CN102936054A - Method for separating naphthalene sulfonic acid, sulfuric acid and sulfurous acid from industrial wastewater - Google Patents
Method for separating naphthalene sulfonic acid, sulfuric acid and sulfurous acid from industrial wastewater Download PDFInfo
- Publication number
- CN102936054A CN102936054A CN2011104623775A CN201110462377A CN102936054A CN 102936054 A CN102936054 A CN 102936054A CN 2011104623775 A CN2011104623775 A CN 2011104623775A CN 201110462377 A CN201110462377 A CN 201110462377A CN 102936054 A CN102936054 A CN 102936054A
- Authority
- CN
- China
- Prior art keywords
- acid
- tower
- exchange
- sulfonic acid
- sulfuric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention provides a method for separating naphthalene sulfonic acid, sulfuric acid and sulfurous acid from industrial wastewater. The method comprises the steps of employing D301R macro-porous weak base anion exchange resin as an exchange adsorbent; connecting three ion exchange adsorption towers in series successively; passing acid-containing industrial wastewater through the three ion exchange adsorption towers successively to make sulfuric acid, 2-naphthalene sulfonic acid and sulfurous acid exchanged and absorbed on corresponding tower; regenerating and exchanging the adsorbed and saturated exchange resins with a concentration gradient elution method; and eluting the absorbed sulfurous acid, 2-naphthalene sulfonic acid and sulfuric acid with a sodium hydroxide solution with a mass percentage concentration of 1%-5%. The method has good separation effect and high selectivity of the resin, and is simple and easy in operations. The exchange adsorbent can be regenerated, and has no secondary pollutions and low processing cost. The method can be used not only for separating naphthalene sulfonic acid, sulfuric acid and sulfurous acid from a beta-salt mother solution, but also for resource comprehensive utilization and treatment of other acid-containing wastewater and for condensation, purification and separation of acids with high added value. The method has wide application fields.
Description
Technical field
The invention provides the separation method of mixing acid in a kind of trade effluent, especially a kind of method of from trade effluent, isolating naphthene sulfonic acid, sulfuric acid, sulfurous acid.
Background technology
In Industrial processes, often produce acid-bearing wastewater a large amount of, of a great variety, complicated component.Acid-bearing wastewater has the advantages that the source is wide, wastewater flow rate is large, corrodibility is strong, contaminative is strong, the COD value is high, belongs to the liquid waste of industrial hazard, is one of main source of water environment pollution.Directly discharging will cause very big pollution and harm to water surrounding and human health, must process before the discharging.Therefore, it is high that exploitation has separation efficiency, the COD clearance is high, processing power is large, non-secondary pollution, separation costs is low, has not only reclaimed the acid product of important value, the water after processing but also satisfied the new and effective isolation technique of general character that reuse requires to be with a wide range of applications and important realistic meaning.
At important dyestuff intermediate---in sodiumβ-naphthalenesulfonate (β-salt) production process, the β of generation-salt mother liquor waste water amount is large, and colourity is dark, and contains a certain amount of naphthene sulfonic acid, sulfuric acid and sulfurous acid, mother solution C OD index reaches more than the 30000mg/L.Naphthene sulfonic acid is important Organic Chemicals, and high economic worth is arranged; Simultaneously, because with sulfonic acid group microorganism being had strong toxicity, to the people, poultry also has certain harm.Therefore mother liquor must be processed before discharging, reduces its naphthene sulfonic acid content.Since soluble in water with the aromatics of sulfonic acid group, make conventional physical, and chemical treatment efficient is very low.And because naphthalene ring is stable, adopts biochemical process or oxidation style also to be difficult to open loop and decompose.Cause this wastewater treatment difficulty, belong to one of extremely unmanageable organic waste water.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of isolating naphthene sulfonic acid, sulfuric acid, sulfurous acid from trade effluent, to improve separating effect, the reduction separation costs.
The present invention is achieved in that the method for isolating naphthene sulfonic acid, sulfuric acid, sulfurous acid from trade effluent, and the step of described method is:
A, take the D301R macroporous weakly basic anion exchange resin as exchange adsorbing substance, adopt three ion-exchange absorption towers to connect successively, be respectively I tower, II tower, III tower, make and contain sour trade effluent successively through these three ion-exchange absorption towers, the starting point concentration of trade effluent is 0.2mol/L～0.4mol/L, flow velocity is 3mL/min～6mL/min, bed height 25cm～40cm, aspect ratio 25/1～40/1, under 20 ℃～30 ℃ temperature, respectively with sulfuric acid, 2-naphthene sulfonic acid and sulfurous acid exchange adsorption to I tower, II tower, III tower;
B, with the saturated exchange resin of concentration gradient elution method regeneration exchange adsorption, be that 25 ℃～35 ℃, flow velocity are under the condition of 2mL/min～5mL/min in temperature, be that sulfurous acid, 2-naphthene sulfonic acid and the sulfuric acid that 1%～5% sodium hydroxide solution will adsorb respectively elutes with mass percent concentration, obtain respectively S-WAT, 2-sodium naphthalene sulfonate and sodium sulfate.
This method of isolating naphthene sulfonic acid, sulfuric acid, sulfurous acid from trade effluent can effectively realize isolating naphthene sulfonic acid, sulfuric acid, sulfurous acid, good separating effect from trade effluent.This method can obtain S-WAT, 2-sodium naphthalene sulfonate, sodium sulfate product.The selectivity of resin is high, and treatment effect is good, and is easy and simple to handle, easy, and exchange adsorbing substance can be regenerated, non-secondary pollution, and processing cost is low.This method not only can be used for the separation of β-salt mother liquor naphthene sulfonic acid, sulfuric acid, sulfurous acid, also can be used for the comprehensive utilization of resources processing of other acid-bearing wastewaters and concentrating, purify and separating of high added value acid, and Application Areas is extensive.
Embodiment
The below further specifies the present invention.
In the sepn process, flow through the successively ion-exchange absorption tower of three series connection of β-salt mother liquor trade effluent, H in I tower effluent liquid
2SO
3Concentration does not change, and 2-naphthene sulfonic acid concentration has trace to reduce, and does not contain H
2SO
4, show H in the I tower
2SO
3Be not adsorbed, a small amount of 2-naphthene sulfonic acid is adsorbed H
2SO
4Adsorbed fully.When I tower effluent liquid was flowed through the II tower, the 2-naphthene sulfonic acid almost completely was adsorbed, and a small amount of outflow is only arranged, and H
2SO
3In the II tower, do not adsorb.When II tower effluent liquid is flowed through the III tower, contained H
2SO
3Almost adsorbed fully with the NSA of trace, micro-H is only arranged
2SO
3Flow out the effluent reuse production process.This is because various acid are different from the reactive force of same resin, causes absorption strong and weak different, so be adsorbed respectively successively.After three ion-exchange absorption tower exchange adsorptions were saturated, the saturated exchange resin with sodium hydroxide solution difference counter flow washing regeneration exchange adsorption tower obtained respectively S-WAT, 2-sodium naphthalene sulfonate, sodium sulfate product, reuses after the exchange resin regeneration.
Behind the exchange adsorption of a step, the pH value of water outlet is 5-8, and 2-naphthene sulfonic acid content is lower than 0.01%, and sulfuric acid content is lower than 0.001%, and sulfurous acid content is lower than 0.001%.
The D301R macroporous weakly basic anion exchange resin is carried out multiple adsorb, wash-out reprocessing cycle, to investigate the stability of resin, reuse more than 5-20 time the total exchange adsorption capacity of resin 3mol/L-5.2mol/L.The regeneration of ion-exchange resin rate is generally 80%-100%.
Embodiment 1
From trade effluent, isolate the method for naphthene sulfonic acid, sulfuric acid, sulfurous acid,, the step of described method is:
A, take the D301R macroporous weakly basic anion exchange resin as exchange adsorbing substance, adopt three ion-exchange absorption towers to connect successively, be respectively I tower, II tower, III tower, make to contain sour trade effluent successively through these three ion-exchange absorption towers, the starting point concentration of trade effluent is 0.2mol/L, and flow velocity is 6mL/min, bed height 25cm, aspect ratio 40/1, under 20 ℃ of temperature, respectively with sulfuric acid, 2-naphthene sulfonic acid and sulfurous acid exchange adsorption to I tower, II tower, III tower;
B, with the saturated exchange resin of concentration gradient elution method regeneration exchange adsorption, be that 35 ℃, flow velocity are under the condition of 2mL/min in temperature, be that sulfurous acid, 2-naphthene sulfonic acid and the sulfuric acid that 5% sodium hydroxide solution will adsorb respectively elutes with mass percent concentration, obtain respectively S-WAT, 2-sodium naphthalene sulfonate and sodium sulfate.
Embodiment 2
Isolate the method for naphthene sulfonic acid, sulfuric acid, sulfurous acid from trade effluent, the step of described method is:
A, take the D301R macroporous weakly basic anion exchange resin as exchange adsorbing substance, adopt three ion-exchange absorption towers to connect successively, be respectively I tower, II tower, III tower, make to contain sour trade effluent successively through these three ion-exchange absorption towers, the starting point concentration of trade effluent is 0.4mol/L, and flow velocity is 3mL/min, bed height 40cm, aspect ratio 25/1, under 30 ℃ of temperature, respectively with sulfuric acid, 2-naphthene sulfonic acid and sulfurous acid exchange adsorption to I tower, II tower, III tower;
B, with the saturated exchange resin of concentration gradient elution method regeneration exchange adsorption, be that 25 ℃, flow velocity are under the condition of 5mL/min in temperature, be that sulfurous acid, 2-naphthene sulfonic acid and the sulfuric acid that 1% sodium hydroxide solution will adsorb respectively elutes with mass percent concentration, obtain respectively S-WAT, 2-sodium naphthalene sulfonate and sodium sulfate.
Embodiment 3
Isolate the method for naphthene sulfonic acid, sulfuric acid, sulfurous acid from trade effluent, the step of described method is:
A, take the D301R macroporous weakly basic anion exchange resin as exchange adsorbing substance, adopt three ion-exchange absorption towers to connect successively, be respectively I tower, II tower, III tower, make to contain sour trade effluent successively through these three ion-exchange absorption towers, the starting point concentration of trade effluent is 0.3mol/L, and flow velocity is 5mL/min, bed height 32cm, aspect ratio 35/1, under 25 ℃ of temperature, respectively with sulfuric acid, 2-naphthene sulfonic acid and sulfurous acid exchange adsorption to I tower, II tower, III tower;
B, with the saturated exchange resin of concentration gradient elution method regeneration exchange adsorption, be that 30 ℃, flow velocity are under the condition of 3.5mL/min in temperature, be that sulfurous acid, 2-naphthene sulfonic acid and the sulfuric acid that 3.5% sodium hydroxide solution will adsorb respectively elutes with mass percent concentration, obtain respectively S-WAT, 2-sodium naphthalene sulfonate and sodium sulfate.
Claims (1)
1. isolate the method for naphthene sulfonic acid, sulfuric acid, sulfurous acid from trade effluent, it is characterized in that, the step of described method is:
A, take the D301R macroporous weakly basic anion exchange resin as exchange adsorbing substance, adopt three ion-exchange absorption towers to connect successively, be respectively I tower, II tower, III tower, make and contain sour trade effluent successively through these three ion-exchange absorption towers, the starting point concentration of trade effluent is 0.2mol/L～0.4mol/L, flow velocity is 3mL/min～6mL/min, bed height 25cm～40cm, aspect ratio 25/1～40/1, under 20 ℃～30 ℃ temperature, respectively with sulfuric acid, 2-naphthene sulfonic acid and sulfurous acid exchange adsorption to I tower, II tower, III tower;
B, with the saturated exchange resin of concentration gradient elution method regeneration exchange adsorption, be that 25 ℃～35 ℃, flow velocity are under the condition of 2mL/min～5mL/min in temperature, be that sulfurous acid, 2-naphthene sulfonic acid and the sulfuric acid that 1%～5% sodium hydroxide solution will adsorb respectively elutes with mass percent concentration, obtain respectively S-WAT, 2-sodium naphthalene sulfonate and sodium sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104623775A CN102936054A (en) | 2011-12-30 | 2011-12-30 | Method for separating naphthalene sulfonic acid, sulfuric acid and sulfurous acid from industrial wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104623775A CN102936054A (en) | 2011-12-30 | 2011-12-30 | Method for separating naphthalene sulfonic acid, sulfuric acid and sulfurous acid from industrial wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102936054A true CN102936054A (en) | 2013-02-20 |
Family
ID=47694990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011104623775A Pending CN102936054A (en) | 2011-12-30 | 2011-12-30 | Method for separating naphthalene sulfonic acid, sulfuric acid and sulfurous acid from industrial wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102936054A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304061A (en) * | 2013-06-30 | 2013-09-18 | 滨州学院 | Treatment method of wastewater generated in production of beta-naphthalene sulfonic acid |
| CN109293475A (en) * | 2018-11-15 | 2019-02-01 | 北京兴高化学技术有限公司 | Coal-ethylene glycol refining methd and system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384069A (en) * | 2001-07-18 | 2002-12-11 | 南京大学 | Method of treating naphthalene-blowing effluence and recovering resource in 2-naphthol producing process |
| CN1911906A (en) * | 2006-08-25 | 2007-02-14 | 南京大学 | Method of separating and recovering 2-naphthalenesulfonic acid from waste water of 2-naphthol production |
-
2011
- 2011-12-30 CN CN2011104623775A patent/CN102936054A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384069A (en) * | 2001-07-18 | 2002-12-11 | 南京大学 | Method of treating naphthalene-blowing effluence and recovering resource in 2-naphthol producing process |
| CN1911906A (en) * | 2006-08-25 | 2007-02-14 | 南京大学 | Method of separating and recovering 2-naphthalenesulfonic acid from waste water of 2-naphthol production |
Non-Patent Citations (5)
| Title |
|---|
| 《化工学报》 20040730 李长海等 弱碱性树脂处理beta-萘磺酸废水的吸附分离热力学性能 第1117-1123页 1 第55卷, 第07期 * |
| 《吉林化工学院学报》 20041225 李长海等 弱碱性树脂分离beta-萘磺酸废水吸附平衡研究 第4-8页 1 第21卷, 第04期 * |
| 李长海等: "弱碱性树脂分离β-萘磺酸废水吸附平衡研究", 《吉林化工学院学报》 * |
| 李长海等: "弱碱性树脂处理β-萘磺酸废水的吸附分离热力学性能", 《化工学报》 * |
| 李长海等: "用弱碱性离子交换树脂分离2-萘磺酸的研究", 《化工环保》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304061A (en) * | 2013-06-30 | 2013-09-18 | 滨州学院 | Treatment method of wastewater generated in production of beta-naphthalene sulfonic acid |
| CN103304061B (en) * | 2013-06-30 | 2014-07-02 | 滨州学院 | Treatment method of wastewater generated in production of beta-naphthalene sulfonic acid |
| CN109293475A (en) * | 2018-11-15 | 2019-02-01 | 北京兴高化学技术有限公司 | Coal-ethylene glycol refining methd and system |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102910757B (en) | Treatment technique of waste water generated in production of o-nitrophenol | |
| CN101560044B (en) | Treatment method of waste water in hydroxybenzoic acid production | |
| CN102423684B (en) | A kind of modified zeolite ammonia nitrogen adsorbent and use thereof and renovation process | |
| CN106882884B (en) | A kind of method of chloride ion in recycling waste water | |
| CN105859010B (en) | A kind for the treatment of process of acid-bearing wastewater | |
| CN102659568B (en) | Method for continuously removing cations out of solution containing citric acid | |
| CN108975556B (en) | Method for purifying and recovering aged phosphoric acid polishing solution | |
| CN101139152A (en) | Printing and dyeing wastewater advanced treatment and recycling method by using resin | |
| CN104129831A (en) | Method for simultaneous removal and recovery of heavy metal ions and organic acid by using chelating resin | |
| CN101337707A (en) | Method for processing dimethylamine waste water by ion-exchange method | |
| CN102417194A (en) | Method for deeply removing magnesium through chelating resin for extracting lithium from salt lake brine | |
| CN103819024B (en) | Pretreatment method for fluorenone production wastewater | |
| CN105036234A (en) | Acetoacetanilide wastewater recycling process | |
| CN108793493A (en) | O-aminophenol recovery and treatment method in a kind of strong brine | |
| CN205556151U (en) | Organic matter waste water adsorbs unit treatment process system | |
| CN103232087A (en) | Method for continuously treating sulfonic acid wastewater | |
| CN103623790B (en) | For polymer-function material and the preparation method of adsorption treatment organic chemical waste water | |
| CN111392946A (en) | Method for recovering 1,3 cyclohexanedione from wastewater containing 1,3 cyclohexanedione | |
| CN205061821U (en) | P hydroxybenzoic acid waste water processing system | |
| CN102936054A (en) | Method for separating naphthalene sulfonic acid, sulfuric acid and sulfurous acid from industrial wastewater | |
| CN104071920B (en) | Printing-dyeing waste water treatment process | |
| CN106984260B (en) | Silicon-magnesium-based nano water treatment agent and preparation method thereof | |
| CN104226285A (en) | Regeneration method of calcium ion sorbent | |
| CN109437486B (en) | Resource utilization method of wastewater containing low-concentration sulfuric acid disperse dye | |
| CN110643818B (en) | Method for recovering nickel from electroplating wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130220 |