CN101665298B - Method for removing phthalate ester in water body by utilizing solid base catalyst - Google Patents
Method for removing phthalate ester in water body by utilizing solid base catalyst Download PDFInfo
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- CN101665298B CN101665298B CN200910184186.XA CN200910184186A CN101665298B CN 101665298 B CN101665298 B CN 101665298B CN 200910184186 A CN200910184186 A CN 200910184186A CN 101665298 B CN101665298 B CN 101665298B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 title claims abstract description 14
- 239000007787 solid Substances 0.000 title claims abstract description 14
- -1 phthalate ester Chemical class 0.000 title claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 159
- 229920005989 resin Polymers 0.000 claims abstract description 88
- 239000011347 resin Substances 0.000 claims abstract description 88
- 238000010521 absorption reaction Methods 0.000 claims abstract description 77
- 238000003795 desorption Methods 0.000 claims abstract description 65
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 33
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 238000001953 recrystallisation Methods 0.000 claims abstract description 17
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011780 sodium chloride Substances 0.000 claims abstract description 16
- 230000008929 regeneration Effects 0.000 claims abstract description 9
- 238000011069 regeneration method Methods 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 31
- 238000001179 sorption measurement Methods 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 3
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims description 2
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical compound CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 abstract description 17
- 230000007062 hydrolysis Effects 0.000 abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 8
- 239000003957 anion exchange resin Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 90
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 45
- 229960001826 dimethylphthalate Drugs 0.000 description 45
- 239000011521 glass Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 8
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical group C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
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- 239000000654 additive Substances 0.000 description 1
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- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
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- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for removing phthalate ester in a water body by utilizing a solid base catalyst, which belongs to the field of wastewater treatment by resin. The method comprises the following steps of: firstly filtering the water body containing phthalate ester pollutants for removing suspended solids in the water body; then leading the obtained filtrate to pass through an absorption tower which is filled with anion exchange resin containing strong base groups; stopping the absorption when the absorption achieves a leakage point, using mixed solution of sodium hydroxide and sodium chloride for carrying out the desorption, and using sodium hydroxide solution for carrying out the regeneration on the resin after the desorption; and obtaining desorption solution which contains sodium phthalate and can be repeatedly recycled, using hydrochloric acid for neutralizing the desorption solution, and recycling phthalic acid after recrystallization. The method adopts the strong base anion exchange resin as the solid base catalyst, deeply removes the phthalate ester pollutants in the water body by catalytic hydrolysis and acid-base absorption, separates and recycles the phthalic acid while reducing the harm of the phthalate ester pollutants and realizes the recycling and the reutilization of resources, the resin has good regeneration performance and can be used repeatedly.
Description
Technical field
The present invention relates to the removal method of phthalate in a kind of water body, say more specifically a kind of take strongly basic anion exchange resin as solid base catalyst, utilize catalytic hydrolysis and the effect of soda acid absorbing synergic, the degree of depth is removed phthalate pollutent in the water body, reduces simultaneously the method for phthalate hazard of contaminant.
Background technology
Main phthalate compound as the modifying plastics additive is that a class has carinogenicity, mutagenicity, teratogenecity, genotoxicity, neurotoxicity, the interfering environmental hormone of internal secretion, also is one of the preferential control in whole world toxic pollutant of generally acknowledging.The pollution of phthalate is mainly from the slow release of PVC plastics in the discharging of the discharging of trade effluent in plasticizer production and the use procedure, percolate and the environment in the water body.In recent years, along with widespread production and the use of plastics, presented phthalate in some rivers and lakes, reservoir, tap water and the bed mud of China compound polluted.The treatment process of polluting for phthalate in the water body at present is still take dilution-biological degradation as main, but effectively administered, and threatens HUMAN HEALTH.
Nanjing University in 2006 has applied for " a kind of method of administering diethyl phthalate waste water and therefrom reclaiming diethyl phthalate " patent (patent No. 200610097239.0), and this patent mainly is the phthalate pollutent that utilizes in the physisorption Adsorption water body of macroporous adsorbent resin.And patent " method of composite function resin and method for making and the processing phthalate pollution of water body " patent (number of patent application 200710190974.0) of Nanjing University's application in 2007, mainly be by phthalate in the physical action adsorption and enrichment water body of resin matrix, then by resin acid functional group catalytic hydrolysis phthalate.
The result of literature search shows: Wolfe, N.L. wait and once used liquid alkali sodium hydroxide catalytic hydrolysis dimethyl phthalate (Chemosphere, 1980 (9), PP403-408) .Pradyot Patnaik etc. with ammoniacal liquor as catalyst hydrolysis dimethyl phthalate and diethyl phthalate (Wat.Res.2001 (35), 6, pp1587-1591).But has not recoverable and can not be with hydrolysate from shortcomings such as liquid phase removals with liquid alkali as catalyzer.For take strongly basic anion exchange resin as solid base catalyst, first phthalate is carried out base catalysis and be hydrolyzed to phthalic acid, then by acid-base function with the phthalic acid Adsorption, reduce simultaneously the method for phthalate hazard of contaminant and have no bibliographical information.
Summary of the invention
1. invent the technical problem that will solve
The purpose of this invention is to provide a kind of method of utilizing solid base catalyst to remove phthalate in the water body, can utilize the phthalate pollutent in base catalysis hydrolytic action and the soda acid adsorption degree of depth removal water body, reduce simultaneously the phthalate hazard of contaminant.
2. technical scheme
Technical solution of the present invention is as follows:
A kind of method of utilizing solid base catalyst to remove phthalate in the water body may further comprise the steps:
A) will contain the water body filtration of phthalate pollutent, remove suspended substance wherein
B) with steps A) in the phthalate concentration that obtains be 1-500mg/L filtrate at room temperature take the flow velocity of 4～20BV/h (BV is as the resin bed volume) by being filled with the adsorption tower of the anionite-exchange resin that contains the highly basic group, when phthalate is flowed through the resin duct, alkaline hydrolysis occurs under katalysis hydroxy, pass through the soda acid adsorption behind product phthalic acid after the hydrolysis and the hydroxide radical acid-base neutralisation by the absorption of the amido on the resin, thereby reach the purpose of final removal.Along with the gradually consumption of basic group, this catalytic hydrolysis and soda acid adsorption fade away, and finally reach leakage point.
C) when absorption reach leakage point (in the absorption effluent the instant concentration of phthalate be influent concentration 2%) time stop absorption, be that the sodium hydroxide of 1%-8% and the mixed solution of the sodium-chlor that concentration is 1%-20% carry out desorption at a certain temperature with concentration.Resin after desorption is complete is regenerated with the sodium hydroxide solution of 1%-4%.
D) desorption liquid that contains sodium phthalate that step C) obtains can recirculation uses, and when the concentration of sodium hydroxide is reduced to 0.5% when following, with hydrochloric acid desorption liquid is neutralized, and reclaims phthalic acid behind the recrystallization.
Step B) anionite-exchange resin that contains the highly basic group described in refers to that specific surface area is 20-500m take vinylbenzene-divinylbenzene or vinylformic acid as skeleton structure
2/ g, contain Trimethylamine 99, triethylamine, Tributylamine, pyrimidyl, pyridyl, pyranyl, dimethyl propanol amine, the exchange capacity of the quaternary amines such as methyldiethanolamine or dioctyl thanomin is the resin of 0.5-4.5mmol/g, comprise D201 (China wins honour for), D201GF (Chinese Nankai), AmberliteIRA-400 (ROHM AND HAAS), Amberlite IRA-900 (ROHM AND HAAS), FPA40 (ROHM AND HAAS), FPA90 (ROHM AND HAAS), FPA98 (ROHM AND HAAS), IRA958 (ROHM AND HAAS), HP555 (ROHM AND HAAS), Dowex-1 (ROHM AND HAAS), Diaion SA-10A (Japan), LmacA-504 (Holland), DuoliteA-101D (France).
Step C) in, desorption liquid carries out desorption and regeneration at 20～40 ℃ with 1～8BV/h flow velocity.The present invention carries out the resin desorption and regeneration after having processed 500-3000BV/ batch polluted water body.Step D) in, gained sodium phthalate purity reaches more than 90%.
The present invention is at step B) described in adsorption tower can adopt the operation scheme of double-column in series absorption, single tower desorption; I, II, three adsorption towers of III are set, and with I, II tower series connection following current absorption, the I tower is as first post first, the II tower after the absorption of I tower is saturated, switches to II, III tower series connection following current absorption as stern post, the II tower is as first post, and the III tower is as stern post, and the I tower carries out desorption and regeneration with desorbing agent simultaneously.
3. beneficial effect
Compared with prior art, beneficial effect of the present invention is: 1, take strongly basic anion exchange resin as solid base catalyst, remove phthalate pollutent in the water body by catalytic hydrolysis and soda acid adsorption deeply; Separable recovery phthalic acid when 2, reducing the phthalate Hazards of pollutants is realized the resource recycling; 3, resin regeneration is functional, and is reusable.
Embodiment
The invention will be further described by the following examples, and wherein following sodium hydroxide and sodium chloride concentration content are weight percent concentration.
Embodiment 1
3.2ml (approximately 1 gram) D201 resin packed in the glass adsorption column of jacketed, and (Ф 12 * 160mm).Dimethyl phthalate concentration is 20mg/L in the water inlet, and after the filtration, in 25 ± 5 ℃, by resin bed, treatment capacity is that 8000mL/ criticizes with the flow of 24mL/h with it.After resin absorption, dimethyl phthalate mean concns＜0.1mg/L in the water outlet.
When absorption reach leakage point (in the absorption effluent the instant concentration of dimethyl phthalate be influent concentration 2%) time stop absorption, the sodium hydroxide of 40mL weight percent concentration 1% and weight percent concentration 10% sodium chloride solution under 30 ± 5 ℃ temperature, are carried out desorption with the flow following current of 3mL/h by resin bed.Desorption liquid can reuse, and when the concentration of sodium hydroxide is lower than 0.5%, mixed solution is neutralized with hydrochloric acid, and recrystallization reclaims sodium phthalate.Resin after desorption is complete is regenerated with the sodium hydroxide solution of 50ml 4%.
Embodiment 2
3.4mL (approximately 1 gram) D201 resin packed in the glass adsorption column of jacketed, and (Ф 12 * 160mm).Dimethyl phthalate concentration is 100mg/L in the water inlet, and after the filtration, in 25 ± 5 ℃, by resin bed, treatment capacity is that 6851mL/ criticizes with the flow of 20mL/h with it.After resin absorption, dimethyl phthalate mean concns＜0.1mg/L in the water outlet.
When absorption reach leakage point (in the absorption effluent the instant concentration of dimethyl phthalate be influent concentration 2%) time stop absorption, 40mL is contained the sodium hydroxide of weight percent concentration 1% and weight percent concentration 10% sodium chloride solution under 30 ± 5 ℃ temperature, carry out desorption with the flow following current of 3mL/h by resin bed.Desorption liquid can reuse, and when the concentration of sodium hydroxide is lower than 0.5%, mixed solution is neutralized with hydrochloric acid, and recrystallization reclaims sodium phthalate.Resin after desorption is complete is regenerated with the sodium hydroxide solution of 80ml weight percent concentration 2%.
Embodiment 3
3.4mL (approximately 1 gram) D201 resin packed in the glass adsorption column of jacketed, and (Ф 12 * 160mm).Dimethyl phthalate concentration is 200mg/L in the water inlet, and after the filtration, in 25 ± 5 ℃, by resin bed, treatment capacity is that 5700mL/ criticizes with the flow of 18mL/h with it.After resin absorption, dimethyl phthalate mean concns＜0.1mg/L in the water outlet.
When absorption reach leakage point (in the absorption effluent the instant concentration of dimethyl phthalate be influent concentration 2%) time stop absorption, 40mL is contained the sodium hydroxide of weight percent concentration 1% and weight percent concentration 10% sodium chloride solution under 30 ± 5 ℃ temperature, carry out desorption with the flow following current of 3mL/h by resin bed.Desorption liquid can reuse, and when the concentration of sodium hydroxide is lower than 0.5%, mixed solution is neutralized with hydrochloric acid, and recrystallization reclaims sodium phthalate.Resin after desorption is complete is regenerated with the sodium hydroxide solution of 100ml weight percent concentration 1%.
Embodiment 4
3.4mL (approximately 1 gram) D201 resin packed in the glass adsorption column of jacketed, and (Ф 12 * 160mm).Dimethyl phthalate concentration is 350mg/L in the water inlet, and after the filtration, in 25 ± 5 ℃, by resin bed, treatment capacity is that 3564mL/ criticizes with the flow of 16mL/h with it.After resin absorption, dimethyl phthalate mean concns＜0.1mg/L in the water outlet.
When absorption reach leakage point (in the absorption effluent the instant concentration of dimethyl phthalate be influent concentration 2%) time stop absorption, the sodium hydroxide of 40mL weight percent concentration 1% and weight percent concentration 10% sodium chloride solution under 30 ± 5 ℃ temperature, are carried out desorption with the flow following current of 3mL/h by resin bed.Desorption liquid can reuse, and when the concentration of sodium hydroxide is lower than 0.5%, mixed solution is neutralized with hydrochloric acid, and recrystallization reclaims sodium phthalate.Resin after desorption is complete is regenerated with the sodium hydroxide solution of 70ml weight percent concentration 3%.
Embodiment 5
3.2ml (approximately 1 gram) D201 resin packed in the glass adsorption column of jacketed, and (Ф 12 * 160mm).Dimethyl phthalate concentration is 500mg/L in the water inlet, and after the filtration, in 25 ± 5 ℃, by resin bed, treatment capacity is that 1500mL/ criticizes with the flow of 12mL/h with it.After resin absorption, dimethyl phthalate mean concns＜1mg/L in the water outlet.
When absorption reach leakage point (in the absorption effluent the instant concentration of dimethyl phthalate be influent concentration 2%) time stop absorption, the sodium hydroxide of 40mL1% and 10% sodium chloride solution under 30 ± 5 ℃ temperature, are carried out desorption with the flow following current of 3mL/h by resin bed.Desorption liquid can reuse, and when the concentration of sodium hydroxide is lower than 0.5%, mixed solution is neutralized with hydrochloric acid, and recrystallization reclaims sodium phthalate.Resin after desorption is complete is regenerated with the sodium hydroxide solution of 50ml 4%.
Embodiment 6
3.2ml (approximately 1 gram) D201 resin packed in the glass adsorption column of jacketed, and (Ф 12 * 160mm).Dimethyl phthalate concentration is 10mg/L in the water inlet, and after the filtration, in 25 ± 5 ℃, by resin bed, treatment capacity is that 9600mL/ criticizes with the flow of 24mL/h with it.After resin absorption, dimethyl phthalate mean concns＜1mg/L in the water outlet.
When absorption reach leakage point (in the absorption effluent the instant concentration of dimethyl phthalate be influent concentration 2%) time stop absorption, the sodium hydroxide of 40mL1% and 10% sodium chloride solution under 30 ± 5 ℃ temperature, are carried out desorption with the flow following current of 3mL/h by resin bed.Desorption liquid can reuse, and when the concentration of sodium hydroxide is lower than 0.5%, mixed solution is neutralized with hydrochloric acid, and recrystallization reclaims sodium phthalate.Resin after desorption is complete is regenerated with the sodium hydroxide solution of 50ml 4%.
Embodiment 7
3.2ml (approximately 1 gram) D201 resin packed in the glass adsorption column of jacketed, and (Ф 12 * 160mm).Dimethyl phthalate concentration is 1mg/L in the water inlet, and after the filtration, in 25 ± 5 ℃, by resin bed, treatment capacity is that 8235mL/ criticizes with the flow of 65mL/h with it.After resin absorption, dimethyl phthalate mean concns＜0.1mg/L in the water outlet.
When absorption reach leakage point (in the absorption effluent the instant concentration of dimethyl phthalate be influent concentration 2%) time stop absorption, the sodium hydroxide of 40mL1% and 10% sodium chloride solution under 30 ± 5 ℃ temperature, are carried out desorption with the flow following current of 3mL/h by resin bed.Desorption liquid can reuse, and when the concentration of sodium hydroxide is lower than 0.5%, mixed solution is neutralized with hydrochloric acid, and recrystallization reclaims sodium phthalate.Resin after desorption is complete is regenerated with the sodium hydroxide solution of 50ml 4%.
Embodiment 8
4mL (approximately 1 gram) Amberlite IRA-400 resin packed in the glass adsorption column of jacketed, and (Ф 12 * 160mm).Dimethyl phthalate concentration is 20mg/L in the water inlet, and after the filtration, in 25 ± 5 ℃, by resin bed, treatment capacity is that 8200mL/ criticizes with the flow of 24mL/h with it.After resin absorption, dimethyl phthalate mean concns＜0.1mg/L in the water outlet.
When absorption reach leakage point (in the absorption effluent the instant concentration of dimethyl phthalate be influent concentration 2%) time stop absorption, the sodium hydroxide of 40mL1% and 10% sodium chloride solution under 30 ± 5 ℃ temperature, are carried out desorption with the flow following current of 3mL/h by resin bed.Desorption liquid can reuse, and when the concentration of sodium hydroxide is lower than 0.5%, mixed solution is neutralized with hydrochloric acid, and recrystallization reclaims sodium phthalate.Resin after desorption is complete is regenerated with the sodium hydroxide solution of 50ml 4%.
Embodiment 9
4mL (approximately 1 gram) Amberlite IRA-400 resin packed in the glass adsorption column of jacketed, and (Ф 12 * 160mm).Dimethyl phthalate concentration is 300mg/L in the water inlet, and after the filtration, in 25 ± 5 ℃, by resin bed, treatment capacity is that 4236mL/ criticizes with the flow of 15mL/h with it.After resin absorption, dimethyl phthalate mean concns＜0.1mg/L in the water outlet.
When absorption reach leakage point (in the absorption effluent the instant concentration of dimethyl phthalate be influent concentration 2%) time stop absorption, the sodium hydroxide of 40mL1% and 10% sodium chloride solution under 30 ± 5 ℃ temperature, are carried out desorption with the flow following current of 3mL/h by resin bed.Desorption liquid can reuse, and when the concentration of sodium hydroxide is lower than 0.5%, mixed solution is neutralized with hydrochloric acid, and recrystallization reclaims sodium phthalate.Resin after desorption is complete is regenerated with the sodium hydroxide solution of 50ml 4%.
Embodiment 10
5mL (approximately 1 gram) Amberlite IRA-900 resin packed in the glass adsorption column of jacketed, and (Ф 12 * 160mm).Dimethyl phthalate concentration is 20mg/L in the water inlet, and after the filtration, in 25 ± 5 ℃, by resin bed, treatment capacity is that 7350mL/ criticizes with the flow of 24mL/h with it.After resin absorption, dimethyl phthalate mean concns＜0.1mg/L in the water outlet.
When absorption reach leakage point (in the absorption effluent the instant concentration of dimethyl phthalate be influent concentration 2%) time stop absorption, the sodium hydroxide of 40mL1% and 10% sodium chloride solution under 30 ± 5 ℃ temperature, are carried out desorption with the flow following current of 3mL/h by resin bed.Desorption liquid can reuse, and when the concentration of sodium hydroxide is lower than 0.5%, mixed solution is neutralized with hydrochloric acid, and recrystallization reclaims sodium phthalate.Resin after desorption is complete is regenerated with the sodium hydroxide solution of 100ml 1%.
Embodiment 11
5mL (approximately 1 gram) Amberlite IRA-900 resin packed in the glass adsorption column of jacketed, and (Ф 12 * 160mm).Dimethyl phthalate concentration is 200mg/L in the water inlet, and after the filtration, in 25 ± 5 ℃, by resin bed, treatment capacity is that 5824mL/ criticizes with the flow of 18mL/h with it.After resin absorption, dimethyl phthalate mean concns＜0.1mg/L in the water outlet.
When absorption reach leakage point (in the absorption effluent the instant concentration of dimethyl phthalate be influent concentration 2%) time stop absorption, the sodium hydroxide of 40mL1% and 10% sodium chloride solution under 30 ± 5 ℃ temperature, are carried out desorption with the flow following current of 3mL/h by resin bed.Desorption liquid can reuse, and when the concentration of sodium hydroxide is lower than 0.5%, mixed solution is neutralized with hydrochloric acid, and recrystallization reclaims sodium phthalate.Resin after desorption is complete is regenerated with the sodium hydroxide solution of 50ml 4%.
Embodiment 12
3.4mL (approximately 1 gram) D201GF resin packed in the glass adsorption column of jacketed, and (Ф 12 * 160mm).Dimethyl phthalate concentration is 20mg/L in the water inlet, and after the filtration, in 25 ± 5 ℃, by resin bed, treatment capacity is that 8352mL/ criticizes with the flow of 24mL/h with it.After resin absorption, dimethyl phthalate mean concns＜0.1mg/L in the water outlet.
When absorption reach leakage point (in the absorption effluent the instant concentration of dimethyl phthalate be influent concentration 2%) time stop absorption, the sodium hydroxide of 40mL1% and 10% sodium chloride solution under 30 ± 5 ℃ temperature, are carried out desorption with the flow following current of 3mL/h by resin bed.Desorption liquid can reuse, and when the concentration of sodium hydroxide is lower than 0.5%, mixed solution is neutralized with hydrochloric acid, and recrystallization reclaims sodium phthalate.Resin after desorption is complete is regenerated with the sodium hydroxide solution of 80ml 2%.
Embodiment 13
3.4mL (approximately 1 gram) D201GF resin packed in the glass adsorption column of jacketed, and (Ф 12 * 160mm).Dimethyl phthalate concentration is 100mg/L in the water inlet, and after the filtration, in 25 ± 5 ℃, by resin bed, treatment capacity is that 7253mL/ criticizes with the flow of 20mL/h with it.After resin absorption, dimethyl phthalate mean concns＜0.1mg/L in the water outlet.
When absorption reach leakage point (in the absorption effluent the instant concentration of dimethyl phthalate be influent concentration 2%) time stop absorption, the sodium hydroxide of 40mL1% and 10% sodium chloride solution under 30 ± 5 ℃ temperature, are carried out desorption with the flow following current of 3mL/h by resin bed.Desorption liquid can reuse, and when the concentration of sodium hydroxide is lower than 0.5%, mixed solution is neutralized with hydrochloric acid, and recrystallization reclaims sodium phthalate.Resin after desorption is complete is regenerated with the sodium hydroxide solution of 50ml 4%.
Embodiment 14
Selecting three specifications are identical, material is 316L stainless steel adsorption tower, (Ф 550 * 3500mm), and numbering is respectively I, II and III, every tower filling strongly basic anion exchange resin D201150 kilogram.Dimethyl phthalate concentration is 500mg/L in the former water, after the filtration, with it in 25 ± 5 ℃, with 6m
3The flow of/h is squeezed into adsorption tower with pump, and the mode of I, II tower double-column in series following current absorption is adopted in absorption, and treatment capacity is 300m
3/ batch.After resin absorption, absorption effluent dimethyl phthalate mean concns＜1mg/L.
When absorption reach leakage point (in the water outlet the instant concentration of dimethyl phthalate be influent concentration 2%) time stops to process, and will process 300m
3The first post I tower of former water breaks away from absorption system and carries out desorption manipulation; And next batch processing operation changes II, the series operation of III tower into, post headed by the II tower becomes.
First raffinate in the I tower is drained, again with 2m
32% sodium hydroxide and 10% sodium-chlor are under 30 ± 5 ℃ temperature, with 1.2m
3The flow following current of/h is carried out desorption by resin bed.The mixed solution that desorption gets off can reuse, and when the concentration of sodium hydroxide is lower than 1%, mixed solution is neutralized with hydrochloric acid, and recrystallization reclaims sodium phthalate.Resin 5m after desorption is complete
34% sodium hydroxide solution is regenerated.
I tower after desorption finishes will be as the stern post of the 3rd batch of adsorption operations.Can guarantee that by the present invention whole treatment unit moves continuously.
Embodiment 15
After changing the dimethyl phthalate among the embodiment 1-13 into diethyl phthalate or other phthalate, or change resin into FPA40, FPA90, FPA98, IRA958, HP555, Dowex-1, Diaion SA-10A, LmacA-504, DuoliteA-101D, other operational conditions remain unchanged, except every batch processing volume and absorption effluent water quality were different, other effects substantially roughly the same.
Claims (4)
1. method of utilizing solid base catalyst to remove phthalate in the water body may further comprise the steps:
A) will contain the waste water filtering of phthalate pollutent, remove suspended substance wherein;
B) with steps A) in the phthalate concentration that obtains be 1-500mg/L filtrate at room temperature with the flow velocity of 4～20BV/h by being filled with the adsorption tower of the anionite-exchange resin that contains the highly basic group;
C) when the instant concentration of phthalate in the absorption effluent be influent concentration 2% the time stop absorption, mixed solution with sodium hydroxide and sodium-chlor carries out desorption, wherein the sodium hydroxide weight percent concentration is 1%-8%, the weight sodium chloride percentage concentration is 1%-20%, and the resin weight percent concentration after desorption is complete is the sodium hydroxide solution regeneration of 1%-4%;
D) the desorption liquid recirculation that step C) obtains is used, and when the weight percent concentration of sodium hydroxide is reduced to 0.5% when following, with hydrochloric acid desorption liquid is neutralized, and reclaims phthalic acid behind the recrystallization.
2. a kind of method of utilizing solid base catalyst to remove phthalate in the water body according to claim 1, it is characterized in that step B) described in contain the highly basic group anionite-exchange resin refer to that specific surface area is 20-500m take vinylbenzene-divinylbenzene or vinylformic acid as skeleton structure
2/ g, the exchange capacity that contains the quaternary amines of Trimethylamine 99, triethylamine, Tributylamine, pyrimidyl, pyridyl, pyranyl, dimethyl propanol amine, methyldiethanolamine or dioctyl thanomin is the resin of 0.5-4.5mmol/g.
3. each described a kind of method of utilizing solid base catalyst to remove phthalate in the water body is characterized in that step C according to claim 1～2) in, desorption liquid carries out desorption and regeneration at 20～40 ℃ with 1～8BV/h flow velocity.
4. each described a kind of method of utilizing solid base catalyst to remove phthalate in the water body is characterized in that step B according to claim 1～2) described in adsorption tower adopt the operation scheme of double-column in series absorption, single tower desorption; I, II, three adsorption towers of III are set, and with I, II tower series connection following current absorption, the I tower is as first post first, the II tower after the absorption of I tower is saturated, switches to II, III tower series connection following current absorption as stern post, the II tower is as first post, and the III tower is as stern post, and the I tower carries out desorption and regeneration with desorbing agent simultaneously.
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| CN102718280B (en) * | 2012-06-18 | 2013-08-28 | 南京信息工程大学 | Method for eliminating phthalic monoester-type environmental hormone in water body |
| CN102874899B (en) * | 2012-10-23 | 2014-04-02 | 南京信息工程大学 | Method for removing phthalic acid monoester pollutants in water body through ion exchange resin |
| CN106219842B (en) * | 2016-08-19 | 2019-02-19 | 环境保护部华南环境科学研究所 | A method of phthalate pollutant in removal water source gathering ground water body |
| CN108728074A (en) * | 2018-06-29 | 2018-11-02 | 成都菲尔特技术开发有限公司 | A kind of liquid and supercritical carbon dioxide thickening switch surfactant and its compound system |
| CN110530835B (en) * | 2019-09-27 | 2022-03-04 | 山西省农业科学院农产品加工研究所 | Fluorescence method detection method for phthalate plasticizer in oil substances |
| CA3206297A1 (en) * | 2020-12-31 | 2022-07-07 | Veolia Environnement | Method for treating organic compounds from industrial wastewaters with resins |
| CN116042198A (en) * | 2023-01-30 | 2023-05-02 | 西南石油大学 | Temperature response type bio-based temporary plugging agent and preparation method thereof |
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Non-Patent Citations (1)
| Title |
|---|
| 许正文等.阴离子交换树脂对水体中邻苯二甲酸二甲酯的催化水解作用.《第六届博士生学术年会论文集》.2009,第695-699页. * |
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