CN104829505B - The separation method of anthraquinone sulfonic acid in the spent acid that a kind of anthraquinone and derivant production process thereof produce - Google Patents
The separation method of anthraquinone sulfonic acid in the spent acid that a kind of anthraquinone and derivant production process thereof produce Download PDFInfo
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Abstract
The invention discloses the separation method of anthraquinone sulfonic acid in the spent acid of a kind of anthraquinone and the generation of derivant production process thereof, comprise the following steps: at (1) 25 DEG C～60 DEG C, resin is soaked in concentrated sulphuric acid and nitric acid 3～8h, is washed with distilled water to neutrality；(2) spent acid is under conditions of 0～50 DEG C and flow are 0.5～10BV/h, by being filled with the adsorption tower of adsorbent resin, makes anthraquinone sulfonic acid adsorb on resin, and spent acid is down to colourless or light yellow clear by black after adsorption treatment；(3) will adsorb the adsorbent resin desorption and regeneration of anthraquinone sulfonic acid with desorbing agent, desorption liquid obtains anthraquinone sulfonic acid after removing desorbing agent.The method is easy and simple to handle, and spent acid and anthraquinone sulfonic acid all can realize recycling, utilizes the inventive method can realize the combination of waste acid treatment and resource recycling.
Description
Technical field
The present invention relates to the separation method of anthraquinone sulfonic acid in anthraquinone and derivant production process thereof.
Background technology
Being mainly composed of of spent acid produced in anthraquinone and derivant production process thereof: anthraquinone sulfonic acid, sulphuric acid,
The mixture such as water.This spent acid has the following characteristics that one, colourity is high；Two, COD is high, but BOD/COD
Being worth less, biodegradability is poor；Three, the anthraquinone sulfonic acid that polarity is bigger, is not readily separated.Wherein anthraquinone sulfonic acid was both
Can be used as the auxiliary agent of steaming and decocting in paper industry, can be used as again the intermediate of dyestuff.Spent acid directly discharges and both polluted
Environment, causes again the wasting of resources.
The primary structure of anthraquinone sulfonic acid is:
Wherein group R is :-CH3,-CH2CH3,-CH2CH2CH3,-C (CH3)2CH2CH3,
-CH(CH3)2,-C (CH3)3Or-CHCH3CH2CH3。
The mainly removing of the Regeneration Treatment of current above-mentioned spent acid wherein causes the Organic substance of colourity, conventional method
Having: a. high temperature pyrolytic cracking (HTP), the sulphuric acid purity that this method reclaims is higher, and shortcoming is high to equipment requirements, energy consumption big and
The most useful Organic substance cannot be reclaimed；B. produce chemical fertilizer, this spent acid may be used for produce ammonium sulfate, general calcium etc.,
But it is served only for the less waste acid reuse of content of organics, and product quality is affected by Organic Materials of Spent acid；c.
Chemical oxidization method, this fado is with O3、H2O2、KMnO4Deng for oxidant, common problem is oxygen
Changing inefficient, cost is high, and as reagent consumption amount is big, catalyst cannot reclaim；D. extraction, this method
It is critical only that the selection of extractant, this method common problem is that solvent boiling point is the highest, is not easily recycled,
And price is high, industrial is poor, and extraction process there is likely to be the dissolving of extractant and carries secretly and flow
Lose in aqueous phase, easily cause secondary pollution；E. active carbon adsorption, activated carbon is to Anthraquinones reactive dye, acid
Property dyestuff have stronger absorbability, but little to the anthraquinone sulfonic acid adsorption capacity of polarity, and be difficult to regeneration.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of anthraquinone and the spent acid of derivant production process generation thereof
The separation of middle anthraquinone sulfonic acid and enrichment method.
The method of the invention is that adsorbent resin concentrated sulphuric acid and nitric acid mixed acid first carry out pretreatment, then will
The spent acid (general CODcr is 8000～15000mg/l) that anthraquinone and derivant production process thereof produce is by tree
Fat adsorption bed, makes anthraquinone sulfonic acid adsorb on resin, and after absorption, the eluant such as resin methanol or acetone is again
Raw, remaining solid is anthraquinone sulfonic acid.Desorption liquid can reclaim the eluant such as methanol or acetone through rectification, wash
De-agent can be recycled.
The separation side of anthraquinone sulfonic acid in the spent acid that anthraquinone of the present invention and derivant production process thereof produce
Method, comprises the following steps:
At 1.25 DEG C～60 DEG C, resin is soaked in concentrated sulphuric acid and nitric acid 3～8h, is washed with distilled water to neutrality.
Wherein pretreatment temperature preferably 35 DEG C～55 DEG C, soak time preferably 4～the volume ratio of 6h, concentrated sulphuric acid and nitric acid
It is 2: 1～8: 1 preferable.
2. spent acid is under conditions of 0～50 DEG C and flow are 0.5～10BV/h, by being filled with adsorbent resin
Adsorption tower, make anthraquinone sulfonic acid adsorb on resin, spent acid is down to colourless or shallow after adsorption treatment by black
Yellow transparent.
3. will adsorb the adsorbent resin desorption and regeneration of anthraquinone sulfonic acid with desorbing agent, after desorption liquid removes desorbing agent
Obtain anthraquinone sulfonic acid.Recovered solvent recycles as desorbing agent.Desorbing agent consumption is generally resin demand
The 50%～200% of (volume), preferably 60%～100%, desorption temperature: 0～40 DEG C, desorbing agent flow velocity
General: 0.5～8BV/h.
Adsorbent resin used can be the series plastics such as nonpolar XDA, HP, D, as XDA-2,
The resins such as XDA-5, XDA-6, XDA-8, HP-10, HP-20, HP-30, HP-50 or D-101,
Or semipolar NDA series, such as resins such as NDA-99, NDA-88, NDA-150, or the LSA of polarity,
The series such as LSA-5 such as LSD, LSA-6, LSA-8, LSA-10, LSD-001, LSD-700, LSD-263,
At least one in the resins such as LSD-280, preferably LSA-8, XDA-5, NDA-99 or multiple combination.
Described desorbing agent is polar solvent, such as methanol, ethanol, ethylene glycol, dimethyl sulfoxide, acetone
Deng, it is also possible to it is NaOH aqueous solution or hot water；Preferably at least one in methanol, ethanol, acetone.
The inventive method can make in anthraquinone and derivant production process thereof produce CODcr be
The atrous spent acid of 8000～15000mg/L becomes colorless or light yellow clear, adsorption column outlet CODcr ＜
150mg/l, CODcr clearance ＞ 98%, has preferable Social benefit and economic benefit.
The method is easy and simple to handle, and spent acid and anthraquinone sulfonic acid all can realize recycling, utilize the inventive method
The combination of waste acid treatment and resource recycling can be realized.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is elaborated.
Embodiment 1
By 100ml LSA-8 adsorbent resin concentrated sulphuric acid and nitric acid dousing 5h, wherein concentrated sulphuric acid and nitre at 25 DEG C
The volume ratio of acid is: 2: 1, and the adsorbent resin distilled water after soaking is washed till neutral loading glass adsorption column
In (Φ 20 × 450mm), by the atrous spent acid that sulphuric acid mass fraction in laboratory is 50.7% under room temperature,
Being criticized by resin bed, spent acid treating capacity 1100ml/ with the flow of 200ml/h, former spent acid CODcr is
10500mg/L, water outlet is clear, yellowish, and CODcr is that 150mg/L, CODcr clearance is: 98.6%,
After process, in liquid, the mass fraction of sulphuric acid is 50.1%, can meet industrial application requirement.
Resin bed is passed through with the methanol solution of 100ml 99.5% flow with 300ml/h at a temperature of 30 DEG C
Being desorbed, the desorption liquid containing anthraquinone sulfonic acid obtains anthraquinone sulfonic acid after steaming methanol, and quality is 4.3g.
Embodiment 2
By 100ml XDA-5 adsorbent resin concentrated sulphuric acid and nitric acid dousing 3h, wherein concentrated sulphuric acid and nitre at 25 DEG C
The volume ratio of acid is: 5: 1, and the adsorbent resin after process loads in glass adsorption column (Φ 20 × 450mm),
By the atrous spent acid that sulphuric acid mass fraction in laboratory is 50.2% under room temperature, pass through with the flow of 300ml/h
Resin bed, spent acid treating capacity 1500ml/ criticizes, and former spent acid CODcr is 9500mg/L, and water outlet is clear pale yellow
Color, CODcr is that 170mg/L, CODcr clearance is: 98.5%, the quality of sulphuric acid in liquid after process
Mark is 49.5%, can meet industrial application requirement.
At room temperature taken off by resin bed with the flow of 300ml/h with the methanol solution of 150ml 99.5%
Attached, desorption liquid containing anthraquinone sulfonic acid obtains anthraquinone sulfonic acid after steaming methanol, and quality is 4.2g.
Embodiment 3
By 100ml LSA-8 adsorbent resin concentrated sulphuric acid and nitric acid dousing 5h, wherein concentrated sulphuric acid and nitric acid at 50 DEG C
Volume ratio be: 5: 1.Other conditions are with embodiment 1, and processed waste water CODcr is 95mg/L, CODcr
Clearance is: 99.1%, and finally giving anthraquinone sulfonic acid quality is 4.5g
Embodiment 4
The volume ratio of concentrated sulphuric acid in embodiment 3 with nitric acid is adjusted to: 8: 1.Other conditions are with embodiment 3, place
After reason, waste water COD cr is that 150mg/L, CODcr clearance is: 98.4%, finally gives anthraquinone sulfonic acid quality
For 4.3g.
Embodiment 5
By XDA-5 adsorbent resin concentrated sulphuric acid and nitric acid dousing 8h at 50 DEG C, other conditions with embodiment 2,
Processed waste water CODcr is that 145mg/L, CODcr clearance is: 98.2%, finally gives anthraquinone sulfonic acid
Quality is 4.3g.
Embodiment 6
By XDA-5 adsorbent resin concentrated sulphuric acid and nitric acid dousing 5h at 50 DEG C, other conditions with embodiment 2,
Processed waste water CODcr is that 120mg/L, CODcr clearance is: 98.7%, finally gives anthraquinone sulfonic acid
Quality is 4.4g.
Comparative example 1
LSA-8 adsorbent resin used is without concentrated sulphuric acid and nitric acid pretreatment, and other conditions are with embodiment 1, place
After reason, waste water COD cr is that 2250mg/L, CODcr clearance is: 78.6%, finally gives anthraquinone sulfonic acid matter
Amount is 3.5g.
Comparative example 2
XDA-5 adsorbent resin used is without concentrated sulphuric acid and nitric acid pretreatment, and other conditions, with embodiment 2, process
Rear waste water COD cr is that 1840mg/L, CODcr clearance is: 80.6%, finally gives anthraquinone sulfonic acid quality
For 3.3g.
Claims (6)
1. a separation method for anthraquinone sulfonic acid in the spent acid that anthraquinone and derivant production process thereof produce, including
Following steps:
At (1) 25 DEG C～60 DEG C, adsorbent resin is soaked in concentrated sulphuric acid and nitric acid 3～8h, uses distilled water wash
To neutral；
(2) spent acid is under conditions of 0～50 DEG C and flow are 0.5～10BV/h, by being filled with absorption tree
The adsorption tower of fat, makes anthraquinone sulfonic acid adsorb on adsorbent resin, and spent acid is down to nothing by black after adsorption treatment
Color or light yellow clear；Adsorbent resin is nonpolar XDA, HP, D series plastics, or semipolar
NDA series plastics, or LSA, LSD series plastics of polarity；
(3) will adsorb the adsorbent resin desorption and regeneration of anthraquinone sulfonic acid with desorbing agent, desorption liquid removes desorbing agent
After obtain anthraquinone sulfonic acid；Desorbing agent is polar solvent or NaOH aqueous solution；Desorbing agent consumption is resin volume
The 50%～200% of consumption, desorption temperature is 0～40 DEG C, and desorbing agent flow velocity is 0.5～8BV/h.
Separation method the most according to claim 1, wherein pretreatment temperature is 35 DEG C～55 DEG C, during immersion
Between be 4～6h, the volume ratio of concentrated sulphuric acid and nitric acid is 2: 1～8: 1.
Separation method the most according to claim 1, adsorbent resin be XDA-2, XDA-5, XDA-6,
XDA-8、HP-10、HP-20、HP-30、HP-50、D-101、NDA-99、NDA-88、NDA-150、
LSA-5、LSA-6、LSA-8、LSA-10、LSD-001、LSD-700、LSD-263、LSD-280。
Separation method the most according to claim 1, adsorbent resin is LSA-8, XDA-5, NDA-99
In at least one or multiple combination.
Separation method the most according to claim 1, described desorbing agent be methanol, ethanol, ethylene glycol,
One or more in dimethyl sulfoxide or acetone.
Separation method the most according to claim 1, it is characterised in that make anthraquinone and derivant thereof produce
The atrous spent acid that CODcr is 8000～15000mg/L produced in journey becomes colorless or light yellow clear,
Adsorption column outlet CODcr ＜ 150mg/L, CODcr clearance ＞ 98%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105384151A (en) * | 2015-12-09 | 2016-03-09 | 南京环保产业创新中心有限公司 | Comprehensive utilization and treatment method of waste sulfuric acid |
| CN110759545A (en) * | 2019-12-02 | 2020-02-07 | 江苏永葆环保科技有限公司 | Treatment method of anthraquinone dye waste acid |
| CN114604901A (en) * | 2022-03-20 | 2022-06-10 | 深圳市长隆科技有限公司 | Method for treating waste acid generated in dye sulfonation |
| CN114804280B (en) * | 2022-05-26 | 2024-06-11 | 西安海润新材料有限公司 | Method for recovering acid and thioxanthone and derivatives thereof from waste acid |
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| US4246180A (en) * | 1977-09-10 | 1981-01-20 | Bayer Aktiengesellschaft | Process for separating off 1-amino-4-bromoanthraquinone-2-sulphonic acid |
| US4942251A (en) * | 1988-01-15 | 1990-07-17 | China Technical Consultants, Inc. | Process for producing α-anthraquinonesulfonic acids and recovering the catalyst used therein |
| CN1280102A (en) * | 2000-07-10 | 2001-01-17 | 南京大学 | Treatment and source recovering method for waste water of 1,4-dihydroxy anthraquinone produetion |
| CN102219191A (en) * | 2011-04-20 | 2011-10-19 | 江苏亚邦染料股份有限公司 | Recycling method for waste sulfuric acid of dye intermediate product |
| CN102976446A (en) * | 2012-12-21 | 2013-03-20 | 南京大学 | Method for synchronously removing and stepwise recovering sulfoacid dye and heavy metal ion through resin |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4246180A (en) * | 1977-09-10 | 1981-01-20 | Bayer Aktiengesellschaft | Process for separating off 1-amino-4-bromoanthraquinone-2-sulphonic acid |
| US4942251A (en) * | 1988-01-15 | 1990-07-17 | China Technical Consultants, Inc. | Process for producing α-anthraquinonesulfonic acids and recovering the catalyst used therein |
| CN1280102A (en) * | 2000-07-10 | 2001-01-17 | 南京大学 | Treatment and source recovering method for waste water of 1,4-dihydroxy anthraquinone produetion |
| CN102219191A (en) * | 2011-04-20 | 2011-10-19 | 江苏亚邦染料股份有限公司 | Recycling method for waste sulfuric acid of dye intermediate product |
| CN102976446A (en) * | 2012-12-21 | 2013-03-20 | 南京大学 | Method for synchronously removing and stepwise recovering sulfoacid dye and heavy metal ion through resin |
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