CN111451254B - Method for recycling industrial waste residue containing benzophenone hydrazone - Google Patents
Method for recycling industrial waste residue containing benzophenone hydrazone Download PDFInfo
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- CN111451254B CN111451254B CN202010368190.8A CN202010368190A CN111451254B CN 111451254 B CN111451254 B CN 111451254B CN 202010368190 A CN202010368190 A CN 202010368190A CN 111451254 B CN111451254 B CN 111451254B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/10—Destroying solid waste or transforming solid waste into something useful or harmless involving an adsorption step
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
Abstract
The invention relates to the field of environmental protection, in particular to a method for recycling industrial waste residue containing benzophenone hydrazone; the invention provides a method for recycling benzophenone hydrazone in industrial waste residues containing benzophenone hydrazone, which changes the waste residues into valuable substances; the method comprises the steps of firstly, dissolving benzophenone hydrazone by using a solvent with a preferable composition, wherein the solvent has the advantages of low cost, small pollution and large dissolving difference, and can effectively remove inorganic salts and part of organic pollutants; then, the invention provides an organic lanthanum adsorption material to remove chromogenic pigment substances contained in waste residues, and a benzophenone hydrazone product with good color and high quality is obtained through crystallization; the invention is an invention creation which changes waste into valuable and greatly saves resources, and has practical value and social benefit.
Description
Technical Field
The invention relates to the field of environmental protection and the field of rare earth materials, in particular to a method for recycling industrial waste residue containing benzophenone hydrazone.
Background
Benzophenone hydrazone is an important organic chemical raw material and is widely applied to the fields of photosensitive materials, spices, ultraviolet absorbers, organic pigments, medicines and insecticides. Along with the increase of the demand, the problem of production waste residue caused by the increase of the demand is more and more serious, and the treatment flow of industrial waste residue containing benzophenone hydrazone is larger and larger.
CN1245501C relates to a decomposing leaven used for treating and utilizing industrial organic waste liquid and waste residue and a production method thereof, which is suitable for occasions requiring fast fermentation temperature rise, short period, strong capability of decomposing cellulose, hemicellulose, lignin, protein and the like and high material decomposition degree, and is particularly suitable for being used as a special decomposing leaven in the comprehensive treatment of molasses alcohol waste liquid, bagasse pith, filter mud and other waste liquid and waste residue in the production of organic fertilizer in the sugar industry of sugarcane. The decomposed leaven is formed by one or the combination of strain koji of cellulose decomposing bacteria, hemicellulose decomposing bacteria, protein decomposing bacteria and starch decomposing bacteria; the species is preferably selected from the following species or combinations thereof: aspergillus niger, Trichoderma viride, Neurospora capsulata, Bacillus subtilis and beer yeast; the strain decomposition capacity is one or corresponding combination of the following: the CMC enzyme activity is 50-1000 mg glucose/g.h, the xylanase activity is 500-5000 mg xylose/g.h, the neutral protease activity is 50-500 micrograms tyrosine/g.h, and the saccharifying enzyme activity is 100-1000 mg glucose/g.h. The production method of the decomposed leaven comprises the steps of firstly collecting and culturing raw strains of cellulase and hemicellulase, then screening high-activity decomposing strains from the collected strains, and finally preparing the decomposed leaven according to the composition and technical parameter requirements of the decomposed leaven.
CN110976487A provides a method for improving hydrogen yield by catalytic pyrolysis of organic solid waste with industrial waste residue, which comprises the following steps: s1, pretreatment of raw materials: sending the organic waste into a jaw crusher through a conveyor to be crushed and storing for later use; s2, activation of the aluminum slag ash: putting the industrial waste residue into a heating furnace, continuously thermally activating within a certain temperature range, S3, putting the industrial waste residue obtained in the step S2 and the organic solid waste into a stirrer according to the mass ratio, and uniformly mixing; s4, respectively feeding the samples uniformly mixed according to the proportion in the step S3 into a pyrolysis reactor for pyrolysis, and introducing a certain protective gas.
CN101691314A discloses a biofertilizer produced by fermenting industrial organic waste residues and waste mother liquor, which is prepared by pretreating bagasse and manioc waste residues by microwave sterilization and the like, then adding waste mother liquor in industrial urea phosphate production, adding strains, fermenting, drying and crushing. The problem of environmental pollution caused by two kinds of industrial waste residues and one kind of industrial waste mother liquor is solved; the method has the advantages of treating wastes with processes of wastes against one another, simple method, easy implementation, changing wastes into valuables and being capable of achieving better economic benefits and environmental protection benefits. Is widely applicable to the harmless and resource utilization of industrial organic waste residues.
The method for treating waste residues containing organic matters in the invention and the prior art generally achieves the aim of treatment by harmlessly degrading the organic matters in modes of incineration, fermentation, oxidation and the like, but has great economic value if the benzophenone hydrazone product can be recovered from the industrial waste residues containing the benzophenone hydrazone due to great demand of the benzophenone hydrazone.
Disclosure of Invention
In order to solve the problems, the invention provides a method for recycling industrial waste residue containing benzophenone hydrazone.
A method for recycling industrial waste residue containing benzophenone hydrazone comprises the following specific scheme:
firstly preparing a solvent, adding 520 parts of 350-one-resin cyclohexane, 300 parts of 100-one-resin ester solvent, 50-120 parts of alcohol solvent and 80-140 parts of petroleum ether in a reaction kettle according to the mass parts, uniformly mixing, adding 210 parts of industrial waste residues into the reaction kettle, controlling the temperature to be 40-60 ℃, stirring and mixing for 10-40min, cooling to be 20-30 ℃ after completion, filtering out insoluble substances, leaching filtrate with the solvent, combining the filtrate, adding 10-18 parts of adsorbent material into the filtrate, controlling the temperature to be 70-90 ℃, performing reflux adsorption for 90-120min, cooling to be 20-30 ℃, filtering out the adsorbent material, condensing the filtrate to be 40-60%, cooling to be 5-20 ℃ under slow stirring, standing for crystallization for 5-10h, filtering after completion, leaching the filter residue with ethanol, and drying to obtain the recovered benzophenone hydrazone.
The adsorbent material is an organic lanthanum adsorption material, and the preparation method comprises the following steps:
uniformly mixing 20-50 parts of macroporous adsorbent resin and 60-80 parts of chloroform according to the parts by weight, controlling the temperature to be 50-60 ℃, swelling for 10-20h, then adding 12-18 parts of 2-chloroethyl chloromethyl ether and 0.5-3.5 parts of zinc chloride, uniformly mixing, controlling the temperature to be 60-70 ℃, carrying out reflux reaction for 10-15h, filtering after the reflux reaction is finished, washing with methanol, uniformly mixing with 5.6-9.4 parts of sodium hydroxide, adding 120-150 parts of 10-25% dimethylformamide aqueous solution serving as a solvent, uniformly mixing, soaking for 10-18h, then 4.2 to 6.8 portions of 1-methyl vinyl amine is added into a reaction kettle, controlling the temperature to be 80-95 ℃ for reacting for 16-24h, filtering after the reaction is finished, washing with water and drying to obtain an intermediate product 1.
The equation is as follows:
according to the mass parts, 100 parts of intermediate product 1, 20-30 parts of 1, 2-bis (dimethylsilyl) benzene, 2-7 parts of lanthanum methacrylate, 3-7 parts of chloroplatinic acid ethanol solution with the mass percent concentration of 3-10%, 1000 parts of n-butyl alcohol, 70-80 ℃, introducing nitrogen, reacting for 3-6 hours, cooling to room temperature after completion, filtering, and drying to obtain the organic lanthanum adsorbing material.
The equation is as follows:
the industrial waste residue is industrial waste residue containing benzophenone hydrazone, and the main components of the industrial waste residue are benzophenone hydrazone, inorganic salt, other organic pollutants and color development substances.
The ester solvent is ethyl acetate or butyl acetate or isopropyl acetate.
The alcohol solvent is isopropanol or propanol or butanol.
And the filtrate after crystallization and filtration is concentrated and recovered and then is adjusted to the designed mixture ratio for recycling.
The invention relates to a method for recycling industrial waste residue containing benzophenone hydrazone, and provides a method for changing the industrial waste residue containing benzophenone hydrazone into valuable and recycling the benzophenone hydrazone in the industrial waste residue; the method comprises the steps of firstly, dissolving benzophenone hydrazone by using a solvent with a preferable composition, wherein the solvent has the advantages of low cost, small pollution and large dissolving difference, and can effectively remove inorganic salts and part of organic pollutants; then, the invention provides an organic lanthanum adsorption material to remove chromogenic pigment substances contained in waste residues, and a benzophenone hydrazone product with good color and high quality is obtained through crystallization; the invention is an invention creation which changes waste into valuable and greatly saves resources, and has practical value and social benefit.
Polystyrene is used as an adsorbent of a base material, the polystyrene is combined with 1, 2-bis (dimethyl silicon-based) benzene and lanthanum methacrylate together through hydrosilylation, the adsorption effect is more selective, and meanwhile, lanthanum complexes on the surface of the adsorbent can comprise pores on the surface, so that the adsorbent is not easy to collapse and break, the adsorption effect of the adsorbent is improved, and the service life of the adsorbent is prolonged.
Drawings
FIG. 1 is a Fourier infrared spectrum of a product of organolanthanum sorbent material prepared in example 2.
At 1603/1504/1451/1375cm-1The expansion absorption peak of benzene ring skeleton is around 3028cm-1The expansion and contraction absorption peak of the hydrocarbon exists nearby, and is 736/692cm-1An out-of-plane bending absorption peak of the hydrocarbon exists nearby, so that the macroporous adsorbent resin participates in the reaction; at 791cm-1The expansion and contraction absorption peak of silicon carbon exists nearby and is at 2150cm-1A stretching absorption peak of silicon hydrogen exists nearby, which indicates that 1, 2-bis (dimethylsilyl) benzene participates in the reaction; at 791cm-1The absorption peak of carbon and chlorine in the vicinity of the peak is 1085cm-1An antisymmetric telescopic absorption peak of carbon and oxygen exists nearby, which indicates that the 2-chloroethyl chloromethyl ether participates in the reaction; at 1034cm-1The absorption peak of expansion and contraction of a carbon-nitrogen single bond is 3330cm-1A stretching absorption peak of nitrogen and hydrogen exists nearby, which indicates that the 1-methyl vinyl amine participates in the reaction; at 1405cm-1A telescopic absorption peak of carboxylate ions exists nearby, and the lanthanum methacrylate participates in the reaction.
Detailed Description
The invention is further illustrated by the following specific examples:
example 1
A method for recycling industrial waste residue containing benzophenone hydrazone comprises the following specific scheme:
firstly preparing a solvent, adding 430kg of cyclohexane, 200kg of an ester solvent, 80kg of an alcohol solvent and 100kg of petroleum ether into a reaction kettle according to the mass parts, uniformly mixing, adding 160kg of industrial waste residues into the reaction kettle, controlling the temperature to be 50 ℃, stirring and mixing for 25min, cooling to 25 ℃ after completion, filtering insoluble substances, leaching filtrate by using the solvent, combining the filtrate, adding 14kg of adsorbent material into the filtrate, controlling the temperature to be 80 ℃, performing reflux adsorption for 100min, cooling to 25 ℃, filtering the adsorbent material, condensing the filtrate to 50%, slowly stirring, cooling to 12 ℃, standing and crystallizing for 8h, filtering after completion, leaching by using ethanol, and drying to obtain the recovered benzophenone hydrazone.
The adsorbent material is an organic lanthanum adsorption material, and the preparation method comprises the following steps:
according to the mass portion, 20 portions of macroporous absorbent resin and 60 portions of chloroform are mixed uniformly, the temperature is controlled at 50 ℃, the swelling is carried out for 10 hours, then 12 portions of 2-chloroethyl chloromethyl ether and 0.5 portion of zinc chloride are added, the temperature is controlled at 60 ℃ after the uniform mixing, the reflux reaction is carried out for 10 hours, the filtration is carried out after the completion, the mixture is washed by methanol, the mixture is mixed uniformly with 5.6 portions of sodium hydroxide, 120 portions of 10% dimethylformamide aqueous solution is added as a solvent, the mixture is soaked for 10 hours after the uniform mixing, then 4.2 portions of 1-methyl vinyl amine are added into a reaction kettle, the temperature is controlled at 80 ℃, the reaction is carried out for 16 hours, the filtration is carried out after the reaction, the water washing and the drying are carried out, and the intermediate product 1 can be obtained.
According to the mass parts, 100 parts of intermediate product 1, 20 parts of 1, 2-bis (dimethylsilyl) benzene, 2 parts of lanthanum methacrylate, 3 parts of chloroplatinic acid ethanol solution with the mass percent concentration of 3%, 1000 parts of n-butanol, 70 ℃, introducing nitrogen, reacting for 3 hours, cooling to room temperature after the reaction is finished, filtering, and drying to obtain the organic lanthanum adsorbing material.
The industrial waste residue is industrial waste residue containing benzophenone hydrazone, and the main components of the industrial waste residue are benzophenone hydrazone, inorganic salt, other organic pollutants and color development substances.
The ester solvent is butyl acetate.
The alcohol solvent is propanol.
And the filtrate after crystallization and filtration is concentrated and recovered and then is adjusted to the designed mixture ratio for recycling.
The recovery rate of the benzophenone hydrazone product from the industrial waste residue containing the benzophenone hydrazone in the experiment is 91.2%, and the product is a white crystal.
Example 2
A method for recycling industrial waste residue containing benzophenone hydrazone comprises the following specific scheme:
firstly preparing a solvent, adding 350kg of cyclohexane, 100kg of an ester solvent, 50kg of an alcohol solvent and 80kg of petroleum ether into a reaction kettle according to the mass parts, uniformly mixing, adding 120kg of industrial waste residue into the reaction kettle, controlling the temperature to be 40 ℃, stirring and mixing for 10min, cooling to 20 ℃ after completion, filtering insoluble substances, leaching filtrate by using the solvent, combining the filtrate, adding 10kg of adsorbent material into the filtrate, controlling the temperature to be 70 ℃, performing reflux adsorption for 90min, cooling to 20 ℃, filtering the adsorbent material, condensing the filtrate to 40%, slowly stirring, cooling to 5 ℃, standing and crystallizing for 5h, filtering after completion, leaching by using ethanol, and drying to obtain the recovered benzophenone hydrazone.
The adsorbent material is an organic lanthanum adsorption material, and the preparation method comprises the following steps:
according to the mass portion, 25 portions of macroporous absorbent resin and 68 portions of chloroform are mixed uniformly, the temperature is controlled to be 55 ℃, swelling is carried out for 15 hours, then 15 portions of 2-chloroethyl chloromethyl ether and 1 portion of zinc chloride are added, the temperature is controlled to be 65 ℃ after uniform mixing, reflux reaction is carried out for 12 hours, after completion, filtration is carried out, after methanol washing, the mixture is mixed uniformly with 7 portions of sodium hydroxide, 140 portions of 18% dimethylformamide aqueous solution is added as a solvent, after uniform mixing, soaking is carried out for 15 hours, then 5 portions of 1-methyl vinyl amine are added into a reaction kettle, the temperature is controlled to be 85 ℃, reaction is carried out for 19 hours, after completion, filtration is carried out, after water washing, drying is carried out, and the intermediate product 1 is obtained.
According to the mass parts, 100 parts of intermediate product 1, 25 parts of 1, 2-bis (dimethylsilyl) benzene, 2-7 parts of lanthanum methacrylate, 5 parts of chloroplatinic acid ethanol solution with the mass percent concentration of 7%, 1500 parts of n-butanol, 72 ℃, introducing nitrogen, reacting for 4 hours, cooling to room temperature after the reaction is finished, filtering, and drying to obtain the organic lanthanum adsorbing material.
The industrial waste residue is industrial waste residue containing benzophenone hydrazone, and the main components of the industrial waste residue are benzophenone hydrazone, inorganic salt, other organic pollutants and color development substances.
The ester solvent is ethyl acetate.
The alcohol solvent is isopropanol.
And the filtrate after crystallization and filtration is concentrated and recovered and then is adjusted to the designed mixture ratio for recycling.
The recovery rate of the benzophenone hydrazone product from the industrial waste residue containing the benzophenone hydrazone in the experiment is 93.1%, and the product is a white crystal.
Example 3
A method for recycling industrial waste residue containing benzophenone hydrazone comprises the following specific scheme:
firstly preparing a solvent, adding 520kg of cyclohexane, 300kg of an ester solvent, 120kg of an alcohol solvent and 140kg of petroleum ether into a reaction kettle according to the mass parts, uniformly mixing, adding 210kg of industrial waste residue into the reaction kettle, controlling the temperature to be 60 ℃, stirring and mixing for 40min, cooling to 30 ℃ after completion, filtering insoluble substances, leaching filtrate by using the solvent, combining the filtrate, adding 18kg of adsorbent material into the filtrate, controlling the temperature to be 90 ℃, performing reflux adsorption for 120min, cooling to 30 ℃, filtering the adsorbent material, condensing the filtrate to 60%, slowly stirring, cooling to 20 ℃, standing and crystallizing for 10h, filtering after completion, leaching by using ethanol, and drying to obtain the recovered benzophenone hydrazone.
The adsorbent material is an organic lanthanum adsorption material, and the preparation method comprises the following steps:
according to the mass portion, 50 portions of macroporous absorbent resin and 80 portions of chloroform are mixed uniformly, the temperature is controlled at 60 ℃, swelling is carried out for 20 hours, then 18 portions of 2-chloroethyl chloromethyl ether and 3.5 portions of zinc chloride are added, the temperature is controlled at 70 ℃ after uniform mixing, reflux reaction is carried out for 15 hours, filtering is carried out after completion, methanol is used for washing, the mixture is mixed uniformly with 9.4 portions of sodium hydroxide, 150 portions of 25% dimethylformamide aqueous solution is added as a solvent, soaking is carried out for 18 hours after uniform mixing, then 6.8 portions of 1-methyl vinyl amine are added into a reaction kettle, the temperature is controlled at 95 ℃, reaction is carried out for 24 hours, filtering is carried out after completion of reaction, water is used for washing, and drying is carried out, thus obtaining the intermediate product 1.
According to the mass parts, 100 parts of intermediate product 1, 30 parts of 1, 2-bis (dimethyl silicon-based) benzene, 7 parts of lanthanum methacrylate, 7 parts of chloroplatinic acid ethanol solution with the mass percent concentration of 10%, 2000 parts of n-butyl alcohol, 80 ℃, nitrogen gas is introduced, reaction is carried out for 6 hours, after the reaction is finished, the reaction product is cooled to the room temperature, and the organic lanthanum adsorption material can be obtained after filtration and drying.
The industrial waste residue is industrial waste residue containing benzophenone hydrazone, and the main components of the industrial waste residue are benzophenone hydrazone, inorganic salt, other organic pollutants and color development substances.
The ester solvent is isopropyl acetate.
The alcohol solvent is butanol.
And the filtrate after crystallization and filtration is concentrated and recovered and then is adjusted to the designed mixture ratio for recycling.
The recovery rate of the benzophenone hydrazone product from the industrial waste residue containing the benzophenone hydrazone in the experiment is 95.3%, and the product is a white crystal.
Comparative example 1
A method for recycling industrial waste residue containing benzophenone hydrazone comprises the following specific scheme:
firstly preparing a solvent, adding 350kg of cyclohexane, 50kg of alcohol solvent and 80kg of petroleum ether into a reaction kettle according to the mass parts, uniformly mixing, adding 120kg of industrial waste residue into the reaction kettle, controlling the temperature to 40 ℃, stirring and mixing for 10min, cooling to 20 ℃ after completion, filtering insoluble substances, leaching filtrate with the solvent, merging filtrate, adding 10kg of adsorbent material into the filtrate, controlling the temperature to 70 ℃, performing reflux adsorption for 90min, cooling to 20 ℃, filtering the adsorbent material, condensing the filtrate to 40%, slowly stirring, cooling to 5 ℃, standing and crystallizing for 5h, filtering after completion, leaching filter residues with ethanol, and drying to obtain the recovered benzophenone hydrazone.
The adsorbent material is an organic lanthanum adsorption material, and the preparation method comprises the following steps:
according to the mass parts, 100 parts of macroporous adsorbent resin, 20 parts of 1, 2-bis (dimethyl silicon-based) benzene, 2 parts of lanthanum methacrylate, 3 parts of chloroplatinic acid ethanol solution with the mass percent concentration of 3%, 1000 parts of n-butyl alcohol, 70 ℃, introducing nitrogen, reacting for 3 hours, cooling to room temperature after the reaction is finished, filtering, and drying to obtain the organic lanthanum adsorption material.
The industrial waste residue is industrial waste residue containing benzophenone hydrazone, and the main components of the industrial waste residue are benzophenone hydrazone, inorganic salt, other organic pollutants and color development substances.
The alcohol solvent is isopropanol.
And the filtrate after crystallization and filtration is concentrated and recovered and then is adjusted to the designed mixture ratio for recycling.
The recovery rate of the benzophenone hydrazone product recovered from the industrial waste residue containing the benzophenone hydrazone in the experiment is 72.7%, and the product is a white crystal.
Comparative example 2
A method for recycling industrial waste residue containing benzophenone hydrazone comprises the following specific scheme:
firstly preparing a solvent, adding 350kg of cyclohexane, 100kg of an ester solvent, 50kg of an alcohol solvent and 80kg of petroleum ether in a reaction kettle according to the mass parts, uniformly mixing, adding 120kg of industrial waste residue into the reaction kettle, controlling the temperature to be 40 ℃, stirring and mixing for 10min, cooling to 20 ℃ after completion, filtering insoluble substances, leaching filtrate by using the solvent, combining the filtrate, condensing the filtrate to 40%, slowly stirring, cooling to 5 ℃, standing for crystallization for 5h, filtering after completion, leaching the filter residue by using ethanol, and drying to obtain the recovered benzophenone hydrazone.
The industrial waste residue is industrial waste residue containing benzophenone hydrazone, and the main components of the industrial waste residue are benzophenone hydrazone, inorganic salt, other organic pollutants and color development substances.
The ester solvent is ethyl acetate.
The alcohol solvent is isopropanol.
And the filtrate after crystallization and filtration is concentrated and recovered and then is adjusted to the designed mixture ratio for recycling.
The recovery rate of the benzophenone hydrazone product from the industrial waste residue containing the benzophenone hydrazone in the experiment is 66.8%, and the product is yellow crystal.
Comparative example 3
A method for recycling industrial waste residue containing benzophenone hydrazone comprises the following specific scheme:
firstly preparing a solvent, adding 350kg of cyclohexane, 100kg of an ester solvent, 50kg of an alcohol solvent and 80kg of petroleum ether into a reaction kettle according to the mass parts, uniformly mixing, adding 120kg of industrial waste residue into the reaction kettle, controlling the temperature to be 40 ℃, stirring and mixing for 10min, cooling to 20 ℃ after completion, filtering insoluble substances, leaching filtrate by using the solvent, combining the filtrate, adding 10kg of macroporous adsorbent resin into the filtrate, controlling the temperature to be 70 ℃, performing reflux adsorption for 90min, cooling to 20 ℃, filtering out the macroporous adsorbent resin, condensing the filtrate to 40%, slowly stirring, cooling to 5 ℃, standing and crystallizing for 5h, filtering after completion, leaching filter residues by using ethanol, and drying to obtain the recovered benzophenone hydrazone.
The industrial waste residue is industrial waste residue containing benzophenone hydrazone, and the main components of the industrial waste residue are benzophenone hydrazone, inorganic salt, other organic pollutants and color development substances.
The ester solvent is ethyl acetate.
The alcohol solvent is isopropanol.
And the filtrate after crystallization and filtration is concentrated and recovered and then is adjusted to the designed mixture ratio for recycling.
The recovery rate of the benzophenone hydrazone product from the industrial waste residue containing the benzophenone hydrazone in the experiment is 79.8%, and the product is a yellowish crystal.
Comparative example 4
A method for recycling industrial waste residue containing benzophenone hydrazone comprises the following specific scheme:
firstly preparing a solvent, adding 430kg of cyclohexane, 200kg of an ester solvent, 80kg of an alcohol solvent and 100kg of petroleum ether into a reaction kettle according to the mass parts, uniformly mixing, adding 160kg of industrial waste residues into the reaction kettle, controlling the temperature to be 50 ℃, stirring and mixing for 25min, cooling to 25 ℃ after completion, filtering insoluble substances, leaching filtrate by using the solvent, combining the filtrate, adding 14kg of adsorbent material into the filtrate, controlling the temperature to be 80 ℃, performing reflux adsorption for 100min, cooling to 25 ℃, filtering the adsorbent material, condensing the filtrate to 50%, slowly stirring, cooling to 12 ℃, standing and crystallizing for 8h, filtering after completion, leaching by using ethanol, and drying to obtain the recovered benzophenone hydrazone.
The adsorbent material is an organic lanthanum adsorption material, and the preparation method comprises the following steps:
according to the mass portion, 20 portions of macroporous absorbent resin and 60 portions of chloroform are mixed uniformly, the temperature is controlled at 50 ℃, the swelling is carried out for 10 hours, then 12 portions of 2-chloroethyl chloromethyl ether and 0.5 portion of zinc chloride are added, the temperature is controlled at 60 ℃ after the uniform mixing, the reflux reaction is carried out for 10 hours, the filtration is carried out after the completion, the mixture is washed by methanol, the mixture is mixed uniformly with 5.6 portions of sodium hydroxide, 120 portions of 10% dimethylformamide aqueous solution is added as a solvent, the mixture is soaked for 10 hours after the uniform mixing, then 4.2 portions of 1-methyl vinyl amine are added into a reaction kettle, the temperature is controlled at 80 ℃, the reaction is carried out for 16 hours, the filtration is carried out after the reaction, the water washing and the drying are carried out, and the intermediate product 1 can be obtained.
According to the mass parts, 100 parts of intermediate product 1, 20 parts of 1, 2-bis (dimethyl silicon-based) benzene, 3 parts of chloroplatinic acid ethanol solution with the mass percent concentration of 3%, 1000 parts of n-butyl alcohol, 70 ℃, introducing nitrogen, reacting for 3 hours, cooling to room temperature after the reaction is finished, filtering, and drying to obtain the organic lanthanum adsorbing material.
The industrial waste residue is industrial waste residue containing benzophenone hydrazone, and the main components of the industrial waste residue are benzophenone hydrazone, inorganic salt, other organic pollutants and color development substances.
The ester solvent is butyl acetate.
The alcohol solvent is propanol.
And the filtrate after crystallization and filtration is concentrated and recovered and then is adjusted to the designed mixture ratio for recycling.
The recovery rate of the benzophenone hydrazone product from the industrial waste residue containing the benzophenone hydrazone in the experiment is 85.5%, and the product is a yellowish crystal.
Claims (5)
1. A method for recycling industrial waste residue containing benzophenone hydrazone comprises the following specific scheme:
firstly preparing a solvent, adding 520 parts of 350-one cyclohexane, 300 parts of 100-one ester solvent, 50-120 parts of alcohol solvent and 80-140 parts of petroleum ether in a reaction kettle according to the mass parts, uniformly mixing, adding 210 parts of industrial waste residue into the reaction kettle, controlling the temperature to be 40-60 ℃, stirring and mixing for 10-40min, cooling to be 20-30 ℃ after completion, filtering out insoluble substances, leaching filtrate with the solvent, combining the solvent into the filtrate, then adding 10-18 parts of adsorbent material into the filtrate, controlling the temperature to be 70-90 ℃, refluxing and adsorbing for 90-120min, then cooling to be 20-30 ℃, filtering out the adsorbent material, condensing the filtrate to be 40-60%, then cooling to be 5-20 ℃ under slow stirring, standing and crystallizing for 5-10h, filtering after completion, leaching filter residues with ethanol, and drying to obtain recovered benzophenone hydrazone;
the adsorbent material is an organic lanthanum adsorption material, and the preparation method comprises the following steps:
uniformly mixing 20-50 parts of macroporous adsorbent resin and 60-80 parts of chloroform according to the parts by weight, controlling the temperature to be 50-60 ℃, swelling for 10-20h, then adding 12-18 parts of 2-chloroethyl chloromethyl ether and 0.5-3.5 parts of zinc chloride, uniformly mixing, controlling the temperature to be 60-70 ℃, carrying out reflux reaction for 10-15h, filtering after the reflux reaction is finished, washing with methanol, uniformly mixing with 5.6-9.4 parts of sodium hydroxide, adding 120-150 parts of 10-25% dimethylformamide aqueous solution serving as a solvent, uniformly mixing, soaking for 10-18h, then 4.2 to 6.8 portions of 1-methyl vinyl amine is added into a reaction kettle, controlling the temperature to be 80-95 ℃ for reacting for 16-24h, filtering after the reaction is finished, washing with water and drying to obtain an intermediate product 1;
according to the mass parts, 100 parts of intermediate product 1, 20-30 parts of 1, 2-bis (dimethylsilyl) benzene, 2-7 parts of lanthanum methacrylate, 3-7 parts of chloroplatinic acid ethanol solution with the mass percent concentration of 3-10%, 1000 parts of n-butyl alcohol, 70-80 ℃, introducing nitrogen, reacting for 3-6 hours, cooling to room temperature after completion, filtering, and drying to obtain the organic lanthanum adsorbing material.
2. The method for recycling industrial waste residue containing benzophenone hydrazone as claimed in claim 1, characterized in that: the industrial waste residue is industrial waste residue containing benzophenone hydrazone, and the main components of the industrial waste residue are benzophenone hydrazone and inorganic salt.
3. The method for recycling industrial waste residue containing benzophenone hydrazone as claimed in claim 1, characterized in that: the ester solvent is ethyl acetate or butyl acetate or isopropyl acetate.
4. The method for recycling industrial waste residue containing benzophenone hydrazone as claimed in claim 1, characterized in that: the alcohol solvent is isopropanol or propanol or butanol.
5. The method for recycling industrial waste residue containing benzophenone hydrazone as claimed in claim 1, characterized in that: and the filtrate after crystallization and filtration is concentrated and recovered and then is adjusted to the designed mixture ratio for recycling.
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Citations (4)
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| CN102718681A (en) * | 2012-07-02 | 2012-10-10 | 江汉大学 | Method for purifying yellowed benzophenone hydrazone |
| CN204625735U (en) * | 2015-04-22 | 2015-09-09 | 江西科技学院 | A kind of ore deposit waste residue recovery and processing system |
| CN107434272A (en) * | 2017-08-10 | 2017-12-05 | 江苏博纳科水务环保科技有限公司 | A kind of process for cleanly preparing of renewable targeting adsorption treatment solubility organic solid castoff |
| CN107617627A (en) * | 2017-09-30 | 2018-01-23 | 湖南瑞寰环境科技有限公司 | A kind of processing method and processing device containing organic materialization work salt slag |
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| WO2013023021A1 (en) * | 2011-08-11 | 2013-02-14 | Cellular Bioengineering, Inc. | Polymer composition |
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| CN102718681A (en) * | 2012-07-02 | 2012-10-10 | 江汉大学 | Method for purifying yellowed benzophenone hydrazone |
| CN204625735U (en) * | 2015-04-22 | 2015-09-09 | 江西科技学院 | A kind of ore deposit waste residue recovery and processing system |
| CN107434272A (en) * | 2017-08-10 | 2017-12-05 | 江苏博纳科水务环保科技有限公司 | A kind of process for cleanly preparing of renewable targeting adsorption treatment solubility organic solid castoff |
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