CN100455350C - Method for leading in surface functional to intensify adsorbing resin regeneration characteristics - Google Patents
Method for leading in surface functional to intensify adsorbing resin regeneration characteristics Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 107
- 239000011347 resin Substances 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000008929 regeneration Effects 0.000 title claims abstract description 27
- 238000011069 regeneration method Methods 0.000 title claims abstract description 27
- 238000001179 sorption measurement Methods 0.000 claims abstract description 62
- 238000003795 desorption Methods 0.000 claims abstract description 52
- 125000000524 functional group Chemical group 0.000 claims abstract description 26
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims description 64
- 238000010521 absorption reaction Methods 0.000 claims description 50
- 239000003463 adsorbent Substances 0.000 claims description 42
- 238000004519 manufacturing process Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 9
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000005416 organic matter Substances 0.000 claims description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 7
- 229960004889 salicylic acid Drugs 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 4
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 claims description 4
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 claims description 4
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 claims description 4
- RXCMFQDTWCCLBL-UHFFFAOYSA-N 4-amino-3-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(N)=C(O)C=C(S(O)(=O)=O)C2=C1 RXCMFQDTWCCLBL-UHFFFAOYSA-N 0.000 claims description 4
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004334 sorbic acid Substances 0.000 claims description 3
- 229940075582 sorbic acid Drugs 0.000 claims description 3
- 235000010199 sorbic acid Nutrition 0.000 claims description 3
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 125000000853 cresyl group Chemical class C1(=CC=C(C=C1)C)* 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 2
- 150000007524 organic acids Chemical class 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical class NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 18
- 238000012545 processing Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 230000007613 environmental effect Effects 0.000 description 10
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 9
- 229940067157 phenylhydrazine Drugs 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 125000003368 amide group Chemical group 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
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- 238000002156 mixing Methods 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
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- -1 pyridine radicals Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical class NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000004992 toluidines Chemical class 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- GWIAAIUASRVOIA-UHFFFAOYSA-N 2-aminonaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(N)=CC=C21 GWIAAIUASRVOIA-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- OQNJZSIPDMTUAJ-JGVFFNPUSA-N 7-(carboxyamino)-8-amino-nonanoic acid Chemical compound OC(=O)N[C@@H]([C@@H](N)C)CCCCCC(O)=O OQNJZSIPDMTUAJ-JGVFFNPUSA-N 0.000 description 1
- TWFZGCMQGLPBSX-UHFFFAOYSA-N Carbendazim Natural products C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 description 1
- 239000006013 carbendazim Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229940060037 fluorine Drugs 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AGBQKNBQESQNJD-UHFFFAOYSA-M lipoate Chemical compound [O-]C(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-M 0.000 description 1
- 235000019136 lipoic acid Nutrition 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
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- 229960001156 mitoxantrone Drugs 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
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- 150000003141 primary amines Chemical group 0.000 description 1
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- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a method of importing surface functional groups enhanced adsorption resin regeneration performance, its steps include: (A) adjusting industrial wastewater of containing organic acidic or industrial wastewater of containing alkali organic pH value to pKa of 25deg.C the organic acid or alkaline the organics, after filtration, remove the suspended solids; (B) the gained filtrate through a acidic complex function or alkaline function adsorb resin adsorption tower; (C) When the adsorption reached to leakage point stop adsorption. This invention does not affect adsorption performance, but enhance adsorption resin regeneration performance, thereby reducing the use dose of desorption and desorption temperature, saving operating costs, it will has great significance of applying and promoting resin adsorption technology.
Description
Technical field
The present invention relates to a kind ofly introduce functional group at the polymeric adsorbent surfaces externally and internally and obtain acid function resin or alkaline functional resin, thereby strengthen the method for polymeric adsorbent regenerability.
Background technology
Polymeric adsorbent replaces the adsorbing separation that activated carbon and extractant are used for the water organic poison gradually owing to have characteristics such as high-specific surface area, good pore structure, easy operation.Since the seventies in 20th century, the various countries scientist uses polymeric adsorbent, the industrial wastewater that contains toxic organic compound has been carried out purifying research.China Nanjing University, units such as Nankai University have also successfully developed the resin adsorption method processing in succession and have contained phenol, cresols, halogenated phenols, paranitrophenol, p-aminophenol, aniline, o-phenylenediamine, adjacent (to) toluidines, phenylacetic acid, phenmethylol, Benzene Chloride, paranitrochlorobenzene, phenylhydrazine, lipoic acid, salicylic acid, sorbic acid, fluorine (chlorine) is for toluene, 2,3-acid, DSD acid, beta naphthal, tobias acid, 1,2,4-acid, 1, the 4-dihydroxy anthraquinone, carbendazim, the a series of improvement and the resource patented technology of plant growth regulator poisonous organic industrial sewages such as " 7841 ".Wherein the partial monopoly technology has been successfully applied to phenol, paranitrophenol, 2,3-acid, beta naphthal, Benzene Chloride, DSD acid, 4B acid, phenylacetic acid, fumaric acid, 1,2,4-acid, phenylhydrazine, o-phenylenediamine, adjacent (to) toluidines, in tens of actual production wastewater treatment engineerings such as p-aminophenol and DMIP-5-sodium sulfonate, produced significant environmental benefit, social benefit and economic benefit are the sustainable development and the Changjiang river of numerous enterprises, Huaihe River, the water environment organic poison in basin such as Taihu Lake and Haihe River pollutes control and has made outstanding contributions with ecological safety.
The technological development of the organic industrial sewage of resin adsorption method purification at present technology mainly concentrates on the absorption property of strengthening polymeric adsorbent, and the most just simple employing of desorption and regeneration resin heats up and the conversion organic pollution is method (the acid organic pollution that promptly adopts the diluted alkaline desorption and regeneration to be adsorbed of ionic state, the alkaline organic pollution that adopts the diluted acid desorption and regeneration to be adsorbed), the desorption and regeneration operation often accounts for the over half of whole technology operating cost.
The result of literature search shows: before the present invention finishes, do not find to introduce the method report that functional group is used to strengthen the polymeric adsorbent regenerability at the polymeric adsorbent surfaces externally and internally.
Summary of the invention
1. invent the technical problem that will solve
The invention provides a kind of at polymeric adsorbent surfaces externally and internally introducing functional group, thereby strengthen the method for polymeric adsorbent regenerability, the regenerability of polymeric adsorbent can be strengthened, desorbing agent use amount, reduction desorbing agent concentration and desorption temperature, saving operating cost can be effectively reduced.
2. technical scheme
This method mainly is to utilize the hydrophily of acidity (alkalescence) the functional group enhancing polymeric adsorbent of polymeric adsorbent surfaces externally and internally introducing; Simultaneously, the acidity in this functional group and the industrial wastewater (alkalescence) organic pollution all is molecular state at absorption process, does not have the Coulomb repulsion effect each other, does not influence the absorption property of polymeric adsorbent; And the acidity in this functional group and the industrial wastewater (alkalescence) organic pollution all is ionic state in the desorption operation, has the Coulomb repulsion effect each other, thereby strengthens the regenerability of polymeric adsorbent.
Technical scheme of the present invention is as follows:
A kind ofly introduce the method that surface functional group is strengthened the polymeric adsorbent regenerability, its step comprises:
(A) industrial wastewater that will contain acid organic industrial wastewater or contain alkaline organic when adjust pH is to 25 ℃ of this acidity organic matters respectively pKa or the pKb during 25 ℃ of alkaline organics after filter, remove suspension wherein;
(B) with the filtrate that obtains by being filled with the adsorption tower of acid complex function adsorption resin or alkaline complex function adsorption resin;
(C) when absorption reaches leakage point, stop absorption, with sodium hydrate aqueous solution as the acid complex function adsorption resin of desorbing agent desorption or with watery hydrochloric acid, dilute sulfuric acid as the alkaline complex function adsorption resin of desorbing agent desorption.
Leakage point is meant that the instant concentration of acid organic matter in the absorption effluent or alkaline organic is 2% of influent concentration, as desorbing agent, carries out desorption and regeneration with sodium hydrate aqueous solution, can obtain acid organic aqueous slkali; Obtain the acid solution of alkaline organic as desorbing agent with watery hydrochloric acid, dilute sulfuric acid.
Step (B) can be so that acid organic matter in the waste water or alkaline organic optionally be adsorbed on the resin.
Acid functional group makes acid complex function adsorption resin or introducing alkaline functional group makes alkaline complex function adsorption resin by introducing at the polymeric adsorbent surfaces externally and internally in the step (B).Polymeric adsorbent is NDA-100, NDA-16, NDA-1800, NDA-7, NDA-8, CHA-101 (productions such as Jiangsu Nanda Gede Environmental Protection Technology Co., Ltd, Langfang, Hebei electric power resin processing plant) resin in described acid complex function adsorption resin or the alkaline complex function, also can be Amberlite XAD-4, XAD-16, XAD-1600 or XAD-7 resin that U.S. Rohm Haas company produces; Acid complex function adsorption resin is NDA-150, JX-101, NDA-110 resin (productions such as Jiangsu Nanda Gede Environmental Protection Technology Co., Ltd, Langfang, Hebei electric power resin processing plant); The alkalescence complex function adsorption resin is NDA-99, NDA-88, NDA-900, NDA-55 resin (productions such as Jiangsu Nanda Gede Environmental Protection Technology Co., Ltd, Langfang, Hebei electric power resin processing plant).Above-mentioned acid functional group is sulfonic group, hydroxyl or carboxyl, and the alkaline functional group is tertiary amine groups, primary amine groups, secondary amine, pyridine radicals or pyrimidine radicals.The content of acid functional group is that the content of 0.5～3.0mmol/g dried resin or alkaline functional group is 0.5～3.0mmol/g dried resin.
Above-mentioned acid organic matter is phenol, cresols, 2,4-two chlorophenols, paranitrophenol, p-aminophenol, phenylacetic acid, salicylic acid, sorbic acid, 2,3-acid, DSD acid, beta naphthal, alpha naphthol, 1,2,4-acid, 4B acid or H acid, its concentration in industrial wastewater is 0.5～50mmol/L; Alkaline organic be aniline, o-phenylenediamine, neighbour (to) toluidines, phenylhydrazine or alpha naphthylamine, its concentration in industrial wastewater is 0.5～50mmol/L.
The mass percent of sodium hydrate aqueous solution is 0.5～5% in the step (C), and the mass percent of watery hydrochloric acid or dilute sulfuric acid is 0.5～4%, carries out desorption and regeneration at 20～60 ℃ with 0.5～5BV/h flow velocity.The quality of desorption and regeneration can be guaranteed so on the one hand, cost can be saved on the other hand.The acid organic aqueous slkali that desorption gets off in the step (C) directly returns its production process, or carries out acid out with acid and filter this acidity organic matter that obtains resource, and filtrate is returned step (B) and crossed post absorption; The acid solution of the alkaline organic that desorption gets off directly returns its production process, or carries out alkali with alkali and analyse this alkaline organic that filtration obtains resource, and filtrate is returned step (B) and crossed post absorption.
3. beneficial effect
The invention discloses a kind of method of introducing surface functional to intensify adsorbing resin regeneration characteristics, compared with prior art, beneficial effect of the present invention is: 1, the same to the absorption property of above-mentioned acid organic matter or alkaline organic and existing polymeric adsorbent of acid complex function adsorption resin or alkaline complex function adsorption resin; 2, under the condition of same assurance resin desorption and regeneration quality, the concentration reduction by 15% of desorbing agent NaOH or watery hydrochloric acid, dilute sulfuric acid aqueous solution, consumption reduce by 10%, and desorption temperature descends 15%; 3, acid or alkaline complex function adsorption resin has good stability, and is reusable.The present invention does not influence absorption property, and reinforcement polymeric adsorbent regenerability, thereby reduce desorbing agent use amount, reduction desorption temperature, saving operating cost, significant for resin adsorption The Application of Technology and popularization.
The specific embodiment
By the following examples the present invention is further described:
Embodiment 1
Get the 30g degree of cross linking and be 8% chlorine ball (production such as Langfang, Hebei electric power resin processing plant), the dichloroethanes swelling 12h in the 250ml there-necked flask that adds 20ml, the control solution temperature is 278K, under certain mixing speed, constantly drip perchloric acid 30ml sustained response 12h, take out and filter, extracting, oven dry, products therefrom is the acid complex function adsorption resin of JX-101, and this resin hydroxyl and carboxyl-content be 0.6mmol/g altogether.
Get the acid complex function adsorption resin of 10mL (about 3g) JX-101 (productions such as Jiangsu Nanda Gede Environmental Protection Technology Co., Ltd, Langfang, Hebei electric power resin processing plant) and pack in the glass adsorption column of strap clamp cover that (Φ 16 * 180mm) into.Gaultherolin factory effluent COD after stripping is removed methyl alcohol is about 16000mg/L, mainly contain salicylic acid and residual ethanol, transfer wastewater pH to salicylic acid pKa (25 ℃) back to filter, with filtrate in 25 ± 5 ℃, flow with 20mL/h passes through resin bed, and treating capacity is that 100mL/ criticizes.After resin adsorption, the about 6800mg/L of absorption effluent COD mean concentration.Waste water is highly acid in the absorption process system, and salicylic acid and polymeric adsorbent surface hydroxyl all are molecular state in the waste water, not only do not have the Coulomb repulsion effect each other, have the hydrogen bond action of attraction on the contrary, help adsorbing separation.
When reaching leakage point (the about 6800mg/L of absorption effluent COD mean concentration), absorption stops absorption, the 15mL mass percent is that 5% sodium hydrate aqueous solution+15mL water is under 50 ± 5 ℃ temperature, resin bed is passed through in flow following current with 10mL/h, and JX-101 resin desorption and regeneration is complete.Be strong basicity at the desorption working procedure systems, salicylic acid and polymeric adsorbent surface hydroxyl all are electronegative ionic state in the desorption liquid, have the Coulomb repulsion effect each other, help the desorption and regeneration of resin.
Embodiment 2
Get the 30g degree of cross linking and be 6% chlorine ball (production such as Langfang, Hebei electric power resin processing plant), the dichloroethanes swelling 12h in the 250ml there-necked flask that adds 20ml, the control solution temperature is 303K, under certain mixing speed, constantly drip phenol 15ml sustained response 12h, take out and filter, extracting, oven dry, products therefrom is the acid complex function adsorption resin of NDA-110, and this resin hydroxy radical content is 1.4mmol/g.
Get the acid complex function adsorption resin of 10mL (about 3g) NDA-110 (productions such as Jiangsu Nanda Gede Environmental Protection Technology Co., Ltd, Langfang, Hebei electric power resin processing plant) and pack in the glass adsorption column of strap clamp cover that (Φ 16 * 180mm) into.In the industrial wastewater 2,4-two chlorophenol concentration are 300mg/L, transfer pH to 2, and 4-two chlorophenol pKa (25 ℃) filter the back, and in 25 ± 5 ℃, by resin bed, treating capacity is that 410mL/ criticizes with the flow of 50mL/h with filtrate.After resin adsorption, absorption effluent 2,4-two chlorophenol mean concentration＜0.5mg/L.Be acid at absorption process system waste water, in the waste water 2,4-two chlorophenols and polymeric adsorbent surface hydroxyl all are molecular state, not only do not have the Coulomb repulsion effect each other, have the hydrogen bond action of attraction on the contrary, help adsorbing separation.
When absorption reaches leakage point (in the absorption effluent 2, the about 0.5mg/L of 4-two chlorophenol mean concentrations) stops absorption the time, the 15mL mass percent be 2% sodium hydrate aqueous solution under 55 ± 5 ℃ temperature,, that NDA-110 resin desorption and regeneration is complete with the flow following current of 5mL/h by resin bed.Be strong basicity at the desorption working procedure systems, in the desorption liquid 2,4-two chlorophenols and polymeric adsorbent surface hydroxyl all are electronegative ionic state, have the Coulomb repulsion effect each other, help the desorption and regeneration of resin.
Embodiment 3
Get the 30g degree of cross linking and be 10% chlorine ball productions such as () Langfang, Hebei electric power resin processing plants, add nitrobenzene swelling 12h in the 250ml there-necked flask of 20ml, control solution temperature is 303K, continuous dropping 10%H under certain mixing speed
2O
225ml sustained response 8h takes out and filters, extracting, and oven dry, products therefrom is the acid complex function adsorption resin of NDA-150, and this resin carboxyl-content is 0.9mmol/g.
Get the acid complex function adsorption resin of 10mL (about 3g) NDA-150 (productions such as Jiangsu Nanda Gede Environmental Protection Technology Co., Ltd, Langfang, Hebei electric power resin processing plant) and pack in the glass adsorption column of strap clamp cover that (Φ 16 * 180mm) into.Azoic coupling component As factory effluent TOC (total organic carbon) is about 16000mg/L, mainly contains 2,3-acid, transfer pH to 2,3-acid pKa (25 ℃) filters the back, and TOC reduces to about 3600mg/L, in 25 ± 5 ℃, by resin bed, treating capacity is that 90mL/ criticizes with the flow of 10mL/h with filtrate.After resin adsorption, the about 18mg/L of absorption effluent TOC mean concentration.Be acid in the absorption process system, in the waste water 2,3-acid all is molecular state with polymeric adsorbent surface carboxyl, does not only have the Coulomb repulsion effect each other, has the hydrogen bond action of attraction on the contrary, helps adsorbing separation.
When reaching leakage point (the about 18mg/L of absorption effluent TOC mean concentration), absorption stops absorption, the 15mL mass percent is that 5% sodium hydrate aqueous solution+10mL water is under 60 ± 5 ℃ temperature, resin bed is passed through in flow following current with 8mL/h, and NDA-150 resin desorption and regeneration is complete.Be strong basicity at the desorption working procedure systems, in the desorption liquid 2,3-acid all is electronegative ionic state with polymeric adsorbent surface carboxyl, has the Coulomb repulsion effect each other, helps the desorption and regeneration of resin.
Embodiment 4
Get the 30g degree of cross linking and be 6% chlorine ball (production such as Langfang, Hebei electric power resin processing plant), the dichloroethanes swelling 12h in the 250ml there-necked flask that adds 20ml, the control solution temperature is 313K, under certain mixing speed, constantly drip dihexylamine 30ml sustained response 16h, take out and filter, extracting, oven dry, products therefrom is NDA-88 alkalescence complex function adsorption resin, and this resin amido content is 1.5mmol/g.
Get 10mL (about 3g) NDA-88 alkalescence complex function adsorption resin (productions such as Jiangsu Nanda Gede Environmental Protection Technology Co., Ltd, Langfang, Hebei electric power resin processing plant) and pack in the glass adsorption column of strap clamp cover that (Φ 16 * 180mm) into.Ortho-aminotoluene concentration is about 17000mg/L in the ortho-aminotoluene factory effluent, transfers pH to filter to ortho-aminotoluene pKb (25 ℃) back, and in 25 ± 5 ℃, by resin bed, treating capacity is that 100mL/ criticizes with the flow of 20mL/h with filtrate.After resin adsorption, absorption effluent ortho-aminotoluene mean concentration is about 90mg/L.Be alkalescence in the absorption process system, ortho-aminotoluene and polymeric adsorbent surface amido all is a molecular state in the waste water, does not have the Coulomb repulsion effect each other, does not influence adsorbing separation.
When reaching leakage point, absorption stops absorption when (absorption effluent ortho-aminotoluene mean concentration is about 90mg/L), the 20mL mass percent is that 4% watery hydrochloric acid is under 45 ± 5 ℃ temperature, resin bed is passed through in flow following current with 8mL/h, and NDA-88 resin desorption and regeneration is complete.Be highly acid at the desorption working procedure systems, ortho-aminotoluene and polymeric adsorbent surface amido all is positively charged ionic state in the desorption liquid, has the Coulomb repulsion effect each other, helps the desorption and regeneration of resin.
Embodiment 5
Get the 30g degree of cross linking and be 8% chlorine ball (production such as Langfang, Hebei electric power resin processing plant), the nitrobenzene swelling 12h in the 250ml there-necked flask that adds 20ml, the control solution temperature is 308K, under certain mixing speed, constantly drip pyrimidine 25ml sustained response 16h, take out and filter, extracting, oven dry, products therefrom is NDA-55 alkalescence complex function adsorption resin, and this resin pyrimidine radicals content is 0.9mmol/g.
Get 10mL (about 3g) NDA-55 alkalescence complex function adsorption resin (productions such as Jiangsu Nanda Gede Environmental Protection Technology Co., Ltd, Langfang, Hebei electric power resin processing plant) and pack in the glass adsorption column of strap clamp cover that (Φ 16 * 180mm) into.Aniline stripping waste water aniline concentration is about 16000mg/L in the phenyl Schollkopf acid production process, transfers pH to filter to aniline pKb (25 ℃) back, and in 25 ± 5 ℃, by resin bed, treating capacity is that 70mL/ criticizes with the flow of 20mL/h with filtrate.After resin adsorption, absorption effluent aniline mean concentration is about 2mg/L.Be alkalescence in the absorption process system, aniline and polymeric adsorbent surface pyrimidine radicals all is a molecular state in the waste water, does not have the Coulomb repulsion effect each other, does not influence adsorbing separation.
When reaching leakage point, absorption stops absorption when (absorption effluent aniline mean concentration is about 2mg/L), the 18mL mass percent is that 5% watery hydrochloric acid is under 40 ± 5 ℃ temperature, resin bed is passed through in flow following current with 10mL/h, and NDA-55 resin desorption and regeneration is complete.Be highly acid at the desorption working procedure systems, aniline and polymeric adsorbent surface pyrimidine radicals all is positively charged ionic state in the desorption liquid, has the Coulomb repulsion effect each other, helps the desorption and regeneration of resin.
Embodiment 6
Get 300 kilograms of degrees of cross linking and be 8% chlorine ball (production such as Langfang, Hebei electric power resin processing plant), the nitrobenzene swelling 12h in the 1500L reactor that adds 200L, the control solution temperature is 298K, under certain mixing speed, constantly drip dimethylamine 250L sustained response 10h, take out and filter, extracting, oven dry, products therefrom is NDA-99 alkalescence complex function adsorption resin, and this resin amido content is 1.0mmol/g.
Select that three specifications are identical, material is that (Φ 550 * 3500mm) for 316L stainless steel adsorption tower for use, volume Shang number is respectively I, II and III, 200 kilograms of (about 0.6m of every tower filling NDA-99 alkalescence complex function adsorption resin (productions such as Jiangsu Nanda Gede Environmental Protection Technology Co., Ltd, Langfang, Hebei electric power resin processing plant)
3).Phenylhydrazine concentration is about 8000mg/L in the phenylhydrazine factory effluent, transfers pH to filter to phenylhydrazine pKb (25 ℃) back, with filtrate in 20 ± 5 ℃, with 1.2m
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 treating capacity is 9m
3/ batch.After resin adsorption, absorption effluent phenylhydrazine mean concentration is about 30mg/L.Be alkalescence in the absorption process system, phenylhydrazine and polymeric adsorbent surface amido all is a molecular state in the waste water, does not have the Coulomb repulsion effect each other, does not influence adsorbing separation.
Stop absorption when (absorption effluent para-totuidine mean concentration is about 30mg/L) when absorption reaches leakage point, will adsorb 9m
3The first post I adsorption tower of waste water breaks away from absorption system and carries out desorption manipulation; And the next batch adsorption operations changes II, the series operation of III tower into, post headed by the II tower becomes.
Earlier raffinate in the I adsorption tower is drained, again with 1.2m
3Mass percent is that 5% dilute sulfuric acid is under 50 ± 5 ℃ temperature, with 0.9m
3The flow following current of/h is carried out desorption by resin bed, and NDA-99 resin desorption and regeneration is complete.Be highly acid at the desorption working procedure systems, phenylhydrazine and polymeric adsorbent surface amido all is positively charged ionic state in the desorption liquid, has the Coulomb repulsion effect each other, helps the desorption and regeneration of resin.
I adsorption 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 waste water treatment device moves continuously.
Embodiment 7
Change the complex function adsorption resin among the embodiment 1～6 into NDA-100, NDA-16, NDA-1800, NDA-7, NDA-8, CHA-101 domestic resin, or resin such as U.S. Amberlite XAD-4, XAD-7, XAD-16, XAD-1600, keep the resin adsorption amount constant, then fully all in various degree increases of the concentration of the required desorbing agent of desorption and regeneration resin and volume, the also corresponding rising of desorption temperature, operating cost increases.
Claims (9)
1. introduce the method that surface functional group is strengthened the polymeric adsorbent regenerability for one kind, its step comprises:
(A) filter behind the pKa in the time of will containing acid organic industrial wastewater adjust pH to 25 ℃ of this acidity organic matters, remove suspension wherein;
(B) with the filtrate that obtains by being filled with the adsorption tower of acid complex function adsorption resin;
(C) when absorption reaches leakage point, stop absorption, use sodium hydrate aqueous solution as the acid complex function adsorption resin of desorbing agent desorption.
2. a kind of method that surface functional group is strengthened the polymeric adsorbent regenerability of introducing according to claim 1 is characterized in that in the step (B) by making acid complex function adsorption resin in polymeric adsorbent surfaces externally and internally introducing acid functional group or hydroxyl.
3. a kind of method that surface functional group is strengthened the polymeric adsorbent regenerability of introducing according to claim 2, it is characterized in that described acid complex function adsorption resin is NDA-100, NDA-16, NDA-1800, NDA-7, NDA-8 or CHA-101 resin, perhaps AmberliteXAD-4, XAD-16, XAD-1600 or the XAD-7 resin produced of U.S. Rohm Haas company, perhaps NDA-150, JX-101 or NDA-110 resin.
4. according to claim 2 or 3 described a kind of methods that surface functional group is strengthened the polymeric adsorbent regenerability of introducing, it is characterized in that acid functional group is sulfonic group or carboxyl.
5. according to claim 2 or 3 described a kind of methods that surface functional group is strengthened the polymeric adsorbent regenerability of introducing, the content that it is characterized in that acid functional group is 0.5～3.0mmol/g dried resin.
6. according to claim 1 or 2 or 3 described a kind of methods that surface functional group is strengthened the polymeric adsorbent regenerability of introducing, it is characterized in that above-mentioned acid organic matter is phenol, cresols, 2,4-two chlorophenols, paranitrophenol, p-aminophenol, phenylacetic acid, salicylic acid, sorbic acid, 2,3-acid, DSD acid, beta naphthal, alpha naphthol, 1,2,4-acid, 4B acid or H acid, its concentration in industrial wastewater is 0.5～50mmol/L.
7. according to claim 1 or 2 or 3 described a kind of methods that surface functional group is strengthened the polymeric adsorbent regenerability of introducing, the mass percent that it is characterized in that sodium hydrate aqueous solution in the step (C) is 0.5～5%, carries out desorption and regeneration at 20～60 ℃ with 0.5～5BV/h flow velocity.
8. according to claim 1 or 2 or 3 described a kind of methods that surface functional group is strengthened the polymeric adsorbent regenerability of introducing, it is characterized in that adsorption tower described in the step (B) adopts the method for operation 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 earlier, 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.
9. according to claim 1 or 2 or 3 described a kind of methods that surface functional group is strengthened the polymeric adsorbent regenerability of introducing, it is characterized in that the acid organic aqueous slkali that desorption gets off in the step (C) directly returns its production process, or carry out acid out with acid and filter this acidity organic matter that obtains resource, filtrate is returned step (B) and is crossed post absorption.
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| CN102643990B (en) * | 2012-05-18 | 2014-03-12 | 南京大学 | Method for removing trace Cu in high-purity Ni by chelate resin |
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| US9950320B2 (en) * | 2014-08-20 | 2018-04-24 | Lanxess Deutschland Gmbh | Sulfonated aminomethylated chelate resins |
| CN108191118A (en) * | 2018-01-31 | 2018-06-22 | 南京大学 | A kind of method for recycling fluorinion in waste water |
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