CN114408980A - Preparation method and equipment of demanganizing agent - Google Patents
Preparation method and equipment of demanganizing agent Download PDFInfo
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- CN114408980A CN114408980A CN202210128432.5A CN202210128432A CN114408980A CN 114408980 A CN114408980 A CN 114408980A CN 202210128432 A CN202210128432 A CN 202210128432A CN 114408980 A CN114408980 A CN 114408980A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000428 dust Substances 0.000 claims abstract description 53
- 239000000779 smoke Substances 0.000 claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- BNBLBRISEAQIHU-UHFFFAOYSA-N disodium dioxido(dioxo)manganese Chemical compound [Na+].[Na+].[O-][Mn]([O-])(=O)=O BNBLBRISEAQIHU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 87
- 238000000034 method Methods 0.000 claims description 37
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 239000001301 oxygen Substances 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003546 flue gas Substances 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011701 zinc Substances 0.000 abstract description 8
- 229910052725 zinc Inorganic materials 0.000 abstract description 8
- 238000005245 sintering Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 27
- 229910052748 manganese Inorganic materials 0.000 description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- 239000003345 natural gas Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- KBAYZRBSZAGGOT-UHFFFAOYSA-N disodium dioxido(oxo)manganese Chemical compound [Na+].[Na+].[O-][Mn]([O-])=O KBAYZRBSZAGGOT-UHFFFAOYSA-N 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- BYTCDABWEGFPLT-UHFFFAOYSA-L potassium;sodium;dihydroxide Chemical compound [OH-].[OH-].[Na+].[K+] BYTCDABWEGFPLT-UHFFFAOYSA-L 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
- C01G45/1214—Permanganates ([MnO]4-) or manganates ([MnO4]2-) containing alkali metals
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B15/00—Fluidised-bed furnaces; Other furnaces using or treating finely-divided materials in dispersion
- F27B15/02—Details, accessories, or equipment peculiar to furnaces of these types
- F27B15/10—Arrangements of air or gas supply devices
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the pyrometallurgical technology, and particularly relates to a preparation method and equipment of a demanganizing agent for zinc hydrometallurgy. The equipment for producing the demanganizing agent comprises a fluidized bed furnace, a cyclone, a ceramic tube dust collector and a water-cooling cylinder, wherein the fluidized bed furnace comprises a furnace body, the top of the fluidized bed furnace is provided with a fluidized bed furnace exhaust port, and the bottom of the fluidized bed furnace is provided with a fluidized bed furnace feed inlet, a fluidized bed furnace air inlet and a fluidized bed furnace discharge port; the discharge port of the fluidized bed furnace is communicated with the water-cooling cylinder; the cyclone and ceramic tube dust collector is provided with a smoke inlet, a smoke outlet and a gas outlet; the exhaust port of the fluidized bed furnace is communicated with a smoke inlet; the air outlet is communicated with the outside atmosphere; the smoke dust discharge port is communicated with the feed port of the fluidized bed furnace. The fluidized bed furnace adopted by the invention has higher smoke dust rate, and the smoke dust returns to the fluidized bed roasting to improve the sintering conversion rate. The sodium manganate of the invention has a sintering conversion rate of more than 90%.
Description
Technical Field
The invention belongs to the pyrometallurgical technology, and particularly relates to a preparation method and equipment of a demanganizing agent for zinc hydrometallurgy.
Background
In the wet zinc smelting process, in order to ensure high current efficiency of zinc electrodeposition and zinc product quality, the electro-deposition liquid is required to contain 5-7 g/L of Mn, manganese needs to be supplemented when the Mn is low, and manganese needs to be removed when the Mn is high. When the manganese content of the zinc concentrate is high, the manganese is gradually accumulated along with the zinc smelting process, so that the redundant manganese in a zinc smelting system needs to be removed. At present, oxidants are mostly adopted to remove manganese in production, such as potassium permanganate, sodium permanganate and persulfate, and the oxidants have good manganese removal effect, but are uneconomical and high in cost. Therefore, how to find an efficient and economic manganese remover is a problem which always troubles the industry. The preparation method of the sodium manganate mainly comprises the following steps: (1) a redox method: sodium permanganate and sodium hydroxide are subjected to oxidation reduction reaction under certain conditions to prepare sodium manganate; (2) water-soluble crystallization method: in the air or in the presence of an oxidant, sodium hydroxide or sodium carbonate and manganese dioxide are co-melted, and after being leached by water, the solution is concentrated and crystallized to prepare sodium manganate; (3) a roasting method: sodium manganate is prepared by roasting sodium hydroxide or sodium carbonate and manganese dioxide in air, the traditional roasting method generally adopts a flat furnace method or an electric heating rotary kiln method, the flat furnace method mostly adopts manual stir-frying, and the defects of high labor intensity, poor environment, low conversion rate of the materials and the air in natural contact firing exist, and the method belongs to a process method which is eliminated. The electric heating rotary kiln method can be automatically operated, the working environment is good, but the problems of poor material turning and insufficient contact with air exist, the firing conversion rate is low, and the sodium manganate firing conversion rate of the traditional firing method is generally 50-60%.
The prior art CN102249342B discloses an oxidation treatment of a mixed roasting material of manganese ore powder and potassium (sodium) hydroxide by using an oxidizing gas, and the method adopts a two-stage roasting process: the first stage is to put manganese carbonate ore or manganese oxide ore powder and sodium hydroxide or potassium hydroxide into an open hearth furnace or a rotary hearth furnace, roast the materials at 300-850 ℃ for 0.5-2 h, grind the sintered materials to-200 meshes with the content of 70-90%, add the ground materials into a gas-solid fluidized bed reactor, introduce oxidizing gas, keep the temperature in the reactor at 220-300 ℃ and react for 0.5-3 h. The method adopts a gas-solid fluidized bed reactor to produce potassium manganate or sodium manganate intermittently, the conversion rate of manganese in the pyrolusite of the method can reach 93.4 percent, but the two-stage roasting process has long flow, complex process, multiple ore grinding and temperature rising and reducing in the middle, discontinuous production, lower efficiency and large energy consumption loss.
Disclosure of Invention
The invention provides a method and equipment for preparing sodium manganate, which have the advantages of short process flow, simple equipment, high oxidation rate, short production period and capability of realizing continuous production.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the equipment for producing the demanganizing agent comprises a fluidized bed furnace, a cyclone, a ceramic tube dust collector and a water-cooling cylinder, wherein the fluidized bed furnace comprises a furnace body, the top of the fluidized bed furnace is provided with a fluidized bed furnace exhaust port, and the bottom of the fluidized bed furnace is provided with a fluidized bed furnace feed inlet, a fluidized bed furnace air inlet and a fluidized bed furnace discharge port; the discharge port of the fluidized bed furnace is communicated with the water-cooling cylinder; the cyclone and ceramic tube dust collector is provided with a smoke inlet, a smoke outlet and a gas outlet; the exhaust port of the fluidized bed furnace is communicated with a smoke inlet; the air outlet is communicated with the outside atmosphere; the smoke dust discharge port is communicated with the feed port of the fluidized bed furnace.
Preferably, the equipment for producing the demanganizing agent further comprises a ball mill communicated with the water-cooling cylinder, and the roasted product is subjected to ball milling and then is conveyed to a closed feeding bin by adopting nitrogen, so that the manganese-removing agent can be used after being roasted.
The other purpose of the invention is realized by the following technical scheme:
the preparation method of the demanganizing agent comprises the following steps: will contain MnO2Mixing 70-80 wt% of pyrolusite and alkali, carrying out fluidized roasting in an oxygen-enriched air state, and roasting at the temperature of 200-300 ℃ for 1-2h to obtain a roasted product and dust-containing flue gas, wherein the roasted product is a demanganizing agent.
Preferably, the pyrolusite is finely ground to 100 meshes which account for 90%, and then the finely ground pyrolusite powder is mixed with alkali.
From the suspension of particles and the increase of the contact surface of three phases of gas-solid, the smaller the particle size of the pyrolusite is, the better the particle size is, the more sufficient the pyrolusite is in contact with reactants, the mass transfer is facilitated, and simultaneously, the diffusion resistance of gas phase to solid particles can be reduced, and the reaction speed is accelerated. But the granularity is too fine, the required energy consumption is increased, and the ore grinding time is correspondingly increased. Certainly, the solid-solid separation is difficult due to the fact that the granularity of the mineral powder is too fine, the total granularity of the mineral powder is 90% of the granularity of-100 meshes, the Mn conversion rate is high, and the cost is low.
Preferably, the oxygen concentration in the oxygen-enriched air is 40-50%.
If the adopted alkali is sodium hydroxide, the reaction principle of the roasting process is as follows:
2NaOH+MnO2+0.5O2＝Na2MnO4+H2O
from the reaction formula, more oxygen required by roasting participates in the reaction, if the oxygen concentration in the air is too low, the reaction time is long, the yield of the obtained manganese removing agent is low, the content of effective components of the manganese removing agent in the roasted product is low, and the manganese removing effect is seriously influenced. However, air with too high oxygen concentration is expensive to produce and not suitable for industrial use, and is therefore limited to oxygen-enriched air with an oxygen concentration of 40-50%.
By controlling the temperature, time and oxygen concentration, the sintering conversion rate of the sodium manganite in the roasted ore can reach over 90 percent, and the roasted product is conveyed to the dense bed by adopting nitrogen after being ball-milledThe feeding bin is closed, and the sodium manganate can be used after being burnt, so that the problem that the sodium manganate is not suitable for storage as an unstable product is solved. The conversion rate of the firing is that NaOH is converted into Na2MnO4Due to MnO during calcination2Excess, so conversion was calculated as NaOH.
Preferably, the alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Preferably, the alkali is sodium hydroxide or potassium hydroxide.
The melting point of the sodium carbonate is about 851 ℃, the melting point of the potassium carbonate is 891 ℃, and the sodium carbonate is not melted when the roasting temperature is only 200-300 ℃. And the melting point of pure NaOH is 318 ℃, the melting point of pure KOH is 360 ℃, the melting point is lower, the reaction can be melted at 200-300 ℃, and the reaction speed is higher.
Preferably, the mass ratio of the manganese dioxide to the alkali is 1.2-1.3: 1.
The proportion is controlled to ensure that the pyrolusite powder is excessive and the sodium hydroxide is insufficient, so that the sodium hydroxide is more completely reacted during roasting, less sodium element is introduced, and the sodium element is easier to remove in the subsequent process.
Preferably, the fluidized roasting device is a fluidized bed furnace.
The oxygen-enriched air and a specific roasting device, namely a fluidized bed furnace, are adopted, so that the oxygen enrichment is in good contact with the materials, the roasting process can be strengthened, the roasting time is shortened, the roasting temperature is reduced, and the labor productivity is improved. Preferably, the preparation method of the manganese removing agent further comprises the following steps: dust is obtained from the dust-containing flue gas after dust collection, and then the dust is returned to be roasted.
The fluidized bed furnace is of a dwarf type, the produced smoke yield is high, the smoke yield is 50-70%, and the smoke returns to roasting to improve the sintering conversion rate.
Preferably, the preparation method of the manganese removing agent further comprises the following steps: and cooling the roasted product to be lower than 80 ℃, thus obtaining the sodium manganate product.
The application also provides an application of the manganese removing agent in removing manganese ions in leachate of high manganese zinc concentrate.
The invention is further explained below:
the equipment and process adopted by the self-made manganese removal agent can be realized on site in a smelting plant, and the storage and transportation cost is greatly reduced. In the invention, the pyrolusite powder and the alkali in the fluidized bed furnace are in a boiling state, and the gas phase and the solid phase are in good contact, so that the contact area between oxygen and the mixture is greatly increased compared with manual stir-frying equipment such as an open hearth furnace and the like. In addition, by adopting oxygen-enriched air, the contact probability of the suspended pyrolusite powder and the effective component oxygen in the air is increased, and the oxidation process is completed within 1-2 h. The adoption of the dwarf fluidized bed furnace increases the dust return amount, returns the incompletely roasted material to roast, improves the conversion rate of converting sodium hydroxide into sodium manganate to over 90 percent, and ensures the high content of the effective components of the manganese remover.
The invention has the following beneficial effects:
(1) the material can be fully mixed and reacted with air by adopting a fluidized bed furnace for roasting.
(2) The oxygen-enriched air is adopted, so that the roasting process can be strengthened, the roasting time is reduced, and the labor productivity is improved.
(3) The fluidized bed furnace is of a dwarf type, the produced smoke dust rate is higher, and the smoke dust returns to the fluidized bed for roasting so as to improve the sintering conversion rate.
(4) The sodium manganate of the invention has a sintering conversion rate of more than 90%.
(5) According to the invention, the roasted product after ball milling is conveyed to the closed feeding bin by adopting nitrogen, and conveyed by adopting inert gas, so that an unstable intermediate product of sodium manganate is protected.
Drawings
FIG. 1 is a diagram of the apparatus of the present invention; the device comprises a fluidized bed furnace 1, a cyclone and ceramic tube dust collector 2, a water-cooled cylinder 3, a ball mill 4, a furnace body 15, a fluidized bed furnace exhaust port 12, a fluidized bed furnace feed inlet 11, a fluidized bed furnace air inlet 14, a fluidized bed furnace discharge port 13, a smoke inlet 21, a smoke discharge port 23 and a smoke discharge port 22.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
Example 1
Referring to fig. 1, the apparatus for producing a demanganizing agent according to the present invention comprises: the device comprises a fluidized bed furnace 1, a cyclone and ceramic tube dust collector 2, a water-cooling cylinder 3 and a ball mill 4, wherein the fluidized bed furnace 1 comprises a furnace body 15, the top of the fluidized bed furnace 1 is provided with a fluidized bed furnace exhaust port 12, and the bottom of the fluidized bed furnace 1 is provided with a fluidized bed furnace feed inlet 11, a fluidized bed furnace air inlet 14 and a fluidized bed furnace discharge port 13; the discharge port 13 of the fluidized bed furnace is communicated with the water-cooling cylinder 3; the cyclone and ceramic tube dust collector 2 is provided with a smoke inlet 21, a smoke outlet 23 and an air outlet 22; the exhaust port 12 of the fluidized bed furnace is communicated with a smoke inlet 21; the air outlet 22 is communicated with the outside atmosphere; the smoke dust discharge port 23 is communicated with the feed port 11 of the fluidized bed furnace, and the other end of the water-cooling cylinder 3 is communicated with the ball mill 4.
The method for preparing the demanganizing agent by utilizing the equipment comprises the following steps of carrying out boiling roasting on a mixture of pyrolusite powder and sodium hydroxide by using oxygen-enriched air at a certain temperature:
A. pyrolusite (containing MnO)270 percent) of the manganese powder is finely ground to 100 meshes which account for 90 percent, and the finely ground pyrolusite powder and sodium hydroxide are fully and uniformly mixed to prepare a mixture, MnO2The mass ratio of the mixed material to NaOH is 1.3:1, and the mixed material is continuously thrown to 6m at the speed of 1.80t/h by a belt feeder2The fluidized bed furnace 1;
B. spraying natural gas from a natural gas nozzle at a feed inlet 11 of the fluidized bed furnace, and spraying oxygen-enriched air with concentration of 40% from an air inlet 14 at the bottom of the fluidized bed furnace, wherein the total flow of the oxygen-enriched air is 3200Nm3Burning natural gas in the fluidized bed furnace 1, heating and roasting the mixture, controlling the roasting temperature at 250 ℃, enabling smoke dust to enter a cyclone and ceramic tube dust collector through a gas outlet 12 and a smoke dust inlet 21 of the fluidized bed furnace after the mixture is roasted for 1 hour in the fluidized bed furnace 1, and discharging roasted ore through a discharge hole 13 of the fluidized bed furnace at the bottom;
C. the sum of the obtained mass of the smoke dust and the roasted ore is 1.786t/h, the mass ratio of the smoke dust to the roasted ore is 60:40, the smoke dust returns to be roasted through the smoke dust discharge port 23 and the feed port 11 of the fluidized bed furnace, the yield of the produced smoke dust is high, and the smoke dust returns to be fluidized bed roasted to improve the roasting conversion rate. The roasted ore is cooled to 80 ℃ by a water-cooling cylinder 3, and the roasted ore is the demanganizing agent, and is conveyed to a closed feeding bin by nitrogen after ball milling. The proportion of manganese in the sodium manganite in the roasted ore to the total manganese was 75.71%, and the proportion of sodium hydroxide converted to sodium manganate was calculated to be 90.50%.
Example 2
The equipment for producing the demanganizing agent of the invention is shown in figure 1.
The method for preparing the demanganizing agent by utilizing the equipment comprises the following steps of carrying out boiling roasting on a mixture of pyrolusite powder and sodium hydroxide by using oxygen-enriched air at a certain temperature:
A. pyrolusite (containing MnO)280%) to 100 meshes accounting for 90%, and mixing the fine-ground pyrolusite powder and sodium hydroxide to obtain a mixture, MnO2The mass ratio of the mixed material to NaOH is 1.2:1, and the mixed material is continuously thrown to 6m at the speed of 1.80t/h by a belt feeder2The fluidized bed furnace 1;
B. spraying natural gas from natural gas nozzle of feed inlet 11 of the boiling furnace, and spraying oxygen-enriched air with concentration of 50% from air inlet 14 of the boiling furnace at the bottom of the boiling furnace, wherein the total flow of the oxygen-enriched air is 3000Nm3Burning natural gas in a fluidized bed furnace 1, heating and roasting the mixture, controlling the roasting temperature at 300 ℃, after the mixture is roasted in the fluidized bed furnace for 1.5 hours, enabling smoke dust to enter a cyclone and ceramic tube dust collector through a gas outlet 12 and a smoke dust inlet 21 of the fluidized bed furnace, and discharging roasted ore through a discharge hole 13 of the fluidized bed furnace at the bottom;
C. the mass sum of the obtained smoke dust and the roasted ore is 1.784t/h, the mass ratio of the smoke dust to the roasted ore is 55:45, the smoke dust returns to be roasted through the smoke dust discharge hole 23 and the feed inlet 11 of the fluidized bed furnace, the yield of the produced smoke dust is high, and the smoke dust returns to be fluidized and roasted to improve the roasting conversion rate. The roasted ore is cooled to 80 ℃ by a water-cooling cylinder 3, and the roasted ore is the demanganizing agent, and is conveyed to a closed feeding bin by nitrogen after ball milling. The proportion of manganese in the sodium manganite in the roasted ore in the total manganese was 84.10%, and the proportion of sodium hydroxide converted into sodium manganate was calculated to be 92.80%.
Compared with intermittent production, the method has the advantages of short production time and high efficiency, and because a two-step method of intermittent production is not needed, the processes of multiple ore grinding and temperature rise and reduction are not existed, and the energy consumption is far lower than that of intermittent production.
Comparative example 1
The same procedure was used to prepare the demanganizing agent using the apparatus of example 1, with the following steps:
A. pyrolusite (containing MnO)270 percent) of the manganese powder is finely ground to 100 meshes which account for 90 percent, and the finely ground pyrolusite powder and sodium hydroxide are fully and uniformly mixed to prepare a mixture, MnO2The mass ratio of the mixed material to NaOH is 1.3:1, and the mixed material is continuously thrown to 6m at the speed of 1.80t/h by a belt feeder2In the fluidized bed furnace;
B. spraying natural gas from a natural gas nozzle of a throwing port, spraying oxygen-enriched air with the concentration of 40% from a blast cap at the bottom of the fluidized bed furnace, wherein the total flow of the oxygen-enriched air is 3200Nm3Burning natural gas in a fluidized bed furnace, heating and roasting the mixture, controlling the roasting temperature to be 250 ℃, collecting smoke dust through a cyclone and a ceramic tube dust collector after the mixture is roasted for 1 hour in the fluidized bed furnace, and discharging roasted ore through a bottom discharge outlet;
C. the mass sum of the obtained smoke dust and the obtained roasted ore is 1.786t/h, the mass ratio of the smoke dust to the roasted ore is 60:40, and the smoke dust does not return to roasting. And cooling the roasted ore to 80 ℃ through a water-cooling cylinder, wherein the roasted ore is the demanganizing agent, and conveying the roasted ore to a closed feeding bin by adopting nitrogen after ball milling. The proportion of manganese in the sodium manganite in the smoke dust accounts for 33.88 percent of the total manganese, and the proportion of converting sodium hydroxide into sodium manganate is calculated to be 40.50 percent; the proportion of manganese in the sodium manganite in the roasted ore to the total manganese was 75.71%, and the proportion of sodium hydroxide converted to sodium manganate was calculated to be 90.50%. In summary, the total proportion of sodium hydroxide converted to sodium manganate was 60.50%.
Because the roasting time of part of the mixture is not enough, the mixture enters smoke along with smoke, the proportion of sodium hydroxide converted into sodium manganate is low, and if the smoke received in the cyclone and ceramic tube dust collector does not return to be roasted, the integral conversion rate is greatly reduced.
Claims (10)
1. The equipment for producing the demanganizing agent is characterized by comprising a fluidized bed furnace, a cyclone, a ceramic tube dust collector and a water-cooling cylinder, wherein the fluidized bed furnace comprises a furnace body, the top of the fluidized bed furnace is provided with a fluidized bed furnace exhaust port, and the bottom of the fluidized bed furnace is provided with a fluidized bed furnace feed port, a fluidized bed furnace air inlet and a fluidized bed furnace discharge port; the discharge hole is communicated with the water-cooling cylinder; the cyclone and ceramic tube dust collector is provided with a smoke inlet, a smoke outlet and an air outlet; the exhaust port is communicated with the smoke inlet; the air outlet is communicated with the outside atmosphere; the smoke dust discharge hole is communicated with the feed inlet.
2. The preparation method of the demanganizing agent is characterized by comprising the following steps: will contain MnO2Mixing 70-80 wt% of pyrolusite and alkali, carrying out fluidized roasting in an oxygen-enriched air state, and roasting at the temperature of 200-300 ℃ for 1-2h to obtain a roasted product and dust-containing flue gas, wherein the roasted product is a demanganizing agent.
3. The method according to claim 2, wherein the pyrolusite is finely ground to 100 mesh of 90%, and the finely ground pyrolusite powder is mixed with an alkali.
4. The method of claim 2, wherein the oxygen concentration in the oxygen-enriched air is 40-50%.
5. The preparation method according to claim 2, wherein the alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, preferably sodium hydroxide and potassium hydroxide.
6. The method of claim 2, wherein the MnO is2The mass ratio of the alkali to the alkali is 1.2-1.3: 1.
7. The method of claim 2, wherein the fluidized roasting apparatus is a fluidized bed furnace.
8. The preparation method of claim 2, wherein the preparation method of the demanganizing agent further comprises: dust is obtained from the dust-containing flue gas after dust collection, and then the dust is returned to be roasted.
9. The preparation method of claim 2, wherein the preparation method of the demanganizing agent further comprises: and cooling the roasted product to be lower than 80 ℃, namely obtaining a sodium manganate product, and conveying the roasted product by adopting nitrogen after ball milling.
10. The use of the demanganizing agent prepared by the preparation method according to any one of claims 2 to 9 for removing manganese ions from a leachate of high manganese zinc concentrate.
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