CN112520782A - Preparation process of fireproof and wear-resistant calcined basic zinc carbonate - Google Patents
Preparation process of fireproof and wear-resistant calcined basic zinc carbonate Download PDFInfo
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- CN112520782A CN112520782A CN202011427752.8A CN202011427752A CN112520782A CN 112520782 A CN112520782 A CN 112520782A CN 202011427752 A CN202011427752 A CN 202011427752A CN 112520782 A CN112520782 A CN 112520782A
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- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 82
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 82
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 82
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 67
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000001914 filtration Methods 0.000 claims abstract description 50
- 238000002386 leaching Methods 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 229910052742 iron Inorganic materials 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000003063 flame retardant Substances 0.000 claims abstract description 28
- 239000011787 zinc oxide Substances 0.000 claims abstract description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 12
- 230000005855 radiation Effects 0.000 claims abstract description 10
- 238000005299 abrasion Methods 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 8
- 238000007865 diluting Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 13
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 13
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 13
- 239000001099 ammonium carbonate Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 8
- 239000000347 magnesium hydroxide Substances 0.000 claims description 8
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 1
- 238000013461 design Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 239000003094 microcapsule Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 4
- 229910000010 zinc carbonate Inorganic materials 0.000 description 4
- 239000011667 zinc carbonate Substances 0.000 description 4
- 235000004416 zinc carbonate Nutrition 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 241000282465 Canis Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- -1 coatings Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- DKWADZDKFNWNNT-UHFFFAOYSA-N diazanium hydrogen carbonate hydrogen sulfate Chemical compound [NH4+].[NH4+].[O-]C([O-])=O.OS(O)(=O)=O DKWADZDKFNWNNT-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
A preparation process of fire-proof and wear-resistant calcined basic zinc carbonate comprises the following steps: (1) preparing a zinc sulfate solution: leaching and filtering zinc oxide ores to obtain a zinc sulfate solution; (2) preparation of reaction solution: performing iron removal, copper removal and cadmium removal purification treatment on the zinc sulfate solution to obtain a high-purity zinc sulfate solution; diluting the high-purity zinc sulfate solution to 0.8-1.0 mol/L; dripping sodium carbonate solution in a constant pressure dropping funnel into the solution until the pH reaches 6.5-7.0, then heating to 60-70 ℃, performing ultrasonic radiation for 30-50min, and then aging for 1-1.5h to obtain reaction liquid; adding a fire retardant and an abrasion resistant agent into the reaction solution; (3) and preparing basic zinc carbonate. The preparation process of the fireproof and wear-resistant calcined basic zinc carbonate is simple and efficient, reasonable in formula design, high in production efficiency and low in comprehensive cost, solves the problems of single basic zinc carbonate product and low added value, and is good in fireproof performance and wear resistance and wide in application prospect.
Description
Technical Field
The invention belongs to the technical field of basic zinc carbonate preparation, and particularly relates to a preparation process of fireproof and wear-resistant calcined basic zinc carbonate.
Background
The basic zinc carbonate is widely applied to desulfurizer, catalyst and the like of medicines, rubber, latex products, petrochemical industry and certain raw materials, and is also a precursor for preparing the zinc carbonate by a thermal decomposition method. The zinc oxide has excellent photoelectric property and is widely applied in the fields of photocatalysis, semiconductors, pressure-sensitive ceramics, coatings, rubber, plastics, antibacterial materials and the like. At present, one process method for producing nano zinc oxide is to calcine basic zinc carbonate precursor, and the morphological structure and granularity of the basic zinc carbonate have great influence on the calcined product zinc carbonate, especially on the nano porous zinc carbonate with very obvious catalytic effect, and the method is an important condition for preparing zinc carbonate with different forms and functions.
Wherein, the chemical formula of the basic zinc carbonate is ZnCO 3.2 Zn (OH) 2. H2O, and the industrial synthesis method of the basic zinc carbonate comprises the following steps: (1) the zinc sulfate/ammonium bicarbonate method (for example, patent CN201310293744.2) uses zinc sulfate and ammonium bicarbonate as raw materials, and the zinc sulfate/ammonium bicarbonate is prepared by reacting in water, the reaction needs to be catalyzed by ammonia water, and the ammonium bicarbonate is easy to decompose in the reaction process, the feeding amount is not easy to control, and the industrial application is less; (2) the zinc sulfate/sodium carbonate method (for example, patent CN201710944366.8) is a method which takes zinc sulfate and sodium carbonate as raw materials and is prepared by reacting in water, and is currently a method which is widely applied in industry, basic zinc carbonate particles generated by the reaction are small (the particle size is 200-500 meshes), the specific surface area is large, a reaction solution is in a suspension state, and the filtration is difficult; the water content of the filtered and separated basic zinc carbonate wet product is 45-50%, the sulfate content is high, and a large amount of water is needed for leaching and desalting; the production of 1 ton of medicinal grade basic zinc carbonate needs 40-50 tons of water, and the leaching and filtering process consumes long time (not less than 16 hours), so that the energy consumption is large, the production efficiency is low, and the comprehensive cost is high. In addition, the preparation process for basic zinc carbonate in the prior art cannot expand the functionality of the basic zinc carbonate and is limited in flexibility.
Therefore, a preparation process of calcining basic zinc carbonate suitable for fire prevention and wear resistance needs to be developed, the zinc product structure of an enterprise is improved, and the preparation process has important significance for improving the economic benefit of the enterprise.
Chinese patent application No. CN201410420362.6 discloses a method for preparing nano basic zinc carbonate, which adopts a hydrogen sulfate-ammonium bicarbonate method to prepare nano basic zinc carbonate, strictly controls the addition of magnesium element to ensure that the grain size reaches the optimal value, and does not solve the problems of large specific surface area, suspended reaction liquid, difficult filtration and single functionality in the preparation of the basic zinc carbonate.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects, the invention aims to provide a preparation process of fireproof and wear-resistant calcined basic zinc carbonate, which has the advantages of simple and efficient preparation process, reasonable formula design, low cost, high product purity, good chemical metering property, improved fireproof performance and wear resistance of basic zinc carbonate, expanded functionality of basic zinc carbonate and wide application prospect.
The purpose of the invention is realized by the following technical scheme:
a preparation process of fireproof and wear-resistant calcined basic zinc carbonate is characterized by comprising the following steps:
(1) preparing a zinc sulfate solution: leaching and filtering zinc oxide ores to obtain a zinc sulfate solution;
(2) preparation of reaction solution: performing iron removal, copper removal and cadmium removal purification treatment on the zinc sulfate solution to obtain a high-purity zinc sulfate solution; diluting the high-purity zinc sulfate solution to 0.8-1.0 mol/L; dripping sodium carbonate solution in a constant pressure dropping funnel into the solution until the pH reaches 6.5-7.0, then heating to 60-70 ℃, performing ultrasonic radiation for 30-50min, and then aging for 1-1.5h to obtain reaction liquid; adding a fire retardant and an abrasion resistant agent into the reaction solution;
(3) preparation of basic zinc carbonate: filtering the reaction solution, and washing the reaction solution after filtering until the conductivity of the filtrate is less than 200 mu s/cm to obtain a filter cake; drying the filter cake at the drying temperature of 100-120 ℃ to obtain the basic zinc carbonate.
The preparation process of the fireproof and wear-resistant calcined basic zinc carbonate has reasonable design of preparation process steps, adopts the zinc oxide ore as the raw material, has low cost, solves the problem of high cost of preparing the basic zinc carbonate in the prior art, leaches and filters the zinc oxide ore, completely dissolves components to be dissolved, removes harmful impurities such as iron, arsenic, antimony, silicon, germanium and the like by hydrolysis, and obtains qualified neutral zinc sulfate solution by liquid-solid separation; the zinc sulfate solution is subjected to purification treatment of iron removal, copper removal and cadmium removal to obtain a high-purity zinc sulfate solution, so that the quality of the subsequent basic zinc carbonate is further improved.
The invention adopts sodium carbonate as a precipitator, solves the problems that ammonium bicarbonate is easy to decompose and the feeding amount is difficult to control in the reaction process, has high precipitation rate, is difficult to introduce impurities, has high product purity, good chemical metering property and lower cost; the ultrasonic radiation is adopted, so that the precise control can be realized, and the ultrasonic cavitation of the ultrasonic radiation can enable the generated high-temperature and high-pressure environment to provide required energy for the formation of the micro particles, so that the generation rate of the precipitation crystal nucleus in the preparation process can be increased by several orders of magnitude, the increase of the generation rate of the precipitation crystal nucleus enables the particle size of the precipitation particles to be reduced, and the particle size distribution is narrower; in addition, the high temperature generated by ultrasonic cavitation and the canine quantity of micro bubbles on the surface of the crystal also greatly reduce the specific surface free energy of the micro product particles, and inhibit the coalescence and growth of crystal nuclei; the shock waves and the micro jet generated by the ultrasonic cavitation have a crushing effect, so that the binding force among ions can be greatly reduced, the generation of an agglomeration phenomenon can be effectively reduced, and the ultrasonic cavitation is higher in efficiency and speed than the traditional stirring, so that crystals can be dispersed in the whole solution in uniform micro particles, and the quality of the basic zinc carbonate is greatly improved; the fire retardant and the wear-resistant agent are added into the reaction liquid, so that the fire resistance and the wear resistance of the basic zinc carbonate are improved, and the functionality of the basic zinc carbonate is expanded.
Further, in the preparation process of the fireproof and wear-resistant calcined basic zinc carbonate, the leaching and filtering in the step (1) specifically comprises the following steps: putting zinc oxide ore into a leaching device, pouring 20-23% sulfuric acid into the leaching device, stirring by using an electric stirring device for 1.5-2.0h, then carrying out acid leaching for 4.0-5.0h, and after leaching, filtering and purifying the leachate in the leaching device to obtain a zinc sulfate solution.
Further, in the preparation process of the fireproof and wear-resistant calcined basic zinc carbonate, the liquid-solid ratio of the zinc oxide ore to the sulfuric acid is 5: 1, the stirring speed of the electric stirring device is 220-250 r/min.
Further, in the preparation process of the above fire-proof and wear-resistant calcined basic zinc carbonate, the zinc oxide ore in the step (1) comprises the following chemical components in percentage by weight: zn40-42%, Pb5-7%, SiO22-4%, Sb0-1% and Fe 0-1%.
Further, in the preparation process of the fireproof and wear-resistant calcined basic zinc carbonate, the iron removal by the purification treatment in the step (2) specifically comprises the following steps:
(1) preliminary iron removal: heating the zinc sulfate solution to 80-90 ℃, adding potassium permanganate to oxidize, mechanically stirring for 1.5-2h, and adjusting the pH to 5.2-5.4 by using ammonia water; keeping the temperature for 1-2h, cooling to room temperature, and filtering to obtain zinc sulfate solution with iron removed preliminarily;
(2) deep iron removal: heating the zinc sulfate solution subjected to preliminary iron removal to 90-95 ℃, adding 28% hydrogen peroxide in batches, mechanically stirring for 0.5-1.0h, and adjusting the pH to 5.2-5.4 by using ammonia water; reacting for 1.0-1.5h at constant temperature, cooling to room temperature, and filtering to obtain the zinc sulfate solution with deep iron removal.
Further, in the preparation process of the fireproof and wear-resistant calcined basic zinc carbonate, copper and cadmium are removed in the step (2), and the preparation process specifically comprises the following steps: heating the zinc sulfate solution to 70-75 ℃, adjusting the pH value to 5.2-5.4 by using ammonia water, adding zinc powder, reacting at constant temperature for 1.0-1.5h, cooling to room temperature, and filtering to obtain the high-purity zinc sulfate solution.
Further, in the preparation process of the fireproof and wear-resistant calcined basic zinc carbonate, the ammonium bicarbonate solution in the step (2) is 0.8-1.0 mol/L.
Further, in the preparation process of the fireproof and wear-resistant calcined basic zinc carbonate, the fireproof agent is microcapsule red phosphorus and nano magnesium hydroxide; the addition amount of the fire retardant relative to the mass of the reaction liquid is 0.1-0.5%; the addition amount of the wear-resisting agent relative to the mass of the reaction liquid is 0.2-0.3%.
The microcapsule red phosphorus and the nano magnesium hydroxide have the flame-retardant synergistic effect, and the fireproof flame-retardant efficiency of the basic zinc carbonate can be greatly improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation process of the fireproof and wear-resistant calcined basic zinc carbonate is simple and efficient, the formula design is reasonable, the zinc oxide ore is adopted as the raw material, the cost of the zinc oxide ore is low, and the problem of high cost in preparation of the basic zinc carbonate in the prior art is solved;
(2) according to the preparation process of the fireproof and wear-resistant calcined basic zinc carbonate, sodium carbonate is used as a precipitator, the problems that ammonium bicarbonate is easy to decompose and the feeding amount is difficult to control in the reaction process are solved, the precipitation rate is high, impurities are difficult to introduce, the product purity is high, the chemical metering performance is good, and the cost is low;
(3) the preparation process of the fireproof and wear-resistant calcined basic zinc carbonate uses ultrasonic radiation, can be accurately controlled, and can improve the generation rate of precipitation crystal nucleus in the preparation process by several orders of magnitude, and the improvement of the generation rate of the precipitation crystal nucleus reduces the particle size of precipitation particles and has narrower particle size distribution; the specific surface free energy of the small product grains is greatly reduced, and the coalescence and growth of crystal nuclei are inhibited; the stirring speed is higher than the traditional stirring speed, so that crystals can be dispersed in the whole solution in uniform micro particles, and the quality of the basic zinc carbonate is greatly improved;
(4) according to the preparation process of the fireproof and wear-resistant calcined basic zinc carbonate, the fireproof agent and the wear-resistant agent are added into the reaction liquid, so that the fireproof performance and the wear-resistant performance of the basic zinc carbonate are improved, and the functionality of the basic zinc carbonate is expanded.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to specific experimental data, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following examples 1, 2, 3, 4, and 5 provide a preparation process of a fire-proof and wear-resistant calcined basic zinc carbonate, wherein the zinc oxide ore comprises the following chemical components in percentage by weight: zn40-42%, Pb5-7%, SiO22-4%, Sb0-1% and Fe 0-1%.
Example 1
The preparation process of the fireproof and wear-resistant calcined basic zinc carbonate comprises the following steps:
(1) preparing a zinc sulfate solution: putting zinc oxide ore into a leaching device, pouring 20% sulfuric acid into the leaching device, stirring by using an electric stirring device for 1.5 hours, then carrying out acid leaching for 4.0 hours, and filtering and purifying a leaching solution in the leaching device after leaching is finished to obtain a zinc sulfate solution; the liquid-solid ratio of the zinc oxide ore to the sulfuric acid is 5: 1, the stirring speed of the electric stirring device is 220 r/min;
(2) preparation of reaction solution: heating the zinc sulfate solution to 80 ℃, adding potassium permanganate to oxidize, mechanically stirring for 1.5h, and adjusting the pH value to 5.2-5.4 by using ammonia water; keeping the temperature for 1h, cooling to room temperature, and filtering to obtain zinc sulfate solution with iron removed preliminarily; heating the zinc sulfate solution subjected to preliminary iron removal to 90 ℃, adding 28% hydrogen peroxide in batches, mechanically stirring for 0.5h, and adjusting the pH to 5.2-5.4 by using ammonia water; reacting for 1.5h at constant temperature, cooling to room temperature, and filtering to obtain zinc sulfate solution with deep iron removal; heating the zinc sulfate solution to 75 ℃, adjusting the pH value to 5.2-5.4 by using ammonia water, adding zinc powder, reacting at constant temperature for 1.5h, cooling to room temperature, and filtering to obtain a high-purity zinc sulfate solution; diluting the high-purity zinc sulfate solution to 0.8-1.0 mol/L; dropwise adding a sodium carbonate solution in a constant-pressure dropping funnel into the solution, wherein the concentration of the ammonium bicarbonate solution is 1.0mol/L until the pH value reaches 6.5-7.0, then heating to 70 ℃, performing ultrasonic radiation for 30min, and then aging for 1.5h to obtain a reaction solution; adding a fire retardant and an abrasion resistant agent into the reaction solution; the fire retardant is microcapsule red phosphorus and nano magnesium hydroxide; the adding amount of the fire retardant relative to the mass of the reaction liquid is 0.3 percent; the addition amount of the wear-resisting agent relative to the mass of the reaction liquid is 0.2 percent; the particle size of the fire retardant and the wear resistant is less than 10 nm;
(3) preparation of basic zinc carbonate: filtering the reaction solution, and washing the reaction solution after filtering until the conductivity of the filtrate is less than 200 mu s/cm to obtain a filter cake; and drying the filter cake at 120 ℃ to obtain the basic zinc carbonate.
Example 2
The preparation process of the fireproof and wear-resistant calcined basic zinc carbonate comprises the following steps:
(1) preparing a zinc sulfate solution: putting zinc oxide ore into a leaching device, pouring 21% sulfuric acid into the leaching device, stirring by using an electric stirring device for 1.8 hours, then carrying out acid leaching for 4.0-5.0 hours, and after leaching, filtering and purifying leachate in the leaching device to obtain a zinc sulfate solution; the liquid-solid ratio of the zinc oxide ore to the sulfuric acid is 5: 1, the stirring speed of the electric stirring device is 250 r/min;
(2) preparation of reaction solution: heating the zinc sulfate solution to 80-90 ℃, adding potassium permanganate for oxidation, mechanically stirring for 1.5h, and adjusting the pH value to 5.2-5.4 by using ammonia water; keeping the temperature for 2 hours, cooling to room temperature, and filtering to obtain zinc sulfate solution with iron removed preliminarily; heating the zinc sulfate solution subjected to preliminary iron removal to 92 ℃, adding 28% hydrogen peroxide in batches, mechanically stirring for 0.8h, and adjusting the pH to 5.2-5.4 by using ammonia water; reacting for 1.5h at constant temperature, cooling to room temperature, and filtering to obtain zinc sulfate solution with deep iron removal; heating the zinc sulfate solution to 70 ℃, adjusting the pH value to 5.2-5.4 by using ammonia water, adding zinc powder, reacting at constant temperature for 1.2h, cooling to room temperature, and filtering to obtain a high-purity zinc sulfate solution; diluting the high-purity zinc sulfate solution to 1.0 mol/L; dropwise adding a sodium carbonate solution in a constant-pressure dropping funnel into the solution, wherein the concentration of the ammonium bicarbonate solution is 1.0mol/L until the pH value reaches 6.5-7.0, then heating to 65 ℃, radiating with ultrasonic waves for 40min, and then aging for 1.0h to obtain a reaction solution; adding a fire retardant and an abrasion resistant agent into the reaction solution; the fire retardant is microcapsule red phosphorus and nano magnesium hydroxide; the adding amount of the fire retardant relative to the mass of the reaction liquid is 0.1 percent; the addition amount of the wear-resisting agent relative to the mass of the reaction liquid is 0.2 percent; the particle size of the fire retardant and the wear resistant is less than 10 nm;
(3) preparation of basic zinc carbonate: filtering the reaction solution, and washing the reaction solution after filtering until the conductivity of the filtrate is less than 200 mu s/cm to obtain a filter cake; and drying the filter cake at 120 ℃ to obtain the basic zinc carbonate.
Example 3
The preparation process of the fireproof and wear-resistant calcined basic zinc carbonate comprises the following steps:
(1) preparing a zinc sulfate solution: putting zinc oxide ore into a leaching device, pouring 20-23% sulfuric acid into the leaching device, stirring by using an electric stirring device for 2.0 hours, then carrying out acid leaching for 4.0 hours, and filtering and purifying a leaching solution in the leaching device after leaching is finished to obtain a zinc sulfate solution; the liquid-solid ratio of the zinc oxide ore to the sulfuric acid is 5: 1, the stirring speed of the electric stirring device is 250 r/min;
(2) preparation of reaction solution: heating the zinc sulfate solution to 80-90 ℃, adding potassium permanganate for oxidation, mechanically stirring for 1.5h, and adjusting the pH value to 5.2-5.4 by using ammonia water; keeping the temperature at 1, cooling to room temperature, and filtering to obtain zinc sulfate solution with iron removed preliminarily; heating the zinc sulfate solution subjected to preliminary iron removal to 92 ℃, adding 28% hydrogen peroxide in batches, mechanically stirring for 0.6h, and adjusting the pH to 5.2-5.4 by using ammonia water; reacting for 1.2h at constant temperature, cooling to room temperature, and filtering to obtain zinc sulfate solution with deep iron removal; heating the zinc sulfate solution to 70 ℃, adjusting the pH value to 5.2-5.4 by using ammonia water, adding zinc powder, reacting at constant temperature for 1.2h, cooling to room temperature, and filtering to obtain a high-purity zinc sulfate solution; diluting the high-purity zinc sulfate solution to 1.0 mol/L; dropwise adding a sodium carbonate solution in a constant-pressure dropping funnel into the solution, wherein the concentration of the ammonium bicarbonate solution is 1.0mol/L until the pH value reaches 6.5-7.0, then heating to 70 ℃, performing ultrasonic radiation for 50min, and then aging for 1.5h to obtain a reaction solution; adding a fire retardant and an abrasion resistant agent into the reaction solution; the fire retardant is microcapsule red phosphorus and nano magnesium hydroxide; the adding amount of the fire retardant relative to the mass of the reaction liquid is 0.3 percent; the addition amount of the wear-resisting agent relative to the mass of the reaction liquid is 0.3 percent; the particle size of the fire retardant and the wear resistant is less than 10 nm;
(3) preparation of basic zinc carbonate: filtering the reaction solution, and washing the reaction solution after filtering until the conductivity of the filtrate is less than 200 mu s/cm to obtain a filter cake; and drying the filter cake at the drying temperature of 110 ℃ to obtain the basic zinc carbonate.
Example 4
The preparation process of the fireproof and wear-resistant calcined basic zinc carbonate comprises the following steps:
(1) preparing a zinc sulfate solution: putting zinc oxide ore into a leaching device, pouring 22% sulfuric acid into the leaching device, stirring by using an electric stirring device for 1.7 hours, then carrying out acid leaching for 4.2 hours, and filtering and purifying a leaching solution in the leaching device after leaching is finished to obtain a zinc sulfate solution; the liquid-solid ratio of the zinc oxide ore to the sulfuric acid is 5: 1, the stirring speed of the electric stirring device is 240 r/min;
(2) preparation of reaction solution: heating the zinc sulfate solution to 90 ℃, adding potassium permanganate to oxidize, mechanically stirring for 1.8h, and adjusting the pH to 5.2-5.4 by using ammonia water; keeping the temperature for 1.5h, cooling to room temperature, and filtering to obtain zinc sulfate solution with iron removed preliminarily; heating the zinc sulfate solution subjected to preliminary iron removal to 92 ℃, adding 28% hydrogen peroxide in batches, mechanically stirring for 0.6h, and adjusting the pH to 5.2-5.4 by using ammonia water; reacting for 1.3h at constant temperature, cooling to room temperature, and filtering to obtain zinc sulfate solution with deep iron removal; heating the zinc sulfate solution to 74 ℃, adjusting the pH value to 5.2-5.4 by using ammonia water, adding zinc powder, reacting at constant temperature for 1.2h, cooling to room temperature, and filtering to obtain a high-purity zinc sulfate solution; diluting the high-purity zinc sulfate solution to 1.0 mol/L; dropwise adding a sodium carbonate solution in a constant-pressure dropping funnel into the solution, wherein the concentration of the ammonium bicarbonate solution is 0.8mol/L until the pH value reaches 6.5-7.0, then heating to 68 ℃, performing ultrasonic radiation for 45min, and then aging for 1.2h to obtain a reaction solution; adding a fire retardant and an abrasion resistant agent into the reaction solution; the fire retardant is microcapsule red phosphorus and nano magnesium hydroxide; the adding amount of the fire retardant relative to the mass of the reaction liquid is 0.3 percent; the addition amount of the wear-resisting agent relative to the mass of the reaction liquid is 0.2 percent;
(3) preparation of basic zinc carbonate: filtering the reaction solution, and washing the reaction solution after filtering until the conductivity of the filtrate is less than 200 mu s/cm to obtain a filter cake; drying the filter cake at the drying temperature of 100-120 ℃ to obtain the basic zinc carbonate.
Example 5
The preparation process of the fireproof and wear-resistant calcined basic zinc carbonate comprises the following steps:
(1) preparing a zinc sulfate solution: putting zinc oxide ore into a leaching device, pouring 21% sulfuric acid into the leaching device, stirring by using an electric stirring device for 1.8 hours, then carrying out acid leaching for 4.2 hours, and filtering and purifying a leaching solution in the leaching device after leaching is finished to obtain a zinc sulfate solution; the liquid-solid ratio of the zinc oxide ore to the sulfuric acid is 5: 1, the stirring speed of the electric stirring device is 220-250 r/min;
(2) preparation of reaction solution: heating the zinc sulfate solution to 85 ℃, adding potassium permanganate to oxidize, mechanically stirring for 2 hours, and adjusting the pH to 5.2-5.4 by using ammonia water; keeping the temperature for 1.5h, cooling to room temperature, and filtering to obtain zinc sulfate solution with iron removed preliminarily; heating the zinc sulfate solution subjected to preliminary iron removal to 94 ℃, adding 28% hydrogen peroxide in batches, mechanically stirring for 0.6h, and adjusting the pH to 5.2-5.4 by using ammonia water; reacting for 1.2h at constant temperature, cooling to room temperature, and filtering to obtain zinc sulfate solution with deep iron removal; heating the zinc sulfate solution to 72 ℃, adjusting the pH to 5.2-5.4 by using ammonia water, adding zinc powder, reacting at constant temperature for 1.5h, cooling to room temperature, and filtering to obtain a high-purity zinc sulfate solution; diluting the high-purity zinc sulfate solution to 1.0 mol/L; dropwise adding a sodium carbonate solution in a constant-pressure dropping funnel into the solution, wherein the concentration of the ammonium bicarbonate solution is 0.8mol/L until the pH value reaches 6.5-7.0, then heating to 70 ℃, performing ultrasonic radiation for 48min, and then aging for 1.4h to obtain a reaction solution; adding a fire retardant and an abrasion resistant agent into the reaction solution; the fire retardant is microcapsule red phosphorus and nano magnesium hydroxide; the adding amount of the fire retardant relative to the mass of the reaction liquid is 0.3 percent; the addition amount of the wear-resisting agent relative to the mass of the reaction liquid is 0.25 percent; the particle size of the fire retardant and the wear resistant is less than 10 nm;
(3) preparation of basic zinc carbonate: filtering the reaction solution, and washing the reaction solution after filtering until the conductivity of the filtrate is less than 200 mu s/cm to obtain a filter cake; and drying the filter cake at 115 ℃ to obtain the basic zinc carbonate.
Effect verification:
the basic zinc carbonate obtained in example 1, example 2, example 3, example 4 and example 5 was subjected to a thermal weight loss test using an EXSTAR 6200 thermal analyzer, and the crystal forms of the basic zinc carbonate obtained in example 1, example 2, example 3, example 4 and example 5 were tested using a DX-2700X-ray powder diffractometer (XRD), and the crystal grain sizes of the basic zinc carbonate obtained in example 1, example 2, example 3, example 4 and example 5 were calculated according to the Scherrer equation in the XRD spectrum of the sample, and the results are shown in table 1.
TABLE 1 sample Performance test results
The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.
Claims (8)
1. A preparation process of fireproof and wear-resistant calcined basic zinc carbonate is characterized by comprising the following steps:
(1) preparing a zinc sulfate solution: leaching and filtering zinc oxide ores to obtain a zinc sulfate solution;
(2) preparation of reaction solution: performing iron removal, copper removal and cadmium removal purification treatment on the zinc sulfate solution to obtain a high-purity zinc sulfate solution; diluting the high-purity zinc sulfate solution to 0.8-1.0 mol/L; dripping sodium carbonate solution in a constant pressure dropping funnel into the solution until the pH reaches 6.5-7.0, then heating to 60-70 ℃, performing ultrasonic radiation for 30-50min, and then aging for 1-1.5h to obtain reaction liquid; adding a fire retardant and an abrasion resistant agent into the reaction solution;
(3) preparation of basic zinc carbonate: filtering the reaction solution, and washing the reaction solution after filtering until the conductivity of the filtrate is less than 200 mu s/cm to obtain a filter cake; drying the filter cake at the drying temperature of 100-120 ℃ to obtain the basic zinc carbonate.
2. The process for preparing the fire-proof and wear-resistant calcined basic zinc carbonate according to claim 1, wherein the leaching and filtering in the step (1) specifically comprise the following steps: putting zinc oxide ore into a leaching device, pouring 20-23% sulfuric acid into the leaching device, stirring by using an electric stirring device for 1.5-2.0h, then carrying out acid leaching for 4.0-5.0h, and after leaching, filtering and purifying the leachate in the leaching device to obtain a zinc sulfate solution.
3. The process of claim 2, wherein the liquid-to-solid ratio of zinc oxide ore to sulfuric acid is 5: 1, the stirring speed of the electric stirring device is 220-250 r/min.
4. The process for preparing the fire-proof and wear-resistant calcined basic zinc carbonate according to claim 1, wherein the zinc oxide ore in the step (1) comprises the following chemical components in percentage by weight: zn40-42%, Pb5-7%, SiO22-4%, Sb0-1% and Fe 0-1%.
5. The process for preparing the fire-proof and wear-resistant calcined basic zinc carbonate according to claim 1, wherein the step (2) of removing iron by purification comprises the following steps:
(1) preliminary iron removal: heating the zinc sulfate solution to 80-90 ℃, adding potassium permanganate to oxidize, mechanically stirring for 1.5-2h, and adjusting the pH to 5.2-5.4 by using ammonia water; keeping the temperature for 1-2h, cooling to room temperature, and filtering to obtain zinc sulfate solution with iron removed preliminarily;
(2) deep iron removal: heating the zinc sulfate solution subjected to preliminary iron removal to 90-95 ℃, adding 28% hydrogen peroxide in batches, mechanically stirring for 0.5-1.0h, and adjusting the pH to 5.2-5.4 by using ammonia water; reacting for 1.0-1.5h at constant temperature, cooling to room temperature, and filtering to obtain the zinc sulfate solution with deep iron removal.
6. The process for preparing the fireproof and wear-resistant calcined basic zinc carbonate according to claim 5, wherein the step (2) of removing copper and cadmium specifically comprises the following steps: heating the zinc sulfate solution to 70-75 ℃, adjusting the pH value to 5.2-5.4 by using ammonia water, adding zinc powder, reacting at constant temperature for 1.0-1.5h, cooling to room temperature, and filtering to obtain the high-purity zinc sulfate solution.
7. The process of claim 1, wherein the ammonium bicarbonate solution in step (2) is 0.8-1.0 mol/L.
8. The process of claim 1, wherein the fire retardant is microencapsulated red phosphorus and nano magnesium hydroxide; the addition amount of the fire retardant relative to the mass of the reaction liquid is 0.1-0.5%; the addition amount of the wear-resisting agent relative to the mass of the reaction liquid is 0.2-0.3%.
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