CN113061202B - Defluorination method of high-fluorine-content petroleum resin - Google Patents
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Abstract
The invention relates to a defluorination method of high fluorine-containing petroleum resin, which comprises the steps of defluorination treatment of dissolved petroleum resin under the action of medium-pressure steam and defluorination agent, then water washing by adding demulsifier, separating out resin liquid containing fluorine water phase, then entering a molecular sieve dehydration tower, and obtaining the defluorinated petroleum resin after dehydration. The petroleum resin defluorination method provided by the invention has the defluorination rate of more than 73%, can effectively delay the fluorosis of the resin hydrogenation catalyst, and is beneficial to the long-period operation of a petroleum resin hydrogenation device.
Description
Technical Field
The invention belongs to the field of petroleum resin defluorination, and particularly relates to a defluorination method of high-fluorine petroleum resin.
Background
The petroleum resin is a thermoplastic resin obtained by heating polymerization or catalytic polymerization reaction of C5 and C9 fractions which are byproducts in the production of industrial ethylene serving as raw materials, and is widely applied to the industries of adhesives, road finishes, printing inks, rubbers and the like due to strong tackifying power and good compatibility with other oils and resins. The C5 and C9 fractions usually contain impurities such as sulfur, nitrogen, olefin and the like, and BF3 catalyst is used in the catalytic polymerization of petroleum resin, so that the petroleum resin contains high fluorine, and the impurities all cause high chromaticity and poor photo-thermal stability of the petroleum resin, so that the application of the petroleum resin is limited to a certain extent. At present, the hydrogenation modification of petroleum resin is the most common and effective method, the added value of the hydrogenated petroleum resin is improved, and the economic benefit is obvious.
At present, the resin hydrogenation in China mainly adopts a fixed bed hydrogenation process, and because petroleum resin contains a certain amount of sulfur and nitrogen impurities, particularly the petroleum resin catalytically polymerized by BF3 contains higher fluorine, the fluorine content can reach 150-400ppm according to the difference of the resin polymerization process, and the harmful substances have poisoning effects on both noble metal catalysts and nickel catalysts. At present, impurities such as sulfur, nitrogen and the like in resin raw materials are generally removed by adopting a diatomite adsorption or hydrogenation pretreatment mode in the hydrogenation of petroleum resin, so that the subsequent inactivation of a main hydrogenation catalyst due to poisoning is protected, but the treatment of fluorine in the resin is less reported at present.
Patent CN102746458A describes a preparation method of hydrogenated C9 resin, which adopts two-stage hydrogenation process, wherein the first-stage hydrogenation catalyst uses macroporous zeolite or diatom as carrier, and cobalt and molybdenum as active ingredients, wherein cobalt accounts for 15-45%, molybdenum accounts for 5-15%. The catalyst is in a sulfuration state, has good sulfur poisoning resistance, can remove sulfur in the resin liquid to 2ppm under the optimal condition, and avoids rapid inactivation of the subsequent hydrogenation catalyst due to sulfur poisoning.
Patent CN106008819A introduces a production device and a production method of low-chroma carbon nine petroleum resin, wherein the cold-polymerized C9 resin is treated by a two-stage hydrogenation process, the first-stage hydrogenation process adopts a nickel-based catalyst, the Ni content is 15-30%, refractory alumina and silica are used as carriers, impurities such as sulfur, chlorine, gel and the like in the resin can be removed under the conditions of 150-200 ℃ and 5-20 MPa, and the activity and the service life of the catalyst of the second-stage hydrogenation are ensured.
Patent CN105175633A describes a combined petroleum resin hydrotreating method, which uses alumina and activated carbon to adsorb resin liquid at high temperature to remove sulfur and chlorine impurities in the resin, and then carries out two-stage hydrotreating.
Patent CN102850491A describes a method for removing fluorine before hydrogenation of petroleum resin, wherein the method comprises the steps of preheating the dissolved resin, adding the preheated resin into a reaction kettle, adding a DTBHQ polymerization inhibitor, sealing the reaction kettle, adding a surfactant polyoxyethylene cetyl ether into the reaction kettle, introducing high-pressure steam, starting stirring, keeping for 5-15min, reducing the temperature in the reaction kettle to 20-70 ℃, standing to separate oil from water, and removing a water layer to obtain the fluorine-removed petroleum resin. The method can control the fluorine content in the resin liquid within 50ppm, so that the total resin treatment amount of a unit catalyst is greatly improved, and the service life of the catalyst is prolonged.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the method for defluorinating the high-fluorine petroleum resin, the defluorination rate of the method is more than 73 percent, the fluorosis of the resin hydrogenation catalyst can be effectively delayed, and the method is favorable for the long-period operation of a petroleum resin hydrogenation device. The invention provides a defluorination method of high fluorine-containing petroleum resin, which comprises the following steps:
dissolving petroleum resin with a solvent to obtain a resin solution, mixing the resin solution with a defluorinating agent, heating, mixing with medium-pressure steam, and entering a defluorinating tower from the bottom of a reactor at the reaction temperature of 170 ℃ and 280 ℃ under the pressure of 2-4 MPa; and mixing the resin liquid after passing through the defluorination tower with a demulsifier and water, then feeding the mixture into a two-stage water washing tower, discharging a fluorine-containing water phase from the bottom of the water washing tower, extracting the resin liquid from the top of the water washing tower, feeding the resin liquid into a molecular sieve dehydration tower, and dehydrating to obtain the defluorinated petroleum resin.
The defluorinating agent is prepared by compounding a phase transfer agent, an alkaline substance, a polymerization inhibitor and an organic solvent according to the following proportion: 5-12% of phase transfer agent, 14-26% of alkaline matter, 0.05-0.2% of polymerization inhibitor and the balance of organic solvent.
In the petroleum resin defluorinating method, the mass fraction of the petroleum resin in the resin liquid is 15-35%, the retention time of the resin liquid in the defluorinating tower is 15-42min, and the proportion of the defluorinating agent to the resin liquid is 500--1The proportion of the demulsifier to the resin liquid is 50-200 mu g.g-1(ii) a The phase transfer agent is ethyl triphenyl phosphonium bromide,One of polyethylene glycol 600 and polyethylene glycol 400; the alkaline matter is diethylamine or ethanolamine; the polymerization inhibitor is 2-tert-butyl hydroquinone or di-tert-butyl hydroquinone; the organic solvent is ethanol; the demulsifier is polyoxyethylene polyoxypropylene block polyether.
Organic fluorine in the resin can react with alkaline substance diethylamine or ethanolamine to generate fatty alcohol and organic ammonium fluoride, the organic ammonium fluoride is water-soluble and can be removed by washing, but the reaction speed is very slow in the absence of a catalyst, and the reaction speed is greatly accelerated by adding phase transfer agents of ethyl triphenyl phosphonium bromide, polyethylene glycol 600 and polyethylene glycol 400, so that the rapid removal of organic fluoride in the resin can be realized.
The petroleum resin is a high molecular weight thermoplastic resin formed by heating polymerization or catalytic polymerization, but a part of unpolymerized unsaturated hydrocarbon substances still remain in the resin, the unsaturated hydrocarbon remaining at the reaction temperature of 170-280 ℃ in a defluorination tower can be subjected to polymerization reaction, the molecular structure of the resin can be changed, the direct appearance is the change of the number average molecular weight of the resin, and the change of the molecular structure of the resin can influence the properties of the resin such as softening point, chromaticity, compatibility and the like, thereby causing adverse effect on the application of the petroleum resin. Therefore, the polymerization inhibitor added into the defluorinating agent is 2-tert-butylhydroquinone or ditert-butylhydroquinone, and the change of the molecular structure of the resin caused by heating can be effectively relieved.
The two-stage dehydration tower is a continuous dehydration process, has higher production efficiency compared with the method that the oil and water are separated after the reaction kettle is kept still, and is more matched with the current mainstream petroleum resin fixed bed continuous hydrogenation process; the molecular sieve dehydration tower can further remove trace water in the resin liquid, and avoids the phenomenon that the resin hydrogenation catalyst accelerates the metal coalescence of active metal components due to overhigh water content of the resin raw material, reduces the hydrogenation activity of the catalyst and influences the stable operation of the device.
According to the petroleum resin defluorination method provided by the invention, the defluorination agent and the organic fluorine compound in the resin are quickly reacted to generate the water-soluble fluorine-containing compound, then the fluoride in the oil phase is removed by oil-water separation, the defluorination rate is high, the defluorination rate is more than 73%, the fluorosis of a resin hydrogenation catalyst can be effectively delayed, and the long-period operation of a petroleum resin hydrogenation device is facilitated.
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FIG. 1 is a schematic diagram of a process flow of a method for defluorinating a high-fluorine petroleum resin, provided by the invention, wherein: 1 is resin liquid, 2 is defluorinating agent, 3 is medium pressure steam, 4 is defluorinating tower, 5 is first-stage water washing tower, 6 is second-stage water washing tower, and 7 is molecular sieve dehydrating tower.
Detailed Description
The characteristics of the catalyst, the preparation method and the catalytic performance of the catalyst of the present invention will be described in detail with reference to the following specific examples, but the present invention is not limited to these examples and does not limit the scope of the present invention.
Example 1:
dissolving petroleum resin with solvent to obtain resin solution, wherein the mass fraction of petroleum resin in the resin solution is 25%, mixing the resin solution with defluorinating agent, and the ratio of defluorinating agent to resin solution is 500 μ g.g-1The catalyst is heated and mixed with medium-pressure steam, the mixture enters a defluorination tower from the bottom of a reactor, the reaction temperature is 170 ℃, the pressure is 4MPa, the residence time of resin liquid in the defluorination tower is 42min, in the defluorination agent, a phase transfer agent is ethyl triphenyl phosphonium bromide, the mass percent of the phase transfer agent is 5%, an alkaline substance is diethylamine, the mass percent of the phase transfer agent is 26%, a polymerization inhibitor is 2-tert-butyl hydroquinone, the mass percent of the polymerization inhibitor is 0.05%, and the balance is an ethanol solvent. The resin liquid after passing through the defluorination tower is mixed with demulsifier polyoxyethylene polyoxypropylene block polyether and water and then enters a two-stage water washing tower, and the proportion of the demulsifier to the resin liquid is 120 mu g.g-1And the fluorine-containing water phase is discharged from the bottom of the washing tower, the resin liquid is extracted from the top of the washing tower, and then enters a molecular sieve dehydration tower to be dehydrated, so that the defluorinated petroleum resin is obtained.
Example 2:
dissolving petroleum resin with solvent to obtain resin solution, wherein the mass fraction of petroleum resin in the resin solution is 15%, mixing the resin solution with defluorinating agent at a ratio of 1700 mu g.g-1Heating, mixing with medium pressure steam, and introducing into defluorinating tower from the bottom of the reactor at 280 deg.C and 3MPa to remove resin liquidThe retention time in the fluorine tower is 29min, in the used defluorinating agent, the phase transfer agent is polyethylene glycol 600 with the mass percent of 12%, the alkaline substance is ethanolamine with the mass percent of 20%, the polymerization inhibitor is di-tert-butylhydroquinone with the mass percent of 0.2%, and the balance is ethanol solvent. The resin liquid after passing through the defluorination tower is mixed with demulsifier polyoxyethylene polyoxypropylene block polyether and water and then enters a two-stage water washing tower, and the proportion of the demulsifier to the resin liquid is 50 mu g.g-1And the fluorine-containing water phase is discharged from the bottom of the washing tower, the resin liquid is extracted from the top of the washing tower, and then enters a molecular sieve dehydration tower to be dehydrated, so that the defluorinated petroleum resin is obtained.
Example 3:
dissolving petroleum resin with solvent to obtain resin solution, wherein the mass fraction of petroleum resin in the resin solution is 35%, mixing the resin solution with defluorinating agent, and the ratio of defluorinating agent to resin solution is 3000 μ g.g-1The resin liquid is heated and mixed with medium-pressure steam, the mixture enters a defluorination tower from the bottom of a reactor, the reaction temperature is 225 ℃, the pressure is 2MPa, the residence time of the resin liquid in the defluorination tower is 15min, in the defluorination agent, the phase transfer agent is polyethylene glycol 400, the mass percent of the polyethylene glycol 400 is 8%, the mass percent of the alkali substance is ethanolamine, the mass percent of the alkali substance is 14%, the mass percent of the polymerization inhibitor is 2-tert-butylhydroquinone, the mass percent of the polymerization inhibitor is 0.12%, and the balance is ethanol solvent. The resin liquid after passing through the defluorination tower is mixed with demulsifier polyoxyethylene polyoxypropylene block polyether and water and then enters a two-stage water washing tower, and the proportion of the demulsifier to the resin liquid is 200 mu g.g-1And the fluorine-containing water phase is discharged from the bottom of the washing tower, the resin liquid is extracted from the top of the washing tower, and then enters a molecular sieve dehydration tower to be dehydrated, so that the defluorinated petroleum resin is obtained.
Comparison 1:
the defluorination process of example 1 was followed without addition of defluorination agent and the remaining steps were identical.
Comparison 2:
the defluorination process of example 1 was followed, except that the defluorination agent was changed to polyethylene glycol 400, and the remaining steps were identical.
A defluorination test was carried out on a commercially available C9 cold polymerization resin having a fluorine content of 326ppm and a resin number average molecular weight of 873 by the defluorination methods of the above examples and comparative examples, and the results are shown in Table 1.
TABLE 1 results of defluorination experiments
| Example 1 | Example 2 | Example 3 | Comparative example 1 | |
|
| Fluorine content ppm | 44 | 48 | 42 | 286 | 157 |
| Defluorination rate% | 86.5 | 85.3 | 87.1 | 12.3 | 51.8 |
| Number average molecular weight of resin | 891 | 887 | 893 | 947 | 942 |
It can be seen from table 1 that the defluorination method provided by the invention can effectively remove fluoride in C9 resin, and the defluorination rate of examples 1-3 exceeds 73%; in comparative example 1, no defluorinating agent is added in the defluorination process, the other steps are consistent with the invention, and the defluorination rate is only 12.3 percent, because the defluorination effect is poor because the defluorination agent has no catalysis and phase transfer effects and only inorganic fluoride in the resin can be removed by water washing; in the comparative example 2, the defluorinating agent is changed into polyethylene glycol 400, the rest steps are consistent, and the defluorination rate reaches 51.8 percent, because the polyethylene glycol 400 has the phase transfer function, part of organic fluorine in the resin can be transferred from an oil phase to a water phase, and part of the organic fluorine can be removed after water washing.
Claims (2)
1. A method for defluorinating high-fluorine petroleum resin is characterized by comprising the following steps:
dissolving petroleum resin with a solvent to obtain a resin solution, mixing the resin solution with a defluorinating agent, heating, mixing with medium-pressure steam, and entering a defluorinating tower from the bottom of a reactor at the reaction temperature of 170 ℃ and 280 ℃ under the pressure of 2-4 MPa;
mixing the resin liquid after passing through the defluorination tower with a demulsifier and water, then feeding the mixture into a two-stage water scrubber, discharging a fluorine-containing water phase from the bottom of the water scrubber, extracting the resin liquid from the top of the water scrubber, feeding the resin liquid into a molecular sieve dehydration tower, and dehydrating to obtain the defluorinated petroleum resin;
in the defluorination method, the mass fraction of the petroleum resin in the resin liquid is 15-35%, the retention time of the resin liquid in the defluorination tower is 15-42min, and the proportion of the defluorination agent to the resin liquid is 500--1The proportion of the demulsifier to the resin liquid is 50-200 mu g.g-1；
The defluorinating agent is prepared by compounding a phase transfer agent, an alkaline substance, a polymerization inhibitor and an organic solvent according to the following proportion: 5-12% of phase transfer agent, 14-26% of alkaline matter, 0.05-0.2% of polymerization inhibitor and the balance of organic solvent; the phase transfer agent is one of ethyl triphenyl phosphonium bromide, polyethylene glycol 600 and polyethylene glycol 400; the alkaline matter is diethylamine or ethanolamine; the polymerization inhibitor is 2-tert-butyl hydroquinone or di-tert-butyl hydroquinone; the organic solvent is ethanol; the demulsifier is polyoxyethylene polyoxypropylene block polyether.
2. The method of claim 1, wherein: the defluorination rate of the petroleum resin defluorinated by the method is more than 85 percent.
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| JPS5918107A (en) * | 1982-07-19 | 1984-01-30 | Central Glass Co Ltd | Modified graphite fluoride |
| CN102850491B (en) * | 2012-08-29 | 2014-04-16 | 宁波职业技术学院 | Method for catalyzing fluorine removal before hydrogenation of polymeric petroleum resin through using fluorine-containing catalyst |
| CN106698375A (en) * | 2015-11-15 | 2017-05-24 | 瓮福（集团）有限责任公司 | Calcining defluorination method in feed-grade tricalcium phosphate production |
| CN106540640B (en) * | 2016-10-28 | 2018-08-21 | 中国石油化工股份有限公司 | The commercial run and device of a kind of hydrogenation of petroleum resin process desulfurization, dechlorination |
| CN111574645B (en) * | 2020-05-27 | 2021-04-20 | 大连理工大学 | Hydrogenation method for high-sulfur petroleum resin |
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