CN116750908A - Post-treatment method and application of pyridine reaction waste liquid - Google Patents
Post-treatment method and application of pyridine reaction waste liquid Download PDFInfo
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- CN116750908A CN116750908A CN202310716708.6A CN202310716708A CN116750908A CN 116750908 A CN116750908 A CN 116750908A CN 202310716708 A CN202310716708 A CN 202310716708A CN 116750908 A CN116750908 A CN 116750908A
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- Prior art keywords
- pyridine
- liquid
- waste liquid
- macroporous resin
- chloropyridine
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 239000007788 liquid Substances 0.000 title claims abstract description 129
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000011282 treatment Methods 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000002699 waste material Substances 0.000 title claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 71
- 229920005989 resin Polymers 0.000 claims abstract description 71
- FNRMMDCDHWCQTH-UHFFFAOYSA-N 2-chloropyridine;3-chloropyridine;4-chloropyridine Chemical compound ClC1=CC=NC=C1.ClC1=CC=CN=C1.ClC1=CC=CC=N1 FNRMMDCDHWCQTH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000003795 desorption Methods 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 26
- 239000000706 filtrate Substances 0.000 claims abstract description 24
- 230000007613 environmental effect Effects 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 131
- 150000003839 salts Chemical class 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000004064 recycling Methods 0.000 claims description 21
- 238000001179 sorption measurement Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000010025 steaming Methods 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 239000008234 soft water Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 17
- 235000019270 ammonium chloride Nutrition 0.000 description 10
- 125000001309 chloro group Chemical group Cl* 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- MAKFMOSBBNKPMS-UHFFFAOYSA-N 2,3-dichloropyridine Chemical compound ClC1=CC=CN=C1Cl MAKFMOSBBNKPMS-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- PVMNPAUTCMBOMO-UHFFFAOYSA-N 4-chloropyridine Chemical compound ClC1=CC=NC=C1 PVMNPAUTCMBOMO-UHFFFAOYSA-N 0.000 description 5
- 239000002156 adsorbate Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VMHZXXPDUOVTHD-UHFFFAOYSA-N 2,3,4-trichloropyridine Chemical compound ClC1=CC=NC(Cl)=C1Cl VMHZXXPDUOVTHD-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- -1 as mentioned above Chemical compound 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The application provides a post-treatment method and application of pyridine reaction waste liquid, and relates to the technical field of environmental organic pollutant treatment, wherein the waste liquid contains pyridine and chloropyridine and comprises the following components: adjusting the PH of the waste liquid to a preset value to obtain target treatment liquid; passing the target treatment liquid through an exchange column with built-in macroporous resin, so that the macroporous resin adsorbs pyridine and chloropyridine in the target treatment liquid, and filtrate is obtained; passing the macroporous resin adsorbed with pyridine and chloropyridine through a column again by adopting an organic solvent to obtain desorption liquid; and rectifying the desorption liquid to separate pyridine, chloropyridine and organic solvent, thereby solving the problems of large energy consumption and emission pollution caused by the existing waste liquid treatment method generated by chloropyridine synthesis reaction.
Description
Technical Field
The application relates to the technical field of environmental organic pollutant treatment, in particular to a pyridine reaction waste liquid post-treatment method and application.
Background
Pyridine, as an important chemical raw material, can be used for producing and synthesizing various compounds including pesticides, herbicides, medicines, disinfectants, dyes and the like, and is widely applied to industries of medicines, pesticides, chemical industry and the like. Pyridine has strong water solubility and is easy to transfer between soil and groundwater; stable structure, and has biotoxicity, teratogenicity and carcinogenicity. Therefore, the remediation of soil and water environments contaminated with pyridine-based heterocyclic compounds has become one of the important topics in the current environmental remediation field.
In order to separate the product from the final mixture during the synthesis of chloropyridine, it is common practice to add water and leave it to stand for delamination. This step causes many organic products and salts to enter the aqueous phase, which creates waste problems. The current practice is to combine acid evaporation reduction and off-site incineration to treat this effluent. Typically, 40% of the waste liquid is evaporated and enters the biochemical system for further treatment. The pyridine content in this portion of the waste liquid must be tightly controlled to less than 50ppm, which would otherwise impact the biochemical system. The concentrated solution left by acid distillation is sent to a liquid incinerator for incineration. This way of treating the waste liquid causes a great deal of energy consumption and discharge pollution.
Disclosure of Invention
In order to overcome the technical defects, the application aims to provide a post-treatment method and application of pyridine reaction waste liquid, and aims to solve the problems of large energy consumption and emission pollution caused by the existing waste liquid treatment method generated by chloropyridine synthesis reaction.
The application discloses a post-treatment method of pyridine reaction waste liquid, wherein the waste liquid contains pyridine and chloropyridine and comprises the following steps:
adjusting the PH of the waste liquid to a preset value to obtain target treatment liquid;
passing the target treatment liquid through an exchange column with built-in macroporous resin, so that the macroporous resin adsorbs pyridine and chloropyridine in the target treatment liquid, and filtrate is obtained;
passing the macroporous resin adsorbed with pyridine and chloropyridine through a column again by adopting an organic solvent to obtain desorption liquid;
and rectifying the desorption liquid to separate pyridine, chloropyridine and an organic solvent.
Preferably, the method further comprises: when the waste liquid is a salt-containing solution containing pyridine and chloropyridine;
the filtrate was separated by salt distillation and then dehydrated to obtain a purified salt containing no pyridine or chloropyridine.
Preferably, the organic solvent is a polar solvent, including methanol, ethanol, acetone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone.
Preferably, the adjusting the pH of the waste liquid to a preset value to obtain the target treatment liquid includes:
and adding acid liquor or alkali liquor to adjust the pH value of the waste liquid to 7-11, thereby obtaining the target treatment liquid.
Preferably, after passing the target treatment liquid through the exchange column with the macroporous resin built in, the method further comprises:
the macroporous resin is washed by adopting process water, and the liquid after passing through the column is collected to a preset buffer tank for recycling to the target treatment liquid; wherein the process water comprises deionized water, soft water and distilled water.
Preferably, the method further comprises:
and quantitatively passing the macroporous resin adsorbed with pyridine and chloropyridine through the column for multiple times by adopting the organic solvent, and carrying out cyclic desorption.
Preferably, the method further comprises:
and after passing through the column for adsorption in a preset period, cleaning the macroporous resin by adopting steam and/or acid-base washing or an organic solvent.
Preferably, before the salt distillation separation, the method further comprises:
presetting a pyridine limit value of filtrate entering a salt steaming reaction kettle; and when the filtrate exceeds the pyridine limit, discharging the filtrate to a preset buffer tank for recycling to the target treatment liquid.
Preferably, after each liquid pass through the column, an inert gas is injected into the exchange column to empty the macroporous resin of the liquid, wherein the liquid comprises the target treatment liquid, the organic solvent and the process water.
The application also provides application of the post-treatment method of the pyridine reaction waste liquid in the pyridine recovery and environmental protection field.
After the technical scheme is adopted, compared with the prior art, the method has the following beneficial effects:
according to the method for post-treatment of the pyridine reaction waste liquid and the application thereof, pyridine and chloropyridine (monochloropyridine and dichloropyridine) are contained after pyridine reaction and waste liquid are subjected to alkali adjustment and then are filtered to obtain target treatment liquid, macroporous resin is adopted to absorb pyridine and chloro matters in the target treatment liquid, organic solvent is adopted to desorb the pyridine and the chloro matters and the organic solvent, and then the adsorbed filtrate (if salt-containing solution) is subjected to distillation and salt distillation to obtain refined salt, so that separation of pyridine and refined salt in the waste liquid after reaction is realized, recycling is facilitated, the pyridine content in the treated waste liquid is greatly reduced, environmental pressure is reduced, and the problems of large energy consumption and emission pollution caused by the waste liquid treatment method generated by the existing chloropyridine synthesis reaction are solved.
Drawings
FIG. 1 is a flow chart of a method for post-treatment of pyridine reaction waste liquid and application thereof;
FIG. 2 is a schematic diagram of a post-treatment method and an applied process flow of pyridine reaction waste liquid.
Detailed Description
Advantages of the application are further illustrated in the following description, taken in conjunction with the accompanying drawings and detailed description.
Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, the same numbers in different drawings refer to the same or similar elements, unless otherwise indicated. The implementations described in the following exemplary examples are not representative of all implementations consistent with the present disclosure. Rather, they are merely examples of apparatus and methods consistent with some aspects of the present disclosure as detailed in the accompanying claims.
The terminology used in the present disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used in this disclosure and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any or all possible combinations of one or more of the associated listed items.
It should be understood that although the terms first, second, third, etc. may be used in this disclosure to describe various information, these information should not be limited to these terms. These terms are only used to distinguish one type of information from another. For example, first information may also be referred to as second information, and similarly, second information may also be referred to as first information, without departing from the scope of the present disclosure. The word "if" as used herein may be interpreted as "at … …" or "at … …" or "responsive to a determination", depending on the context.
In the description of the present application, it should be understood that the terms "longitudinal," "transverse," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like indicate orientations or positional relationships based on the orientation or positional relationships shown in the drawings, merely to facilitate describing the present application and simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present application.
In the description of the present application, unless otherwise specified and defined, it should be noted that the terms "mounted," "connected," and "coupled" are to be construed broadly, and may be, for example, mechanical or electrical, or may be in communication with each other between two elements, directly or indirectly through intermediaries, as would be understood by those skilled in the art, in view of the specific meaning of the terms described above.
In the following description, suffixes such as "module", "component", or "unit" for representing elements are used only for facilitating the description of the present application, and are not of specific significance per se. Thus, "module" and "component" may be used in combination.
Embodiment one: in the present embodiment, pyridine is used as reactant in the existing medicine synthesizing process to produce pyridine through chlorination reaction, and the waste liquid includes monochloro isomerism (2-CP, 3CP is typical), dichloro isomerism (2, 3-DCP,2,6-DCP is typical), trichloro isomerism (2, 3,6-TCPD is typical) and ammonium chloride coexistence. Because of the existence of high-concentration molecular pyridine, the waste liquid single treatment cost is high, and the post-treatment method provided by the application realizes the adsorption of pyridine and chloro compounds in reaction waste liquid by utilizing the adsorption function of macroporous resin, thereby realizing the separation and recovery of pyridine and chloro compounds, as mentioned above, pyridine reaction waste liquid contains pyridine and chloro compounds, specifically an ammonium chloride solution containing pyridine, monochloropyridine and dichloropyridine, the concentration range is 0-30000 ppm, and specifically, referring to fig. 1 and 2, the method comprises the following steps:
s10: adjusting the PH of the waste liquid to a preset value to obtain target treatment liquid;
in this embodiment, the waste liquid after the pyridine reaction is acidic, ph=5.5, and pyridine is present in an aqueous solution as pyridine hydrochloride under acidic conditions in the presence of chloride ions. In the ionic state, the macroporous resin cannot adsorb pyridine hydrochloride under the action of Van der Waals force. However, under alkaline conditions, pyridine and its chloride are in molecular form and can be adsorbed by using macroporous resins.
Adjusting the pH value of the waste liquid based on the above-mentioned alkali lye addition, wherein the waste liquid is alkaline due to the presence of other impurities after the pyridine reaction in addition to the above-mentioned examples, and therefore, the above-mentioned target treatment liquid comprises: and adding acid liquor or alkali liquor to adjust the pH value of the waste liquid to 7-11, thereby obtaining the target treatment liquid. The pH is adjusted by adding alkali liquor (such as NaOH) for specific example/acid liquor to improve the dynamic adsorption stability of the subsequent resin, after the alkali adjustment, pyridine and chloro compounds thereof can be quickly polymerized into macromolecular polymers such as bipyridine, and the macromolecular polymers have the property of tar and can cause the phenomenon of resin tail removal, and the service life of the macromolecular polymers can be influenced by macroporous resin. In order to reduce the influence of the macromolecular polymer on the service life of macroporous resin, the macromolecular polymer can be filtered after being fully flocculated and precipitated after standing, specifically, the layered water after alkali adjustment is subjected to solid-liquid separation through a filter, the solid trapped in the filter core is macromolecular polymer such as bipyridine, the solid slag is accumulated and then sent to an incineration working section, and the effluent liquid is target treatment liquid after alkali adjustment.
S20: passing the target treatment liquid through an exchange column with built-in macroporous resin, so that the macroporous resin adsorbs pyridine and chloropyridine in the target treatment liquid, and filtrate is obtained;
in the embodiment, macroporous resin, namely high molecular porous microspheres, is an organic high polymer adsorbent with better adsorption performance, has a three-dimensional space stereo pore structure inside, has larger pore diameter and specific surface area, and is insoluble in organic solvents such as acid, alkali, ethanol, acetone, hydrocarbons and the like. Macroporous resins are generally granular and mostly have no functional groups. The adsorption resin with different apertures and different performances can be prepared according to different adsorbed organic matters so as to adapt to different treatment purposes, so that the macroporous resin is utilized in the scheme to realize the adsorption of pyridine and chloro-compounds in waste liquid, and the salt-containing solution (ammonium chloride) is in an ionic state in a water system environment, and the molecular weight is smaller and cannot be adsorbed by the macroporous resin, so that the salt-containing solution is used as effluent to flow out of a pore canal, thereby realizing the separation of pyridine and chloro-compounds and ammonium salt in the waste liquid, realizing the recycling of the pyridine, and reducing the waste liquid treatment cost and environmental pressure.
As a supplementary explanation, this embodiment takes an example of producing an ammonium chloride solution containing pyridine and chloropyridine after the pyridine reaction, and the waste liquid post-treatment method provided in this embodiment may not include salt, i.e. may be other solution or water, and at this time, ionic substances in the solution cannot be adsorbed by the macroporous resin, but flows out of the macroporous resin in the form of filtrate after passing through the macroporous resin as described above.
In addition, the macroporous resin is pre-cleaned before being adsorbed in the embodiment. Specifically, deionized water is adopted to clean the macroporous resin column, so as to remove salt. Particularly in the example of the embodiment, the target treatment liquid is provided with a salt-containing solution, particularly ammonium chloride salt, and in the subsequent rectification process of the desorption liquid, the ammonium chloride is decomposed to enhance the acidity of the mother liquid, so that the equipment is corroded. Therefore, the macroporous resin needs to be cleaned with water before methanol desorption so as to reduce the equipment corrosion problem generated by subsequent rectification.
After passing the target treatment liquid through the macroporous resin-embedded exchange column in S20, the method further comprises: the macroporous resin is washed by adopting process water, and the liquid after passing through the column is collected to a preset buffer tank for recycling to the target treatment liquid; wherein the process water comprises deionized water, soft water and distilled water, and after the target treatment liquid passes through macroporous resin to adsorb pyridine and chloropyridine, the macroporous resin is subjected to column cleaning to remove the residual filtrate (possibly salt-containing solution as an example) in the resin. The liquid (water) produced after the cleaning can be collected into the target treatment liquid with the pH value adjusted in the next adsorption period for adsorption. The method is used for reducing the condition that impurities are generated in the processes of cleaning, cleaning and the like to influence the subsequent pyridine separation recovery rate by utilizing the process water.
S30: passing the macroporous resin adsorbed with pyridine and chloropyridine through a column again by adopting an organic solvent to obtain desorption liquid;
the organic solvent is a polar solvent, including but not limited to methanol, ethanol, acetone, dimethylformamide (DMF), dimethylacetamide (DMAC), dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), etc., and methanol is taken as an example in this embodiment.
In this embodiment, in the above step, pyridine and its chloro (i.e., chloropyridine) are adsorbed by the macroporous resin, water, ammonium chloride and a small amount of methanol as components of the column filtrate flow out from the pores of the macroporous resin into the evaporation salt precipitation section, and the macroporous resin is conventionally regenerated by using methanol as a desorbent, i.e., the methanol column is carried away with pyridine and its chloro, and then the macroporous resin can be used for cyclic adsorption in the above step. The existing method can also adopt steam for desorption, but the implementation conditions are complex, the desorption is incomplete, methanol is adopted for desorption in the example, the concentration of pyridine substances is high, and the desorption liquid amount is small.
S40: rectifying the desorption liquid to separate pyridine, chloropyridine and organic solvent;
in the step S20, when the resin reaches a saturated adsorption state, the macroporous resin adsorbs pyridine and its chloride in the target treatment fluid, methanol is adopted to pass through a column, pyridine and its chloride are enriched in the desorption fluid, the methanol desorption fluid is sent to a methanol rectifying still (for rectification), high-purity methanol is extracted from the top of the still, and the enriched pyridine and its chloride are at the bottom of the still. The target treatment liquid is recorded as an adsorption period from the beginning of methanol feeding into the resin column to the maximum penetrating adsorption amount, for example, 7BV (about 1120L), after the adsorption is completed, 4BV of methanol is used for column passing desorption, and the separated pyridine and methanol can be respectively subjected to pyridine reaction and reutilization of the post-treatment.
As described above, the step S10 to S40 can directly separate pyridine and chloropyridine from the waste liquid containing pyridine and chloropyridine generated after the pyridine reaction, and as described above, the waste liquid generated by pyridine may be a salt-containing solution or water, if it is water or water containing other impurities that can be separated by physical means, it may be directly terminated after the step S40, and if the waste liquid is a salt-containing solution containing pyridine and chloropyridine, such as an ammonium chloride solution as exemplified in the present embodiment, the following step S50 may be optionally performed to obtain a purified salt.
S50: the filtrate was separated by salt distillation and then dehydrated to obtain a purified salt containing no pyridine or chloropyridine.
In the step S20, as described above, pyridine and its chloride are adsorbed by macroporous resin, and filtrate formed by salt-containing solution (such as ammonium chloride) and water flows out of macroporous resin, and by-product ammonium chloride without organic phase is obtained at bottom of the kettle after evaporating salt from filtrate,
in the above steps, the next cycle is started after an adsorption-desorption cycle is performed, and then the macroporous resin applied in the next cycle may contain an organic solvent (i.e. methanol) used as a desorbent in the previous cycle, and the methanol may also carry pyridine in the target treatment fluid into the filtrate, so after entering the salt steaming reaction kettle, the method further comprises: presetting a pyridine limit value of filtrate entering a salt steaming reaction kettle; when the content of pyridine in the filtrate is too high, the specific kettle top extraction of a salt steaming kettle is set as the requirement that the pyridine limit value is the biochemical requirement and is less than or equal to 50ppm; the pyridine limit at the bottom of the salt steaming kettle is related to the quality of salt at the bottom of the kettle, the limit requirement of byproduct salt is less than or equal to 5ppm, and when the pyridine limit exceeds the threshold (namely the filtrate in fig. 2 does not reach the standard), the pyridine limit is recycled to the target treatment fluid, and the adsorption process of macroporous resin passing through the column can be executed in the next period.
Further optionally, after each liquid pass through the column, an inert gas is injected into the exchange column to empty the liquid in the macroporous resin, wherein the liquid comprises target treatment liquid, organic solvent and process water. After the target treatment liquid and the organic solvent (methanol) are passed through the column, or even each time the liquid including the process water passes through the column, inert gas is injected, specifically, for example, nitrogen is used for emptying the target treatment liquid or the organic solvent (methanol), so that the target treatment liquid or the organic solvent and the like are reduced to stay in the holes of the macroporous resin or between the macroporous resin and the exchange column after passing through the column, thereby influencing the next adsorption-desorption period and influencing the pyridine separation effect of the subsequent treatment.
Based on the above-described treatments of steps S10 to S50, in a preferred embodiment, the macroporous resin column to which pyridine and chloropyridine (e.g., monochloropyridine, dichloropyridine) are adsorbed is quantitatively passed through the column a plurality of times with methanol, and cyclic desorption is performed. Specifically, considering that the concentration difference of the adsorbate (pyridine and its chloride) exists in the methanol eluent in the eluting process, a quantitative methanol cyclic desorption mode can be adopted. As an example, four methanol reuse barrels A, B, C, D are provided, and the concentration of the adsorbate in the methanol eluent in methanol reuse barrels a-D is in a decreasing trend, with a large difference. The concentration of the adsorbate in the methanol recycling bin A is highest and almost reaches the state of adsorbate saturation, so that the desorption liquid in the methanol recycling bin A directly enters the state that the adsorbate in the desorption liquid in the methanol recycling bins B-D in the rectification section is not saturated, the methanol in the methanol recycling bin A sequentially passes through columns in the next desorption period, specifically, the methanol in the methanol recycling bin A is desorbed in the first period and enters the rectification in the step S40, the methanol recycling bin B, C, D is not saturated after being desorbed in the first period, and therefore the methanol recycling bin B, C, D enters the rectification section after being desorbed continuously in the subsequent second period, the third period and the like, specifically, after the total amount of 4BV in the methanol recycling bin is set to be 4BV, the 3BV passing through the columns is set, the methanol recycling bin can be provided with 1BV of high-purity methanol to complete the regeneration of the 4BV, and the cycle can be provided. It should be noted that the methanol replenishing barrels can replenish methanol after entering the rectification section in each methanol recycling barrel, so as to realize the uninterrupted desorption process of reuse of methanol.
In this embodiment, as described above, the macroporous resin is used to adsorb pyridine and its chloride, and then desorbed by methanol, so that the macroporous resin is regenerated for the next adsorption period, and to further increase the use period of the macroporous resin, such as the use of the resin over a period of time, the adsorption performance is significantly reduced, and considering that a part of impurities may be adsorbed in the resin pores, in a preferred embodiment, after the macroporous resin column is subjected to column passing adsorption for a preset period, the macroporous resin column is cleaned by steam and/or acid-base washing. When the cleaning is performed by using steam, a refrigerant cycle (through a condenser) is provided in the post-treatment process in advance to match with the steam regeneration of the macroporous resin (for example, when the volume of the condensate reaches 320L, the steam feeding is stopped, the condensate is rectified, etc.). When acid-base washing is adopted, 5% dilute acid solution and 4% sodium hydroxide solution can be used for carrying out column deep regeneration on the resin, and after the regeneration treatment is finished, the alkali liquor remained in the column is washed by water until the pH of an outlet is 7-9.
In order to reflect the separation effect of pyridine and its chloro compounds in the post-treatment method for pyridine reaction waste liquid provided in this embodiment, reference is made to the following experimental data of the implementation examples, as shown in table 1 below:
wherein dichloropyridine (DCPD) and Trichloropyridine (TCPD) are pollutants in desorption liquid: including NH 3-containing and ammonium salts, DCPD, TCPD, and color-containing impurities.
Based on the table above, it can be shown that: the macroporous resin can be adopted to carry out adsorption and desorption to realize the recycling of pyridine, and concretely, based on experimental calculation of an example provided by the embodiment (the macroporous resin and methanol are adopted to treat waste liquid containing pyridine, monochloropyridine and chloropyridine as organic solvents, and the post-treatment cost of the waste liquid can be reduced by 30% -80% compared with the prior post-treatment cost according to different recycling treatments of filtrate (namely whether refined salt is prepared or not and the treatment of the refined salt) and pyridine and chloropyridine.
Embodiment two: the present embodiment provides an application of the method for post-treating pyridine reaction waste liquid in the pyridine recycling field, specifically, based on the method for post-treating pyridine reaction waste liquid in the first embodiment, finally separated pyridine and its chloro (monochloropyridine, dichloropyridine) and ammonium chloride can be used for the chlorination reaction of original pyridine, so as to realize pyridine recycling, and be applied to environmental protection and post-treatment of organic matters reaction.
It should be noted that the embodiments of the present application are preferred and not limited in any way, and any person skilled in the art may make use of the above-disclosed technical content to change or modify the same into equivalent effective embodiments without departing from the technical scope of the present application, and any modification or equivalent change and modification of the above-described embodiments according to the technical substance of the present application still falls within the scope of the technical scope of the present application.
Claims (10)
1. A method for post-treatment of pyridine reaction waste liquid, characterized in that the waste liquid contains pyridine and chloropyridine, comprising:
adjusting the PH of the waste liquid to a preset value to obtain target treatment liquid;
passing the target treatment liquid through an exchange column with built-in macroporous resin, so that the macroporous resin adsorbs pyridine and chloropyridine in the target treatment liquid, and filtrate is obtained;
passing the macroporous resin adsorbed with pyridine and chloropyridine through a column again by adopting an organic solvent to obtain desorption liquid;
and rectifying the desorption liquid to separate pyridine, chloropyridine and an organic solvent.
2. The method for post-treatment of waste liquid according to claim 1, further comprising:
when the waste liquid is a salt-containing solution containing pyridine and chloropyridine;
the filtrate was separated by salt distillation and then dehydrated to obtain a purified salt containing no pyridine or chloropyridine.
3. The method for post-treatment of waste liquid according to claim 1, wherein:
the organic solvent is polar solvent including methanol, ethanol, acetone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
4. The method according to claim 1, wherein the adjusting the pH of the waste liquid to a preset value to obtain the target treatment liquid comprises:
and adding acid liquor or alkali liquor to adjust the pH value of the waste liquid to 7-11, thereby obtaining the target treatment liquid.
5. The method according to claim 1, wherein after passing the target treatment liquid through the column containing macroporous resin, the method further comprises:
the macroporous resin is washed by adopting process water, and the liquid after passing through the column is collected to a preset buffer tank for recycling to the target treatment liquid; wherein the process water comprises deionized water, soft water and distilled water.
6. The method for post-treatment of waste liquid according to claim 1, further comprising:
and quantitatively passing the macroporous resin adsorbed with pyridine and chloropyridine through the column for multiple times by adopting the organic solvent, and carrying out cyclic desorption.
7. The method for post-treatment of waste liquid according to claim 1, further comprising:
and after passing through the column for adsorption in a preset period, cleaning the macroporous resin by adopting steam and/or acid-base washing or an organic solvent.
8. The method for post-treatment of waste liquid according to claim 2, further comprising, before the salt distillation separation:
presetting a pyridine limit value of filtrate entering a salt steaming reaction kettle; and when the filtrate exceeds the pyridine limit, discharging the filtrate to a preset buffer tank for recycling to the target treatment liquid.
9. The method for post-treatment of waste liquid according to claim 1 or 5, characterized in that:
after each liquid pass through the column, inert gas is injected into the exchange column to empty the liquid in the macroporous resin, wherein,
the liquid comprises target treatment liquid, organic solvent and process water.
10. Use of the method for post-treatment of pyridine reaction effluent according to any one of claims 1 to 9 in the field of pyridine recovery and environmental protection.
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