CN102010014A - 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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- CN102010014A CN102010014A CN2010106135593A CN201010613559A CN102010014A CN 102010014 A CN102010014 A CN 102010014A CN 2010106135593 A CN2010106135593 A CN 2010106135593A CN 201010613559 A CN201010613559 A CN 201010613559A CN 102010014 A CN102010014 A CN 102010014A
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- iron oxide
- desulfurizing agent
- red iron
- waste
- waste desulfurizing
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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 preparing the 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.Specifically a kind of waste desulfurizing agent prepares the method for red iron oxide.
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, advantage such as renewable, is to remove H
2The sweetening agent that S is commonly used, described ferric oxide desulfurizer is main raw material with the ferric oxide, adds the organic binder bond preparation.
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 ", be that the iron oxide based desulfurizing agent for high-temp gas that main ingredient prepares is an example wherein with steel mill's red mud, 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, feed high nitrogen then, temperature rises to and feeds reactant gases after the given temperature of reaction again and carry out sweetening agent regeneration, be attended by the generation of vitriol in the regenerative process, collect the ferric oxide after regenerating, can be used in the preparation of sweetening agent once more.
Though 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,, it is regenerated as red iron oxide if make full use of this part useless agent, 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, this 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 ", with iron oxide content is that industrial burned dregs more than 40% is after 100 to 210 ℃ of concentrated acids are handled, alkaline crystallizing agents such as adding yellow soda ash are finished crystallization under 80 to 150 ℃ of conditions, in calciner, finish calcining at last, it is 600 to 1300 ℃ that calcining temperature requires, aforesaid method uses concentrated acid to handle, spent acid after the use and sulfide are discharged in the external environment, have caused the serious environmental pollution.
Summary of the invention
For this reason, technical problem to be solved by this invention is that the waste desulfurizing agent discharging that exists in the prior art causes environmental pollution, regeneration cost height, red iron oxide production cost height and the disagreeableness problem of environment, provides low, the eco-friendly waste desulfurizing agent of a kind of production cost to prepare the method for red iron oxide.
For solving the problems of the technologies described above, a kind of waste desulfurizing agent of the present invention prepares the method for red iron oxide, 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 described useless agent particle blowing air and heating make the waste desulfurizing agent oxidation; (4) stop to be heated to the powder cooling, 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:
Waste desulfurizing agent provided by the invention prepares the method for red iron oxide, and step grinds to form particle with waste desulfurizing agent in (1), and bigger specific surface area is arranged, the distillation of sulphur when being beneficial to heating, and make waste desulfurizing agent be 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 coming out, thereby improve product purity; After reaching certain temperature in the step (3), the blowing air heating, 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 shape sulphur, and helps the decomposition of organic binder bond; The ferric oxide of handling 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 Significance for Environment and economic implications preferably.Utilize the red iron oxide of method for preparing not have 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/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 helps the magnetic resolution in the subsequent step.
Secluding air is heated to 200 to 400 ℃ in the step (2), heat so far temperature after logical again oxygen carry out oxidation, the sulphur of other forms is removed in the useless agent, avoids the compound that side reaction produces the iron of other forms takes place, and influences the productive rate of the ferric oxide in the product; Be 1 to 3 hours heat-up time, and the sulphur of other forms in the feasible useless agent fully distils, separates.
Be heated to 250 to 600 ℃ in the step (3), it is more thorough that the oxidizing reaction that 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 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 below.
Embodiment
Embodiment 1
The sweetening agent that with the main component is activated ferric oxide and organic binder bond carboxymethyl cellulose (CMC) is an example, uses the back sulphur content to be 15% of butt sweetening agent.
The step of utilizing this waste desulfurizing agent to prepare red iron oxide is: 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 ℃ under the situation of the logical nitrogen of secluding air, the time is controlled at 2 to 3h, and under this environment, different shape sulphur contained in the waste desulfurizing agent has certain distillation;
(3) stop logical nitrogen, change blowing air into, controlled 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) stop heating after, continue bubbling 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, the material that is magnetic can move 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, as waste treatment.Red iron oxide purity after separating reaches 90.3%.
Embodiment 2
The sweetening agent that with the main component is activated ferric oxide and organic binder bond starch is an example, uses the back sulphur content to be 13% of butt sweetening agent.
The step of utilizing this waste desulfurizing agent to prepare red iron oxide is: 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 ℃ under the situation of the logical nitrogen of secluding air, the time is controlled at 1.5 to 2.5h, and under this environment, different shape sulphur contained in the waste desulfurizing agent has certain distillation;
(3) stop logical nitrogen, change blowing air into, controlled 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) stop heating after, continue bubbling 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, the material that is magnetic can move 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, as waste treatment.Red iron oxide purity after separating reaches 90.3%.
Embodiment 3
The sweetening agent that with the main component is activated ferric oxide and organic binder bond starch is an example, uses the back sulphur content to be 13% of butt sweetening agent.
The step of utilizing this waste desulfurizing agent to prepare red iron oxide is: 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 ℃ under the situation of the logical nitrogen of secluding air, the time is controlled at 1 to 2h, and under this environment, different shape sulphur contained in the waste desulfurizing agent has certain distillation;
(3) stop logical nitrogen, change blowing air into, controlled 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) stop heating after, continue bubbling 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, the material that is magnetic can move 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, as waste treatment.Red iron oxide purity after separating reaches 90.3%.
Obviously, the foregoing description only is for example clearly is described, and is not the qualification 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 exhaustive to all embodiments.And conspicuous variation of being extended out thus or change still are among the protection domain of the invention.
Claims (7)
1. a waste desulfurizing agent prepares the method for red iron oxide, it 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 described useless agent particle blowing air and heating make the waste desulfurizing agent oxidation; (4) stop to be heated to the powder cooling, the ferric oxide in the product has magnetic, and the ferric oxide in the described product is carried out magnetic resolution.
2. waste desulfurizing agent according to claim 1 prepares the method for red iron oxide, it is characterized in that: described ferric oxide desulfurizer comprises ferric oxide and organic binder bond.
3. waste desulfurizing agent according to claim 2 prepares the method for red iron oxide, it is characterized in that: useless agent particle is crossed 100 mesh sieves described in the step (1).
4. prepare the method for red iron oxide according to any described waste desulfurizing agent in the claim 1 to 3, it is characterized in that: be heated to 200 ℃ to 400 ℃ in the step (2).
5. waste desulfurizing agent according to claim 4 prepares the method for red iron oxide, it is characterized in that: be 1 to 3 hours heat-up time in the step (2).
6. waste desulfurizing agent according to claim 5 prepares the method for red iron oxide, it is characterized in that: be heated to 250 ℃ to 600 ℃ in the step (3).
7. waste desulfurizing agent according to claim 6 prepares the method for red iron oxide, it is characterized in that: be 2 to 4 hours heat-up time in the step (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010613559.3A CN102010014B (en) | 2010-12-30 | 2010-12-30 | Method for preparing iron oxide red from waste desulfurizer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010613559.3A CN102010014B (en) | 2010-12-30 | 2010-12-30 | Method for preparing iron oxide red from waste desulfurizer |
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| CN102010014A true CN102010014A (en) | 2011-04-13 |
| CN102010014B CN102010014B (en) | 2013-10-16 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108728664A (en) * | 2018-04-27 | 2018-11-02 | 中南大学 | A kind of method that spent ferric oxide desulfurizer strengthens copper smelting slag dilution |
| 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 |
Citations (2)
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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 |
-
2010
- 2010-12-30 CN CN201010613559.3A patent/CN102010014B/en active Active
Patent Citations (2)
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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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|---|
| 侯鹏飞等: "含氧气氛下氧化铁基高温煤气脱硫剂再生行为", 《煤炭学报》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108728664A (en) * | 2018-04-27 | 2018-11-02 | 中南大学 | A kind of method that spent ferric oxide desulfurizer strengthens copper smelting slag dilution |
| 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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| Publication number | Publication date |
|---|---|
| CN102010014B (en) | 2013-10-16 |
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Address after: 100080 9th floor, Dahang Jiye building, No.1 building, 33 Renmin North Road, Haidian District, Beijing Patentee after: Beijing Haixin Energy Technology Co.,Ltd. Address before: 100080, Beijing, Haidian District people's Congress Road 33, the big line foundation building 17 floor Patentee before: BEIJING SANJU ENVIRONMENTAL PROTECTION & NEW MATERIALS Co.,Ltd. |
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