CN108485706B - Preparation method of oxidized safety-shaped paraffin - Google Patents
Preparation method of oxidized safety-shaped paraffin Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/36—Recovery of petroleum waxes from other compositions containing oil in minor proportions, from concentrates or from residues; De-oiling, sweating
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- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
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Abstract
The invention discloses a preparation method of oxidized safety-shaped paraffin, belonging to the technical field of paraffin preparation. The invention uses a small amount of microcrystalline wax to increase the hardness and wear resistance of the soft paraffin, the invention utilizes soybean oil which is easily oxidized to form epoxidized soybean oil, the epoxidized soybean oil has excellent thermal stability and light stability, nitrogen free radicals become very stable under the influence of benzene ring conjugation effect, insufficient activity is available to react with ester oil molecules and only can react with other free radicals, the nitrogen free radicals and peroxy free radicals can continuously react with peroxy free radicals to generate nitroxide free radicals, the generated antioxidant intermediate is subjected to the conjugation of the benzene ring, the stability is very high, the chain termination reaction of the free radicals can only occur with other active free radicals and peroxy free radicals, the thermal stability is high, the epoxidized soybean oil and diphenylamine have good synergistic antioxidant effect, and thus the prepared activated paraffin has good thermal stability and oxidation stability, and the application prospect is wide.
Description
Technical Field
The invention discloses a preparation method of oxidized safety-shaped paraffin, belonging to the technical field of paraffin preparation.
Background
The paraffin is a common name of a solid high-grade alkane mixture, can be prepared from a wax-containing fraction of natural or artificial petroleum by cold pressing or solvent dewaxing, sweating and other methods, is a white and tasteless waxy solid, and has about 18-30 carbon atoms. Generally divided into three types, fully refined paraffin, semi-refined paraffin and crude paraffin. The paraffin has wide application, and the wax paper with good waterproof performance can be prepared after the paper is immersed in the paraffin; after the paraffin is added into the cotton yarn, the textile is soft, smooth and elastic.
Paraffin is one of petroleum processed products. A mixture of solid alkanes. Odorless and tasteless white or light yellow solid. Is prepared from natural petroleum and artificial wax-contained fraction through cold pressing or solvent dewaxing, sweating, etc. It can be used for preparing higher fatty acid, higher alcohol, match, candle, water repellent, ointment, and electric insulating material.
Paraffin wax is one of mineral waxes and also one of petroleum waxes; it is a flaky or needle crystal obtained by refining the fraction of lubricating oil obtained by distilling crude oil with solvent, dewaxing with solvent or freezing crystallization of wax, squeezing dewaxing to obtain cerate, and then deoiling with solvent and refining. The main components of the hydrocarbon mixture, also called crystal wax, with about 18-30 carbon atoms are straight-chain alkanes (about 80-95%), and also a small amount of alkanes with individual branches and monocyclic cycloalkanes with long side chains (the total content of the two is less than 20%). The main quality indexes are melting point and oil content, the former represents temperature resistance, and the latter represents purity. The two materials have wide application range, are mainly used as components and packaging materials of foods and other commodities, coating materials of baking containers and cosmetic raw materials, are used for keeping fruits fresh, improving the ageing resistance of rubber, increasing the flexibility, insulating electrical elements, performing precision casting and the like, and can also be used for generating synthetic fatty acid through oxidation.
The high value-added paraffin product is developed, and the market competitiveness of the paraffin product can be further improved by improving the technical content of the paraffin deep-processing product. The paraffin can be widely applied to the industries of chemicals, medicines, foods, transportation and the like. China is the country with the largest paraffin yield in the world, but the paraffin products with high added values are few, and most special waxes with special purposes need to be imported. With the development of scientific technology, paraffin products with common hardness and melting point cannot meet the requirements of the market. At present, paraffin is poor in oxidation and setting, easy to oxidize and deteriorate, dark in color and even smelly, and can turn yellow under the condition of illumination when being used, and the paraffin is large in brittleness and easy to wear and crack under the impact of external force or friction.
Therefore, the invention of the oxidized stable paraffin has positive significance in the technical field of paraffin preparation.
Disclosure of Invention
The invention mainly solves the technical problems that the existing paraffin wax is poor in oxidation-setting stability, easy to oxidize and deteriorate, dark in color and even smelly, the paraffin wax can turn yellow under the condition of illumination when in use, the paraffin wax is large in brittleness and easy to wear and crack under the impact of external force or friction, and the preparation method of the oxidation-setting paraffin wax is provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation method of the oxidized fixed paraffin is characterized by comprising the following specific preparation steps:
(1) adding 3.4-3.8 g of 2, 6-di-tert-butylphenol and 3.6-4.0 g of diphenylamine into a single-neck flask, continuously adding 40-50 mL of n-decane, stirring by using a magnetic stirrer under the protection of nitrogen, heating to raise the temperature, adding 8.5-10.0 mL of di-tert-butyl peroxide into the single-neck flask, and stirring for reaction to obtain a reaction product;
(2) installing the single-mouth flask on a condensation reflux device, heating to raise the temperature, distilling, naturally cooling to room temperature, placing the distillation flask in absolute ethyl alcohol for freezing to obtain a reaction product containing crystals, performing suction filtration on the reaction product, removing filtrate to obtain a filter cake, washing the filter cake for 3-5 times by using n-decane, placing the filter cake in an oven, heating to raise the temperature, and drying to obtain 2, 6 di-tert-butyl-4- (dianilino) phenol;
(3) mixing soybean oil, potassium hydroxide and an ethanol solution, heating, raising the temperature, stirring and reacting to obtain a mixed solution, placing the mixed solution into a separating funnel, adding hydrochloric acid into the separating funnel, adjusting the pH value of the mixed solution, standing, separating to remove a water layer to obtain an oil layer, washing the oil layer with distilled water for 3-5 times to obtain a purified oil layer, namely esterified oleic acid;
(4) mixing corn straws and rice bran, putting the mixture into a crusher for crushing, sieving to obtain mixed bran powder, putting 80-100 g of the mixed bran powder, 20-30 g of oil refinery waste oil and 40-50 g of esterified oleic acid into a fermentation tank, sequentially adding 40-50 g of soft paraffin and 20-30 g of microcrystalline wax into a crucible, heating to raise the temperature to completely melt the mixture, dropwise adding the mixture into the fermentation tank while the mixture is hot, and performing heat preservation and fermentation to obtain a fermentation product;
(5) heating the fermentation product, filtering to remove filter residues to obtain a filtrate, cooling the filtrate to room temperature to obtain fermented wax powder, mixing the fermented wax powder with 2, 6-di-tert-butyl-4- (diphenylamino) phenol, washing with ethanol and deionized water for 3-5 times in sequence, and standing and drying at room temperature to obtain activated wax powder;
(6) and sequentially adding 70-80 g of the activated wax powder, 20-25 g of quick lime and 10-15 g of diatomite into a three-neck flask with a stirrer, heating the three-neck flask in an oil bath, starting the stirrer, stirring and mixing, adding 0.10-0.15 g of manganese stearate to obtain a reaction product, pouring the reaction product of the three-neck flask into a plate-frame mold, cooling to room temperature, and demolding to obtain the oxidized safety-shaped paraffin.
The stirring speed in the step (1) is 300-350 r/min, the temperature after heating is 140-160 ℃, and the stirring reaction time is 3-4 h.
The temperature of the heated and heated product in the step (2) is 140-150 ℃, the distillation time is 1-2 h, the temperature of absolute ethyl alcohol is-20 to-15 ℃, the freezing time is 2-3 h, the temperature of the heated product in an oven is 90-100 ℃, and the drying time is 4-5 h.
The mass fraction of the ethanol solution in the step (3) is 75%, the mixing mass ratio of the soybean oil, the potassium hydroxide and the ethanol solution is 5: 1: 8, the temperature is 40-50 ℃ after heating, the stirring reaction time is 15-20 min, the mass fraction of hydrochloric acid is 20%, the PH of the mixed solution is adjusted to 2-3, and the standing time is 5-8 min.
The mixing mass ratio of the corn straws to the rice bran in the step (4) is 4:1, the granularity of the obtained mixed bran powder is 200 meshes, the temperature after heating is 60-80 ℃, the temperature is increased to 40-50 ℃ in a fermentation tank, and the heat preservation and fermentation time is 4-5 days.
And (3) heating the fermentation product obtained in the step (5) to raise the temperature to 70-80 ℃, mixing the fermentation wax powder and 2, 6-di-tert-butyl-4- (diphenylamino) phenol in a mass ratio of 5:1, and standing and drying at normal temperature for 30-40 min to obtain the activated wax powder.
And (4) raising the temperature of the three-neck flask oil bath in the step (6) to 120-150 ℃, stirring at the rotating speed of 300-350 r/min, and stirring and mixing for 10-15 min.
The invention has the beneficial effects that:
(1) the method comprises the steps of using 2, 6-di-tert-butylphenol and diphenylamine as main materials, carrying out oxidation reaction to obtain an oxidation product, carrying out reflux, freezing and drying to obtain 2, 6-di-tert-butyl-4- (diphenylamine) phenol, using soybean oil, azelaic acid and neopentyl glycol as raw materials to esterify to obtain mixed ester, carrying out liquid separation and washing to obtain a purified oil layer, namely esterified oleic acid, mixing and crushing rice straws and rice bran to obtain mixed bran powder, mixing and fermenting the mixed bran powder, oil refinery waste oil, esterified oleic acid, soft paraffin and microcrystalline wax, carrying out heat preservation fermentation to obtain a fermentation product, heating and filtering the fermentation product, cooling to obtain fermented wax powder, adding 2, 6-di-tert-butyl-4- (diphenylamine) phenol, carrying out washing, standing and drying to obtain activated wax powder, and finally mixing the activated wax powder, quick lime, diatomite and the like according to a certain mass ratio, Adding a small amount of manganese stearate, putting the mixture into a plate frame die, cooling and demoulding to obtain the oxidized safety-fixed paraffin, increasing the hardness and the wear resistance of the soft paraffin by using a small amount of microcrystalline wax, improving the friction performance of the paraffin by using fine-grained diatomite, protecting the paraffin from being oxidized by light due to the porous characteristic of the diatomite, and improving the shock resistance and the wear resistance of the paraffin by using calcium oxide in quicklime to resist water absorption and pulverization of the paraffin during curing and forming so as to improve the density of the paraffin;
(2) the invention utilizes soybean oil which is easy to oxidize to form epoxidized soybean oil, which has excellent thermal stability and light stability, can be esterified into esterified oleic acid under the action of alcohol and alkali, can generate alkyl free radicals and alkyl peroxy radicals under the action of oxidation factors such as molecular oxygen of ester oil and the like, the alkyl free radicals and the alkyl peroxy radicals react with 2, 6 di-tert-butyl-4- (dianilino) phenol to generate nitrogen free radicals and alcohol and acid compounds with lower activity, the nitrogen free radicals are very stable under the influence of benzene ring conjugation effect, do not have enough activity to react with the molecular of ester oil and can only react with other free radicals, the nitrogen free radicals and the peroxy radicals can continuously react to generate the nitroxide radicals, thus the nitroxide radicals are continuously regenerated, namely the anti-oxidation effect of the 2, 6 di-tert-butyl-4- (dianilino) phenol is regenerated, the anti-oxidation process is continued, the generated antioxidant intermediate is subjected to the conjugation of a benzene ring, has high stability, can only generate chain termination reaction of free radicals with other active free radicals and peroxy free radicals, has high thermal stability, and has good synergistic anti-oxidation effect with diphenylamine, so that the prepared activated paraffin has good thermal stability and oxidation stability, and has wide application prospect.
Detailed Description
Adding 3.4-3.8 g of 2, 6-di-tert-butylphenol and 3.6-4.0 g of diphenylamine into a single-neck flask, continuously adding 40-50 mL of n-decane, stirring for 3-4 h at the rotating speed of 300-350 r/min by using a magnetic stirrer under the protection of nitrogen, heating to 140-160 ℃, adding 8.5-10.0 mL of di-tert-butyl peroxide into the single-neck flask, and stirring for reacting for 3-4 h to obtain a reaction product; installing the single-neck flask on a condensation reflux device, heating to 140-150 ℃, distilling for 1-2 h, naturally cooling to room temperature, placing the distillation flask in absolute ethyl alcohol at-20 to-15 ℃ for freezing for 2-3 h to obtain a reaction product containing crystals, performing suction filtration on the reaction product to remove filtrate to obtain a filter cake, washing the filter cake with n-decane for 3-5 times, placing the filter cake in an oven, heating to 90-100 ℃, and drying for 4-5 h to obtain 2, 6 di-tert-butyl-4- (dianilino) phenol; mixing soybean oil, potassium hydroxide and 75% by mass of ethanol solution according to a mass ratio of 5: 1: 8, heating to 40-50 ℃, stirring for reaction for 15-20 min to obtain a mixed solution, placing the mixed solution into a separating funnel, adding 20% by mass of hydrochloric acid into the separating funnel, adjusting the pH of the mixed solution to 2-3, standing for 5-8 min, separating to remove a water layer to obtain an oil layer, washing the oil layer with distilled water for 3-5 times to obtain a purified oil layer, namely esterified oleic acid; mixing corn straws and rice bran according to a mass ratio of 4:1, putting the mixture into a crusher for crushing, sieving to obtain 200-mesh mixed bran powder, putting 80-100 g of the mixed bran powder, 20-30 g of oil refinery waste oil and 40-50 g of esterified oleic acid into a fermentation tank, sequentially adding 40-50 g of soft paraffin and 20-30 g of microcrystalline wax into a crucible, heating to 60-80 ℃, completely melting the mixture, dropwise adding the mixture into the fermentation tank while the mixture is hot, heating to 40-50 ℃, and performing heat preservation and fermentation for 4-5 days to obtain a fermentation product; heating the fermentation product to 70-80 ℃, filtering to remove filter residues to obtain filtrate, cooling the filtrate to room temperature to obtain fermented wax powder, mixing the fermented wax powder with 2, 6-di-tert-butyl-4- (diphenylamino) phenol according to the mass ratio of 5:1, washing with ethanol and deionized water for 3-5 times in sequence, and standing and drying at room temperature for 30-40 min to obtain activated wax powder; and sequentially adding 70-80 g of the activated wax powder, 20-25 g of quicklime and 10-15 g of diatomite with the granularity of 300 meshes into a three-neck flask with a stirrer, heating the three-neck flask in oil bath to 120-150 ℃, starting the stirrer, stirring and mixing at the rotating speed of 300-350 r/min for 10-15 min, adding 0.10-0.15 g of manganese stearate to obtain a reaction product, pouring the reaction product of the three-neck flask into a plate-frame mold, cooling to room temperature, and demolding to obtain the oxidized safety-shaped paraffin.
Adding 2, 6-di-tert-butylphenol and 3.6g diphenylamine in 3.4g into a single-neck flask, continuously adding 40mL of n-decane, stirring for 3h at the rotating speed of 300r/min by using a magnetic stirrer under the protection of nitrogen, heating to 140 ℃, adding 8.5mL of di-tert-butyl peroxide into the single-neck flask, and stirring for reacting for 3h to obtain a reaction product; installing a condensation reflux device on the single-neck flask, heating to 140 ℃, distilling for 1h, naturally cooling to room temperature, placing the distillation flask in absolute ethyl alcohol at the temperature of-20 ℃ for freezing for 2h to obtain a reaction product containing crystals, performing suction filtration on the reaction product, removing filtrate to obtain a filter cake, washing the filter cake for 3 times by using n-decane, placing the filter cake in an oven, heating to 90 ℃, and drying for 4h to obtain 2, 6 di-tert-butyl-4- (dianilino) phenol; mixing soybean oil, potassium hydroxide and 75% by mass of ethanol solution according to a mass ratio of 5: 1: 8, heating to 40 ℃, stirring for reaction for 15min to obtain a mixed solution, placing the mixed solution into a separating funnel, adding 20% by mass of hydrochloric acid into the separating funnel, adjusting the pH of the mixed solution to 2, standing for 5min, separating to remove a water layer to obtain an oil layer, washing the oil layer with distilled water for 3 times to obtain a purified oil layer, namely esterified oleic acid; mixing corn straws and rice bran according to a mass ratio of 4:1, putting the mixture into a crusher for crushing, sieving to obtain 200-mesh mixed bran powder, putting 80g of the mixed bran powder, 20g of oil refinery waste oil and 40g of esterified oleic acid into a fermentation tank, sequentially adding 40g of soft paraffin and 20g of microcrystalline wax into a crucible, heating to 60 ℃ for complete melting, dropwise adding the mixture into the fermentation tank while the mixture is hot, heating to 40 ℃, and carrying out heat preservation and fermentation for 4 days to obtain a fermentation product; heating the fermentation product to 70 ℃, filtering to remove filter residues to obtain filtrate, cooling the filtrate to room temperature to obtain fermented wax powder, mixing the fermented wax powder with 2, 6-di-tert-butyl-4- (diphenylamino) phenol according to the mass ratio of 5:1, washing with ethanol and deionized water for 3 times in sequence, and standing and drying at normal temperature for 30min to obtain activated wax powder; and sequentially adding 70g of the activated wax powder, 20g of quicklime and 10g of diatomite with the granularity of 300 meshes into a three-neck flask with a stirrer, heating the three-neck flask in oil bath to 120 ℃, starting the stirrer, stirring and mixing at the rotating speed of 300r/min for 10min, adding 0.10g of manganese stearate to obtain a reaction product, pouring the reaction product of the three-neck flask into a plate-and-frame mold, cooling to room temperature, and demolding to obtain the oxidized safety-typed paraffin.
Adding 2, 6-di-tert-butylphenol and 3.8g diphenylamine in 3.6g into a single-neck flask, continuously adding 45mL of n-decane, stirring for 3.5h at the rotating speed of 320r/min by using a magnetic stirrer under the protection of nitrogen, heating to 150 ℃, adding 9.0mL of di-tert-butyl peroxide into the single-neck flask, and stirring for reacting for 3.5h to obtain a reaction product; installing a condensation reflux device on the single-neck flask, heating to 145 ℃, distilling for 1.5h, naturally cooling to room temperature, placing the distillation flask in absolute ethyl alcohol at-17 ℃ for freezing for 2.5h to obtain a reaction product containing crystals, performing suction filtration on the reaction product, removing filtrate to obtain a filter cake, washing the filter cake with n-decane for 4 times, placing the filter cake in an oven, heating to 95 ℃, and drying for 4.5h to obtain 2, 6 di-tert-butyl-4- (diphenylamine) phenol; mixing soybean oil, potassium hydroxide and 75% by mass of ethanol solution according to a mass ratio of 5: 1: 8, heating to 45 ℃, stirring for reaction for 17min to obtain a mixed solution, placing the mixed solution into a separating funnel, adding 20% by mass of hydrochloric acid into the separating funnel, adjusting the pH of the mixed solution to 2, standing for 7min, separating to remove a water layer to obtain an oil layer, washing the oil layer with distilled water for 4 times to obtain a purified oil layer, namely esterified oleic acid; mixing corn straws and rice bran according to a mass ratio of 4:1, putting the mixture into a crusher for crushing, sieving to obtain 200-mesh mixed bran powder, putting 90g of the mixed bran powder, 25g of oil refinery waste oil and 45g of esterified oleic acid into a fermentation tank, sequentially adding 45g of soft paraffin and 25g of microcrystalline wax into a crucible, heating to 70 ℃ for complete melting, dropwise adding the mixture into the fermentation tank while the mixture is hot, heating to 45 ℃, and carrying out heat preservation and fermentation for 4 days to obtain a fermentation product; heating the fermentation product to 75 ℃, filtering to remove filter residues to obtain filtrate, cooling the filtrate to room temperature to obtain fermented wax powder, mixing the fermented wax powder with 2, 6-di-tert-butyl-4- (diphenylamino) phenol according to the mass ratio of 5:1, washing with ethanol and deionized water for 4 times in sequence, and standing and drying at normal temperature for 35min to obtain activated wax powder; and sequentially adding 75g of the activated wax powder, 22g of quicklime and 12g of diatomite with the granularity of 300 meshes into a three-neck flask with a stirrer, heating the three-neck flask in oil bath to 140 ℃, starting the stirrer, stirring and mixing at the rotating speed of 320r/min for 12min, adding 0.12g of manganese stearate to obtain a reaction product, pouring the reaction product of the three-neck flask into a plate-and-frame mold, cooling to room temperature, and demolding to obtain the oxidized safety-typed paraffin.
Adding 8978.8 g of 2, 6-di-tert-butylphenol and 4.0g of diphenylamine into a single-neck flask, continuously adding 50mL of n-decane, stirring for 4h at the rotating speed of 350r/min by using a magnetic stirrer under the protection of nitrogen, heating to 160 ℃, adding 10.0mL of di-tert-butyl peroxide into the single-neck flask, and stirring for reacting for 4h to obtain a reaction product; installing a condensation reflux device on the single-neck flask, heating to 150 ℃, distilling for 2 hours, naturally cooling to room temperature, placing the distillation flask in absolute ethyl alcohol at the temperature of-15 ℃ for freezing for 3 hours to obtain a reaction product containing crystals, performing suction filtration on the reaction product, removing filtrate to obtain a filter cake, washing the filter cake for 5 times by using n-decane, placing the filter cake in an oven, heating to 100 ℃, and drying for 5 hours to obtain 2, 6 di-tert-butyl-4- (dianilino) phenol; mixing soybean oil, potassium hydroxide and 75% by mass of ethanol solution according to a mass ratio of 5: 1: 8, heating to 50 ℃, stirring for 20min to obtain a mixed solution, placing the mixed solution into a separating funnel, adding 20% by mass of hydrochloric acid into the separating funnel, adjusting the pH of the mixed solution to 3, standing for 8min, separating to remove a water layer to obtain an oil layer, washing the oil layer with distilled water for 5 times to obtain a purified oil layer, namely esterified oleic acid; mixing corn straws and rice bran according to a mass ratio of 4:1, putting the mixture into a crusher for crushing, sieving to obtain 200-mesh mixed bran powder, putting 100g of the mixed bran powder, 30g of oil refinery waste oil and 50g of esterified oleic acid into a fermentation tank, sequentially adding 50g of soft paraffin and 30g of microcrystalline wax into a crucible, heating to 80 ℃ for complete melting, dropwise adding the mixture into the fermentation tank while the mixture is hot, heating to 50 ℃, and carrying out heat preservation and fermentation for 5 days to obtain a fermentation product; heating the fermentation product to 80 ℃, filtering to remove filter residues to obtain filtrate, cooling the filtrate to room temperature to obtain fermented wax powder, mixing the fermented wax powder with 2, 6-di-tert-butyl-4- (diphenylamino) phenol according to the mass ratio of 5:1, washing the mixture with ethanol and deionized water for 5 times in sequence, and standing and drying the mixture for 40min at normal temperature to obtain activated wax powder; adding 80g of the activated wax powder, 25g of quicklime and 15g of diatomite with the granularity of 300 meshes into a three-neck flask with a stirrer in sequence, heating the three-neck flask in oil bath to 150 ℃, starting the stirrer, stirring and mixing at the rotating speed of 350r/min for 15min, adding 0.15g of manganese stearate to obtain a reaction product, pouring the reaction product of the three-neck flask into a plate-and-frame mold, cooling to room temperature, and demolding to obtain the oxidized safety-typed paraffin.
The performance of the oxidized fixed paraffin wax prepared by the invention and the performance of the oxidized fixed paraffin wax in the comparative example are detected by taking the oxidized fixed paraffin wax produced by Guangzhou company as the comparative example, and the detection results are shown in Table 1:
the test method comprises the following steps:
the hardness test adopts a hardness tester for detection;
the method for testing the oxidation resistance comprises the following steps: a Schaal oven method is adopted for an accelerated oxidation test, the paraffin in examples 1-3 and the paraffin in a comparative example are respectively placed in a thermostat with relatively good air for 4d, sampling is carried out every 24h, the peroxide value is measured according to the method of national regulation GB/T5009.37-2003, and the surface change condition is observed.
TABLE 1 measurement of Paraffin Properties
According to the data, the oxidation-stable paraffin wax prepared by the method has the advantages of small peroxide value, reduced oxidation speed, greatly improved oxidation stability, greatly improved oxidation resistance, unchanged color, no odor, high hardness, good impact resistance, difficult abrasion and wide application prospect.
Claims (7)
1. The preparation method of the oxidized fixed paraffin is characterized by comprising the following specific preparation steps:
(1) adding 3.4-3.8 g of 2, 6-di-tert-butylphenol and 3.6-4.0 g of diphenylamine into a single-neck flask, continuously adding 40-50 mL of n-decane, stirring by using a magnetic stirrer under the protection of nitrogen, heating to raise the temperature, adding 8.5-10.0 mL of di-tert-butyl peroxide into the single-neck flask, and stirring for reaction to obtain a reaction product;
(2) installing the single-mouth flask on a condensation reflux device, heating to raise the temperature, distilling, naturally cooling to room temperature, placing the distillation flask in absolute ethyl alcohol for freezing to obtain a reaction product containing crystals, performing suction filtration on the reaction product, removing filtrate to obtain a filter cake, washing the filter cake for 3-5 times by using n-decane, placing the filter cake in an oven, heating to raise the temperature, and drying to obtain 2, 6 di-tert-butyl-4- (dianilino) phenol;
(3) mixing soybean oil, potassium hydroxide and an ethanol solution, heating, raising the temperature, stirring and reacting to obtain a mixed solution, placing the mixed solution into a separating funnel, adding hydrochloric acid into the separating funnel, adjusting the pH value of the mixed solution, standing, separating to remove a water layer to obtain an oil layer, washing the oil layer with distilled water for 3-5 times to obtain a purified oil layer, namely esterified oleic acid;
(4) mixing corn straws and rice bran, putting the mixture into a crusher for crushing, sieving to obtain mixed bran powder, putting 80-100 g of the mixed bran powder, 20-30 g of oil refinery waste oil and 40-50 g of esterified oleic acid into a fermentation tank, sequentially adding 40-50 g of soft paraffin and 20-30 g of microcrystalline wax into a crucible, heating to raise the temperature to completely melt the mixture, dropwise adding the mixture into the fermentation tank while the mixture is hot, and performing heat preservation and fermentation to obtain a fermentation product;
(5) heating the fermentation product, filtering to remove filter residues to obtain a filtrate, cooling the filtrate to room temperature to obtain fermented wax powder, mixing the fermented wax powder with 2, 6-di-tert-butyl-4- (diphenylamino) phenol, washing with ethanol and deionized water for 3-5 times in sequence, and standing and drying at room temperature to obtain activated wax powder;
(6) and sequentially adding 70-80 g of the activated wax powder, 20-25 g of quick lime and 10-15 g of diatomite into a three-neck flask with a stirrer, heating the three-neck flask in an oil bath, starting the stirrer, stirring and mixing, adding 0.10-0.15 g of manganese stearate to obtain a reaction product, pouring the reaction product of the three-neck flask into a plate-frame mold, cooling to room temperature, and demolding to obtain the oxidized safety-shaped paraffin.
2. The method for preparing an oxidized fixed paraffin according to claim 1, wherein the method comprises the following steps: the stirring speed in the step (1) is 300-350 r/min, the temperature after heating is 140-160 ℃, and the stirring reaction time is 3-4 h.
3. The method for preparing an oxidized fixed paraffin according to claim 1, wherein the method comprises the following steps: the temperature of the heated and heated product in the step (2) is 140-150 ℃, the distillation time is 1-2 h, the temperature of absolute ethyl alcohol is-20 to-15 ℃, the freezing time is 2-3 h, the temperature of the heated product in an oven is 90-100 ℃, and the drying time is 4-5 h.
4. The method for preparing an oxidized fixed paraffin according to claim 1, wherein the method comprises the following steps: the mass fraction of the ethanol solution in the step (3) is 75%, the mixing mass ratio of the soybean oil, the potassium hydroxide and the ethanol solution is 5: 1: 8, the temperature is 40-50 ℃ after heating, the stirring reaction time is 15-20 min, the mass fraction of hydrochloric acid is 20%, the PH of the mixed solution is adjusted to 2-3, and the standing time is 5-8 min.
5. The method for preparing an oxidized fixed paraffin according to claim 1, wherein the method comprises the following steps: the mixing mass ratio of the corn straws to the rice bran in the step (4) is 4:1, the granularity of the obtained mixed bran powder is 200 meshes, the temperature after heating is 60-80 ℃, the temperature is increased to 40-50 ℃ in a fermentation tank, and the heat preservation and fermentation time is 4-5 days.
6. The method for preparing an oxidized fixed paraffin according to claim 1, wherein the method comprises the following steps: and (3) heating the fermentation product obtained in the step (5) to raise the temperature to 70-80 ℃, mixing the fermentation wax powder and 2, 6-di-tert-butyl-4- (diphenylamino) phenol in a mass ratio of 5:1, and standing and drying at normal temperature for 30-40 min to obtain the activated wax powder.
7. The method for preparing an oxidized fixed paraffin according to claim 1, wherein the method comprises the following steps: and (4) raising the temperature of the three-neck flask oil bath in the step (6) to 120-150 ℃, stirring at the rotating speed of 300-350 r/min, and stirring and mixing for 10-15 min.
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