CN102515252B - Film-coating production technology for nano zinc oxide - Google Patents
Film-coating production technology for nano zinc oxide Download PDFInfo
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- CN102515252B CN102515252B CN 201110450912 CN201110450912A CN102515252B CN 102515252 B CN102515252 B CN 102515252B CN 201110450912 CN201110450912 CN 201110450912 CN 201110450912 A CN201110450912 A CN 201110450912A CN 102515252 B CN102515252 B CN 102515252B
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Abstract
The invention provides a film-coating production technology for nano zinc oxide and belongs to the technical field of fine petrochemicals and chemicals. The technological process is that an alkali carbonic acid zinc film is coated uniformly on the surfaces of light calcium carbonate and inner pores thereof, subjected to decentralized processing, and then calcined and activated in a dynamic calcination furnace at the temperature of 400 to 500 DEG C, so as to prepare the nano zinc oxide. The nano zinc oxide prepared through the technology belongs to a low-zinc product (containing 24 to 30 percent zinc), has the advantages of stable nano size, stable nano material properties, completely developed crystal grains, small particle diameter, uniformity in distribution, low reunion degree, high activity and good dispersivity, and can be widely applied to rubber, tires, catalysis, magnetism, optics, electricity, chemistry, physics, biology and the like.
Description
Technical field
The present invention relates to a kind of production technique of petrochemical industry chemical fine chemicals, specifically, particularly production technique of planting the membranous type nano zine oxide.
Background technology
Nano zine oxide is a kind of novel meticulous inorganic chemical product of multi-functional, high added value.Its particle diameter is called again ultra-fine zinc oxide between the 1-100 nanometer.Granular due to crystal grain, specific surface area sharply increases, its Electronic Structure and crystalline structure change, and have produced the characteristics such as the surface effects that macro object did not have, volume effect, quantum size effect and macroscopical tunnel effect and high-clarity, polymolecularity.Research in recent years finds that it has the incomparable property of general zinc oxide product and new purposes at aspects such as catalysis, magnetic, light, electricity, chemistry, physics, biology, susceptibility.Show wide application prospect in rubber, coating, printing ink, face (filling out) material, catalyzer, the cosmetics of super quality and medicine and other fields.Due to a series of superiority of nano zine oxide and very tempting application prospect, the research and development nano zine oxide has become the focus that many scientific and technical personnel pay close attention to.
The nano zine oxide Product Activity is high, has the function of counter infrared ray, ultraviolet ray and sterilization.Be widely used in the products such as sun-proof type makeup, antibacterial deodourizing and anti-ultraviolet new functional fiber, self-cleaning antibacterial glass, pottery, anti-infrared, ultraviolet shielding material, sanitary ware, sewage disposal and photocatalyst material.
The most effective inorganic active agent and vulcanization accelerator in nano zine oxide or rubber industry.It is used in rubber, has vulcanization rate fast, and the reaction temperature field width is converted into the transformation efficiency high of zinc sulphide.Can improve smooth finish, physical strength, temperature tolerance and the ageing-resistant performance of rubber item, particularly improve its wear resisting property etc.Practice shows, nano zine oxide is used with common zinc oxide more not a halfpenny the worse in these areas, more greatly can realize the decrement adapted, and then reduce costs because of its surfactivity.
Nano zine oxide is applied in high-grade paint, printing ink, coating, plastics, can greatly improve product opacifying power and tinting strength; Be used as the fusing assistant of breast erosion glaze in ceramic industry.In addition, nano zine oxide also can be widely used in the industries such as cable, papermaking, medicine, printing and dyeing, pigment and national defence.
The method for preparing the nano zine oxide super-fine powder is mainly divided Physical and chemical method.Wherein, chemical method is the most frequently used method.Below each method is set forth.
1. Physical
Physical comprises mechanical crushing method and severe plastic deformation.Mechanical crushing method is to adopt the technology such as special mechanical disintegration, electrical spark blast, is broken to the oxide powder and zinc of common grade ultra-fine.Wherein the people such as Zhang Wei utilizes vertical vibration grinder to prepare nano-powder, has obtained α-Al
2O
3, ZnO, MgSiO
3Deng super-fine powder, fine granularity reaches 0.1 μ m.Although this method technique is simple, has energy consumption large, product purity is low, and size-grade distribution is inhomogeneous, and the shortcomings such as usefulness are pulverized in the size of grinding medium and the impact of the fineness of charging.Maximum deficiency is the powder that this method can not get 1-100nm, and is therefore industrial and seldom use this method.
And severe plastic deformation is to make starting material that serious plastic deformation occur under the fine pressure effect, makes the size of material refine to nanometer scale.This unique method is grown up at the beginning of 1994 by people such as Islamgaliev at first.The Zinc oxide powder purity that the method makes is high, granularity is controlled, but very high to the requirement of production unit.Generally speaking, the shortcoming such as Physical prepares nano zine oxide, and to exist power consumption large, and product granularity is inhomogeneous, does not even reach nano level, and product purity is not high industrially seldom adopts, and its development prospect is also little.
2. chemical method
Chemical method has that cost is low, and equipment is simple, easily amplifies characteristics such as carrying out large-scale industrial production.Mainly be divided into sol-gel method, alkoxide hydrolysis, direct precipitation method, sluggish precipitation etc.
2.1 sol-gel method
The work that sol-gel method prepares nano-powder starts from the sixties in 20th century.In recent years, the report with the standby nanoparticle of this legal system, nano thin-film, nano composite material etc. is a lot.It is the alkoxide Zn (OR) with metal
2Be raw material, in organic medium to its be hydrolyzed, polycondensation, make solution obtain gel through solation.Gel again drying, be sintered into the method for powder.The product granularity that this method is produced is little, purity is high, temperature of reaction low (can than low 400--500 ℃ of traditional method), process are easy to control, even particle distribution, reunion are lacked, dielectric properties are better.But cost is expensive, and discharge has pollution to environment, and is to be improved.
Described hydrolysis, polycondensation formula are as follows:
Hydrolysis reaction: Zn (OR)
2+ 2H
2O → Zn (OH)
2+ 2ROH
Polycondensation: Zn (OH)
2→ ZnO+H
2O
2.2 alkoxide hydrolysis
Alkoxide hydrolysis is to utilize metal alkoxide fast hydrolyzing in water, forms precipitation of hydroxide, and throw out obtains the method for nano-powder again through washing, dry, calcining.The advantage that the method is outstanding is that reaction conditions is less demanding, and is simple to operate.Shortcoming is easily to form heterogeneous nucleation in reaction, and raw materials cost is high.For example with Zn (OC
2H
5)
2Be raw material, following reaction occur:
Zn(OC
2H
5)
2+2H
2O→Zn(OH)
2+2C
2H
5OH
Zn(OH)
2→ZnO+H
2O
2.3 direct precipitation method
Direct precipitation method is a kind of method that the preparation nano zine oxide the most extensively adopts.Its principle is to add precipitation agent or remove solvating agent in comprising the soluble salt solution of one or more ions, generate throw out under certain condition, and its throw out is separated out from solution, then negatively charged ion is removed, throw out finally makes nano zine oxide through thermolysis.Wherein select different precipitation agents, can obtain different precipitated products.See with regard to document announcement, common precipitation agent is ammoniacal liquor, bicarbonate of ammonia, urea etc.
With NH
3H
2It is as follows that O makes the precipitation agent reaction formula:
Zn
2++2NH
3·H
2O→Zn(OH)
2+2NH
4 +
Zn(OH)
2→ZnO+H
2O
Make the precipitation agent reaction formula with bicarbonate of ammonia as follows:
3Zn
2++2NH
4HCO
3+H
2O→ZnCO
3·2Zn(OH)
2·H
2O+2NH
4 +
ZnCO
3·2Zn(OH)
2·H
2O→3ZnO+CO
2+H
2O
Make the precipitation agent reaction formula with urea as follows:
CO(NH
2)
2+2H
2O→CO
2+2NH
3·H
2O
3Zn
2++CO
3 2-+4OH
-+H
2O→ZnCO
3·2Zn(OH)
2·H
2O
ZnCO
3·2Zn(OH)
2·H
2O→3ZnO+CO
2+H
2O
Operation is simple for direct precipitation method, less demanding to equipment and technology, and product purity is high, is difficult for introducing other impurity, and cost is lower.But the shortcoming of this method is that the negatively charged ion in washing precipitate is more difficult, and the product pellet size distribution that generates is wider.Must tackle key problems on large-scale commercial production and overcome these shortcomings.
2.4 sluggish precipitation
Sluggish precipitation be utilize a certain chemical reaction make the brilliant particulate of structure in solution from solution lentamente, discharge equably.The precipitation agent that adds does not directly react with precipitated component, but by chemical reaction, it is evenly separated out lentamente in whole solution.Precipitation from homogeneous solution agent commonly used has urea CO (NH
2)
2With vulkacit H C
6H
12N
3The gained powder diameter is generally 8-60nm.Its centre halfback's will is virtuous waits the people to prepare zinc oxide take urea and zinc nitrate as raw material, reaches a conclusion: temperature is the susceptibility factor that affects product cut size.Temperature is low, and hydrolysis of urea is slow, and in solution, the supersaturation ratio of zinc hydroxide is low, and particle diameter is large; Excess Temperature, urea produces condensation reaction and generates biuret etc., and the zinc hydroxide supersaturation ratio is low, and the solution thickness is difficult for drying, and the finished product particle is larger.In addition, the proportioning of reactant concn and urea and zinc nitrate also affects the supersaturation ratio of zinc hydroxide in solution.Concentration is higher, and at identical temperature, the supersaturation ratio of zinc hydroxide is larger.But the ratio of too high concentration and urea and zinc nitrate makes washing, the drying of product become difficult, and the reaction times is long, also will cause later stage solution supersaturation ratio to reduce, and it is large that particle diameter becomes.Therefore their optimum process condition that obtains is: the proportioning 2.5-4.0 of temperature of reaction＜130 ℃, reaction times 150min, urea and zinc nitrate: 1 (mol ratio).Can find out thus, the particle size distribution that sluggish precipitation obtains is narrower, good dispersity, and industrial prospect is good, is preparation nano zine oxide ideal method.But when specifically being applied to large-scale commercial production, still need be optimized as the case may be perfect.
2.5 hydrothermal method
Hydrothermal method is to study a kind of means of the earth mineral origin cause of formation at first.It is to realize constructing with crystal from the particulate of atom level, molecular level by the chemical reaction under suitable hydrothermal condition in autoclave growing.This method is that two water acetic acid zinc are dissolved in divinyl ethylene glycol, and heating is also constantly stirred and obtained zinc oxide with this, then be at room temperature cooling, with whizzer with moisture from, finally obtain Zinc oxide powder through super-dry.The standby powder crystal grain of this legal system is grown complete, and particle diameter is little and be evenly distributed, and the reunion degree is little, and is active high in sintering process.But it is high pressure resistant that shortcoming is equipment requirements, and energy expenditure is also very large, therefore is unfavorable for suitability for industrialized production.
2.6 microemulsion method
Transparent, isotropic thermodynamic stable system that microemulsion normally is comprised of tensio-active agent, cosurfactant (being generally alcohols), oil (being generally hydrocarbon polymer) and water (or aqueous electrolyte liquid).In microemulsion, small " pond " (water pool) surrounded and forms the micro emulsion particle by tensio-active agent and cosurfactant formed unimolecular layer interface, and its size can be controlled in several between tens nanometers.Small " pond " yardstick is little and separated from one another, thereby does not consist of water, and this special microenvironment has been proved to be the perfect medium of number of chemical reaction.Xu Jia waits by force the people to add hexanaphthene, propyl carbinol, ABS to stir in zinc nitrate solution, then adds hydrogen peroxide, and with ammoniacal liquor as precipitation agent, finally synthesized nano particle (19nm), gas sensitivity is high and working temperature is low nano zine oxide.The nano zine oxide of microemulsion method preparation, size distribution is even, but agglomeration is serious.This is that the nano material particle diameter that makes due to microemulsion method is too little, and specific surface is large, due to surface effects is serious.
In sum, nano zine oxide has broad application prospects, but its conventional preparation method all has deficiency at present.Simultaneously, also prepare nano zine oxide with first at microparticle surfaces and inner pore surface grafting zinc subcarbonate film mode thereof without any processing method.
Summary of the invention
For the problems referred to above, the invention provides one kind and plant membranous type nano zine oxide production technique, be zinc subcarbonate film in the plantation of light calcium carbonate surface and inner pore surface uniform thereof, and through dispersion treatment, then in dynamic calcining furnace through 400-500 ℃ of calcining and activating.The nano zine oxide of making by technique belongs to low zinc type (containing zinc 24-32%) product, has stable nano-scale and nano material character, and crystal grain is grown complete, and particle diameter is little and be evenly distributed, and the reunion degree is little, and is active high, good dispersity.Can be widely used in the aspects such as rubber, tire, catalysis, magnetic, light, electricity, chemistry, physics, biology.
The present invention realizes by following technique means: plant membranous type nano zine oxide production technique, it is characterized in that comprising the following steps for one kind:
(1) leach: make leaching solvent with ammoniacal liquor and carbon ammonium, the zinc in secondary zinc oxide is leached make zinc ammonia complex solution;
(2) iron removal by oxidation, manganese: add potassium permanganate to carry out oxidizing reaction in the leach liquor that above-mentioned steps obtains, with the Fe in leach liquor
2+, Mn
2+Be oxidized to the Fe of indissoluble
3+, Mn
4+Be precipitated out, and remove by filter, obtain filtrate;
(3) zinc dust precipitation copper removal, cadmium, lead: add the zinc dust precipitation reaction in the filtrate that above-mentioned steps obtains, copper, cadmium, lead are precipitated out, and remove by filter, be purified liquid;
(4) scavenging solution is refining: add ammonium sulfide in the scavenging solution that above-mentioned steps obtains, make metal ion remaining in scavenging solution generate the metal sulphide salt of indissoluble, remove by filter, obtain refined liquid;
(5) pre-nanometer is planted work: add the dilution of desalination pure water in the refined liquid that above-mentioned steps obtains after, add the white carbon black of light calcium carbonate, conduct activation and nanometer catalyzer as dispersion agent, carry out pre-nanometer and plant work;
(6) ammonia still process: the aaerosol solution after pre-nanometer is planted work that above-mentioned steps obtains is sent into the ammonia still process of ammonia still process tank, namely directly being passed into pre-nanometer with water vapor more than 100 ℃ under negative pressure plants in solution after living, make zinc ammonia complex be decomposed into zinc subcarbonate, ammonia and carbonic acid gas, described zinc subcarbonate evenly is attached to the dispersion agent surface and separate out on the inner pore surface, obtains planting the membranous type nano zinc oxide suspension; The ammonia that is evaporated and carbonic acid gas absorb through cooling, water cycle makes recovery ammoniacal liquor, also can get back to leaching section and recycle as leaching solvent;
(7) calcining: the suspension that above-mentioned steps is obtained adds water washing, and through the pressure filter press filtration, filter cake is sent into 400-500 ℃ of calcining and activating of dynamic drying and calcining all-in-one oven can obtain planting the nano oxidized zinc product of membranous type;
(8) packing of product: product enters that airflow screen, deironing and automatic packaging system sieve, deironing after cooling, then packing.The present invention also can do following improvement:
In step (1), described leaching is two-part, carry out in two are leached the pond respectively, filter residue after first paragraph is leached under agitation adds second segment to leach leaching again in the pond, the filter residue that second segment leaches discards, and two immersion liquid that second segment leaches add first paragraph to leach in the pond as leaching solvent, and under agitation drop into secondary zinc oxide to the first and leach in the pond, one immersion liquid of leaching enters next step, so moves in circles.Wherein, first paragraph leaches take the excessive leaching solvent of abundant consumption as purpose, and the complex reaction of ammonia and zinc is fully carried out, and improves the content of zinc in infusion solution, reduces consumption of planting steam in membranous type nano zine oxide ammonia still process process per ton; Second segment leaches in operation and guarantees that with a large amount of excessive leaching solvents the content of zinc in leached mud is low as much as possible, facts have proved and can reduce by 2%, to improve the zinc metal recovery rate.
When described second segment leached, in leaching solvent, ammonia concentration was 75-90g/L, and the carbon ammonium concentration is 105-126g/L; When leaching, presses described first paragraph total mol ratio NH
4 +: Zn=4:1.1 drops into secondary zinc oxide, and described first paragraph leaches and is 3-3.5 hour, and second segment leached as 2-2.5 hour.
In step (2), described oxidation reaction condition is 40-55 ℃, stirs, and the amount that drops into potassium permanganate is Fe in an immersion liquid
2++ Mn
2+The 3-9 of total mass doubly; Reaction times is 1-1.5 hour.
In step (3), conditions of replacement reaction is for doubly adding zinc powder by the 2-4 of copper, cadmium, plumbous total mass in solution, and stirring reaction 45 minutes.
In step (4), ammonium sulfide used is the ammonium sulfide of effective sulfur content 8-9%, and 10 times of dilute with waters under agitation slowly add in scavenging solution, react press filtration after 1-1.5 hour; The add-on of described ammonium sulfide be copper, cadmium, plumbous impurity the molar weight sum 1-1.15 doubly.Can allow when impurity concentration is low namely that 10-15%'s is excessive.
In step (5), it is 40-50g/L that described refined liquid is diluted to Zn content.
In step (5), described dispersion agent is light calcium carbonate, and activation and nanometer catalyzer are white carbon black; Wherein, zinc: dispersion agent: the mol ratio 25:62:7 of activation and nanometer catalyzer; Described pre-nanometer is planted the reaction of living to be needed to stir, and the reaction times is 30-40 minute.
In step (6), described ammonia still process adopts " bitangent is directly squeezed into steam " technique.Namely establish two opposite directions and be distributed in parallel to each other the steam-pipe of ammonia still process tank cylindrical shell both sides, and all be oriented in a tangential direction with ammonia still process tank cylindrical shell and stretch in tank, one side Yi Bian allow twice high pressure steam stream drive liquid or with clockwise or carry out abundant hybrid reaction with counterclockwise the rotation at high speed along barrel.
When beginning, described ammonia still process controls speed of response by controlling quantity of steam; When can dropping to, zinc ion concentration in solution namely stops ammonia still process below 1g/L.
Compared with prior art, the beneficial effect that has of the present invention is:
1) plant membranous type nano zine oxide production technique for one kind provided by the invention, further improve and innovation on the basis of direct precipitation method, can be applicable to large-scale industrial production.
2) adopt one kind provided by the invention to plant the nano zine oxide that membranous type nano zine oxide production technique produces and have stable nano-scale and nano material character, crystal grain is grown complete, and particle diameter is little and be evenly distributed, and the reunion degree is little, and is active high, good dispersity.
3) adopt one kind provided by the invention and plant in membranous type nano zine oxide production process, gentle friendly, the safety of reaction conditions, cost is low, is applicable to large-scale industrial production.
Description of drawings
Fig. 1 is one kind of the present invention and plants membranous type nano zine oxide production technological process.
Embodiment
The present invention is described further below in conjunction with embodiment, but the present invention is not caused any restriction.
Embodiment 1
Plant membranous type nano zine oxide production technique, it is characterized in that comprising the following steps for one kind:
(1) leach: make leaching solvent with ammoniacal liquor and carbon ammonium, the zinc in secondary zinc oxide is leached make zinc ammonia complex solution; This step
Rapid principal reaction formula is as follows:
ZnO+3NH
3·H
2O+NH
4HCO
3=Zn(NH
3)
4CO
3+4H
2O
Described leaching is two-part, carry out in two are leached the pond respectively, filter residue after first paragraph is leached under agitation adds second segment to leach leaching again in the pond, the filter residue that second segment leaches discards, two immersion liquid that second segment leaches add first paragraph to leach in the pond as leaching solvent, and under agitation drop into secondary zinc oxide to the first and leach in the pond, an immersion liquid of leaching enters next step, so moves in circles.Wherein, first paragraph leaches take the excessive leaching solvent of abundant consumption as purpose, and the complex reaction of ammonia and zinc is fully carried out, and improves the content of zinc in infusion solution, reduces consumption of planting steam in membranous type nano zine oxide ammonia still process process per ton; Second segment leaches in operation and guarantees that with a large amount of excessive leaching solvents the content of zinc in leached mud is low as much as possible, facts have proved and can reduce by 2%, to improve the zinc metal recovery rate.
When described second segment leached, in leaching solvent, ammonia concentration was 80g/L, and the carbon ammonium concentration is 120g/L; When leaching, presses described first paragraph total mol ratio NH
4 +: Zn=4:1.1 drops into secondary zinc oxide, and it is 3 hours that described first paragraph leaches, and it is 2 hours that second segment leaches.
(2) iron removal by oxidation, manganese: add potassium permanganate to carry out oxidizing reaction in the leach liquor that above-mentioned steps obtains, with the Fe in leach liquor
2+, Mn
2+Be oxidized to the Fe of indissoluble
3+, Mn
4+Be precipitated out, and remove by filter, obtain filtrate; This step principal reaction formula is as follows:
Fe
2++3Mn
7+=Fe
3+↓+3Mn
4+↓ 5Mn
2++2Mn
7+=7Mn
4+↓
Above-mentioned oxidation reaction condition is 50 ℃, stirs, and the amount that drops into potassium permanganate is Fe in an immersion liquid
2++ Mn
2+6 times of total mass; Reaction times is 1 hour.Can make iron level is that 0.012g/L, manganese content are that the immersion liquid of 0.025g/L is oxidized to iron level 0.0003g/L, manganese content 0.0001g/L.
(3) zinc dust precipitation copper removal, cadmium, lead: add the zinc dust precipitation reaction in the filtrate that above-mentioned steps obtains, copper, cadmium, lead are precipitated out, and remove by filter, be purified liquid; This step principal reaction formula is as follows:
Pb
2+Zn=Zn
2++Pb↓ Cu
2++Zn=Zn
2++Cu↓ Cd
2++Zn=Zn
2++Cd↓
Reaction conditions is for adding zinc powder by copper in solution, cadmium, plumbous total mass 3 times, and stirring reaction 45 minutes.
Can make copper content by 0.0212g/L be down to 0.0002g/L, lead content by 0.021-0.031g/L be down to 0.002-0.005g/L, cadmium content is down to 0.0001g/L by 0.025g/L.
(4) scavenging solution is refining: add ammonium sulfide in the scavenging solution that above-mentioned steps obtains, make metal ion remaining in scavenging solution generate the metal sulphide salt of indissoluble, remove by filter, obtain refined liquid; This step principal reaction formula is as follows:
Cd
2++S
2-=CdS↓ Cu
2++S
2-=CuS↓ Pb
2++S
2-=PbS↓ Zn
2++S
2-=ZnS↓
Ammonium sulfide used is the ammonium sulfide of effective sulfur content 8%, and 10 times of dilute with waters under agitation slowly add in scavenging solution, react press filtration after 1 hour; The add-on of described ammonium sulfide is the molar weight sum of copper, cadmium, lead etc. impurity.
(5) pre-nanometer is planted work: after adding the desalination pure water to be diluted to Zn50g/L, add dispersion agent, activation and nanometer catalyzer in the refined liquid that above-mentioned steps obtains, carry out pre-nanometer and plant work;
Described dispersion agent is light calcium carbonate, and activation and nanometer catalyzer are white carbon black; Wherein, zinc: dispersion agent: the mol ratio 25:62:7 of activation and nanometer catalyzer; Described pre-nanometer is planted the reaction of living to be needed to stir, and the reaction times is 30 minutes.
(6) ammonia still process: the aaerosol solution after pre-nanometer is planted work that above-mentioned steps obtains is sent into the ammonia still process of ammonia still process tank, namely directly being passed into pre-nanometer with water vapor more than 100 ℃ under negative pressure plants in solution after living, make zinc ammonia complex be decomposed into zinc subcarbonate, ammonia and carbonic acid gas, described zinc subcarbonate evenly is attached to the dispersion agent surface and separate out on the inner pore surface, obtains planting the membranous type nano zinc oxide suspension; This step principal reaction formula is as follows:
3Zn（NH
3）
4CO
3+4H
2O=ZnCO
3·2Zn(OH)
2·H
2O↓+12NH
3↑+2CO
2↑
Described ammonia still process adopts " bitangent is directly squeezed into steam " technique.
Control speed of response by controlling quantity of steam when ammonia still process begins, be beneficial to nanoparticle and generate.Along with ammonia still process is constantly carried out, zinc subcarbonate is constantly separated out.In 3.5 hours after beginning, after this eduction rate of zinc subcarbonate is separated out and is slowed down gradually more than 98%, and after 4 hours, in solution, zinc ion concentration drops to and namely stops ammonia still process below 1g/L.
The ammonia that is evaporated and carbonic acid gas absorb through cooling, water cycle makes recovery ammoniacal liquor, also can get back to leaching section and recycle as leaching solvent.It is as follows that ammonia reclaims chemical equation:
NH
3+H
2O=NH
3·H
2O
NH
3·H
2O+CO
2=NH
4HCO
3
(7) calcining: the suspension that above-mentioned steps is obtained adds water washing, and through the pressure filter press filtration, filter cake is sent into 400-500 ℃ of calcining and activating of dynamic drying and calcining all-in-one oven can obtain planting the nano oxidized zinc product of membranous type.This step reaction formula is:
ZnCO
3·2Zn（OH）
2·H
2O=3ZnO+4H
2O↑+CO
2↑
(8) packing of product: product enters that airflow screen, deironing and automatic packaging system sieve, deironing after cooling, then packing.
The above embodiments are only the preferred embodiments of the present invention, can not limit interest field of the present invention with this, and therefore, the equivalent variations according to the present patent application the scope of the claims is done still belongs to the scope that the present invention is contained.
Claims (10)
1. plant membranous type nano zine oxide production technique for one kind, it is characterized in that comprising the following steps:
(1) leach: make leaching solvent with ammoniacal liquor and carbon ammonium, the zinc in secondary zinc oxide is leached make zinc ammonia complex solution;
(2) iron removal by oxidation, manganese: add potassium permanganate to carry out oxidizing reaction in the leach liquor that above-mentioned steps obtains, with the Fe in leach liquor
2+, Mn
2+Be oxidized to the Fe of indissoluble
3+, Mn
4+Be precipitated out, and remove by filter, obtain filtrate;
(3) zinc dust precipitation copper removal, cadmium, lead: add the zinc dust precipitation reaction in the filtrate that above-mentioned steps obtains, copper, cadmium, lead are precipitated out, and remove by filter, be purified liquid;
(4) scavenging solution is refining: add ammonium sulfide in the scavenging solution that above-mentioned steps obtains, make metal ion remaining in scavenging solution generate the metal sulphide salt of indissoluble, remove by filter, obtain refined liquid;
(5) pre-nanometer is planted work: add the dilution of desalination pure water in the refined liquid that above-mentioned steps obtains after, add the white carbon black of light calcium carbonate, conduct activation and nanometer catalyzer as dispersion agent, carry out pre-nanometer and plant work;
(6) ammonia still process: the aaerosol solution after pre-nanometer is planted work that above-mentioned steps obtains is sent into the ammonia still process of ammonia still process tank, namely directly being passed into pre-nanometer with water vapor more than 100 ℃ under negative pressure plants in solution after living, make zinc ammonia complex be decomposed into zinc subcarbonate, ammonia and carbonic acid gas, described zinc subcarbonate evenly is attached to the dispersion agent surface and separate out on the inner pore surface, obtains planting the membranous type nano zinc oxide suspension;
(7) calcining: the suspension that above-mentioned steps is obtained adds water washing, and through the pressure filter press filtration, filter cake is sent into dynamic drying and calcining all-in-one oven calcining and activating can obtain planting the nano oxidized zinc product of membranous type;
(8) packing of product: product enters that airflow screen, deironing and automatic packaging system sieve, deironing after cooling, then packing.
2. plant membranous type nano zine oxide production technique for one kind according to claim 1, it is characterized in that: in step (1), described leaching is two-part, carry out in two are leached the pond respectively, filter residue after first paragraph is leached under agitation adds second segment to leach leaching again in the pond, the filter residue that second segment leaches discards, two immersion liquid that second segment leaches add first paragraph to leach in the pond as leaching solvent, and under agitation drop into secondary zinc oxide to the first and leach in the pond, one immersion liquid of leaching enters next step, so moves in circles.
3. plant membranous type nano zine oxide production technique for one kind according to claim 2, it is characterized in that: when described second segment leached, in leaching solvent, ammonia concentration was 75-90g/L, and the carbon ammonium concentration is 105-126g/L; When leaching, presses described first paragraph total mol ratio NH
4 +: Zn=4:1.1 drops into secondary zinc oxide, and described first paragraph leaches and is 3-3.5 hour, and second segment leached as 2-2.5 hour.
4. described one kind of any one is planted membranous type nano zine oxide production technique according to claim 2-3, and it is characterized in that: in step (2), described oxidation reaction condition is 40-55 ℃, stirs, and the amount that drops into potassium permanganate is Fe in an immersion liquid
2++ Mn
2+The 3-9 of total mass doubly; Reaction times is 1-1.5 hour.
5. described one kind of any one is planted membranous type nano zine oxide production technique according to claim 1-3, and it is characterized in that: in step (3), conditions of replacement reaction doubly adds zinc powder for the 2-4 by copper, cadmium, plumbous total mass in solution, and stirring reaction 45 minutes.
6. described one kind of any one is planted membranous type nano zine oxide production technique according to claim 1-3, it is characterized in that: in step (4), ammonium sulfide used is the ammonium sulfide of effective sulfur content 8-9%, 10 times of dilute with waters, under agitation slowly add in scavenging solution, react press filtration after 1-1.5 hour; The add-on of described ammonium sulfide be copper, cadmium, plumbous impurity the molar weight sum 1-1.15 doubly.
7. described one kind of any one is planted membranous type nano zine oxide production technique according to claim 1-3, and it is characterized in that: in step (5), it is 40-50g/L that described refined liquid is diluted to Zn content.
8. plant membranous type nano zine oxide production technique for one kind according to claim 7, it is characterized in that: in step (5), described dispersion agent is light calcium carbonate, and activation and nanometer catalyzer are white carbon black; Wherein, zinc: dispersion agent: the mol ratio 25:62:7 of activation and nanometer catalyzer; Described pre-nanometer is planted the reaction of living to be needed to stir, and the reaction times is 30-40 minute.
9. described one kind of any one is planted membranous type nano zine oxide production technique according to claim 1-3, and it is characterized in that: in step (6), described ammonia still process adopts " bitangent is directly squeezed into steam " technique; Namely establish two opposite directions and be distributed in parallel to each other the steam-pipe of ammonia still process tank cylindrical shell both sides, and all be oriented in a tangential direction with ammonia still process tank cylindrical shell and stretch in tank, one side Yi Bian allow twice high pressure steam stream drive liquid or with clockwise or carry out abundant hybrid reaction with counterclockwise the rotation at high speed along barrel.
10. plant membranous type nano zine oxide production technique for one kind according to claim 9, it is characterized in that: in step (6), control speed of response by controlling quantity of steam when described ammonia still process begins; When can dropping to, zinc ion concentration in solution namely stops ammonia still process below 1g/L.
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| US9528170B2 (en) | 2012-09-25 | 2016-12-27 | Sichuan Xinhong Technology Co., Ltd | Method for producing a high-purity nanometer zinc oxide from steel plant smoke and dust by ammonia decarburization |
| CN102838158B (en) * | 2012-09-25 | 2014-04-23 | 四川巨宏科技有限公司 | Method for producing high-purity nano-zinc oxide by ammonia decarburization of electrolytic zinc acid-leaching residues |
| WO2014047762A1 (en) | 2012-09-25 | 2014-04-03 | 四川巨宏科技有限公司 | Method for producing high-purity nanometer zinc oxide from low-grade zinc oxide ore by ammonia decarburization |
| WO2014047760A1 (en) * | 2012-09-25 | 2014-04-03 | 四川巨宏科技有限公司 | Method for producing high-purity nanometer zinc oxide from electrolytic zinc acid-leaching residues by ammonia decarburization |
| CN102826588B (en) * | 2012-09-25 | 2014-06-18 | 四川锌鸿科技有限公司 | Method for producing high-purity nanometer zinc oxide by using ammonia process decarburization of steel plant dust |
| CN102849782B (en) * | 2012-09-25 | 2014-06-18 | 四川锌鸿科技有限公司 | Method for producing high-purity zinc oxide by steel mill smoke dust ash ammonia method decarburization |
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| CN103482680B (en) * | 2013-08-30 | 2015-09-09 | 济源职业技术学院 | A kind of technique of being produced nano zine oxide by secondary zinc oxide |
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| CN103896325B (en) * | 2014-04-04 | 2017-01-11 | 梁鹤贤 | Calcined zinc oxide production technology |
| CN104591259B (en) * | 2015-02-09 | 2017-02-22 | 黄有余 | Engraftment type nano-zinc oxide and production process thereof |
| CN104862487B (en) * | 2015-04-21 | 2017-03-01 | 上海交通大学 | A kind of resource high-efficiency method for transformation of non-ferrous metal zinc metallurgy flying dust |
| CN105692683A (en) * | 2016-03-17 | 2016-06-22 | 安徽颖达锌业发展有限公司 | Ultra-fine zinc oxide production technology |
| CN110482592B (en) * | 2019-08-19 | 2022-02-11 | 西北矿冶研究院 | Process for preparing nano zinc oxide from steelmaking ash |
| CN110724831A (en) * | 2019-10-31 | 2020-01-24 | 重庆赛迪热工环保工程技术有限公司 | Carbon circulating system and method for producing zinc oxide by industrially recycling zinc |
| CN113830819A (en) * | 2021-10-20 | 2021-12-24 | 安徽锦华氧化锌有限公司 | Preparation method of skin-color zinc oxide |
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