CN114130349B - Tubular reactor and application thereof in treatment of fluorine-containing organic matter wastewater - Google Patents

Tubular reactor and application thereof in treatment of fluorine-containing organic matter wastewater Download PDF

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CN114130349B
CN114130349B CN202111502362.7A CN202111502362A CN114130349B CN 114130349 B CN114130349 B CN 114130349B CN 202111502362 A CN202111502362 A CN 202111502362A CN 114130349 B CN114130349 B CN 114130349B
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length
packing
straight
corrugated
tubular reactor
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CN114130349A (en
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李纯婷
杜丽君
范文彬
范杰
王建文
程兆富
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Changshu 3f Zhonghao New Chemical Materials Co ltd
Inner Mongolia 3f Wanhao Fluoro Chemical Co ltd
Shanghai Huayi Sanaifu New Material Co ltd
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Changshu 3f Zhonghao New Chemical Materials Co ltd
Inner Mongolia 3f Wanhao Fluoro Chemical Co ltd
Shanghai Huayi Sanaifu New Material Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/32—Packing elements in the form of grids or built-up elements for forming a unit or module inside the apparatus for mass or heat transfer
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B01J2219/322—Basic shape of the elements
    • B01J2219/32203—Sheets
    • B01J2219/32206—Flat sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B01J2219/322—Basic shape of the elements
    • B01J2219/32203—Sheets
    • B01J2219/3221—Corrugated sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B01J2219/322—Basic shape of the elements
    • B01J2219/32203—Sheets
    • B01J2219/32213—Plurality of essentially parallel sheets
    • 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
    • C02F2101/36—Organic compounds containing halogen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A tubular reactor and its use in the treatment of organic fluorine-containing wastewater are provided. The tubular reactor comprises a tube shell and corrugated plate packing and straight plate packing which are alternately arranged in the tube shell along the length direction of the tube shell, and the length of each section of straight plate packing is 1.5-3 times of that of each section of corrugated plate. The corrugated plate packing A and the straight plate packing B are arranged in the mode of ABABAB in the tubular reactor.

Description

Tubular reactor and application thereof in treatment of fluorine-containing organic matter wastewater
Technical Field
The present invention relates to a tubular reactor with which reaction efficiency can be improved and reaction time can be shortened. The invention also relates to a method for treating the fluorine-containing organic wastewater by adopting the tubular reactor in a continuous reaction mode, thereby greatly improving the treatment efficiency of the wastewater.
Background
The emulsion polymerization method of the fluorine-containing polymer comprises the steps of polymerization, coagulation demulsification, filtration, washing, drying and the like, wherein fluorine-containing organic matters are taken as a surfactant and do not participate in the polymerization reaction process in the polymerization process, but a large amount of waste water containing the fluorine-containing organic matters is generated in the treatment process, and the direct discharge of the waste water causes huge environmental pollution and increases the production cost. On the other hand, in the production process of some fluorine-containing fine chemicals, more fluorine-containing organic byproducts are also generated after a series of complex chemical reactions and post-treatment, and if fluorine-containing organic matters in the wastewater are recovered and purified as byproducts, the water environment is protected, and the economic benefit is increased.
At present, the common chemical reaction and separation method of fluorine-containing organic matters is a batch method, and the specific operation process is as follows:
(1) And (3) neutralization reaction: dropwise adding inorganic acid (such as sulfuric acid, hydrochloric acid and nitric acid) or inorganic base (such as sodium hydroxide and potassium hydroxide) into the concentrated fluorine-containing organic matter wastewater in a reaction kettle with a stirrer while stirring for reaction;
(2) Standing for the first time: standing the reacted fluorine-containing organic matter and wastewater in a reaction kettle for layering, wherein the standing time is usually more than 4 hours;
(3) Primary layering: discharging the layered lower fluorine-containing organic matter from the reaction kettle to obtain most of crude products;
(4) And (3) secondary standing: placing the upper-layer wastewater in the reaction kettle into another layering tank, continuously standing for 24 hours, and further separating a small amount of residual fluorine-containing organic matters;
(5) Secondary layering: and after the secondary standing interface is clear, discharging a small amount of fluorine-containing organic crude product from the lower end of the layering tank.
The intermittent method for reacting and separating fluorine-containing organic matters and wastewater has the advantages of low automation degree, more manual operations, long time period, poor safety and poor reliability. In addition, because more fluorine-containing organic matters can be remained in the upper-layer wastewater, secondary standing and layering are needed, and the steps are complicated and redundant.
The pipe reactor can change the flowing state of fluid in the pipe through the internal parts unit in the pipe, can realize the purpose of good dispersion and full mixing between different fluids, creates plug flow under the reaction condition of precise control, greatly improves the mass transfer and heat transfer in the fluid, and realizes rapid reaction. Compared with a reaction kettle, the pipeline type reactor has the characteristics of small volume, low maintenance, simple installation, easy cleaning, strong reliability and the like.
CN2460514Y discloses a mixing reaction device for treating oily sewage, which comprises a mixing pipeline and a reaction pipeline connected with the mixing pipeline at the back, wherein corrugated sheet fillers are arranged in the mixing pipeline and the reaction pipeline. Because the corrugated packing is arranged in the mixing pipe and the reaction pipe, the mixing is strong, the reaction is sufficient, and the separation of the medicament and the sewage in a short time is promoted. Although the packed corrugated packing advantageously promotes the reaction, there is room for further improvement in the reaction efficiency.
Accordingly, there is also a need in the art to provide an improved tubular reactor having improved reaction efficiency.
Disclosure of Invention
It is an object of the present invention to provide an improved tubular reactor having improved reaction efficiency.
Another object of the present invention is to provide a method for treating fluorine-containing organic wastewater by using the above tubular reactor in a continuous reaction manner, thereby greatly improving the wastewater treatment efficiency.
Accordingly, one aspect of the present invention is a tubular reactor comprising a shell and, disposed alternately within the shell along the length of the shell, corrugated sheet packings and straight sheet packings, each section of the straight sheet packings having a length 1.5 to 3 times the length of each section of the corrugated sheet.
Another aspect of the present invention relates to a continuous treatment method of fluorine-containing organic matter wastewater, comprising the steps of:
providing a reaction apparatus comprising the tubular reactor and a liquid-liquid separator fluidly connected to the tubular reactor;
adding the concentrated fluorine-containing organic wastewater and acid or alkali into the tubular reactor together for neutralization reaction;
and inputting the reaction liquid into the liquid-liquid separator to enable the fluorine-containing organic matters to be coalesced and separated.
Drawings
FIG. 1 is a schematic cross-sectional view of a tubular reactor according to an embodiment of the present invention.
Detailed Description
A. Tubular reactor
The inventors of the present invention have found that, although placing corrugated packings in a tubular reactor helps to mix reactants well and advantageously promote the reaction, the reaction efficiency of the tubular reactor can be further improved if a length of straight plate packing is placed between two sections of corrugated packing. The present invention has been completed based on this finding.
Thus, the tubular reactor of the present invention comprises a shell and corrugated sheet packing and straight sheet packing alternately disposed within the shell along the length of the shell.
In one embodiment of the present invention, the corrugated sheet packing is cylindrical and includes a hollow outer cylinder and corrugated sheets arranged in parallel in the hollow outer cylinder along the length direction, and when there are a plurality of corrugated sheets, the plurality of corrugated sheets have the same length and the same or different widths, and the lines thereof are parallel or not parallel to each other, preferably, the lines of the corrugated sheets are parallel to each other. In one example of the present invention, the corrugated sheet packing includes 1 to 6 corrugated sheets arranged in parallel.
In one embodiment of the invention, the outer diameter of the cylindrical corrugated sheet packing is matched to the inner diameter of the tubular reactor so that it can be substantially snugly placed within the tubular reactor.
In the present invention, the term "substantially closed" means that the packing cylinder can be easily placed in the tubular reactor and that the outer diameter of the cylinder is substantially free from a gap with the inner diameter of the tubular reactor.
In one embodiment of the present invention, the straight plate packing is cylindrical and comprises a hollow outer cylinder and straight plates arranged in parallel in the cylinder along the length direction, and when there are a plurality of straight plates, the plurality of straight plates have the same length and the same or different widths, and are parallel or not parallel to each other, preferably, the straight plates are parallel to each other. In one example of the invention, the straight plate filler comprises 1-6 straight plates which are placed in parallel.
In one example of the present invention, the corrugated sheet packing and the straight sheet packing have the same or different number of sheets.
In one embodiment of the invention, the corrugated sheet packing and the straight sheet packing are alternately arranged in the tube shell along the length direction of the tube shell, and the corrugated sheet packing and the straight sheet packing are basically free of phase difference.
In the present invention, the term "parallel" means that the angle between the planes of two corrugated or straight sheets is less than 5 °, preferably less than 3 °, and most preferably 0 °.
In the present invention, the term "substantially phase-retardation-free" means that the angle between the parallel straight-plate packing and the packing sheets of the parallel corrugated-plate packing is less than 5 °, preferably less than 3 °, and most preferably 0 °.
In one embodiment of the invention, the length of the cylinder of each section of the straight plate filler is 1.5 to 3 times the length of the cylinder of each section of the corrugated plate filler. Preferably 1.8 to 2.5 times, more preferably 1.9 to 2.2 times, for example 2.0 times.
In one example of the invention, if the corrugated sheet packing is denoted by a and the straight sheet packing by B, the two packings are arranged in the tube reactor in the manner of abaababab.
In one embodiment of the invention, the tubular reactor comprises a plurality of sections of corrugated packing and straight packing which are arranged at intervals, each section of corrugated packing has the same or different number of corrugated sheets, and each section of straight packing has the same or different number of straight sheets.
In one example of the invention, the tubular reactor comprises a plurality of sections of corrugated packing and straight packing which are arranged at intervals, adjacent corrugated packing sections and straight packing sections have the same number of sheets, and corresponding corrugated sheets and straight packing sections are arranged on the same horizontal plane in a zero phase difference mode.
FIG. 1 is a sectional view of a tubular reactor according to an example of the present invention. As shown in fig. 1, the tubular reactor comprises a feed port 1, baffles 2, a reaction tube shell 4, corrugated packing 3 and straight packing 5. If the corrugated packing is denoted by A and the straight packing by B, the two packings disposed along the length of the tubular reactor as shown are arranged in the manner of ABABABA, with the two packing sheets disposed without phase difference from each other.
When the tubular reactor is used, reaction raw materials enter the tubular reactor from the reactor feeding port 1, enter the reaction tube along the baffle plate 2, alternately perform oscillation mixing reaction through the corrugated packing and the straight packing, and an obtained reaction product enters the post-treatment section along the baffle plate for processing treatment.
The pipe reactor changes the flowing state of the fluorine-containing organic matter solution in the pipe through the mixing unit body, improves the mass transfer and heat transfer, and realizes the rapid acid-base neutralization reaction of the fluorine-containing organic matter salt under the condition of accurately controlling the reaction condition.
B. Continuous treatment method of fluorine-containing organic matter wastewater
The invention also relates to a continuous treatment method for the fluorine-containing organic matter wastewater by adopting the reactor. The method of the invention comprises the following steps:
i) Providing a reaction device comprising the tubular reactor and a liquid-liquid separator in fluid communication with the tubular reactor
A suitable reactor is the tubular reactor of the invention described above.
The separator for liquid-liquid separation is not particularly limited, and may be a conventional liquid-liquid separator known in the art. Non-limiting examples of separators for liquid-liquid separation are, for example, one or a combination of conventional gravity settling tanks, coalescer separators, and fiber membrane surface separators. In one example of the present invention, the liquid-liquid separator disclosed in CN210214870U is used.
In one embodiment of the invention, a coalescer is used as the liquid-liquid separator. Suitable coalescer separators are those conventional in the art, which comprise two filter elements, namely: a coalescing filter element and a separating filter element. In the treatment of the fluorine-containing organic matter wastewater, the wastewater flows into the coalescence separator, and then flows through the coalescence filter element firstly, the coalescence filter element filters solid impurities, and tiny fluorine-containing organic matter liquid beads are coalesced into larger fluorine-containing organic matter liquid beads. Most of the coalesced fluorine-containing organic matters can be separated and removed from the waste water by the dead weight and then settled in an oil collecting tank. The wastewater then flows through a separation filter element, and because the separation filter element has good hydrophile-lipophobe properties, oil content is further separated, and finally, clean wastewater flows out of the coalescence separator.
The connection of the tubular reactor of the present invention to the liquid-liquid separator may be a conventional connection known in the art.
ii) adding the concentrated fluorine-containing organic matter wastewater and acid or alkali into the tubular reactor together for neutralization reaction;
since the concentration of fluorine-containing organic matter in the wastewater is very low, a pre-concentration step is required. The suitable preconcentration method is not particularly limited, and may be a conventional concentration method known in the art. In one embodiment of the present invention, the fluorine-containing organic compound in the wastewater is concentrated by a membrane concentration method or an evaporation method.
The method comprises the step of adding the concentrated fluorine-containing organic matter wastewater and acid or alkali into the tubular reactor together for neutralization reaction. The acid to be used is not particularly limited, and may be a conventional acid known in the art, for example, an inorganic acid such as sulfuric acid, hydrochloric acid, nitric acid or a mixture thereof formed in any ratio. Also, the suitable base will not be particularly limited and may be a conventional base known in the art, for example, an alkali metal hydroxide or an alkaline earth metal hydroxide, such as sodium hydroxide, potassium hydroxide or a mixture thereof.
The amount of acid or base added to the tubular reactor will depend on the particular fluoroorganic wastewater. The amount of the particular acid or base added can be readily determined by one of ordinary skill in the art based on the principles of the neutralization reaction.
iii) And (3) conveying the reaction liquid into the liquid-liquid separator to enable the fluorine-containing organic matters to be coalesced and separated.
The method comprises the steps of continuously conveying the mixed liquid after the neutralization reaction is finished through the pipeline type reactor to a liquid-liquid separator, and carrying out coalescence and separation of fluorine-containing organic matter liquid drops through a screen in the liquid-liquid separator.
The method optionally comprises collecting the crude fluorine-containing organic matter separated by the liquid-liquid separator, and rectifying and purifying.
In one embodiment of the present invention, the continuous reaction and continuous separation method of fluorine-containing organic compounds in wastewater according to the present invention comprises:
a) Concentrating the fluorine-containing organic matter in the wastewater by a membrane concentration method or an evaporation method;
b) Inorganic acid (sulfuric acid, hydrochloric acid and nitric acid) or inorganic base (sodium hydroxide and potassium hydroxide) and concentrated fluorine-containing organic matter wastewater are conveyed into the pipeline reactor according to a proportion;
c) Continuously conveying the mixed solution after the neutralization reaction is finished by the pipeline type reactor into a liquid-liquid separator, and carrying out coalescence and separation of fluorine-containing organic matter droplets through a screen in the liquid-liquid separator;
d) And collecting the crude fluorine-containing organic matter separated by the liquid-liquid separator, and rectifying and purifying.
The method for chemical reaction and separation of fluorine-containing organic matters in the continuous wastewater treatment method has the advantages of high automation degree, short time period, no need of manual operation, high safety and good stability.
In a preferred embodiment of the present invention, the method comprises the steps of:
-concentrating the concentration of the fluoroorganic compounds in the wastewater by membrane concentration or evaporation to a concentration in the range of 1-20 wt%, preferably 2-18 wt%, more preferably 3-15 wt%, even more preferably 5-10 wt%;
conveying the concentrated fluorine-containing organic matter aqueous solution to a pipeline type reactor at a flow rate of 0.1-20 t/h, preferably 0.2-15 t/h, more preferably 0.5-10 t/h, more preferably 0.8-8 t/h, and most preferably 1-5 t/h;
simultaneously feeding a concentration of mineral acid (sulfuric acid, hydrochloric acid, nitric acid) or mineral base (sodium hydroxide, potassium hydroxide) into the tubular reactor at a flow rate in the range of 0.01 to 2t/h, preferably 0.02 to 1.5t/h, more preferably 0.05 to 1t/h, even more preferably 0.1 to 0.5t/h; so that the ratio of the fluorine-containing organic matter aqueous solution to the inorganic acid or inorganic base is in the range of 50 to 2:1, preferably 40 to 5:1, more preferably 30 to 8:1, and still more preferably 20;
-feeding the mixed liquid after the completion of the reaction in the pipe-line reactor to a liquid-liquid separator at a flow rate in the range of 0.1 to 20t/h, preferably 0.2 to 15t/h, more preferably 0.5 to 10t/h, still more preferably 0.8 to 8t/h, most preferably 1 to 5t/h, for coalescence and separation of liquid droplets;
-collecting the crude fluorine-containing organic matter after rapid separation by a liquid-liquid separator.
The present invention will be further described with reference to the following examples.
Examples
Test method
Determination of concentration of fluorine-containing organic matter in wastewater and concentration of fluorine-containing organic matter in crude product
And establishing a standard curve of the ratio of the peak area of the fluorine-containing organic matter pure substance to the peak area of another known fluorine-containing organic matter internal standard peak to the concentration of the fluorine-containing organic matter pure substance by taking the pure substance of the target fluorine-containing organic matter as a standard sample and another known fluorine-containing organic matter (perfluorodecanoic acid) as an internal standard. And (3) determining the concentration of the fluorine-containing organic matters in the wastewater and the concentration of the fluorine-containing organic matters in the crude product by an LC-MS method.
Comparative example 1
In this comparative example, the neutralization reaction and separation of sodium nonafluorovalerate were carried out in a batch process.
3t of 5wt% aqueous solution of sodium nonafluorovalerate was added to 5m 3 300kg of 98wt% concentrated sulfuric acid is added dropwise into the reaction kettle with the stirrer, and stirring is continued for 4 hours after the dropwise addition is finished. And after the reaction is finished, standing in the reaction kettle for 8 hours, collecting the crude product of the lower layer of the nonafluorovaleric acid after the reaction, putting the supernatant after the first layering into a layering tank, continuously standing, carrying out the second layering, and continuously collecting the crude product of the lower layer of the nonafluorovaleric acid after standing for 16 hours. Taking the crude product, the supernatant after the first layering and the supernatant after the second layering respectively, performing LC-MS test by taking perfluorodecanoic acid as an internal standard, and analyzing the concentration of residual nonafluorovaleric acid in the supernatant, wherein the results are shown in the following table.
Comparative example 2
In this comparative example, the neutralization reaction and separation of sodium nonafluorovalerate were carried out in a batch process.
3t of 5wt% aqueous solution of sodium nonafluorovalerate was added to 5m 3 600kg of 50wt% concentrated sulfuric acid is added dropwise into the reaction kettle, and stirring is continued for 4 hours after the dropwise addition is finished. And after the reaction is finished, standing in the reaction kettle for 8 hours, collecting the crude product of the lower layer of the nonafluorovaleric acid after the reaction, putting the supernatant after the first layering into a layering tank, continuously standing, carrying out the second layering, and continuously collecting the crude product of the lower layer of the nonafluorovaleric acid after standing for 16 hours. Taking the crude product, the supernatant after the first layering and the supernatant after the second layering respectively, performing LC-MS test by taking perfluorodecanoic acid as an internal standard, and analyzing the concentration of residual nonafluorovaleric acid in the supernatant, wherein the results are shown in the following table.
Comparative example 3
In this comparative example, the neutralization reaction and separation of sodium nonafluorovalerate were carried out in a batch process.
3t of 10wt% aqueous solution of sodium nonafluorovalerate was added to 5m 3 600kg of 98wt% concentrated sulfuric acid is added dropwise into the reaction kettle, and after the dropwise addition is finished, stirring is continued for 4 hours. And after the reaction is finished, standing in the reaction kettle for 8 hours, collecting the crude product of the lower layer of the nonafluorovaleric acid after the reaction, putting the supernatant after the first layering into a layering tank, continuously standing, carrying out the second layering, and continuously collecting the crude product of the lower layer of the nonafluorovaleric acid after standing for 16 hours. Taking the crude product, the supernatant after the first layering and the supernatant after the second layering respectively, performing LC-MS test by taking perfluorodecanoic acid as an internal standard, and analyzing the concentration of residual nonafluorovaleric acid in the supernatant, wherein the results are shown in the following table.
Comparative example 4
In this comparative example, CF was performed as a batch process 3 -CF 2 -O-CF(CF 3 )-CF 2 -O-CF(CF 3 ) -COONa neutralization and separation.
3t of CF with a concentration of 5wt% 3 -CF 2 -O-CF(CF 3 )-CF 2 The aqueous solution of-O-CF (CF 3) -COONa was added to 5m 3 300kg of 98wt% concentrated sulfuric acid is added dropwise into the reaction kettle, and then the mixture is added dropwiseAfter completion, stirring was continued for 4h. After the reaction is finished, standing for 8 hours in the reaction kettle, and collecting the CF after the lower layer reaction 3 -CF 2 -O-CF(CF 3 )-CF 2 -O-CF(CF 3 ) Putting the coarse-COOH, supernatant after the first layering into a layering tank, continuously standing for the second layering, and continuously collecting the lower CF after standing for 16h 3 -CF 2 -O-CF(CF 3 )-CF 2 -O-CF(CF 3 ) -crude product of-COOH. Respectively taking the crude product, supernatant after the first layering and the second layering, performing LC-MS test by taking perfluorodecanoic acid as an internal standard, and analyzing the residual CF in the supernatant 3 -CF 2 -O-CF(CF 3 )-CF 2 -O-CF(CF 3 ) -COOH concentration, results are given in the table below.
Comparative example 5
In this comparative example, CF was performed as a batch process 3 -(CF 2 ) 5 -CH 2 CH 2 -SO 3 Reaction and separation of Na.
3t of CF with a concentration of 5wt% 3 -(CF 2 ) 5 -CH 2 CH 2 -SO 3 Adding Na aqueous solution to 5m 3 300kg of 98wt% concentrated sulfuric acid is added dropwise into the reaction kettle, and stirring is continued for 4 hours after the dropwise addition is finished. And after the reaction is finished, standing in the reaction kettle for 8 hours, collecting the crude product after the lower layer reaction, putting the supernatant after the first layering into a layering tank, continuously standing, carrying out the second layering, and continuously collecting the crude product at the lower layer after standing for 16 hours. Respectively taking the crude product, supernatant after the first layering and the second layering, performing LC-MS test by taking perfluorodecanoic acid as an internal standard, and analyzing CF 3 -(CF 2 ) 5 -CH 2 CH 2 -SO 3 The concentration of H, the results are shown in the following table.
Example 1
In this example, the neutralization reaction and separation of sodium nonafluorovalerate were carried out in a continuous process using a tubular reactor as shown in FIG. 1.
3t of a sodium nonafluorovalerate wastewater solution with the concentration of 5wt% is conveyed into a pipeline reactor through a pump at the flow rate of 1t/h, 300kg of sulfuric acid with the concentration of 98wt% is simultaneously conveyed into the pipeline reactor at the flow rate of 0.1t/h, then the sulfuric acid directly enters a liquid-liquid separator at the flow rate of 1.1t/h to carry out rapid separation of an organic phase and a water phase containing a crude product of the nonafluorovalerate, a supernatant flows out from an outlet at the upper end of the liquid-liquid separator, and a lower crude product is collected from the lower end of the liquid-liquid separator. Taking the supernatant and the lower crude product respectively, performing LC-MS test by using perfluorodecanoic acid as an internal standard, and analyzing the concentration of the nonafluorovaleric acid, wherein the results are shown in the following table.
Example 2
In this example, the neutralization reaction and separation of sodium nonafluorovalerate were carried out in a continuous process using a tubular reactor as shown in FIG. 1.
Conveying 3t of sodium nonafluorovalerate wastewater solution with the concentration of 5wt% into a pipeline reactor at the flow rate of 1t/h through a pump, simultaneously conveying 600kg of sulfuric acid with the concentration of 50wt% into the pipeline reactor at the flow rate of 0.2t/h, then directly feeding into a liquid-liquid separator at the flow rate of 1.2t/h for rapid separation of an organic phase and a water phase containing a crude product of nonafluorovalerate, allowing a supernatant to flow out of an outlet at the upper end of the liquid-liquid separator, and collecting a lower crude product from the lower end of the liquid-liquid separator. Taking the supernatant and the lower crude product respectively, performing LC-MS test by using perfluorodecanoic acid as an internal standard, and analyzing the concentration of the nonafluorovaleric acid, wherein the results are shown in the following table.
Example 3
In this example, the neutralization reaction and separation of sodium nonafluorovalerate were carried out in a continuous process using a tubular reactor as shown in FIG. 1.
Conveying 3t of a sodium nonafluorovalerate aqueous solution with the concentration of 10wt% into a pipeline reactor at the flow rate of 1t/h through a pump, simultaneously conveying 600kg of sulfuric acid with the concentration of 98wt% into the pipeline reactor at the flow rate of 0.2t/h, then directly feeding into a liquid-liquid separator at the flow rate of 1.2t/h for rapid separation of an organic phase and a water phase containing a crude product of nonafluorovalerate, allowing a supernatant to flow out of an outlet at the upper end of the liquid-liquid separator, and collecting a lower crude product from the lower end of the liquid-liquid separator. Taking the supernatant and the lower crude product respectively, performing LC-MS test by using perfluorodecanoic acid as an internal standard, and analyzing the concentration of the nonafluorovaleric acid, wherein the results are shown in the following table.
Example 4
In this example, the neutralization reaction and separation of sodium nonafluorovalerate were carried out in a continuous process using a tubular reactor as shown in FIG. 1.
Conveying 3t of 5wt% sodium nonafluorovalerate aqueous solution into a pipeline reactor at a flow rate of 1t/h, simultaneously conveying 600kg of 98wt% sulfuric acid into the pipeline reactor at a flow rate of 0.2t/h, directly feeding the sulfuric acid into a liquid-liquid separator at a flow rate of 1.2t/h to rapidly separate an organic phase and a water phase containing a crude product of the nonafluorovalerate, allowing a supernatant to flow out from an outlet at the upper end of the liquid-liquid separator, and collecting a lower crude product from the lower end of the liquid-liquid separator. Taking the supernatant and the lower crude product respectively, performing LC-MS test by using perfluorodecanoic acid as an internal standard, and analyzing the concentration of the nonafluorovaleric acid, wherein the results are shown in the following table.
Example 5
In this example, CF was carried out as a continuous process using the tubular reactor shown in FIG. 1 3 -(CF 2 ) 5 -CH 2 CH 2 -SO 3 And (4) carrying out neutralization reaction and separation on Na.
3t of CF with a concentration of 5wt% 3 -(CF 2 ) 5 -CH 2 CH 2 -SO 3 The Na aqueous solution was fed into a pipe reactor at a flow rate of 1t/h, 300kg of 98wt% sulfuric acid was simultaneously fed into the pipe reactor at a flow rate of 0.1t/h, and then directly fed into a liquid-liquid separator at a flow rate of 1.1t/h to effect CF-containing 3 -(CF 2 ) 5 -CH 2 CH 2 -SO 3 And (3) quickly separating an organic phase and a water phase of the crude product H, wherein the supernatant flows out from an outlet at the upper end of the liquid-liquid separator, and the crude product at the lower layer is collected from the lower end of the liquid-liquid separator. Respectively taking supernatant and lower crude product, performing LC-MS test with perfluorodecanoic acid as internal standard, and analyzing CF 3 -(CF 2 ) 5 -CH 2 CH 2 -SO 3 H concentration, results are given in the table below.
Example 6
In this example, CF was carried out as a continuous process using the tubular reactor shown in FIG. 1 3 -CF 2 -O-CF(CF 3 )-CF 2 Neutralization reaction and separation of-O-CF (CF 3) -COONa.
3t of CF at a concentration of 5wt% 3 -CF 2 -O-CF(CF 3 )-CF 2 The aqueous solution of-O-CF (CF 3) -COONa was fed at a flow rate of 1t/h to the pipe reactor, 300kg of 98wt% sulfuric acid was simultaneously fed at a flow rate of 0.1t/h to the pipe reactor, and then directly fed at a flow rate of 1.1t/h to the liquid-liquid separator for CF-containing treatment 3 -CF 2 -O-CF(CF 3 )-CF 2 And (3) quickly separating an organic phase and an aqueous phase of the crude product of the-O-CF (CF 3) -COOH, wherein a supernatant liquid flows out from an upper end outlet of the liquid-liquid separator, and a lower crude product is collected from a lower end of the liquid-liquid separator. Respectively taking supernatant and lower crude product, performing LC-MS test with perfluorodecanoic acid as internal standard, and analyzing CF 3 -CF 2 -O-CF(CF 3 )-CF 2 The concentration of-O-CF (CF 3) -COOH, the results are given in the following table.
Comparative example 6
In this comparative example, CF was carried out in a continuous process using a tubular reactor similar to that of FIG. 1 3 -CF 2 -O-CF(CF 3 )-CF 2 Neutralization reaction and separation of-O-CF (CF 3) -COONa. But the tubular reactor used is only provided with corrugated sheet packing.
3t of CF with a concentration of 5wt% 3 -CF 2 -O-CF(CF 3 )-CF 2 The aqueous solution of-O-CF (CF 3) -COONa was fed into the pipe reactor at a flow rate of 1t/h, 300kg of 98wt% sulfuric acid was simultaneously fed into the pipe reactor at a flow rate of 0.1t/h, and then directly fed into the liquid-liquid separator at a flow rate of 1.1t/h to conduct CF-containing reaction 3 -CF 2 -O-CF(CF 3 )-CF 2 And (3) quickly separating an organic phase and an aqueous phase of the crude product of the-O-CF (CF 3) -COOH, wherein a supernatant liquid flows out from an upper end outlet of the liquid-liquid separator, and a lower crude product is collected from a lower end of the liquid-liquid separator. Respectively taking supernatant and lower crude product, performing LC-MS test with perfluorodecanoic acid as internal standard, and analyzing CF 3 -CF 2 -O-CF(CF 3 )-CF 2 The concentration of-O-CF (CF 3) -COOH, the results are given in the following table.
TABLE 1 Experimental data for examples and comparative examples
Figure BDA0003402256350000111
The above are only a few specific examples of the present invention, but the technical features of the present invention are not limited thereto. On the basis of the present invention, in order to solve the substantially same technical problems, the fluorine-containing organic substance with similar structure or the fluorine-containing organic substance in other water tank systems are used for continuous reaction and separation to achieve substantially the same technical effects, and simple changes, equivalent substitutions or modifications and the like are all covered in the protection scope of the present invention.

Claims (5)

1. A continuous treatment method of wastewater containing organic fluorine comprises the following steps:
providing a reaction device, wherein the reaction device comprises a tubular reactor and a liquid-liquid separator which is in fluid connection with the tubular reactor, the tubular reactor comprises a tube shell and corrugated plate packing and straight plate packing which are alternately arranged in the tube shell along the length direction of the tube shell, and the length of each section of straight plate packing is 1.5-3 times of that of each section of corrugated plate;
adding the concentrated organic fluorine-containing wastewater and acid or alkali into the tubular reactor together for neutralization reaction;
inputting the reaction liquid into the liquid-liquid separator to enable the fluorine-containing organic matters to be coalesced and separated;
the corrugated sheet packing is cylindrical and comprises a hollow outer cylinder and corrugated sheets arranged in the hollow outer cylinder in parallel along the length direction;
the straight plate filler is cylindrical and comprises a hollow outer cylinder and straight plates arranged in the cylinder in parallel along the length direction;
the corrugated sheet packing comprises a plurality of corrugated sheets, the plurality of corrugated sheets have the same length and the same or different widths, and the grains of the plurality of corrugated sheets are parallel or not parallel;
the straight plate filler comprises a plurality of straight plates, and the plurality of straight plates have the same length and the same or different widths and are parallel or not parallel to each other; the corrugated sheet packing and the straight sheet packing are alternately arranged in the pipe shell along the length direction of the pipe shell, and the phase difference between the corrugated sheet packing and the straight sheet packing is less than 5 o 。
2. The method of claim 1, wherein the length of the cylinder of each length of the straight packing is 1.8 to 2.5 times the length of the cylinder of each length of the corrugated sheets.
3. The method of claim 1, wherein the length of the cylinder of each length of the straight packing is 1.9 to 2.2 times the length of the cylinder of each length of the corrugated sheets.
4. The method of claim 1, wherein the length of the cylinder of each length of straight packing is 2.0 times the length of the cylinder of each length of corrugated packing.
5. The tubular reactor of claim 1 wherein the corrugated plate packing a and straight plate packing B are arranged in an abaababa fashion in the tubular reactor.
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US6280819B1 (en) * 1999-06-25 2001-08-28 The Boc Group, Inc. Structured packing
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