CN108144589A - A kind of resin and preparation method thereof and the method using the resin treatment waste water - Google Patents
A kind of resin and preparation method thereof and the method using the resin treatment waste water Download PDFInfo
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- CN108144589A CN108144589A CN201711437849.5A CN201711437849A CN108144589A CN 108144589 A CN108144589 A CN 108144589A CN 201711437849 A CN201711437849 A CN 201711437849A CN 108144589 A CN108144589 A CN 108144589A
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- 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
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- 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
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- 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
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- 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
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
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- 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
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- 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
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Abstract
The present invention relates to a kind of preparation methods of modified porous absorption resin, include the following steps：1) porous copolymerization Archon is mixed and is swollen with sweller, more vinyl function monomers, obtain swelling product, wherein the raw material of the porous copolymerization Archon includes α ring-alkylated styrenes and aromatic multi-vinyl based compound；2) swelling product polymerize in an inert atmosphere obtained by step 1), obtains modified porous absorption resin.The invention further relates to the modified porous absorption resin for using above method preparation and the resin treatment waste water is used, the method for organic matter particularly in the difficult biochemistry of low concentration.After resin treatment of the present invention, the TOC elimination factors of low concentration difficulty biochemical waste water are up to more than 90%.The present invention is especially suitable for the qualified discharge processing of the waste water such as the biochemical tail water containing low concentration biorefractory organic, reverse osmosis concentrated water, applied widely, effect stability, processing cost is low, and new solution is provided to realize industrial water zero-emission, reducing environmental pollution.
Description
Technical field
The invention belongs to technical field of sewage, and in particular to a kind of modified porous absorption resin and preparation method thereof,
And the method using organic matter in the modified porous absorption resin treatment waste water, the particularly difficult biochemistry of low concentration.
Background technology
With increasingly stringent and social environment consciousness the continuous enhancing of national environmental protection policy, regulation, with biological oxidation skill
Art, reverse osmosis membrane technology etc. are received significant attention for the wastewater treatment and reuse technique of representative.However, due to industrial wastewater, it is special
It is not the waste water composition complexity of chemical industry, pharmacy, dyeing, organic matter therein is often difficult to go completely by above-mentioned technique
It removes, leading to that treated, the total organic carbons such as biochemical tail water, reverse osmosis concentrated water (TOC) are exceeded, can not direct emission or reuse.More
It is important, although remaining organic matter content is relatively low in tail water, the usually derivative of aromatic hydrocarbon such as phenol, benzoquinones, double
Phenol A, chlorobenzene, 2,3- acid, beta naphthal, aniline etc. have the mankind and environment higher toxicity, and there are carcinogenic, causes for moieties
Abnormal, mutagenic potential danger.Development and application low concentration difficulty biochemical waste water treatment process are to mitigating environmental pollution, improving resource
Utilization rate is of great significance.
It is a kind of artificial synthesized sorbing material with porous three dimensional structure to adsorb resin, passes through its huge specific surface
Product, effect is isolated and purified by netted segment and by performances such as Van der Waals force, the hydrogen bonds between binding molecule (adsorbate), is applied
In low concentration difficulty biochemical waste water process field, with cocnentration factor is high, operating cost is low, simple operation and other advantages.But absorption tree
The adsorption capacity of fat and the polarity of material, specific surface area, aperture etc. are closely related, due to waste water composition complexity, adsorptive hindrance because
Element is more, and conventional single commercial absorption resin is difficult to realize the efficient absorption to the Organic substance in water that gives up and desorption.Chinese invention
Patent CN104230079B discloses a kind of method for detaching reverse osmosis concentrated Organic substance in water using resin is adsorbed, and is directed to
Two kinds of commercial resins.For different low concentration difficulty biochemical waste water systems, the different absorption tree of design, selection polarity, pore structure
Fat can further improve the treatment effeciency of resin absorption technique.Chinese invention patent CN 100554291C disclose one kind and contain
There is the preparation method of the linear block copolymers of alpha-methyl styrol structural unit, utilize α-methylstyrenecopolymer structure list
First depolymerization at a certain temperature generates free radicals, and forms macromole evocating agent, causes block, the grafting of other function monomers.So
And the scope of application of this method is the linear α-methylstyrenecopolymer that can be dissolved in solvent, to cross-linking polymer
How graft modification is not directed to for system.
On the other hand, in resin desorption liquid how tree is properly disposed containing high concentration, high toxicity, difficult biochemical organic matter
Steatolysis imbibition becomes the bottleneck of the development and application.Chinese invention patent CN101659457B discloses a kind of using alkaline-resisting
The method of the property inorganic stripping liquid of nanofiltration membrane treatment resin, however this method is not related to for how the organic stripping liquid of resin is handled
And.
Therefore it needs to seek a kind of modified porous absorption resin and using the modified porous absorption resin treatment waste water, it is special
It is not the method for organic matter during low concentration is difficult biochemical, for solving, sewage treating efficiency in the prior art is low, the low, resin of selectivity
It is difficult to recycle, the problems such as processing cost is high and complicated for operation.
Invention content
The purpose of the present invention is overcoming above-mentioned deficiency of the prior art, the present invention provides a kind of modified porous absorption resin
Preparation method, use this method prepare resin and use the resin treatment waste water, particularly low concentration difficulty biochemical waste water
The method of middle organic matter realizes the efficient absorption to the Organic substance in water that gives up and desorption.
The present invention provides a kind of preparation methods of modified porous absorption resin, include the following steps：
1) porous copolymerization Archon is mixed and is swollen with sweller, more vinyl function monomers, obtain swelling product, wherein institute
The raw material for preparing for stating porous copolymerization Archon includes alpha-alkyl phenylethylene and aromatic multi-vinyl based compound；
2) swelling product polymerize in an inert atmosphere obtained by step 1), obtains modified porous absorption resin.
In some embodiments of the present invention, alpha-alkyl phenylethylene can be C in step 1)1~C10Alkyl-substituted benzene
It is one or more in ethylene.In preferred technical solution, alpha-alkyl phenylethylene is polymerization activity height and structure in step 1)
More stable α-methylstyrene, α-ethyl styrene, α-isopropyl styrene or α-the tertiary fourth of generation free radical after unit fracture
It is one or more in base styrene.
In embodiments of the invention, aromatic multi-vinyl based compound is containing at least two unsaturations in step 1)
It is one or more in the aromatic compound and its derivative of carbon-carbon double bond.In some preferred embodiments, aromatic series
More vinyl compounds can be o- divinylbenzene, m- divinylbenzene, p- divinylbenzene, trivinylbenzene, diethyl
It is one or more in alkenyl toluene, divinylxylene.In a more preferred embodiment, aromatic multi-vinyl base chemical combination
Object is one or more in o- divinylbenzene, m- divinylbenzene, p- divinylbenzene or trivinylbenzene.Into
In one step preferred embodiment, aromatic multi-vinyl based compound is m- divinylbenzene.
In some embodiments of the present invention, the quality that feeds intake of alpha-alkyl phenylethylene and aromatic multi-vinyl based compound
Than being 1:20~1:1, preferably 1:10~1:2.
In some embodiments of the present invention, the preparation method of porous copolymerization Archon described in step 1) includes following step
Suddenly：Under pore-foaming agent effect, suspension copolymerization alpha-alkyl phenylethylene and the aromatic multi-vinyl based compound as crosslinking agent, gained
Product obtains porous copolymerization Archon after washing, extracting pore-foaming agent；Preferably, it is also added in the reaction system of the suspension copolymerization
There are initiator, deionized water, dispersant, reagent and additive in polymerization；Preferably, oil phase composition is in the suspension copolymerization：Alpha-alkyl second
Alkene, more vinyl aromatic crosslinking agents, pore-foaming agent, initiator；Water phase forms：Deionized water, dispersant, reagent and additive in polymerization.
In some embodiments of the present invention, the preparation method of porous copolymerization Archon described in step 1) is more specifically：
Under pore-foaming agent effect, suspension copolymerization alpha-alkyl phenylethylene and aromatic multi-vinyl based cross-linker, through washing, extracting
Porous copolymerization Archon is obtained after pore-foaming agent.Wherein, oil phase composition is in suspension copolymerization：Alpha-alkyl phenylethylene, aromatic multi-vinyl
Based compound, pore-foaming agent, initiator；Water phase forms：Deionized water, dispersant, reagent and additive in polymerization.Oil phase/water phase mass ratio is
1:5~1:2, polymerization temperature is 65~75 DEG C, 4~10h of polymerization time.
To the restriction of aromatic multi-vinyl based cross-linker and alpha-alkyl phenylethylene as hereinbefore defined.
In some embodiments, the amount ratio of alpha-alkyl phenylethylene and aromatic multi-vinyl based cross-linker is 1:20~1:
1, preferably 1:10~1:2.
In some embodiments, above-mentioned pore-foaming agent is one in toluene, dimethylbenzene, ethylbenzene, 3# white oils, 200# solvent naphthas
Kind is a variety of, and monomer/pore-foaming agent mass ratio is 3:1~1:3, preferred mass ratio is 2:1~1:2；
In some embodiments, above-mentioned initiator is selected from azodiisobutyronitrile, dibenzoyl peroxide, peroxidating spy penta
It is one or more in tert-butyl acrylate, peroxidating two (2- toluyls), dioctanoyl peroxide, dilauroyl peroxide, it is excellent
Azodiisobutyronitrile is selected as initiator.In some embodiments, alpha-alkyl phenylethylene and aromatic multi-vinyl based cross-linker
Quality sum be 200 to the mass ratio of initiator:1~50:1.
In some embodiments, above-mentioned dispersant is selected from polyvinyl alcohol, gelatin, hydroxypropyl methyl cellulose, ethoxy
One or more in cellulose, hydroxypropyl cellulose, preferred dispersants are polyvinyl alcohol or gelatin.In some embodiments
In, dispersant accounts for 0.01~0.1wt.% of water phase, preferably accounts for 0.025~0.075wt.% of water phase.In some embodiments
In, also sodium chloride can be added in into suspension copolymerization system as dispersing aid, the dispersing aid accounts for the mass percent of water phase
For 1~10wt.%.
In some embodiments, the one kind of above-mentioned reagent and additive in polymerization in methylene blue, sodium nitrite, sodium thiosulfate
It is or a variety of.The reagent and additive in polymerization is the 10 of water phase quality-6~10-7Times.
In some embodiments, porous copolymerization Archon is dried before use.Then those of ordinary skill in the art
It is known that, if inherent characteristic such as particle diameter distribution and specific surface area for not influencing porous copolymerization Archon etc. is dried.This is dry
The method that this field routine can be used in dry step carries out.In some embodiments, using mode of heating to porous copolymerization Archon
It is dried, heating temperature is 60~80 DEG C, and heating time is 5~10h.
In other embodiments of the present invention, porous copolymerization Archon can also be by polymerization commonly used in the art
Prepared by method.Books《Ion exchange and absorption resin》(He Ping Lin, Huang Wenqiang, the publication of education of science and technology of Shanghai society, nineteen ninety-five go out
Version) in this method is described in detail.
The porous copolymerization Archon of the present invention is preferably comprised in polymerized unit：At least one α-alkane of (1) 5~50 mass parts
Base styryl repetitive unit；At least one aromatic multi-vinyl base repetitive unit of (2) 50~95 mass parts.
The porous copolymerization Archon of the present invention has following characteristics：(1) particle diameter distribution is 100~1500 μm；(2) BET compares table
Area is 200~800m2/ g, BET absorption average pore size are 3.0~30.0nm, and single-point absorption total pore volume is 0.3~1.5mL/g.
Function in more vinyl function monomers alleged by the present invention refers to there is adsorption function to useless Organic substance in water.At this
Invention some embodiments in, in step 1) more vinyl function monomers can be aromatic monomer or polarity esters monomer or
A combination thereof, wherein aromatic monomer are nonpolarity or low pole monomers.In some preferred embodiments, aromatic monomer
Including o- divinylbenzene, m- divinylbenzene, p- divinylbenzene, trivinylbenzene, divinyl toluene, divinyl
It is one or more in base dimethylbenzene.In a more preferred embodiment, aromatic monomer is divinylbenzene.It is excellent at other
In the embodiment of choosing, polarity esters monomer includes ethyleneglycol dimethyacrylate, allyl methacrylate, itaconic acid alkene
Propyl ester, trimethacrylate acid glyceride, trimethacrylate acid trimethylolpropane ester, acrylic acid tricyclodecenyl esters, metering system
It is one or more in sour dicyclopentenyl 2-ethoxyethyl acetate and trimerization triallyl isocyanurate.In other preferred embodiment party
In case, polarity esters monomer is selected from one or both of ethyleneglycol dimethyacrylate and allyl methacrylate.
In some embodiments of the present invention, step 1) is relative to the porous copolymerization Archons of 1g, more vinyl functions
The inventory of monomer is 0.1~2.0mL, preferably 0.5~1.5mL.
In some embodiments of the present invention, the one kind of the sweller of step 1) in high boiling aromatic hydrocarbon class solvent
It is or a variety of.In some preferred embodiments, high boiling aromatic hydrocarbon class solvent is the aromatic hydrocarbon solvent of boiling point >=80 DEG C.
In some preferred embodiments, sweller is one or more in substituted benzene solvent.In further preferred implementation
In scheme, the one kind of sweller in toluene, dimethylbenzene, ethylbenzene, isopropylbenzene, chlorobenzene, o-dichlorohenzene, nitrobenzene, methyl phenyl ethers anisole
It is or a variety of.In more preferred embodiment, sweller is one or both of paraxylene and ethylbenzene.
In some embodiments of the present invention, relative to the porous copolymerization Archons of 1g, the throwing of the sweller in step 1)
Doses is 1~10mL, preferably 2~5mL.
In some embodiments of the present invention, the swelling in step 1) carries out at room temperature, and the time of swelling is at least
1h, preferably at least 2h.
In the preparation method of the present invention, under the capillarity of porous copolymerization Archon pore structure, sweller and more vinyl
Function monomer is inhaled into inside Archon, forms swelling product.In some embodiments of the present invention, the porous copolymerization Archons of 1g are inhaled
Attached 0.5~5.0mL swellers and more vinyl function monomers, the porous copolymerization Archon absorption 1~3mL swellers of preferably 1g and more second
Alkenyl function monomer.
In some embodiments of the present invention, step 1) is further included after swelling step by the swelling product filtering
And/or the step of centrifuging to purify, for removing extra sweller and more vinyl function monomers.
In preparation method step 2) of the present invention, under inert environments and heating condition, the alpha-alkyl in porous copolymerization Archon
Styrol structural unit molecular chain rupture generates macromolecular radical, causes more vinyl function monomer polymerizations, crosslinking, grafting
It is fixed on porous copolymerization Archon surface and inside.
In some embodiments of the present invention, step 2) be aggregated in 80~140 DEG C at a temperature of carry out.The present invention's
In some embodiments, the inert environments that polymerisation occurs are provided by inert gas, for example, nitrogen, argon gas etc., it is preferable to use
Nitrogen.In some embodiments of the present invention, the polymerization reaction time of step 2) is 1~10h, is reacted by being cooled to room temperature
Or it is passed through air and terminates.
In some embodiments of the present invention, polymeric reaction temperature should be less than selected more vinyl function lists in step 2)
The minimum temperature of thermal-initiated polymerization occurs for body, in order to avoid system is lumpd, influences final resin property.
In some embodiments of the present invention, it after step 2) carries out polymerisation, further includes and uses more ethylene
Obtained by good solvent cleaning, filtering and the drying of base function monomer the step of modified porous absorption resin.Herein referred more second
The good solvent of alkenyl function monomer refer mainly to toluene, ethylbenzene, dimethylbenzene, diethylbenzene, acetone, methanol, ethyl alcohol, ethyl acetate,
Propyl acetate, tetrahydrofuran, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide etc..
In some embodiments, modified porous absorption resin is dried before use.Then ordinary skill
Personnel it is known that, if be dried do not influence it is modified porous absorption resin inherent characteristic such as particle diameter distribution and specific surface area
Deng.The method that this field routine can be used in the drying steps carries out.
The present invention also provides a kind of modified porous absorption resins prepared using aforementioned preparation process.The modified porous suction
Attached resin preferably comprises in polymerized unit：At least one alpha-alkyl phenylethylene base monomer of (1) 4~48 mass parts repeats single
Member；At least one aromatic multi-vinyl base monomeric repeating unit of (2) 40~90 mass parts；At least the one of (3) 5~20 mass parts
The more vinyl function monomer repetitive units of kind.
In some embodiments, above-mentioned modified porous absorption resin is also equipped with following characteristics：(1) particle diameter distribution is 200
~2000 μm；BET specific surface area is 600~1500m2/ g, BET absorption average pore size are 3.0~30.0nm, and single-point adsorbs total hole
Hold for 0.7~2.5mL/g.
The present invention also provides a kind of methods for handling useless Organic substance in water, include the following steps：Waste water is changed by filling
Property porous adsorption resin resin column adsorbed, collect efflux, it is therein it is modified porous absorption the above-mentioned preparation method of resin
Modified porous absorption resin obtained.
In some embodiments of the present invention, the TOC of waste water is 20~1000mg/L, preferably 50~500mg/L.
In some embodiments of the present invention, for the waste water of processing be low concentration be difficult to using standard biologic aoxidize
The waste water of technical finesse, i.e. low concentration difficulty biochemical waste water.
In some embodiments of the present invention, low concentration difficulty biochemical waste water is containing aromatic hydrocarbon derivative such as phenol, quinone, virtue
Fragrant race's acid, aromatic amine, halogenated aromatic etc. are difficult to the waste water of the organic matter using the processing of standard biologic oxidation technology, these have
Machine object can be such as phenol, benzoquinones, bisphenol-A, chlorobenzene, 2,3- acid, beta naphthal, aniline in one kind or its mixture.It is low
The methods of FT-IR, GC-MS, HPLC-MS can be used in the concrete composition of organic matter in concentration difficulty biochemical waste water determines.
In some embodiments of the present invention, the adsorption process that low concentration difficulty biochemical waste water flows through resin column is to connect
What continuous, dynamic form carried out, flow velocity is 0.1~7BV/h, and preferably 0.5~3BV/h, wherein BV are defined as handling this useless
The volume of the modified porous absorption resin of water.In some preferred embodiments, low concentration difficulty biochemical waste water is adsorbed
Temperature is 4~50 DEG C, preferably 15~40 DEG C.In embodiments of the invention, it is modified more to refer to waste water stream for the temperature of absorption
Temperature during macroporous adsorbent resin.In some embodiments, which is maintained by external temperature controlling instruments.
The present invention it is modified porous absorption resin polarity and polymerized unit composition should with it is organic in low concentration difficulty biochemical waste water
The polarity and concrete composition of object match, i.e., low pole, middle polarity, Qiang Ji is respectively adopted in low polarity, middle polarity, highly polar waste water
Property resin treatment.The polarity of modified porous absorption resin is determined by the type and ratio of vinyl function monomers more in step 1).
When the molar ratio that aromatic monomer accounts for more vinyl function monomer total amounts in step 1) is higher than 80%, i.e. polarity esters monomer mole
When only containing aromatic monomer during than being less than 20% or in the modified porous absorption resin, which is weak
Polar resin；When the molar ratio that aromatic monomer accounts for more vinyl function monomer total amounts in step 1) is less than 20%, i.e. polarity ester
When containing only polarized esters monomer when class monomer mole ratio is higher than 80% or in the modified porous absorption resin, this is modified porous
Absorption resin is highly polar resin；When the molar ratio that aromatic monomer accounts for more vinyl function monomer total amounts in step 1) is in
When between 20%-80%, modified porous absorption resin is middle polar resin.
It is rough that the paper chromatography in the organic solvent of opposed polarity can be used in the polarity of organic matter in low concentration difficulty biochemical waste water
Judgement.The different solubility of the different organic matter of polarity in a solvent, the distance moved on filter paper, i.e. Rf value are different, such as
The fruit Organic substance in water majority Rf value in nonpolar solvent such as petroleum ether, carbon tetrachloride, toluene that gives up is larger, then judges that this is low
Concentration difficulty biochemical waste water is low polarity waste water；, whereas if compare in polar solvent such as tetrahydrofuran, ethyl acetate, acetone
Shifting value is larger, then it is highly polar waste water to judge the low concentration difficulty biochemical waste water；If useless Organic substance in water is in non-polar and polar
Rf value is suitable in solvent, then it is middle polarity waste water to judge the low concentration difficulty biochemical waste water.
In some embodiments of the present invention, the pH before low concentration difficulty biochemical waste water is adsorbed is 2~13, preferably
3~12.In some embodiments of the present invention, it needs to be pre-adjusted pH according to useless Organic substance in water composition, it is more to improve modification
The adsorption efficiency of macroporous adsorbent resin.If Phenol for Waste Water, quinone, aromatic series acid are more, wastewater pH is adjusted to meta-acid
Property；If aromatic amine substance is more in waste water, wastewater pH is adjusted to meta-alkalescence.
In some embodiments of the present invention, the method for handling useless Organic substance in water further includes following steps：
Collect efflux after, using in acid solution, aqueous slkali, alcoholic solvent or acetone it is one or more as desorption elution
The desorption eluent is flowed through the modified porous absorption resin being loaded in the resin and carries out desorption and regeneration to it, received by liquid
Collect efflux, obtain stripping liquid；
In some preferred embodiments, acid solution mass concentration is 0.1~6wt.%, and the quality of the aqueous slkali is dense
It spends for 0.1~6wt.%.
In a further preferred embodiment, acid solution is one or both of aqueous solution of hydrochloric acid or sulfuric acid；Alkali
Solution is one or more in the aqueous solution or ammonium hydroxide of NaOH, KOH；Alcoholic solvent is one kind in methanol, ethyl alcohol or isopropanol
It is or a variety of.
In some embodiments of the present invention, desorption process is carried out in the form of continuous, dynamic, desorbs eluent
Flow velocity be 0.1~7BV/h, preferably 0.5~3BV/h；The temperature of desorption and regeneration is 4~50 DEG C, preferably 25~45 DEG C.
In embodiment of the present invention, the temperature of desorption and regeneration refers to temperature when desorption eluent flows through modified porous absorption resin.
In some embodiments, which is maintained by external temperature controlling instruments.
In some embodiments of the present invention, the purifying techniques pair commonly used in the art such as distillation, extraction need to be used
Stripping liquid carries out purification concentration, to improve the cycles of concentration of organic matter in stripping liquid, obtains the concentrate of the stripping liquid, while real
The reuse of existing stripping liquid.In some preferred embodiments, the TOC of the concentrate of stripping liquid or the stripping liquid for 2000~
40000mg/L, preferably 10000~35000mg/L.
In some embodiments of the present invention, it using Wet Oxidation Process commonly used in the art, is particularly catalyzed
Wet Oxidation Process, such as catalytic wet oxidation technology and device disclosed in patent CN104761041B, processing is above-mentioned to be contained
The stripping liquid of organic matter or its concentrate, to obtain TOC removal rates>95% waste water.
The beneficial effects of the present invention are：
(1) polarity of the absorption resin prepared using the method for the present invention and pore structure can be easily according to useless Organic substance in water
Composition is adjusted, and by the initiation of alpha-alkyl phenylethylene structural unit at high temperature, further improves the ratio table of absorption resin
Area and Kong Rong optimize aperture size, while grafting can enhance to Organic substance in water adsorption capacity of giving up in resin is adsorbed
Functional group improves the treatment effeciency and the scope of application of resin absorption technique.In general, the aperture of absorption resin is waste water
2-7 times of middle organic molecule diameter, adsorption efficiency highest.The aperture of resin is adsorbed on the one hand by suspension polymerisation step, α-
The ratio of ring-alkylated styrenes, more vinyl aromatic crosslinking agents and pore-foaming agent determines that pore-foaming agent accounting is higher, adsorbs the hole of resin
Diameter is bigger.On the other hand it is modified porous absorption resin preparation process in, can further by control it is porous copolymerization Archon and
The proportion adjustment pore structure of more vinyl function monomers enhances its adsorption capacity to the Organic substance in water that gives up.
(2) removal of the modified porous absorption resin prepared using the method for the present invention to TOC in low concentration difficulty biochemical waste water
Rate is at least 80%, preferably at least 90%.
(3) using the desorption method of the present invention, desorption efficiency reaches as high as 99%, can realize low dense up to more than 95%
The harmless treatment and reuse of the difficult biochemical waste water of degree.
(4) highly concentrated, highly toxic resin desorption liquid is handled using catalytic wet oxidation technology, solves resin desorption liquid
Pollution problem, resin adsorption technology is combined with catalytic wet oxidation technology so that the low concentrations such as biochemical tail water, reverse osmosis concentrated water are difficult
Biochemical waste water has reuse possibility, is of great significance to mitigating environmental pollution, improving resource utilization.
(5) it is used in combination catalytic wet oxidation technology treated the removal rate of TOC in low concentration difficulty biochemical waste water>
95%.
Specific embodiment
Raw material sources information：
Instrument information in embodiment：
The BET specific surface area of porous copolymerization Archon and modified porous absorption resin, BET absorption average pore sizes and single-point absorption
Kong Rong is obtained using Micromeritics ASAP2020M, and detection foundation is GB/T19587-2004.Low concentration is difficult before and after absorption
The TOC of biochemical waste water is measured by Analytik Jena AG 2100S.
The present invention is described in more detail by following embodiment, but the embodiment does not form the limit to the present invention
System.
Embodiment 1
Reverse osmosis concentrated water process, waste water TOC are 80mg/L, and organic matter composition is dinitrotoluene (DNT), aniline, chlorobenzene, nitro
Cabisan, pH=9.
At room temperature, the water phase of premix is added in 1L four-hole boiling flasks, form for deionized water 484.25g, sodium chloride 15g,
Polyvinyl alcohol 0.25g, 0.1wt.% aqueous solution of methylene blue 0.5g.Stirring is opened, is warming up to 40 DEG C.Stirring is closed, is added in pre-
Mixed oil phase is formed as α-methylstyrene 16.6g, divinylbenzene 66.3g, toluene 41.4g, 3# white oil 41.4g, azo two
Isobutyronitrile 0.8g.Stirring is opened, rotating speed is adjusted according to required grain size.70 DEG C, constant temperature 6h are warming up to, through washing, extracting pore-foaming agent
After obtain porous copolymerization Archon.The grain size of the porous copolymerization Archon is 400~1200 μm, BET specific surface area 600m2/ g, BET
Absorption average pore size is 5.0nm, and single-point adsorption hole holds for 0.9mL/g.
The above-mentioned porous copolymerization Archons of 5g is taken to be placed in room temperature in 10mL dimethylbenzene and 5mL allyl methacrylates and are swollen 2h,
The adsorbance of porous copolymerization Archon paraxylene and allyl methacrylate for 2mL/g, be filtered to remove extra dimethylbenzene and
Allyl methacrylate.In a nitrogen environment, 90 DEG C, reaction time 6h are warming up to, room temperature is cooled to and terminates reaction.Add in second
Porous copolymerization Archon after acetoacetic ester cleaning reaction, modified porous absorption resin is obtained after filtering, drying.The modified porous absorption
The grain size of resin is 400~1200 μm, BET specific surface area 1100m2/ g, BET absorption average pore size are 5.0nm, and single-point adsorbs
Kong Rongwei 2.0mL/g.
Using the organic matter in above-mentioned modified porous absorption resin adsorption low concentration difficulty biochemical waste water, the flow velocity of waste water is
2BV/h, adsorption temp are 25 DEG C, TOC in waste water after absorption<1mg/L adds methanol desorption and is adsorbed in above-mentioned modified porous suction
Organic matter in attached resin, regenerating and modifying porous adsorption resin, desorption liquid stream are 1BV/h, and desorption temperature is 25 DEG C, desorption efficiency
98%.Stripping liquid is distilled, overhead is recycled as stripping liquid, and bottom of towe ingredient TOC is 20000mg/L, is sent to catalysis
The processing of wet oxidation device, TOC removal efficiencies 98%.
Comparative example 1
Reverse osmosis concentrated water process, waste water TOC are 80mg/L, and organic matter composition is dinitrotoluene (DNT), aniline, chlorobenzene, nitro
Cabisan, pH=9.
Organic matter in the AMBERLITE XAD4 adsorption of Low Concentration difficulty biochemical waste waters produced using Dow companies, waste water
Flow velocity is 2BV/h, and adsorption temp is 25 DEG C, and TOC is 20mg/L in waste water after absorption, adds methanol desorption and is adsorbed in above-mentioned suction
Organic matter in attached resin, regenerative adsorption resin, desorption liquid stream are 1BV/h, and desorption temperature is 25 DEG C, desorption efficiency 95%.Distillation
Stripping liquid, overhead are recycled as stripping liquid, and bottom of towe ingredient TOC is 10000mg/L, are sent to catalytic wet oxidation and are filled
Put processing, TOC removal efficiencies 98%.
Comparative example 2
Reverse osmosis concentrated water process, waste water TOC are 80mg/L, and organic matter composition is dinitrotoluene (DNT), aniline, chlorobenzene, nitro
Cabisan, pH=9.
Organic matter in the AMBERLITE XAD7 adsorption of Low Concentration difficulty biochemical waste waters produced using Dow companies, waste water
Flow velocity is 2BV/h, and adsorption temp is 25 DEG C, and TOC is 15mg/L in waste water after absorption, adds methanol desorption and is adsorbed in above-mentioned suction
Organic matter in attached resin, regenerative adsorption resin, desorption liquid stream are 1BV/h, and desorption temperature is 25 DEG C, desorption efficiency 96%.Distillation
Stripping liquid, overhead are recycled as stripping liquid, and bottom of towe ingredient TOC is 12000mg/L, are sent to catalytic wet oxidation and are filled
Put processing, TOC removal efficiencies 98%.
Embodiment 2
Biochemical tail water processing, waste water TOC are 200mg/L, and organic matter composition is bisphenol-A, p-tert-butylphenol, beta naphthal,
PH=4.
At room temperature, the water phase of premix is added in 1L four-hole boiling flasks, is formed as deionized water 359.6g, gelatin 0.05g, chlorine
Change sodium 5g, 0.1wt.% sodium nitrite in aqueous solution 0.05g.Stirring is opened, is warming up to 40 DEG C.Stirring is closed, adds in the oil of premix
Phase is formed as α-isopropyl styrene 1.2g, trivinylbenzene 23.8g, dimethylbenzene 37.4g, 200# solvent naphtha 37.4g, peroxide
Change dibenzoyl 0.12g.Stirring is opened, rotating speed is adjusted according to required grain size.75 DEG C, constant temperature 10h are warming up to, through washing, extracting
Porous copolymerization Archon is obtained after pore-foaming agent.The grain size of the porous copolymerization Archon is 300~1000 μm, and BET specific surface area is
400m2/ g, BET absorption average pore size are 3.0nm, and single-point adsorption hole holds for 0.5mL/g.
The above-mentioned porous copolymerization Archons of 5g is taken to be placed in room temperature in 5mL ethylbenzene and 0.5mL ethyleneglycol dimethyacrylates to be swollen
4h, porous copolymerization Archon are 0.5mL/g to the adsorbance of ethylbenzene and ethyleneglycol dimethyacrylate, are filtered to remove extra second
Benzene and ethyleneglycol dimethyacrylate.Under ar gas environment, 100 DEG C, reaction time 10h are warming up to, is cooled to room temperature termination
Reaction.The porous copolymerization Archon after ethyl acetate cleaning reaction is added in, modified porous absorption resin is obtained after filtering, drying.It should
The grain size of modified porous absorption resin is 300~1000 μm, BET specific surface area 600m2/ g, BET adsorb average pore size
3.0nm, single-point adsorption hole hold for 0.7mL/g.
Using the organic matter in above-mentioned modified porous absorption resin adsorption low concentration difficulty biochemical waste water, the flow velocity of waste water is
1BV/h, adsorption temp are 25 DEG C, and TOC is 15mg/L in waste water after absorption, add the desorption absorption of 4% sodium hydrate aqueous solution
Organic matter in above-mentioned modified porous absorption resin, regenerating and modifying porous adsorption resin, desorption liquid stream is 1BV/h, and desorption is warm
It is 25 DEG C to spend, and desorption efficiency 99%, stripping liquid, which is recycled to TOC, reaches 10000mg/L, send to catalytic wet oxidation device
Reason, TOC removal efficiencies 97%.
Embodiment 3
Biochemical tail water processing, waste water TOC are 1000mg/L, and organic matter composition is phenol, benzoquinones, 2,3- acid, pH=2.
At room temperature, the water phase of premix is added in 1L four-hole boiling flasks, is formed as deionized water 449g, hydroxypropyl methyl fiber
Plain 0.5g, sodium chloride 50g, 0.1wt.% aqueous solution of methylene blue 0.5g.Stirring is opened, is warming up to 40 DEG C.Stirring is closed, is added in
The oil phase of premix is formed as α-ethyl styrene 92.4g, divinyl toluene 92.4g, ethylbenzene 61.6g, peroxidating pivalic acid uncle
Butyl ester 3.7g.Stirring is opened, rotating speed is adjusted according to required grain size.65 DEG C, constant temperature 5h are warming up to, after washing, extracting pore-foaming agent
Obtain porous copolymerization Archon.The grain size of the porous copolymerization Archon is 100~700 μm, BET specific surface area 300m2/ g, BET inhale
Attached average pore size is 4.0nm, and single-point adsorption hole holds for 0.5mL/g.
The above-mentioned porous copolymerization Archons of 5g is taken to be placed in room temperature in 50mL toluene and 10mL allyl itaconates and are swollen 1h, it is porous common
Poly- Archon is 5mL/g to the adsorbance of toluene and allyl itaconates, is filtered to remove extra toluene and allyl itaconates.
Under nitrogen environment, 140 DEG C, reaction time 1h are warming up to, air is passed through and terminates reaction.It adds in more after ethyl acetate cleaning reaction
Hole is copolymerized Archon, and modified porous absorption resin is obtained after filtering, drying.The grain size of the modified porous absorption resin is 200~750
μm, BET specific surface area 650m2/ g, BET absorption average pore size are 5.0nm, and single-point adsorption hole holds for 0.9mL/g.
Using the organic matter in above-mentioned modified porous absorption resin adsorption low concentration difficulty biochemical waste water, the flow velocity of waste water is
0.1BV/h, adsorption temp are 4 DEG C, and TOC is 200mg/L in waste water after absorption, and adding ethyl alcohol desorption, to be adsorbed in above-mentioned modification more
Organic matter in macroporous adsorbent resin, regenerating and modifying porous adsorption resin, desorption liquid stream are 0.1BV/h, and desorption temperature is 50 DEG C, solution
Suction rate 95%.Distill stripping liquid, overhead as stripping liquid recycle, bottom of towe ingredient TOC be 40000mg/L, send to
The processing of catalytic wet oxidation device, TOC removal efficiencies 95%.
Embodiment 4
Biochemical tail water processing, waste water TOC be 20mg/L, organic matter composition for aniline, m-phenylene diamine (MPD), o-phenylenediamine, to benzene
Diamines, pH=13.
At room temperature, the water phase of premix is added in 1L four-hole boiling flasks, is formed as deionized water 499.4g, hydroxyethyl cellulose
0.025g, hydroxypropyl cellulose 0.025g, 0.1wt.% aqueous solution of methylene blue 0.5g.Stirring is opened, is warming up to 40 DEG C.It closes
Stirring, adds in the oil phase of premix, forms as α-t-butyl styrene 5g, divinylxylene 40g, toluene 90g, 3# white oil
20g, peroxidating two (2- toluyls) 1g.Stirring is opened, rotating speed is adjusted according to required grain size.65 DEG C, constant temperature 6h are warming up to,
Porous copolymerization Archon is obtained after washing, extracting pore-foaming agent.The grain size of the porous copolymerization Archon is 500~1500 μm, and BET compares table
Area is 800m2/ g, BET absorption average pore size are 15.0nm, and single-point adsorption hole holds for 1.5mL/g.
The above-mentioned porous copolymerization Archons of 5g is taken to be placed in 20mL isopropylbenzenes, 20mL chlorobenzenes and 1mL divinylbenzenes, 1.5mL trimethyls
Room temperature is swollen 3h in glycerol acrylate, 2.5mL trimethacrylate acid trimethylolpropane esters, and porous copolymerization Archon is to isopropyl
Benzene, chlorobenzene, divinylbenzene, trimethacrylate acid glyceride and trimethacrylate acid trimethylolpropane ester adsorbance be 4mL/
G is centrifuged off sour three methanol-baseds of extra isopropylbenzene, chlorobenzene, divinylbenzene, trimethacrylate acid glyceride and trimethacrylate
Propane ester.In a nitrogen environment, 80 DEG C, reaction time 1h are warming up to, air is passed through and terminates reaction.It is anti-to add in ethyl acetate cleaning
Porous copolymerization Archon after answering obtains modified porous absorption resin after filtering, drying.This it is modified porous absorption resin grain size be
600~2000 μm, BET specific surface area 1500m2/ g, BET absorption average pore size are 10.0nm, and single-point adsorption hole appearance is
2.5mL/g。
Using the organic matter in above-mentioned modified porous absorption resin adsorption low concentration difficulty biochemical waste water, the flow velocity of waste water is
7BV/h, adsorption temp are 50 DEG C, and TOC is in waste water after absorption<1mg/L adds 6% hydrochloric acid desorption and is adsorbed in above-mentioned modification
Organic matter in porous adsorption resin, regenerating and modifying porous adsorption resin, desorption liquid stream are 7BV/h, and desorption temperature is 50 DEG C, solution
Suction rate 96%, stripping liquid, which is recycled to TOC, reaches 2000mg/L, send to the processing of catalytic wet oxidation device, TOC removal efficiencies
97%.
Embodiment 5
Biochemical tail water processing, waste water TOC are 500mg/L, and organic matter forms unknown, pH=13, sentenced according to paper chromatography result
It is set to middle polarity waste water.
At room temperature, the water phase of premix is added in 1L four-hole boiling flasks, is formed as deionized water 484.5g, polyvinyl alcohol
0.3g, sodium chloride 15g, 0.1wt.% aqueous solution of methylene blue 0.2g.Stirring is opened, is warming up to 40 DEG C.Stirring is closed, is added in pre-
Mixed oil phase, form for α-methylstyrene 5g, α-ethyl styrene 5g, divinylbenzene 40g, toluene 25g, 3# white oil 25g,
Dioctanoyl peroxide 0.5g, dilauroyl peroxide 0.25g.Stirring is opened, rotating speed is adjusted according to required grain size.It is warming up to 70
DEG C, constant temperature 5h obtains porous copolymerization Archon after washing, extracting pore-foaming agent.The grain size of the porous copolymerization Archon is 300~1000
μm, BET specific surface area 600m2/ g, BET absorption average pore size are 20.0nm, and single-point adsorption hole holds for 0.6mL/g.
The above-mentioned porous copolymerization Archons of 5g is taken to be placed in 5mL o-dichlorohenzenes, 5mL nitrobenzenes, 5mL methyl phenyl ethers anisoles and 1mL acrylic acid three
Room temperature is swollen 5h in cyclodecene ester, 2.5mL methacrylic acid dicyclopentenyls 2-ethoxyethyl acetate, 1mL trimerization triallyl isocyanurates,
Porous copolymerization Archon is to o-dichlorohenzene, nitrobenzene, methyl phenyl ethers anisole, acrylic acid tricyclodecenyl esters, methacrylic acid dicyclopentenyl oxygen
Ethyl ester, trimerization triallyl isocyanurate adsorbance for 5mL/g, be centrifuged off extra o-dichlorohenzene, nitrobenzene, benzene first
Ether, acrylic acid tricyclodecenyl esters, methacrylic acid dicyclopentenyl 2-ethoxyethyl acetate, trimerization triallyl isocyanurate.In nitrogen ring
Under border, 85 DEG C, reaction time 8h are warming up to, air is passed through and terminates reaction.Add in the porous copolymerization after ethyl acetate cleaning reaction
Archon obtains modified porous absorption resin after filtering, drying.The grain size of the modified porous absorption resin is 400~1100 μm,
BET specific surface area is 1000m2/ g, BET absorption average pore size are 30.0nm, and single-point adsorption hole holds for 1.6mL/g.
Using the organic matter in above-mentioned modified porous absorption resin adsorption low concentration difficulty biochemical waste water, the flow velocity of waste water is
4BV/h, adsorption temp be 4 DEG C, after absorption in waste water TOC be 15mg/L, add acetone desorption be adsorbed in it is above-mentioned modified porous
The organic matter in resin, regenerating and modifying porous adsorption resin are adsorbed, desorption liquid stream is 2BV/h, and desorption temperature is 4 DEG C, desorption efficiency
98%, stripping liquid is distilled, overhead is recycled as stripping liquid, and bottom of towe ingredient TOC is 25000mg/L, is sent to catalysis
The processing of wet oxidation device, TOC removal efficiencies 99%.
Embodiment 6
Biochemical tail water processing, waste water TOC are 200mg/L, and organic matter forms unknown, pH=8, according to paper chromatography result judgement
For middle polarity waste water.
At room temperature, the water phase of premix is added in 1L four-hole boiling flasks, is formed as deionized water 481.1g, polyvinyl alcohol
0.25g, sodium chloride 12g, 0.1wt.% aqueous solution of methylene blue 0.2g.Stirring is opened, is warming up to 40 DEG C.Stirring is closed, is added in
The oil phase of premix is formed as α-methylstyrene 10g, divinylbenzene 40g, toluene 30g, 3# white oil 20g, dioctanoyl peroxide
1g.Stirring is opened, rotating speed is adjusted according to required grain size.70 DEG C are warming up to, constant temperature 5h is obtained more after washing, extracting pore-foaming agent
Hole is copolymerized Archon.The grain size of the porous copolymerization Archon is 300~1100 μm, BET specific surface area 550m2/ g, BET absorption are average
Aperture is 16.0nm, and single-point adsorption hole holds for 0.55mL/g.
The above-mentioned porous copolymerization Archons of 5g is taken to be placed in room temperature in 15mL o-dichlorohenzenes and 5mL acrylic acid tricyclodecenyl esters to be swollen
5h, porous copolymerization Archon are 4mL/g to the adsorbance of o-dichlorohenzene, acrylic acid tricyclodecenyl esters, are centrifuged off extra neighbour two
Chlorobenzene, acrylic acid tricyclodecenyl esters.In a nitrogen environment, 85 DEG C, reaction time 8h are warming up to, air is passed through and terminates reaction.Add
Enter the porous copolymerization Archon after ethyl acetate cleaning reaction, modified porous absorption resin is obtained after filtering, drying.This is modified porous
The grain size for adsorbing resin is 300~1100 μm, BET specific surface area 950m2/ g, BET adsorb average pore size as 14.0nm, single-point
Adsorption hole holds for 1.2mL/g.
Using the organic matter in above-mentioned modified porous absorption resin adsorption low concentration difficulty biochemical waste water, the flow velocity of waste water is
3BV/h, adsorption temp are 30 DEG C, and TOC is in waste water after absorption<1mg/L adds 0.1% sodium hydrate aqueous solution desorption and inhales
The organic matter in above-mentioned modified porous absorption resin is invested, regenerating and modifying porous adsorption resin, desorption liquid stream is 1.5BV/h, is solved
It is 50 DEG C to inhale temperature, and desorption efficiency 97%, stripping liquid, which is recycled to TOC, reaches 2000mg/L, send to catalytic wet oxidation device
Processing, TOC removal efficiencies 98%.
Embodiment 7
Biochemical tail water processing, waste water TOC are 200mg/L, and organic matter composition is aniline, o-phenylenediamine, p-phenylenediamine, isophthalic
Diamines, nitrobenzene, pH=11.
At room temperature, the water phase of premix is added in 1L four-hole boiling flasks, is formed as deionized water 490g, hydroxyethyl cellulose
0.05g, 0.1wt.% aqueous solution of methylene blue 0.25g.Stirring is opened, is warming up to 40 DEG C.Stirring is closed, adds in the oil of premix
Phase is formed as α-t-butyl styrene 10g, divinylxylene 40g, toluene 60g, 3# white oil 5g, (the 2- methyl of peroxidating two
Benzoyl) 1g.Stirring is opened, rotating speed is adjusted according to required grain size.65 DEG C, constant temperature 6h are warming up to, after washing, extracting pore-foaming agent
Obtain porous copolymerization Archon.The grain size of the porous copolymerization Archon is 400~1300 μm, BET specific surface area 600m2/ g, BET inhale
Attached average pore size is 12.0nm, and single-point adsorption hole holds for 1.0mL/g.
The above-mentioned porous copolymerization Archons of 5g is taken to be placed in 40mL isopropylbenzenes and 2.5mL trimethacrylates acid glyceride, 1.5mL front threes
Room temperature is swollen 3h in base acrylic acid trimethylolpropane ester, and porous copolymerization Archon is to isopropylbenzene, trimethacrylate acid glyceride, three
The adsorbance of methacrylic acid trimethylolpropane ester is 5mL/g, is centrifuged off extra isopropylbenzene, trimethacrylate acid glycerol
Ester, trimethacrylate acid trimethylolpropane ester.In a nitrogen environment, 75 DEG C, reaction time 2h are warming up to, is passed through air termination
Reaction.The porous copolymerization Archon after ethyl acetate cleaning reaction is added in, modified porous absorption resin is obtained after filtering, drying.It should
The grain size of modified porous absorption resin is 400~1300 μm, BET specific surface area 900m2/ g, BET adsorb average pore size
10.0nm, single-point adsorption hole hold for 1.5mL/g.
Using the organic matter in above-mentioned modified porous absorption resin adsorption low concentration difficulty biochemical waste water, the flow velocity of waste water is
4BV/h, adsorption temp are 40 DEG C, and TOC is in waste water after absorption<1mg/L adds 0.1% hydrochloric acid desorption and is adsorbed in above-mentioned change
Property porous adsorption resin in organic matter, regenerating and modifying porous adsorption resin, desorption liquid stream be 2BV/h, desorption temperature be 50 DEG C,
Desorption efficiency 97%, stripping liquid, which is recycled to TOC, reaches 2000mg/L, send to the processing of catalytic wet oxidation device, TOC removal efficiencies
99%.
Embodiment 8
Biochemical tail water processing, waste water TOC are 300mg/L, and organic matter composition is benzene,toluene,xylene, diethylbenzene, naphthalene, pH
=7.
At room temperature, the water phase of premix is added in 1L four-hole boiling flasks, is formed as deionized water 485g, hydroxyethyl cellulose
0.1g, 0.1wt.% aqueous solution of methylene blue 0.2g.Stirring is opened, is warming up to 40 DEG C.Stirring is closed, adds in the oil phase of premix,
It forms as α-methylstyrene 10g, divinylbenzene 60g, toluene 35g, 3# white oil 35g, dibenzoyl peroxide 0.7g.It opens
Stirring adjusts rotating speed according to required grain size.80 DEG C, constant temperature 8h are warming up to, it is white that porous copolymerization is obtained after washing, extracting pore-foaming agent
Ball.The grain size of the porous copolymerization Archon is 300~1200 μm, BET specific surface area 700m2/ g, BET adsorb average pore size
5.0nm, single-point adsorption hole hold for 0.8mL/g.
The above-mentioned porous copolymerization Archons of 5g is taken to be placed in room temperature in 40mL dimethylbenzene and 5mL divinylbenzenes and are swollen 3h, it is porous common
Poly- Archon paraxylene, divinylbenzene adsorbance for 5mL/g, be centrifuged off extra dimethylbenzene, divinylbenzene.In nitrogen
Under compression ring border, 75 DEG C, reaction time 4h are warming up to, air is passed through and terminates reaction.It adds in porous common after dimethylbenzene cleaning reaction
Poly- Archon obtains modified porous absorption resin after filtering, drying.The grain size of the modified porous absorption resin is 300~1200 μm,
BET specific surface area is 1050m2/ g, BET absorption average pore size are 5.0nm, and single-point adsorption hole holds for 1.4mL/g.
Using the organic matter in above-mentioned modified porous absorption resin adsorption low concentration difficulty biochemical waste water, the flow velocity of waste water is
6BV/h, adsorption temp are 20 DEG C, and TOC is in waste water after absorption<1mg/L, add acetone desorption be adsorbed in it is above-mentioned modified porous
The organic matter in resin, regenerating and modifying porous adsorption resin are adsorbed, desorption liquid stream is 3BV/h, and desorption temperature is 40 DEG C, desorption efficiency
99%, stripping liquid is distilled, overhead is recycled as stripping liquid, and bottom of towe ingredient TOC is 25000mg/L, is sent to catalysis
The processing of wet oxidation device, TOC removal efficiencies 99%.
Claims (14)
1. a kind of preparation method of modified porous absorption resin, which is characterized in that include the following steps：
1) porous copolymerization Archon is mixed and is swollen with sweller, more vinyl function monomers, swelling product is obtained, wherein described more
The raw material for preparing of hole copolymerization Archon includes alpha-alkyl phenylethylene and aromatic multi-vinyl based compound；
2) swelling product polymerize in an inert atmosphere obtained by step 1), obtains modified porous absorption resin.
2. preparation method according to claim 1, which is characterized in that alpha-alkyl phenylethylene described in step 1) is selected from by C1
~C10It is one or more in alkyl-substituted styrene, it is preferably selected from α-methylstyrene, α-ethyl styrene, α-isopropyl
It is one or more in styrene or α-t-butyl styrene；
Preferably, step 1) the aromatic multi-vinyl based compound is selected from the fragrance containing at least two unsaturated carbon-carbon double bonds
It is one or more in compounds of group and its derivative；Preferably, the aromatic multi-vinyl based compound is selected from o- divinyl
One in base benzene, m- divinylbenzene, p- divinylbenzene, trivinylbenzene, divinyl toluene, divinylxylene
Kind is a variety of；It is further preferred that the aromatic multi-vinyl based compound is selected from o- divinylbenzene, m- divinyl
It is one or more in benzene, p- divinylbenzene or trivinylbenzene；It is furthermore preferred that the aromatic multi-vinyl based compound
For m- divinylbenzene；
Preferably, the mass ratio that feeds intake of the alpha-alkyl phenylethylene and aromatic multi-vinyl based compound is 1:1~1:20, preferably
1:2~1:10.
3. preparation method according to claim 1 or 2, which is characterized in that the system of porous copolymerization Archon described in step 1)
Preparation Method includes the following steps：Under pore-foaming agent effect, alpha-alkyl phenylethylene described in suspension copolymerization and aromatic multi-vinyl base
Object is closed, products therefrom obtains the porous copolymerization Archon after washing, extracting pore-foaming agent；
Preferably, it is described outstanding also added with initiator, water, dispersant and reagent and additive in polymerization in the reaction system of the suspension copolymerization
Its oil phase composition includes in the reaction system of floating copolymerization：Alpha-alkyl phenylethylene, aromatic multi-vinyl based compound, pore-foaming agent and draw
Send out agent；Water phase composition includes：Water, dispersant, reagent and additive in polymerization.
4. preparation method according to claim 1 or 2, which is characterized in that more vinyl function monomers described in step 1)
Selected from aromatic monomer or polarity esters monomer or combination；Preferably, the aromatic monomer be selected from o- divinylbenzene,
M- divinylbenzene, p- divinylbenzene, trivinylbenzene, divinyl toluene, one kind in divinylxylene or
It is a variety of；It is furthermore preferred that the aromatic monomer is divinylbenzene；Preferably, the polarity esters monomer is selected from double methyl-props
Olefin(e) acid glycol ester, allyl methacrylate, allyl itaconates, trimethacrylate acid glyceride, trimethacrylate acid three
Methanol-based propane ester, three allyl of acrylic acid tricyclodecenyl esters, methacrylic acid dicyclopentenyl 2-ethoxyethyl acetate and trimerization isocyanuric acid
It is one or more in ester；It is furthermore preferred that the polarity esters monomer is selected from ethyleneglycol dimethyacrylate and metering system
One or both of allyl propionate；
Preferably, in step 1) relative to the porous copolymerization Archons of 1g, the inventorys of more vinyl function monomers for 0.1~
2.0mL, preferably 0.5~1.5mL.
5. preparation method according to claim 1 or 2, which is characterized in that sweller described in step 1) be selected from boiling point >=
It is one or more in 80 DEG C of aromatic hydrocarbon solvent；Preferably, one kind in substituted benzene solvent of the sweller or
It is a variety of；It is further preferred that the sweller be selected from toluene, dimethylbenzene, ethylbenzene, isopropylbenzene, chlorobenzene, o-dichlorohenzene, nitrobenzene,
It is one or more in methyl phenyl ethers anisole；It is furthermore preferred that the sweller is one or two kinds of in paraxylene and ethylbenzene；
Preferably, in step 1) relative to the porous copolymerization Archons of 1g, the inventory of the sweller is 1~10mL, more preferably 2
~5mL；
Preferably, porous copolymerization Archon absorption 0.5~5.0mL swellers and more vinyl function monomers described in 1g in step 1),
It is preferred that the porous copolymerization Archon absorption 1~3mL swellers of 1g and more vinyl function monomers.
6. preparation method according to claim 1 or 2, which is characterized in that swelling time described in step 1) is at least 1h,
Preferably at least 2h；
Preferably, step 1) is after the swelling, the step of further including the swelling product filtering and/or centrifugation.
7. preparation method according to claim 1 or 2, which is characterized in that the step 2) temperature for being aggregated in 80~140 DEG C
Degree is lower to carry out；Preferably, less than more vinyl function monomers thermal-initiated polymerization occurs for the temperature of the step 2) polymerization
Minimum temperature；
Preferably, the inert environments are provided by inert gas；It is furthermore preferred that the inert gas is nitrogen or argon gas, it is optimal
Select nitrogen；Preferably, the time of the polymerization is 1~10h；
Preferably, it described in step 2) after polymerisation, further includes clear using the good solvent of more vinyl function monomers
The step of washing, filter and dry the modified porous absorption resin.
8. a kind of modified porous absorption resin prepared by preparation method using described in any one of claim 1~7；
Preferably, the particle diameter distribution of the modified porous absorption resin is 200~2000 μm；BET specific surface area for 600~
1500m2/ g, BET absorption average pore sizes are 3.0~30.0nm, single-point absorption total pore volume is 0.7~2.5mL/g.
A kind of 9. method for handling useless Organic substance in water, which is characterized in that include the following steps：The waste water is changed by being filled with
Property porous adsorption resin resin column adsorbed, collect efflux；The modified porous absorption resin is described in claim 8
Modified porous absorption resin.
10. according to the method described in claim 9, it is characterized in that, the TOC of the waste water is 20~1000mg/L, preferably
50~500mg/L.
11. method according to claim 9 or 10, which is characterized in that the waste water is low concentration difficulty biochemical waste water；
Preferably, the low concentration difficulty biochemical waste water is the waste water containing aromatic hydrocarbon derivative；Preferably, the aromatic hydrocarbon derives
Object is one or more in phenol, quinone, aromatic acid, aromatic amine, halogenated aromatic；It is furthermore preferred that the aromatic hydrocarbon derives
Object is one or more in phenol, benzoquinones, bisphenol-A, chlorobenzene, 2,3- acid, beta naphthal, aniline.
12. method according to claim 9 or 10, which is characterized in that the waste water flow through the flow velocity of resin column for 0.1~
7BV/h, preferably 0.5~3BV/h；Preferably, the temperature of the absorption is 4~50 DEG C, more preferably 15~40 DEG C；It is preferred that
, the pH before the low concentration difficulty biochemical waste water is adsorbed is 2~13, preferably 3~12.
13. method according to claim 9 or 10, which is characterized in that the method further includes following steps：
After collecting the efflux, using in acid solution, aqueous slkali, alcoholic solvent or acetone it is one or more as desorption elute
The desorption eluent is flowed through the modified porous absorption resin being loaded in the resin and carries out desorption and regeneration to it, received by liquid
Collect efflux, obtain stripping liquid；
Preferably, the acid solution mass concentration is 0.1~6wt.%, and the mass concentration of the aqueous slkali is 0.1~6wt.%；
Preferably, the acid solution is one or both of aqueous solution of hydrochloric acid or sulfuric acid；The aqueous slkali is NaOH, KOH
Aqueous solution or ammonium hydroxide in it is one or more；Preferably, the alcoholic solvent is one kind or more in methanol, ethyl alcohol or isopropanol
Kind.
14. according to the method for claim 13, which is characterized in that the flow velocity of the desorption eluent is 0.1~7BV/h,
Preferably 0.5~3BV/h；The temperature of the desorption and regeneration is 4~50 DEG C, preferably 25~45 DEG C；
Preferably, the method further includes following steps：Purification concentration is carried out to the stripping liquid, to obtain the stripping liquid
Concentrate；Preferably, the TOC of the concentrate of the stripping liquid or the stripping liquid is 2000~40000mg/L, preferably
10000~35000mg/L；
Preferably, the concentrate that wet oxidation method handles the stripping liquid or the stripping liquid is further used.
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| CN201711437849.5A CN108144589B (en) | 2017-12-26 | 2017-12-26 | Resin, preparation method thereof and method for treating wastewater by using resin |
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| CN110639624A (en) * | 2019-10-11 | 2020-01-03 | 丹东明珠特种树脂有限公司 | Anion and cation exchange resin for purifying caprolactam production wastewater and wastewater purification method |
| WO2020043861A1 (en) * | 2018-08-30 | 2020-03-05 | Suez Groupe | Method for the desorption of a solid adsorbent and associated device |
| CN110898818A (en) * | 2019-12-13 | 2020-03-24 | 福州大学 | Preparation method and application of adsorption resin for treating dinitrotoluene-containing wastewater |
| CN111040053A (en) * | 2019-12-10 | 2020-04-21 | 万华化学集团股份有限公司 | Device and method for preparing uniform-particle macroporous adsorption resin by using screw extruder |
| CN111138668A (en) * | 2020-01-02 | 2020-05-12 | 万华化学集团股份有限公司 | Cyclodextrin modified macroporous adsorption resin and preparation method thereof |
| CN111825062A (en) * | 2020-07-28 | 2020-10-27 | 安徽东至广信农化有限公司 | Method for recovering waste sulfuric acid |
| CN113145086A (en) * | 2021-05-19 | 2021-07-23 | 万华化学集团股份有限公司 | Fatty acid modified adsorption resin, preparation method and method for treating anionic surfactant wastewater by using same |
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| CN111040053A (en) * | 2019-12-10 | 2020-04-21 | 万华化学集团股份有限公司 | Device and method for preparing uniform-particle macroporous adsorption resin by using screw extruder |
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| CN110898818B (en) * | 2019-12-13 | 2021-08-31 | 福州大学 | Preparation method and application of adsorption resin for treating dinitrotoluene-containing wastewater |
| CN111138668A (en) * | 2020-01-02 | 2020-05-12 | 万华化学集团股份有限公司 | Cyclodextrin modified macroporous adsorption resin and preparation method thereof |
| CN111138668B (en) * | 2020-01-02 | 2022-07-12 | 万华化学集团股份有限公司 | Cyclodextrin modified macroporous adsorption resin and preparation method thereof |
| CN111825062A (en) * | 2020-07-28 | 2020-10-27 | 安徽东至广信农化有限公司 | Method for recovering waste sulfuric acid |
| CN113145086A (en) * | 2021-05-19 | 2021-07-23 | 万华化学集团股份有限公司 | Fatty acid modified adsorption resin, preparation method and method for treating anionic surfactant wastewater by using same |
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Denomination of invention: The invention relates to a resin and a preparation method thereof, and a method for treating wastewater with the resin Effective date of registration: 20211123 Granted publication date: 20200828 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
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Date of cancellation: 20220622 Granted publication date: 20200828 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |