CN113122017A - Storage battery shell recycling and granulating process - Google Patents
Storage battery shell recycling and granulating process Download PDFInfo
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- CN113122017A CN113122017A CN202110593831.4A CN202110593831A CN113122017A CN 113122017 A CN113122017 A CN 113122017A CN 202110593831 A CN202110593831 A CN 202110593831A CN 113122017 A CN113122017 A CN 113122017A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The invention discloses a storage battery shell recycling and granulating process, which belongs to the technical field of plastic preparation, wherein a storage battery shell is cleaned and crushed to obtain plastic master batches, then 100-120 parts of the plastic master batches, 4-8 parts of flame-retardant filler, 3-10 parts of plasticizer and 3-5 parts of lubricant are weighed, and finally melting, extruding, cooling and granulating are carried out; and a flame-retardant filler is prepared in the process of recycling and granulating, when plastics are burnt, oxyacid of phosphorus on the flame-retardant filler catalyzes hydroxyl-containing compounds to dehydrate into carbon, so that a coke layer is generated on the surface of the material, the coke layer can insulate oxygen and heat and further extinguish flame, and aluminum hydroxide on the surface of the flame-retardant filler is decomposed to generate water and oxide, so that heat generated by combustion is absorbed, the heat is reduced, and simultaneously a large amount of water vapor is generated, so that the flame is quickly extinguished.
Description
Technical Field
The invention relates to the technical field of plastic preparation, in particular to a recycling and granulating process for a storage battery shell.
Background
The accumulator is a device for directly converting chemical energy into electric energy, is a battery designed according to rechargeability, realizes recharging through reversible chemical reaction, is usually a lead-acid accumulator, is one of batteries, belongs to a secondary battery, uses a lead-based grid filled with spongy lead as a negative electrode, uses a lead-based grid filled with lead dioxide as a positive electrode, and uses dilute sulfuric acid with the density of 1.26-1.33 g/mlg/ml as an electrolyte;
when the battery discharges, the metal lead is a negative electrode and generates oxidation reaction to generate lead sulfate; lead dioxide is a positive electrode and is subjected to reduction reaction to generate lead sulfate, when the battery is charged by direct current, elemental lead and lead dioxide are respectively generated at two electrodes, and after a power supply is removed, the battery is restored to a state before discharge to form a chemical battery, and as the demand of the storage battery is increased and increased along with the development of times, more and more storage battery shells age, and the storage battery shell recycling process also gradually enters the visual field of people;
in the existing plastic recycling and granulating process, recycled plastic is only crushed, cleaned and melted, so that the prepared recycled plastic has poor performance, especially the flame retardant effect is greatly reduced, and the market prospect of the recycled plastic is general;
in view of the above technical drawbacks, a solution is proposed.
Disclosure of Invention
The invention aims to provide a recycling and granulating process for a storage battery shell.
The technical problems to be solved by the invention are as follows:
the existing plastic recycling and granulating process only crushes, cleans and melts recycled plastic, so that the prepared recycled plastic has poor performance, especially the flame retardant effect is greatly reduced, and the market prospect of the recycled plastic is common.
The purpose of the invention can be realized by the following technical scheme:
a recycling and granulating process for a storage battery shell specifically comprises the following steps:
step S1: cleaning and crushing the storage battery shell to obtain plastic master batches;
step S2: weighing 120 parts of 100-120 parts of plastic master batch, 4-8 parts of flame-retardant filler, 3-10 parts of plasticizer and 3-5 parts of lubricant;
step S3: melting, extruding, cooling and granulating the raw materials.
Further, the plasticizer is one or more of di (2-ethylhexyl) phthalate, dibutyl phthalate and diethyl phthalate which are mixed in any proportion, and the lubricant is one or more of oleamide, n-butyl stearate and erucamide which are mixed in any proportion.
Further, the flame-retardant filler is prepared by the following steps:
step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring and adding potassium permanganate under the conditions that the rotating speed is 150-plus-200 r/min and the temperature is 0-5 ℃, reacting for 2-3h, heating to the temperature of 30-40 ℃, stirring for 3-5h, adding deionized water, reacting for 30-40min under the temperature of 90-95 ℃, adding hydrogen peroxide until no bubbles are generated, washing the reaction solution until the reaction solution is free of SO4 2-Filtering ions, and drying a filter cake to obtain graphene oxide;
step A2: dispersing graphene oxide in deionized water, adding 1-hydroxybenzotriazole, stirring and adding ethylenediamine under the conditions that the rotating speed is 150-plus-200 r/min and the temperature is 40-50 ℃, reacting for 3-5h to obtain modified graphene, dispersing the modified graphene in the deionized water, adding aluminum hydroxide under the conditions that the temperature is 200-plus-220 ℃ and the pH value is 10-12, reacting for 2-3h, cooling to the temperature of 20-25 ℃, filtering, washing with deionized water, and drying to obtain a flame retardant carrier;
step A3: adding diphenylphosphinic chloride into a reaction kettle, stirring and adding aluminum trichloride and liquefied methane chloride under the conditions that the rotation speed is 150-200r/min and the temperature is 50-60 ℃, reacting for 3-5h to obtain an intermediate 1, adding the intermediate 1, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 8-10h under the condition that the temperature is 80-90 ℃ to obtain an intermediate 2, adding the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, performing reflux reaction for 2-3h to obtain an intermediate 3, dispersing a flame-retardant carrier into toluene, adding the intermediate 3, and stirring for 2-3h under the condition that the rotation speed is 200-300r/min to obtain a modified carrier;
the reaction process is as follows:
step A4: adding phenyl phosphoryl dichloride and chloroform into a reaction kettle, stirring until the phenyl phosphoryl dichloride is completely dissolved under the condition of the rotation speed of 150-, to prepare an intermediate 6;
the reaction process is as follows:
step A5: adding the intermediate 6, tin powder and concentrated hydrochloric acid into a reaction kettle, heating and reacting for 20-25min under the condition of boiling water bath, adjusting the pH value of reaction liquid to 10-11 to obtain an intermediate 7, dissolving cyanuric chloride in acetone, adding the intermediate 7, reacting for 5-8h under the conditions that the rotating speed is 150 plus materials/min and the temperature is 40-50 ℃, adding a modified carrier, continuously stirring for 3-5h, filtering to remove filtrate, and drying a filter cake to obtain the flame-retardant filler.
The reaction process is as follows:
further, the usage ratio of the graphite, the sodium nitrate, the concentrated sulfuric acid, the potassium permanganate, the deionized water and the hydrogen peroxide in the step A1 is 5 g: 23 g: 100mL of: 25g of: 150mL of: 15mL, and the mass fraction of concentrated sulfuric acid is 95%.
Further, the usage mass ratio of the graphene oxide, the 1-hydroxybenzotriazole and the ethylenediamine in the step A2 is 5: 1.5: 1, the mass ratio of the modified graphene to the aluminum hydroxide is 1: 1.2.
further, the molar ratio of the diphenylphosphinic chloride and the monochloromethane in the step A3 is 1: 2, the dosage of the aluminum trichloride is 8 percent of the mass of the diphenylphosphine chloride, and the dosage ratio of the intermediate 1, the nitrogen-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride is 0.1 mol: 0.12 mol: 0.15 g: 300mL, and the mass ratio of the flame-retardant carrier to the intermediate 3 is 5: 1.
further, the dosage ratio of the phenyl phosphoryl dichloride and the mixed acid in the step A4 is 1 g: 5mL, wherein the mixed acid is concentrated nitric acid with the mass fraction of 68% and concentrated sulfuric acid with the mass fraction of 95% in a volume ratio of 1: 2, mixing the intermediate 4 and the benzenediol in a molar ratio of 1: 2, the amount of triethylamine is 25% of the mass of the intermediate 4, and the molar ratio of the intermediate 5 to the diphenyl chlorophosphate is 1: 2, the dosage of triethylamine is 15 percent of the mass of the intermediate 5.
Further, the dosage ratio of the intermediate 6, the tin powder and the concentrated hydrochloric acid in the step A5 is 2 g: 7 g: 20g, the mass fraction of concentrated hydrochloric acid is 36%, and the dosage ratio of cyanuric chloride, the intermediate 7 and the modified carrier is 0.01 mol: 0.02 mol: 5g of the total weight.
The invention has the beneficial effects that:
the invention prepares a flame-retardant filler in the process of recycling and granulating the shell of a storage battery, the flame-retardant filler takes graphite as a raw material to be oxidized to prepare graphene oxide, the graphene oxide and ethylenediamine are subjected to dehydration condensation to graft A level on the surface of the graphene oxide to prepare modified graphene, the modified graphene and aluminum hydroxide are subjected to hydrothermal reaction to embed aluminum hydroxide on the surface of the modified graphene to prepare a flame-retardant carrier, diphenylphosphinic chloride reacts with methane chloride to prepare an intermediate 1, the intermediate 1 is treated with nitrogen-bromosuccinimide to prepare an intermediate 2, the intermediate 2 is further treated to prepare an intermediate 3, the intermediate 3 reacts with the flame-retardant carrier to react chlorine atom sites of the intermediate 3 with amino groups on the surface of the flame-retardant carrier to prepare the modified carrier, the method comprises the steps of treating phenylphosphoryl dichloride with mixed acid to obtain an intermediate 4, further reacting the intermediate 4 with benzenediol to obtain an intermediate 5, reacting the intermediate 5 with diphenyl chlorophosphate to obtain an intermediate 6, reducing the intermediate 6 to obtain an intermediate 7, reacting the intermediate 7 with cyanuric chloride through temperature control to ensure that amino of the intermediate 7 reacts with two chlorine atom sites of the cyanuric chloride, reacting with amino on the surface of a modified carrier through temperature control to obtain the flame-retardant filler, dehydrating oxyacid of phosphorus on the flame-retardant filler into carbon in a catalysis manner of a hydroxyl-containing compound during the combustion of plastics, further generating a coke layer on the surface of a material, wherein the coke layer can insulate oxygen and heat to extinguish the flame, and aluminum hydroxide on the surface of the flame-retardant filler is decomposed to generate water and oxide to absorb the combustion to generate heat and reduce the heat, simultaneously, a large amount of water vapor is generated, so that the flame is rapidly extinguished.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a recycling and granulating process for a storage battery shell specifically comprises the following steps:
step S1: cleaning and crushing the storage battery shell to obtain plastic master batches;
step S2: weighing 100 parts of plastic master batch, 4 parts of flame-retardant filler, 3 parts of dibutyl phthalate and 3 parts of lubricant according to the following parts by weight;
step S3: melting, extruding, cooling and granulating the raw materials.
The flame-retardant filler is prepared by the following steps:
step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring and adding potassium permanganate under the conditions that the rotating speed is 150r/min and the temperature is 0 ℃, reacting for 2 hours, heating to the temperature of 30 ℃, stirring for 3 hours, adding deionized water, reacting for 30 minutes under the condition that the temperature is 90 ℃, adding hydrogen peroxide until no bubbles are generated, washing the reaction solution until no SO is generated in the reaction solution4 2-Filtering ions, and drying a filter cake to obtain graphene oxide;
step A2: dispersing graphene oxide in deionized water, adding 1-hydroxybenzotriazole, stirring and adding ethylenediamine at the rotation speed of 150r/min and the temperature of 40 ℃, reacting for 3 hours to obtain modified graphene, dispersing the modified graphene in the deionized water, adding aluminum hydroxide at the temperature of 200 ℃ and the pH value of 10, reacting for 2 hours, cooling to the temperature of 20 ℃, filtering, washing with deionized water, and drying to obtain a flame-retardant carrier;
step A3: adding diphenylphosphinic chloride into a reaction kettle, stirring and adding aluminum trichloride and liquefied methane chloride under the conditions that the rotating speed is 150r/min and the temperature is 50 ℃, reacting for 3 hours to obtain an intermediate 1, adding the intermediate 1, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 8 hours at the temperature of 80 ℃ to obtain an intermediate 2, adding the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, performing reflux reaction for 2 hours to obtain an intermediate 3, dispersing a flame-retardant carrier into toluene, adding the intermediate 3, and stirring for 2 hours at the rotating speed of 200r/min to obtain a modified carrier;
step A4: adding phenylphosphoryl dichloride and chloroform into a reaction kettle, stirring at the rotation speed of 150r/min until the phenylphosphoryl dichloride is completely dissolved, heating to the temperature of 50 ℃, dropwise adding mixed acid for 1h, reacting for 20min after the dropwise addition is finished to obtain an intermediate 4, adding benzenediol, dichloroethane and triethylamine into the reaction kettle, introducing nitrogen for protection, adding the intermediate 4 at the rotation speed of 120r/min and the temperature of 0 ℃, reacting for 3h, washing with water until the pH value of a reaction solution is 7, distilling to remove a solvent to obtain an intermediate 5, adding the intermediate 5, diphenyl chlorophosphate, dichloromethane and triethylamine into the reaction kettle, and stirring at the rotation speed of 200r/min for 20min to obtain an intermediate 6;
step A5: adding the intermediate 6, tin powder and concentrated hydrochloric acid into a reaction kettle, heating and reacting for 20min under the condition of boiling water bath, adjusting the pH value of reaction liquid to 10 to prepare an intermediate 7, dissolving cyanuric chloride in acetone, adding the intermediate 7, reacting for 5h at the rotation speed of 150r/min and the temperature of 40 ℃, adding a modified carrier, continuously stirring for 3h, filtering to remove filtrate, and drying a filter cake to prepare the flame-retardant filler.
Example 2:
a recycling and granulating process for a storage battery shell specifically comprises the following steps:
step S1: cleaning and crushing the storage battery shell to obtain plastic master batches;
step S2: weighing 105 parts of plastic master batch, 6 parts of flame-retardant filler, 5 parts of dibutyl phthalate and 4 parts of oleamide;
step S3: melting, extruding, cooling and granulating the raw materials.
The flame-retardant filler is prepared by the following steps:
step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring and adding potassium permanganate under the conditions that the rotating speed is 150r/min and the temperature is 5 ℃, reacting for 2 hours, heating to 40 ℃, stirring for 3 hours, adding deionized water, reacting for 30 minutes under the condition that the temperature is 95 ℃, adding hydrogen peroxide until no bubbles are generated, and washing for reactionLiquid until the reaction liquid is free of SO4 2-Filtering ions, and drying a filter cake to obtain graphene oxide;
step A2: dispersing graphene oxide in deionized water, adding 1-hydroxybenzotriazole, stirring and adding ethylenediamine at the rotation speed of 200r/min and the temperature of 40 ℃ to react for 5 hours to obtain modified graphene, dispersing the modified graphene in the deionized water, adding aluminum hydroxide at the temperature of 200 ℃ and the pH value of 12 to react for 2 hours, cooling to the temperature of 25 ℃, filtering, washing with deionized water, and drying to obtain a flame-retardant carrier;
step A3: adding diphenylphosphinic chloride into a reaction kettle, stirring and adding aluminum trichloride and liquefied methane chloride under the conditions that the rotating speed is 150r/min and the temperature is 60 ℃, reacting for 3 hours to obtain an intermediate 1, adding the intermediate 1, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 8 hours at the temperature of 90 ℃ to obtain an intermediate 2, adding the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, performing reflux reaction for 3 hours to obtain an intermediate 3, dispersing a flame-retardant carrier into toluene, adding the intermediate 3, and stirring for 3 hours at the rotating speed of 200r/min to obtain a modified carrier;
step A4: adding phenylphosphoryl dichloride and chloroform into a reaction kettle, stirring at the rotation speed of 150r/min until the phenylphosphoryl dichloride is completely dissolved, heating to 55 ℃, dropwise adding mixed acid for 1h, reacting for 30min after the dropwise addition is finished to obtain an intermediate 4, adding benzenediol, dichloroethane and triethylamine into the reaction kettle, introducing nitrogen for protection, adding the intermediate 4 at the rotation speed of 120r/min and the temperature of 3 ℃, reacting for 3h, washing with water until the pH value of a reaction solution is 7, distilling to remove a solvent to obtain an intermediate 5, adding the intermediate 5, diphenyl chlorophosphate, dichloromethane and triethylamine into the reaction kettle, and stirring at the rotation speed of 300r/min for 20min to obtain an intermediate 6;
step A5: adding the intermediate 6, tin powder and concentrated hydrochloric acid into a reaction kettle, heating and reacting for 25min under the condition of boiling water bath, adjusting the pH value of reaction liquid to 10 to obtain an intermediate 7, dissolving cyanuric chloride in acetone, adding the intermediate 7, reacting for 8h at the rotation speed of 200r/min and the temperature of 40 ℃, adding a modified carrier, continuously stirring for 3h, filtering to remove filtrate, and drying a filter cake to obtain the flame-retardant filler.
Example 3:
a recycling and granulating process for a storage battery shell specifically comprises the following steps:
step S1: cleaning and crushing the storage battery shell to obtain plastic master batches;
step S2: weighing 110 parts of plastic master batch, 7 parts of flame-retardant filler, 8 parts of dibutyl phthalate and 4 parts of oleamide;
step S3: melting, extruding, cooling and granulating the raw materials.
The flame-retardant filler is prepared by the following steps:
step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring and adding potassium permanganate under the conditions that the rotating speed is 200r/min and the temperature is 0 ℃, reacting for 3 hours, heating to the temperature of 30 ℃, stirring for 5 hours, adding deionized water, reacting for 40 minutes under the condition that the temperature is 90 ℃, adding hydrogen peroxide until no bubbles are generated, washing the reaction solution until no SO is generated in the reaction solution4 2-Filtering ions, and drying a filter cake to obtain graphene oxide;
step A2: dispersing graphene oxide in deionized water, adding 1-hydroxybenzotriazole, stirring and adding ethylenediamine at the rotation speed of 150r/min and the temperature of 50 ℃, reacting for 3 hours to obtain modified graphene, dispersing the modified graphene in the deionized water, adding aluminum hydroxide at the temperature of 220 ℃ and the pH value of 10, reacting for 3 hours, cooling to 20 ℃, filtering, washing with deionized water, and drying to obtain a flame-retardant carrier;
step A3: adding diphenylphosphinic chloride into a reaction kettle, stirring and adding aluminum trichloride and liquefied methane chloride under the conditions that the rotating speed is 200r/min and the temperature is 50 ℃, reacting for 5 hours to obtain an intermediate 1, adding the intermediate 1, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 10 hours under the condition that the temperature is 80 ℃ to obtain an intermediate 2, adding the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, performing reflux reaction for 2 hours to obtain an intermediate 3, dispersing a flame-retardant carrier into toluene, adding the intermediate 3, and stirring for 2 hours under the condition that the rotating speed is 300r/min to obtain a modified carrier;
step A4: adding phenylphosphoryl dichloride and chloroform into a reaction kettle, stirring at the rotation speed of 200r/min until the phenylphosphoryl dichloride is completely dissolved, heating to the temperature of 50 ℃, dropwise adding mixed acid for 1.5h, reacting for 20min after the dropwise addition is finished to obtain an intermediate 4, adding benzenediol, dichloroethane and triethylamine into the reaction kettle, introducing nitrogen for protection, adding the intermediate 4 at the rotation speed of 130r/min and the temperature of 0 ℃, reacting for 5h, washing with water until the pH value of reaction liquid is 7, distilling to remove the solvent to obtain an intermediate 5, adding the intermediate 5, diphenyl chlorophosphate, dichloromethane and triethylamine into the reaction kettle, and stirring at the rotation speed of 200r/min for 30min to obtain an intermediate 6;
step A5: adding the intermediate 6, tin powder and concentrated hydrochloric acid into a reaction kettle, heating and reacting for 20min under the condition of boiling water bath, adjusting the pH value of reaction liquid to 11 to prepare an intermediate 7, dissolving cyanuric chloride in acetone, adding the intermediate 7, reacting for 5h at the rotation speed of 150r/min and the temperature of 50 ℃, adding a modified carrier, continuously stirring for 5h, filtering to remove filtrate, and drying a filter cake to prepare the flame-retardant filler.
Example 4:
a recycling and granulating process for a storage battery shell specifically comprises the following steps:
step S1: cleaning and crushing the storage battery shell to obtain plastic master batches;
step S2: weighing 120 parts of plastic master batch, 8 parts of flame-retardant filler, 10 parts of dibutyl phthalate and 5 parts of oleamide;
step S3: melting, extruding, cooling and granulating the raw materials.
The flame-retardant filler is prepared by the following steps:
step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring and adding potassium permanganate under the conditions that the rotating speed is 200r/min and the temperature is 5 ℃, reacting for 3 hours, heating to 40 ℃, stirring for 5 hours, adding deionized water, reacting for 40 minutes under the condition that the temperature is 95 ℃, adding hydrogen peroxide until no bubbles are generated, washing the reaction solution until the reaction solution is free of SO4 2-Filtering ions, and drying a filter cake to obtain graphene oxide;
step A2: dispersing graphene oxide in deionized water, adding 1-hydroxybenzotriazole, stirring and adding ethylenediamine at the rotation speed of 200r/min and the temperature of 50 ℃, reacting for 5 hours to obtain modified graphene, dispersing the modified graphene in the deionized water, adding aluminum hydroxide at the temperature of 220 ℃ and the pH value of 12, reacting for 3 hours, cooling to 25 ℃, filtering, washing with deionized water, and drying to obtain a flame-retardant carrier;
step A3: adding diphenylphosphinic chloride into a reaction kettle, stirring and adding aluminum trichloride and liquefied methane chloride under the conditions that the rotating speed is 200r/min and the temperature is 60 ℃, reacting for 5 hours to obtain an intermediate 1, adding the intermediate 1, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 10 hours at the temperature of 90 ℃ to obtain an intermediate 2, adding the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, performing reflux reaction for 3 hours to obtain an intermediate 3, dispersing a flame-retardant carrier into toluene, adding the intermediate 3, and stirring for 3 hours at the rotating speed of 300r/min to obtain a modified carrier;
step A4: adding phenylphosphoryl dichloride and chloroform into a reaction kettle, stirring at the rotation speed of 200r/min until the phenylphosphoryl dichloride is completely dissolved, heating to 55 ℃, dropwise adding mixed acid for 1.5h, reacting for 30min after the dropwise addition is finished to obtain an intermediate 4, adding benzenediol, dichloroethane and triethylamine into the reaction kettle, introducing nitrogen for protection, adding the intermediate 4 at the rotation speed of 130r/min and the temperature of 3 ℃, reacting for 3-5h, washing with water until the pH value of a reaction solution is 7, distilling to remove a solvent to obtain an intermediate 5, adding the intermediate 5, diphenyl chlorophosphate, dichloromethane and triethylamine into the reaction kettle, and stirring at the rotation speed of 300r/min for 30min to obtain an intermediate 6;
step A5: adding the intermediate 6, tin powder and concentrated hydrochloric acid into a reaction kettle, heating and reacting for 25min under the condition of boiling water bath, adjusting the pH value of reaction liquid to 11 to obtain an intermediate 7, dissolving cyanuric chloride in acetone, adding the intermediate 7, reacting for 8h at the rotation speed of 200r/min and the temperature of 50 ℃, adding a modified carrier, continuously stirring for 5h, filtering to remove filtrate, and drying a filter cake to obtain the flame-retardant filler.
Comparative example 1:
this comparative example compared to example 1, where aluminum hydroxide was used in place of the flame retardant filler, the same procedure was followed.
Comparative example 2:
the comparative example compares with example 1 without adding flame retardant filler and the rest of the procedure is the same.
The plastic master batches obtained in examples 1 to 4 and comparative examples 1 to 2 were subjected to a performance test in the form of a strip having a length of 30cm, and the test results are shown in table 1 below;
TABLE 1
As can be seen from Table 1 above, the burning length of the strand-shaped plastics obtained in examples 1 to 4 was 3.1 to 3.5cm, that of the strand-shaped plastics obtained in comparative example 1 was 6.5cm, that of the strand-shaped plastics obtained in comparative example 2 was 12.3cm, and that the strand-shaped plastics obtained in examples 1 to 4 did not drip when burned, indicating that the flame retardant effect of the present invention is excellent.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (8)
1. A recycling and granulating process for a storage battery shell is characterized by comprising the following steps: the method specifically comprises the following steps:
step S1: cleaning and crushing the storage battery shell to obtain plastic master batches;
step S2: weighing 120 parts of 100-120 parts of plastic master batch, 4-8 parts of flame-retardant filler, 3-10 parts of plasticizer and 3-5 parts of lubricant;
step S3: melting, extruding, cooling and granulating the raw materials.
2. The battery case recycling and pelletizing process according to claim 1, characterized in that: the plasticizer is one or more of di (2-ethylhexyl) phthalate, dibutyl phthalate and diethyl phthalate which are mixed in any proportion, and the lubricant is one or more of oleamide, n-butyl stearate and erucamide which are mixed in any proportion.
3. The battery case recycling and pelletizing process according to claim 1, characterized in that: the flame-retardant filler is prepared by the following steps:
step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring and adding potassium permanganate under the conditions that the rotating speed is 150-plus-200 r/min and the temperature is 0-5 ℃, reacting for 2-3h, heating to the temperature of 30-40 ℃, stirring for 3-5h, adding deionized water, reacting for 30-40min under the temperature of 90-95 ℃, adding hydrogen peroxide until no bubbles are generated, washing the reaction solution until the reaction solution is free of SO4 2-Filtering ions, and drying a filter cake to obtain graphene oxide;
step A2: dispersing graphene oxide in deionized water, adding 1-hydroxybenzotriazole, stirring and adding ethylenediamine under the conditions that the rotating speed is 150-plus-200 r/min and the temperature is 40-50 ℃, reacting for 3-5h to obtain modified graphene, dispersing the modified graphene in the deionized water, adding aluminum hydroxide under the conditions that the temperature is 200-plus-220 ℃ and the pH value is 10-12, reacting for 2-3h, cooling to the temperature of 20-25 ℃, filtering, washing with deionized water, and drying to obtain a flame retardant carrier;
step A3: adding diphenylphosphinic chloride into a reaction kettle, stirring and adding aluminum trichloride and liquefied methane chloride under the conditions that the rotation speed is 150-200r/min and the temperature is 50-60 ℃, reacting for 3-5h to obtain an intermediate 1, adding the intermediate 1, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 8-10h under the condition that the temperature is 80-90 ℃ to obtain an intermediate 2, adding the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, performing reflux reaction for 2-3h to obtain an intermediate 3, dispersing a flame-retardant carrier into toluene, adding the intermediate 3, and stirring for 2-3h under the condition that the rotation speed is 200-300r/min to obtain a modified carrier;
step A4: adding phenyl phosphoryl dichloride and chloroform into a reaction kettle, stirring until the phenyl phosphoryl dichloride is completely dissolved under the condition of the rotation speed of 150-, to prepare an intermediate 6;
step A5: adding the intermediate 6, tin powder and concentrated hydrochloric acid into a reaction kettle, heating and reacting for 20-25min under the condition of boiling water bath, adjusting the pH value of reaction liquid to 10-11 to obtain an intermediate 7, dissolving cyanuric chloride in acetone, adding the intermediate 7, reacting for 5-8h under the conditions that the rotating speed is 150 plus materials/min and the temperature is 40-50 ℃, adding a modified carrier, continuously stirring for 3-5h, filtering to remove filtrate, and drying a filter cake to obtain the flame-retardant filler.
4. The battery case recycling and pelletizing process according to claim 3, characterized in that: the use amount ratio of the graphite, the sodium nitrate, the concentrated sulfuric acid, the potassium permanganate, the deionized water and the hydrogen peroxide in the step A1 is 5 g: 23 g: 100mL of: 25g of: 150mL of: 15mL, and the mass fraction of concentrated sulfuric acid is 95%.
5. The battery case recycling and pelletizing process according to claim 3, characterized in that: the dosage mass ratio of the graphene oxide, the 1-hydroxybenzotriazole and the ethylenediamine in the step A2 is 5: 1.5: 1, the mass ratio of the modified graphene to the aluminum hydroxide is 1: 1.2.
6. the battery case recycling and pelletizing process according to claim 3, characterized in that: the molar ratio of the diphenyl phosphinic chloride to the monochloromethane in the step A3 is 1: 2, the dosage of the aluminum trichloride is 8 percent of the mass of the diphenylphosphine chloride, and the dosage ratio of the intermediate 1, the nitrogen-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride is 0.1 mol: 0.12 mol: 0.15 g: 300mL, and the mass ratio of the flame-retardant carrier to the intermediate 3 is 5: 1.
7. the battery case recycling and pelletizing process according to claim 3, characterized in that: the dosage ratio of the phenyl phosphoryl dichloride and the mixed acid in the step A4 is 1 g: 5mL, wherein the mixed acid is concentrated nitric acid with the mass fraction of 68% and concentrated sulfuric acid with the mass fraction of 95% in a volume ratio of 1: 2, mixing the intermediate 4 and the benzenediol in a molar ratio of 1: 2, the amount of triethylamine is 25% of the mass of the intermediate 4, and the molar ratio of the intermediate 5 to the diphenyl chlorophosphate is 1: 2, the dosage of triethylamine is 15 percent of the mass of the intermediate 5.
8. The battery case recycling and pelletizing process according to claim 3, characterized in that: the dosage ratio of the intermediate 6, the tin powder and the concentrated hydrochloric acid in the step A5 is 2 g: 7 g: 20g, the mass fraction of concentrated hydrochloric acid is 36%, and the dosage ratio of cyanuric chloride, the intermediate 7 and the modified carrier is 0.01 mol: 0.02 mol: 5g of the total weight.
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