stronger than the color development ability of praseodymium yellow one times, wrap up the life of true yellow pigment
Production will alleviate demand of the praseodymium yellow production to praseodymium, in the case where praseodymium price increasingly goes up, wrap up gilvous pigment
Will there are more preferable cost advantage and quality-advantage.
Before the present invention, the processing of the acidified waste water in being produced to occlusion pigment is mostly：Neutralization reaction is taken to generate
Precipitation, and cadmium selenium is precipitated by press filtration by precipitating reagent and flocculant and carries out solid-liquid diversion, make discharged wastewater met the national standard, the sludge of precipitation
Environmental protection company recovery is transferred after drying to be handled, this processing method, secondary pollution, increase processing can be caused to environment
Waste water, give up solid treatment cost.The extracting method that cadmium is carried out to the cadmium in acidified waste water is even taken, extraction cadmium is re-used as original
Materials'use, also inevitably increase cost recovery and recovery utilization rate is low, while will also result in secondary pollution.Will acidifying
Waste acid water in process directly carries out recycling, and its utilization rate is not only high, and greatly possible reduces to environment
Pollution.
Claims (4)
- A kind of 1. method that parcel gilvous pigment is prepared using acid soak acid pickle containing cadmium, it is characterised in that：Sour bubble is handled Cadmium wastewater directly using produce zirconium silicate crystallite parcel cadmium sulfide colorant, pass through zinc sulfate introduce doping zinc ion, formed Cadmium sulfide, zinc sulphide solid solution colour former, the parcel true yellow pigment of production zirconium silicate crystallite parcel cadmium zinc sulfide；Sour bubble is handled Cadmium wastewater directly using produce zirconium silicate crystallite parcel cadmium sulfide colorant be by acid soak acid pickle containing cadmium utilization chemistry side After method carries out integrated treatment, it is directly used in and produces production zirconium silicate crystallite parcel cadmium sulfoselenide colorant and parcel gilvous colorant； Wherein, it is to utilize basic zirconium chloride and zinc sulfate and acid soak acid soak acid pickle containing cadmium to be carried out into integrated treatment using chemical method The alkaline mixed solution that the acidic mixed solution that acid pickle containing cadmium is prepared is prepared with sodium hydroxide and vulcanized sodium is entered in reactor Row coprecipitation reaction, after the completion of reaction, pressure filtration washing is carried out, is dried；Dried material: white carbon: mineralizer :=100: 35 is pressed again ~ 40: 5~12 ratio mixing homogenizing, by high-temperature calcination, calcined product is acidified, ball milling, press filtration, washing, after drying Cadmium sulfide yellow colorant is wrapped up to zirconium silicate or wraps up the parcel gilvous colorant product of zinc-cadmium sulfide；Basic zirconium chloride, hydroxide Sodium and solution of zinc sulfate are that basic zirconium chloride and zinc sulfate first are made into basic zirconium chloride, cadmium and sulphur with acid soak acid pickle containing cadmium together Sour zincic acid mixed solution；Zinc sulfate quality in acidic mixed solution is according to cadmium: the mol ratio 1: 0.165 ~ 0.65 of zinc, meter Calculate the quality of zinc sulfate；The quality of the sodium hydroxide of described input is according to basic zirconium chloride amount, by basic zirconium chloride and hydrogen-oxygen Change the mol ratio 1: 2 of sodium, calculate sodium hydroxide quality, and plus the hydrogen ion according to taken acid pickle volume V and acid pickle Concentration, sodium hydroxide quality needed for neutralization spent acid is calculated for 10.5 according to pH value is neutralized；Contain in described alkaline mixed solution Sodium hydroxide mass concentration is 30 ~ 50g/L；Basic zirconium chloride quality in described acidic mixed solution is the body according to acid pickle Product and concentration of cadmium ions, the total amount of cadmium is calculated, then by the mol ratio 1: 0.15~0.52 of cadmium in basic zirconium chloride and acid pickle, Calculate the quality of basic zirconium chloride.
- 2. preparing the method for parcel gilvous pigment using acid soak acid pickle containing cadmium as claimed in claim 1, its feature exists In：The mass concentration containing zirconium is 10 ~ 50g/L in described acidic mixed solution；Matter containing zirconium in described acidic mixed solution Amount concentration determines according to the volume and concentration of cadmium ions of acid pickle, when acid pickle concentration of cadmium ions is low, is thrown in acid pickle Enter cadmium sulfate, to change concentration of cadmium ions in acid pickle, so as to change the mass concentration containing zirconium in acidic mixed solution；Described The preparation for adding the sodium hydroxide, vulcanized sodium alkaline mixed solution of water preparation is in a kettle plus after water, puts into sodium hydroxide；Again In mixer plus after water, input vulcanized sodium is made into mass concentration 20-30% solution, and reactor is added to after clarification, is passed through Stirring is made into alkaline mixed solution.
- 3. preparing the method for parcel gilvous pigment using acid soak acid pickle containing cadmium as claimed in claim 1, its feature exists In：The vulcanized sodium quality of described input is according to the total amount of cadmium, zinc in acidic mixed solution, by rubbing for cadmium, zinc and vulcanized sodium That ratio 1: 1.10 ~ 1.70, calculate the quality of vulcanized sodium.
- 4. preparing the method for parcel gilvous pigment using acid soak acid pickle containing cadmium as claimed in claim 1, its feature exists In：Described is handled acid soak acid pickle containing cadmium using basic zirconium chloride, zinc sulfate and sodium hydroxide, vulcanized sodium, including Following steps：1）Acid solution separating clarifying zirconium silicate wrapped up in cadmium sulfoselenide colorant acid soak production process is collected in storage tank is homogenized, Quantitative chemical analysis is carried out to acid pickle in storage tank, detects cadmium in acid pickle, selenium, hydrogen ion concentration；2）Certain volume amount V clarification acid pickle is taken to be put into dispensing agitator A, it is dense according to the volume V and cadmium ion of acid pickle Degree, calculate the total amount of cadmium in mixer A；Chlorine is calculated by the mol ratio 1: 0.15~0.52 of cadmium in basic zirconium chloride and acid pickle The mass M 1 of zirconium oxide；3）According to basic zirconium chloride M1 amounts, by basic zirconium chloride and sodium hydroxide mol ratio 1: 2, sodium hydroxide mass M 2, root are calculated Calculated according to taken acid pickle volume V and acid pickle hydrogen ion concentration and neutralize sodium hydroxide mass M 3 needed for spent acid；4）When doing yellow：In Mix and dosing bucket A during acid pickle, addition basic zirconium chloride M1 is made into basic zirconium chloride and the A1 of cadmium is molten Liquid；Do gilvous：In Mix and dosing bucket A during acid pickle, add basic zirconium chloride M1 and zinc sulfate is made into basic zirconium chloride, cadmium and sulphur The A2 solution of sour zinc, the concentration of zirconium is in 10 ~ 50g/L in the mass concentration of A1, A2 solution；5）According to the total amount of cadmium in mixer A, by the mol ratio 1: 1.10 ~ 1.70 of cadmium and vulcanized sodium, the matter of vulcanized sodium is calculated Measure M4；6）By M2+M3+M4 plus water-soluble in the B solution in synthesis reaction vessel, being made into 30 ~ 50g/L of quality naoh concentration；7）Synthesis reaction vessel B solution is stirred, while solution A is added to reactor and reacted, when control ph is 10.5, is completed Reaction；8）After the completion of reaction, pressure filtration washing is carried out, is dried；Moisture content is dried to less than 2%, dried feed is crushed, crosses 320~400 Day sieves, in dried material: white carbon: mineralizer :=100: 35~40: 5~12 ratio mixing homogenizing, 950 DEG C~1100 DEG C calcining, calcined product is acidified, ball milling, press filtration, washing step, obtained after drying zirconium silicate parcel cadmium sulfide or parcel sulphur Change the occlusion pigment product of zinc cadmium.
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