CN108298592A - On a kind of eliminating hydroxide iron oxide the method for sulphur and go sulphur removal FeOOH application - Google Patents
On a kind of eliminating hydroxide iron oxide the method for sulphur and go sulphur removal FeOOH application Download PDFInfo
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- CN108298592A CN108298592A CN201810265832.4A CN201810265832A CN108298592A CN 108298592 A CN108298592 A CN 108298592A CN 201810265832 A CN201810265832 A CN 201810265832A CN 108298592 A CN108298592 A CN 108298592A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/027—Recovery of sulfur from material containing elemental sulfur, e.g. luxmasses or sulfur containing ores; Purification of the recovered sulfur
- C01B17/033—Recovery of sulfur from material containing elemental sulfur, e.g. luxmasses or sulfur containing ores; Purification of the recovered sulfur using a liquid extractant
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C01G49/0009—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C01P2006/80—Compositional purity
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Abstract
The present invention provides a kind of methods of sulphur on eliminating hydroxide iron oxide, by the water content for strictly controlling sulfur-bearing FeOOH, it realizes under the premise of efficiently sulphur being made to be detached with FeOOH, effectively ensures the purity of the desulphurizing ability of FeOOH and the sulphur of recycling；This is because the water content in FeOOH is excessively high, it can be dispersed into small particle in organic solvent, not only resulting in the desulphurizing ability of FeOOH reduces, but also can to contain a large amount of ferro element in the sulphur after recycling.
Description
Technical field
The present invention relates to FeOOH technical fields, belong to one kind under the premise of not destroying FeOOH structure,
Realize the technology of the separation of FeOOH surface and sulphur.
Background technology
FeOOH is in neutrality, and predominant crystal form includes α-FeooH, β-FeooH, γ-FeooH and amorphous hydroxyl
Base iron oxide is important one of desulfurizing agent, especially to containing higher concentration CO2Sulfurous gas desulfurization when, have nothing
Alternative advantage.
The desulfurization principle of FeOOH is：Hydroxyl (- OH) in FeOOH and H2HS displacements after S dissociation generate
FeSSH after FeOOH reaches its Sulfur capacity, is passed through oxygen, makes FeOOH thereto to achieve the effect that desulfurization
Regeneration, can then recycle.The specific desulfurization of FeOOH and regenerated reaction equation are as follows：
FeOOH+2H2S=FeSSH+2H2O
FeSSH+O2=FeOOH+2S；
But in actual production application, the sulphur generated after regeneration is attached to the surface of FeOOH mostly, blocks up
The gap on FeOOH is filled in so that the specific surface area of FeOOH reduces, while also making FeOOH surface
Desulphurizing activated site is reduced, and is declined so as to cause the desulphurizing ability of the FeOOH after regeneration, or even lose desulphurizing ability.
In order to solve the problems, such as to adhere to a large amount of sulphur on the FeOOH after regeneration, a variety of separation hydroxyls have been worked out
The method of iron oxide and sulphur.Currently, being using two kinds of relatively broad separation methods：
One, so that FeOOH and sulphur is detached by solvent of oil plants such as diesel oil, for example, Chinese patent literature
In CN104548934A, CN103771346A and CN103768944A, it is solvent, dissolving attachment to disclose using cracked diesel oil
Sulphur on FeOOH surface makes sulphur be precipitated then by crystallizing at low temperature.Although this method realizes hydroxyl oxygen
The separation of change iron and sulphur, but the complicated component of oil plant, this to increase the not true of many during dissolution of sulphur
It is qualitative, it is not only likely to result in new impurity and is introduced on FeOOH, but also is also unstable to the solubility of sulphur, increase
Operating error, and the sulphur of also part can form organic sulfur in diesel oil, and the difficult of organic sulfur is removed in oil plant.
Two, so that FeOOH and sulphur is detached by solvent of organic solution, for example, Lv Shiqi et al. is in " desulfurizing agent oxygen
Change the recycling research of sulphur in iron " text (《Contemporary chemical industry》, 2015) in disclose using tetrachloro-ethylene be solvent, in 40-80
At DEG C, dissolving is attached to the sulphur on FeOOH；Tetrachloro-ethylene toxicity is very big in the technical method, and environmental pollution is tight
Again, after and detaching FeOOH using the above method, the desulphurizing ability of FeOOH can be caused to reduce, the sulphur isolated
Contain a large amount of ferro element in sulphur.
Invention content
Therefore, the technical problem to be solved in the present invention is hydroxyl in the method for overcoming existing separation FeOOH and sulphur
The defect that base iron oxide desulphurizing ability declines, and then the method for sulphur and the hydroxyl for going sulphur removal on a kind of eliminating hydroxide iron oxide of offer
The application of iron oxide.
For this purpose, technical solution used by the present invention solves the above problems is as follows：
The method of sulphur, includes the following steps on a kind of eliminating hydroxide iron oxide：
(1) at less than or equal to 90 DEG C, sulfur-bearing FeOOH is carried out to remove water process, it is 0.1wt%- to make its water content
5wt%；
(2) by treated, sulfur-bearing FeOOH is mixed with toluene, is extracted, and is separated by solid-liquid separation, is obtained the hydroxyl of sulphur removal
Iron oxide.
Preferably, in the method, dry sulfur-bearing FeOOH to its water content is 0.2wt%-4wt%.
Preferably, in the method, extraction temperature is 50-90 DEG C.
Preferably, in the method, the mass ratio of sulfur-bearing FeOOH and toluene is 1：(5-30).
Preferably, in the method, further include：
(3) FeOOH of sulphur removal will be gone to be mixed with toluene, extracted, is separated by solid-liquid separation；Repeat the step at least twice.
Preferably, further include being separated by solid-liquid separation obtained sulfur-bearing solvent to step (2) to cool down in the method
Crystallization is separated by solid-liquid separation, the step of obtaining sulphur and recycle toluene.
Preferably, in the method, crystallisation by cooling temperature is 5-20 DEG C.
Preferably, in the method, the recycling toluene is recycled to step (2) or step (3).
A kind of desulfurizing agent includes the FeOOH for going sulphur removal obtained by herein described method.
It is a kind of to go application of the FeOOH of sulphur removal in desulfurization by what herein described method obtained.
Heretofore described sulfur-bearing FeOOH refers to the FeOOH that FeOOH surface is attached with sulphur.
The above-mentioned technical proposal of the present invention has the following advantages that：
1. the method for sulphur on eliminating hydroxide iron oxide provided by the invention, by strictly controlling containing for sulfur-bearing FeOOH
Water realizes under the premise of efficiently sulphur being made to be detached with FeOOH, effectively ensures the de- of FeOOH
The purity of sulphur ability and the sulphur of recycling；This is because inventor is it was unexpectedly observed that water content is to influence product sulphur and hydroxyl
The key for aoxidizing weight of iron can be dispersed into small particle when the water content in FeOOH is excessively high in organic solvent,
Not only increase the difficulty being separated by solid-liquid separation, but also the desulphurizing ability of FeOOH can be made to reduce, while also resulting in recycling
Contain a large amount of ferro element in sulphur afterwards.
It is solvent that toluene is selected in the present invention, and not only to the solubility of sulphur height, but also toxicity is low, is easily recycled profit
With.
2. the method for sulphur on eliminating hydroxide iron oxide provided by the invention is selected water content to be less than or equal to 1% toluene, is had
The FeOOH that avoids of effect disperses in toluene solvant, ensure that the desulfurization performance of FeOOH.
Specific implementation mode
Technical scheme of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair
Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
There is the every other embodiment obtained under the premise of making creative work, shall fall within the protection scope of the present invention.In addition, below
Involved technical characteristic as long as they do not conflict with each other can be mutual in described different embodiments of the present invention
In conjunction with.
For the ease of comparing, sulfur-bearing FeOOH in following example 1-6 and comparative example is to regenerate hydroxyl after desulfurization
Iron oxide, sulfur content 78%, iron content 16.7%, water content 29%, median are 18 μm, total surface area (BET method
Detection) 0.5m2/ g, Kong Rong (PV) 0.000378mL/g, bore dia (PD) 1.4nm.
Embodiment 1
The method for present embodiments providing sulphur on a kind of eliminating hydroxide iron oxide, includes the following steps：
(1) at a temperature of 10 DEG C, it is 5wt% to air-dry sulfur-bearing FeOOH to its water content；
(2) it is 1 according to mass ratio with toluene by the sulfur-bearing FeOOH after air-drying：10 are stirred 2h at 90 DEG C,
It is separated by solid-liquid separation, obtains sulfur-bearing solvent and removes the FeOOH A of sulphur removal；
(3) crystallisation by cooling at sulfur-bearing solvent is 5 DEG C in temperature, is separated by solid-liquid separation, obtains sulphur A (soluble sulphur).
Embodiment 2
The method for present embodiments providing sulphur on a kind of eliminating hydroxide iron oxide, includes the following steps：
(1) dry sulfur-bearing FeOOH to its water content is 0.1wt% at 90 DEG C；
(2) it is 1 according to mass ratio with toluene by the sulfur-bearing FeOOH after air-drying：15 are stirred 1h at 80 DEG C,
It is separated by solid-liquid separation, obtains the first sulfur-bearing solvent and the first FeOOH；
(3) it is 1 according to mass ratio by the first FeOOH and toluene：15 are stirred 1h at 80 DEG C, obtain second
Sulfur-bearing solvent and the second FeOOH；
(4) it is 1 according to mass ratio by the second FeOOH and toluene：15 are stirred 1h at 80 DEG C, are separated by solid-liquid separation,
It obtains third sulfur-bearing solvent and removes the FeOOH B of sulphur removal；
(5) merge the first, second, and third sulfur-bearing solvent, crystallisation by cooling at being 20 DEG C in temperature is separated by solid-liquid separation, obtains sulphur
Sulphur B (soluble sulphur).
Embodiment 3
The method for present embodiments providing sulphur on a kind of eliminating hydroxide iron oxide, includes the following steps：
(1) it is 0.2wt% that sulfur-bearing FeOOH to its water content is air-dried at 20 DEG C；
(2) it is 1 according to mass ratio with toluene by the sulfur-bearing FeOOH after air-drying：7 are stirred 3h at 50 DEG C, Gu
Liquid detaches, and obtains the first sulfur-bearing solvent and the first FeOOH；
(3) it is 1 according to mass ratio by the first FeOOH and toluene：7 are stirred 3h at 50 DEG C, are separated by solid-liquid separation,
Obtain the second sulfur-bearing solvent and the second FeOOH；
(4) it is 1 according to mass ratio by the second FeOOH and toluene：7 are stirred 3h at 50 DEG C, are separated by solid-liquid separation,
It obtains third sulfur-bearing solvent and removes the FeOOH C of sulphur removal；
(5) merge the first, second, and third sulfur-bearing solvent, crystallisation by cooling at being 10 DEG C in temperature is separated by solid-liquid separation, obtains sulphur
Sulphur C (soluble sulphur) and recycling toluene；
Recycling toluene can be recycled in step (2), (3) or (4) to be mixed with FeOOH, extracts sulphur thereon.
Embodiment 4
The method for present embodiments providing sulphur on a kind of eliminating hydroxide iron oxide, includes the following steps：
(1) it is 2wt% that sulfur-bearing FeOOH to its water content is air-dried at 35 DEG C；
(2) it is 1 according to mass ratio with toluene by the sulfur-bearing FeOOH after air-drying：10 are stirred 2h at 60 DEG C,
It is separated by solid-liquid separation, obtains the first sulfur-bearing solvent and the first FeOOH；
(3) it is 1 according to mass ratio by the first FeOOH and toluene：10 are stirred 2h at 60 DEG C, are separated by solid-liquid separation,
Obtain the second sulfur-bearing solvent and the second FeOOH；
(4) it is 1 according to mass ratio by the second FeOOH and toluene：10 are stirred 2h at 60 DEG C, are separated by solid-liquid separation,
It obtains third sulfur-bearing solvent and removes the FeOOH D of sulphur removal；
(5) merge the first, second, and third sulfur-bearing solvent, crystallisation by cooling at being 7 DEG C in temperature is separated by solid-liquid separation, obtains sulphur
Sulphur D (soluble sulphur).
Embodiment 5
The method for present embodiments providing sulphur on a kind of eliminating hydroxide iron oxide, includes the following steps：
(1) it is 4wt% that sulfur-bearing FeOOH to its water content is air-dried at 10 DEG C；
(2) it is 1 according to mass ratio with toluene by the sulfur-bearing FeOOH after air-drying：20 are stirred 2h at 65 DEG C,
It is separated by solid-liquid separation, obtains the first sulfur-bearing solvent and the first FeOOH；
(3) it is 1 according to mass ratio by the first FeOOH and toluene：20 are stirred 2h at 65 DEG C, are separated by solid-liquid separation,
Obtain the second sulfur-bearing solvent and the second FeOOH；
(4) it is 1 according to mass ratio by the second FeOOH and toluene：20 are stirred 2h at 65 DEG C, are separated by solid-liquid separation,
It obtains third sulfur-bearing solvent and removes the FeOOH E of sulphur removal；
(5) merge the first, second, and third sulfur-bearing solvent, crystallisation by cooling at being 11 DEG C in temperature is separated by solid-liquid separation, obtains sulphur
Sulphur E (soluble sulphur).
Embodiment 6
The method for present embodiments providing sulphur on a kind of eliminating hydroxide iron oxide, includes the following steps：
(1) it is 3wt% that sulfur-bearing FeOOH to its water content is air-dried at 15 DEG C；
(2) it is 1 according to mass ratio with toluene by the sulfur-bearing FeOOH after air-drying：30 are stirred 2h at 55 DEG C,
It is separated by solid-liquid separation, obtains the first sulfur-bearing solvent and the first FeOOH；
(3) it is 1 according to mass ratio by the first FeOOH and toluene：30 are stirred 2h at 55 DEG C, are separated by solid-liquid separation,
Obtain the second sulfur-bearing solvent and the second FeOOH；
(4) it is 1 according to mass ratio by the second FeOOH and toluene：30 are stirred 2h at 55 DEG C, are separated by solid-liquid separation,
It obtains third sulfur-bearing solvent and removes the FeOOH F of sulphur removal；
(5) merge the first, second, and third sulfur-bearing solvent, crystallisation by cooling at being 15 DEG C in temperature is separated by solid-liquid separation, obtains sulphur
Sulphur F (soluble sulphur).
Embodiment 7
The method for present embodiments providing sulphur on a kind of eliminating hydroxide iron oxide, includes the following steps：
(1) it is 3.5wt% to air-dry sulfur-bearing FeOOH to its water content at 5 DEG C；
(2) it is 1 according to mass ratio with toluene by the sulfur-bearing FeOOH after air-drying：5 are stirred 2h at 65 DEG C, Gu
Liquid detaches, and obtains the first sulfur-bearing solvent and the first FeOOH；
(3) it is 1 according to mass ratio by the first FeOOH and toluene：5 are stirred 2h at 65 DEG C, are separated by solid-liquid separation,
Obtain the second sulfur-bearing solvent and the second FeOOH；
(4) it is 1 according to mass ratio by the second FeOOH and toluene：5 are stirred 2h at 65 DEG C, are separated by solid-liquid separation,
It obtains third sulfur-bearing solvent and removes the FeOOH G of sulphur removal；
(5) merge the first, second, and third sulfur-bearing solvent, crystallisation by cooling at being 15 DEG C in temperature is separated by solid-liquid separation, obtains sulphur
Sulphur G (soluble sulphur).
Comparative example 1
The method that this comparative example provides sulphur on a kind of eliminating hydroxide iron oxide, includes the following steps：
(1) at a temperature of 10 DEG C, it is 10% to air-dry sulfur-bearing FeOOH to its water content；
(2) it is 1 according to mass ratio with toluene by the sulfur-bearing FeOOH after air-drying：10 are stirred 2h at 90 DEG C,
It is separated by solid-liquid separation, obtains sulfur-bearing solvent and removes the FeOOH H of sulphur removal；
(3) crystallisation by cooling at sulfur-bearing solvent is 5 DEG C in temperature, is separated by solid-liquid separation, obtains sulphur H.
Comparative example 2
The method that this comparative example provides sulphur on a kind of eliminating hydroxide iron oxide, includes the following steps：
(1) at a temperature of 100 DEG C, it is 10% to air-dry sulfur-bearing FeOOH to its water content；
(2) it is 1 according to mass ratio with toluene by the sulfur-bearing FeOOH after air-drying：10 are stirred 2h at 90 DEG C,
It is separated by solid-liquid separation, obtains sulfur-bearing solvent and removes the FeOOH I of sulphur removal；
(3) crystallisation by cooling at sulfur-bearing solvent is 5 DEG C in temperature, is separated by solid-liquid separation, obtains sulphur I.
Experimental example
1. what couple embodiment 1-6 was prepared goes the sulfur content of the FeOOH A-F of sulphur removal to be detected, the results are shown in Table
1。
Table 1
2. what couple embodiment 1-6 was prepared goes the removal that the FeOOH A-F of sulphur removal and comparative example 1-2 are prepared
The median of the FeOOH H and I of sulphur are detected, and the results are shown in Table 2.
Table 2
3. the purity of sulphur H and I that sulphur A-F and comparative example 1-2 that couple embodiment 1-6 is prepared are prepared carry out
Detection, the results are shown in Table 3.
Table 3
4. what couple embodiment 1-6 was prepared goes the removal that the FeOOH A-F of sulphur removal and comparative example 1-2 are prepared
The desulphurizing ability of the FeOOH H and I of sulphur the results are shown in Table 4 as detection.
Specifically detection method is：
It is 40 DEG C that the FeOOH of sulphur removal, control fixed bed reactors temperature are removed in filling in fixed bed reactors, will
The gas to be desulfurization of a concentration of 10000ppm of hydrogen sulfide passes through the fixed bed reactors desulfurization with the flow velocity of 0.4m/s.It detects
The concentration of hydrogen sulfide, testing result are shown in Table 4 at mouthful.
Table 4
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. the method for sulphur, includes the following steps on a kind of eliminating hydroxide iron oxide：
(1) at less than or equal to 90 DEG C, sulfur-bearing FeOOH is carried out to remove water process, it is 0.1wt%- to make its water content
5wt%；
(2) by treated, sulfur-bearing FeOOH is mixed with toluene, is extracted, and is separated by solid-liquid separation, and the hydroxyl oxidation of sulphur removal is obtained
Iron.
2. according to the method described in claim 1, it is characterized in that, dry sulfur-bearing FeOOH to its water content is
0.2wt%-4wt%.
3. method according to claim 1 or 2, which is characterized in that extraction temperature is 50-90 DEG C.
4. according to any methods of claim 1-3, which is characterized in that the mass ratio of sulfur-bearing FeOOH and toluene is
1：(5-30).
5. according to any methods of claim 1-4, which is characterized in that further include：
(3) FeOOH of sulphur removal will be gone to be mixed with toluene, extracted, is separated by solid-liquid separation；Repeat the step at least twice.
6. according to any methods of claim 1-5, which is characterized in that further include obtained by being separated by solid-liquid separation to step (2)
Sulfur-bearing solvent carry out crystallisation by cooling, be separated by solid-liquid separation, obtain sulphur and recycling toluene the step of.
7. according to the method described in claim 6, it is characterized in that, crystallisation by cooling temperature is 5-20 DEG C.
8. the method described according to claim 6 or 7, which is characterized in that the recycling toluene is recycled to step (2) or step
(3)。
9. a kind of desulfurizing agent, which is characterized in that the hydroxyl for going sulphur removal obtained including any the methods of claim 1-8 aoxidizes
Iron.
10. what a kind of any the methods of claim 1-8 obtained goes application of the FeOOH of sulphur removal in desulfurization.
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| CN201810265832.4A CN108298592B (en) | 2018-03-28 | 2018-03-28 | Method for removing sulfur on iron oxyhydroxide and application of iron oxyhydroxide for removing sulfur |
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| CN201810265832.4A CN108298592B (en) | 2018-03-28 | 2018-03-28 | Method for removing sulfur on iron oxyhydroxide and application of iron oxyhydroxide for removing sulfur |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110747004A (en) * | 2019-11-15 | 2020-02-04 | 河南科技大学 | Application of spinel ferrite magnetic nano catalyst in oil product desulfurization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1635057A (en) * | 2004-11-22 | 2005-07-06 | 太原理工大学 | Process for reclaiming sulfur from coal gas ferric oxide waste desulphurizer |
| CN101767777A (en) * | 2008-12-30 | 2010-07-07 | 北京三聚环保新材料股份有限公司 | Amorphous FeOOH and method for regenerating desulfurizing agent taking amorphous FeOOH as active ingredient |
-
2018
- 2018-03-28 CN CN201810265832.4A patent/CN108298592B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1635057A (en) * | 2004-11-22 | 2005-07-06 | 太原理工大学 | Process for reclaiming sulfur from coal gas ferric oxide waste desulphurizer |
| CN101767777A (en) * | 2008-12-30 | 2010-07-07 | 北京三聚环保新材料股份有限公司 | Amorphous FeOOH and method for regenerating desulfurizing agent taking amorphous FeOOH as active ingredient |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110747004A (en) * | 2019-11-15 | 2020-02-04 | 河南科技大学 | Application of spinel ferrite magnetic nano catalyst in oil product desulfurization |
| CN110747004B (en) * | 2019-11-15 | 2021-08-24 | 河南科技大学 | Application of spinel ferrite magnetic nano catalyst in oil product desulfurization |
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