CN104876354B - The technique that a kind of utilization high-selectivity adsorption agent processes PTA refined wastewaters - Google Patents
The technique that a kind of utilization high-selectivity adsorption agent processes PTA refined wastewaters Download PDFInfo
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Abstract
The invention discloses the technique that a kind of utilization high-selectivity adsorption agent processes PTA refined wastewaters, flow is：Extract, selective absorption, ultra filtering reverse osmosis, metal adsorption are carried out to paraxylene using high-selectivity adsorption agent.Prepared by described high-selectivity adsorption agent concretely comprises the following steps：Silicon source, silicon source, template and water are mixed in proportion, stirring and dissolving, be then transferred in the stainless steel crystallizing kettle with polytetrafluoroethyllining lining, heating crystallization, through filtering, washing, dry, roasting, obtain the good initial molecular sieve of crystallinity；Initial molecular sieve is prepared as strip high selectivity molecular sieve by deep processing, shaping again.The present invention is by using the paraxylene in high-selectivity adsorption agent absorption waste water, paraxylene can reach 7890 to the adsorptive selectivity coefficient of cobalt ions, paraxylene can reach 9578 to the selectivity factor of manganese ion, the adsorption capacity of paraxylene also can reach more than 40mg/g, can be prevented effectively from erosion of the paraxylene to reverse osmosis membrane.
Description
Technical field
A kind of water treatment field of the present invention, and in particular to the technique that utilization high-selectivity adsorption agent processes PTA refined wastewaters.
Background technology
Molecular sieve is by (Si, Al) O4Tetrahedron composition skeleton construction, be filled with its space grid structure cavity with
Duct, with larger open and huge internal surface area (400-800m2/ g), and balance cation on zeolite framework with
Framework combines not tight, and exchange interaction easily occurs with the cation in the aqueous solution, thus with good absorption, exchangeability
Energy.When main channel diameter is bigger or essentially identical than paraxylene motion diameter, and silica alumina ratio is higher so that the metal for containing
Ion is less or contains the stronger H of adsorption capacity+Or metal ion, make it weaker with the exchange interaction of metal ion in solution
When, this allows for its selective absorption paraxylene and is possibly realized.
The molecular sieve of preparation causes it to have larger hydrophobicity due to there is silica alumina ratio higher, therefore can be by electrostatic
Effect and hydrophobic effect are adsorbed to organic matter.And for Co-Mn metal ion, although high silica alumina ratio molecular sieve is to theirs
Adsorbance very little, but can reach preferably absorption selection by loading the stronger hydrogen ion of adsorption capacity and metal ion
Property.Because the sodium ion for being easy to carry out ion exchange in molecular sieve can be cemented out by modified, cause absorption mixed
Absorption affinity when closing solution to metal ion is further reduced, and for the absorption of paraxylene, because being carried by modification
Aperture high, so its adsorption capacity can be improved.So molecular sieve can improve the absorption of paraxylene by preparing post processing
Selectivity.The actually present research about molecular sieve adsorption and post processing is mainly for the choosing between dimethylbenzene isomer
Select or organic matter and metal ion individually to adsorb research more, and lack the selection under organic matter and metal ion concurrent conditions
Property absorption correlative study.
Often contain heavy metal and organic pollution, and the difference of organic matter and heavy metal in actual industrial wastewater simultaneously
Reclaim and utilize, not only with environmental protection, and resource utilization can be effectively improved.PTA refined wastewaters contain organic dirt simultaneously
Dye thing and heavy metal ion, organic matter is reclaimed in conventionally employed " extraction-ultra filtering reverse osmosis-absorption " technique in extraction process
Afterwards, extractant PX can be remained in waste water so as to produce corrosion function to ultra filtering reverse osmosis film, cause the technique steady for a long time
It is fixed effectively to run.Therefore, on the basis of high-selectivity adsorption agent preparation, using " extraction-PX selection absorption-ultrafiltration is anti-
Infiltration-metal adsorption " new technology, be capable of achieving PTA refined wastewaters by after PX extraction and recovery organic matters to waste water in remain PX
Selective absorption PX therein is carried out with metal ion, so as to be prevented effectively from erosions of the PX to ultra filtering reverse osmosis film.Refine PTA
Organic matter and metal ion in waste water realize that high selectivity is separately recovered, and ensure that system is run steadily in the long term.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art, there is provided one kind is using high-selectivity adsorption agent treatment PTA
The technique of refined wastewater.The technique increases using high-selectivity adsorption agent to diformazan by between extraction and ultra filtering reverse osmosis
The selective absorption of benzene, can optionally remove the organic pollution in industrial wastewater without heavy-metal ion removal, it is to avoid
The residual of paraxylene produces corrosion function to ultra filtering reverse osmosis films.
In order to reach foregoing invention purpose, the technical scheme is that：
A kind of utilization high-selectivity adsorption agent processes the technique of PTA refined wastewaters, and described technological process is：Extraction, profit
Selective absorption, ultra filtering reverse osmosis, metal adsorption are carried out to paraxylene with high-selectivity adsorption agent；Described high selectivity is inhaled
Attached dose is obtained as follows：Silicon source, silicon source, template and water are mixed in proportion, then stirring and dissolving is transferred to
In stainless steel crystallizing kettle with polytetrafluoroethyllining lining, heating crystallization, through filtering, washing, dry, roasting, obtains crystallinity
Good initial molecular sieve；Initial molecular sieve is made powder synthesis of molecular sieve by deep processing again, and powder synthesis of molecular sieve passes through
Prepared by shaping turn into strip high selectivity molecular sieve.
Described silicon source is the one kind in waterglass, white carbon, and silicon source is in sodium metaaluminate, aluminum sulfate, aluminium isopropoxide
One kind, template is the one kind in alcohol, inorganic amine, morpholine.
Contained silica and the mol ratio of alundum (Al2O3) contained in silicon source are 25 in silicon source:1~200:1, template
Agent is 0.18 with the mol ratio of silica contained in silicon source:1, water is with the mol ratio of silica contained in silicon source
30:1。
The temperature of heating crystallization is 170 DEG C ~ 190 DEG C, and crystallization time is 30 ~ 40h.
The deep processing of described initial molecular sieve is concretely comprised the following steps：Modifying agent is mixed with the molecular sieve for preparing, 90
Stirring reaction 2h under DEG C water bath condition, then cleans filtering repeatedly with deionized water, and 12h, 700 DEG C of roastings are dried at 80 DEG C
2h.Added modifying agent be 0.02mol/L cobalt acetate solutions, 0.02mol/L ferric chloride solutions, 0.02mol/L acetic acid manganese solution,
One or two mixtures in 5wt% ammonium chloride solutions.
Powder synthesis of molecular sieve forming agent used when being molded is inertia kaolin, and extruding is into strips.
Using high-selectivity adsorption agent to paraxylene carry out select absorption specific operation process be：Will be by diformazan
Benzene extraction after PTA refined wastewaters with certain flow by the adsorbent bed equipped with particular size high-selectivity adsorption agent, with reality
The Selective Separation of existing paraxylene and metal ion.
High-selectivity adsorption agent of the invention, being capable of Gao Xuan when the wastewater treatment containing heavy metal and organic matter is applied to
Paraxylene in selecting property absorption waste water, paraxylene can reach 7890 to the adsorptive selectivity coefficient of cobalt ions, to two
Toluene can reach 9578 to the selectivity factor of manganese ion, and the adsorption capacity of paraxylene also can reach 50mg/g, can have
Effect avoids reverse osmosis membrane from being corroded by paraxylene.
For various adsorbates in the mixed liquor of adsorption equilibrium, A is to the selective size of B with selectivity factork A/BRepresent：
K d=Q e/C e
k A/B =K d （A）/ K d （B）
Q e(mg·g-1)-equilibrium adsorption capacity
C e(mg·L-1)-equilibrium concentration
Remarkable advantage of the present invention is：With the high-selectivity adsorption agent developed of the present invention, with reference to existing extraction-super
Filter reverse osmosis process, can effectively be separately recovered organic matter and metal ion in PTA refined wastewaters, and solving reverse osmosis membrane makes
With the problem of short life, cost is reduced while economizing on resources again, with good industrial realistic feasibility.Specially：
（1）The production of molecular sieve is more ripe with modification technology, and raw material are also commonplace, so industrialization
Prospect is more optimistic.
（2）Metal ion and various organic matters in waste water are recycled to significantly reduce and are produced into by selective recovery
This, while the waste water through processing can also realize cycling and reutilization.
（3）Using traditional " extraction-ultra filtering reverse osmosis " technique, because the corrosiveness of PX is, it is necessary to often change reverse osmosis
Permeable membrane, influences the operation steady in a long-term of reverse osmosis unit, and waste water also contains a small amount of PX through treatment, can cause environmental pollution,
PX in waste water can effectively be removed to avoid its dissolving to reverse osmosis membrane by modified molecular screen selective absorption technique, together
When, the high selectivity of adsorbent makes it possible being separately recovered of organic matter and metal ion.
Brief description of the drawings
Accompanying drawing is " extraction-PX selects absorption-ultra filtering reverse osmosis-metal adsorption " process flow diagram.
Specific embodiment
The present invention is further elaborated below by embodiment, but protection scope of the present invention is not limited to following reality
Apply example.
Waterglass, aluminum sulfate are added in a certain amount of deionized water, are stirred at room temperature to dissolving, then under agitation
N-butylamine, mixture is added gradually to react and form gel, be stirred at room temperature overnight, the crystallization 35h at a temperature of 180 DEG C, warp
Filtering, washing, dry, roasting, obtain initial molecular sieve adsorbant, i.e. high-selectivity adsorption agent.
Embodiment 1
Filling 50mg/L paraxylene（PX）, 30mg/LCo2+And Mn2+100ml waste water iodine flask in add acetic acid
The silica alumina ratio of cobalt post processing is 25,50,80 molecular sieve 0.1g, with 200r/min in constant temperature（25 degrees Celsius）In water bath chader
Concussion 240min, is then centrifuged 10min, PX concentration headspace sampling-gas chromatography analysis, gold under the conditions of 4000r/min
Category concentration is analyzed with atomic absorption spectrophotometer.The different quality modified molecular screen for obtaining is for absorption PX selectivity and absorption
Capacity such as following table.
Embodiment 2
Filling 50mg/L paraxylene（PX）, 30mg/L Co2+And Mn2+100ml waste water iodine flask in add vinegar
The silica alumina ratio of sour manganese post processing is 25,50,80 molecular sieve 0.1g, with 200r/min in constant temperature（25 degrees Celsius）Water bath chader
Middle concussion 240min, is then centrifuged 10min under the conditions of 4000r/min, PX concentration headspace sampling-gas chromatography analysis,
Metal concentration is analyzed with atomic absorption spectrophotometer.The different quality modified molecular screen for obtaining is for absorption PX selectivity and inhales
Attached capacity such as following table.
Embodiment 3
Filling 50mg/L paraxylene（PX）, 30mg/L Co2+And Mn2+100ml waste water iodine flask in add chlorine
The silica alumina ratio for changing ammonium post processing is 25,50,80 molecular sieve 0.1g, with 200r/min in constant temperature（25 degrees Celsius）Water bath chader
Middle concussion 240min, is then centrifuged 10min under the conditions of 4000r/min, PX concentration headspace sampling-gas chromatography analysis,
Metal concentration is analyzed with atomic absorption spectrophotometer.The different quality modified molecular screen for obtaining is for absorption PX selectivity and inhales
Attached capacity such as following table.
Embodiment 4
Filling the paraxylene of 50mg/L（PX）, the Co of 30mg/L2+And Mn2+100ml waste water iodine flask in add
The silica alumina ratio of iron chloride post processing is 25,50,80 molecular sieve 0.1g, with 200r/min in constant temperature（25 degrees Celsius）Water-bath is vibrated
240min is shaken in device, 10min, PX concentration headspace sampling-gas chromatography point are then centrifuged under the conditions of 4000r/min
Analysis, metal concentration is analyzed with atomic absorption spectrophotometer.The different quality modified molecular screen for obtaining is for absorption PX selectivity
And adsorption capacity such as following table.
Embodiment 5
Filling the paraxylene of 50mg/L（PX）, the Co of 30mg/L2+And Mn2+100ml waste water iodine flask in add
The silica alumina ratio of barium acetate post processing is 25,50,80 molecular sieve 0.1g, with 200r/min in constant temperature（25 degrees Celsius）Water-bath is vibrated
240min is shaken in device, 10min, PX concentration headspace sampling-gas chromatography point are then centrifuged under the conditions of 4000r/min
Analysis, metal concentration is analyzed with atomic absorption spectrophotometer.The different quality modified molecular screen for obtaining is for absorption PX selectivity
And adsorption capacity such as following table.
Embodiment 6
The paraxylene containing 50mg/L is filled with the stainless steel cask of 20L（PX）, the Co of 30mg/L2+And Mn2+Waste water,
Using flow in 66ml/min, the experiment level constant-flux pump for being capable of stability contorting solution flow rate sucks waste water from the bucket, so
After be injected into 1000mm high, internal diameter 50mm, volume 1.96L, equipped with 1226g ammonium chlorides post processing silica alumina ratio be 25,50,80
The absorption column bottom of molecular sieve, is adsorbed treated solution and is flowed out from adsorption column top, with a stainless steel cask for sky by its
Collect.PX concentration headspace sampling-gas chromatography analysis, metal concentration is analyzed with atomic absorption spectrophotometer.Obtain
The molecular sieve of different silica alumina ratio ammonium chloride post processings is for absorption PX, Co2+、Mn2+Experimental data such as following table.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modification, should all belong to covering scope of the invention.
Claims (6)
1. the technique that a kind of utilization high-selectivity adsorption agent processes PTA refined wastewaters, it is characterised in that：Described technological process
For：Extract, selective absorption, ultra filtering reverse osmosis, metal adsorption are carried out to paraxylene using high-selectivity adsorption agent；Described
High-selectivity adsorption agent is obtained as follows：Silicon source, silicon source, template and water are mixed in proportion, is stirred molten
Solution, is then transferred in the stainless steel crystallizing kettle with polytetrafluoroethyllining lining, heating crystallization, through filtering, washing, dry, roasting,
Obtain the good initial molecular sieve of crystallinity；Modifying agent is mixed with the initial molecular sieve for preparing, under 90 DEG C of water bath conditions
Stirring reaction 2h, then cleans filtering repeatedly with deionized water, and 12h, 700 DEG C of roasting 2h are dried at 80 DEG C, is made powder conjunction
Into molecular sieve, powder synthesis of molecular sieve turns into strip high selectivity molecular sieve by being molded to prepare；Described modifying agent is
In 0.02mol/L cobalt acetate solutions, 0.02mol/L ferric chloride solutions, 0.02mol/L acetic acid manganese solution, 5wt% ammonium chloride solutions
One or two mixtures.
2. the technique that utilization high-selectivity adsorption agent according to claim 1 processes PTA refined wastewaters, it is characterised in that：
Described silicon source is the one kind in waterglass, white carbon, and silicon source is the one kind in sodium metaaluminate, aluminum sulfate, aluminium isopropoxide, template
Agent is the one kind in alcohol, inorganic amine, morpholine.
3. the technique that utilization high-selectivity adsorption agent according to claim 1 processes PTA refined wastewaters, it is characterised in that：
Contained silica and the mol ratio of alundum (Al2O3) contained in silicon source are 25 in silicon source:1~200:1, template and silicon source
In the mol ratio of contained silica be 0.18:1, water is 30 with the mol ratio of silica contained in silicon source:1.
4. the technique that utilization high-selectivity adsorption agent according to claim 1 processes PTA refined wastewaters, it is characterised in that：
The temperature of heating crystallization is 170 DEG C ~ 190 DEG C, and crystallization time is 30 ~ 40h.
5. the technique that utilization high-selectivity adsorption agent according to claim 1 processes PTA refined wastewaters, it is characterised in that：
Powder synthesis of molecular sieve forming agent used when being molded is inertia kaolin, and extruding is into strips.
6. the technique that utilization high-selectivity adsorption agent according to claim 1 processes PTA refined wastewaters, it is characterised in that：
It is to the specific operation process of the carrying out selection absorption of paraxylene using high-selectivity adsorption agent：To be extracted by paraxylene
PTA refined wastewaters afterwards with certain flow by the adsorbent bed equipped with particular size high-selectivity adsorption agent, to realize to two
The Selective Separation of toluene and metal ion.
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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 |
| CN107519837A (en) * | 2017-08-31 | 2017-12-29 | 长沙埃比林环保科技有限公司 | A kind of method that microwave prepares heavy metals sorbing material |
| CN107551991A (en) * | 2017-08-31 | 2018-01-09 | 长沙埃比林环保科技有限公司 | A kind of preparation method of heavy metals sorbing material |
| CN107551993A (en) * | 2017-08-31 | 2018-01-09 | 长沙埃比林环保科技有限公司 | A kind of method that heavy metals sorbing material is prepared using Organic Ingredients |
| 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 |
| CN107551992A (en) * | 2017-08-31 | 2018-01-09 | 长沙埃比林环保科技有限公司 | A kind of method that heavy metals sorbing material is prepared using inorganic raw material |
| 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 |
| 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 |
| 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 |
| CN112794500B (en) * | 2020-12-29 | 2021-09-10 | 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 |
| CN117534269B (en) * | 2024-01-10 | 2024-04-02 | 惠州金茂源环保科技有限公司 | Method for recycling heavy metal wastewater |
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