CN110128275B - Treatment method of catalyst-containing waste liquid in pentafluoroethane production - Google Patents
Treatment method of catalyst-containing waste liquid in pentafluoroethane production Download PDFInfo
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- CN110128275B CN110128275B CN201910316339.5A CN201910316339A CN110128275B CN 110128275 B CN110128275 B CN 110128275B CN 201910316339 A CN201910316339 A CN 201910316339A CN 110128275 B CN110128275 B CN 110128275B
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Abstract
The invention discloses a method for treating catalyst-containing waste liquid in pentafluoroethane production, which comprises the following steps: (1) adding the waste liquid containing the catalyst into lime, and stirring for reaction for a certain time; (2) filtering and separating a solid-liquid phase, wherein the solid phase is a solid containing calcium fluoride, and the liquid phase is an organic amine solution mainly containing a catalyst; (3) and performing reduced pressure distillation on the liquid phase, and collecting the liquid phase in a segmented manner to obtain high-purity organic amine which is used as a catalyst for producing pentafluoroethane. The method has the advantages of simple operation, high purity of the collected organic amine, realization of recycling of the catalyst-containing waste liquid, and environmental protection.
Description
Technical Field
The invention belongs to the technical field of three-waste treatment, and particularly relates to a method for treating catalyst-containing waste liquid in pentafluoroethane production, in particular to recycling of an organic amine-containing catalyst.
Background
US5912392 and US5969199, chinese patent CN1724490A, both disclose a synthesis method for producing pentafluoroethane using tetrafluoroethylene and hydrogen fluoride as raw materials and organic amine as a catalyst. The organic amine catalyst is typically triethylamine, tri-N-butylamine, tripropylamine, N-dimethylaniline, diisopropylethylamine, or the like. In industrial production, the organic amine catalyst can cause the viscosity of a reaction system to increase along with the increase of the cycle number, the catalytic activity of the catalyst to decrease, and the catalyst is discharged in the form of catalyst-containing waste liquid. The catalyst-containing waste liquid mainly contains an organic amine catalyst, a complex of the catalyst and hydrogen fluoride and some macromolecular polymers. Because the catalyst-containing waste liquid has strong acidity and contains a large amount of fluorine elements and nitrogen elements, the waste liquid is treated by incineration, so that the material requirement of a treatment device is high, and resources are wasted; and the post-treatment process is complex, the cost is high, and secondary pollution is easy to cause.
CN101934239A discloses a method for treating catalyst-containing waste liquid in pentafluoroethane production, comprising the following steps: 1) placing the catalyst-containing waste liquid in a storage tank for standing for 22-26 hours to obtain the standing waste liquid; 2) taking the waste liquid which is positioned at the upper half part and is 50 percent of the volume ratio after standing as the waste liquid to be treated; transferring the waste liquid to be treated into a reaction kettle, and setting the waste liquid to be treated to be all composed of (n-C)4H9)3N.2.6 HF; then adding alkali liquor with equivalent weight, and stirring and reacting at room temperature; 3) filtering the reacted material obtained in the step 2), and then sending the filtered material to a distillation device for distillation, and collecting 150-220 ℃ fractions. The method is not thorough in treatment and only treats 50% of waste liquid by volume. In addition, patent CN1962064 discloses a method for treating a waste catalyst in pentafluoroethane production. The method recovers the catalyst through three steps of water dilution, alkali liquor neutralization and rectification, and has the defects of insufficient consideration of primary separation of substances, increased waste liquid amount after treatment and high energy consumption.
Disclosure of Invention
The invention aims to provide a method for treating catalyst-containing waste liquid in pentafluoroethane production, which has the advantages of simple and convenient operation, small amount of waste liquid to be treated, pollution reduction to a certain extent and production cost reduction.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for treating catalyst-containing waste liquid in pentafluoroethane production is characterized by comprising the following steps:
(1) adding the catalyst-containing waste liquid into lime, stirring and reacting for a certain time to decompose and convert organic amine fluoride salt in the catalyst-containing waste liquid into organic amine and calcium fluoride;
(2) filtering and separating a solid phase and a liquid phase from the reaction liquid obtained in the step (1), wherein the solid phase is a solid containing calcium fluoride, and the liquid phase mainly contains an organic amine solution of a catalyst;
(3) and (3) carrying out reduced pressure rectification on the liquid phase obtained in the step (2), and collecting the liquid phase in sections to obtain high-purity organic amine which is used as a catalyst for producing pentafluoroethane.
Further, the adding amount of lime in the step 1) is 1.05-1.5 times of the theoretical amount of free fluorine in the catalyst-containing waste liquid. Along with the increase of the lime consumption, the slag amount is increased in proportion, and in consideration of the purity of lime, if the lime addition is lower than an equivalent amount, part of organic amine fluoride salt in the waste liquid can not be converted into organic amine, so that the separation rate of the organic amine is reduced, and the treatment difficulty is increased for subsequent solid treatment. Meanwhile, the waste liquid containing the catalyst is added into the lime, so that the decomposition reaction speed can be effectively controlled, and the phenomenon of pot overflow caused by too high reaction speed is avoided.
Further, the mixing reaction time of the catalyst-containing waste liquid and the lime is 0.5-6 hours. The mixed reaction of the catalyst-containing waste liquid and lime requires a certain reaction time, if the reaction time is short, the reaction is not thorough, and part of organic amine salt is not converted into organic amine; if the reaction time is too long, the treatment efficiency is lowered and the power consumption is increased. The test result shows that the mixing reaction time is preferably 0.5 to 6 hours.
The method mainly relates to the following reactions:
2(CnH2n+1)3N·nHF+n(CaOH)2→2(CnH2n+1)3N+nCaF2+nH2O
the method is technically characterized in that the catalyst-containing waste liquid generated in the production of pentafluoroethane is effectively treated, organic amine in the waste liquid is recovered, and the organic amine is recycled to the system for producing the catalyst of pentafluoroethane. Because the complex of the catalyst organic amine and the hydrogen fluoride in the catalyst-containing waste liquid is efficiently separated, the solid phase is mainly calcium fluoride, and the solid phase can be considered to enter a cement rotary kiln to produce cement; and some macromolecular polymers in the waste liquid exist in a solid phase together with calcium fluoride in the form of solid materials after mixing reaction, so that the difficulty of recovering organic amine through vacuum rectification is reduced, and the high-purity organic amine is obtained.
The method for treating the catalyst-containing waste liquid in the production of pentafluoroethane has the following advantages:
(1) the catalyst-containing waste liquid is treated by lime, and the generated calcium fluoride is insoluble in water, so that the high-efficiency separation of organic amine and other impurity components in the waste liquid can be realized, the method is simple and convenient to operate, the separation efficiency is high, and the separation rate of organic nitrogen is over 95 percent.
(2) The organic amine product obtained by recycling has good quality, the organic amine in the catalyst-containing waste liquid can be effectively recycled, the purity of the organic amine obtained by recycling reaches more than 99.5 percent, the organic amine can be directly used for the production of pentafluoroethane, the catalyst-containing waste liquid can be recycled, and the method has the characteristics of environmental protection.
Drawings
FIG. 1 is a flow chart of a process for treating a catalyst-containing waste liquid in the production of pentafluoroethane.
Detailed Description
The invention is further illustrated by the following examples:
as shown in the process flow of figure 1, the method for treating the catalyst-containing waste liquid in the production of pentafluoroethane has the advantages that the purity of the recovered organic amine is high, the catalyst-containing waste liquid can be recycled, and the method is green and environment-friendly.
Example 1
(1) Weighing 1000g of waste liquid (free fluorine 13.59%) containing the catalyst, slowly adding the waste liquid into 295g of lime, and stirring the waste liquid with a stirrer for reaction for 6 hours to decompose and convert organic amine fluoride salt in the waste liquid containing the catalyst into organic amine and calcium fluoride;
(2) filtering the reaction liquid obtained in the step (1) to separate a solid-liquid phase, wherein 533g of the solid phase is mainly a solid containing calcium fluoride, and 691g of the liquid phase is mainly an organic amine solution containing a catalyst;
(3) and (3) carrying out reduced pressure rectification on the liquid phase obtained in the step (2), and collecting the high-purity organic amine 524.6g (with the purity of 99.3%) in sections for the catalyst for producing pentafluoroethane.
Example 2
(1) Weighing 700g of waste liquid containing the catalyst (free fluorine is 12.57 percent), slowly adding the waste liquid into 255g of lime, and stirring the waste liquid with a stirrer for reaction for 2 hours to decompose and convert organic amine fluoride salt in the waste liquid containing the catalyst into organic amine and calcium fluoride;
(2) filtering the reaction liquid obtained in the step (1) to separate a solid-liquid phase, wherein 491g of the solid phase is mainly a solid containing calcium fluoride, and 416g of the liquid phase is mainly an organic amine solution containing a catalyst;
(3) and (3) performing reduced pressure rectification on the liquid phase obtained in the step (2), and collecting 326.6g (with the purity of 99.2%) of high-purity organic amine by stages for producing the catalyst for pentafluoroethane.
Example 3
(1) Weighing 600g of waste liquid containing the catalyst (free fluorine 15.61%) and slowly adding the waste liquid into 292g of lime, stirring the waste liquid by a stirrer to react for 0.5 hour, so that organic amine fluoride in the waste liquid containing the catalyst is decomposed and converted into organic amine and calcium fluoride;
(2) filtering the reaction liquid obtained in the step (1) to separate a solid phase and a liquid phase, wherein 459g of the solid phase is mainly a solid containing calcium fluoride, and 386g of the liquid phase is mainly an organic amine solution containing a catalyst;
(3) and (3) carrying out reduced pressure rectification on the liquid phase obtained in the step (2), and collecting the high-purity organic amine 293.2g (with the purity of 99.5%) in sections for the catalyst for producing pentafluoroethane.
Example 4
(1) Weighing 800g of waste liquid containing the catalyst (free fluorine 14.89%), slowly adding the waste liquid into 308g of lime, stirring the waste liquid by a stirrer to react for 4 hours, and decomposing and converting organic amine fluoride salt in the waste liquid containing the catalyst into organic amine and calcium fluoride;
(2) filtering the reaction liquid obtained in the step (1) to separate a solid-liquid phase, wherein a solid phase is 572g and mainly comprises a solid containing calcium fluoride, and a liquid phase is 480g and mainly comprises an organic amine solution containing a catalyst;
(3) and (3) carrying out reduced pressure rectification on the liquid phase obtained in the step (2), and collecting the liquid phase in sections to obtain 369.8g (with the purity of 99.4%) of high-purity organic amine used for producing the catalyst for the pentafluoroethane.
Comparative example 1
(1) 500g of waste liquid containing the catalyst is taken to stand in a storage tank for 24 hours, and the upper layer of 50 percent (volume ratio) of waste liquid is taken as the waste liquid to be treated, and the mass is 190 g.
(2) Adding the waste liquid to be treated obtained in the step (1) into a 500ml three-neck flask, adding 421g of 20% (mass content) NaOH aqueous solution according to reaction equivalent, and reacting for 1h at room temperature (10-30 ℃) under stirring.
(3) Filtering the reacted waste liquid obtained in the step (2), sending the filtrate to a rectification device, collecting 150-220 ℃ middle distillate through distillation to obtain 167g of liquid, and detecting the mass fraction of the tri-n-butylamine to be 89.0% through chromatography.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions or modifications made on the basis of the present invention to solve the same technical problems and achieve the same technical effects are all covered in the protection scope of the present invention.
Claims (2)
1. A method for treating catalyst-containing waste liquid in pentafluoroethane production is characterized by comprising the following steps:
(1) adding the catalyst-containing waste liquid into lime, wherein the addition amount of the lime is 1.05-1.5 times of the theoretical amount of free fluorine in the catalyst-containing waste liquid, and stirring for reacting for a certain time to decompose and convert organic amine fluoride in the catalyst-containing waste liquid into organic amine and calcium fluoride;
(2) filtering and separating a solid phase and a liquid phase from the reaction liquid obtained in the step (1), wherein the solid phase is a solid containing calcium fluoride, and the liquid phase mainly contains an organic amine solution of a catalyst;
(3) and (3) carrying out reduced pressure rectification on the liquid phase obtained in the step (2), and collecting the liquid phase in sections to obtain high-purity organic amine which is used as a catalyst for producing pentafluoroethane.
2. The method of claim 1 for treating a catalyst-containing waste liquid from the production of pentafluoroethane, characterized in that: and the mixing reaction time of the catalyst-containing waste liquid and the lime is 0.5-6 hours.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962064A (en) * | 2006-11-29 | 2007-05-16 | 山东东岳高分子材料有限公司 | Method for processing waste catalyst in production of pentafluoro ethane |
| CN101934239A (en) * | 2010-07-19 | 2011-01-05 | 浙江大学 | Method for treating waste liquor containing catalyst in pentafluoroethane prodcution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962064A (en) * | 2006-11-29 | 2007-05-16 | 山东东岳高分子材料有限公司 | Method for processing waste catalyst in production of pentafluoro ethane |
| CN101934239A (en) * | 2010-07-19 | 2011-01-05 | 浙江大学 | Method for treating waste liquor containing catalyst in pentafluoroethane prodcution |
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