CN101029357A - Method for managing, circulating and utilizing nitronic oxide during golden smelting process - Google Patents
Method for managing, circulating and utilizing nitronic oxide during golden smelting process Download PDFInfo
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- CN101029357A CN101029357A CNA2007100554888A CN200710055488A CN101029357A CN 101029357 A CN101029357 A CN 101029357A CN A2007100554888 A CNA2007100554888 A CN A2007100554888A CN 200710055488 A CN200710055488 A CN 200710055488A CN 101029357 A CN101029357 A CN 101029357A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
Method for treating and circulation utilizing nitro-oxide during gold smelting process is carried out by refining for gold mud by high-pressure reactor, nitric-acid reacting to obtain nitro-oxide yellow smoke, enclosing it into reactor, adding oxygen into reactor, oxidizing by nitric oxide while converting into nitric acid, metal oxidation and leaching-out reacting, removing nitric acid and purifying gold. It's cheap, circulated utilizes NOx, has less nitric acid, waste-gas discharge and no environmental pollution.
Description
Technical field
The present invention relates to the environment protection class, produce oxynitride in particularly a kind of gold smelting process and administer and cyclic utilization method, method of the present invention is specially adapted to use the gold smelting factory of nitric acid.
Background technology
As everyone knows, oxynitride is the principal pollutant that cause topsoil, and the oxynitride that produces in the gold smelting process has discontinuity, moment concentration height, the fast characteristics of the concentration rate of decay, does not take measures to handle, and is bigger to environment, human health damage; The harm of oxynitride, the one, corrosive nature, oxynitride is circuitous can to form acidic substance behind water or water vapour, can produce corrodibility destruction to most metals and organism, its also can burn people and other biological tissue, moisture content in the biological tissue is destroyed, produce aggressive chemistry and change; The 2nd,, find that in the nitrogen oxides pollution district, people's breathing function descends to the toxic action of human body according to the investigation of U.S. environmental protection organization, the respiratory organs sickness rate increases, when nitrous oxides concentration reaches 0.062～0.109mg/m
3The time, acute respiration organopathy patient increases, and epidemiological study shows that nitrous oxides concentration reaches 0.063～0.083mg/m
3The time, acute bronchitis patient obviously increases; The 3rd, oxynitride easily and hydrocarbon polymer under uviolizing, form photo-chemical smog, it is a kind of poisonous gas, its oxidisability and corrodibility are extremely strong, can make people's eyes redness, eyesight weaken, breathe anxiety, headache, pectoralgia, general paralysis, pulmonary edema even death; The 4th, to the harm of plant, though oxynitride can not cause leaf film mottle evil, can suppress light and the effect of plant, and the plant leaf pore absorbs dissolving NO
2, will cause the vein necrosis, thereby influence the g and D of plant, can reduce output to farm crop, as being in 2～3mg/m for a long time
3High density under, will make plant produce the acute symptom of being injured; Oxynitride still influences the major cause of acid rain in addition; Oxynitride still is the destructive gas of atmospheric ozone layer, therefore must be controlled oxynitride, and this is the current problem that urgently will solve.
Summary of the invention
The object of the present invention is to provide in a kind of gold smelting process oxynitride to administer and cyclic utilization method, it is serious to topsoil to have solved oxynitride, is detrimental to health and the problem such as grow of animal and plant.
Technical scheme of the present invention is: people know very well four harm greatly of oxynitride, thus must be controlled, the one, source control, do not produce or produce less oxynitride as far as possible; The 2nd, advanced technology and measure of control are adopted in process control in process of production, reduce the generation of oxynitride; The 3rd, end treatment is taked the necessary processing measure for the oxynitride that effluxes, and makes the discharge of oxynitride economy, environmental protection; The nitrogen oxides pollution control method that burning produces does not reach the practical stage at present as yet; The present invention adopts the control of the oxynitride of non-burning generation to mainly contain two methods, the one, improve production technique, reduce the generation of oxynitride, as flue gas specific to gold smelting, usually in smelting process, all can use nitric acid, then unavoidably can produce NOx, if use other oxygenant instead, simultaneously do not produce harmful exhaust again, then can not discharge NOx; Perhaps the add-on of in use strict control nitric acid can reduce the discharging of NOx equally; By technology controlling and process, in the nitric acid reaction process,, gas phase each minute of reaction is pressed in keeps relative equilibrium in the enclosed system, thereby realize minimizing of NOx quantity discharged by control NO dividing potential drop; The 2nd, treating tail gas, reduce the quantity discharged of oxynitride, particularly importantly discharging will meet the relevant criterion of environmental protection, control by first step, concentration and the total amount of NOx reduce and reduce in the waste gas that needs are handled, by behind the effective governing measure, make the concentration of the NOx in the discharging waste gas reach discharging standards again;
Principle of the present invention is: the feasibility of recycle oxynitride, the reaction of from (1) to (4) formula as can be seen:
2NO+O
2→2NO
2+Q (1)
3NO
2+H
2O→2HNO
3+NO+Q (2)
The principal reaction of NOx alkali absorption method is as follows:
2NO
2+2HaOH→NaNO
3+NaNO
2+H
2O (3)
NO+NO
2+2NaOH→2NaNO
2+H
2O (4)
At NO
2By H
2O absorbs and generates HNO
3Simultaneously, there is 1/3 NO to emit to show no matter which kind of oxidation and absorption technique, NO are set
2By H
2The efficient that O absorbs can not reach 100%, this means that containing NOx in the tail gas is inevitable, and but, because the difference of absorption technique, the mass concentration of NOx can be distinguished to some extent in the tail gas; Utilize NO
2Water-soluble characteristic, in confined conditions, under the effect of oxygen, the NO that produces in the absorption reaction process is dissolved in the water, thus the dividing potential drop of control NO in gas phase, make reaction system reach the equilibrated state, the key of this process is under the effect of oxygen, and the dividing potential drop of NO remains on maintenance level, and does not have the effect of oxygen, the reaction gas phase pressure can continue to rise, and test shows that its pressure surpasses 2.5Mpa; Under the prerequisite of aerobic, the NOx that reaction process produces, the overwhelming majority is converted to nitric acid again, can make to be reflected under the metastable concentration of nitric acid to carry out, and promptly improves the consumption that speed of response has reduced nitric acid again, has reached the recycle of NOx; Present method can make the NOx of generation be reduced to the volume of container upper gas section after reaction finishes, just about 1/3 of reaction vessel volume, subsequent disposal only need be handled this part and get final product, and can reduce by 90% the outer discharge capacity of NOx, makes the NOx amount of final generation reduce to minimum; The NOx amount that present method produces seldom, so by the control discharge rate, make NOx amount that the unit time enters absorption unit in its process range, what can effectively guarantee to efflux is up to standard;
Concrete grammar of the present invention comprises the following steps:
(1) nitric acid removal of impurities:
Gold mud and water are joined in the autoclave, liquid-solid ratio 4～6: 1 behind the adding nitric acid, the control amount of water, sealing high pressure kettle cover stirs; Open the oxygen supply valve of autoclave then, aerating oxygen in still is all discharged air in the still, reaches at 99.9% o'clock up to the oxygen level of venting port eluting gas, closes oxygen supply valve, closes vent valve again; Add nitric acid with the nitric acid charging point in still, begin the reacting by heating still simultaneously, temperature of reaction is controlled at 70～90 ℃, when temperature reaches 70～90 ℃, picks up counting 4～6 hours reaction times; Adding nitric acid aerating oxygen in still simultaneously, and controlling the autoclave internal pressure between 0.2～0.3Mpa, guaranteeing that NOx is converted into nitric acid, gradation quantitatively feeds oxygen in still; After leach finishing, open the autoclave vent valve and slowly discharge tail gas, and tail gas is fed emptying up to standard after the washing column washing, concentration of lye is controlled at about 20% in the washing column, measures the amount of nitrogen oxides behind the washing tail gas again, guarantees to efflux the tail gas qualified discharge;
(2) chloroazotic acid is carried gold:
Gold mud after the nitric acid removal of impurities and water are joined in the autoclave, control amount of water by liquid-solid ratio 4～6: 1 after adding chloroazotic acid, and sealing high pressure kettle cover, begin to stir; The oxygen supply valve of opening autoclave again feeds oxidation in still, air in the still is all discharged, and reaches at 99.9% o'clock up to the content of venting port eluting gas oxygen, and closes oxygen supply valve and vent valve; Add hydrochloric acid with charging point in still, the control concentration of hydrochloric acid is 8～12%; Add nitric acid with charging point in still again, the nitric acid add-on is control concentration of nitric acid 6～9%; Add nitric acid and begin the reacting by heating still simultaneously, temperature of reaction is controlled at 70～90 ℃, and temperature reaches 70～90 ℃ and picks up counting, and the reaction times was controlled at 4～6 hours; Adding nitric acid aerating oxygen simultaneously, and controlling the autoclave internal pressure between 0.2～0.3Mpa, gradation quantitatively feeds oxygen in still then, guarantees that NOx is converted into nitric acid; After leaching end, open the autoclave vent valve and slowly discharge tail gas, and tail gas is fed washing column washing emptying afterwards, concentration of lye is controlled at about 20% in the washing column, with the way that alkali lye absorbs, measure washing tail gas front and back amount of nitrogen oxides, guarantee to efflux the tail gas qualified discharge.
The invention has the advantages that: method of the present invention be from the source, the process, three links of discharging of terminal tail gas have realized improvement and recycle to oxynitride, first recycle NOx can reduce the add-on of nitric acid, reduces production costs; It two is that the NOx amount of final generation is reduced to is minimum, can reduce by 90% the outer discharge capacity of NOx, has reduced the off gas treatment cost; It three is the speed that effluxes of control NOx, but after absorbing standard discharge.
Embodiment:
Embodiment 1:
(1) nitric acid removal of impurities:
Gold mud and water are joined in the autoclave, add concentration of nitric acid 20%, liquid-solid ratio 6: 1, sealing high pressure kettle cover stirs; Open the oxygen supply valve of autoclave then, aerating oxygen in still reaches at 99.9% o'clock up to the content of venting port eluting gas oxygen, closes oxygen supply valve and vent valve; Adding concentration with the nitric acid charging point in still is 20% nitric acid, begins the reacting by heating still simultaneously, and temperature of reaction is controlled at 70 ℃, and in still aerating oxygen, and control autoclave internal pressure is at 0.2Mpa, 4 hours reaction times; After leaching end, open the autoclave vent valve and slowly discharge tail gas, and tail gas is fed washing column washing emptying up to standard afterwards, concentration of lye is controlled at 20% in the washing column; This embodiment nitric acid slag rate is 42%, and effluxing tail gas NOx concentration is 23.5mg/m
3
(2) chloroazotic acid is carried gold:
Gold mud after the nitric acid removal of impurities and water are joined in the autoclave, control amount of water at 6: 1 by liquid-solid ratio after adding chloroazotic acid, and sealing high pressure kettle cover, begin to stir; Open oxygen supply valve aerating oxygen in still of autoclave again, air in the still is all discharged, reach at 99.9% o'clock, close oxygen supply valve and vent valve up to the content of venting port eluting gas oxygen; Add hydrochloric acid with charging point in still, the control concentration of hydrochloric acid is 8%; Add nitric acid with charging point in still again, the nitric acid add-on is control concentration of nitric acid 6%; Add nitric acid and begin the reacting by heating still simultaneously, temperature of reaction is controlled at 70 ℃, 5 hours reaction times; Adding nitric acid aerating oxygen simultaneously, and control autoclave internal pressure is between 0.2Mpa; After leaching end, open the autoclave vent valve and slowly discharge tail gas, and tail gas is fed washing column washing emptying up to standard afterwards, concentration of lye is controlled at 20% in the washing column, guarantees to efflux the tail gas qualified discharge; This embodiment gold recovery is 99.92%, effluxes tail gas NOx concentration 20.8mg/m
3
Embodiment 2:
(1) nitric acid removal of impurities:
Gold mud and water are joined in the autoclave, add concentration of nitric acid 24%, liquid-solid ratio 5: 1, sealing high pressure kettle cover stirs; Open the oxygen supply valve of autoclave then, aerating oxygen in still reaches at 99.9% o'clock up to the content of venting port eluting gas oxygen, closes oxygen supply valve and vent valve; Adding concentration with the nitric acid charging point in still is 24% nitric acid, begins the reacting by heating still simultaneously, and temperature of reaction is controlled at 80 ℃, and in still aerating oxygen, and control autoclave internal pressure is at 0.25Mpa, 5 hours reaction times; After leaching end, open the autoclave vent valve and slowly discharge tail gas, and tail gas is fed washing column washing emptying up to standard afterwards, concentration of lye is controlled at 20% in the washing column; The nitric acid slag rate of this embodiment is 41.2%, and effluxing tail gas NOx concentration is 33.2mg/m
3
(2) chloroazotic acid is carried gold:
Gold mud after the nitric acid removal of impurities and water are joined in the autoclave, control amount of water at 5: 1 by liquid-solid ratio after adding chloroazotic acid, and sealing high pressure kettle cover, begin to stir; Open oxygen supply valve aerating oxygen in still of autoclave again, air in the still is all discharged, reach at 99.9% o'clock, close oxygen supply valve and vent valve up to the content of venting port eluting gas oxygen; Add hydrochloric acid with charging point in still, the control concentration of hydrochloric acid is 9.6%; Add nitric acid with charging point in still again, the nitric acid add-on is control concentration of nitric acid 7.2%; Add nitric acid and begin the reacting by heating still simultaneously, temperature of reaction is controlled at 80 ℃, 4 hours reaction times; Adding nitric acid aerating oxygen simultaneously, and control autoclave internal pressure is between 0.25Mpa; After leaching end, open the autoclave vent valve and slowly discharge tail gas, and tail gas is fed washing column washing emptying up to standard afterwards, concentration of lye is controlled at 20% in the washing column, guarantees to efflux the tail gas qualified discharge; This embodiment gold recovery is 99.93%, effluxes tail gas NOx concentration 24.7mg/m
3
Embodiment 3:
(1) nitric acid removal of impurities:
Gold mud and water are joined in the autoclave, add concentration of nitric acid 30%, liquid-solid ratio 4: 1, sealing high pressure kettle cover stirs; Open the oxygen supply valve of autoclave then, aerating oxygen in still reaches at 99.9% o'clock up to the content of venting port eluting gas oxygen, closes oxygen supply valve and vent valve; Adding concentration with the nitric acid charging point in still is 30% nitric acid, begins the reacting by heating still simultaneously, and temperature of reaction is controlled at 90 ℃, and in still aerating oxygen, and control autoclave internal pressure is at 0.3Mpa, 4 hours reaction times; After leaching end, open the autoclave vent valve and slowly discharge tail gas, and tail gas is fed washing column washing emptying up to standard afterwards, concentration of lye is controlled at 20% in the washing column; The nitric acid slag rate of this embodiment is 40.4%, and effluxing tail gas NOx concentration is 40.8mg/m
3
(2) chloroazotic acid is carried gold:
Gold mud after the nitric acid removal of impurities and water are joined in the autoclave, control amount of water at 4: 1 by liquid-solid ratio after adding chloroazotic acid, and sealing high pressure kettle cover, begin to stir; Open oxygen supply valve aerating oxygen in still of autoclave again, air in the still is all discharged, reach at 99.9% o'clock, close oxygen supply valve and vent valve up to the content of venting port eluting gas oxygen; Add hydrochloric acid with charging point in still, the control concentration of hydrochloric acid is 12%; Add nitric acid with charging point in still again, the nitric acid add-on is control concentration of nitric acid 9%; Add nitric acid and begin the reacting by heating still simultaneously, temperature of reaction is controlled at 90 ℃, is adding nitric acid aerating oxygen simultaneously, and is controlling the autoclave internal pressure between 0.3Mpa, 4 hours reaction times; After leaching end, open the autoclave vent valve and slowly discharge tail gas, and tail gas is fed washing column washing emptying up to standard afterwards, concentration of lye is controlled at 20% in the washing column; This embodiment gold recovery is 99.94%, effluxes tail gas NOx concentration 30.1mg/m
3
Claims (1)
1, oxynitride is administered and cyclic utilization method in a kind of gold smelting process, and it is characterized in that: this method comprises the following steps:
(1) nitric acid removal of impurities:
Gold mud and water are joined in the autoclave, liquid-solid ratio 4～6: 1 behind the adding nitric acid, sealing high pressure kettle cover stirs; Open the oxygen supply valve of autoclave then, aerating oxygen in still reaches at 99.9% o'clock up to the content of venting port eluting gas oxygen, closes oxygen supply valve and vent valve; Add nitric acid with the nitric acid charging point in still, begin the reacting by heating still simultaneously, temperature of reaction is controlled at 70～90 ℃, 4～6 hours reaction times; Adding nitric acid aerating oxygen in still simultaneously, and control autoclave internal pressure is between 0.2～0.3Mpa; After leaching end, open the autoclave vent valve and slowly discharge tail gas, and tail gas is fed washing column washing emptying up to standard afterwards, concentration of lye is controlled at 20% in the washing column;
(2) chloroazotic acid is carried gold:
Gold mud after the nitric acid removal of impurities and water are joined in the autoclave, control amount of water by liquid-solid ratio 4～6: 1 after adding chloroazotic acid, and sealing high pressure kettle cover, begin to stir; Open oxygen supply valve aerating oxygen in still of autoclave again, air in the still is all discharged, reach at 999% o'clock up to the content of venting port eluting gas oxygen, and close oxygen supply valve and vent valve; Add hydrochloric acid with charging point in still, the control concentration of hydrochloric acid is 8～12%; Add nitric acid with charging point in still again, the nitric acid add-on is control concentration of nitric acid 6～9%; Add nitric acid and begin the reacting by heating still simultaneously, temperature of reaction is controlled at 70～90 ℃, and the reaction times was at 4～6 hours; Adding nitric acid aerating oxygen simultaneously, and control autoclave internal pressure is between 0.2～0.3Mpa; After leaching end, open the autoclave vent valve and slowly discharge tail gas, and tail gas is fed washing column washing emptying up to standard afterwards, concentration of lye is controlled at 20% in the washing column.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710055488A CN101029357B (en) | 2007-04-04 | 2007-04-04 | Method for managing, circulating and utilizing nitronic oxide during golden smelting process |
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|---|---|---|---|
| CN200710055488A CN101029357B (en) | 2007-04-04 | 2007-04-04 | Method for managing, circulating and utilizing nitronic oxide during golden smelting process |
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| CN101029357A true CN101029357A (en) | 2007-09-05 |
| CN101029357B CN101029357B (en) | 2010-05-19 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103409632A (en) * | 2013-07-18 | 2013-11-27 | 山东国大黄金股份有限公司 | Method for comprehensively recovering gold mud wet technology tail gas |
| CN103482591A (en) * | 2013-10-22 | 2014-01-01 | 严俊 | Green preparation process method of Copper-based catalyst nitrate |
| CN109173602A (en) * | 2018-07-25 | 2019-01-11 | 华东理工大学 | A kind of circulation utilization method of the nitrous oxides exhaust gas generated in dichloro quinolinic acid synthesis |
| US11319613B2 (en) | 2020-08-18 | 2022-05-03 | Enviro Metals, LLC | Metal refinement |
-
2007
- 2007-04-04 CN CN200710055488A patent/CN101029357B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103409632A (en) * | 2013-07-18 | 2013-11-27 | 山东国大黄金股份有限公司 | Method for comprehensively recovering gold mud wet technology tail gas |
| CN103409632B (en) * | 2013-07-18 | 2016-01-13 | 山东国大黄金股份有限公司 | A kind of method of gold mud wet processing tail gas comprehensive reutilization |
| CN103482591A (en) * | 2013-10-22 | 2014-01-01 | 严俊 | Green preparation process method of Copper-based catalyst nitrate |
| CN109173602A (en) * | 2018-07-25 | 2019-01-11 | 华东理工大学 | A kind of circulation utilization method of the nitrous oxides exhaust gas generated in dichloro quinolinic acid synthesis |
| US11319613B2 (en) | 2020-08-18 | 2022-05-03 | Enviro Metals, LLC | Metal refinement |
| US11578386B2 (en) | 2020-08-18 | 2023-02-14 | Enviro Metals, LLC | Metal refinement |
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| Publication number | Publication date |
|---|---|
| CN101029357B (en) | 2010-05-19 |
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Effective date of registration: 20180823 Address after: 562400 gold road, Golden Road, Xingren County, Guizhou Province, Southwest Guizhou Province. Patentee after: Guizhou Jinxing Gold Mining Co., Ltd. Address before: 130012 Changchun Gold Research Institute, No. 6760 nanhu road, Chaoyang District, Changchun, Jilin Patentee before: Changchun Gold Research Institute Co., Ltd. |
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