CN108217810A - A kind of method of benzotriazole pollutant in removal waste water - Google Patents
A kind of method of benzotriazole pollutant in removal waste water Download PDFInfo
- Publication number
- CN108217810A CN108217810A CN201711447870.3A CN201711447870A CN108217810A CN 108217810 A CN108217810 A CN 108217810A CN 201711447870 A CN201711447870 A CN 201711447870A CN 108217810 A CN108217810 A CN 108217810A
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- benzotriazole
- methanol
- pollutant
- waste water
- 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
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000012964 benzotriazole Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 39
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 39
- 239000002351 wastewater Substances 0.000 title claims abstract description 35
- 239000003463 adsorbent Substances 0.000 claims abstract description 66
- 238000001179 sorption measurement Methods 0.000 claims abstract description 19
- 230000008929 regeneration Effects 0.000 claims abstract description 15
- 238000011069 regeneration method Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- -1 nitrogen-containing heterocycle compound Chemical class 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 129
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- PZBQVZFITSVHAW-UHFFFAOYSA-N 5-chloro-2h-benzotriazole Chemical class C1=C(Cl)C=CC2=NNN=C21 PZBQVZFITSVHAW-UHFFFAOYSA-N 0.000 claims description 2
- DBPUFHGYHVQTQQ-UHFFFAOYSA-N N1N=NC=C1.CC=1C=CC=C(C1C)C1=CC=CC=C1 Chemical class N1N=NC=C1.CC=1C=CC=C(C1C)C1=CC=CC=C1 DBPUFHGYHVQTQQ-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000013110 organic ligand Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 9
- 230000009102 absorption Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910018516 Al—O Inorganic materials 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000002905 metal composite material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000009938 salting Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 150000003852 triazoles Chemical group 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of method for removing benzotriazole pollutant in waste water, this method, which includes preparing, reacts soluble metallic salt with nitrogen-containing heterocycle compound, obtains the adsorbent that inorganic metal unit is formed with organic ligand unit by Coordination interaction；It adds an adsorbent into the waste water of the pollutant containing benzotriazole, waste water is adsorbed；Regeneration recycling finally is carried out to adsorbent.The present invention has adsorption efficiency height, good to benzotriazole pollutant removal, and adsorbent is affected by environment small, regenerates the advantages that facilitating.
Description
Technical field
The invention belongs to water-treatment technology field, more particularly to a kind of side for removing benzotriazole pollutant in waste water
Method.
Background technology
Benzotriazole is that the aromatic compound containing phenyl ring and triazole ring, benzotriazole substance are wide simultaneously in molecule
The general corrosion inhibiter and preservative for being applied to light stabilizer and metal, especially using silver-colored or copper as the inhibition of host material
Agent.Meanwhile this kind of substance, in coolant, anti-icing fluid, aircraft deicing agent and detergent etc., which similarly have, widely should
With.According to statistics, the benzotriazole substance that the whole world produces every year is just at 9000 tons or more.It is however, wide with benzotriazole
General application also becomes a kind of emerging chemical pollutant, and benzotriazole is soluble easily in water, resistance to biodegradation, it is difficult to biography
The biological method removal of system, it has also become the difficult point of wastewater treatment.
At present, it is relatively fewer to the research of benzotriazole pollutant both at home and abroad, and physical absorption due to it is simple for process, into
This is low, easy to operate, has become one of main stream approach of water pollution control, existing to benzotriazole dirt in the prior art
The adsorbent for contaminating object includes activated carbon, Zn-Al-O metal composite oxides etc..For example, Chinese patent discloses CN101215039A
Using bentonite as the heterocyclic aromatic compounds in adsorbent removal waste water, including benzotriazole pollutant, the adsorbent
Resourceful, technology requirement is low.But stir process is needed, and need high temperature regeneration, complex process.Chinese patent discloses
For CN101564674A using Zn-Al-O metal composite oxides as adsorbent, the adsorbent use condition is mild, can be fast
Speed is effectively adsorbed and removes benzotriazole pollutant.However the Zn-Al-O metal composite oxide specific surface areas are inadequate
Greatly, it is inadequate to the adsorbance of benzotriazole pollutant, and acid resistance is inadequate, can not meet practical application.
To sum up, the present invention is directed to the defects of above-mentioned existing wastewater treatment method containing benzotriazole and the market demand, exploitation
Go out a kind of method for removing benzotriazole pollutant in waste water, this method is to the method adsorption efficiency of benzotriazole pollutant
Height, removal effect is good, in addition, the adsorbent that this method uses is affected by environment small, regeneration is convenient.
Invention content
The purpose of the present invention is to provide a kind of methods for removing benzotriazole pollutant in waste water.The present invention, which has, to inhale
It is attached efficient, it is good to benzotriazole pollutant removal, and adsorbent is affected by environment small, regenerates the advantages that facilitating.
To achieve the above object, the present invention takes following technical scheme：
The method of benzotriazole pollutant, includes the following steps in a kind of removal waste water：
(1) preparation of adsorbent：By soluble metallic salt ultrasonic dissolution in methanol, the methanol of soluble metallic salt is obtained
Solution then by the methanol solution of soluble metallic salt, is added under agitation to the methanol solution of nitrogen-containing heterocycle compound
In, certain time is reacted at room temperature, obtains white precipitate, through centrifugation, after methanol washing, by solid product re-ultrasonic dispersion in first
In alcoholic solution, finally dry to get to adsorbent；
(2) it adds an adsorbent into the waste water of the pollutant containing benzotriazole, quality hundred of the adsorbent in waste water
Dividing ratio, then waste water discharges after filtering for 0.2-1.5%, adsorption time 5-30min；
(3) adsorbent for being adsorbed with benzotriazole pollutant being obtained by filtration is scattered in desorbing agent, then solid-liquid
Separation, the solid of gained washs successively through pure water, methanol again, dries, completes the regeneration of adsorbent, and the adsorbent after regeneration can be with
It is recycled in return to step (2).
In the above-mentioned methods, it is preferred that the soluble metallic salt in the step (1) is selected from the nitric acid of transition metal element
It is one or more in salt, sulfate and chlorate；The transition metal element in iron, zinc, zirconium, copper, silver and cobalt one
Kind is a variety of.
In the above-mentioned methods, it is preferred that the nitrogen-containing heterocycle compound in the step (1) is selected from 2-methylimidazole, benzo
It is one or more in imidazoles and benzotriazole.
In the above-mentioned methods, it is preferred that the mass ratio of soluble metallic salt and nitrogen-containing heterocycle compound in the step (1)
It is 1:4.
In the above-mentioned methods, it is preferred that washing is washs at least 3 times with methanol in the step (1).
In the above-mentioned methods, it is preferred that put into waste water again after the adsorbent grinding in the step (2).
In the above-mentioned methods, it is preferred that the adsorption temp in the step (2) is 20-35 DEG C.
In the above-mentioned methods, it is preferred that mixing of the desorbing agent for 1M NaOH aqueous solutions and methanol in the step (3)
Liquid, wherein, the volume ratio of NaOH aqueous solutions and methanol is 10:90.
In the above-mentioned methods, it is preferred that the adsorbent and desorption of benzotriazole pollutant are adsorbed in the step (3)
The mass volume ratio of agent is 5mg/mL.
In the above-mentioned methods, it is preferred that the benzotriazole pollutant include benzotriazole, 5- methylbenzotrazoles,
It is one or more in 5- chlorobenzotriazoles and 5,6 dimethylbiphenyl triazoles.
The present invention technical principle be：The adsorbent being prepared is a kind of high-specific surface area composite material, by specific
The coordination of steric configuration organic ligand and transition metal ions synthesizes a kind of adjustable height of pore size in a manner of self assembly
Specific surface area composite material, with suitable duct size and the heteroatomic Van der Waals force of channel surfaces ligand, hydrophobic effect, hydrogen bond
With π-πconjugation efficient absorption benzotriazole pollutant.
The present invention has following technical characterstic：
(1) adsorbent of the invention has big specific surface area, and has between target contaminant molecule more strong
Action site has lower density than inorganic oxide material.
(2) by changing the arranging scheme of metal ion and ligand, it can be achieved that regulation and control to adsorbent pore size size；
Simultaneously organic ligand have can further functionalization group, the duct for adsorbent is modified and improvement provides possibility, suitable
The absorption and enrichment of the serial benzotriazole analog derivative of unification.
(3) adsorbent heat resistance of the invention reaches 400 DEG C, can under 2~10 environment of pH ranges normal use, and to from
The adsorptive hindrance object humic acid of generally existing and high salinity environment have resistant function in right water body, and adsorption capacity is not easily susceptible to do
It disturbs.
(4) adsorbent of the invention is rapid to the absorption of benzimidazole pollutant, thorough, is not required to be vigorously stirred, especially right
What residual contaminants index request was higher in water carry, and mark application scenario has better applicability.
(5) adsorbent of the invention specific surface area higher compared with conventional adsorbent, on adsorption rate and adsorption capacity
All there is apparent advantage, and regenerate conveniently.
Specific embodiment
Specific examples below is the further explanation to method provided by the invention and technical solution, but is not construed as
Limitation of the present invention.
Embodiment 1：The method of benzotriazole pollutant, includes the following steps in a kind of removal waste water：
(1) preparation of adsorbent：Weigh the Zn (NO of 1.15g3)2·6H2O in 100mL beakers, with 80mL methanol by its
Ultrasonic dissolution.The 2-methylimidazole of 2.5g is weighed in the round-bottomed flask of 250mL, after adding in 80mL methanol stirring and dissolvings, is continued
Under conditions of stirring, the salting liquid dissolved is added in, reacts 1h at room temperature, solution becomes muddy, there is white precipitate generation, centrifuges
Upper solution is removed, centrifugal speed 10000rpm, centrifugation time 10min, obtained solid is washed 3 times with methanol, then uses first
Alcohol ultrasonic disperse after remaining solid is dried 12h with 90 DEG C of baking ovens, and is ground 15min；
(2) by the waste water of adsorbent input pollutant containing benzotriazole after grinding, the adsorbent is in waste water
Mass percent for 1.5%, adsorption time 5min, adsorption temp is 25 DEG C, and then waste water discharges after filtering；
(3) adsorbent for being adsorbed with benzotriazole pollutant being obtained by filtration is scattered in 1M NaOH aqueous solutions and first
In the mixed liquor of alcohol, wherein, the volume ratio of NaOH aqueous solutions and methanol is 10:90, then separation of solid and liquid, the solid of gained pass through again
Pure water, methanol wash successively, and the regeneration of adsorbent is completed in drying, and the adsorbent after regeneration can be made with cycle in return to step (2)
With.
Embodiment 2：The method of benzotriazole pollutant, includes the following steps in a kind of removal waste water：
(1) preparation of adsorbent：Weigh the ZnCl of 1.2g2·6H2O is ultrasonic by it with 80mL methanol in 100mL beakers
Dissolving.The benzimidazole of 3g is weighed in the round-bottomed flask of 250mL, after adding in 80mL methanol stirring and dissolvings, continues the item of stirring
Under part, the salting liquid dissolved is added in, reacts 1h at room temperature, solution becomes muddy, there is white precipitate generation, centrifugation removal upper strata
Solution, centrifugal speed 10000rpm, centrifugation time 10min, obtained solid are washed 3 times with methanol, again with methanol ultrasound point
It dissipates, after remaining solid is dried 12h with 90 DEG C of baking ovens, and is ground 15min；
(2) by the waste water of adsorbent input pollutant containing benzotriazole after grinding, the adsorbent is in waste water
Mass percent for 0.8%, adsorption time 10min, adsorption temp is 20 DEG C, and then waste water discharges after filtering；
(3) adsorbent for being adsorbed with benzotriazole pollutant being obtained by filtration is scattered in 1M NaOH aqueous solutions and first
In the mixed liquor of alcohol, wherein, the volume ratio of NaOH aqueous solutions and methanol is 10:90, then separation of solid and liquid, the solid of gained pass through again
Pure water, methanol wash successively, and the regeneration of adsorbent is completed in drying, and the adsorbent after regeneration can be made with cycle in return to step (2)
With.
Embodiment 3：The method of benzotriazole pollutant, includes the following steps in a kind of removal waste water：
(1) preparation of adsorbent：Weigh the Cu (NO of 2.45g3)2·6H2O in 100mL beakers, with 80mL methanol by its
Ultrasonic dissolution.The benzimidazole of 4.5g is weighed in the round-bottomed flask of 250mL, after adding in 80mL methanol stirring and dissolvings, continues to stir
Under conditions of mixing, the salting liquid dissolved is added in, reacts 1h at room temperature, solution becomes muddy, has white precipitate generation, centrifugation is gone
Except upper solution, centrifugal speed 10000rpm, centrifugation time 10min, obtained solid washs 3 times with methanol, again with methanol
Ultrasonic disperse after remaining solid is dried 12h with 90 DEG C of baking ovens, and is ground 15min；
(2) by the waste water of adsorbent input pollutant containing benzotriazole after grinding, the adsorbent is in waste water
Mass percent for 0.5%, adsorption time 20min, adsorption temp is 30 DEG C, and then waste water discharges after filtering；
(3) adsorbent for being adsorbed with benzotriazole pollutant being obtained by filtration is scattered in 1M NaOH aqueous solutions and first
In the mixed liquor of alcohol, wherein, the volume ratio of NaOH aqueous solutions and methanol is 10:90, then separation of solid and liquid, the solid of gained pass through again
Pure water, methanol wash successively, and the regeneration of adsorbent is completed in drying, and the adsorbent after regeneration can be made with cycle in return to step (2)
With.
Embodiment 4：The method of benzotriazole pollutant, includes the following steps in a kind of removal waste water：
(1) preparation of adsorbent：Weigh the Zn (NO of 3g3)2·6H2O is surpassed in 100mL beakers with 80 mL methanol
Sound dissolves.The benzotriazole of 4g is weighed in the round-bottomed flask of 250mL, after adding in 80 mL methanol stirring and dissolvings, continues stirring
Under the conditions of, the salting liquid dissolved is added in, reacts 1 h at room temperature, solution becomes muddy, there is white precipitate generation, centrifugation removal
Upper solution, centrifugal speed 10000rpm, centrifugation time 10min, obtained solid are washed 3 times with methanol, and again with methanol surpasses
Sound disperses, and after remaining solid is dried 12h with 90 DEG C of baking ovens, and is ground 15min；
(2) by the waste water of adsorbent input pollutant containing benzotriazole after grinding, the adsorbent is in waste water
Mass percent for 0.2%, adsorption time 30min, adsorption temp is 25 DEG C, and then waste water discharges after filtering；
(3) adsorbent for being adsorbed with benzotriazole pollutant being obtained by filtration is scattered in 1M NaOH aqueous solutions and first
In the mixed liquor of alcohol, wherein, the volume ratio of NaOH aqueous solutions and methanol is 10:90, then separation of solid and liquid, the solid of gained pass through again
Pure water, methanol wash successively, and the regeneration of adsorbent is completed in drying, and the adsorbent after regeneration can be made with cycle in return to step (2)
With.
Embodiment 5：The maximum adsorption of adsorbent prepared by embodiment 1 is calculated by the benzotriazole substance in simulation water
Amount experiment
The benzotriazole for weighing certain mass is dissolved in pure water, the benzo three of configuration various concentration (50-1000mg/L)
The pure water solution of azoles.The adsorbent of 10.0mg is weighed in the centrifuge tube of 10mL, add in thereto 5mL a certain concentrations (50,200,
500th, 1000mg/L) benzotriazole aqueous solution, 30 DEG C carry out thermostatic absorptions.After adsorbing 25min, take 1mL's with syringe
Solution simultaneously passes through 0.22 μm of microporous fibre element film and is filtered, by high-efficient liquid phase color spectrometry filtrate object it is dense
Degree, with the raising of benzotriazole concentration, when benzotriazole is a concentration of 50,200,500,1000mg/L when, the adsorbance of adsorbent
Be followed successively by 25.7,50.8,99.4,139.6mg/g, wherein 139.6mg/g be the Zn-Al-O metal composite oxides reported
30~50 times of adsorption capacity.
Embodiment 6：The amount of desorbing agent tests the influence for being desorbed efficiency
50.0mg high-ratio surfaces composite material is weighed in the centrifuge tube of 50mL, adds in the benzene of 25mL 400mg/L thereto
And triazole solution, 30 DEG C of mixing 12h of constant temperature, centrifugation (10000rpm × 10min) separates and collects solid, as what is adsorbed in advance
Adsorbent.
Use 1M NaOH aqueous solutions and the mixed liquor (10 of methanol:90, v/v) as desorbing agent.Weigh 10.0mg pre-suctions
Attached adsorbent is in the centrifuge tube of 10mL, addition 2,4,6,8mL desorbing agents.Centrifuged after ultrasonic 5min (10000rpm ×
It 10min) detaches, the concentration of object in supernatant is measured with high performance liquid chromatography.By the object mass in supernatant with
The ratio of the general objective amount of substance of absorption calculates desorption efficiency.With same method come evaluate the amount of desorbing agent for 2,4,6,8mL
To desorption process and be desorbed the influence of efficiency, by the washing of 3-4 time, be desorbed efficiency be respectively 82.3%, 86.1%,
91.4%th, 99.2%.Experimental data illustrates that, with the increasing of desorbing agent dosage, desorption efficiency is increased, reached as high as
More than 99%.
The explanation of above example is only intended to help to understand the method for the present invention and its core concept.It should be pointed out that for
For those skilled in the art, without departing from the principle of the present invention, if can also be carried out to the present invention
Dry improvement and modification, these improvement and modification are also fallen into the claims in the present invention protection domain.
Claims (10)
- A kind of 1. method for removing benzotriazole pollutant in waste water, which is characterized in that include the following steps：(1) preparation of adsorbent：By soluble metallic salt ultrasonic dissolution in methanol, the methanol for obtaining soluble metallic salt is molten Liquid then by the methanol solution of soluble metallic salt, is added under agitation into the methanol solution of nitrogen-containing heterocycle compound, Certain time is reacted at room temperature, obtains white precipitate, through centrifugation, after methanol washing, by solid product re-ultrasonic dispersion in methanol In solution, finally dry to get to adsorbent；(2) it adds an adsorbent into the waste water of the pollutant containing benzotriazole, mass percent of the adsorbent in waste water For 0.2-1.5%, adsorption time 5-30min, then waste water discharges after filtering；(3) adsorbent for being adsorbed with benzotriazole pollutant being obtained by filtration is scattered in desorbing agent, then separation of solid and liquid, The solid of gained washs successively through pure water, methanol again, and drying completes the regeneration of adsorbent, the adsorbent after regeneration can return It is recycled in step (2).
- 2. the method as described in claim 1, which is characterized in that the soluble metallic salt in the step (1) is selected from transition gold Belong to one or more in the nitrate, sulfate and chlorate of element；The transition metal element be selected from iron, zinc, zirconium, copper, It is one or more in silver and cobalt.
- 3. the method as described in claim 1, which is characterized in that the nitrogen-containing heterocycle compound in the step (1) is selected from 2- first It is one or more in base imidazoles, benzimidazole and benzotriazole.
- 4. the method as described in claim 1, which is characterized in that soluble metallic salt is cyclized with nitrogen-containing hetero in the step (1) The mass ratio for closing object is 1:4.
- 5. the method as described in claim 1, which is characterized in that washing is washs at least 3 times with methanol in the step (1).
- 6. the method as described in claim 1, which is characterized in that put into waste water again after the adsorbent grinding in the step (2) In.
- 7. the method as described in claim 1, which is characterized in that the adsorption temp in the step (2) is 20-35 DEG C.
- 8. the method as described in claim 1, which is characterized in that desorbing agent in the step (3) for 1M NaOH aqueous solutions with The mixed liquor of methanol, wherein, the volume ratio of NaOH aqueous solutions and methanol is 10:90.
- 9. the method as described in claim 1, which is characterized in that be adsorbed with benzotriazole pollutant in the step (3) The mass volume ratio of adsorbent and desorbing agent is 5mg/mL.
- 10. the method as described in claim 1, which is characterized in that the benzotriazole pollutant includes benzotriazole, 5- first It is one or more in base benzotriazole, 5- chlorobenzotriazoles and 5,6 dimethylbiphenyl triazoles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711447870.3A CN108217810A (en) | 2017-12-27 | 2017-12-27 | A kind of method of benzotriazole pollutant in removal waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711447870.3A CN108217810A (en) | 2017-12-27 | 2017-12-27 | A kind of method of benzotriazole pollutant in removal waste water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108217810A true CN108217810A (en) | 2018-06-29 |
Family
ID=62649160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711447870.3A Pending CN108217810A (en) | 2017-12-27 | 2017-12-27 | A kind of method of benzotriazole pollutant in removal waste water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108217810A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114409009A (en) * | 2022-01-12 | 2022-04-29 | 青岛职业技术学院 | Method for adsorbing hydroquinone based on polymer PIM-1 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002035773A (en) * | 2000-07-27 | 2002-02-05 | Hitachi Plant Eng & Constr Co Ltd | Method and apparatus for treating benzotriazole-containing wastewater |
| US20080264870A1 (en) * | 2007-04-24 | 2008-10-30 | Duke Dan A | Cooling water corrosion inhibition method |
| CN101564674A (en) * | 2009-05-20 | 2009-10-28 | 中国环境科学研究院 | Composite metal oxide adsorbent and method using same to remove azimino-benzene in water |
| CN103209934A (en) * | 2010-09-21 | 2013-07-17 | 诺维信公司 | Removal of selenocyanate or selenite from aqueous solutions |
| WO2014028574A2 (en) * | 2012-08-15 | 2014-02-20 | Arkema Inc. | Adsorption systems using metal-organic frameworks |
| CN107416915A (en) * | 2015-08-28 | 2017-12-01 | 邓忆凯 | A kind of high efficiency sewage treating agent and preparation method thereof |
-
2017
- 2017-12-27 CN CN201711447870.3A patent/CN108217810A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002035773A (en) * | 2000-07-27 | 2002-02-05 | Hitachi Plant Eng & Constr Co Ltd | Method and apparatus for treating benzotriazole-containing wastewater |
| US20080264870A1 (en) * | 2007-04-24 | 2008-10-30 | Duke Dan A | Cooling water corrosion inhibition method |
| CN101564674A (en) * | 2009-05-20 | 2009-10-28 | 中国环境科学研究院 | Composite metal oxide adsorbent and method using same to remove azimino-benzene in water |
| CN103209934A (en) * | 2010-09-21 | 2013-07-17 | 诺维信公司 | Removal of selenocyanate or selenite from aqueous solutions |
| WO2014028574A2 (en) * | 2012-08-15 | 2014-02-20 | Arkema Inc. | Adsorption systems using metal-organic frameworks |
| CN107416915A (en) * | 2015-08-28 | 2017-12-01 | 邓忆凯 | A kind of high efficiency sewage treating agent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JUN-QING JIANG等: "Zeolitic Imidazolate Framework‑8 for Fast Adsorption and Removal of Benzotriazoles from Aqueous Solution", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| 蒋俊清等: "金属有机骨架 ZIF-8 纳米材料对苯并三唑类污染物的吸附与去除", 《全国环境纳米技术及生物效应学术研讨会摘要集》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114409009A (en) * | 2022-01-12 | 2022-04-29 | 青岛职业技术学院 | Method for adsorbing hydroquinone based on polymer PIM-1 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zou et al. | Removal of Pb (II) from aqueous solutions by adsorption on magnetic bentonite | |
| Niu et al. | A conveniently synthesized redox-active fluorescent covalent organic framework for selective detection and adsorption of uranium | |
| Wang et al. | Adsorption kinetics of nitrate from aqueous solutions onto modified wheat residue | |
| Zhou et al. | Removal of bisphenol A from aqueous solution using modified fibric peat as a novel biosorbent | |
| CN101301604B (en) | Preparation method of magnetic powder heavy metal ion imprinted chitosan composite adsorbent | |
| Ma et al. | Preparation of novel polysulfone capsules containing zirconium phosphate and their properties for Pb2+ removal from aqueous solution | |
| Moghimi et al. | Adsorption behavior of Sb (III) in single and binary Sb (III)—Fe (II) systems on cationic ion exchange resin: Adsorption equilibrium, kinetic and thermodynamic aspects | |
| CN104475056A (en) | Preparation method of clomiphene polymer capable of adsorbing heavy metal ions and application of clomiphene polymer | |
| CN101898937B (en) | Method for adsorbing and recycling phenol in wastewater by polyamine macroporous resin | |
| CN102527087A (en) | Method for absorbing and recycling heavy metals by using persimmon tannins | |
| CN105670635A (en) | Preparation method of nano Ni/Fe-biochar composite material and application of nano Ni/Fe-biochar composite material in in-situ restoration of polybrominated diphenyl ether polluted soil | |
| CN1805086B (en) | Preparation method of silane coupled nanometer magnetic composite ferroferric oxide material | |
| CN107265548A (en) | A kind of method using the attapulgite depth adsorption and dephosphorization for loading hydrated ferric oxide | |
| CN106732481A (en) | A kind of pertechnetate adsorbent and its synthetic method and the application in radioactive wastewater is processed | |
| Dong et al. | Research on the application potential of spent biological activated carbon from BAC process to remove radionuclides Sr 2+ from water | |
| Rahman et al. | Cyclic tetra [(indolyl)-tetra methyl]-diethane-1, 2-diamine (CTet) impregnated hydrous zirconium oxide as a novel hybrid material for enhanced removal of fluoride from water samples | |
| CN103127916A (en) | Preparation method of tourmaline/magnetic chitosan microsphere treatment agent | |
| Yang et al. | High-efficiency and fast removal of As (III) from water by cerium oxide needles decorated macroporous carbon sponge | |
| CN108217810A (en) | A kind of method of benzotriazole pollutant in removal waste water | |
| CN104841368B (en) | A kind of leacheate regrown material and its application | |
| Huang et al. | Chitosan immobilized Chinese gallotannin: A potential adsorbent to enrich the rare metals Ge (Ⅳ), Ga (Ⅲ), and In (Ⅲ) | |
| CN106588951B (en) | A kind of porous metal-organic framework compound and its preparation method and application based on zinc | |
| CN104992740A (en) | Application of micropore MIL-101 material for adsorbing trace iodine in water | |
| Prasetyo et al. | Sol–gel synthesis of a humic acid-silica gel composite material as low-cost adsorbent for thorium and uranium removal | |
| Boutemedjet et al. | Sorption of malachite green by eucalyptus bark as a non-conventional low-cost biosorbent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180629 |
|
| RJ01 | Rejection of invention patent application after publication |