CN102875717B - Synthetic resin, and preparation method and application thereof - Google Patents
Synthetic resin, and preparation method and application thereof Download PDFInfo
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- CN102875717B CN102875717B CN201110246699.6A CN201110246699A CN102875717B CN 102875717 B CN102875717 B CN 102875717B CN 201110246699 A CN201110246699 A CN 201110246699A CN 102875717 B CN102875717 B CN 102875717B
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Abstract
The invention discloses a synthetic resin, a preparation method for the synthetic resin and a method for removing oil efficiently by using the resin. The resin is prepared by the following steps of: performing suspension copolymerization of styrene and divinylbenzene, and performing chloromethylation, amination and alkylation reaction. A 10-100mg/L oil-containing stock solution is filled in a glass chromatographic column of the synthetic resin at the temperature of between 25 and 80DEG C and the flow of between 10 and 25BV/h, and the oil content can be reduced to be below 1mg/L. The oil removal rate is over 99 percent and the oil recovery rate is over 90 percent.
Description
Technical field
The present invention relates to the preparation method of a kind of novel synthetic resins, this resin, and utilize the application of this resin in oil water separation process.
Background technology
Oily water separation technique is often applied to the processing of oily(waste)water.Deoiling method of the prior art mainly contains gas flotation process, biochemical process, membrane separation process, coalescence etc., the shortcoming that the many existence of these deoiling methods are easily secondary polluted, treatment capacity is little, processing efficiency is low.Absorption method is the effective ways of generally acknowledging advanced treatment oily(waste)water both at home and abroad, conventionally oil-contg can be down to below 1mg/L.In prior art, the conventional sorbent material of absorption method mainly contains gac, resin etc., and wherein resin sorbent common are domestic resin NDA-18, domestic resin NDA-16, the U.S. produces XAD series plastics.But in the market except oleo-resinous ubiquity cost high, the problems such as regeneration difficulty.So the polymeric adsorbent of exploitation efficient economy is the effective way that realizes utilization of wastewater resource, the more good resin absorption material of selectivity has become the key breakthrough point of degreasing technique.
Summary of the invention
One of object of the present invention is to provide a kind of novel synthetic resins, two of object is to provide its preparation method, three of object is to provide the application of this synthetic resins in oil water separation process, utilize this resin effectively to remove the micro oil in steam condenses, realize Oil recovery, utilization of resources, reduces the pressure of waste water to environment.
Therefore, synthetic resins provided by the invention, is a kind of cross-linked polystyrene resin with long-chain hydrocarbon chain, it is characterized in that:
Wherein, n=2 or 3 or 4, R be 2-14 carbon straight chained alkyl, the straight chained alkyl that the R of optimization is 6-12 carbon.
The present invention also provides the preparation method of above-mentioned synthetic resins, comprises the steps:
(1) vinylbenzene that mass ratio is 5:1-10:1 and Vinylstyrene carry out free radical suspension copolymerization under the initiation of initiator Diisopropyl azodicarboxylate or benzoyl peroxide, obtain Archon;
(2) Archon obtains chlorine ball through chloromethylation;
(3) chlorine ball warp obtains formula I compound after crossing amination, it is characterized in that this compound has for the structural unit shown in following formula I, wherein, and said n=2 or 3 or 4;
(4) formula I compound obtains formula II compound through alkylated reaction in ethanolic soln.
More particularly, the preparation method of synthetic resins provided by the present invention is to be that 5:1-10:1 vinylbenzene mixes with divinylbenzene by mass ratio, and vinylbenzene and divinylbenzene total mass are A, in mixture, adding quality is Diisopropyl azodicarboxylate or the benzoyl peroxide of (0.5%-1%) A, adding quality is the whiteruss of (25%-50%) A again, after mixing, be made into oil phase, this oil phase is suspended in to polyvinyl alcohol, sodium-chlor, in the water that water is made into, regulate stirring velocity to make the oil droplet in water mainly be distributed in 20-50 orders, react 8h at 70 ℃-95 ℃ more than, obtain Archon, Archon and chloromethyl ether react 10h in 38 ℃ under the katalysis of zinc chloride, obtain chlorine ball, chlorine ball and diethylenetriamine or triethylene tetramine or tetraethylene pentamine are reacted 10h at 40 ℃, obtain formula I compound, formula I compound reacts 10h with the bromo straight-chain paraffin of 2-14 carbon in the ethanolic soln of pH=9-11 at 80 ℃, obtains formula
compound, is synthetic resins of the present invention, and reaction formula is as follows:
Alkylating reagent RBr used is bromo straight-chain paraffin, and chemical formula is: C
nh
2n+1br, n=2,3 ..., 14.
The present invention also provides the application method of above-mentioned synthetic resins in steam condenses oil removing, comprises the process that resin and oil-containing stoste are contacted under the condition of the temperature of 25-80 ℃ and 10-25BV/h flow.
Method provided by the invention, normally by said resin filling in glass chromatography column, in a specific embodiments of the present invention, the high 300mm of glass chromatography column, internal diameter 50mm, is leaving water outlet apart from post mouth 100mm place, and post mouth is joined a stopper with piston, the height of potting resin layer is 40mm, and loading level is about 80mL.Oil removing application process provided by the invention, steam condenses is down to below 1mg/L the content of oil in water by being filled with the resin column of oil-absorbing resin.
Novel synthetic resins provided by the invention has very high wetting ability, and its wetting ability makes the water that contains micro oil can diffuse into rapidly resin inside, and oil-containing water is fully contacted with resin; Contain again oil loving aromatic nucleus and chain alkyl, the oil in planar water rapidly, in the time that the oil of resin absorption increases gradually simultaneously, alligatoring form larger oil droplet, when these larger oil droplets have reached after critical volume, will with resin isolation, upwards floating, thus reach the object of oily water separation.This resin oil removing stable performance, gets final product autoregeneration without wash-out.
After aforesaid method is processed, the stoste that oleaginousness is 10-100mg/L, oil removal rate is more than 99%, and oil recovery rate is greater than 90%.Resin oil removing stable performance provided by the invention, reach more than 5 years the work-ing life of resin.The method processing step is simple, easy and simple to handle, and cost is lower, avoids secondary pollution, processes waste water efficiency higher.
embodiment
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
Embodiment 1
The present embodiment illustrates the preparation process of resin provided by the invention.
The preparation of step 1, vinylbenzene-divinylbenzene copolymer: add 20g sodium-chlor in the 1000mL there-necked flask that agitator, prolong and thermometer are housed, 40mL polyvinyl alcohol water solution (mass percent is 5%), 340mL distilled water, stirring is fully dissolved it and is made into water.Add the oil phase that is equivalent to water 25%, oil phase consist of 41g vinylbenzene, 9g divinylbenzene (purity is 55%), 25g whiteruss, 0.5g Diisopropyl azodicarboxylate (AIBN).Regulate stirring velocity oil droplet is of moderate size, be warming up to 75 ℃ of initiated polymerization 5h with the speed of 5 ℃/min, then be warming up to 80 ℃ reaction 3h go out ball, naturally dry.Put in cable type extractor according with more than sherwood oil extracting 8h, dry and obtain Archon.
Step 2, chloromethylation: in the 500mL there-necked flask that agitator, prolong and thermometer are housed, add 35g Archon and 250mL chloromethyl ether, the swelling 2h of mixed solution.Then add at twice ZnCl
2, add 11g, interval half an hour at every turn.Be warming up to 38 ± 2 ℃ of reaction 10h, by chlorination mother solution sucking-off, fully wash with ethanol, naturally dry, obtain chlorine ball.
Step 3, amination: after adding 20g chlorine ball and 20g ethylene dichloride to mix swelling 20min in the 250mL there-necked flask that agitator, prolong and thermometer are housed, add 100g diethylenetriamine as ammonification reagent, at 40 ℃, react 10h.Reaction finishes to pump mother liquor, dimethyl formamide washing three times, and hot water wash is naturally dried to pH=6, obtains formula
compound.
Step 4, alkylation: install same step 3, in the there-necked flask of 250mL, add 20g formula
compound is suspended in 100mL ethanol, adds 10g bromo normal hexane, stirring reaction 10h at 80 ℃.With filter flask, by liquor abstraction, resin is successively with obtaining formula after ethanol, distilled water wash
compound, wherein n=2, R is the straight chained alkyl of six carbon.
Embodiment 2
The present embodiment illustrates the preparation process of resin provided by the invention.
The ratio of step 1, device, water, water and oil phase is with embodiment 1, and oil phase consists of 36.7g vinylbenzene, 13.3g divinylbenzene, 25g whiteruss, 0.5g benzoyl peroxide, 80 ℃ of initiated polymerization 5h, be warming up to 95 ℃ of reaction 3h, other operational conditions are with the step 1 in embodiment 1.
Step 2, with the step 2 in embodiment 1.
Step 3, with the step 3 in embodiment 2.
Step 4, change alkylating reagent into n-octane bromide, reaction solvent changes the sodium hydroxide ethanolic soln of 100mL pH=9 into, and other conditions, with the step 4 in embodiment 1, obtain formula
compound, wherein n=2, R is the straight chained alkyl of eight carbon.
Embodiment 3
The present embodiment illustrates the preparation process of resin provided by the invention.
The formula of filling in this device
compound also can make by following four-step reaction:
The ratio of step 1, device, water, water and oil phase is with embodiment 1, and oil phase consists of 42.3g vinylbenzene, 7.7g divinylbenzene, and 25g whiteruss, 0.5g Diisopropyl azodicarboxylate, other operational conditions are with the step 1 in embodiment 1.
Step 2, with the step 2 in embodiment 1.
Step 3, except amination reagent is changed to triethylene tetramine, other conditions are with the step 3 in embodiment 1.
Step 4, change alkylating reagent into bromododecane, reaction solvent changes the sodium hydroxide ethanolic soln of 100mL pH=11 into, and other conditions, with the step 4 in embodiment 1, obtain formula
compound, wherein n=3, R is the straight chained alkyl of 12 carbon.
Embodiment 4
The present embodiment illustrates the application of synthetic resins provided by the invention in steam condensate oil removing process.
By prepared 80mL embodiment 1 formula
compound packs in glass chromatography column.Under room temperature (25 ℃ of left and right) by oil-containing stoste with the traffic flow of 800mL/h through resin bed, treatment capacity be 15L/batch.Oil-containing stoste oleaginousness is 95mg/L, water outlet oleaginousness≤0.63mg/L after resin column.
Embodiment 5
The present embodiment illustrates the application of synthetic resins provided by the invention in steam condensate oil removing process.
Other implementation conditions are with embodiment 4, change flow velocity, by oil-containing stoste with the traffic flow of 1280mL/h through resin bed, treatment capacity be 15L/batch.Oil-containing stoste oleaginousness is 60 mg/L, water outlet oleaginousness≤0.65mg/L after resin column.
Embodiment 6
The present embodiment illustrates the application of synthetic resins provided by the invention in steam condensate oil removing process.
Other implementation conditions are with embodiment 4, change flow velocity, by oil-containing stoste with the traffic flow of 2000mL/h through resin bed, treatment capacity be 15L/batch.Oil-containing stoste oleaginousness is 42 mg/L, is≤0.68 mg/L through resin water outlet oleaginousness.
Embodiment 7
The present embodiment illustrates the application of synthetic resins provided by the invention in steam condensate oil removing process.
By prepared 80mL embodiment 2 formula
compound packs in glass chromatography column.Control temperature in 60 ℃ of left and right, by oil-containing stoste with the traffic flow of 800mL/h through resin bed, treatment capacity be 15L/batch.Oil-containing stoste oleaginousness is 80 mg/L, and after resin column, water outlet oleaginousness is≤0.73 mg/L.
Embodiment 8
The present embodiment illustrates the application of synthetic resins provided by the invention in steam condensate oil removing process.
Other implementation conditions are with embodiment 7, change flow velocity, by oil-containing stoste with the traffic flow of 1280mL/h through resin bed, treatment capacity be 15L/batch.Oil-containing stoste oleaginousness is 50 mg/L, and the water outlet oleaginousness after resin column is≤0.82 mg/L.
Embodiment 9
Other implementation conditions are with embodiment 7, change flow velocity, by oil-containing stoste with the traffic flow of 2000mL/h through resin bed, treatment capacity be 15L/batch.Oil-containing stoste oleaginousness is 30 mg/L, and the water outlet oleaginousness after resin column is≤0.80 mg/L.
Embodiment 10
The present embodiment illustrates the application of synthetic resins provided by the invention in steam condensate oil removing process.
By prepared 80mL embodiment 3 formula
compound packs in glass chromatography column.Control temperature in 80 ℃ of left and right, by oil-containing stoste with the traffic flow of 800mL/h through resin bed, treatment capacity be 15L/batch.Oil-containing stoste oleaginousness is 80 mg/L, and the water outlet oleaginousness after resin column is≤0.79 mg/L.
Embodiment 11
The present embodiment illustrates the application of synthetic resins provided by the invention in steam condensate oil removing process.
Other implementation conditions are with embodiment 10, change flow velocity, by oil-containing stoste with the traffic flow of 1280mL/h through resin bed, treatment capacity be 15L/batch.Oil-containing stoste oleaginousness is 30mg/L, and the water outlet oleaginousness after resin column is≤0.91 mg/L.
Embodiment 12
The present embodiment illustrates the application of synthetic resins provided by the invention in steam condensate oil removing process.
Other implementation conditions are with embodiment 10, change flow velocity, by oil-containing stoste with the traffic flow of 2000mL/h through resin bed, treatment capacity be 15L/batch.Oil-containing stoste oleaginousness is 12mg/L, and after resin column, water outlet oleaginousness is≤0.86 mg/L.
Claims (9)
1. a synthetic resins, is a kind of cross-linked polystyrene resin with long-chain hydrocarbon chain, it is characterized in that this resin has the structure of illustrating for following formula,
Wherein, said n=2 or 3 or 4, the R straight chained alkyl that is 2-14 carbon.
2. synthetic resins as claimed in claim 1, is characterized in that R is the straight chained alkyl of 6-12 carbon.
3. prepare a method for synthetic resins claimed in claim 1, it is characterized in that comprising the following steps:
(1) mass ratio is 5:1-10:1 vinylbenzene and Vinylstyrene carry out free radical suspension copolymerization, obtain cross-linked polystyrene resin, are called Archon;
(2) Archon obtains chlorine ball through chloromethylation;
(3) chlorine ball warp obtains formula I compound after crossing amination, it is characterized in that this compound has as shown in the formula the structural unit shown in I,
Wherein, said n=2 or 3 or 4;
(4) formula I compound obtains the synthetic resins shown in claim 1 through alkylated reaction in ethanolic soln.
4. according to preparation method claimed in claim 3, it is characterized in that in step (3), the amination reagent of using in said amination is diethylenetriamine or triethylene tetramine or tetraethylene pentamine.
5. according to preparation method claimed in claim 3, it is characterized in that in step (4), alkylated reaction alkylating reagent used is bromo straight-chain paraffin, chemical formula is: C
nh
2n+1br, n=2,3 ..., 14.
6. a deoiling method, is characterized in that the synthetic resins of right to use requirement 1 contacts with oil-containing stoste.
7. in accordance with the method for claim 6, wherein, the oleaginousness of oil-containing stoste is 10-100mg/L.
8. in accordance with the method for claim 6, it is characterized in that the synthetic resins of claim 1 to be filled in glass chromatography column φ 1 × 6mm, blade diameter length ratio 1:6, post height is 300mm, resin filling amount is in mL.
9. in accordance with the method for claim 8, the height that it is characterized in that potting resin layer is 40mm, and resin filling amount is 80mL, at control temperature is 25-80 ℃, the stoste that is 95mg/L by oleaginousness is passed through resin bed with the flow of 800mL/h, and water outlet oleaginousness can be controlled in below 1.0mg/L.
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| CN104086679B (en) * | 2014-06-17 | 2017-07-21 | 宁波争光树脂有限公司 | A kind of apparatus and method of its oil removing of macromolecule resin and application |
| CN104530270A (en) * | 2014-10-17 | 2015-04-22 | 常州大学 | Diethylenetriamine chelate resin and synthetic method thereof |
| CN105037601B (en) * | 2015-08-26 | 2017-10-31 | 同济大学 | A kind of anti-pollution moldeed depth degree softens the synthetic method of chelating resin |
| CN105504131B (en) * | 2016-01-26 | 2018-07-17 | 重庆希尔康血液净化器材研发有限公司 | β is removed for blood purification2The preparation method of the resin of microglobulin |
| CN107226873B (en) * | 2017-06-27 | 2019-07-23 | 湖南师范大学 | A kind of method and products thereof preparing 2,6 di t butyl phenol anti-oxidation resin |
| CN113101902A (en) * | 2021-04-13 | 2021-07-13 | 北京赛科康仑环保科技有限公司 | Adsorption material for acidic phosphate extraction system, preparation method and application |
| CN113083256A (en) * | 2021-04-13 | 2021-07-09 | 北京赛科康仑环保科技有限公司 | Adsorbing material for deep oil removal of neutral phosphorus-containing extraction system and preparation and application methods thereof |
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| US4384095A (en) * | 1978-07-24 | 1983-05-17 | Rohm And Haas Company | Vinylbenzyl alcohol polymer beads and thermally crosslinked derivatives thereof |
| US4297452A (en) * | 1980-01-04 | 1981-10-27 | The Dow Chemical Company | Process for the manufacture of oxazoline and/or oxazine-modified adsorbent polymer resins |
| CN1320013C (en) * | 2004-10-10 | 2007-06-06 | 南京理工大学 | Method for preparing high oil absorption resin |
| CN101792513B (en) * | 2010-01-28 | 2012-03-07 | 王颖华 | Polymer material, preparation method thereof and application thereof to oil removal |
| CN101857652A (en) * | 2010-05-26 | 2010-10-13 | 鲁东大学 | Preparation and applications of low-substituted dendrimer adsorption material loaded on crosslinked polystyrene |
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