CN103406007A - Recovery process for sulphur in gold concentrate roasting smoke - Google Patents
Recovery process for sulphur in gold concentrate roasting smoke Download PDFInfo
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- CN103406007A CN103406007A CN2013101816794A CN201310181679A CN103406007A CN 103406007 A CN103406007 A CN 103406007A CN 2013101816794 A CN2013101816794 A CN 2013101816794A CN 201310181679 A CN201310181679 A CN 201310181679A CN 103406007 A CN103406007 A CN 103406007A
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Abstract
The invention discloses a recovery process for sulphur in gold concentrate roasting smoke, which is capable of reducing SO2 into elementary substance S and/or CaS, and reducing SO2 in the smoke by virtue of a sulphate reduction function of sulphate reducing bacteria to generate H2S, thus further producing elementary-substance S and/or CaS with a high added value, and further reaching the purposes of pollution abatement and resource utilization of tail gas. The recovery process disclosed by the invention comprises the following steps of: (1) feeding a part of the gold concentrate roasting smoke in NaOH solution, so as to prepare Na2SO3 solution; (2) diluting the Na2SO3 solution by water until SO3<2-> concentration is less than 1%; (3) introducing the diluted solution in an anaerobic fermentation reaction device with the sulphate reducing bacteria, so as to prepare H2S; (4) mixing the obtained H2S with the gold concentrate roasting smoke to prepare elementary-substance S; and (5) extracting the fermentation liquor effluent of the anaerobic fermentation reaction device and performing solid-solution separation, refluxing sludge containing active microbes, which is obtained by the separation, mixing wastewater which is obtained by the separation with clear water, and then diluting the Na2SO3 solution.
Description
Technical field
The present invention relates to a kind of sulfur recovery technique, specifically be applied to recycle the SO2 in the gold concentrate roasting flue gas.
Background technology
In order to improve the leaching rate of gold in Gold Concentrate under Normal Pressure, some companies adopt the mode of roasting to carry out pretreatment to Gold Concentrate under Normal Pressure at present, again slag are carried out to conventional cyaniding and leaching process after pretreatment is complete.Its Roasting And Leaching overall craft as shown in Figure 2.
Utilize the multielement chemical results of the Gold Concentrate under Normal Pressure of this technique output to see the following form (remarks: gold and silver unit is g/t, and other are percentage composition).Sulphur after roasting in ore deposit is transferred in gas phase with forms such as SO2.
The recovery of current conventional sulfureous in flue gas is that SO2 is catalyzed into to SO3, then with dilute sulfuric acid, absorbs extracting sulfuric acid.By the sulfur content of smelting scale and Gold Concentrate under Normal Pressure, estimate every day and will produce the sulfuric acid of 100t left and right.But the market demand of a lot of local sulfuric acid is less, it is very inconvenient that smeltery is positioned at the mountain area transportation.Liquid sulfuric acid, as controlled dangerous material, also is faced with problems aspect storage simultaneously.
Meanwhile, in the occurring in nature oxygen-free environment, ubiquity a class and can be reduced to sulfate, sulphite, thiosulfate, single sulphur the microorganism of sulfide, is distributed in bacterium and ancient bacterium territory, referred to as sulfate reducing bacteria (SRB).The important physiological characteristic of SRB is that growing power is strong, and it extensively is present in soil, rice terrace, seawater, salt solution, running water, thermal water, underground heat area, oil well and the natural gas well, sulfur deposition, river bed mud, sewage, animal cud and enteron aisle etc.Another physiological property is that the existence of sulfate can promote its growth, but is not the necessary condition of its existence and growth.Under the environment that lacks sulfate, SRB is by carrying out the metabolic way participated in without SO42-existence and growth; After enough sulfate in environment, having occurred, SRB be take SO42-and is the electron acceptor oxidation of organic compounds, by organic dissimilation, obtains the required energy of existence, and activity sustains life.The SRB of separate study has 18 to belong to nearly more than 40 kinds at present.Common are 9 genus, be mainly Desulfovibrio (Desultphovibrio) and Desulfotomaculum (Desulphfotomaculum).The former does not produce spore, generally is middle temperature or low temperature properties, lethal while surpassing 43 ℃; The latter produces spore, is middle temperature or high warm nature.According to the substrate utilized, SRB can be divided into to four classes: a class is the sulfate reducing bacteria (HSRB) of hydrogen oxide; One class is the sulfate reducing bacteria (ASRB) of acetic oxide; One class is the sulfate reducing bacteria (FASRB) of oxidation higher fatty acids; Also having a class is the sulfate reducing bacteria (PSRB) of oxidizable aromatic compound.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned deficiency of the prior art, sulfur recovery technique in a kind of gold concentrate roasting flue gas is provided, it can be reduced into SO2 simple substance S and/or CaS, the function of utilizing sulfate reducing bacteria to carry out sulfate reduction is reduced and is produced H2S the SO2 in flue gas, thereby further produce and have simple substance S or the CaS than high added value, realize that simultaneously tail gas pollution is administered and the purpose of recycling.
The technical solution adopted for the present invention to solve the technical problems is: the sulfur recovery technique in the gold concentrate roasting flue gas comprises following steps:
The part that (1) will contain the gold concentrate roasting flue gas of SO2 imports in NaOH solution, and NaOH is converted into Na2SO3 by SO2 and forms Na2SO3 solution;
(2) the Na2SO3 solution with water obtained in step (1) is diluted to SO32-concentration and is less than 1%;
(3) solution after step (2) dilution is introduced to the anaerobic fermentation reaction unit with sulfate reducing bacteria, sulfate reducing bacteria is reduced to H2S by SO32-;
(4) after another part of the H2S obtained in step (3) and the gold concentrate roasting flue gas that contains SO2 is mixed, make simple substance S by chemical reaction;
(5) the zymotic fluid water outlet of anaerobic fermentation reaction unit is drawn and carried out Separation of Solid and Liquid, the sludge reflux that contains active microorganism that separation is obtained is to the anaerobic fermentation reaction unit, in order to increase the biomass in the anaerobic fermentation reaction unit; The waste water that will obtain by Separation of Solid and Liquid and clear water refer and synthesize after for the dilution of step (2) to Na2SO3 solution.
Be further: also comprise that the H2S will made in step (3) is converted into the step of CaS simultaneously by chemical precipitation method.
Be further: the SO2 gold concentrate roasting flue gas that contains imported in NaOH solution in above-mentioned steps (1) is 50% of amount of flue gas emission; The gold concentrate roasting flue gas used in step (4) is 50% of amount of flue gas emission.
Be further: also comprise in the anaerobic fermentation reaction unit and supplement organic matter in order to supply the step of the required carbon source of sulfate reducing bacteria; Described organic matter is the organic waste of agricultural wastes or food processing and production.
Preferably: above-mentioned organic matter is resident's sanitary sewage, fowl and animal excrement or stalk.
Be further: the solution after diluting in above-mentioned steps (3) is introduced the anaerobic fermentation reaction unit, and the solution after dilution stopped 8 hours in the anaerobic fermentation reaction unit, the anaerobic fermentation reaction unit that described anaerobic fermentation reaction unit is four 420m3 specifications.
Be further: in above-mentioned anaerobic fermentation reaction unit, the growing environment of sulfate reducing bacteria is:
In the anaerobic fermentation reaction unit, the pH value is controlled between 6.48～7.43, and in the anaerobic fermentation reaction unit, temperature is controlled at 28～38 ℃, and oxidation-reduction potential in the anaerobic fermentation reaction unit (Eh) is lower than-100 mV.
Further preferably: in the anaerobic fermentation reaction unit, the pH value is 6.6, and in the anaerobic fermentation reaction unit, temperature is 35 ℃.
The present invention compared with prior art has the following advantages:
The present invention is by the gold concentrate roasting process, and the SO2 in flue gas is reduced into hydrogen sulfide by sulfate reducing bacteria; Whole process does not need to make a large amount of sulfuric acid, organic waste can also be recycled simultaneously; In whole process, water and organic waste have been carried out to cycling and reutilization to greatest extent; Finally be prepared into elemental sulfur and/or the CaS of high added value, realized simultaneously improvement and the recycling of smoke pollution.
The accompanying drawing explanation
Fig. 1 is process chart of the present invention;
Fig. 2 is the gold concentrate roasting process flow diagram.
The specific embodiment
Below in conjunction with drawings and Examples, the specific embodiment of the invention is described:
Fig. 1 shows the technological process of a kind of specific embodiment of the present invention; The present invention is the deficiency that overcomes the catalysis process for preparing sulfuric acid, utilize the sulfate reduction of microorganism (hydrochlorate reducing bacteria) that SO32-is reduced into to H2S, with chemical method, utilize SO2 that H2S is oxidized to elemental sulfur again, perhaps utilize chemical precipitation method that H2S is converted into to CaS, H2S is removed scheming, thereby realize the recovery of sulphur in baking flue gas;
As shown in Figure 1, use the absorption of NaOH solution, make part (for example 50%) SO2 be converted into Na2SO3 solution.The Na2SO3 solution with water is diluted to SO32-concentration and is less than 1%, introduce the anaerobic fermentation reaction unit, use sulfate reducing bacteria that SO32-is reduced to H2S, the H2S that obtains and remaining (for example 50%) SO2 reaction are obtained to simple substance S.Simultaneously the zymotic fluid water outlet is drawn and carried out Separation of Solid and Liquid, separate the sludge reflux that contains active microorganism obtained, to increase the biomass in the anaerobic fermentation reaction unit; And the waste water obtained and part clear water are reused for dilution Na2SO3 solution after referring and synthesizing.Wherein by the sulphur acid meter that will produce 100t every day, to 50% SO2 wherein, become dilution Na2SO3 solution to need the water of 5000t left and right, be that the anaerobic fermentation reaction unit need be processed 5000t every day, hydraulic detention time, by 8h, needs the anaerobic fermentation reaction unit of 4 420m3 specifications.
In the process of anaerobism sulfate reduction, need to supplement organic matter with the required carbon source of supply sulfate reducing bacteria, these organic matters can derive from the organic waste that agricultural wastes, the food processing etc. such as resident's sanitary sewage, fowl and animal excrement, stalk produce etc.So this technique not only can be removed the pollution of SO2, also can remove organic pollution, have dual environmental benefit.
In order to make above-mentioned sulfate reducing bacteria under best growing environment, to complete the process of sulphate reducing, we are studied the growing environment of sulfate reducing bacteria (SRB):
Generally, the reduction of sulfate reducing bacteria is affected by following factor, comprising:
1) carbon source: SRB belongs to heterotrophic microorganism, and namely its growth metabolism transforms sulfate needs certain carbon source, and these carbon sources are that to increase biomass required, as electron donor, sulfate is reduced to alienation again.Many results of study show in recent years, under the condition that has sulfate to exist, in the microbial ecosystem that separate sources, different domestication condition obtain, utilize the distribution of the SRB of various carbon source matrix that bigger difference must be arranged, and then have influence on their rates of reduction to sulfate.The carbon source that the different Pseudomonas growths of SRB utilize is different, the most generally utilizes C3, C4 aliphatic acid, as lactate, pyruvic acid, malic acid.SRB has shown very strong ability and diversity when utilizing diversified compound as electron donor, find so far to support the matrix of its growth over 100 kinds.
2) pH:pH is one of principal element affected the SRP vigor, and suitable pH environment is necessary to microbial growth and metabolism.The height of [H+] directly affects conformation, character and the BA of sulfate reduction enzyme system.Be mainly reflected in: a, pH value cause the variation of cell electric charge, thereby affect the absorption of SRB to substrate; B, the activity that affects various enzymes in the SRB metabolic process and stability, the toxicity of giving property and poisonous substance (if affected the existence of H2S) of substrate in the change ecological environment; The organic acid of c, permeate through cell membranes is ionization again in the SRP cell, changes the pH value in born of the same parents, and the carrying out of the many biochemical reactions of impact and ATP's is synthetic.SRB does not generally grow under the condition of pH<6.0, SRB growth optimum pH is generally in neutral range.There are some researches show that the sulfate reduction effect is best when the pH value is between 6.48 ~ 7.43, and when the pH value is 6.6, can obtain maximum sulfate reduction rate.SRB also can grow under the strong acid environment of pH4.0, its tolerable maximum alkalescence value is pH9.5.Sulfate reduction during every reduction 1gSO42-, generates 1. 042g basicity (CaCO3), therefore also can reach neutral to the quite high water of some acidity through SRP.
3) temperature: temperature is the environmental parameters that affects the SO42-reduction.So far the SRB Pseudomonas be separated to is mesothermal mostly, and its optimum temperature is generally 30 ℃ of left and right.SRB grows best in the time of 28 ~ 38 ℃, its critical high temperature value is 45 ℃.Have research to think, the optimum temperature of SO42-reduction is 31 ℃, and its high temperature critical value is generally between 45 ~ 48 ℃.There are some researches show again, in the complex system with other various microorganism mixobiosises, the sulfate reduction rate of SRB not only depends on the temperature of environment, also will be subjected to the competitive influence of other microorganism, generally in the time of 35 ℃, and its sulfate reduction rate maximum.
4) oxidation-reduction potential: it is believed that in early days SRB belongs to strict anaerobes, also can survive in the environment of micro-oxygen but recent research shows SRP, but generally speaking any SRB is not all usingd O2 and grown as electron acceptor.For guaranteeing that sulfate effectively reduces, the oxidation-reduction potential (Eh) of SRB growth must be lower than-100 mV.
The above is explained in detail the preferred embodiment for the present invention by reference to the accompanying drawings, but the invention is not restricted to above-mentioned embodiment, in the ken that those of ordinary skills possess, can also under the prerequisite that does not break away from aim of the present invention, make a variety of changes.
Do not break away from the spirit and scope of the present invention and can make many other changes and remodeling.Should be appreciated that and the invention is not restricted to specific embodiment, scope of the present invention is defined by the following claims.
Claims (8)
1. the sulfur recovery technique in the gold concentrate roasting flue gas comprises following steps:
The part that (1) will contain the gold concentrate roasting flue gas of SO2 imports in NaOH solution, and NaOH is converted into Na2SO3 by SO2 and forms Na2SO3 solution;
(2) the Na2SO3 solution with water obtained in step (1) is diluted to SO32-concentration and is less than 1%;
(3) solution after step (2) dilution is introduced to the anaerobic fermentation reaction unit with sulfate reducing bacteria, sulfate reducing bacteria is reduced to H2S by SO32-;
(4) after another part of the H2S obtained in step (3) and the gold concentrate roasting flue gas that contains SO2 is mixed, make simple substance S by chemical reaction;
(5) the zymotic fluid water outlet of anaerobic fermentation reaction unit is drawn and carried out Separation of Solid and Liquid, the sludge reflux that contains active microorganism that separation is obtained is to the anaerobic fermentation reaction unit, in order to increase the biomass in the anaerobic fermentation reaction unit; The waste water that will obtain by Separation of Solid and Liquid and clear water refer and synthesize after for the dilution of step (2) to Na2SO3 solution.
2. the sulfur recovery technique in gold concentrate roasting flue gas as claimed in claim 1, is characterized in that: also comprise that the H2S will made in step (3) is converted into the step of CaS simultaneously by chemical precipitation method.
3. the sulfur recovery technique in gold concentrate roasting flue gas as claimed in claim 1 is characterized in that: the SO2 gold concentrate roasting flue gas that contains imported in NaOH solution in step (1) is 50% of amount of flue gas emission; The gold concentrate roasting flue gas used in step (4) is 50% of amount of flue gas emission.
4. the sulfur recovery technique in gold concentrate roasting flue gas as claimed in claim 1, is characterized in that: also comprise in the anaerobic fermentation reaction unit and supplement organic matter in order to supply the step of the required carbon source of sulfate reducing bacteria; Described organic matter is the organic waste of agricultural wastes or food processing and production.
5. the sulfur recovery technique in gold concentrate roasting flue gas as claimed in claim 4 is characterized in that: described organic matter is resident's sanitary sewage, fowl and animal excrement or stalk.
6. the sulfur recovery technique in gold concentrate roasting flue gas as claimed in claim 1, it is characterized in that: the solution after diluting in step (3) is introduced the anaerobic fermentation reaction unit, solution after dilution stopped 8 hours in the anaerobic fermentation reaction unit, the anaerobic fermentation reaction unit that described anaerobic fermentation reaction unit is four 420m3 specifications.
7. the sulfur recovery technique in described gold concentrate roasting flue gas as arbitrary as claim 1-6, it is characterized in that: in described anaerobic fermentation reaction unit, the growing environment of sulfate reducing bacteria is:
In the anaerobic fermentation reaction unit, the pH value is controlled between 6.48～7.43, and in the anaerobic fermentation reaction unit, temperature is controlled at 28～38 ℃, and oxidation-reduction potential in the anaerobic fermentation reaction unit (Eh) is lower than-100 mV.
8. the sulfur recovery technique in gold concentrate roasting flue gas as claimed in claim 7, it is characterized in that: in the anaerobic fermentation reaction unit, the pH value is 6.6, in the anaerobic fermentation reaction unit, temperature is 35 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254023A (en) * | 2015-11-26 | 2016-01-20 | 中国科学院重庆绿色智能技术研究院 | Integrated device for treating acid mine wastewater and process method |
| CN106587114A (en) * | 2016-12-07 | 2017-04-26 | 锦西化工研究院有限公司 | Method for preparing sodium sulfite solution by using polysulfide rubber polymerized mother liquor acidized gas |
| CN109052659A (en) * | 2018-07-27 | 2018-12-21 | 昆明理工大学 | A kind of method of sulfur dioxide in flue gas removing and sulfur recovery |
| CN111704113A (en) * | 2020-08-20 | 2020-09-25 | 中国恩菲工程技术有限公司 | Method for preparing sulfur by using complex concentrate smelting flue gas |
| CN114432842A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Method and device for coupling desulfurization and preparing sulfur |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037271A (en) * | 2007-04-28 | 2007-09-19 | 阮文权 | Biological desulfurizing device for transforming sulfur-containing compound to elemental sulfur |
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- 2013-05-16 CN CN2013101816794A patent/CN103406007A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037271A (en) * | 2007-04-28 | 2007-09-19 | 阮文权 | Biological desulfurizing device for transforming sulfur-containing compound to elemental sulfur |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254023A (en) * | 2015-11-26 | 2016-01-20 | 中国科学院重庆绿色智能技术研究院 | Integrated device for treating acid mine wastewater and process method |
| CN106587114A (en) * | 2016-12-07 | 2017-04-26 | 锦西化工研究院有限公司 | Method for preparing sodium sulfite solution by using polysulfide rubber polymerized mother liquor acidized gas |
| CN109052659A (en) * | 2018-07-27 | 2018-12-21 | 昆明理工大学 | A kind of method of sulfur dioxide in flue gas removing and sulfur recovery |
| CN111704113A (en) * | 2020-08-20 | 2020-09-25 | 中国恩菲工程技术有限公司 | Method for preparing sulfur by using complex concentrate smelting flue gas |
| CN114432842A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Method and device for coupling desulfurization and preparing sulfur |
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Application publication date: 20131127 |