CN102010014B - Method for preparing iron oxide red from waste desulfurizer - Google Patents
Method for preparing iron oxide red from waste desulfurizer Download PDFInfo
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- CN102010014B CN102010014B CN201010613559.3A CN201010613559A CN102010014B CN 102010014 B CN102010014 B CN 102010014B CN 201010613559 A CN201010613559 A CN 201010613559A CN 102010014 B CN102010014 B CN 102010014B
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- iron oxide
- waste
- desulfurizer
- waste desulfurizer
- oxide red
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Abstract
The invention discloses a method for preparing iron oxide red from a waste desulfurizer, which comprises the following steps of: crushing and grinding the waste desulfurizer into particles; isolating the particles of the waste desulfurizer from air and heating the particles of the waste desulfurizer to a certain temperature; introducing the air into the particles of the waste desulfurizer, and heating the particles of the waste desulfurizer; and continuously introducing the air until the particles are cooled, and performing magnetic separation on obtained iron oxides. The method for preparingthe iron oxide red from the waste desulfurizer solves the problems of environmental pollutions and high regeneration cost caused by the emission of the waste desulfurizer in the prior art, and ensures low production cost and environmental friendliness.
Description
Technical field
The present invention relates to a kind of method for preparing red iron oxide.A kind of method of preparing iron oxide red from waste desulfurizer specifically.
Background technology
Ferric oxide desulfurizer (Fe
2O
3Sweetening agent or Fe
2O
3H
2The O sweetening agent) have desulphurizing activated good, Sulfur capacity is high, the advantage such as renewable, is to remove H
2The sweetening agent that S is commonly used, described ferric oxide desulfurizer add the organic binder bond preparation take ferric oxide as main raw material.
The desulphurization mechanism of ferric oxide desulfurizer is as follows:
Fe
2O
3?+3H
2S→Fe
2S
3?+3H
2O
Fe
2O
3?+3H
2S→2FeS+S+4H
2O
Or Fe
2O
3H
2O+3H
2S → Fe
2S
3H2O+3H
2O Fe
2O
3H2O+3H
2S → 2FeS+S+4H
2O,
Ferric oxide desulfurizer has reproducibility, and under aerobic conditions, renewable is ferric oxide.The regeneration mechanism of generally acknowledging is as follows:
Fe
2S
3+3/2O
2→Fe
2O
3+3S
4FeS+O
2=2Fe
2O
3+4S
Or Fe
2S
3H2O+3/2O
2→ Fe
2O
3+ 3S+H
2O
4FeS+O
2=2Fe
2O
3+4S
In the prior art, " coal journal " 2009 the 34th volume the 1st is interim to disclose one piece and has been entitled as the document of " iron oxide based desulfurizing agent for high-temp gas regeneration behavior under the oxygen-containing atmosphere ", wherein the iron oxide based desulfurizing agent for high-temp gas of preparation is example take steel mill's red mud as main ingredient, the sweetening agent that takes by weighing after a certain amount of use is loaded in the crystal reaction tube, at first be warming up to 300 ℃, sulphur and oxygen in the waste desulfurizing agent reacts at this moment, then pass into high nitrogen, temperature rises to and passes into reactant gases after the given temperature of reaction again and carry out desulfurizer regeneration, be attended by the generation of vitriol in the regenerative process, collect the ferric oxide after regenerating, can again be used in the preparation of sweetening agent.
Although ferric oxide desulfurizer can be regenerated by aforesaid method, but the aforesaid method cost is higher, be not suitable for being applied to large-scale commercial production, so general spent ferric oxide sweetening agent directly abandons or buries after using, cause the environmental pollution wasting of resources, if take full advantage of this part useless agent, it is regenerated as red iron oxide, can reduce the production cost of red iron oxide, turn waste into wealth.
Traditional red iron oxide preparation method is, with the iron sheet vitriolization, regulates the precipitation of hydroxide that ph value to alkalescence obtains iron, gained is precipitated carry out drying, roasting obtains red iron oxide, the method cost is higher; Similar red iron oxide preparation method is disclosed among the patent documentation CN1108618A " method of production of high-content ferric oxide red colorant from iron-contained industrial burned dregs ", be that industrial burned dregs more than 40% is after 100 to 210 ℃ of concentrated acids are processed with iron oxide content, the alkaline crystallizing agents such as adding yellow soda ash are finished crystallization under 80 to 150 ℃ of conditions, in calciner, finish at last calcining, it is 600 to 1300 ℃ that calcining temperature requires, aforesaid method uses concentrated acid to process, spent acid after the use and sulfide are discharged in the external environment, have caused serious environmental pollution.
Summary of the invention
For this reason, the waste desulfurizing agent discharging that technical problem to be solved by this invention is to exist in the prior art causes that environmental pollution, regeneration cost are high, red iron oxide production cost height and the disagreeableness problem of environment, provides that a kind of production cost is low, the method for eco-friendly preparing iron oxide red from waste desulfurizer.
For solving the problems of the technologies described above, the method for a kind of preparing iron oxide red from waste desulfurizer of the present invention may further comprise the steps: the waste desulfurizing agent that (1) obtains after with the ferric oxide desulfurizer desulfurization is pulverized grinding, obtains useless agent particle; (2) the agent particle that will give up heats under inert gas atmosphere, makes the sulphur distillation; (3) then in the described useless agent particle blowing air and heating make the waste desulfurizing agent oxidation; (4) stopped heating to powder cools off, and the ferric oxide in the product has magnetic, and the ferric oxide in the described product is carried out magnetic resolution.
Described ferric oxide desulfurizer comprises ferric oxide and organic binder bond.
Useless agent particle is crossed 100 mesh sieves described in the step (1).
Be heated to 200 to 400 ℃ in the step (2).
Be heated to 250 to 600 ℃ in the step (3).
Be 2 to 4 hours heat-up time in the step (3).
Technique scheme of the present invention has the following advantages compared to existing technology:
The method of preparing iron oxide red from waste desulfurizer provided by the invention, step grinds to form particle with waste desulfurizing agent in (1), and larger specific surface area is arranged, the distillation of sulphur when being beneficial to heating, and so that waste desulfurizing agent is heated evenly, fully react with oxygen; The logical rare gas element heating of step (2) secluding air, described rare gas element comprises VIII A family's gas and nitrogen, sulphur exists with variform in the waste desulfurizing agent, under the condition of starvation, can be effectively with part sulphur content from out, thereby improve product purity; After reaching certain temperature in the step (3), the blowing air heating, the product after isolated heating and oxygen reaction are difficult for producing vitriol, are easy to generate ferric oxide, also are beneficial to the decomposition of organic binder bond; The type of heating of two step staging treating is beneficial to removing of different morphologic sulphur, and is conducive to the decomposition of organic binder bond; The ferric oxide of processing by above-mentioned steps possesses magnetic, selects magnetic resolution in the step (4), and it is higher to reclaim the ferric oxide purity that obtains, and has preferably Significance for Environment and economic implications.Utilize the red iron oxide of aforesaid method preparation without desulphurizing activated, and the ferric oxide particles aperture that is used for sweetening agent after the regeneration is different from red iron oxide, have desulphurizing activated, both crystalline state are also different, the red iron oxide purity of utilizing aforesaid method to obtain reaches 90%, judgement criteria according to standard GB/T/T1863-2008-iron oxide pigment reaches national requirements.
Described sweetening agent comprises ferric oxide and organic binder bond, and when organic binder bond wherein led to oxygen under hot conditions, burning generated CO
2And H
2O is removed, and is beneficial to the recovery of high-purity mangesium oxide iron oxide red.
Useless agent particle is crossed 100 mesh sieves described in the step (1), and such granularity helps the oxidation of impurity distillation, iron sulfide in the described useless agent to carry out largely, also is conducive to the magnetic resolution in the subsequent step.
Secluding air is heated to 200 to 400 ℃ in the step (2), heats so far after the temperature again that logical oxygen carries out oxidation, and the sulphur of other forms is removed in the useless agent, avoids the compound that side reaction produces the iron of other forms occurs, and affects the productive rate of the ferric oxide in the product; Be 1 to 3 hours heat-up time, so that the sulphur of other forms in the useless agent fully distils, separates.
Be heated to 250 to 600 ℃ in the step (3), it is more thorough that the oxidizing reaction that the useless agent of sweetening agent and air carry out under this temperature is carried out; Be 2 to 4 hours heat-up time, guaranteed that the oxidizing reaction that the useless agent of sweetening agent and air carry out has the enough reaction times, and organic binder bond can fully decompose to be removed, and has guaranteed the high yield of red iron oxide.
The present invention is further detailed explanation according to a particular embodiment of the invention for the below.
Embodiment
Embodiment 1
Take main component as activated ferric oxide and the sweetening agent of organic binder bond carboxymethyl cellulose (CMC) be example, use after sulphur content be 15% of butt sweetening agent.
Utilize the step of this preparing iron oxide red from waste desulfurizer to be: the waste desulfurizing agent after (1) will use is pulverized and is separated the removal macrobead with 100 mesh sieve, gets the sweetening agent 10g that crushes and is positioned in the airtight silica tube;
(2) be heated to 200 to 300 ℃ in the situation of the logical nitrogen of secluding air, the time is controlled at 2 to 3h, and under this environment, contained different morphologic sulphur has certain distillation in the waste desulfurizing agent;
(3) stop logical nitrogen, change blowing air into, the control temperature is between 250 to 350 ℃, and the time is controlled at 3 to 4h, the main component FeS of waste desulfurizing agent can with the oxygen generation red iron oxide that reacts, and the residual organic substances in the waste desulfurizing agent can be burnt and generated CO
2And H
2O is removed;
(4) behind the stopped heating, continue to pass into air to powder and cool off.The 7.5g ferric oxide that obtains is carried out magnetic resolution, the step of magnetic resolution is that powder is positioned on the veneer, common magnet is placed in the veneer below, magnet is moved from the powder below, being magnetic material can be mobile together along with magnet, nonmagnetic material is still in the original place, by making the 6g red iron oxide after the magnetic separation.Wherein nonmagnetic material amounts to 1.5g, processes as refuse.Red iron oxide purity after separating reaches 90.3%.
Embodiment 2
Take main component as activated ferric oxide and the sweetening agent of organic binder bond starch be example, use after sulphur content be 13% of butt sweetening agent.
Utilize the step of this preparing iron oxide red from waste desulfurizer to be: the waste desulfurizing agent after (1) will use is pulverized and is separated the removal macrobead with 100 mesh sieve, gets the sweetening agent 10g that crushes and is positioned in the airtight silica tube;
(2) be heated to 250 to 350 ℃ in the situation of the logical nitrogen of secluding air, the time is controlled at 1.5 to 2.5h, and under this environment, contained different morphologic sulphur has certain distillation in the waste desulfurizing agent;
(3) stop logical nitrogen, change blowing air into, the control temperature is between 350 to 500 ℃, and the time is controlled at 2.5 to 3.5h, the main component FeS of waste desulfurizing agent can with the oxygen generation red iron oxide that reacts, and the residual organic substances in the waste desulfurizing agent can be burnt and generated CO
2And H
2O is removed;
(4) behind the stopped heating, continue to pass into air to powder and cool off.The 7.5g ferric oxide that obtains is carried out magnetic resolution, the step of magnetic resolution is that powder is positioned on the veneer, common magnet is placed in the veneer below, magnet is moved from the powder below, being magnetic material can be mobile together along with magnet, nonmagnetic material is still in the original place, by making the 6g red iron oxide after the magnetic separation.Wherein nonmagnetic material amounts to 1.5g, processes as refuse.Red iron oxide purity after separating reaches 90.3%.
Embodiment 3
Take main component as activated ferric oxide and the sweetening agent of organic binder bond starch be example, use after sulphur content be 13% of butt sweetening agent.
Utilize the step of this preparing iron oxide red from waste desulfurizer to be: the waste desulfurizing agent after (1) will use is pulverized and is separated the removal macrobead with 100 mesh sieve, gets the sweetening agent 10g that crushes and is positioned in the airtight silica tube;
(2) be heated to 300 to 400 ℃ in the situation of the logical nitrogen of secluding air, the time is controlled at 1 to 2h, and under this environment, contained different morphologic sulphur has certain distillation in the waste desulfurizing agent;
(3) stop logical nitrogen, change blowing air into, the control temperature is between 500 to 600 ℃, and the time is controlled at 2 to 3h, the main component FeS of waste desulfurizing agent can with the oxygen generation red iron oxide that reacts, and the residual organic substances in the waste desulfurizing agent can be burnt and generated CO
2And H
2O is removed;
(4) behind the stopped heating, continue to pass into air to powder and cool off.The 7.5g ferric oxide that obtains is carried out magnetic resolution, the step of magnetic resolution is that powder is positioned on the veneer, common magnet is placed in the veneer below, magnet is moved from the powder below, being magnetic material can be mobile together along with magnet, nonmagnetic material is still in the original place, by making the 6g red iron oxide after the magnetic separation.Wherein nonmagnetic material amounts to 1.5g, processes as refuse.Red iron oxide purity after separating reaches 90.3%.
Obviously, above-described embodiment only is for example clearly is described, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give all embodiments exhaustive.And the apparent variation of being extended out thus or change still are among the protection domain of the invention.
Claims (7)
1. the method for a preparing iron oxide red from waste desulfurizer is characterized in that, may further comprise the steps: the waste desulfurizing agent that (1) obtains after with the ferric oxide desulfurizer desulfurization is pulverized grinding, obtains useless agent particle; (2) the agent particle that will give up heats under inert gas atmosphere, makes the sulphur distillation; (3) then in the described useless agent particle blowing air and heating make the waste desulfurizing agent oxidation; (4) stopped heating to powder cools off, and the ferric oxide in the product has magnetic, and the ferric oxide in the described product is carried out magnetic resolution.
2. the method for preparing iron oxide red from waste desulfurizer according to claim 1, it is characterized in that: described ferric oxide desulfurizer comprises ferric oxide and organic binder bond.
3. the method for preparing iron oxide red from waste desulfurizer according to claim 2 is characterized in that: useless agent particle is crossed 100 mesh sieves described in the step (1).
4. the method for the described preparing iron oxide red from waste desulfurizer of any one in 3 according to claim 1 is characterized in that: be heated to 200 ℃ to 400 ℃ in the step (2).
5. the method for preparing iron oxide red from waste desulfurizer according to claim 4 is characterized in that: be 1 to 3 hours heat-up time in the step (2).
6. the method for preparing iron oxide red from waste desulfurizer according to claim 5 is characterized in that: be heated to 250 ℃ to 600 ℃ in the step (3).
7. the method for preparing iron oxide red from waste desulfurizer according to claim 6 is characterized in that: be 2 to 4 hours heat-up time in the step (3).
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CN108728664B (en) * | 2018-04-27 | 2020-07-24 | 中南大学 | Method for strengthening dilution of copper smelting slag by waste iron oxide desulfurizer |
CN109848172A (en) * | 2018-12-26 | 2019-06-07 | 安徽万纬工程管理有限责任公司 | A kind of petrochemical industry refuse processing method |
CN110762541A (en) * | 2019-10-23 | 2020-02-07 | 马鞍山钢铁股份有限公司 | Waste desulfurizer utilization treatment device and treatment method thereof |
CN114906822A (en) * | 2022-04-26 | 2022-08-16 | 马鞍山钢铁股份有限公司 | Harmless treatment method and application of coke oven gas waste desulfurizer |
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CN101585557A (en) * | 2008-05-23 | 2009-11-25 | 北京三聚环保新材料股份有限公司 | Method for preparing magnetic oxide iron and magnetic oxide iron desulfurizer prepared thereby |
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CN1108618A (en) * | 1994-03-16 | 1995-09-20 | 南京化学工业(集团)公司研究院 | Method for production of high-content ferric oxide red colorant from iron-contained industrial burned dregs |
CN101585557A (en) * | 2008-05-23 | 2009-11-25 | 北京三聚环保新材料股份有限公司 | Method for preparing magnetic oxide iron and magnetic oxide iron desulfurizer prepared thereby |
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