CN100334186C - Process of purifying and recovering waste acid after coking refined benzene - Google Patents
Process of purifying and recovering waste acid after coking refined benzene Download PDFInfo
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- CN100334186C CN100334186C CNB2004100607650A CN200410060765A CN100334186C CN 100334186 C CN100334186 C CN 100334186C CN B2004100607650 A CNB2004100607650 A CN B2004100607650A CN 200410060765 A CN200410060765 A CN 200410060765A CN 100334186 C CN100334186 C CN 100334186C
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- benzol
- ammonium sulfate
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Abstract
The present invention relates to a process for purifying and recovering the waste acid of coking refinement benzene. The new process for purifying the waste acid of the refinement benzene by a polycondensing and extraction processing process is used, and a polymerization promoting agent is added into the waste acid of the refinement benzene to carry out stirring reaction for 10 to 240 min at the temperature of 40 to 160DEGC. After a product is cooled to room temperature to 60DEGC, the product is filtered to remove a solid polymer; a salt separating agent and an extraction agent are added to carry out heat preservation stirring for 5 to 120 min at the temperature of 25 to 120 DEG C, and heat preservation temperature is preferably the room temperature to 60DEGC; then, the mixture is statically placed for 1.0 to 24 hr at the constant temperature of 25 to 110DEGC to obtain purified acid. The added compound has a volume ratio that the waste acid to the polymerization promoting agent to the salt separating agent to the extraction agent is equal to 100/1 to 50/0 to 60/10 to 100. The present invention has the characteristics of low cost, small energy consumption, simple flow path, less investment, low processing temperature and difficult secondary pollution. A COD elimination rate of the purified acid obtained after purification recovery is from 75 to 95%. The purified acid of which the chrominance elimination rate is larger than 90% is used as replenishing acid for producing acid ammonium to be used, and solid residues can be returned to a coal depot to be used as mixing coal.
Description
One, technical field
The invention belongs to the refining recovery technology of coke-oven plant's sulfuric acid scrubbing light benzene, relate in particular to a kind of method that reclaims the coking waste acid from benzol refining that purifies.
Two, background technology
The coking waste acid from benzol refining claims regenerating acid (being designated hereinafter simply as waste acid from benzol refining) again, is the coke-oven plant with the spent acid of a kind of chocolate of producing in the sulfuric acid scrubbing light benzene refining and reclaiming technology.In the light benzene acid cleaning process, some arenes such as compounds such as benzene, naphthalene in the light benzene, resemble in addition thiophene like this some heterogeneous ring compounds all can generate sulfonated bodies and be dissolved among the spent acid with sulfuric acid generation sulfonation reaction.In addition, but some unsaturated hydro carbons polymerization reaction take place also under an acidic catalyst effect generates the different polymkeric substance of the polymerization degree.In the process of leaving standstill, the polymkeric substance that the polymerization degree is higher, macromolecular sulfonated bodies and the miscible formation chocolate of spent acid heavy-gravity acid tar are called Acid Tar in Crude Benzene mutually; And mutually sour than polymkeric substance, the small molecules sulfonated bodies of low polymerization degree with the miscible formation chocolate of sulfur waste acid, be called waste acid from benzol refining.Acid content 25～35% in the Acid Tar in Crude Benzene, and acid content accounts for 35～50% in the waste acid from benzol refining.
Waste acid from benzol refining is extremely unmanageable industrial effluent, though multiple treatment process was researched and proposed in the chamber by experiment, does not see examples of industrial applications so far as yet.The method of document suggestion has absorption method, extraction process, combustion method and hot polymerization legal etc.Absorption method is to use sorbent material, removes organism and pigment.This method greatest problem is that most sorbent materials are acidproof indifferent and very fragile, and most sorbent material costs an arm and a leg, and running cost is very high, makes process hard to carry on; Combustion method is under 600～800 ℃ high temperature, and sulfuric acid in the waste acid from benzol refining and organism are decomposed into SO
2, CO
2And H
2O absorbs SO with contact process then
2Produce concentration and be 96%～98% the vitriol oil.But this method need be in the coke-oven plant be built a cover sulfuric acid production line separately for utilizing waste acid from benzol refining to produce sulfuric acid, and flow process is complicated and facility investment is big, also can be potential the dirty source problem of new environment occurs because of gas washing in SA production; Extraction process is according to the similar principle that mixes, and selects the organism in the suitable extraction agent purification separation waste acid from benzol refining, and normally used extraction agent has dimethylbenzene Residual oil, heavy benzol solvent oil, removal phenol carbolic oil, benzene slag and crude phenols etc.Wherein the effect of extracting with crude phenols is best, and it is fast that it has a layering, handles the advantage such as light and transparent of after acid.COD clearance in the extraction back acid can reach 50%～80%.The problem that extraction process exists is that extraction agent may form polymkeric substance with the unsaturated compound that exists in the waste acid from benzol refining, and causes the consumption of extraction agent excessive, and running cost rises; Hot polymerization is legal to be that waste acid from benzol refining is condensed into 75%～85% concentration, and is heated to 160 ℃～220 ℃, makes the unsaturated compound reacting generating copolymer, and thin up makes polymkeric substance fold, filter then, obtains can be used for the purification acid that ammonium sulfate is produced.This method temperature of reaction height, energy consumption is big, and the sour quality after the regeneration is still relatively poor.
Three, summary of the invention
The objective of the invention is to reclaim on the technology basis in traditional pickling, provide that a kind of technical process is simple, temperature of reaction is low, energy consumption is little, less investment, cost coking waste acid from benzol refining low, that be difficult for taking place to pollute once more purify recovery technology, pollutes control problem to solve waste acid from benzol refining.
For achieving the above object, the present invention adopts polycondensation-extraction treatment method to purify the novel process of waste acid from benzol refining, and concrete technical scheme is: add short poly-agent in waste acid from benzol refining, stirring reaction 10～240min between 40～160 ℃, after being cooled to room temperature～60 ℃, remove by filter solid polymer; Add salting-out agent, extraction agent again, insulated and stirred under 25～120 ℃, 5～120min condition, constant temperature leaves standstill 1.0～24hr under 25～110 ℃ of conditions then.The insulated and stirred temperature that adds salting-out agent, extraction agent is with room temperature～60 ℃ the best.Wherein:
Short poly-agent is a kind of compound in formaldehyde, hexamethylenetetramine, ethene, propylene, divinyl, the cyclopentadiene or the mixture be made up of more than one compound;
Salting-out agent are one or more the mixture in solid ammonium sulfate, ammonium sulfate solution, the ammonium sulfate liquor;
Extraction agent is one or more the mixture in crude phenols, mixed phenol, carbolic oil, washing oil, solvent oil, the heavy benzol Residual oil.
The volume ratio of above-mentioned admixture is: waste acid from benzol refining/short poly-agent/salting-out agent/extraction agent is 100/1～50/0～60/10～100.Extraction agent adopts to steam and blows method regeneration, and steaming is blown back gained solvent cycle and used.
Owing to adopt technique scheme, the present invention has that cost is low, energy consumption is little, flow process is simple, less investment, temperature of reaction are low, be difficult for taking place pollution characteristics once more, has solved the spent acid pollution problem effectively.Purifying the purification acid COD decreasing ratio that obtains after reclaiming is 75～95%, and the colourity decreasing ratio is＞90%.
Four, description of drawings
Fig. 1 is a kind of process flow sheet of the present invention.
Five, embodiment
Below in conjunction with embodiment, the present invention is further described.
[embodiment] 1
Get a certain amount of coking waste acid from benzol refining, add desired compound by technical process shown in Figure 1, the volume ratio that adds compound is: waste acid from benzol refining/formaldehyde/ammonium sulfate liquor/crude phenols are 100/30/30/30.
The technical process of present embodiment as shown in Figure 1, its processing condition are to add short poly-agent formaldehyde in the coking waste acid from benzol refining, are heated to 95 ℃ of stirrings, after carrying out polycondensation 1hr, be cooled to below 60 ℃, remove by filter the particulate solid thing, the particulate solid thing can be delivered coal and to be recycled.Add the salting-out agent ammonium sulfate liquor in the filtrate after overanxious, under 100 ℃ of conditions, stir 30min and saltout, add the extraction agent crude phenols again, keep and stir extraction 1hr under the same temperature.Extraction back obtains faint yellow purifications acid at 70 ℃ of following constant temperature standing demix 2hr, send ammonium sulfate workshop section to be used as supplemental acid, the recovery of delivering coal of the regeneration slag of generation.Extraction phase makes extraction agent obtain regeneration after steaming is blown, and recycles.Filter residue is the porous solid particle, and is dry down at 105 ℃.Use aforesaid method, solid residue productive rate 11.7%, COD decreasing ratio 81.7%, colourity decreasing ratio 96.5%.
[embodiment] 2
Get a certain amount of coking waste acid from benzol refining, add desired compound by technical process shown in Figure 1, the volume ratio that adds compound is: waste acid from benzol refining/formaldehyde/ammonium sulfate liquor/crude phenols are 100/35/10/30.
The technical process of present embodiment is with embodiment 1.Add short poly-agent formaldehyde in the coking waste acid from benzol refining, stirring reaction 20min removes by filter solid polymer between 100～125 ℃.Add the salting-out agent ammonium sulfate liquor filtrate, add the extraction agent crude phenols behind the stirring 20min down,,, obtain faint yellow purification acid at 70 ℃ of following constant temperature standing demix 2hr to stir extraction 15min under the same temperature at 100 ℃.Filter residue is the porous solid particle, and is dry down at 105 ℃.Use aforesaid method, the solid residue productive rate is 12.00%, COD decreasing ratio 83.5%, colourity decreasing ratio 95.6%.
[embodiment] 3
Get a certain amount of coking waste acid from benzol refining, add desired compound by technical process shown in Figure 1, the volume ratio that adds compound is: waste acid from benzol refining/formaldehyde/ammonium sulfate liquor/crude phenols are 100/40/10/30.
The technical process of present embodiment is with embodiment 1.In the coking waste acid from benzol refining, add short poly-agent formaldehyde, stirring reaction 20hr between 100～125 ℃.Remove by filter solid polymer.Add the salting-out agent ammonium sulfate liquor filtrate, after stirring 10min between 45～50 ℃, add the extraction agent crude phenols, keep and stir extraction 15min under the same temperature, naturally cool to room temperature, leave standstill 12 hr after, it is sour to obtain faint yellow purifications.Filter residue is the porous solid particle, and is dry down at 105 ℃.Use aforesaid method, the solid residue productive rate is 12.20%, COD decreasing ratio 82.85%, colourity decreasing ratio 96.2%.
[embodiment] 4
Get a certain amount of coking waste acid from benzol refining, add desired compound by technical process shown in Figure 1, the volume ratio that adds compound is: waste acid from benzol refining/formaldehyde/sulphur ammonium crystal/crude phenols are 100/35/10/30.
The technical process of present embodiment is with embodiment 1.In the coking waste acid from benzol refining, add short poly-agent formaldehyde, stirring reaction 20min between 100～125 ℃.Remove by filter solid polymer.Add salting-out agent sulphur ammonium crystal filtrate, holding temperature stirs 10min between 40～60 ℃, add the extraction agent crude phenols, under above-mentioned uniform temp, stirs extraction 20min, naturally cools to room temperature, leave standstill 12hr after, it is sour to obtain faint yellow purifications.Filter residue is the porous solid particle, and is dry down at 105 ℃.Use aforesaid method, the solid residue productive rate is 13.20%, COD decreasing ratio 85.65%, colourity decreasing ratio 93.20%.
[embodiment] 5
Get a certain amount of coking waste acid from benzol refining, add desired compound down by technical process shown in Figure 1, the volume ratio of admixture is: waste acid from benzol refining/formaldehyde/crude phenols are 100/35/30.
The technical process of present embodiment is with embodiment 1.In the coking waste acid from benzol refining, add short poly-agent formaldehyde, stirring reaction 20min between 100～125 ℃.Remove by filter solid polymer.Add the extraction agent crude phenols filtrate, temperature stirs extraction 20min between 40～60 ℃, naturally cool to room temperature, leave standstill 12hr after, it is sour to obtain faint yellow purifications.Filter residue is the porous solid particle, and is dry down at 105 ℃.Use aforesaid method, the solid residue productive rate is 12.83%, COD decreasing ratio 80.65%, colourity decreasing ratio 90.2%.
Claims (3)
1, a kind of method that reclaims the coking waste acid from benzol refining that purifies is characterized in that adding short poly-agent in described waste acid from benzol refining, stirring reaction 10～240min between 40～160 ℃, be cooled to room temperature～60 ℃ after, remove by filter solid polymer; Add salting-out agent, extraction agent again, insulated and stirred under 25～120 ℃, 5～120min condition; Constant temperature leaves standstill 1.0～24hr under 25～110 ℃ of conditions then;
Described short poly-agent is a kind of compound in formaldehyde, hexamethylenetetramine, ethene, propylene, divinyl, the cyclopentadiene or the mixture be made up of more than one compound;
Described salting-out agent are one or more the mixture in solid ammonium sulfate, ammonium sulfate solution, the ammonium sulfate liquor;
Described extraction agent is a kind of in crude phenols, mixed phenol, carbolic oil, washing oil, solvent oil, the heavy benzol Residual oil.
2, a kind of method that reclaims the coking waste acid from benzol refining that purifies is characterized in that adding short poly-agent in described waste acid from benzol refining, stirring reaction 10～240min between 40～160 ℃, be cooled to room temperature～60 ℃ after, remove by filter solid polymer; Add salting-out agent, extraction agent again, insulated and stirred under 25～120 ℃, 5～120min condition; Constant temperature leaves standstill 1.0～24hr under 25～110 ℃ of conditions then;
Described short poly-agent is a kind of compound in formaldehyde, hexamethylenetetramine, ethene, propylene, divinyl, the cyclopentadiene or the mixture be made up of more than one compound;
Described salting-out agent are one or more the mixture in solid ammonium sulfate, ammonium sulfate solution, the ammonium sulfate liquor;
Described extraction agent is a kind of in crude phenols, mixed phenol, carbolic oil, washing oil, solvent oil, the heavy benzol Residual oil;
The volume ratio of admixture is: waste acid from benzol refining/short poly-agent/salting-out agent/extraction agent is 100/1～50/0～60/10～100.
3, the method for coking waste acid from benzol refining is reclaimed in purification according to claim 1, it is characterized in that described extraction agent adopts steaming to blow method regeneration, and steaming is blown back gained solvent cycle and used.
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| CNB2004100607650A CN100334186C (en) | 2004-08-25 | 2004-08-25 | Process of purifying and recovering waste acid after coking refined benzene |
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| CN100334186C true CN100334186C (en) | 2007-08-29 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0121337A1 (en) * | 1983-03-03 | 1984-10-10 | Unitika Ltd. | Method for purification of sulfuric acid solution |
| CN1113214A (en) * | 1994-06-06 | 1995-12-13 | 李静怡 | Method for purifying and treating regenerated acid of coking plant |
| CN1255457A (en) * | 1998-11-30 | 2000-06-07 | 上海梅山(集团)有限公司 | Process for purifying and reclaiming regenerated acid in coking plant |
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2004
- 2004-08-25 CN CNB2004100607650A patent/CN100334186C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0121337A1 (en) * | 1983-03-03 | 1984-10-10 | Unitika Ltd. | Method for purification of sulfuric acid solution |
| CN1113214A (en) * | 1994-06-06 | 1995-12-13 | 李静怡 | Method for purifying and treating regenerated acid of coking plant |
| CN1255457A (en) * | 1998-11-30 | 2000-06-07 | 上海梅山(集团)有限公司 | Process for purifying and reclaiming regenerated acid in coking plant |
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| CN1740275A (en) | 2006-03-01 |
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