CN100515929C - Cinder processing method in acid preparing process from pyrite ore - Google Patents
Cinder processing method in acid preparing process from pyrite ore Download PDFInfo
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- CN100515929C CN100515929C CNB2005101057864A CN200510105786A CN100515929C CN 100515929 C CN100515929 C CN 100515929C CN B2005101057864 A CNB2005101057864 A CN B2005101057864A CN 200510105786 A CN200510105786 A CN 200510105786A CN 100515929 C CN100515929 C CN 100515929C
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- slag
- pyrite
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- iron
- sulfuric acid
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Abstract
The new acid preparing process with pyrite ore belongs to the technology field of roasting pyrite ore to prepare acid and sorting slag to obtain iron ore. The acid preparing process includes the steps of treating material and roasting at 750-800 deg.c, and features the reduction of the desulfurized and roasted slag with reductant at 550-570 deg.c. The process can convert the iron in the slag into ferric-ferrous oxide capable of being magnetically separated. The present invention results in raised resource utilization rate.
Description
Technical field
The invention belongs to pyrite burning relieving haperacidity and burn slag and choose the iron ore technical field, relate in particular to a kind of can the raising and burn the acid-making process that iron ore in the slag is chosen efficient.
Background technology
Sulfurous iron ore production sulfuric acid process is a kind of traditional acid preparation method, and China's ferro-sulphur ore is abundanter, so China is at present still based on pyrite-based sulfuric acid production.Annual about more than 700 ten thousand tons of the sulfuric acid of producing of China wherein adopts sulfurous iron ore to produce about more than 500 ten thousand tons of sulfuric acid at present, and the burning slag that produces after the annual relieving haperacidity is up to more than 500 ten thousand tons.Though ferrous grade is up to 35～50% in most of burning slag, because of the pyrite-based sulfuric acid production technology of continuing to use decades ago always, the iron overwhelming majority in the burning slag is with ferric oxide Fe
2O
3, iron protoxide FeO and ferric metasilicate form exist, have only few part with Z 250 Fe
3O
4Form exist, the magnetic of burning iron ore in the slag too a little less than, be not suitable for magnetic separation.Gravity treatment and floatation process not only need facility investment bigger, and complex process, beneficiation cost is higher, the two is difficult to the while washed ore grade and the rate of recovery take into account, the every technical indicator of ore dressing is all undesirable, so the burning slag behind the present pyrite-based sulfuric acid production wastes a large amount of precious resources mainly as the raw materials for production in cement mill, the iron ore resource wretched insufficiency of China on the other hand, every year need be from a large amount of iron ores of external import to satisfy the demand of Iron and Steel Enterprises in China.
The formation of tradition pyrite-based sulfuric acid production technology for decades, was only considered the demand of relieving haperacidity at that time, considered to burn the problem that the slag exploitation utilizes again.Its master operation comprises pulverizing pre-treatment, high-temperature roasting, the SO of sulfurous iron ore raw material
2Steps such as gas sweetening conversion and absorption, wherein the temperature of high-temperature roasting is 880～920 ℃, but when temperature surpasses 900 ℃, silicon-dioxide and iron containing compounds react and very easily generate ferric metasilicate, too high maturing temperature of while need increase roasting time and guarantee, this causes the peroxidation roasting again, burns the Z 250 Fe in the slag
3O
4The component major part is reduced to ferric oxide Fe
2O
3With iron protoxide FeO, the burning slag after the roasting is after furnace bottom is discharged, and wherein the main forms of iron is iron protoxide, ferric oxide and ferric metasilicate, and this brings certain degree of difficulty for the ore dressing of burning slag.
Re-treating process is adopted in domestic present processing to the ore dressing of burning slag more, required cost does not conform to the benefit that China utilizes this resource to produce at present, obviously do not meet the free selective rule under the market economy, therefore can not get promotion and application, this Technology Need obtains the utilization that pyrite-based sulfuric acid production burns the slag greatest benefit from the prerequisite of low cost consumption.
Summary of the invention
The purpose of this invention is to provide a kind of new acid preparing process with pyrite ore, but can realize relieving haperacidity and obtain the burning slag that contains the higher-grade iron ore of magnetic separation by process modification to existing pyrite-based sulfuric acid production technology.。
The technical solution used in the present invention is as follows:
A kind of new acid preparing process with pyrite ore comprises that raw material is handled and calcining process, it is characterized in that in the calcining process sulfurous iron ore through stoving oven 750～800 ℃ of oxidizing roastings.
Another kind of new acid preparing process with pyrite ore comprises raw material processing and calcining process, it is characterized in that sulfurous iron ore reduces through reductive agent under 550～570 ℃ through the burning slag behind the desulphurizing roasting.
Another new acid preparing process with pyrite ore comprises raw material processing and calcining process, it is characterized in that, 750～800 ℃ of oxidizing roastings, the burning slag after the roasting through the reductive agent reduction, carries out the iron ore magnetic separation to sulfurous iron ore then under 550～570 ℃ through stoving oven in the calcining process.
Described reductive agent is coal dust or coke powder solid reductant.
Described reductive agent is water-gas, mixed gas or coke-oven gas.
Described stoving oven is three-dimensional stoving oven.
In original pyrite burning desulfurization acid-making process, maturing temperature is 880～920 ℃, in order to obtain this maturing temperature, ore particle is fully burnt, therefore a large amount of gases have been fed, making the roasting furnace atmosphere is oxidizing atmosphere, and most iron exists with iron protoxide and ferric oxide, and the iron ore that therefore burns in the slag can't be selected through magnetic separation.Simultaneously, because the ore particle sufficient combustion, local maturing temperature usually can be higher than 920 ℃, and the oxide compound of iron is very easy to and silicon dioxde reaction generation ferric metasilicate under this high temperature, causes the minimizing of burning available iron ore deposit in the slag.Pyrite burning temperature provided by the invention is 750～800 ℃, because the boiling point of sulphur is 444.6 ℃, under 750～800 ℃ of maturing temperatures, can guarantee sulphur, the separation of oxygenated of iron, satisfy the requirement of relieving haperacidity, changed the existence form of burning iron in the slag simultaneously, avoid the generation of ferric metasilicate to greatest extent, the roasting of peroxidation simultaneously phenomenon alleviates, the iron that the Z 250 form exists increases, the iron that corresponding iron protoxide and form of iron oxide exist reduces, and reduces maturing temperature and can adopt the multiple technologies measure to realize, at first, can in the scope that other devices allow, increase feeding coal, quicken deslagging etc., this method also can increase the vitriolic unit output; When sulfurous iron ore sulfur-bearing grade was low, it was fit closely increasing feed and quickening deslagging; Secondly, the flame retardant coating thickening of stoving oven can be reduced the volume of body of heater, deslagging is speeded up; The oxidizing atmosphere that can take at last to regulate in the stoving oven ventilation reduction stoving oven reduces maturing temperature, reduces the conversion of Z 250 to iron protoxide and ferric oxide, thereby increases the magnetic separation rate of burning iron ore in the slag.
Give air quantity and shortening pyrite burning time that the preceding blower fan of stoving oven is adjusted and reduced in employing are the working method that Z 250 content in the slag is burnt in effectively raising.When sulfurous iron ore sulfur-bearing grade is low, also can reduce maturing temperature by increasing delivery rate.By test, adopt aforesaid method can't obviously reduce the desulfurization degree of sulfurous iron ore, therefore consider it is very feasible from the angle of economic benefit.
Iron ore major part in the burning slag after roasting still exists with the form of iron protoxide and ferric oxide, the burning slag temperature of discharging from stoving oven is still very high, add reductive agent in the burning slag at high temperature, reductive agent can be gas or solid type reductive agent, as the conventional water-gas that uses of fertilizer plant, mixed gas, coke-oven gas or solid carbon powder, it mainly is reduced into and is divided into carbon monoxide, hydrogen or powdered carbon, also can adopt the tail gas or the charcoal ash of carbonaceous particles, 550～670 ℃ is best reduction temperature, and the ferric oxide of the overwhelming majority and iron protoxide are reduced to the Z 250 that can be selected by magnetic separation process.For the technology that simplifies the operation, can below existing roasting apparatus, set up reducing apparatus such as reduction chamber or reduction bed, the reductive agent import is set in the reducing apparatus, burns slag and discharge at the bottom of the stoving oven and enter the reduction chamber, utilize slag roasting waste heat not need heating in addition just can finish restore job.
Beneficial effect of the present invention is, improve or/and slag roasting reduction is handled by simple acid-making process, but the iron in the pyrite cinder can be converted into the Z 250 of magnetic separation, use weak magnetic separator sorting can access the powdered iron ore of high grade, the magnetic separation rate of burning iron ore in the slag can reach 95～96%, not only can improve sulfuric acid relieving haperacidity enterprise and burn the economic benefit that slag is handled, can also alleviate the situation of the raw material anxiety of Iron and Steel Enterprises in China, improve the utilising efficiency of china natural resources.The relieving haperacidity and the ore-dressing technique of the applicable various grade ferro-sulphur ore relieving haperacidity of the present invention enterprise.
Embodiment
The invention will be further elaborated to experiment that technical scheme of the present invention is done below in conjunction with the contriver, but the present invention is not limited to following embodiment, and following percentage ratio unless otherwise indicated is mass percent.
Embodiment 1 low-temperature bake sulfurous iron ore desulfurization test
This pyrite-based sulfuric acid production technology selects for use small-sized stoving oven as experimental installation, and the stoving oven furnace diameter is 0.36m, and high 0.8m adopts thermopair as temperature measuring equipment, and feeding coal measures with electronic scale, adopts gas blower to give wind, but the rotation speed of fan manual regulation.Have square reduction chamber below the roasting chamber, reduction chamber specification is (length) 30cm * (wide) 30cm * (height) 50cm.
Select for use Jianchang, Liaoning Province sulfurous iron ore as the relieving haperacidity raw material, block sulfurous iron ore mixes with powdery sulfurous iron ore equal portions after crushed and sieves, and the maximum particle diameter of screening is less than 3mm, and detecting the sulfur-bearing grade is 28%, moisture 6%.
Adopt sinter process roasting pyrite provided by the invention relieving haperacidity, and the oxidation burning yield of detection sulphur and the percentage composition that burns all cpds of iron in the slag, the maturing temperature of this sinter process is controlled at 750～800 ℃, is per hour 100 cubic metres to air quantity, adopts following two kinds of control methods:
1. the delivery rate of roasting is 60-75Kg per hour, obtains burning slag specimen product 1, and the iron grade of burning after testing in the slag specimen product 1 is 48%.
2. with the thickening of the flame retardant coating of above-mentioned stoving oven, it is original about 75% that the volume of body of heater is become, delivery rate be 50Kg per hour, obtain burning slag specimen product 2, the iron grade of burning after testing in the slag specimen product 2 is 48%.
The per-cent that the oxidation burning yield of the sulphur of sample 1 and sample 2 and the various existence forms of burning iron in the slag are accounted for the iron total content detects and obtains following table 1.
Table 1
Comparative Examples 1 adopts traditional pyrite-based sulfuric acid production technology roasting relieving haperacidity, calciner and the raw material while embodiment 1 that selects for use, the delivery rate of roasting is 50Kg per hour, the amount of following the wind is per hour 100 cubic metres, maturing temperature is controlled at 880～920 ℃, gets every 48 hours and once burns the slag specimen product, gets altogether three times, obtain sample 3, sample 4 and sample 5 respectively, the iron grade of burning after testing in slag specimen product 3,4 and 5 is 48%.Detect the per-cent that oxidation burning yield that burns sulphur in the slag and the various existence forms of burning iron in the slag account for the iron total content, analytical results sees the following form 2.
Table 2
Every data contrast by above embodiment and Comparative Examples can obtain, under the condition of low-temperature bake temperature provided by the invention, the burning yield of sulphur there is no considerable change in the sulfurous iron ore, but very big variation has taken place in the content of all cpds of iron in the burning slag, after adopting low-temperature bake technology provided by the invention, the percentage composition that the Z 250 of easy magnetic separation accounts for iron cpd has had tangible increase, but the magnetic separation rate of iron ore improves greatly in the burning slag, can effectively improve the utilization ratio of burning the slag ore dressing.
Embodiment 2 burns the slag reduction test
Roasting apparatus that adopts and sulfurous iron ore raw material be with embodiment 1, and reduce to the burning slag of embodiment 1 the reduction chamber that is provided with by the below, roasting chamber, and reduction temperature is controlled in 550～570 ℃ of scopes.And adopt different reductive agents to reduce experiment:
1. adopt water-gas to make reductive agent and obtain burning slag specimen product 6, the iron grade of burning after testing in the slag specimen product 6 is 48%, and effective reduction components content of water-gas is: CO 37%, H
250%.The feeding amount is per hour 8.67 cubic metres.
2. adopt blast furnace gas to obtain burning slag specimen product 7 as reductive agent, the iron grade of burning after testing in the slag specimen product 7 is 48%, and effective reduction components content of blast furnace gas is: CO 25.37%, H
22.11%.The feeding amount is per hour 299.1 cubic metres.
3. adopt mixed gas to obtain burning slag specimen product 8 as reductive agent, the iron grade of burning after testing in the slag specimen product 8 is 48%, and effective reduction components content of mixed gas is: CO 22.3%, H
214.3%.The feeding amount is per hour 50.25 cubic metres.
4. adopt coke-oven gas to obtain burning slag specimen product 9 as reductive agent, the iron grade of burning after testing in the slag specimen product 9 is 48%, and effective reduction components content of coke-oven gas is: CO 8.6%, H
259%.The feeding amount is per hour 31.68 cubic metres.
5. adopt coal dust to obtain burning slag specimen product 10 as reductive agent, the iron grade of burning after testing in the slag specimen product 10 is 48%, and effective reduction components content of coal dust is: C 60%.The feeding amount is 1.44Kg per hour.
Because feed, roasting and deslagging are operate continuouslys in the pyrite-based sulfuric acid production technology, so the recovery time approximates roasting time.The content detection of the burning slag after the reduction being carried out various iron cpds obtains following table 3:
Table 3
As can be seen from the above table, utilize the waste heat after the roasting, reduce to burning slag at a certain temperature, can be converted into the form of Z 250 burning iron cpd major part in the slag.
The pyrite cinder that embodiment 2 is obtained carries out the iron ore magnetic separation, will burn the slag classification earlier, then ball mill pulverizing to particle fineness less than 80 orders, the burning slag after the pulverizing carries out three grades of magnetic concentrators and carries out magnetic separation after magnetic dewater cone dehydration.After testing, the expectation elimination factor that burns the iron in the slag is 91～95%, and the actual elimination factor that burns iron ore in the slag is up to more than 85%, and the content of iron is up to 66.18% in the iron ore of selecting.
Claims (4)
1, the burning slag treatment process in a kind of pyrite-based sulfuric acid production technology, it is characterized in that the high temperature in pyrite-based sulfuric acid production technology behind desulfurization with roasting technique burns slag and enters in the reducing apparatus, utilize and burn the slag waste heat under 550-570 ℃, add reductive agent again and directly reduce, burn the slag magnetic separation then.
2, the burning slag treatment process in the pyrite-based sulfuric acid production technology as claimed in claim 1 is characterized in that, reduction chamber or reduction bed are installed in the dreg removing system of pyrite-based sulfuric acid production.
3, as the burning slag treatment process in claims 1 described pyrite-based sulfuric acid production technology, it is characterized in that described reductive agent is water-gas, mixed gas or coke-oven gas.
As the burning slag treatment process in claims 1 described pyrite-based sulfuric acid production technology, it is characterized in that 4, described reductive agent is coal dust, coke powder solid reductant.
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| CN100515929C true CN100515929C (en) | 2009-07-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101935176B (en) * | 2010-07-27 | 2012-10-10 | 西南科技大学 | Method for preparing conductive admixture from pyrite smelting slag |
| CN101914674B (en) * | 2010-08-11 | 2011-11-16 | 山东华恒矿业有限公司 | Process for high-temperature roasting high-sulfur high-arsenic limonite in rotary kiln |
| CN103589857A (en) * | 2013-11-06 | 2014-02-19 | 施可丰泸州化工有限公司 | Full utilization method for middle and low-grade pyrite |
| CN105502305A (en) * | 2015-12-30 | 2016-04-20 | 贵州省大方润丰化工有限公司 | Pyrite low-oxygen roasting method for increasing proportion of Fe3O4 in total iron of roasted residues |
| CN109266802A (en) * | 2018-12-10 | 2019-01-25 | 山东大学 | In conjunction with the technique and device of short route iron-smelting process roasted pyrite resource utilization |
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Non-Patent Citations (4)
| Title |
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| 富氧空气焙烧硫铁矿工艺技术分析. 张文红.硫磷设计与粉体工程，第2001年第2期. 2001 |
| 富氧空气焙烧硫铁矿工艺技术分析. 张文红.硫磷设计与粉体工程，第2001年第2期. 2001 * |
| 硫铁矿烧渣磁化焙烧的实验研究. 王雪松，李朝祥，付元坤.钢铁研究学报，第17卷第3期. 2005 |
| 硫铁矿烧渣磁化焙烧的实验研究. 王雪松，李朝祥，付元坤.钢铁研究学报，第17卷第3期. 2005 * |
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