CN108479727A - A kind of method of phenyl amines component in styrene polymer and its adsorption recovery industrial wastewater that salicylic acid is modified - Google Patents
A kind of method of phenyl amines component in styrene polymer and its adsorption recovery industrial wastewater that salicylic acid is modified Download PDFInfo
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- CN108479727A CN108479727A CN201810227039.5A CN201810227039A CN108479727A CN 108479727 A CN108479727 A CN 108479727A CN 201810227039 A CN201810227039 A CN 201810227039A CN 108479727 A CN108479727 A CN 108479727A
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- China
- Prior art keywords
- modified
- salicylic acid
- styrene polymer
- phenyl amines
- sorbing material
- Prior art date
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- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 title claims abstract description 46
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 37
- 150000001448 anilines Chemical class 0.000 title claims abstract description 27
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 26
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229960004889 salicylic acid Drugs 0.000 title claims abstract description 23
- 229920000642 polymer Polymers 0.000 title claims abstract description 20
- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 14
- 238000011084 recovery Methods 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 38
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229960004050 aminobenzoic acid Drugs 0.000 claims abstract description 11
- 230000010355 oscillation Effects 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003463 adsorbent Substances 0.000 claims description 11
- 238000003795 desorption Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 230000008961 swelling Effects 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 238000009738 saturating Methods 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims 2
- 239000002351 wastewater Substances 0.000 abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 239000010881 fly ash Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 9
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KFUSEUYYWQURPO-UHFFFAOYSA-N 1,2-dichloroethene Chemical class ClC=CCl KFUSEUYYWQURPO-UHFFFAOYSA-N 0.000 description 2
- DQRXJTQZENKXNW-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.ClCC=CC1=CC=CC=C1 DQRXJTQZENKXNW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- -1 ozone oxidation-modified activated carbon Chemical class 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 240000000203 Salix gracilistyla Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A kind of method of phenyl amines component in the styrene polymer and its adsorption recovery industrial wastewater that are modified the invention discloses salicylic acid.The styrene polymer that this method is modified using the salicylic acid of synthesis adsorbs the phenyl amines components such as aniline, para-totuidine, parachloroanilinum and p-aminobenzoic acid in waste water as sorbing material, and maximum adsorption capacity respectively reaches 132,155,229,113 mg/g.The experimental results showed that adsorption capacity is apparently higher than maximum adsorption capacity of the sorbing materials such as activated carbon, flyash, modified zeolite to amino benzenes compounds.The method of the present invention has many advantages, such as that material preparation process is simple, reusable, adsorption conditions are mild, energy conservation and environmental protection, of low cost.
Description
Technical field
The invention belongs to the synthesis of adsorbent and technical field of sewage, specifically, being related to a kind of adsorption recovery work
The method of industry Aniline class component and its preparation of sorbing material.
Background technology
Pernicious water pollution accident frequently occurs with the development of modern industry.According to statistics, water dirt occurs altogether for 2000-2011
Dye accident 1176 rises, and the generation of these contamination accidents threatens the safety of water source.In these accidents, organic pollution accounts for sizable
Ratio.Such as 100 tons of benezene materials after Jilin Petrochemical Shuan Ben factories of company workshop is exploded occur within 2005（Benzene, nitrobenzene etc.）
Song Hua River is flowed into, river is caused and seriously pollutes, the life of littoral millions of residents is affected so that Harbin experience is up to
Five days cut off the water, is industrial disaster together.Major accident together has occurred in December, 2012 again, and there are about 8.7 tons of aniline to let out at that time
It drains in the turbid Zhanghe River, the water supply of Handan City is cut off, and causes the insufficient water of more than 100 ten thousand people.So administering water pollution problems
The problem of being paid close attention to jointly as global human.
Industrial wastewater is main pollution source of water body, there is millions of kinds of toxic compounds in industrial wastewater water body,
In just have phenyl amines component, they be widely present in dyestuff manufacture, textile and dyeing industry, plastic processing and pharmaceuticals industry etc. row
Industry.Phenyl amines component is one of main pollution sources as a kind of important Organic Chemicals, even if concentration can if very low
Endanger aquatile and polluted source.In fact, the waste water for the component containing phenyl amines discharged from these industries has become one
The environmental problem of a sternness.One kind should be developed, and quickly and effectively method removes it from industrial wastewater.So far, domestic
Method of the processing of outer report containing amino benzene analog waste water is broadly divided into three classes：The first kind is Physical, which is to pass through physical action
The component containing phenol in waste water is handled, includes mainly absorption method, solvent extraction, membrane separation process etc., wherein absorption method application is most；
Second class is chemical method, includes mainly Fenton oxidizing process, ultraviolet/hydrogen peroxide advanced oxidation processes, photocatalytic degradation method etc.；The
Three classes are bioanalysis, include mainly the methods of activated sludge process, biodegradation, enzymatic treatment.But the treatment effect of most methods
All undesirable, generally existing is of high cost, secondary pollution is serious, discharges the problems such as not up to standard.
Such as the disclosed use ozone oxidation-modified activated carbon of patent of invention document of Publication No. CN102001765A/
Modified montmorillonoid adsorbs process integration to handle aniline waste water, is first with ozone to waste water preliminary oxidation, successively by waste water then
It flows into modified activated carbon adsorption tank and modified montmorillonoid adsorption tank, aniline pollutant is adsorbed and removed, be Physical joint chemistry
The treatment technology of method, wherein ozone are very limited to the degree of oxidation of aniline, used modified activated carbon, modified montmorillonoid absorption
Agent prepares more complex, and adsorbent reactivation is difficult, discharge of wastewater problem not up to standard easily occurs.Such as publication number
CN102001765A's handles aniline waste water using the modified activated carbon of ozone oxidation/modified montmorillonoid absorption process integration,
It is that waste water is successively then flowed into modified activated carbon adsorption tank and modified montmorillonoid adsorbs first with ozone to waste water preliminary oxidation
Pond, aniline pollutant are adsorbed and removed, and are the treatment technology of Physical joint chemical method, wherein degree of oxidation of the ozone to aniline
Very limited, used modified activated carbon, modified montmorillonoid adsorbent prepare more complex, and adsorbent reactivation is difficult, easily occurs
Discharge of wastewater problem not up to standard.In addition, publication number CN103420475A and CN103663831A are all made of Fenton catalysis drops
Reaction treatment aniline waste water is solved, they pass through catalyzing and decomposing H2O2Macromolecular degrading aniline is small point by the hydroxyl radical free radical of generation
Sub- organic matter or mineralising are CO2And H2The inorganic matters such as O achieve the purpose that purify waste water.However, this method has the shortcomings that maximum
It is that in aniline waste water purification process, will produce a large amount of sludge, to increase the difficulty and cost of enterprise's after-treatment.Cause
This, it is extremely urgent to find a kind of method that really can handle to economical and efficient amino benzene analog waste water.
Absorption method using wide, and had using absorption method in sewage treatment field and can be used repeatedly, operate letter
Just the features such as recycling that is, of low cost, environmental-friendly, can realizing resource, therefore absorption method is applied to remove in waste water
Phenyl amines component meets green, the efficient theme of environment in recent years engineering circles promotion.
Invention content
The purpose of the present invention is being directed to problems of the prior art, a kind of economic, environmental protection removing Industry Waste is provided
The method and its adsorbent of phenyl amines component in water.
To achieve the goals above, the present invention adopts the following technical scheme that：
The present invention is reacted to it using Friedel-Crafts on the basis of polystyrene -1-chloro-4-methyl-benzene polymer
While carrying out super crosslinking, bigcatkin willow acid molecule is loaded to it has high absorption property to prepare to Aniline class component
The styrene polymer that salicylic acid is modified.
A kind of styrene polymer that salicylic acid is modified, is made of following steps：
（1）Polystyrene-chloromethyl styrene resin and 1,2- dichloroethane solutions are pressed 1:30~1:80 mass ratios mix,
Swelling is overnight；
（2）Catalyst and modifying agent salicylic acid, catalyst and the polystyrene -1-chloro-4-methyl-benzene of addition is added to swelling product
The mass ratio of resin is 1:8~1:12；The modifying agent of addition and the mass ratio of polystyrene-chloromethyl styrene resin are
1:40~1:60.It is warming up to 105 ~ 125 DEG C in 1 ~ 2 h the reaction was continued 11 ~ 15 h；
（3）After completion of the reaction, filtration product alternately washs 1% aqueous hydrochloric acid solution of product and absolute ethyl alcohol to cleaning solution in saturating
Bright shape, the pH for being then washed with distilled water to cleaning solution again are neutrality, filter resin, and 80 ~ 85 DEG C of 10 ~ 14 h of vacuum drying are obtained
The styrene polymer being modified to salicylic acid.
In the styrene polymer that above-mentioned salicylic acid is modified, preferably, the catalyst is zinc chloride or chlorination
Iron.
The styrene polymer being modified using above-mentioned salicylic acid is as sorbing material come the benzene in adsorption recovery industrial wastewater
The method of amine component, includes the following steps：
（1）The styrene polymer that sorbing material salicylic acid is modified is put into the industrial wastewater containing phenyl amines component, room
The lower oscillation of temperature or stirring, are separated by filtration, phenyl amines component, which is adsorbed, in solution stays in sorbing material；
（2）The sorbing material of adsorption saturation is put into desorbing agent, vibrate at room temperature or is stirred, is separated by filtration, recycling obtains
Desorption agent solution containing phenyl amines component and adsorbent；
（3）Recycling is obtained into sorbing material and is placed in 75 ~ 85 DEG C of drying in oven, dry 8 ~ 10 h, storage is in case repeat next time to make
With.
In the methods described above, preferably, at least containing aniline, parachloroanilinum in the phenyl amines component and to ammonia
Yl benzoic acid is one such.
In the methods described above, preferably, the mass volume ratio of sorbing material and industrial wastewater is 1:12~18:1
g/ml.Duration of oscillation is 10 ~ 24 h, and temperature is 15 ~ 45 DEG C.
In the methods described above, preferably, the desorbing agent is absolute ethyl alcohol or industrial alcohol.Desorption time be 8 ~
18 h, temperature are 15 ~ 35 DEG C.After desorption, sorbing material is recyclable after drying and reuses.
Compared with prior art, the present invention has the advantages that：
1, the method for synthesis sorbing material of the present invention is the synthesis technology and condition of conventional absorbtion separation resin, side
Method is simple, non-secondary pollution, easily realizes that industrialized production, production cost are low.In the method for adsorption recovery phenyl amines component, institute
It elutes the eluent containing phenyl amines component to recycle by way of vacuum distillation, secondary pollution will not be caused.In addition,
Phenyl amines constituent content in industrial wastewater after adsorption treatment is low.And the sorbing material prepared has preferable stablize
Property, Reusability can be recycled, this to applying expanding production significant in the industry.
2, the present invention prepares the sorbing material of gained, has insoluble in properties such as acid, alkali, organic solvents, and with good
Good mechanical strength, can be repeated several times use, is easy to store and transport.
3, adsorption separating method of the present invention is directly to put into sorbing material in the industrial wastewater containing phenyl amines component,
Adsorption separation process can be completed at normal temperatures and pressures.
4, the present invention use absolute ethyl alcohol or industrial alcohol to be used as desorbing agent, the regeneration technology of sorbing material simply, recycle
It is at low cost.
5, the sorbing material of present invention gained carries out static and dynamic to the phenyl amines component in waste water at normal temperatures and inhales
It is attached, there is good adsorption effect and desorption effect, and after desorptive activation, reuse, adsorption capacity does not change substantially.
Specific implementation mode
With reference to embodiment, the present invention is described further, but scope of protection of the present invention is not limited thereto.
Embodiment 1：
The preparation for the styrene polymer sorbing material that salicylic acid is modified（1）：
Take styrene-chloromethyl styrene resin（5 g）In in 50ml three neck round bottom flask, 1,2-, bis- chloroethenes of 25 mL are added
Alkane swelling is overnight.Catalyst zinc chloride is added into the swelling product（0.6 g）With 0.1 g of modifying agent salicylic acid, it is slowly stirred
It is uniformly mixed to system.In 1.5 h, 115 DEG C are to slowly warm up to, the reaction was continued at such a temperature 12 h.After completion of the reaction,
1 % aqueous hydrochloric acid solutions of product and absolute ethyl alcohol are alternately washed to cleaning solution and are transparent by filtration product, then again with distillation
The pH of water washing to cleaning solution is neutrality.Resin is filtered, product is placed in vacuum drying chamber, 80 DEG C are dried under reduced pressure 12 h, obtain
The styrene polymer sorbing material being modified to final product salicylic acid.
Embodiment 2：
The preparation for the styrene polymer sorbing material that salicylic acid is modified（2）：
Take styrene-chloromethyl styrene resin（5 g）In in 50ml three neck round bottom flask, 1,2-, bis- chloroethenes of 25 mL are added
Alkane swelling is overnight.Catalyst iron chloride is added into the swelling product（0.6 g）With about 0.15 g of modifying agent salicylic acid, slowly stir
It mixes to system and is uniformly mixed.In 1.5 h, 115 DEG C are to slowly warm up to, the reaction was continued at such a temperature 12 h.Reaction finishes
Afterwards, 1 % aqueous hydrochloric acid solutions of product and absolute ethyl alcohol are alternately washed to cleaning solution and are transparent, then used again by filtration product
The pH for distilling water washing to cleaning solution is neutrality.Resin is filtered, product is placed in vacuum drying chamber, 80 DEG C are dried under reduced pressure 12
H obtains the styrene polymer sorbing material of final product salicylic acid modification.
Embodiment 3：
The processing of the solution containing aniline waste water：
The aniline waste water solution of the 1000mg/L of 50 mL is placed in the conical flask of 100 mL, is then put into the conical flask
0.05 g of sorbing material of embodiment 1 is placed in 20 DEG C, vibrates 18 h with the full temperature culture shaking table of the speed oscillation of 200 rpm.It shakes
After swinging, take supernatant, using ultraviolet-visible spectrophotometer to adsorb the concentration of the front and back waste water solution aniline into
Row analysis.It is learnt by result, sorbing material is 132 mg/g to the adsorption capacity of aniline；Then it is eluted with absolute ethyl alcohol,
The content that aniline in desorption solution is surveyed using ultraviolet-visible spectrophotometer, the eluting rate known to result are 93 %.
Embodiment 4：
The processing of the waste water solution containing para-totuidine：
The para-totuidine waste water solution of the 1000mg/L of 50 mL is placed in the conical flask of 100 mL, then into the conical flask
0.05 g of sorbing material for putting into embodiment 1 is placed in 20 DEG C, with the full temperature culture shaking table oscillation 18 of the speed oscillation of 200 rpm
h.After oscillation, supernatant is taken, using ultraviolet-visible spectrophotometer to adsorbing the front and back waste water solution para-totuidine
Concentration analyzed.It is learnt by result, sorbing material is 155 mg/g to the adsorption capacity of para-totuidine；Then with anhydrous second
Alcohol is eluted, and the content of para-totuidine in desorption solution is surveyed using ultraviolet-visible spectrophotometer, the elution known to result
Rate is 95 %.
Embodiment 5：
The processing of the waste water solution containing parachloroanilinum：
The parachloroanilinum waste water solution of the 1000mg/L of 50 mL is placed in the conical flask of 100 mL, then into the conical flask
0.05 g of sorbing material for putting into embodiment 2 is placed in 20 DEG C, with the full temperature culture shaking table oscillation 18 of the speed oscillation of 200 rpm
h.After oscillation, supernatant is taken, using ultraviolet-visible spectrophotometer to adsorbing the front and back waste water solution parachloroanilinum
Concentration analyzed.It is learnt by result, sorbing material is 229 mg/g to the adsorption capacity of parachloroanilinum；Then with anhydrous second
Alcohol is eluted, and the content of parachloroanilinum in desorption solution is surveyed using ultraviolet-visible spectrophotometer, the elution known to result
Rate is 95 %.
Embodiment 6：
The processing of the waste water solution containing p-aminobenzoic acid：
The p-aminobenzoic acid waste water solution of the 1000mg/L of 50 mL is placed in the conical flask of 100 mL, then to the taper
0.05 g of sorbing material of input embodiment 2 in bottle is placed in 20 DEG C, is shaken with the full temperature culture shaking table of the speed oscillation of 200 rpm
Swing 18 h.After oscillation, supernatant is taken, using ultraviolet-visible spectrophotometer to adsorbing the front and back waste water solution pair
The concentration of aminobenzoic acid is analyzed.It is learnt by result, sorbing material is 113 mg/ to the adsorption capacity of p-aminobenzoic acid
g；Then it is eluted with absolute ethyl alcohol, p-aminobenzoic acid in desorption solution is surveyed using ultraviolet-visible spectrophotometer
Content, the eluting rate known to result are 96 %.
Embodiment 7：
The regeneration of sorbing material and repeat performance：
Grey black spherical shape adsorbent is obtained after sorbing material after being desorbed in embodiment 6 is dried in vacuo 6 h at 80 DEG C.It will
The p-aminobenzoic acid waste water solution of the 1000mg/L of 50 mL is placed in the conical flask of 100 mL, is then thrown into the conical flask
Enter the above adsorbent, is placed in 20 DEG C, 18 h are vibrated with the full temperature culture shaking table of the speed oscillation of 200 rpm.After oscillation,
Take supernatant, using ultraviolet-visible spectrophotometer to adsorb the concentration of the front and back waste water solution p-aminobenzoic acid into
Row analysis.It is learnt by result, sorbing material is 109 mg/g to the adsorption capacity of p-aminobenzoic acid.Adsorption/desorption repeats 5 altogether
After secondary, it is found that the adsorbent prepared is held essentially constant the absorption property of p-aminobenzoic acid.
Claims (6)
1. the styrene polymer that a kind of salicylic acid is modified, it is characterised in that be made of following steps：
（1）Polystyrene-chloromethyl styrene resin and 1,2- dichloroethane solutions are pressed 1:30~1:80 mass ratios mix,
Swelling is overnight；
（2）Catalyst and modifying agent salicylic acid, catalyst and the polystyrene -1-chloro-4-methyl-benzene of addition is added to swelling product
The mass ratio of resin is 1:8~1:12；The modifying agent of addition and the mass ratio of polystyrene-chloromethyl styrene resin are
1:40~1:60；It is warming up to 105 ~ 125 DEG C in 1 ~ 2 h the reaction was continued 11 ~ 15 h；
（3）After completion of the reaction, filtration product alternately washs 1% aqueous hydrochloric acid solution of product and absolute ethyl alcohol to cleaning solution in saturating
Bright shape, the pH for being then washed with distilled water to cleaning solution again are neutrality, filter resin, and 80 ~ 85 DEG C of 10 ~ 14 h of vacuum drying are obtained
The styrene polymer being modified to salicylic acid.
2. the styrene polymer that salicylic acid as described in claim 1 is modified, which is characterized in that the catalyst be zinc chloride or
Iron chloride.
3. the styrene polymer being modified using salicylic acid described in claim 1 is as sorbing material come adsorption recovery industrial wastewater
In phenyl amines component method, it is characterised in that include the following steps：
（1）The styrene polymer that sorbing material salicylic acid is modified is put into the industrial wastewater containing phenyl amines component, room
The lower oscillation of temperature or stirring, are separated by filtration, phenyl amines component, which is adsorbed, in solution stays in sorbing material；
（2）The sorbing material of adsorption saturation is put into desorbing agent, vibrate at room temperature or is stirred, is separated by filtration, recycling obtains
Desorption agent solution containing phenyl amines component and adsorbent；
（3）Recycling is obtained into adsorbent and is placed in 75 ~ 85 DEG C of drying in oven, dry 8 ~ 10 h, storage is in case reuse next time.
4. according to the method described in claim 3, it is characterized in that, at least containing aniline in the phenyl amines component, to chlorobenzene
One kind in amine and p-aminobenzoic acid.
5. according to the method described in claim 3, it is characterized in that, the mass volume ratio of sorbing material and industrial wastewater is 1:12
~18:1 g/ml, duration of oscillation are 10 ~ 24 h, and temperature is 15 ~ 45 DEG C.
6. according to the method described in claim 3, it is characterized in that, the desorbing agent is absolute ethyl alcohol or industrial alcohol；Desorption
Time is 8 ~ 18 h, and temperature is 15 ~ 35 DEG C.
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| CN116162793A (en) * | 2021-11-24 | 2023-05-26 | 西藏矿业发展股份有限公司 | Method and device for removing soluble organic matters, calcium and magnesium in carbonic acid type salt lake brine |
| CN116285079A (en) * | 2021-02-22 | 2023-06-23 | 李丽 | A preparation method of insulating material for cables used in charging piles of new energy vehicles |
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| CN116162793A (en) * | 2021-11-24 | 2023-05-26 | 西藏矿业发展股份有限公司 | Method and device for removing soluble organic matters, calcium and magnesium in carbonic acid type salt lake brine |
| CN116162793B (en) * | 2021-11-24 | 2024-07-26 | 西藏矿业发展股份有限公司 | Method and device for removing dissolved organic matter and calcium and magnesium from carbonate salt lake brine |
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