CN1033265A - Process for directly producing graded antimony white from antimony ore - Google Patents
Process for directly producing graded antimony white from antimony ore Download PDFInfo
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- CN1033265A CN1033265A CN 87108010 CN87108010A CN1033265A CN 1033265 A CN1033265 A CN 1033265A CN 87108010 CN87108010 CN 87108010 CN 87108010 A CN87108010 A CN 87108010A CN 1033265 A CN1033265 A CN 1033265A
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- antimony
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Abstract
The present invention relates to a process for directly producing graded antimony white by using antimony ore. The process is based on the production of antimony oxide white by changing the process conditions, directly produces antimony white with different grain sizes, and controls the grain size of the antimony white through the condition changes of leaching, hydrolysis and neutralization. The process can be used for randomly treating antimony sulfide ores of various grades and mixed materials of the antimony sulfide ores and the antimony oxide ores to obtain antimony white of different grain grades, wherein the whiteness of the antimony white is more than 90%, and when the grade of the antimony ores is more than 20%, the chemical components of the product with the yield of more than 94% can completely reach the standard of national GB-4062-83 zero-grade antimony white; the method has the advantages of short process flow, good comprehensive utilization, good environment-friendly condition and lower processing cost of products with different grain sizes than the prior art.
Description
The present invention relates to a kind of method of field of metallurgy and chemical engineering production classification stibium trioxide.
Stibium trioxide is the main products that the antimony product are produced, and is widely used in industrial sectors such as plastics, weaving, rubber, paint, electronics, enamel.Because all departments are different to the specification of quality of stibium trioxide, so need to produce different stibium trioxide products such as different grain size, whiteness, purity; Up to now, international stibium trioxide classification all is to adopt thermal process to achieve the goal, and promptly uses direct staging and indirect staging.Directly staging is to utilize the very low stibnite concentrate of detrimental impurity for raw material, by the direct oxidation volatilization, produces the product that closes the symbol customer requirements, is widely used in ground such as North America, West Europe as two kiln methods.The stibnite concentrate that this method adopted generally contains antimony more than 60%, makes material be similar to the rotary kiln of flash volatilization roasting through first rotary kiln, obtains containing the thick weisspiessglanz of small amount of impurities; Second rotary kiln is boiling kiln, and the control felicity condition then can obtain varigrained product.The product of the chemical company that continues is breathed out by Red Star board that U.S. peace Tibetan company produces and white star board and the U.S., wherein contains arsenic 0.20～0.35%, contains aluminium 0.1～0.25%, and the content of main component ANTIMONY TRIOXIDE SB 203 99.8 PCT can only reach 99.3%; Indirect method is to be raw material with high-grade metallic antimony, obtains purified stibium trioxide by steps such as fusing, voloxidation, cooling, distillations.The stibium trioxide stove of this method divides self-heating and two kinds of outer heat.Self-heating stove is to utilize liquid antimony oxidation liberated heat to keep processing temperature; Outer hot stove is that outer supplying heat source guarantees normally carrying out of process.The rate of recovery that these methods have is low, poor product quality, and the processing charges height that has is to the bad adaptability of material.At present also useful wet processing is produced stibium trioxide, but does not carry out classification, and technology is tediously long, processing charges also very high (seeing Chinese patent application numbers 85107329 and Fig. 1 thereof).
The objective of the invention is to adopt new process program, reduce the production process of prior art, reduce processing charges, and can use antimony ore direct production classification oxidation stibium trioxide.
Main flow of the present invention as shown in Figure 2.
The used raw mineral materials of the present invention is antimony ore or antimony concentrate, and strong to the equal adaptability of each constituent content in the material, containing the antimony amount can choose arbitrarily in antimony ore; As≤1%, Pb≤11%, and unrestricted substantially to the iron in the ore, sulfur content, promptly antimony sulfide ore and antimony sulfide and weisspiessglanz mixes the ore deposit and can both adapt to.But, during low excessively or antimony oxide ore too high levels, can cause metal recovery rate low when the antimony ore grade, the processing charges height, the waste residue productive rate is big.The average grade of ore≤80 orders.
This invention is made up of following several roads master operation:
One, the leaching of antimony ore
This operation is carried out under condition of normal pressure, and employed leaching agent is the mixture of hydrochloric acid and chlorine.Use proportioning visual environment between them is to the supply situation of hydrochloric acid and chlorine and decide, but free adjustment.The consumption of leaching agent (leaching dosage/antimony amount) can fluctuate in 0.5～2 scope.Extraction time generally is less than 2 hours; Solid-to-liquid ratio (S/L) is 1: 1～2; Extraction temperature generally is controlled in 70～90 ℃, and Sb is about 400g/l in the leach liquor;
In the ordinary course of things, the leaching yield of antimony increases with the consumption of oxygenant, then increases when reaching a certain amount of slowly; Leaching yield carefully increases with ore grain size, and increase in time and increasing then increases when reaching more than 2 hours slowly.
Two, the hydrolysis of leach liquor
Solid-liquid material after leaching carries out solid-liquid separation with filter, needs with sour water slag to be cleaned in filtering process, washing lotion is returned former process use, and its slag is pending, reclaims sulphur and precious metal; Leach liquor is hydrolyzed in hydrolysis device.
The basic function of hydrolysis is with ANTIMONY TRIOXIDE SB 203 99.8 PCT in the leach liquor and water effect, generate antimony oxychloride, and according to the hydrolysis prods of certain condition (for example equipment, structure, hydrolysis method, stirring intensity, temperature, time, terminal point acidity etc.) the production size fractionated of market demand, control.The extension rate of hydrolysis can be 2～20 times, generally is that extension rate is high more, and percent hydrolysis is high more; Hydrolysis temperature is generally 25～80 ℃, and its terminal point acidity (N) is 0.1～2.0, preferably is controlled in below 1.The time of hydrolysis can require to be controlled in 0.4～10 hour scope according to the product grade.The water produced liquid waste solution part of hydrolyzing process is returned use, and a part is outwards discharging after antipollution Wingdale is handled.During this operation gained antimony oxychloride is sent to and operation.
The control product granularity is mainly realized by this procedure.If needing the average grade of control is the grade of 0.4～0.7 μ, then the mixing time with hydrolysis and solution was controlled at about 0.5 hour, total acidity is about 0.5N, temperature is about 60 ℃, if need to produce 4～5 μ or more coarsely graded, controlling acidity is 1～2N, 50～60 ℃ of temperature prestige, and hydrolysis time is prolonged and leave standstill.The condition of middle grade is analogized.
Three, the neutralization of antimony oxychloride
In and the basic function of operation be with in the alkali and antimony oxychloride, make it to be converted into stibium trioxide, neutral pH can generate weisspiessglanz more than 7.5, in it and pH value and solid-to-liquid ratio what influence the production stibium trioxide is not had.
Neutralized product gets filtrate and returns the hydrolysis use through filtering, and the dehydration of stibium trioxide drying device promptly gets the stibium trioxide product.
Compared with the prior art the present invention has specific effect, is embodied in:
(1) adaptability to antimong-containing material is strong.Can handle the antimony sulfide ore of various grades and the mixture of antimony sulfide ore and antimony oxide ore thereof arbitrarily, all can obtain the stibium trioxide of size fractionated, its whiteness is greater than 90%; The chemical ingredients of product also can reach the standard of national GB4062-83 zero level stibium trioxide fully.
(2) leaching the used leaching agent of operation is chloro non-salt material, does not need special processing, has avoided in the prior art therefore and the processing charges that produces;
(3) solid-to-liquid ratio in the leaching generally is controlled at below 2, and the antimony ion concentration in the leach liquor reaches 300～500 grams per liters, makes the equipment size of whole operation more much smaller than the production equipment of the same processing power in the prior art, can save initial cost;
(4) hydrolysis is taked the hydrolysis reaction mode and is left standstill the method that combines, and makes it to produce different granularities, has solved the difficult problem of wet production classification stibium trioxide easily;
(5) filtrate of each operation of process is returned use respectively, has saved the consumption of new water greatly, and has reduced the treatment capacity before the sewage discharge, also can reduce the metal loss of antimony;
(6) because technical process is short, and the yield of antimony is greater than 94%, and comprehensive utilization is made good use of, and the raw material of use is direct mineral material, and the particulate stibium trioxide processing charges of being produced is all lower than prior art.
Embodiment 1: get somewhere antimony ore 198 grams, contain Sb 24.60%, As 0.502%, and Fe 1.59%, and S 9.89, SiO
253.48%, granularity-100 order accounts for 98%, and the concentration that leaches hydrochloric acid is 6N, and logical chlorine 24 grams, and hierarchy of control extraction temperature is 90 ℃, and solid-to-liquid ratio is 2, leaches 5 hours, filters; Filtrate is hydrolyzed with purifying waste water, and hydrolysis temperature is controlled to be 60 ℃, and Cl concentration is～0.6N in the control aqueous solution, and hydrolysis time is 0.5 hour, just obtains the antimony oxychloride precipitation.Filter cake after filtering with the pulp of purifying waste water, is added the ammoniacal liquor neutralization at normal temperatures, and control pH is 7～8, in and the time be 0.5 hour, through filtering also oven dry, stibium trioxide 56.75 restrains, its mean particle size is 0.56 μ, whiteness is 92%, Sb
2O
3Be 99.80%, foreign matter content Pb 0.0067%, As 0.0045%, and Fe 0.0045%, meets GB-4062-83 zero level standard.
Embodiment 2, get somewhere antimony ore 196 grams and contain antimony 14.15%, and As 0.64%, and Pb 0.0152%, and Fe 1.86%, and S 6.14%, SiO
266.20%, its granularity accounts for 95% for-100 orders, and leaching concentration of hydrochloric acid is 6N, logical chlorine 11 grams, and hierarchy of control extraction temperature is 87 ℃, solid-to-liquid ratio is 2.3, leaches 2 hours, filters; Immersion liquid is hydrolyzed with purifying waste water, and hydrolysis temperature is controlled to be 50 degree, and control terminal point acidity is～0.7N that hydrolysis time is 0.5 hour, just obtains the antimony oxychloride precipitation.Filter cake after filtering with the pulp of purifying waste water, is added the ammoniacal liquor neutralization at normal temperatures, and control pH is 7～8, in and the time be 0.5 hour, through filtering also oven dry, stibium trioxide 32.6 restrains, its mean particle size is 1.3 μ, whiteness is 91%, Sb
2O
3Be 99.84%, Pb 0.0029%, and As 0.0059%, and Fe 0.0016%, meets GB-4062-83 zero level stibium trioxide standard.
Embodiment 3, get somewhere antimony ore 186 grams, contain antimony 38.4%, and As 0.045%, and Pb 0.14%, and Fe 1.15%, and S 15.48%, SiO
234.16%, its granularity accounts for 91% for-100 orders, leaches that (concentration of hydrochloric acid is 4N, logical chlorine 34 grams, hierarchy of control extraction temperature is～85 ℃, and solid-to-liquid ratio is 1.5, leaches 3 hours, filter, immersion liquid is hydrolyzed with purifying waste water, 30 ℃ of hydrolysis temperatures, control acid eventually is 0.8N, hydrolysis time 0.5 hour just obtains the antimony oxychloride precipitation.Filter cake after filtering with the pulp of purifying waste water, is added the ammoniacal liquor neutralization down at 50 ℃, and control pH is 7～8, in and 0.5 hour time, through filtering also oven dry, stibium trioxide 83.88 restrains, its mean particle size is 2.9 μ, whiteness is 93.4%, Sb
2O
3Be 99.7%, Pb 0.06%, and As 0.023, and Fe 0.002%, meets Gb-4062-83, zero level stibium trioxide standard.
Claims (7)
1, with the technology of ore deposit direct production classification stibium trioxide, relates to a kind of material production method in metallurgy, the chemical field.The invention is characterized in: by the change of processing condition, based on production oxidation stibium trioxide, direct production goes out the stibium trioxide of size fractionated.Its technological process is leaching, hydrolysis, neutralization and drying, and controls the stibium trioxide granularity by the variation of these conditions.
2, technology according to claim 1 is characterized in that: directly make leaching agent with hydrochloric acid and chlorine, the fat of leaping up of the use proportioning moisture in the soil between them pulls circle drone cave Austria around the tomb └ pavilion assorted stupid Gu of ǎ spoon that sheds baby teeth
3, according to the technology described in the claim 1, the consumption of leaching agent promptly leaches dosage and can fluctuate in 0.3～2 scope than antimony amount;
4, technology according to claim 1 is characterized in that: solid-to-liquid ratio (S/L) is 1: 1～2, Sb200 in the leach liquor～500 grams per liters;
5, according to the technology described in the claim 1, it is characterized in that: if the average grade of needs control is the grade of 0.4～0.7 μ, then the mixing time with water and solution was controlled at about 0.5 hour, and whole acid concentration is about 0.6N, and temperature is 50～80 ℃; If need to produce 4～5 μ or thicker particle, then appropriate change acidity and temperature, and hydrolysis time is prolonged and leave standstill.
6, technology according to claim 1 is characterized in that: remove some waste water of hydrolysis operation (handling through Wingdale) and discharge, surplus then whole Returning utilizations.
7, the described technology of claim 1, it is characterized in that: used raw mineral materials is antimony ore or the equal wide adaptability of antimony concentrate, containing the antimony amount can choose arbitrarily in antimony ore, As≤1%, Pb≤11%, and unrestricted substantially to the iron in the ore, sulfur content, promptly antimony sulfide and antimony sulfide and weisspiessglanz mixes the ore deposit and can both adapt to.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87108010 CN1022477C (en) | 1987-11-25 | 1987-11-25 | Process for directly producing graded antimony white from antimony ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87108010 CN1022477C (en) | 1987-11-25 | 1987-11-25 | Process for directly producing graded antimony white from antimony ore |
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| Publication Number | Publication Date |
|---|---|
| CN1033265A true CN1033265A (en) | 1989-06-07 |
| CN1022477C CN1022477C (en) | 1993-10-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87108010 Expired - Fee Related CN1022477C (en) | 1987-11-25 | 1987-11-25 | Process for directly producing graded antimony white from antimony ore |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102251127A (en) * | 2011-07-04 | 2011-11-23 | 邹光平 | Comprehensive wet recovery method for removing lead slag from stibium through pyrorefining |
| CN105603217A (en) * | 2015-12-28 | 2016-05-25 | 中南大学 | Method for enriching and recovering antimony in contaminated acid vulcanization residue |
| CN106517324A (en) * | 2016-10-28 | 2017-03-22 | 乐山凯亚达光电科技有限公司 | Method for preparing antimonous oxide from antimony sulfide ore |
| CN108585039A (en) * | 2018-06-12 | 2018-09-28 | 江苏新蓝智能装备股份有限公司 | A kind of production technology of antimony oxide |
| CN108793249A (en) * | 2018-08-31 | 2018-11-13 | 锡矿山闪星锑业有限责任公司 | A method of from cupric, lead low-grade antimony ore in extract antimony oxide |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614573B (en) * | 2013-12-11 | 2016-03-23 | 青海省化工设计研究院有限公司 | A kind of low grade lead, antimony complex multi-metal ore deposit produces cubic stibium trioxide technique |
-
1987
- 1987-11-25 CN CN 87108010 patent/CN1022477C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102251127A (en) * | 2011-07-04 | 2011-11-23 | 邹光平 | Comprehensive wet recovery method for removing lead slag from stibium through pyrorefining |
| CN105603217A (en) * | 2015-12-28 | 2016-05-25 | 中南大学 | Method for enriching and recovering antimony in contaminated acid vulcanization residue |
| CN106517324A (en) * | 2016-10-28 | 2017-03-22 | 乐山凯亚达光电科技有限公司 | Method for preparing antimonous oxide from antimony sulfide ore |
| CN108585039A (en) * | 2018-06-12 | 2018-09-28 | 江苏新蓝智能装备股份有限公司 | A kind of production technology of antimony oxide |
| CN108793249A (en) * | 2018-08-31 | 2018-11-13 | 锡矿山闪星锑业有限责任公司 | A method of from cupric, lead low-grade antimony ore in extract antimony oxide |
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| Publication number | Publication date |
|---|---|
| CN1022477C (en) | 1993-10-20 |
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