CN103408097B - Method for removing sulfides in coking wastewater - Google Patents
Method for removing sulfides in coking wastewater Download PDFInfo
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- CN103408097B CN103408097B CN201310377300.7A CN201310377300A CN103408097B CN 103408097 B CN103408097 B CN 103408097B CN 201310377300 A CN201310377300 A CN 201310377300A CN 103408097 B CN103408097 B CN 103408097B
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Abstract
The invention discloses a method for removing sulfides in coking wastewater. The method comprises the following steps of: (1) putting dry-quenched coke particles into an airtight carbonization chamber, and heating for 1-3 hours under the protection of N2 gas to increase the temperature to the range from 750 to 850 DEG C; (2) taking out the dry-quenched coke particles and cooling the coke particles until the temperature of the dry-quenched coke particles reaches the room temperature, and then putting the dry-quenched coke particles into an alkaline liquor activator, and furthermore, putting the dry-quenched coke particles into a K2CO3 solution for oxidizing modification to improve the adsorption performance of the coke particles; (3) drying the modified coke particles in an oven, thus obtaining a modified similar activated carbon material; (4) feeding the similar activated carbon material into coking wastewater, and rotating on a magnetic stirrer at the normal temperature; and (5) filtering the coking wastewater treated previously, and then adding H2O2, and rotating by using the magnetic stirrer at the normal temperature to remove the sulfides in the wastewater. On one hand, the method is capable of remarkably improving the sulfide removal efficiency; and on the other hand, the method is capable of reducing the cost of removing the sulfides from the coking wastewater, realizing recycling of partial solid wastes and thus achieving the purpose of energy conservation and environmental protection.
Description
Technical field
The present invention relates to field of waste water treatment, specifically refer to a kind of method removing coking chemical waste water medium sulphide content.
Background technology
Along with the fast development of China's industry, a large amount of sulfide enters into waste water, due to sulfide poisonous and harmful, causes very large threat to ecotope.In recent years, along with country is to the further strengthening of environmental requirement, simultaneously in order to ensure that whole water technology, equipment are steady in a long-term, reliability service, taking suitable method to carry out effectively process to the sulfide in waste water and seeming particularly urgent.
The waste water sulfide composition that different industries is discharged differs greatly, and the method for process is also different.Common treatment process has following several:
1. acidifying absorption process: by acid adding in sulfur-containing waste water, make sulfide generate the hydrogen sulfide of highly volatile in acid condition, then use alkali liquor absorption hydrogen sulfide, generates Sodium Sulphide reuse.
2. chemical precipitation method: by adding ferrous salt or molysite in waste water, is made itself and H2S generate insoluble solid, is then removed by solid-liquid separation.
3. absorption method: by adding suitable sorbent material in waste water, utilizes that its specific surface area is large, the feature of high adsorption capacity makes sulfide be adsorbed removing.
4. air oxidation process: utilize air that negative sulfidion is oxidized to nontoxic thiosulphate and vitriol.
5. advanced oxidation processes: advanced oxidation processes uses electricity, optical radiation, catalyzer etc. to be combined with common oxidizer, produces the strong oxidizer hydroxyl radical free radical etc. that oxidation capacity is extremely strong, oxidation removal sulfide.
6. biochemical process: utilize various microorganism make sulfide oxidized and reclaim, product is sulphur simple substance or vitriol.
Sulfides from wastewater minimizing technology respectively has superiority and defect: although air oxidation process and acidifying absorption process easy to operate, equipment is simple, and efficiency is not high, and easily causes hydrogen sulfide to enter topsoil environment; Chemical precipitation method and absorption method instant effect, but consume pharmaceutical quantities greatly, cost is high; Advanced oxidation processes efficiency is high, but requires high to reactor, capital intensive; Biochemical process investment is less, but stability is not as physico-chemical process, and is not suitable for the very high waste water of sulfide concentration.Therefore, for the sulfur-containing waste water of different sources, theoretical analysis is combined with field experiment and determines suitable method or combination process, be only wise move.
The various removal technology Problems existing of current coking chemical waste water sulfide mainly contain the following aspects: 1, removal efficiency is not high, easy contaminate environment; 2, capital intensive, cost is high; 3, engineer applied stability is inadequate.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of removal efficiency high, free from environmental pollution; Cost of investment is low; Engineer applied stability removes by force the method for coking chemical waste water medium sulphide content.
For achieving the above object, the method for removal coking chemical waste water medium sulphide content provided by the invention, is characterized in that: it comprises the steps:
(1) dry coke quenching is broken or be sieved into particle diameter 80 ~ 300 object dry coke quenching particle, then put into airtight coking chamber, at N
2750 ~ 850 DEG C are warmed up to, heating 1 ~ 3h under gas shield;
(2) the dry coke quenching particle after heating taken out be cooled to room temperature, put into that temperature is 80 ~ 100 DEG C, mass concentration be 15 ~ 50% alkali lye activator process 1.5 ~ 2.5h, put into that temperature is 60 ~ 80 DEG C, mass concentration is the K of 30 ~ 35% subsequently
2cO
3carry out oxidation modification in solution, treatment time 1 ~ 3h, increase the absorption property of burnt grain;
(3) modified dry coke quenching grain is dried under 100 ~ 150 DEG C of conditions, obtain the class absorbent charcoal material of modification;
(4) such absorbent charcoal material is dropped in coking chemical waste water, under normal temperature, on magnetic stirring apparatus, rotate 0.5 ~ 3h;
(5) coking chemical waste water after process is filtered, add H subsequently
2o
2, rotate 0.5 ~ 1h with magnetic stirring apparatus under normal temperature, sulfide wherein can be removed.
Preferably, in described step (2), alkali lye activator is KOH or NaOH.
Preferably, in described step (2), at K
2cO
3the temperature of carrying out oxidation modification in solution is 70 DEG C.
Preferably, in described step (3), it is 100 DEG C by modified dry coke quenching grain bake out temperature.
Preferably, in described step (4), the concentration of class absorbent charcoal material in coking chemical waste water of input is 50g/L, and the rotating speed on magnetic stirring apparatus is 200r/min.
Preferably, in described step (5), H
2o
2be 0.03 ~ 0.05: 1 with the volume ratio of coking chemical waste water; Rotating speed on magnetic stirring apparatus is 100r/min.
The invention has the advantages that: the invention provides a kind of hydrogen peroxide oxidation and class absorbent charcoal material adsorbs the method combined, sulfide removal efficiency can be significantly improved on the one hand, the cost removing coking chemical waste water sulfide can be reduced on the other hand, realize the resource utilization of part solid waste, reach the object of energy-saving and environmental protection, specific as follows:
1) hydrogen peroxide oxidation ability is strong, and efficiency is high, and can remove sulfide by the efficient oxidation, simultaneously follow-up adsorption precipitation effect, treatment effect is more obvious; The sludge quantity produced is few, and cost is low.
2) hydrogen peroxide and class absorbent charcoal material adsorb the catalysed oxidn that conbined usage occurs, and water outlet can be made to reach GB16171-2012 " coking chemistry emission of industrial pollutants standard " (< 0.5mg/L).
3) such absorbent charcoal material adopts coking to discard the self-control of dry coke quenching grain to form, can reduce on the one hand the cost removing coking chemical waste water sulfide, can realize the resource utilization of part solid waste on the other hand, reach the object of energy-saving and environmental protection.
4) the method has effective, and flow process is simple, easy handling, management.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment one:
(1) be that 250 order dry coke quenching particle 25g put into the inherent N of airtight coking chamber by particle diameter
2850 DEG C of heating 1h are warmed up under gas shield;
(2), after above-mentioned particle taking-up being cooled to room temperature, the concentration putting into 80 DEG C is treatment time 2h in 15%KOH solution (wt, mass concentration), and the concentration putting into 80 DEG C is subsequently 32%K
2cO
3solution carries out oxidation modification, treatment time 1h, increases the absorption property of dry coke quenching;
(3) by dry for modified dry coke quenching grain drying in oven under 100 DEG C of conditions, the class absorbent charcoal material of modification is namely obtained.
(4) dropped in 100ml coking chemical waste water by such absorbent charcoal material 5g, under normal temperature, on magnetic stirring apparatus, (200r/min) rotates 0.5h;
(5) coking chemical waste water is after treatment filtered, add 5mlH subsequently
2o
2, under normal temperature, on magnetic stirring apparatus, (100r/min) rotates 0.5h;
(6) through aforesaid method process, the clearance of sulfide can reach 90%.
Embodiment two:
(1) be that 300 order dry coke quenching particle 30g put into the inherent N of airtight coking chamber by particle diameter
2750 DEG C of heating 2h are warmed up under gas shield;
(2), after above-mentioned particle taking-up being cooled to room temperature, the concentration putting into 85 DEG C is treatment time 2h in 30%KOH solution (wt, mass concentration), and the concentration putting into 60 DEG C is subsequently 35%K
2cO
3solution carries out oxidation modification, treatment time 3h, increases the absorption property of dry coke quenching;
(3) by dry for modified dry coke quenching grain drying in oven under 130 DEG C of conditions, the class absorbent charcoal material of modification is namely obtained.
(4) dropped in 200ml coking chemical waste water by such absorbent charcoal material 10g, under normal temperature, on magnetic stirring apparatus, (200r/min) rotates 3h;
(5) coking chemical waste water is after treatment filtered, add 10mlH subsequently
2o
2, under normal temperature, on magnetic stirring apparatus, (100r/min) rotates 1h;
(6) through aforesaid method process, the clearance of sulfide can reach 90%.
Embodiment three:
(1) be that 80 order dry coke quenching particle 30g put into the inherent N of airtight coking chamber by particle diameter
2800 DEG C of heating 3h are warmed up under gas shield;
(2), after above-mentioned particle taking-up being cooled to room temperature, the concentration putting into 100 DEG C is treatment time 2h in 50%NaOH solution (wt, mass concentration), and the concentration putting into 70 DEG C is subsequently 30%K
2cO
3solution carries out oxidation modification, treatment time 2h, increases the absorption property of dry coke quenching;
(3) by dry for modified dry coke quenching grain drying in oven under 150 DEG C of conditions, the class absorbent charcoal material of modification is namely obtained.
(4) dropped in 300ml coking chemical waste water by such absorbent charcoal material 15g, under normal temperature, on magnetic stirring apparatus, (200r/min) rotates 2h;
(5) coking chemical waste water is after treatment filtered, add 10mlH subsequently
2o
2, under normal temperature, on magnetic stirring apparatus, (100r/min) rotates 0.8h;
(6) through aforesaid method process, the clearance of sulfide can reach 90%.
The present invention in August, 2012 ~ November carried out lab scale test in laboratory, under suitable processing condition, experimental result indicates that water cure thing reaches GB 16171-2012 " coking chemistry emission of industrial pollutants standard " (< 0.5mg/L).
Claims (5)
1. remove a method for coking chemical waste water medium sulphide content, it is characterized in that: it comprises the steps:
(1) by dry coke quenching grain breakage or be sieved into particle diameter 80 ~ 300 object dry coke quenching particle, airtight coking chamber is then put into, at N
2750 ~ 850 DEG C are warmed up to, heating 1 ~ 3h under gas shield;
(2) the dry coke quenching particle after heating taken out be cooled to room temperature, put into that temperature is 80 ~ 100 DEG C, mass concentration be 15 ~ 50% alkali lye activator process 1.5 ~ 2.5h, put into that temperature is 60 ~ 80 DEG C, mass concentration is the K of 30 ~ 35% subsequently
2cO
3carry out oxidation modification in solution, treatment time 1 ~ 3h, increase the absorption property of burnt grain;
(3) modified dry coke quenching grain is dried under 100 ~ 150 DEG C of conditions, obtain the class absorbent charcoal material of modification;
(4) such absorbent charcoal material is dropped in coking chemical waste water, under normal temperature, on magnetic stirring apparatus, rotate 0.5 ~ 3h;
(5) coking chemical waste water after process is filtered, add H subsequently
2o
2, rotate 0.5 ~ 1h with magnetic stirring apparatus under normal temperature, sulfide wherein can be removed;
In described step (2), alkali lye activator is KOH or NaOH.
2. the method for removal coking chemical waste water medium sulphide content according to claim 1, is characterized in that: in described step (2), at K
2cO
3the temperature of carrying out oxidation modification in solution is 70 DEG C.
3. the method for removal coking chemical waste water medium sulphide content according to claim 1, is characterized in that: in described step (3), is 100 DEG C by modified dry coke quenching grain bake out temperature.
4. the method for removal coking chemical waste water medium sulphide content according to claim 1, is characterized in that: in described step (4), and the concentration of class absorbent charcoal material in coking chemical waste water of input is 50g/L, and the rotating speed on magnetic stirring apparatus is 200r/min.
5. the method for removal coking chemical waste water medium sulphide content according to claim 1, is characterized in that: in described step (5), H
2o
2be 0.03 ~ 0.05: 1 with the volume ratio of coking chemical waste water; Rotating speed on magnetic stirring apparatus is 100r/min.
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|---|---|---|---|
| CN201310377300.7A CN103408097B (en) | 2013-08-27 | 2013-08-27 | Method for removing sulfides in coking wastewater |
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|---|---|---|---|
| CN201310377300.7A CN103408097B (en) | 2013-08-27 | 2013-08-27 | Method for removing sulfides in coking wastewater |
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| CN103408097A CN103408097A (en) | 2013-11-27 |
| CN103408097B true CN103408097B (en) | 2015-06-10 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004204132A (en) * | 2002-12-26 | 2004-07-22 | Nippon Steel Corp | Method for reducing sulfur compound contained in gas in coke dry quenching equipment |
| CN101434422A (en) * | 2008-12-03 | 2009-05-20 | 中国石油大学(华东) | Method for pretreatment of sulfur-containing wastewater after refinery gas extraction by using activated refinery coke |
| CN102921375A (en) * | 2012-10-09 | 2013-02-13 | 常州大学 | Composite adsorption material for removing sulfur ions in natural water and preparation method of composite adsorption material |
| CN103159330A (en) * | 2013-04-07 | 2013-06-19 | 武汉钢铁(集团)公司 | Porous light-weight carbon-based biological carrier and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8097185B2 (en) * | 2002-02-26 | 2012-01-17 | University Of Utah Research Foundation | Magnetic activated carbon particles for adsorption of solutes from solution |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004204132A (en) * | 2002-12-26 | 2004-07-22 | Nippon Steel Corp | Method for reducing sulfur compound contained in gas in coke dry quenching equipment |
| CN101434422A (en) * | 2008-12-03 | 2009-05-20 | 中国石油大学(华东) | Method for pretreatment of sulfur-containing wastewater after refinery gas extraction by using activated refinery coke |
| CN102921375A (en) * | 2012-10-09 | 2013-02-13 | 常州大学 | Composite adsorption material for removing sulfur ions in natural water and preparation method of composite adsorption material |
| CN103159330A (en) * | 2013-04-07 | 2013-06-19 | 武汉钢铁(集团)公司 | Porous light-weight carbon-based biological carrier and preparation method thereof |
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Effective date of registration: 20170718 Address after: 430083, Hubei Wuhan Qingshan District Factory No. 2 Gate joint stock company organs Patentee after: Wuhan iron and Steel Company Limited Address before: 430080 Wuchang, Hubei Friendship Road, No. A, block, floor 999, 15 Patentee before: Wuhan Iron & Steel (Group) Corp. |
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Granted publication date: 20150610 Termination date: 20190827 |