CN108101735B - Method for catalyzing degradation of perfluorocarboxylic acid compound and simultaneously preparing short-chain fluorine-containing olefin - Google Patents
Method for catalyzing degradation of perfluorocarboxylic acid compound and simultaneously preparing short-chain fluorine-containing olefin Download PDFInfo
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Abstract
The invention discloses a method for catalyzing degradation of a perfluorocarboxylic acid compound and simultaneously preparing short-chain fluorine-containing olefin, belonging to the technical field of solid waste treatment and preparation of fluoroolefin organic chemical raw materials. The method comprises the steps of mixing a perfluorocarboxylic acid compound and a solid acid catalyst at normal temperature and normal pressure, placing the mixture in a ball milling reactor, weakening a terminal acid group and a C-F bond of the perfluorocarboxylic acid compound by virtue of a hydroxyl group and a Lewis acid center on the surface of the solid acid catalyst respectively, continuously updating an active center on the surface of the catalyst by utilizing the mechanical ball milling effect, realizing controllable deacidification and defluorination conversion degradation of the perfluorocarboxylic acid compound, and preparing short-chain fluorine-containing olefin, wherein the degradation conversion rate of the perfluorocarboxylic acid is more than 90%, and the selectivity of the product is more than 80%.
Description
Technical Field
The invention belongs to the technical field of high-toxicity organic solid waste treatment and fluoroolefin organic chemical raw material preparation, and particularly relates to a method for catalyzing degradation of a perfluorocarboxylic acid compound and simultaneously preparing short-chain fluorine-containing olefin.
Background
Perfluorooctanoic acid (PFOA) is a linear compound with a C8 type perfluoro compound structure, and is widely applied to the fields of textile clothing, surfactants, fluorine-containing polymers, surface coatings and the like. However, toxicology studies have shown that PFOA has potential long-term stability, bioaccumulation and toxicity, and was listed as Persistent Organic Pollutants (POPs) in 2015. Therefore, techniques for reducing and eliminating PFOA are receiving much attention.
PFOA concentration in industrial wastewater is high and difficult to biodegrade. To treat high concentrations of PFOA, a method originally proposed was "reclamation". Methods developed include direct acidification, metal salt precipitation, anion exchange resin and vacuum concentration. DuPont proposes to use anion exchange resin to adsorb perfluorooctanoate anion, and then obtain high-purity PFOA product through desorption, rectification and purification (Chinese patent: CN 101454353). The Shandong Yue uses metal salt as precipitant and flocculant to treat perfluoro ammonium caprylate waste water, so that the concentration of perfluoro ammonium caprylate in the waste water is lower than 10ppm, and PFOA with purity of more than 95% is recovered (Chinese patent: CN 1935771). The morning light chemical research institute adopts vacuum rectification concentration to obtain a high-concentration ammonium perfluorooctanoate solution, and then acidification and rectification are carried out to obtain a PFOA product with the purity of more than 83% (Chinese patent: CN 1465612). According to the stipulation of the 'stockholm convention', the use of PFOA is exempted in early years, and the recovery technology can reduce the discharge of PFOA and reduce the production cost through resource recycling. However, in 2015, PFOA was incorporated into the national institutes of stockholm convention, promising to gradually and fully limit the use of this class of materials. The PFOA recovered by the method is forbidden to be used and becomes 'recovery type' PFOA solid waste. Moreover, the currently-stocked PFOA products are also limited in use and become 'product type' PFOA solid wastes.
Since organofluorine is an important and expensive compound, converting rejected high-concentration PFOA solid waste into other high-value and non-limiting organofluorine is a feasible resource disposal strategy. From the organic chemical reaction path, if the degree of deacidification and partial defluorination of PFOA molecules can be regulated, the PFOA molecules can be converted into short-chain perfluoroolefin. Short-chain perfluoroolefins are perfluoroolefins with a carbon chain length of less than 9, which are easily polymerized to form ionic oligomers or undergo addition reactions with nucleophiles, and are commonly used as precursors for the preparation of fluoropolymers and as intermediates for fire extinguishing and propellant agents. However, the preparation of short-chain perfluoroolefin by using PFOA solid waste has not attracted attention.
The basic working principle of the mechanochemical method is that grinding aid is activated by mechanical collision and local high temperature to react with halogenated organic pollutants to realize dehalogenation degradation, the controllable conversion of PFOA into short-chain perfluoroolefin mainly comprises two reaction paths, wherein one reaction path is 'removal of carboxyl at the tail end of a molecule', the other reaction path is 'fracture of C-F bond of skeleton carbon', and aiming at decarboxylation, according to the theory of organic chemical reaction, carboxylic acid substituted by halogen on α -carbon is easy to pass through negative ionSub-mechanism decarboxylation of the carboxylate to form a halogenated hydrocarbon with one less carbon, whichever is favorable for RCOO-And R-The formed factors are favorable for the decarboxylation reaction; the ionization of carboxylic acid can be promoted by adding alkaline substances and heating, so that the decarboxylation reaction can be accelerated; however, too high a temperature may break the carbon chain and reduce the decarboxylation efficiency (chemical and biological engineering 2008, 25 (4): 1-6). In the aspect of C-F bond cleavage, the reaction for gas phase catalysis of HF removal from fluorine-containing alkanes generally proceeds by a unimolecular elimination mechanism (E1), and the rate-dependent step is the formation of carbenium ions, i.e., C-F bond heterolysis (chem. Commun.2016,52, 1505-1508). Based on the strong electronegativity of fluorine atoms, the activated heterolytic cleavage of C-F bonds can be accelerated by further strengthening the interaction between F atoms and Lewis acid centers on the surface of the catalyst. The temperature is increased to expose more Lewis acid sites to the catalyst. Based on the analysis, the invention provides a novel method for recycling the perfluorocarboxylic acid solid waste by using solid acid rich in surface hydroxyl and Lewis acid sites as a grinding agent and utilizing a mechanochemical effect. In addition, the closeness and lack of solvation of the mechanochemical disposal system facilitates the collection of short chain fluoroolefin products.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing fluorine-containing olefin by treating a perfluorocarboxylic acid compound by using a solid acid catalyst as a grinding agent and performing mechanochemical treatment, which sequentially comprises the following steps:
the method comprises the following steps: mixing a perfluorocarboxylic acid compound and a solid acid catalyst to serve as a reaction material, adding the reaction material into a ball milling tank, and adding grinding balls into the ball milling tank;
step two: fixing a ball milling tank after charging on a ball mill, and starting a mechanical ball milling reaction at normal temperature and normal pressure, wherein the revolution speed of the ball milling is 250-350 rpm, and the ball milling is autorotation: and (3) setting the revolution speed to be 2:1, ball milling time to be 30-200 min, changing ball milling revolution direction every 10-30 min, stopping ball milling after ball milling reaction is finished, and collecting a product by adopting an organic solvent.
Preferably: ball milling time is 120min, and products are collected by adopting acetone.
Further, the perfluorocarboxylic acid compound is perfluorocarboxylic acid or perfluorocarboxylic acid salt;
further, the perfluorocarboxylic acid is perfluorofatty acid; further, the perfluorocarboxylic acid is a perfluorinated straight chain fatty acid; still further, the perfluorocarboxylic acid is a linear saturated perfluorofatty acid.
The perfluorocarboxylic acid salt is a perfluorofatty acid salt; further, the perfluorocarboxylic acid salt is a linear perfluoroaliphatic acid salt; still further, the perfluorocarboxylic acid salt is a linear perfluorinated saturated fatty acid salt.
Further, the C number of the perfluorocarboxylic acid and the perfluorocarboxylic acid salt is 3-9, preferably C3-C9 linear perfluorosaturated fatty acid and C3-C9 linear perfluorosaturated fatty acid salt.
Further, the perfluorocarboxylic acid is perfluorooctanoic acid or perfluoroheptanoic acid.
Further, the solid acid catalyst is any one or two or more of oxides such as iron oxide, nickel oxide, and aluminum oxide, further, the solid acid catalyst is alpha-alumina, gamma-alumina, or theta-alumina, and most preferably gamma-alumina.
Furthermore, the mass of the perfluorocarboxylic acid compound accounts for 2-20%, preferably 5-10% of the total mass of the reaction materials.
Further, the ratio of the mass of the grinding balls to the total mass of the reaction materials is 10: 1-100: 1, preferably, the ratio of the grinding balls to the total mass of the reaction materials is 50: 1-100: 1, and more preferably, the ratio of the grinding balls to the total mass of the reaction materials is 55-60: 1.
Further, the product is short-chain fluorine-containing olefin, and the C number of the short-chain fluorine-containing olefin is 1 less than that of the raw material.
Further, the short-chain fluorine-containing olefin is linear fluorine-containing olefin with unsaturated terminal group.
The diameter range of the grinding balls is 5-20mm, the grinding balls comprise large grinding balls and small grinding balls, the diameter ratio of the large grinding balls to the small grinding balls is 2: 1-5: 1, and the total mass ratio of the large grinding balls to the small grinding balls is 5: 1-1: 2.
The grinding ball is preferably a stainless steel grinding ball.
The invention utilizes mechanical force to activate and regulate the relative activity and quantity of hydroxyl on the surface of the solid acid catalyst and Lewis acid center to realize the controllable deacidification and defluorination of perfluorocarboxylic acid substances, thereby preparing the fluorine-containing olefin.
Compared with the prior art, the invention has the following advantages:
1. according to the molecular structure characteristics of perfluorocarboxylic acid, mechanochemical, solid acid catalytic chemistry and organic synthetic chemistry are combined, the chemical characteristics of the surface of the solid acid are regulated and controlled by utilizing a mechanical force effect, a micro-interface reaction environment suitable for deacidification and controllable defluorination is created, the perfluorocarboxylic acid compound is converted into short-chain fluorine-containing olefin, and the recycling of solid wastes is realized.
2. When the perfluorocarboxylic acid compound is treated by mechanical ball milling, the short-chain fluorine-containing olefin with higher economic value is obtained, wherein the conversion rate of the perfluorocarboxylic acid compound is more than 90%, the selectivity of the product is more than 80%, and particularly when the PFOA organic solid waste is treated by mechanical ball milling, the short-chain fluorine-containing olefin with higher economic value is obtained, wherein the degradation rate of the PFOA is more than 97%, the selectivity of the product is more than 80%, and the selectivity can reach 92%; when the perfluoroheptanoic acid is treated, the degradation rate of the perfluoroheptanoic acid can reach 98 percent, and the circular economy concept is met.
3. The catalyst selected by the method is cheap industrial products such as iron oxide, nickel oxide and/or alumina and the like, so that the cost is low; the mechanochemical reaction condition is mild, and the reaction process does not need to use an organic solvent, so that the environment is protected.
Drawings
FIG. 1 is a graph showing the relationship between the ball milling time and the residual rate of perfluorooctanoic acid in the process of mechanochemical catalysis of perfluorooctanoic acid with alumina in example 1.
FIG. 2 is a graph of the infrared absorption spectrum of a fluoroolefin product prepared by mechanochemical catalysis of perfluorooctanoic acid with alumina in test 1 of example 2.
Figure 3 is a high resolution mass spectrum of the fluoroolefin product from test 2 of example 2 using alumina mechanochemical catalysis for the conversion degradation of perfluorooctanoic acid.
FIG. 4 is a nuclear magnetic resonance spectrum of a fluoroolefin product from test 3 of example 2 using alumina mechanochemical catalysis for the conversion degradation of perfluorooctanoic acid.
FIG. 5 is a graph of ball milling time versus product yield and selectivity for the mechanochemical catalysis of perfluoroheptanoic acid conversion using alumina of example 3.
Detailed description of the invention
In order to make the objects, technical solutions and advantages of the present invention more apparent to those skilled in the art, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1A method for catalyzing the degradation of perfluorocarboxylic acid compounds and simultaneously producing short-chain fluoroolefins
The method comprises the following steps: mixing 0.3g of perfluorooctanoic acid solid and 3.9g of alpha-alumina in a mortar, and transferring the mixture to a dry stainless steel ball milling tank; then 10 stainless steel grinding balls (the mass ratio of the big balls to the small balls is about 40: 9) with the diameter of 10mm and 18 balls with the diameter of 5mm are added into the tank, the total weight of the grinding balls is 240g, the volume of the ball-milling tank is 250mL, the depth of the interior of the tank body is 70mm, the inner diameter of the tank opening is 77mm, and the ball-milling tank and the ball-milling cover are connected by a sealing ring.
Step two: fixing a ball milling tank on a ball mill, setting revolution and rotation speeds of the ball milling tank to be 350rpm and 700rpm respectively, carrying out ball milling reaction at normal temperature and normal pressure, changing the revolution direction of the ball milling once every 15min, taking out the ball milling tank after the ball milling reaction is carried out for 15min, 30min, 60 min, 90 min and 120min respectively, and collecting solid powder in the tank body.
Step three: accurately weighing 0.02g of solid powder reacted for a certain time in the second step, extracting for 10min by an ultrasonic-assisted method by using absolute ethyl alcohol as an extracting agent, centrifuging for 10min at 14000rpm to obtain supernatant, repeating the extraction process for 2 times on the centrifuged solid, combining the obtained extract, filtering by a 0.22 mu m filter membrane, and measuring by using a high performance liquid chromatography-electro-spray detector, wherein the obtained result is shown in figure 1. Fig. 1 shows that in the ball milling reaction process, the perfluorooctanoic acid is continuously degraded, and after the reaction is carried out for 120min, the degradation rate of the perfluorooctanoic acid is as high as 97.8%.
Example 2A method for catalyzing degradation of a perfluorocarboxylic acid compound and simultaneously preparing a short-chain fluoroolefin
Steps one and two of example 1 were repeated except that: and in the second step, the ball milling reaction time is set to be 120min, and the ball milling tank is taken out after the reaction is finished, and the following tests are respectively carried out.
Test 1: the gas in the ball mill tank was directly collected by the gas sampling bag, and the infrared absorption spectrum was measured, and the result is shown in fig. 2. As can be seen, the gas product is at 3000cm-1，1735cm-1And 1100 to 1300cm-1There are strong absorption peaks in the range, assigned to the vibrational absorption of the C-H, C ═ C and C-F bonds, respectively, indicating that the gaseous product is a vinylidene fluoride.
And (3) testing 2: after the ball milling reaction is stopped, acetone is used as absorption liquid to be injected into a ball milling tank, gas-phase products and products adsorbed on the surface of a catalyst are collected, then, the centrifugal separation is carried out to obtain supernatant, and the accurate molecular weight of the supernatant is detected by using an ultrahigh resolution quadrupole rod series Fourier transform mass spectrometer. As can be seen from FIG. 3, the charge-to-mass ratio of the major component of the gaseous product was 330.93884, which is consistent with the molecular weight of 1-H-1-perfluoroheptene.
And (3) testing: the product was collected by the method in test 2 and analyzed for structure by nuclear magnetic resonance fluorine spectroscopy. As shown in FIG. 4, the product shows a series of resonance peaks at corresponding chemical shifts of 1-H-1-perfluoroheptene, which is consistent with the structure of 1-H-1-perfluoroheptene. Combining the results of the infrared absorption spectrum and the high-resolution mass spectrum, the gas product is determined to be 1-H-1-perfluoroheptene.
Example 3A method for catalyzing degradation of a perfluorocarboxylic acid compound and simultaneously preparing a short-chain fluoroolefin
Steps one and two of example 1 were repeated except that: adding 65mg of fluorobenzene as an internal standard while adding the perfluorooctanoic acid and the aluminum oxide in the first step, respectively carrying out ball milling reaction for 15min, 30min, 60 min, 90 min and 120min in the second step, taking out a ball milling tank, and collecting a gas product in the tank body.
The product in the tank was collected as in test 2 of example 2 and the yield of 1-H-1-perfluoroheptene as a gaseous product was quantitatively analyzed by hot purge-FID gas chromatography. The yield and selectivity of the product were calculated according to equations (1) and (2), respectively. As shown in FIG. 5, the yield of 1-H-1-perfluoroheptene gradually increases with the extension of the ball milling reaction time, after 120min of reaction, the yield reaches 88%, and the selectivity of the perfluorooctanoic acid for defluorination to generate 1-H-1-perfluoroheptene reaches 90%.
Example 4A method for catalyzing the degradation of perfluorocarboxylic acid compounds and simultaneously preparing short-chain fluoroolefins
The procedure of example 1 was repeated except that the alumina used in the procedure of example 1 was gamma-type, and the test was carried out in the same manner as in example 2 and example 3. With the prolonging of the ball milling reaction time, the residue of the perfluorooctanoic acid is gradually reduced, and the gas product obtained by detection is 1-H-1-perfluoroheptene; after the reaction is carried out for 120min, the degradation rate of the perfluoro caprylic acid reaches 98%, the yield of the 1-H-1-perfluoro heptene reaches 90%, and the selectivity of the perfluoro caprylic acid for defluorination to generate the 1-H-1-perfluoro heptene reaches 92%.
Example 5A method for catalyzing the degradation of a perfluorocarboxylic acid compound and simultaneously producing a short-chain fluoroolefin
The procedure of example 1 was repeated to carry out the examination in the same manner as in example 2 and example 3 except that the alumina used in the procedure of the procedure one was of the theta type. With the prolonging of the ball milling reaction time, the residue of the perfluorooctanoic acid is gradually reduced, and the gas product obtained by detection is 1-H-1-perfluoroheptene; after the reaction is carried out for 120min, the degradation rate of the perfluoro caprylic acid reaches 93 percent, the yield of the 1-H-1-perfluoro heptene reaches 75 percent, and the selectivity of the perfluoro caprylic acid for generating the 1-H-1-perfluoro heptene by defluorination reaches 81 percent.
Example 6A method for catalyzing the degradation of a perfluorocarboxylic acid compound and simultaneously producing a short-chain fluoroolefin
Steps one to three in example 1 were repeated except that: the materials used in step one were 0.25g perfluoroheptanoic acid and 3.8g alpha-alumina.
According to the detection method in the embodiments 2 and 3, after the ball milling reaction is carried out for 120min, the degradation rate of the perfluoroheptanoic acid is higher than 98%, the generated product is 1-H-1-perfluorohexene, the yield reaches 85%, and the selectivity of the perfluoroheptanoic acid for defluorination to generate 1-H-1-perfluorohexene reaches 87%, which shows that the treatment method of the invention can efficiently degrade the perfluoroheptanoic acid.
Thus, the above results demonstrate that linear perfluorocarboxylic acid or perfluorocarboxylate materials having a total carbon chain length n can be catalytically defluorinated under the mechanochemical action of alumina, the product being a linear fluoroalkene unsaturated at the end group having a carbon chain length n-1.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (4)
1. A method for catalyzing degradation of perfluorocarboxylic acid compounds and simultaneously producing short-chain fluoroolefins, the method comprising the steps of:
the method comprises the following steps: mixing a perfluorocarboxylic acid compound and a solid acid catalyst to serve as a reaction material, adding the reaction material into a ball milling tank, and adding grinding balls into the ball milling tank;
step two: fixing the ball milling tank after charging on a ball mill, and starting mechanical ball milling reaction under normal temperature and normal pressure, wherein the revolution speed of ball milling is 250-350 rpm, the ball milling time is 30-200 min, changing the revolution direction of ball milling every 10-30 min, stopping ball milling after the ball milling reaction is finished, and collecting a product by adopting an organic solvent;
the solid acid catalyst is alpha-alumina, gamma-alumina or theta-alumina;
the perfluorocarboxylic acid compound is a perfluorinated linear saturated fatty acid of C3-C9 and a perfluorinated linear saturated fatty acid salt of C3-C9;
the product is short-chain fluorine-containing olefin, and the C number of the product is less than 1 of that of the raw material.
2. The method according to claim 1, wherein the mass of the perfluorocarboxylic acid compound is 2-20% of the total mass of the reaction materials, and the ratio of the mass of the grinding ball to the total mass of the reaction materials is 10: 1-100: 1.
3. The method of claim 2, wherein the perfluorocarboxylic acid compound is perfluorooctanoic acid or perfluoroheptanoic acid.
4. The method of claim 3, wherein the short chain fluoroolefin is a linear fluoroolefin having terminal unsaturation.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB861271A (en) * | 1958-05-12 | 1961-02-15 | Du Pont | Improvements in the preparation of perfluoro-olefines |
| CN1398840A (en) * | 2001-07-23 | 2003-02-26 | "皮姆投资"科学生产联合股份公司 | Prepn of aliphatic fluoride |
| CN102824719A (en) * | 2012-09-03 | 2012-12-19 | 清华大学 | Mechanochemistry-based method for treating perfluorinated and polyfluorinated compound solid waste |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB861271A (en) * | 1958-05-12 | 1961-02-15 | Du Pont | Improvements in the preparation of perfluoro-olefines |
| CN1398840A (en) * | 2001-07-23 | 2003-02-26 | "皮姆投资"科学生产联合股份公司 | Prepn of aliphatic fluoride |
| CN102824719A (en) * | 2012-09-03 | 2012-12-19 | 清华大学 | Mechanochemistry-based method for treating perfluorinated and polyfluorinated compound solid waste |
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