CN104876354A - Process for treatment of PTA refining wastewater through high-selectivity adsorbent - Google Patents
Process for treatment of PTA refining wastewater through high-selectivity adsorbent Download PDFInfo
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Abstract
The invention discloses a process for treatment of PTA refining wastewater through a high-selectivity adsorbent. The process comprises the following steps: extracting, selectively adsorbing p-xylene through the high-selectivity adsorbent, carrying out ultrafiltration and reverse osmosis and carrying out metal adsorption. The high-selectivity adsorbent is prepared through the following specific steps: uniformly mixing a silicon source, an aluminium source, a template agent and water according to a ratio, stirring for dissolving, transferring the mixture to a stainless steel crystallization kettle with a polytetrafluoroethylene liner, heating for crystallization, filtering, washing, drying and roasting so as to obtain an initial molecular sieve with good degree of crystallinity; deeply processing the initial molecular sieve, and forming to prepare into a strip-shaped high-selectivity molecular sieve. According to the process provided by the invention, the high-selectivity adsorbent is adopted to adsorb p-xylene in wastewater, the adsorption selectivity coefficient of p-xylene to cobalt ions can reach 7890 maximally, the adsorption selectivity coefficient of p-xylene to manganese ions can reach 9578 maximally and the adsorption capacity of p-xylene can reach 40 mg/g or above, so that erosion of p-xylene to a reverse osmosis membrance can be effectively avoided.
Description
Technical field
Water treatment field of the present invention, is specifically related to a kind of technique utilizing high-selectivity adsorption agent treatment PTA refined wastewater.
Background technology
Molecular sieve is by (Si, Al) O
4the cage construction of tetrahedron composition, is filled with cavity and duct, has larger opening and huge internal surface area (400-800m in its space grid structure
2/ g), and the balance cation on zeolite framework is combined not tight with framework, very easily with the positively charged ion generation exchange interaction in the aqueous solution, thus have good absorption, switching performance.When main channel diameter is larger than p-Xylol motion diameter or substantially identical, and silica alumina ratio is higher to such an extent as to the metal ion contained is less or containing the stronger H of adsorptive power
+or metal ion, when making the exchange interaction of itself and metal ion in solution more weak, this just makes its selective adsorption p-Xylol become possibility.
The molecular sieve of preparation, owing to there being higher silica alumina ratio, being caused it to have larger hydrophobicity, therefore can be adsorbed organism by electrostatic interaction and hydrophobic interaction.And for Co-Mn metal ion, although high silica alumina ratio molecular sieve is very little to their adsorptive capacity, the hydrogen ion stronger by load adsorptive power and metal ion can reach better adsorption selectivity.This is because the sodium ion being easy to carry out ion-exchange in molecular sieve can be cemented out by modification, cause during absorption mixing solutions and metal biosorption avidity is reduced further, and for the absorption of p-Xylol, because improve aperture by modification, so its loading capacity can be improved.So molecular sieve can improve the adsorption selectivity of p-Xylol by preparation aftertreatment.The research of relevant molecular sieve adsorption and aftertreatment in fact is now adsorbed separately mainly for the selection between dimethylbenzene isomers or organism and metal ion and is studied more, and lacks the selective adsorption correlative study under organism and metal ion concurrent conditions.
Often simultaneously containing heavy metal and organic pollutant in actual trade effluent, and the difference Collection and utilization of organism and heavy metal, not only can protection of the environment, and effectively improve resource utilization.PTA refined wastewater is simultaneously containing organic pollutant and heavy metal ion, in tradition employing " extraction-ultra filtering reverse osmosis-absorption " technique after extraction process reclaims organism, extraction agent PX can remain thus produce erosion action to ultra filtering reverse osmosis film in waste water, causes this technique long-term stability effectively to run.Therefore, on basis prepared by high-selectivity adsorption agent, adopt " extraction-PX adsorption selection-ultra filtering reverse osmosis-metal adsorption " novel process, can realize PTA refined wastewater after PX extraction and recovery organism to waste water in residual PX and metal ion carry out selective adsorption PX wherein, thus effectively avoid PX to the erosion of ultra filtering reverse osmosis film.Make the organism in PTA refined wastewater and metal ion realize highly selective to reclaim respectively, and guarantee that system long-term stability is run.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of technique utilizing high-selectivity adsorption agent treatment PTA refined wastewater is provided.This technique utilizes high-selectivity adsorption agent to the selective adsorption of p-Xylol by increasing between extraction and ultra filtering reverse osmosis, optionally can remove organic pollutant in trade effluent and not heavy-metal ion removal, avoid the residual of p-Xylol and erosion action is produced to ultra filtering reverse osmosis film.
In order to reach foregoing invention object, technical scheme of the present invention is:
Utilize a technique for high-selectivity adsorption agent treatment PTA refined wastewater, described technical process is: extract, utilize high-selectivity adsorption agent to carry out selective adsorption, ultra filtering reverse osmosis, metal adsorption to p-Xylol; Described high-selectivity adsorption agent obtains as follows: silicon source, aluminium source, template and water are mixed in proportion, stirring and dissolving, then proceed to in teflon-lined stainless steel crystallizing kettle, heating crystallization, after filtration, washing, dry, roasting, obtain the initial molecular sieve that degree of crystallinity is good; Initial molecular sieve makes powder synthesis of molecular sieve through deep processing again, and powder synthesis of molecular sieve becomes strip highly selective molecular sieve by shaping preparation.
Described silicon source is the one in water glass, white carbon black, and aluminium source is the one in sodium metaaluminate, Tai-Ace S 150, aluminum isopropylate, and template is the one in alcohol, inorganic amine, morpholine.
The mol ratio of aluminium sesquioxide contained in silicon-dioxide contained in silicon source and aluminium source is 25:1 ~ 200:1, and the mol ratio of the silicon-dioxide contained by template and aluminium source is 0.18:1, and the mol ratio of the silicon-dioxide contained by water and silicon source is 30:1.
The temperature of heating crystallization is 170 DEG C ~ 190 DEG C, and crystallization time is 30 ~ 40h.
The deep processing concrete steps of described initial molecular sieve are: mixed with the molecular sieve prepared by properties-correcting agent, stirring reaction 2h under 90 DEG C of water bath condition, then by deionized water cleaning and filtering repeatedly, at 80 DEG C, dry 12h, 700 DEG C of roasting 2h.Added properties-correcting agent is one or both mixtures in 0.02mol/L cobalt acetate solution, 0.02mol/L ferric chloride Solution, 0.02mol/L manganese acetate solution, 5wt% ammonium chloride solution.
Forming agent used when powder synthesis of molecular sieve is shaping is inertia kaolin, is squeezed into strip.
Utilize high-selectivity adsorption agent to the specific operation process that p-Xylol carries out adsorption selection to be: by the PTA refined wastewater after p-Xylol extraction with certain flow by being equipped with the adsorption bed of specific size high-selectivity adsorption agent, to realize the selective separation of p-Xylol and metal ion.
High-selectivity adsorption agent of the present invention is when being applied to containing heavy metal and organic wastewater treatment, can p-Xylol in high-selectivity adsorption waste water, the adsorption selectivity coefficient of p-Xylol to cobalt ion can reach 7890, the selectivity coefficient of p-Xylol to mn ion can reach 9578, the loading capacity of p-Xylol also can reach 50mg/g, can effectively avoid reverse osmosis membrane to be subject to the erosion of p-Xylol.
For adsorbate various in the mixed solution of adsorption equilibrium, A to the selectivity size of B with selectivity coefficient
k a/Brepresent:
K d=
Q e/
C e
k A/B =K d （A）/
K d （B）
q e(mgg
-1)-equilibrium adsorption capacity
c e(mgL
-1)-equilibrium concentration
Remarkable advantage of the present invention is: the high-selectivity adsorption agent of developing with the present invention, in conjunction with existing extraction-ultra filtering reverse osmosis technique, effectively can reclaim the organism in PTA refined wastewater and metal ion respectively, solve short problem in reverse osmosis membrane work-ing life, again reduce cost while economizing on resources, there is good industrial realistic feasibility.Be specially:
(1) production of molecular sieve and modification technology are comparatively ripe, and starting material are also commonplace, so industrial prospect is comparatively optimistic.
(2) metal ion in waste water and various organism significantly can reduce production cost by selective recovery recycling, and treated waste water also can realize cycling and reutilization simultaneously.
(3) traditional " extraction-ultra filtering reverse osmosis " technique is adopted, due to the corrosive nature of PX, need often to change reverse osmosis membrane, the long-term stability affecting reverse osmosis unit is run, and waste water is treated can cause environmental pollution also containing a small amount of PX, PX in waste water effectively can be removed to avoid it to the dissolving of reverse osmosis membrane by modified molecular screen selective adsorption technique, meanwhile, the highly selective of sorbent material makes the recovery respectively of organism and metal ion become possibility.
Accompanying drawing explanation
Accompanying drawing is " extraction-PX adsorption selection-ultra filtering reverse osmosis-metal adsorption " process flow diagram.
Embodiment
Below by embodiment, the present invention is further elaborated, but protection scope of the present invention is not limited to the following example.
Water glass, Tai-Ace S 150 are joined in a certain amount of deionized water, at room temperature be stirred to dissolving, then under agitation n-Butyl Amine 99 is added, mixture reacts gradually and forms gel, at room temperature stir and spend the night, crystallization 35h at 180 DEG C of temperature, after filtration, washing, dry, roasting, obtain initial molecular sieve adsorbant, i.e. high-selectivity adsorption agent.
Embodiment 1
Filling 50mg/L p-Xylol (PX), 30mg/LCo
2+and Mn
2+100ml waste water iodine flask in add Cobaltous diacetate aftertreatment silica alumina ratio be 25,50,80 molecular sieve 0.1g, in constant temperature (25 degrees Celsius) water bath chader, 240min is shaken with 200r/min, then centrifugal 10min under 4000r/min condition, PX concentration headspace sampling-gc analysis, metal concentration atomic absorption spectrophotometer is analyzed.The different mass modified molecular screen obtained for absorption PX selectivity and loading capacity as following table.
Embodiment 2
Filling 50mg/L p-Xylol (PX), 30mg/L Co
2+and Mn
2+100ml waste water iodine flask in add manganese acetate aftertreatment silica alumina ratio be 25,50,80 molecular sieve 0.1g, in constant temperature (25 degrees Celsius) water bath chader, 240min is shaken with 200r/min, then centrifugal 10min under 4000r/min condition, PX concentration headspace sampling-gc analysis, metal concentration atomic absorption spectrophotometer is analyzed.The different mass modified molecular screen obtained for absorption PX selectivity and loading capacity as following table.
Embodiment 3
Filling 50mg/L p-Xylol (PX), 30mg/L Co
2+and Mn
2+100ml waste water iodine flask in add ammonium chloride aftertreatment silica alumina ratio be 25,50,80 molecular sieve 0.1g, in constant temperature (25 degrees Celsius) water bath chader, 240min is shaken with 200r/min, then centrifugal 10min under 4000r/min condition, PX concentration headspace sampling-gc analysis, metal concentration atomic absorption spectrophotometer is analyzed.The different mass modified molecular screen obtained for absorption PX selectivity and loading capacity as following table.
Embodiment 4
Filling the p-Xylol (PX) of 50mg/L, the Co of 30mg/L
2+and Mn
2+100ml waste water iodine flask in add iron(ic) chloride aftertreatment silica alumina ratio be 25,50,80 molecular sieve 0.1g, in constant temperature (25 degrees Celsius) water bath chader, 240min is shaken with 200r/min, then centrifugal 10min under 4000r/min condition, PX concentration headspace sampling-gc analysis, metal concentration atomic absorption spectrophotometer is analyzed.The different mass modified molecular screen obtained for absorption PX selectivity and loading capacity as following table.
Embodiment 5
Filling the p-Xylol (PX) of 50mg/L, the Co of 30mg/L
2+and Mn
2+100ml waste water iodine flask in add barium acetate aftertreatment silica alumina ratio be 25,50,80 molecular sieve 0.1g, in constant temperature (25 degrees Celsius) water bath chader, 240min is shaken with 200r/min, then centrifugal 10min under 4000r/min condition, PX concentration headspace sampling-gc analysis, metal concentration atomic absorption spectrophotometer is analyzed.The different mass modified molecular screen obtained for absorption PX selectivity and loading capacity as following table.
Embodiment 6
The p-Xylol (PX) containing 50mg/L is filled, the Co of 30mg/L with the stainless steel cask of 20L
2+and Mn
2+waste water, use traffic is at 66ml/min, the experiment level constant-flux pump of stability contorting solution flow rate can suck waste water from this bucket, then high 1000mm is injected into, internal diameter 50mm, volume 1.96L, the silica alumina ratio that the aftertreatment of 1226g ammonium chloride is housed is bottom the adsorption column of 25,50,80 molecular sieves, flowed out from adsorption column top by the solution that adsorption treatment is crossed, collected with an empty stainless steel cask.PX concentration headspace sampling-gc analysis, metal concentration atomic absorption spectrophotometer is analyzed.The molecular sieve of the different Different Silicon aluminum ratio ammonium chloride aftertreatment obtained is for absorption PX, Co
2+, Mn
2+experimental data as following table.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (8)
1. utilize a technique for high-selectivity adsorption agent treatment PTA refined wastewater, it is characterized in that: described technical process is: extract, utilize high-selectivity adsorption agent to carry out selective adsorption, ultra filtering reverse osmosis, metal adsorption to p-Xylol; Described high-selectivity adsorption agent obtains as follows: silicon source, aluminium source, template and water are mixed in proportion, stirring and dissolving, then proceed to in teflon-lined stainless steel crystallizing kettle, heating crystallization, after filtration, washing, dry, roasting, obtain the initial molecular sieve that degree of crystallinity is good; Initial molecular sieve makes powder synthesis of molecular sieve through deep processing again, and powder synthesis of molecular sieve becomes strip highly selective molecular sieve by shaping preparation.
2. the technique utilizing high-selectivity adsorption agent treatment PTA refined wastewater according to claim 1, it is characterized in that: described silicon source is the one in water glass, white carbon black, aluminium source is the one in sodium metaaluminate, Tai-Ace S 150, aluminum isopropylate, and template is the one in alcohol, inorganic amine, morpholine.
3. the technique utilizing high-selectivity adsorption agent treatment PTA refined wastewater according to claim 1, it is characterized in that: the mol ratio of the aluminium sesquioxide contained by silicon-dioxide contained in silicon source and aluminium source is 25:1 ~ 200:1, the mol ratio of silicon-dioxide contained in template and aluminium source is 0.18:1, and the mol ratio of the silicon-dioxide contained by water and silicon source is 30:1.
4. the technique utilizing high-selectivity adsorption agent treatment PTA refined wastewater according to claim 1, is characterized in that: the temperature of heating crystallization is 170 DEG C ~ 190 DEG C, and crystallization time is 30 ~ 40h.
5. the technique utilizing high-selectivity adsorption agent treatment PTA refined wastewater according to claim 1, it is characterized in that: the deep processing concrete steps of described initial molecular sieve are: mixed with the molecular sieve prepared by properties-correcting agent, stirring reaction 2h under 90 DEG C of water bath condition, then by deionized water cleaning and filtering repeatedly, 12h is dried, 700 DEG C of roasting 2h at 80 DEG C.
6. the technique utilizing high-selectivity adsorption agent treatment PTA refined wastewater according to claim 5, is characterized in that: added properties-correcting agent is one or both mixtures in 0.02mol/L cobalt acetate solution, 0.02mol/L ferric chloride Solution, 0.02mol/L manganese acetate solution, 5wt% ammonium chloride solution.
7. the technique utilizing high-selectivity adsorption agent treatment PTA refined wastewater according to claim 1, is characterized in that: forming agent used when powder synthesis of molecular sieve is shaping is inertia kaolin, is squeezed into strip.
8. the technique utilizing high-selectivity adsorption agent treatment PTA refined wastewater according to claim 1, it is characterized in that: utilize the specific operation process of carrying out adsorption selection of high-selectivity adsorption agent to p-Xylol to be: by the PTA refined wastewater after p-Xylol extraction with certain flow by being equipped with the adsorption bed of specific size high-selectivity adsorption agent, to realize the selective separation of p-Xylol and metal ion.
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| CN106423048A (en) * | 2016-09-29 | 2017-02-22 | 福州大学 | High-selectivity Fe/Co/Mn composite-modified molecular sieve adsorbent and adsorbing device |
| CN107442092A (en) * | 2017-08-31 | 2017-12-08 | 长沙埃比林环保科技有限公司 | A kind of method that hydro-thermal prepares heavy metals sorbing material |
| CN107486145A (en) * | 2017-08-31 | 2017-12-19 | 长沙埃比林环保科技有限公司 | A kind of method that solid-state prepares heavy metals sorbing material |
| CN107497395A (en) * | 2017-08-31 | 2017-12-22 | 长沙埃比林环保科技有限公司 | A kind of method that heavy metals sorbing material is prepared under ion hot system |
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| CN108057417A (en) * | 2017-12-25 | 2018-05-22 | 北京益清源环保科技有限公司 | For the modified zeolite adsorbent of benzene in Adsorption wastewater from chemical industry |
| CN111097392A (en) * | 2018-10-25 | 2020-05-05 | 南京化学工业园环保产业协同创新有限公司 | Novel process for treating PTA refining wastewater by using high-selectivity adsorbent |
| CN111348795A (en) * | 2020-03-26 | 2020-06-30 | 福州大学 | Electrodialysis-based PTA refining wastewater resource recycling device and method |
| CN112794500A (en) * | 2020-12-29 | 2021-05-14 | 华夏碧水环保科技有限公司北京分公司 | Coking wastewater strong brine near-zero emission treatment system and treatment method thereof |
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| CN106423048B (en) * | 2016-09-29 | 2019-07-19 | 福州大学 | A kind of composite modified adsorbent of molecular sieve of highly selective Fe/Co/Mn and adsorption plant |
| CN106423048A (en) * | 2016-09-29 | 2017-02-22 | 福州大学 | High-selectivity Fe/Co/Mn composite-modified molecular sieve adsorbent and adsorbing device |
| CN107442092A (en) * | 2017-08-31 | 2017-12-08 | 长沙埃比林环保科技有限公司 | A kind of method that hydro-thermal prepares heavy metals sorbing material |
| CN107486145A (en) * | 2017-08-31 | 2017-12-19 | 长沙埃比林环保科技有限公司 | A kind of method that solid-state prepares heavy metals sorbing material |
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| CN111348795A (en) * | 2020-03-26 | 2020-06-30 | 福州大学 | Electrodialysis-based PTA refining wastewater resource recycling device and method |
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