CN105948293A - Wastewater resourceful treatment process based on nanocomposite targeted separation - Google Patents

Wastewater resourceful treatment process based on nanocomposite targeted separation Download PDF

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CN105948293A
CN105948293A CN201610438135.5A CN201610438135A CN105948293A CN 105948293 A CN105948293 A CN 105948293A CN 201610438135 A CN201610438135 A CN 201610438135A CN 105948293 A CN105948293 A CN 105948293A
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composite material
nano composite
waste water
targeting
separator
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CN105948293B (en
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王文波
王颜亭
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Shandong Homology And Genie Et Environnement
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Shandong Homology And Genie Et Environnement
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • 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

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic 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)

Abstract

The invention relates to a wastewater resourceful treatment process based on nanocomposite targeted separation, in particular to a method for resourceful recycling of valuable materials in degradation-resistant benzene series wastewater in chemical industries such as dye, medicine and pesticide, and belongs to the field of benzene series wastewater resourcezation. The method is used for resourcefully recycling valuable materials in benzene series wastewater based on nanocomposite targeted separation. For different materials in wastewater, an existing nanocomposite with different functional groups or developed novel nanocomposite is utilized, the pretreatment process is adopted, it is ensured that treated water reaches the standard, and the wastewater treating cost is reduced by recycling materials; when the high-value materials are resourcefully treated and recycled, the treatment cost can be offset, and economic benefits can be created for an enterprise.

Description

A kind of waste water reclaiming separated based on nano composite material targeting processes technique
Technical field
The present invention relates to the method for resource of a kind of difficult degradation benzene homologues waste water, change particularly to a kind of dyestuff, medicine, pesticide etc. In industrial and commercial bank's industry difficult degradation benzene homologues waste water, the resource recycle method of valuable substance, belongs to benzene homologues field of wastewater reclamation.
Background technology
Benzene homologues or benzene series derivant, refer in particular to benzene (benzene) in the narrow sense, toluene (toluene), ethylbenzene (ethylbenzene), Dimethylbenzene (xylene) etc. interior have in human being's production living environment certain distribution and human body is worked the mischief containing phenyl ring Compound, also referred to as BTEX；Referring broadly to aromatic organic compounds, (Monoaromatic Hydrocarbons, is abbreviated as MACHs), for benzene and the general name of derivant, it is the common contaminant of mankind's activity discharge.
In the chemical industries such as dyestuff, medicine, pesticide, common benzene homologues is mainly benzene series, naphthalene system, anthraquinone system etc., passes through On these a few class materials load as therein in hydroxyl, carboxyl, amino, sulfonic group, halogen etc. one or more, and then production not Same product.In process of production, raw material and product inevitably enter in production technology water, and then fresh water (FW) is become For the waste water containing benzene homologues, this class waste water generally have hardly degraded organic substance content high (CODcr > 2000mg/L, BOD5/ CODcr<0.2), salt content high (salt content>10000mg/L), the feature such as abnormal flavour is big, water quality and quantity is unstable.
Owing to benzene homologues waste water has " high concentration ", the big characteristic of " difficult degradation " two so that when processing this type of waste water, be used alone The conventional biodegrading process such as bioanalysis or physico-chemical process loses possibility.The most commonly used " pretreatment+advanced oxidation processes+biochemical process " group Close technique, improved the biodegradability of waste water by advanced oxidation processes after, the organic matter degradation in recycling biochemical process waste water, mineralising.
High-level oxidation technology, also known as advanced oxidation processes, refers to utilize hydroxyl radical free radical (HO) effectively degraded water pollutant Chemical reaction.Its principle is to run electricity, photoirradiation, catalyst, is the most also combined with oxidant, produces activity in the reaction Extremely strong free radical (such as HO), this free radical has strong oxidizing property, and oxidoreduction point position is up to 2.80V, is only second to F2's 2.87V, by the adduction between free radical and organic compound, replacement, electron transfer, scission of link etc., makes the difficult degradation in water body Oxidation operation degraded journey low toxicity or nontoxic small-molecule substance, be the most directly degraded into CO2And H2O, close to permineralization.
But, " pretreatment+advanced oxidation processes+biochemical process " group technology " and processing naphthalene system reactive dye H-acid, anthraquinone based dye Such as bromamine acid, pesticide intermediate such as 2, during the benzene homologues waste water produced in the production process such as 3-bis-chloro-5-trifluoromethylpyridine, deposit In problems, mainly have:
(1) group technology processes H-acid, bromamine acid etc. and produces waste water, and influent COD cr is 4000mg/L～50000mg/L, Water outlet CODcr is generally 500mg/L～1000mg/L, does not reaches far away country and local discharge standard requirement.
(2), during the waste water that process Benzene series Concentrations is higher, it is 3360kJ/mol (benzene) by energy needed for thorough for benzene homologues mineralising ～11400kJ/mol (benzo a pyrene), the equivalent direct operating cost of ton water 20 yuan～75 yuan, operating cost is high；
(3) material that structure is complex such as naphthalene derivative, anthraquinone system derivant etc. cannot thoroughly be degraded, it is necessary to be aided with throwing Adding a large amount of medicament, ton water running expense increases by 5 yuan～10 yuan；
As can be seen here, technique produce water cannot up to standard, the drawback such as operating cost is high, directly limit the application of this group technology. Meanwhile, waste water needs degraded remove " pollutant ", the product that enterprise produces often, as H-acid produces the H-acid in waste water Being important reactive dye, current price is 50000～60000 yuan/ton, and the bromamine acid in bromamine acid waste water is in important dyestuff Mesosome, current price is 60000～65000 yuan/ton, has great recovery value, is simply limited to technology limitation, and enterprise is without warp This partial material is recycled by feasible technology of helping.
Summary of the invention
For drawbacks described above present in existing benzene homologues refractory wastewater technology, the invention provides a kind of based on Nano composite material targeting partition method resource reclaims the method for valuable substance in benzene homologues waste water, for things different in waste water Material, by utilizing the existing nano composite material with different functional groups or the novel nanocomposite materials of research and development, and combines front place Science and engineering skill, while guaranteeing that process product water is up to standard, by recovered material, reduces waste water processing cost, returns in recycling treatment When receiving costly material, it is possible not only to offset processing cost, it is also possible to create economic benefit for enterprise.
The present invention is achieved by the following technical solution:
A kind of waste water resource metallization processes separated based on nano composite material targeting, specifically comprises the following steps that
(1) pretreatment: pending used water difficult to degradate is pumped into pretreatment system, pretreatment system can be " multi-medium filtering Device or back-flushing filter+1um accurate filter " or " ultrafiltration+1um accurate filter ", isolate the float of waste water, oils and fats, The particulate contaminant more than micron orders such as colloidal substance, it is ensured that follow-up targeting piece-rate system stable operation.
(2) targeting separates: pretreatment is produced water with 0.5BV/H～2BV/H flow velocity (BV:Bed Volume SEW-105 Nano composite material admission space) by being filled with the separator of SEW-105 nano composite material, waste water is carried out at resource Reason, when separator product water does not meets emission request, shows that nano material separation and concentration is saturated, and now separator is out of service；
(3) resolve regeneration: by the parsing agent of 1.5BV～3BV (resolve agent because of material characteristic to be recycled different, can be hydrochloric acid, Sulphuric acid, sodium hydroxide, potassium hydroxide, methanol, ethanol, acetone, chloroform etc.) squeeze into running the flow velocity of flow velocity 40%～50% In separator, due to resolve the adhesion of agent and the material being enriched in SEW-105 nano composite material more than SEW-105 with The adhesion of material, the hydrophilic-hydrophobic balance condition of system changes, and material enters and resolves in agent, becomes desorbed solution, the most saturated SEW-105 recover its adsorbing separation ability, desorbed solution is collected to resolving in flow container；
(4) gas emptying: a certain amount of oil-free compressed air is blasted by separator top, the desorbed solution remained in separator is ejected, Collect to resolving in flow container；Separator enters next cycle of operation；
(5) material recycle: according to resolving the characteristic of desorbed solution in flow container, or direct reuse is to material production workshop section, or by steaming The method that evaporates separates and resolves agent and material, and recovered material resolves agent and recycles.
Described SEW-105 nano composite material, is that divinylbenzene is cross-linking agent, with polyvinyl alcohol with styrene polymerization monomer For dispersant, add toluene, dimethylbenzene, liquid wax is as porogen, and add NaCl solution, by controlling the stirring of blender Speed, on the premise of initiator exists, carries out suspension polymerisation, reacts 4-6 hour at 76 DEG C-80 DEG C, anti-at 85 DEG C-98 DEG C Answering 6-10 hour, product is scrubbed, chloromethylation, cross-link afterwards, and a kind of high-crosslinking-degree bigger serface prepared also has The nano composite material in suitable aperture.
Wherein, described porogen is preferably the mixed liquor of toluene, dimethylbenzene and liquid wax, and weight is divinylbenzene and styrene gross weight The 60%-130% of amount；
Described dispersant is preferably polyvinyl alcohol, and for divinylbenzene and the 0.5%-1.0% of styrene gross weight, polyvinyl alcohol is polymerized Degree is preferably 800～1000, and alcoholysis degree is preferably 70%～75%；The dispersive property of the polyvinyl alcohol excellence of this parameter can ensure that outstanding Grain graininess produced by floating copolymerization method is uniform；
Described NaCl solution concentration is preferably 7%-12%, weight be divinylbenzene, the 200% of styrene gross weight～300%；
Described initiator is preferably benzoyl peroxide or azodiisobutyronitrile, and weight is divinylbenzene and styrene gross weight 0.5%-1.1%；
Described blender mixing speed is 750-1000r/min, to guarantee that carrier granular granularity is between 0.1mm～0.3mm；
Described washing is that the product after suspension polymerisation is placed in extracting solution leaching 10-20 hour, extracts porogen, Carrying out 100 DEG C of washings the most again, washing time is 10-20 hour, is dried afterwards, and drying time is 8-10 hour, system Obtain copolymer spheroid；Prepare copolymer spheroid；Described extracting solution is any one or a few in acetone, methanol, petroleum ether Mixture.Preferably, described extracting solution is the mixture of acetone, petroleum ether, and its mass ratio is: 1:1～1:0.5.
Described chloromethylation is at normal temperatures, will the copolymer spheroid that prepare in chloromethyl ether swelling 3-4 hour after washing, then add Enter zinc chloride, be warmed up to 40～50 DEG C, insulation reaction 20～25 hours；
Wherein said copolymer spheroid and chloromethyl ether mass ratio are 1:2.5-4；
The quality of described zinc chloride is the 40%～60% of copolymer spheroid；
Described rear crosslinking is to add catalyst: SnCl in the reactor4, dosage is the 20%～50% of copolymer spheroid mass, Adding a certain amount of 1-chloromethyl-4-Nitrobenzol, dosage is the 5%～10% of copolymer spheroid mass, controls temperature and is 130～140 DEG C, react 10-15 hour, washing, be dried.
Nano composite material in the present invention for apolar substance such as nitrobenzene contained in benzene homologues waste water, Methylnitrobenzene class, Naphthalenes, anthracene class etc., use SEW-105 nano composite material, is made by the intermolecular electrostatic between composite and above-mentioned substance Firmly, selectively by its separating from waste water of targeting accurately.
Because the SEW-105 carrier of preparation is the nitro loading about 4%～6% content on benzene homologues skeleton, and by rational work It is 0.1-0.3mm that skill controls to make carrier granular mean diameter, and it is processing containing the valuable and industrial wastewater of difficult degradation benzene homologues Time, SEW-105 can be by the dispersion force between skeleton and nitrobenzene, Methylnitrobenzene class, naphthalenes, anthracene class, dipole-dipole force grade Level key active force, and for the benzenesulfonic acid in waste water, aniline, LOMAR PWA EINECS 246-676-2, naphthylamines, croceine acid, anthraquinone and derivant thereof Deng the material that a class is highly polar, hydrogen bond can be formed by the nitro of its load and this class material, so selective by waste water The absorption of the accurate targeting of this moieties on carrier.After SEW-105 adsorbing separation is saturated, can for the character of adsorbate, Select industry soda acid or the machine solvent of common are such as methanol, chloroform, acetone etc. to resolve targetedly, recover SEW-105's Adsorption separation performance, desorbed solution is the concentrated solution of valuable material simultaneously.
By using equal grain SEW-105 nano composite material, nano material is used to shrink supersaturation filling method, by existing separation Device (patent CN 203346118U) improves, and separator no longer arranges middle row's mouth, and nanometer composite layer is led with separator Stream plate directly contacts, after improvement:
(1) SEW-105 nano composite material (0.1mm-0.3mm) is than conventional absorbtion material (0.3mm-1.25mm) particle diameter Less so that its specific surface area is bigger, adsorbance is bigger, and then separation cycle is more long, when processing identical water inlet, and average period Increase about 40%-50%；
(2) after the SEW-105 nano composite material of equal grain is soaked by 20% concentration NaCl solution, particle collapses, loadings Supersaturation, granule is uniform simultaneously, and then guarantees to produce bias current when processing industrial wastewater so that the backwash of separator is again without must Want, and then brief adsorbing separation controls process, and more former adsorber is economized on water about 20%-30%；
(3) cyclone separator arrangement is simpler, is not only convenient for manual operation, and is not provided with middle row's mouth every separator can be made to join less Putting about 3-4 automatic valve, do not stay backwash expansion space to make separator more save raw material, about 5%-10% is saved in investment；
In place of instant invention overcomes the deficiencies in the prior art, use nano composite material that difficult degradation benzene homologues waste water is carried out resource Process, by SEW-105, the accurate formula targeting of the valuable substances such as benzene series, naphthalene system, anthraquinone system is separated, and enriching and recovering, Compared with traditional technique processing such waste water, water outlet can stably meet country and local harsh emission request, and passes through Reclaim valuable material, be possible not only to offset operating cost, it is also possible to create benefit for enterprise.
SEW is that the English name of Shandong homology and environment (SEEWATER) is write a Chinese character in simplified form, and 105 is the sequence of this nano composite material Number.
Accompanying drawing explanation
Fig. 1 is the process chart described in embodiment one；
Reference
1-waste water tank (pond), 2-intake pump, 3-pretreatment system, 4-nano composite material targeting separator, 5-product water tank (pond), 6-resolves agent storage tank (pond), 7-resolves pump, 8-desorbed solution collecting box (pond), 9-blower fan.
Detailed description of the invention
Below by the embodiment of indefiniteness and combine accompanying drawing to further instruction of the present invention:
Following example, the most for the purpose of description, not in order to limit the present invention, all within the spirit and principles in the present invention, Any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Embodiment 1
A kind of benzene homologues used water difficult to degradate process for reclaiming separated based on nano composite material targeting, specifically comprises the following steps that
(1) pretreatment: pending used water difficult to degradate is pumped into pretreatment system, pretreatment system can be " multi-medium filtering Device or back-flushing filter+1um accurate filter " or " ultrafiltration+1um accurate filter ", isolate the float of waste water, oils and fats, The particulate contaminant more than micron orders such as colloidal substance, it is ensured that follow-up targeting piece-rate system stable operation.
(2) targeting separates: pretreatment is produced water with 0.5BV/H～2BV/H flow velocity (BV:Bed Volume SEW-105 Nano composite material admission space) by being filled with the separator of SEW-105 nano composite material, waste water is carried out at resource Reason, when separator product water does not meets emission request, shows that nano material separation and concentration is saturated, and now separator is out of service；
(3) resolve regeneration: by the parsing agent of 1.5BV～3BV, squeeze in separator running the flow velocity of flow velocity 40%～50%, Owing to resolving the combination more than SEW-105 with material of the agent adhesion with the material being enriched in SEW-105 nano composite material Power, the hydrophilic-hydrophobic balance condition of system changes, and material enters and resolves in agent, becomes desorbed solution, the most saturated SEW-105 Recovering its adsorbing separation ability, desorbed solution is collected to resolving in flow container；
(4) gas emptying: a certain amount of oil-free compressed air is blasted by separator top, the desorbed solution remained in separator is ejected, Collect to resolving in flow container；Separator enters next cycle of operation；
(5) material recycle: according to resolving the characteristic of desorbed solution in flow container, or direct reuse is to material production workshop section, or by steaming The method that evaporates separates and resolves agent and material, and recovered material resolves agent and recycles.
Idiographic flow is as follows: the waste water in 1-waste water tank (pond) promotes through 2-intake pump, enters 3-pretreatment system, separates After going out the micron particles impurity such as float and bulky grain thing, antibacterial, colloid, enter 4-nano composite material targeting separator and enter The valuable material targeting separation and concentration of row reclaims, and produces water and enters 5-product water tank (pond)；
Separate saturated after, separator is out of service, and 7-resolves the parsing agent that resolved by 6-in agent storage tank (pond) of pump and pumps into 4-nanometer In composite targeting separator, according to the difference of separation and concentration material characteristic, resolving agent can be that hydrochloric acid, sulphuric acid etc. are without extremely strong Acid, or the inorganic strong alkali such as sodium hydroxide, potassium hydroxide, or the organic solvent such as methanol, ethanol, acetone, chloroform；Owing to resolving The adhesion of agent and the material being enriched in the SEW-105 nano composite material adhesion more than SEW-105 with material, system Hydrophilic-hydrophobic balance condition change, material enters and resolves in agent, becomes desorbed solution, and the most saturated SEW-105 recovers it and inhales Attached separating power, desorbed solution is collected to 8-desorbed solution collecting box (pond)；
After resolving terminates, it is out of service that 7-resolves pump, opens 9-blower fan, by residual in 4-nano composite material targeting separator The desorbed solution stayed is squeezed in 8-desorbed solution collecting box (pond)；So far, SEW-105 nano composite material resolves regeneration and completes, 4- Nano composite material targeting separator enters next periodic duty.
According to resolving the characteristic of desorbed solution in flow container, desorbed solution or direct reuse are to material production workshop section, or pass through conventional distil-lation method Separate and resolve agent and material, recovered material, resolve agent and recycle.
Embodiment 2
The preparation 1 of SEW-105 nano composite material
(1) suspension copolymerization
In the polymerization reaction kettle of 5000L, adding 3000kg concentration is the NaCl solution of 7%, the addition degree of polymerization 800, Alcoholysis degree is preferably the polyvinyl alcohol 5.0kg of 70%, is heated to 55 DEG C, makes polyvinyl alcohol be well-dispersed in solution；Add matter Divinylbenzene 600kg, the styrene 900kg of amount degree 60%, liquid wax 400kg, toluene 250kg, dimethylbenzene 250kg, Benzoyl peroxide 7.5kg, mix homogeneously, keeping temperature is 45～55 DEG C, and meanwhile, blender is carried out with 1000r/min constant speed Stirring, stirs 1h.
After 1h, temperature is promoted to 76 DEG C, and is incubated 6h；It is promoted to 85 DEG C, and is incubated 5h；It is promoted to 98 DEG C, insulation 5h, releases the NaCl solution in reactor afterwards, is prepared into copolymerization spheroid (1).
(2) wash and be dried
Copolymerization spheroid (1) is transferred in 3000L distillating still, addition 1500kg acetone and the mixed liquor of petroleum ether, acetone 750kg, Petroleum ether 750kg；After leaching time is 10h, extracting solution acetone is released with petroleum ether, add 1500L pure water, be heated to 100 DEG C, water steams 10h, is steamed with petroleum ether by the acetone of residual；
The polymer spheres steaming porogen is transferred to vacuum drier, after being dried 8h, obtains copolymerization spheroid by copolymerization spheroid Send into screening machine to sieve, choose copolymerization spheroid (3) that particle diameter is 0.05-0.1mm.
(3) chloromethylation
At 10-25 DEG C, 500kg copolymerization spheroid (3) is added in 2000L reactor, add 1250kg chloromethyl ether And after swelling 3h, add 200kg zinc chloride, be warmed up to 40 DEG C, insulation reaction 20h.Product is carried out washing process, Prepare copolymerization spheroid (4)；
(4) cross-link afterwards
100kg catalyst SnCl is added in reactor in reaction (3)4, and add 1-chloromethyl-4-Nitrobenzol 25kg, will Temperature is slowly promoted to 130 DEG C, reacts 10 hours, washs polymer with 500L acetone after completion of the reaction and is dried, Prepare target product SEW-105 nano composite material.
Experimental example 3
The preparation 2 of SEW-105 nano composite material
(1) suspension copolymerization
In the polymerization reaction kettle of 4000L, adding 2400kg concentration is the NaCl solution of 12%, the addition degree of polymerization 1000, Alcoholysis degree is preferably the polyvinyl alcohol 8.0kg of 75%, is heated to 55 DEG C, makes polyvinyl alcohol be well-dispersed in solution；Addition contains Divinylbenzene 300kg, the styrene 500kg of amount 80%, liquid wax 500kg, toluene 300kg, dimethylbenzene 240kg, azo two Isopropyl cyanide 8.8kg, mix homogeneously, keeping temperature is 45～55 DEG C, and meanwhile, blender is stirred with 750r/min constant speed, stirs Mix 1.5h.
After 1.5h, temperature is promoted to 80 DEG C, and is incubated 4h；It is promoted to 85 DEG C, and is incubated 3h；It is promoted to 98 DEG C, insulation 3h, releases the NaCl solution in reactor afterwards, is prepared into copolymerization spheroid (1).
(2) wash and be dried
Copolymerization spheroid (1) is transferred in 3000L distillating still, addition 1200kg acetone and the mixed liquor of petroleum ether, acetone 800kg, Petroleum ether 400kg；After leaching time is 20h, extracting solution acetone is released with petroleum ether, add 1000L pure water, be heated to 100 DEG C, water steams 20h, is steamed with petroleum ether by the acetone of residual；
The polymer spheres steaming porogen is transferred to vacuum drier, after being dried 10h, obtains copolymerization spheroid by copolymerization ball Body is sent into screening machine and is sieved, and chooses copolymerization spheroid (3) that particle diameter is 0.05-0.1mm.
(3) chloromethylation
At 10-25 DEG C, 600kg copolymerization spheroid (3) is added in 4000L reactor, add 2400kg chloromethyl ether And after swelling 4h, add 360kg zinc chloride, be warmed up to 50 DEG C, insulation reaction 25h.Product is carried out washing process, Prepare copolymerization spheroid (4)；
(4) cross-link afterwards
300kg catalyst SnCl is added in reactor in reaction (3)4, and add 1-chloromethyl-4-Nitrobenzol 60kg, will Temperature is slowly promoted to 140 DEG C, reacts 15 hours, washs polymer with 400kg acetone after completion of the reaction and is dried, Prepare target product SEW-105 nano composite material.
Experimental example 4
The preparation 3 of SEW-105 nano composite material
(1) suspension copolymerization
In the polymerization reaction kettle of 5000L, adding 2500kg concentration is the NaCl solution of 10%, the addition degree of polymerization 900, Alcoholysis degree is preferably the polyvinyl alcohol 7.5kg of 73%, is heated to 55 DEG C, makes polyvinyl alcohol be well-dispersed in solution；Addition contains Divinylbenzene 450kg, the styrene 550kg of amount 70%, liquid wax 600kg, toluene 200kg, dimethylbenzene 200kg, azo two Isopropyl cyanide 7.6kg, mix homogeneously, keeping temperature is 45～55 DEG C, and meanwhile, blender is stirred with 900r/min constant speed, stirs Mix 2h.
After 2h, temperature is promoted to 77 DEG C, and is incubated 5h；It is promoted to 86 DEG C, and is incubated 4h；It is promoted to 98 DEG C, insulation 5h, releases the NaCl solution in reactor afterwards, is prepared into copolymerization spheroid (1).
(2) wash and be dried
Copolymerization spheroid (1) is transferred in 2000L distillating still, addition 1500kg acetone and the mixed liquor of petroleum ether, acetone 900kg, Petroleum ether 600kg；After leaching time is 15h, extracting solution acetone is released with petroleum ether, add 1500L pure water, be heated to 100 DEG C, leach 15h, the acetone of residual is steamed with petroleum ether；
The polymer spheres steaming porogen is transferred to vacuum drier, after being dried 9h, obtains copolymerization spheroid by copolymerization spheroid Send into screening machine to sieve, choose copolymerization spheroid (3) that particle diameter is 0.05-0.1mm.
(3) chloromethylation
At 10-25 DEG C, 800kg copolymerization spheroid (3) is added in 2000L reactor, add 2400kg chloromethyl ether And after swelling 3.5h, add 400kg zinc chloride, be warmed up to 45 DEG C, insulation reaction 23h.Product is carried out washing process, Prepare copolymerization spheroid (4)；
(4) cross-link afterwards
320kg catalyst SnCl is added in reactor in reaction (3)4, and add 1-chloromethyl-4-Nitrobenzol 64kg, will Temperature is slowly promoted to 135 DEG C, reacts 13 hours, washs polymer with 600L acetone after completion of the reaction and is dried, Prepare target product SEW-105 nano composite material.
Experimental example 5
The SEW-105 nano composite material prepared by embodiment 2 is utilized to carry out following experiment:
Bromamine acid (1-amino-4-bromo anthraquinone-2-sulfonic acid) is a kind of important benzene series derivatives active dyestuff, is weight in dye industry The dark kind wanted.
Certain dyestuff factory bromamine acid annual capacity is 2000 tons, and wastewater flow rate is about 99000 tons/year, and waste water COD cr is about 4000～20000mg/L, salinity 10000～30000mg/L.The waste water treatment process used at present is " neutralization+Fenton oxidation + iron-carbon micro-electrolysis+the most floating+A/O+ flocculation ", producing CODcr of intaking after waste water mixes with other is 1000mg/L, and system goes out Water CODcr is 500mg/L, and water outlet is the most up to standard.Moreover, waste water per ton there are about 1kg～1.5kg bromamine acid product and run off, Calculating with 60000 yuan/ton of products, annual bromamine acid runs off about 148.5 tons with waste water, causes economic loss about 8,910,000 yuan.
Use the waste water reclaiming group technology separated based on SEW-105 nano composite material targeting to process, have according to water quality Body situation, uses " pretreatment removing micron particles thing+nano composite material targeting separates " technique, pretreatment use ceramic membrane or " more medium filter+accurate filter ", it is ensured that water turbidity ＜ 5 is produced in pretreatment, it is 0.5BV/H that targeting piece-rate system processes flow velocity, Water outlet CODcr is generally 20mg/L～40mg/L, CODcr removal efficiency ＞ 92%；Produce water and meet national and local CODcr Discharge standard requirement, meanwhile, the value that water per ton is created because reclaiming bromamine acid is 45 yuan～50 yuan, and (creation of value calculates and detains Except resolving the expenses such as agent consumption, the electricity charge).
Experimental example 6
The SEW-105 nano composite material prepared by embodiment 3 is utilized to carry out following experiment:
2,3-bis-chloro-5-trifluoromethylpyridines are a kind of organic intermediates, are widely used in the fields such as pesticide, medicine, fine chemistry industry, Certain chemical plant annual output 2,3-bis-chloro-5-trifluoromethylpyridine 1000 tons, it is 50t/d that production process is fluorinated the wastewater flow rate of workshop section's generation, CODcr is 4500～5000mg/L, wherein 2, and 3-bis-chloro-5-trifluoromethylpyridine is about 220～300mg/L, and this product is current Market price is 220000 yuan/ton.
This factory original process technique is " iron-carbon micro-electrolysis+A/O+ coagulant precipitation ", and due to 2,3-bis-chloro-5-trifluoromethylpyridine divides Minor structure is stable, it is extremely difficult to biodegradation, and even across iron-carbon micro-electrolysis pretreatment, biochemical system still cannot be properly functioning, produces water CODcr is 2000-3000mg/L.
The waste water reclaiming group technology separated based on SEW-105 nano composite material targeting is used to process, by " secondary filter Device+nano composite material targeting separates " technique, after using 5um accurate filter to guarantee that product water is without entering more than 5um particulate matter Continuous system, it is 0.5BV/H that targeting piece-rate system processes flow velocity, and water outlet CODcr is 30mg/L～50mg/L, CODcr removal efficiency ＞ 95%；Producing water and meet national and local CODcr discharge standard requirement, meanwhile, water per ton is because of recovery 2, the chloro-5-of 3-bis-tri- Fluoromethylpyridin and the value created is 50 yuan～60 yuan (creation of value calculates expenses such as having deducted parsing agent consumption, the electricity charge).

Claims (8)

1. the waste water reclaiming separated based on nano composite material targeting processes technique, it is characterised in that specifically comprise the following steps that
(1) pretreatment: pending used water difficult to degradate is pumped into pretreatment system, pretreatment system be " more medium filter or Back-flushing filter+1um accurate filter " or " ultrafiltration+1um accurate filter "；
(2) targeting separates: pretreatment produces water with 0.5BV/H～2BV/H flow velocity, nano combined by being filled with SEW-105 The separator of material, carries out recycling treatment to waste water, when separator product water does not meets emission request, shows that nano material is divided Saturated from enrichment, now separator is out of service；
(3) regeneration is resolved: by the parsing agent of 1.5BV～3BV, the flow velocity producing water flow velocity 40%～50% with pretreatment squeezes into separation In device, the material being enriched in SEW-105 nano composite material enters and resolves in agent, becomes desorbed solution, the most saturated SEW-105 recovers its targeting separating power, and desorbed solution is collected to resolving in flow container；
(4) gas emptying: blasted by separator top by oil-free compressed air, the desorbed solution remained ejected in separator, collects To resolving in flow container, separator enters next cycle of operation；
(5) material recycle: according to resolving the characteristic of desorbed solution in flow container, or direct reuse is to material production workshop section, or by steaming The method that evaporates separates and resolves agent and material, and recovered material resolves agent and recycles.
2. the waste water reclaiming separated based on nano composite material targeting as claimed in claim 1 processes technique, it is characterised in that Described SEW-105 nano composite material, is with styrene polymerization monomer, and divinylbenzene is cross-linking agent, with polyvinyl alcohol for dividing Powder, adds toluene, dimethylbenzene, liquid wax is as porogen, and adds NaCl solution, by controlling the mixing speed of blender, On the premise of initiator exists, carry out suspension polymerisation, react 4-6 hour at 76 DEG C-80 DEG C, react 6-10 at 85 DEG C-98 DEG C Hour, product is scrubbed, chloromethylation, cross-link afterwards, nano combined between 0.1mm～0.3mm of the grain graininess prepared Material.
3. the waste water resource metallization processes separated based on nano composite material targeting as claimed in claim 2, it is characterised in that institute Stating the mixed liquor that porogen is toluene, dimethylbenzene and liquid wax, weight is divinylbenzene and the 60%-130% of styrene gross weight.
4. the waste water resource metallization processes separated based on nano composite material targeting as claimed in claim 2, it is characterised in that institute Stating dispersant is polyvinyl alcohol, and for divinylbenzene and the 0.5%-1.0% of styrene gross weight, the polyvinyl alcohol degree of polymerization is preferably 800～1000, alcoholysis degree is preferably 70%～75%；
Described NaCl solution concentration is preferably 7%-12%, weight be divinylbenzene, the 200% of styrene gross weight～300%；
Described initiator is preferably benzoyl peroxide or azodiisobutyronitrile, and weight is divinylbenzene and styrene gross weight 0.5%-1.1%；Described blender mixing speed is 750-1000r/min.
5. the waste water reclaiming separated based on nano composite material targeting as claimed in claim 2 processes technique, it is characterised in that
Described washing is that the product after suspension polymerisation is placed in extracting solution leaching 10-20 hour, extracts porogen, Carrying out 100 DEG C of washings the most again, washing time is 10-20 hour, is dried afterwards, and drying time is 8-10 hour, system Obtain copolymer spheroid；Described extracting solution is any one or a few the mixture in acetone, methanol, petroleum ether.Preferably, Described extracting solution is the mixture of acetone, petroleum ether, and its mass ratio is: 1:1～1:0.5.
6. the waste water resource metallization processes separated based on nano composite material targeting as claimed in claim 2, it is characterised in that
Described chloromethylation is at normal temperatures, will the copolymer spheroid that prepare in chloromethyl ether swelling 3-4 hour after washing, then add Enter zinc chloride, be warmed up to 40～50 DEG C, insulation reaction 20～25 hours；
Wherein said copolymer spheroid and chloromethyl ether mass ratio are 1:2.5-4；
The quality of described zinc chloride is the 40%～60% of copolymer spheroid.
7. the waste water reclaiming separated based on nano composite material targeting as claimed in claim 2 processes technique, it is characterised in that
Described rear crosslinking is to add catalyst: SnCl in the reactor4, dosage is the 20%～50% of copolymer spheroid mass, Adding a certain amount of 1-chloromethyl-4-Nitrobenzol, dosage is the 5%～10% of copolymer spheroid mass, controls temperature and is 130～140 DEG C, react 10-15 hour, washing, be dried.
8. the benzene homologues used water difficult to degradate process for reclaiming separated based on nano composite material targeting as claimed in claim 1, its Being characterised by, described parsing agent is hydrochloric acid, sulphuric acid, sodium hydroxide, potassium hydroxide, methanol, ethanol, acetone, chloroform.
CN201610438135.5A 2016-06-16 2016-06-16 It is a kind of to target isolated waste water reclaiming treatment process based on nanocomposite Expired - Fee Related CN105948293B (en)

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