CN116332836B - Method for recovering pyridine waste solvent - Google Patents
Method for recovering pyridine waste solvent Download PDFInfo
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- CN116332836B CN116332836B CN202210914096.7A CN202210914096A CN116332836B CN 116332836 B CN116332836 B CN 116332836B CN 202210914096 A CN202210914096 A CN 202210914096A CN 116332836 B CN116332836 B CN 116332836B
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- waste solvent
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 253
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000010887 waste solvent Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000010533 azeotropic distillation Methods 0.000 claims abstract description 56
- 238000010992 reflux Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001704 evaporation Methods 0.000 claims abstract description 30
- 230000008020 evaporation Effects 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 30
- OENLEHTYJXMVBG-UHFFFAOYSA-N pyridine;hydrate Chemical compound [OH-].C1=CC=[NH+]C=C1 OENLEHTYJXMVBG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 28
- 239000012141 concentrate Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 230000018044 dehydration Effects 0.000 claims abstract description 14
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 14
- 238000005373 pervaporation Methods 0.000 claims abstract description 14
- 230000008878 coupling Effects 0.000 claims abstract description 13
- 238000010168 coupling process Methods 0.000 claims abstract description 13
- 238000005859 coupling reaction Methods 0.000 claims abstract description 13
- 238000004821 distillation Methods 0.000 claims abstract description 13
- 238000007781 pre-processing Methods 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000002808 molecular sieve Substances 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 12
- 235000011152 sodium sulphate Nutrition 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 58
- 239000000047 product Substances 0.000 description 37
- 239000011698 potassium fluoride Substances 0.000 description 29
- 235000003270 potassium fluoride Nutrition 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 12
- 210000004379 membrane Anatomy 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 239000002699 waste material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 229930013930 alkaloid Natural products 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 206010029279 Neurogenic bladder Diseases 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical group O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 239000004058 oil shale Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- -1 pyridine compound Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004078 waterproofing Methods 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
Abstract
The invention relates to the technical field of solvent recovery, and discloses a method for recovering pyridine waste solvents, which comprises the following steps: s1, conveying a pyridine waste solvent containing solid salt into an evaporation concentration kettle, extracting pyridine-water enriched components from a gas phase at the top of the tower, and extracting solid salt concentrate from the tower kettle; s2, introducing the pyridine-water enriched component into an azeotropic distillation tower, adding an azeotropic agent for distillation, and obtaining water and organic composition of the azeotropic agent at the tower top and a crude pyridine product at the tower bottom; s3, drying and preprocessing the crude pyridine product, and then introducing the crude pyridine product into an atmospheric tower for rectification treatment to obtain industrial-grade pyridine; s4, introducing water extracted from the azeotropic distillation tower and the organic composition of the entrainer into a pervaporation membrane in a steam form for coupling dehydration, and refluxing the entrainer after moisture removal to the azeotropic distillation tower. The recovery method of the waste solvent has the characteristics of high yield, low energy consumption, good quality, recycling, simple production process and stable operation, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of solvent recovery, in particular to a method for recovering pyridine waste solvents.
Background
Pyridine of formula C 5 H 5 N is a flammable colorless liquid at normal temperature, has pungent smell and is mutually soluble with water, the aqueous solution of the N is alkaline, and for many organic compounds, pyridine is an excellent solvent, and can be used for producing conductive solution with many inorganic compounds, such as silver bromide, silver nitrate, copper chloride, cuprous chloride, ferric chloride, lead nitrate, lead acetate and the like, and can be dissolved in various organic solvents, thus being a high boiling point solvent commonly used in laboratories. Pyridine is toxic and malodorous, the highest concentration allowed in the air is 5ppm, and the steam and liquid of the pyridine have strong local irritation to human skin, especially mucous membrane, and if the human is contacted with the pyridine compound for a long time, the symptoms such as nerve disorder, bladder paralysis and the like can be caused.
Pyridine itself does not exist in nature but its various derivatives are indeed essential components of many natural drugs, dyes, vitamins and various alkaloids, pyridine and its homologs picoline are mainly found in certain enzymes and alkaloids, and natural substances such as coal, oil shale and the like are produced with pyridine products upon degradation. For example, coal gas and coal tar obtained during enzyme coking contain oily pyridine compounds, usually pyridine bases, and the content of pyridine bases is about 100-150g per ton of coal; pyridine is also used in parent mixtures of various important biological derivatives, as solvents or waterproofing agents, and in the manufacture of various drugs and vitamins. The pyridine has higher unit consumption and higher price in industrial production and has certain pollution to the environment, so the pyridine has practical economic benefit and environmental protection significance for pyridine recovery in industrial production.
Disclosure of Invention
In view of the above, the invention provides a method for recovering pyridine waste solvent, which solves the problems of poor recovery effect and easy environmental pollution of the existing pyridine.
In order to solve the technical problems, the invention adopts the following technical scheme:
the method for recovering the pyridine waste solvent comprises the following steps:
s1, conveying a pyridine waste solvent containing solid salt into an evaporation concentration kettle, extracting pyridine-water enriched components from a gas phase at the top of the tower, and extracting solid salt concentrate from the tower kettle;
s2, introducing the pyridine-water enriched component into an azeotropic distillation tower, adding an azeotropic agent for distillation, and obtaining water and organic composition of the azeotropic agent at the tower top and a crude pyridine product at the tower bottom;
s3, drying and preprocessing the crude pyridine product, and then introducing the crude pyridine product into an atmospheric tower for rectification treatment to obtain industrial-grade pyridine;
s4, introducing water extracted from the azeotropic distillation tower and the organic composition of the entrainer into a pervaporation membrane in a steam form for coupling dehydration, and refluxing the entrainer after moisture removal to the azeotropic distillation tower.
Preferably, in the above method for recovering pyridine waste solvent, the waste solvent in step S1 is used in an amount of 0.1 to 3m 3 Delivering the rate of/h to an evaporation concentration kettle; further preferably, the waste solvent is used in an amount of 1-2m 3 The rate of/h is fed to an evaporation and concentration tank.
Preferably, in the above method for recovering a pyridine waste solvent, the pyridine-water enriched fraction in step S2 is in the range of 0.1 to 2.5m 3 The rate of/h is conveyed to an azeotropic distillation tower; further preferably, the pyridine-water enriched fraction is in the range of 1 to 1.5m 3 The rate of/h is fed to the azeotropic distillation column.
Preferably, in the above method for recovering pyridine waste solvent, the operation pressure of the azeotropic distillation column in step S2 is 0.09-0.15MPa, the column top temperature is 80-125 ℃, the column bottom temperature is 88-133 ℃, and the reflux ratio is 2-10.
Preferably, in the above method for recovering pyridine waste solvent, the entrainer in step S2 includes dichloromethane, cyclohexane, ethanol, and potassium fluoride; further, the entrainer is potassium fluoride.
Preferably, in the above method for recovering pyridine waste solvent, the drying pretreatment in step S3 is to treat the crude pyridine product sequentially with sodium sulfate and 4A molecular sieve.
Experimental study shows that when the crude pyridine product is treated by sodium sulfate alone, treated by a 4A molecular sieve alone, and any desiccant is replaced or sequentially treated by the 4A molecular sieve and sodium sulfate, the quality of the pyridine product cannot be optimized, and only when the crude pyridine product is firstly treated by sodium sulfate in a drying way and then treated by the 4A molecular sieve, the purity, the water content and the like of the pyridine product can reach a good level.
Preferably, in the above method for recovering pyridine waste solvent, in the step S3, the temperature of the top of the atmospheric tower is 98-105 ℃, the temperature of the bottom of the atmospheric tower is 110-125 ℃, and the reflux ratio is 0.5-3.
Preferably, in the above method for recovering pyridine waste solvent, the method further comprises the steps of: and drying the solid salt concentrate extracted from the tower kettle of the evaporation concentration kettle.
Preferably, in the above method for recovering a pyridine waste solvent, the solid salt comprises sodium sulfonate and/or sodium chloride.
The invention provides a method for recovering pyridine waste solvent, which has the beneficial effects that compared with the prior art:
the industrial grade pyridine is obtained through evaporation concentration, azeotropic distillation, pretreatment drying and normal pressure distillation, and the water content of the pyridine is greatly reduced on the basis of ensuring the purity of the pyridine; and the azeotropic solvent can be recycled through evaporation concentration, azeotropic distillation and dehydration of the pervaporation membrane, so that the waste of the organic azeotropic solvent is avoided.
The method for recovering the pyridine waste solvent has the characteristics of high yield, low energy consumption, good quality, capability of recycling, simple and convenient production process and stable operation, and is suitable for large-scale industrial production.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a method for recycling pyridine waste solvent, which comprises the following steps:
s1, adding a waste solvent containing 35% of pyridine into the mixture at a concentration of 1m 3 Delivering the rate of/h to an evaporation concentration kettle, extracting pyridine-water enriched components from the gas phase at the top of the tower, and extracting solid salt concentrate from the tower kettle;
s2, mixing the pyridine-water enriched component with 1m 3 Introducing the rate of/h into an azeotropic distillation tower, wherein the operation pressure of the azeotropic distillation tower is 0.1MPa, the temperature of the tower top is 120 ℃, the temperature of the tower bottom is 128 ℃, the reflux ratio is 5, simultaneously adding an entrainer potassium fluoride for distillation, and obtaining the organic composition of water and potassium fluoride at the tower top and a crude pyridine product at the tower bottom;
s3, drying and preprocessing the crude pyridine product sequentially through sodium sulfate and a 4A molecular sieve, and then introducing the crude pyridine product into an atmospheric tower for rectification treatment, wherein the temperature of the top of the atmospheric tower is 100 ℃, the temperature of the tower kettle is 115 ℃, and the reflux ratio is 2, so that industrial grade pyridine is obtained;
s4, introducing water extracted from the azeotropic distillation tower and organic components of potassium fluoride into a pervaporation membrane in a steam form for coupling dehydration, and refluxing the potassium fluoride after moisture removal to the azeotropic distillation tower;
s5, drying the solid salt concentrate extracted from the tower kettle of the evaporation concentration kettle.
Example 2
The embodiment provides a method for recycling pyridine waste solvent, which comprises the following steps:
s1, mixing waste pyridine solvent containing 50% of pyridine by 2m 3 Delivering the rate of/h to an evaporation concentration kettle, extracting pyridine-water enriched components from the gas phase at the top of the tower, and extracting solid salt concentrate from the tower kettle;
s2, concentrating the pyridine-water enriched component to 2m 3 Introducing the rate of/h into an azeotropic distillation tower, wherein the operation pressure of the azeotropic distillation tower is 0.12MPa, the tower top temperature is 100 ℃, the tower bottom temperature is 110 ℃, the reflux ratio is 2, simultaneously adding an entrainer dichloromethane to carry out distillation, obtaining an organic composition of water and dichloromethane at the tower top, and obtaining a pyridine crude product at the tower bottom;
s3, drying and preprocessing the crude pyridine product sequentially through sodium sulfate and a 4A molecular sieve, and then introducing the crude pyridine product into an atmospheric tower for rectification treatment, wherein the temperature of the top of the atmospheric tower is 98 ℃, the temperature of the tower kettle is 110 ℃, and the reflux ratio is 0.5, so that the industrial grade pyridine is obtained;
s4, introducing water extracted from the azeotropic distillation tower and organic composition of dichloromethane into a pervaporation membrane in a steam form for coupling dehydration, and refluxing the entrainer after moisture removal to the azeotropic distillation tower;
s5, drying the solid salt concentrate extracted from the tower kettle of the evaporation concentration kettle.
Example 3
The embodiment provides a method for recycling pyridine waste solvent, which comprises the following steps:
s1, mixing waste pyridine solvent containing 30% with 3m 3 Delivering the rate of/h to an evaporation concentration kettle, extracting pyridine-water enriched components from the gas phase at the top of the tower, and extracting solid salt concentrate from the tower kettle;
s2, concentrating the pyridine-water enriched component to 2.5m 3 /hIntroducing the velocity into an azeotropic distillation tower, wherein the operation pressure of the azeotropic distillation tower is 0.15MPa, the tower top temperature is 80 ℃, the tower bottom temperature is 88 ℃, the reflux ratio is 8, simultaneously adding an entrainer cyclohexane for distillation, and obtaining the organic composition of water and cyclohexane at the tower top and the crude pyridine product at the tower bottom;
s3, drying and preprocessing the crude pyridine product sequentially through sodium sulfate and a 4A molecular sieve, and then introducing the crude pyridine product into an atmospheric tower for rectification treatment, wherein the temperature of the top of the atmospheric tower is 102 ℃, the temperature of the tower kettle is 118 ℃, and the reflux ratio is 3, so that the industrial grade pyridine is obtained;
s4, introducing water extracted from the azeotropic distillation tower and organic components of cyclohexane into a pervaporation membrane in a steam form for coupling dehydration, and refluxing the entrainer after water removal to the azeotropic distillation tower;
s5, drying the solid salt concentrate extracted from the tower kettle of the evaporation concentration kettle.
Example 4
The embodiment provides a method for recycling pyridine waste solvent, which comprises the following steps:
s1, mixing waste pyridine solvent with 40% of waste pyridine solvent at a concentration of 0.5m 3 Delivering the rate of/h to an evaporation concentration kettle, extracting pyridine-water enriched components from the gas phase at the top of the tower, and extracting solid salt concentrate from the tower kettle;
s2, concentrating the pyridine-water enriched component to 0.5m 3 Introducing the rate of/h into an azeotropic distillation tower, wherein the operation pressure of the azeotropic distillation tower is 0.09MPa, the temperature of the tower top is 125 ℃, the temperature of the tower bottom is 133 ℃, the reflux ratio is 4, simultaneously adding an entrainer potassium fluoride for distillation, and obtaining the organic composition of water and potassium fluoride at the tower top and a crude pyridine product at the tower bottom;
s3, drying and preprocessing the crude pyridine product sequentially through sodium sulfate and a 4A molecular sieve, and then introducing the crude pyridine product into an atmospheric tower for rectification treatment, wherein the temperature of the top of the atmospheric tower is 105 ℃, the temperature of the tower kettle is 125 ℃, and the reflux ratio is 1, so that industrial grade pyridine is obtained;
s4, introducing water extracted from the azeotropic distillation tower and organic composition of potassium fluoride into a pervaporation membrane in a steam form for coupling dehydration, and refluxing the entrainer after moisture removal to the azeotropic distillation tower;
s5, drying the solid salt concentrate extracted from the tower kettle of the evaporation concentration kettle.
Example 5
The embodiment provides a method for recycling pyridine waste solvent, which comprises the following steps:
s1, mixing waste pyridine solvent containing 45% with 0.1m 3 Delivering the rate of/h to an evaporation concentration kettle, extracting pyridine-water enriched components from the gas phase at the top of the tower, and extracting solid salt concentrate from the tower kettle;
s2, concentrating the pyridine-water enriched component to 0.1m 3 Introducing the rate of/h into an azeotropic distillation tower, wherein the operation pressure of the azeotropic distillation tower is 0.1MPa, the tower top temperature is 122 ℃, the tower bottom temperature is 130 ℃, the reflux ratio is 10, simultaneously adding an entrainer ethanol for distillation, obtaining an organic composition of water and ethanol at the tower top, and obtaining a pyridine crude product at the tower bottom;
s3, drying and preprocessing the crude pyridine product sequentially through sodium sulfate and a 4A molecular sieve, and then introducing the crude pyridine product into an atmospheric tower for rectification treatment, wherein the temperature of the top of the atmospheric tower is 101 ℃, the temperature of the tower kettle is 113 ℃, and the reflux ratio is 1.5, so that industrial grade pyridine is obtained;
s4, enabling organic compositions of water and ethanol extracted from the azeotropic distillation tower to enter a pervaporation membrane in a steam form for coupling dehydration, and refluxing the entrainer after moisture removal to the azeotropic distillation tower;
s5, drying the solid salt concentrate extracted from the tower kettle of the evaporation concentration kettle.
The invention performs relevant performance detection on pyridine recovered in examples 1-5, and the measurement results are shown in Table 1.
TABLE 1 examples 1-5 pyridine assay results
Comparative example 1
The comparative example provides a method for recovering pyridine waste solvent, comprising the following steps:
s1, adding a waste solvent containing 35% of pyridine into the mixture at a concentration of 1m 3 Delivering the rate of/h to an evaporation concentration kettle, extracting pyridine-water enriched components from the gas phase at the top of the tower, and extracting solid salt concentrate from the tower kettle;
s2, mixing the pyridine-water enriched component with 1m 3 Introducing the rate of/h into an azeotropic distillation tower, wherein the operation pressure of the azeotropic distillation tower is 0.1MPa, the temperature of the tower top is 120 ℃, the temperature of the tower bottom is 128 ℃, the reflux ratio is 5, simultaneously adding an entrainer potassium fluoride for distillation, and obtaining the organic composition of water and potassium fluoride at the tower top and a crude pyridine product at the tower bottom;
s3, introducing the crude pyridine product into an atmospheric tower for rectification treatment, wherein the temperature of the top of the atmospheric tower is 100 ℃, the temperature of the tower kettle is 115 ℃, and the reflux ratio is 2, so as to obtain a pyridine product;
s4, introducing water extracted from the azeotropic distillation tower and organic components of potassium fluoride into a pervaporation membrane in a steam form for coupling dehydration, and refluxing the potassium fluoride after moisture removal to the azeotropic distillation tower;
s5, drying the solid salt concentrate extracted from the tower kettle of the evaporation concentration kettle.
Comparative example 2
The comparative example provides a method for recovering pyridine waste solvent, comprising the following steps:
s1, adding a waste solvent containing 35% of pyridine into the mixture at a concentration of 1m 3 Delivering the rate of/h to an evaporation concentration kettle, extracting pyridine-water enriched components from the gas phase at the top of the tower, and extracting solid salt concentrate from the tower kettle;
s2, mixing the pyridine-water enriched component with 1m 3 Introducing the rate of/h into an azeotropic distillation tower, wherein the operation pressure of the azeotropic distillation tower is 0.1MPa, the temperature of the tower top is 120 ℃, the temperature of the tower bottom is 128 ℃, the reflux ratio is 5, simultaneously adding an entrainer potassium fluoride for distillation, and obtaining the organic composition of water and potassium fluoride at the tower top and a crude pyridine product at the tower bottom;
s3, drying and preprocessing the crude pyridine product sequentially by sodium sulfate, and then introducing the dried pyridine product into an atmospheric tower for rectification treatment, wherein the temperature of the top of the atmospheric tower is 100 ℃, the temperature of a tower kettle is 115 ℃, and the reflux ratio is 2, so that a pyridine product is obtained;
s4, introducing water extracted from the azeotropic distillation tower and organic components of potassium fluoride into a pervaporation membrane in a steam form for coupling dehydration, and refluxing the potassium fluoride after moisture removal to the azeotropic distillation tower;
s5, drying the solid salt concentrate extracted from the tower kettle of the evaporation concentration kettle.
Comparative example 3
The comparative example provides a method for recovering pyridine waste solvent, comprising the following steps:
s1, adding a waste solvent containing 35% of pyridine into the mixture at a concentration of 1m 3 Delivering the rate of/h to an evaporation concentration kettle, extracting pyridine-water enriched components from the gas phase at the top of the tower, and extracting solid salt concentrate from the tower kettle;
s2, mixing the pyridine-water enriched component with 1m 3 Introducing the rate of/h into an azeotropic distillation tower, wherein the operation pressure of the azeotropic distillation tower is 0.1MPa, the temperature of the tower top is 120 ℃, the temperature of the tower bottom is 128 ℃, the reflux ratio is 5, simultaneously adding an entrainer potassium fluoride for distillation, and obtaining the organic composition of water and potassium fluoride at the tower top and a crude pyridine product at the tower bottom;
s3, drying and preprocessing the crude pyridine product by a 4A molecular sieve, and then introducing the crude pyridine product into an atmospheric tower for rectification treatment, wherein the temperature of the top of the atmospheric tower is 100 ℃, the temperature of a tower kettle is 115 ℃, and the reflux ratio is 2, so that a pyridine product is obtained;
s4, introducing water extracted from the azeotropic distillation tower and organic components of potassium fluoride into a pervaporation membrane in a steam form for coupling dehydration, and refluxing the potassium fluoride after moisture removal to the azeotropic distillation tower;
s5, drying the solid salt concentrate extracted from the tower kettle of the evaporation concentration kettle.
Comparative example 4
The comparative example provides a method for recovering pyridine waste solvent, comprising the following steps:
s1, adding a waste solvent containing 35% of pyridine into the mixture at a concentration of 1m 3 Delivering the rate of/h to an evaporation concentration kettle, extracting pyridine-water enriched components from the gas phase at the top of the tower, and extracting solid salt concentrate from the tower kettle;
s2, mixing the pyridine-water enriched component with 1m 3 Feeding the rate of/h into an azeotropic distillation column, and operating the azeotropic distillation columnThe pressure is 0.1MPa, the temperature of the tower top is 120 ℃, the temperature of the tower bottom is 128 ℃, the reflux ratio is 5, simultaneously, the entrainer potassium fluoride is added for rectification, the organic composition of water and potassium fluoride is obtained at the tower top, and the crude pyridine is obtained at the tower bottom;
s3, drying and preprocessing the crude pyridine product sequentially through sodium hydroxide and a 4A molecular sieve, and then introducing the crude pyridine product into an atmospheric tower for rectification treatment, wherein the temperature of the top of the atmospheric tower is 100 ℃, the temperature of the tower kettle is 115 ℃, and the reflux ratio is 2, so that a pyridine product is obtained;
s4, introducing water extracted from the azeotropic distillation tower and organic components of potassium fluoride into a pervaporation membrane in a steam form for coupling dehydration, and refluxing the potassium fluoride after moisture removal to the azeotropic distillation tower;
s5, drying the solid salt concentrate extracted from the tower kettle of the evaporation concentration kettle.
Comparative example 5
The comparative example provides a method for recovering pyridine waste solvent, comprising the following steps:
s1, mixing waste pyridine solvent containing sodium sulfonate and sodium chloride by 1m 3 Delivering the rate of/h to an evaporation concentration kettle, extracting pyridine-water enriched components from the gas phase at the top of the tower, and extracting solid salt concentrate from the tower kettle;
s2, mixing the pyridine-water enriched component with 1m 3 Introducing the rate of/h into an azeotropic distillation tower, wherein the operation pressure of the azeotropic distillation tower is 0.1MPa, the temperature of the tower top is 120 ℃, the temperature of the tower bottom is 128 ℃, the reflux ratio is 5, simultaneously adding an entrainer potassium fluoride for distillation, and obtaining an organic composition of water and potassium fluoride at the tower top and a pyridine product at the tower bottom;
s3, introducing water extracted from the azeotropic distillation tower and organic components of potassium fluoride into a pervaporation membrane in a steam form for coupling dehydration, and refluxing the potassium fluoride after moisture removal to the azeotropic distillation tower;
s4, drying the solid salt concentrate extracted from the tower kettle of the evaporation concentration kettle.
The pyridine recovered in comparative examples 1 to 5 was subjected to the relevant performance test, and the measurement results are shown in Table 1.
TABLE 2 comparative examples 1-5 pyridine determination results
As shown in Table 2, the drying pretreatment and the normal pressure rectification process have great influence on the purity, the moisture and the like of the pyridine, and can effectively improve the purity of the pyridine, reduce the water content of the pyridine and obviously improve the quality of the pyridine when the drying agent is a combination of sodium sulfate and a 4A molecular sieve.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the solution disclosed in the embodiments, since it corresponds to the method disclosed in the embodiments, the description is relatively simple, and the relevant points refer to the description of the method section.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. The method for recycling the pyridine waste solvent is characterized by comprising the following steps of:
s1, conveying a pyridine waste solvent containing solid salt into an evaporation concentration kettle, extracting pyridine-water enriched components from a gas phase at the top of the tower, and extracting solid salt concentrate from the tower kettle;
s2, introducing the pyridine-water enriched component into an azeotropic distillation tower, adding an azeotropic agent for distillation, and obtaining water and organic composition of the azeotropic agent at the tower top and a crude pyridine product at the tower bottom;
s3, drying and preprocessing the crude pyridine product, and then introducing the crude pyridine product into an atmospheric tower for rectification treatment to obtain industrial-grade pyridine;
s4, introducing water extracted from the azeotropic distillation tower and organic components of the entrainer into a pervaporation membrane in a steam form for coupling dehydration, and refluxing the entrainer after moisture removal to the azeotropic distillation tower;
the entrainer in the step S2 is dichloromethane, cyclohexane or ethanol;
in the step S3, the drying pretreatment is that the crude pyridine product is treated by sodium sulfate and a 4A molecular sieve in sequence; the temperature of the top of the atmospheric tower is 98-105 ℃, the temperature of the bottom of the atmospheric tower is 110-125 ℃, and the reflux ratio is 0.5-3.
2. The method for recovering pyridine waste solvent as defined in claim 1, wherein said waste solvent in step S1 is used in an amount of 0.1 to 3m 3 The rate of/h is fed to an evaporation and concentration tank.
3. The method for recovering a pyridine waste solvent according to claim 1, wherein the pyridine-water enriched fraction in step S2 is in the range of 0.1 to 2.5m 3 The rate of/h is fed to the azeotropic distillation column.
4. The method for recovering pyridine waste solvent according to claim 1, wherein the operation pressure of the azeotropic distillation column in the step S2 is 0.09-0.15MPa, the column top temperature is 80-125 ℃, the column bottom temperature is 88-133 ℃, and the reflux ratio is 2-10.
5. The method for recovering a pyridine waste solvent according to claim 1, further comprising the steps of: and drying the solid salt concentrate extracted from the tower kettle of the evaporation concentration kettle.
6. The method for recovering a pyridine waste solvent according to claim 1 or 5, wherein the solid salt is sodium sulfonate and/or sodium chloride.
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