CN1740275A - 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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- CN1740275A CN1740275A CNA2004100607650A CN200410060765A CN1740275A CN 1740275 A CN1740275 A CN 1740275A CN A2004100607650 A CNA2004100607650 A CN A2004100607650A CN 200410060765 A CN200410060765 A CN 200410060765A CN 1740275 A CN1740275 A CN 1740275A
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Abstract
The present invention adopts polycondensation-extraction process to purify refined benzene waste acid. The process includes adding polymerization promoter into the waste acid to react at 40-160 deg.c via stirring for 10-240 min, cooling to room temperature-60 deg.c and filtering to eliminate solid polymer; adding salting out agent and extractant, maintaining in room temperature-60 deg.c and stirring; and maintaining at 25-110 deg.c for 1-24 hr to obtain purified acid. The added chemicals are in the volume ratio of waste acid 100, polymerization promoter 1-50, salting out agent 0-60 and extractant 10-100. The present invention has low cost, low power consumption, simple process, low investment, low treating temperature and less secondary pollution. The purified acid has COD eliminating rate of 75-95 % and chroma eliminating rate higher than 90 %.
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 regenerating acid 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 spent acid 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 spent acid, 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 spent acid, and causes the consumption of extraction agent excessive, and running cost rises; Hot polymerization is legal to be that spent acid 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.
The volume ratio that adds above-claimed cpd is: spent acid/short is poly-, and agent/salting-out agent/extraction agent is 100/1～50/0～60/10～100.Wherein:
Short poly-agent is one or both or the two or more compound in the olefines unsaturated compounds such as formaldehyde, hexamethylenetetramine, ethene, propylene, divinyl, cyclopentadiene;
Salting-out agent are a kind of in solid ammonium sulfate, ammonium sulfate solution, the ammonium sulfate liquor;
Extraction agent be in crude phenols, mixed phenol, carbolic oil, washing oil, solvent oil, the heavy benzol Residual oil one or both or two or more compound; Extraction agent also can adopt to steam and blow method regeneration, and steaming is blown back gained solvent and be can be recycled.
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 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 12.20%, 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 (7)
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.
2, the method for coking waste acid from benzol refining is reclaimed in purification according to claim 1, it is characterized in that adding the insulated and stirred temperature of salting-out agent, extraction agent with room temperature～60 ℃ the best.
3, the method for coking waste acid from benzol refining is reclaimed in purification according to claim 1, it is characterized in that the volume ratio that adds compound is: spent acid/short is poly-, and agent/salting-out agent/extraction agent is 100/1～50/0～60/10～100.
4, reclaim the method for coking waste acid from benzol refining according to claim 1 and 3 described purifications, it is characterized in that described short poly-agent is one or both or the two or more compound in the olefines unsaturated compounds such as formaldehyde, hexamethylenetetramine, ethene, propylene, divinyl, cyclopentadiene.
5, reclaim the method for coking waste acid from benzol refining according to claim 1 and 2 described purifications, it is characterized in that described salting-out agent are one or both or the two or more compounds in solid ammonium sulfate, ammonium sulfate solution, the ammonium sulfate liquor.
6, reclaim the method for coking waste acid from benzol refining according to claim 1 and 2 described purifications, it is characterized in that described extraction agent is a kind of in crude phenols, mixed phenol, carbolic oil, washing oil, solvent oil, the heavy benzol Residual oil.
7, the method for coking waste acid from benzol refining is reclaimed in purification according to claim 6, it is characterized in that described extraction agent also can adopt steaming to blow method regeneration, and steaming is blown back gained solvent and be can be recycled.
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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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| CNB2004100607650A CN100334186C (en) | 2004-08-25 | 2004-08-25 | Process of purifying and recovering waste acid after coking refined benzene |
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| CN1740275A true CN1740275A (en) | 2006-03-01 |
| CN100334186C CN100334186C (en) | 2007-08-29 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59162108A (en) * | 1983-03-03 | 1984-09-13 | Tadao Nagai | Washing of solution of sulfuric acid |
| CN1036129C (en) * | 1994-06-06 | 1997-10-15 | 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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