CN114671447A - Method for treating sodium tetrachloroaluminate solid waste residues generated in methyl phosphorus dichloride production process - Google Patents
Method for treating sodium tetrachloroaluminate solid waste residues generated in methyl phosphorus dichloride production process Download PDFInfo
- Publication number
- CN114671447A CN114671447A CN202210316255.3A CN202210316255A CN114671447A CN 114671447 A CN114671447 A CN 114671447A CN 202210316255 A CN202210316255 A CN 202210316255A CN 114671447 A CN114671447 A CN 114671447A
- Authority
- CN
- China
- Prior art keywords
- solid waste
- sodium tetrachloroaluminate
- sodium
- tetrachloroaluminate
- production process
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5095—Separation; Purification; Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/52—Halophosphines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention relates to the technical field of chemical production, and particularly discloses a method for treating sodium tetrachloroaluminate solid waste residues generated in the production process of methyl phosphorus dichloride. Firstly, melting solid waste residues, adding a specific extracting agent, extracting most organic phosphorus impurities in the molten sodium tetrachloroaluminate waste residues into an extraction liquid, and completely removing a small amount of organic phosphorus impurities remained in the molten sodium tetrachloroaluminate waste residues by firing treatment; then adding the burnt sodium tetrachloroaluminate into water, filtering to obtain a mixed salt solution of sodium chloride and aluminum chloride without organic phosphorus impurities, removing part of water from the mixed salt solution, and filtering to obtain a sodium chloride product and an aluminum chloride solution; adding calcium silicate powder into the aluminum chloride solution for reaction to obtain the polyaluminum chloride. The method not only reduces the generation of solid hazardous waste, but also realizes the resource utilization of the sodium tetrachloroaluminate in the solid waste residue, obtains high-quality sodium chloride products and polyaluminium chloride products, and has higher economic benefit and environmental protection benefit and wide market prospect.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a method for treating sodium tetrachloroaluminate solid waste residues generated in the production process of methyl phosphorus dichloride.
Background
Methyl phosphorus dichloride is an important organic chemical intermediate, is widely applied to the fields of pesticides, medicines, synthetic materials and the like, and is mainly used for synthesizing key intermediates of glufosinate-ammonium, namely diethyl methylphosphonite and mono-n-butyl methylphosphonite at present. The main domestic synthesis processes for preparing the methyl phosphorus dichloride include a ternary complex method and an alkyl aluminum method. The two synthesis processes can generate a large amount of solid waste after the product of methyl phosphorus dichloride is separated, the main component of the solid waste is sodium tetrachloroaluminate, and the solid waste also contains a small amount of impurities such as organic phosphorus and the like. Because the sodium tetrachloroaluminate is easy to dissolve in water, the existing sodium tetrachloroaluminate solid waste residue is directly discharged after being dissolved in water, which not only causes great pollution to the environment, but also causes waste of resources. How to reasonably treat the sodium tetrachloroaluminate solid waste is an urgent problem to be solved in the industrial production of glufosinate-ammonium.
At present, there are reports in the literature of the following processes for treating sodium tetrachloroaluminate solid waste residues: firstly, adding a decomposing agent of alcohol and ether into the sodium tetrachloroaluminate solid waste residue, separating out sodium chloride obtained by decomposition, dissolving aluminum trichloride obtained by decomposition in the decomposing agent, filtering to obtain sodium chloride solid, cooling and crystallizing filtrate to obtain aluminum trichloride solid, circularly using the aluminum trichloride solid for synthesis of methyl phosphorus dichloride after the aluminum trichloride purification reaches the raw material standard, and adding sodium hydroxide into the aluminum trichloride to synthesize polyaluminium chloride after the complexing ability is reduced. The process is complex to operate, the recovered aluminum trichloride can be used only by further purification treatment, the purity of sodium chloride is low, and the prepared polyaluminum chloride has high content of organic impurities and cannot be directly used in the field of industrial sewage treatment. Therefore, there is a need to develop an effective method for treating tetrachloro sodium aluminate solid waste, so as to achieve the purpose of low cost, high efficiency and thorough resource utilization of tetrachloro sodium aluminate solid waste.
Disclosure of Invention
The invention provides a method for treating tetrachloro sodium aluminate solid waste residues generated in the production process of methyl phosphorus dichloride, aiming at the problems of complex process and incapability of realizing thorough resource utilization of the tetrachloro sodium aluminate solid waste residues in the existing method for treating tetrachloro sodium aluminate solid waste residues.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for treating sodium tetrachloroaluminate solid waste residues generated in the production process of methyl phosphorus dichloride comprises the following steps:
melting the sodium tetrachloroaluminate solid waste residue, adding an extracting agent under the condition of air isolation, uniformly mixing, standing, and separating liquid to obtain an extraction solution and molten sodium tetrachloroaluminate; wherein the extracting agent is at least one of n-hexadecane, pseudocumene, industrial solvent oil or tributyl phosphate;
b, firing the molten sodium tetrachloroaluminate under an aerobic condition, then adding the fired sodium tetrachloroaluminate into water, and filtering to obtain a mixed salt solution;
c, removing part of water from the mixed salt solution, and filtering to obtain an aluminum chloride solution and a sodium chloride product;
and d, adding calcium aluminate powder into the aluminum chloride solution, and reacting to obtain a polyaluminum chloride product.
The most difficult point for recycling the sodium tetrachloroaluminate in the sodium tetrachloroaluminate solid waste residue is that the sodium tetrachloroaluminate solid waste residue contains organic impurities such as methyl phosphorus dichloride and a small amount of dimethyl phosphorus chloride. In the prior art, the polyaluminium chloride product or the secondary salt product obtained by recycling the sodium tetrachloroaluminate solid waste residue contains organic impurities, the purity does not reach the standard, and secondary treatment is needed.
Compared with the prior art, the method for treating the tetrachloro sodium aluminate solid waste residue generated in the production process of methyl phosphorus dichloride provided by the invention comprises the steps of firstly melting the solid waste residue, adding a specific extracting agent, extracting most of organophosphorus impurities in the molten tetrachloro sodium aluminate into an extraction liquid, and completely removing a small amount of organophosphorus impurities remained in the molten tetrachloro sodium aluminate through firing treatment; and then adding the molten sodium tetrachloroaluminate into water, filtering to obtain a mixed salt solution of sodium chloride and aluminum chloride without organic phosphorus impurities, and further processing to obtain a high-purity sodium chloride product and high-added-value polyaluminum chloride.
Preferably, in step a, the temperature of the melting is 150 ℃ to 200 ℃.
Preferably, in the step a, the extracting agents are pseudocumene and tributyl phosphate in a mass ratio of 2-3: 1.
Preferably, in the step a, the mass ratio of the extracting agent to the sodium tetrachloroaluminate solid waste residue is 1-5: 1.
The preferable addition amount of the extracting agent and the extracting agent can fully extract the organophosphorus impurities in the sodium tetrachloroaluminate solid waste residue into the extraction liquid, and especially can extract most of methyl phosphorus dichloride into the extraction liquid, so that the full recovery of the methyl phosphorus dichloride in the solid waste residue is favorably realized, high-quality sodium chloride and polyaluminium chloride products are favorably obtained, and the thorough resource utilization of the sodium tetrachloroaluminate solid waste residue is favorably realized.
Preferably, step b specifically comprises: and heating the molten sodium tetrachloroaluminate to 250-300 ℃, and then introducing high-temperature air into the molten sodium tetrachloroaluminate to ensure that a small amount of organic phosphorus in the sodium tetrachloroaluminate is spontaneously combusted.
Further, in the step b, the temperature of the high-temperature air is 150-180 ℃.
The optimized process can fully burn a small amount of organic phosphorus impurities remained in the molten sodium tetrachloroaluminate to thoroughly remove the organic phosphorus impurities in the sodium tetrachloroaluminate.
Preferably, in the step b, the mass ratio of the water to the sodium tetrachloroaluminate solid waste residue is 1-5: 1.
Optionally, in the step b, the calcined sodium tetrachloroaluminate is added into room temperature water.
The preferable temperature and addition amount of water are beneficial to improving the hydrolysis efficiency of sodium tetrachloroaluminate.
Optionally, in the step b, the molten sodium tetrachloroaluminate is added into water in a feeding manner, wherein the feeding rate is controlled by controlling the temperature of the water to be 80-100 ℃.
Optionally, in the step b, the filtering temperature is controlled to be 50-100 ℃.
Preferably, in the step c, the dehydration amount is 15-40% of the mass of the mixed salt solution.
Preferably, in the step c, a negative pressure dehydration mode is adopted, the absolute pressure of dehydration is 5KPa to 20KPa, and the dehydration temperature is 80 ℃ to 100 ℃.
The optimal dehydration amount is beneficial to the full precipitation of sodium chloride and the improvement of the yield of the sodium chloride on the premise of reducing the dehydration energy consumption and ensuring the treatment efficiency.
Optionally, in step c, the filtration temperature is controlled to be 80-100 ℃.
Preferably, in the step d, the reaction temperature is 100-130 ℃, and the reaction time is 4-6 h.
Optionally, in the step d, the adding amount of the calcium aluminate powder is 1-1.1 times of the mass of the aluminum chloride in the aluminum chloride solution.
Preferably, the extraction solution obtained in the step a is rectified to obtain a recovery solvent and methyl phosphorus dichloride; and (e) the recovered solvent is recycled to the step (a) to be used as an extracting agent for extracting the next batch of sodium tetrachloroaluminate solid waste residues.
Rectifying the extraction solution, recovering methyl phosphorus dichloride with the content of more than 99% from the top of the tower, and continuously using the recovered extractant in the tower kettle for extracting the sodium tetrachloroaluminate of the next batch.
Further, the rectification is negative pressure rectification, the absolute pressure of the rectification is 5KPa to 20KPa, and the temperature of the tower kettle is controlled to be 80 ℃ to 100 ℃.
The preferable rectification condition is favorable for improving the recovery rate of the methyl phosphorus dichloride.
The method for treating the tetrachloro sodium aluminate solid waste residues generated in the production process of the methyl phosphorus dichloride, provided by the invention, can realize the recovery of the methyl phosphorus dichloride in the solid waste residues, the purity of the obtained methyl phosphorus dichloride product can reach more than 99%, and the full recycling of the tetrachloro sodium aluminate is also realized, so that a sodium chloride product with the purity of more than 99.9% and a polyaluminum chloride product reaching the standard for drinking water are obtained, and an extracting agent added in the treatment process is not directly discharged out of a system, but is continuously recycled into the system to serve as an extracting agent for the next batch of tetrachloro sodium aluminate, so that no liquid hazardous waste is generated in the whole system, the method is a green, resource and low-cost method for treating the tetrachloro sodium aluminate solid waste residues, accords with the current trend of clean production, and has high popularization and application values.
Drawings
FIG. 1 is a process scheme of a method for treating sodium tetrachloroaluminate solid waste residue in the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the following examples and comparative examples, the sodium tetrachloroaluminate solid waste residue is obtained from a production process of synthesizing diethyl methylphosphite by using phosphorus trichloride, methyl chloride, aluminum trichloride, aluminum powder, sodium chloride and the like as raw materials, wherein the sodium tetrachloroaluminate solid waste residue contains 2-3% of organic phosphorus substances.
Example 1
The embodiment provides a method for treating sodium tetrachloroaluminate solid waste residues generated in a methyl phosphorus dichloride production process, wherein the sodium tetrachloroaluminate solid waste residues contain 2.55% of organic phosphorus substances, and the treatment method specifically comprises the following steps:
step a, adding 200g of sodium tetrachloroaluminate solid waste residue into a high-temperature melting kettle at 150 ℃ for melting, adding 200g of n-hexadecane into the high-temperature melting kettle under the condition of air isolation, stirring for 0.5h, standing for 0.5h, and then separating liquid, wherein the lower layer is molten sodium tetrachloroaluminate, and the upper layer is an extraction solution; the mass of the organic phosphorus in the lower layer of extraction solution is measured to be 2.8g, which accounts for 54.9 percent of the total amount of the organic phosphorus;
b, transferring the lower layer of molten sodium tetrachloroaluminate into a high-temperature oxidation kettle, heating to 260 ℃, introducing high-temperature air of 160 ℃ into the molten sodium tetrachloroaluminate to burn a small amount of organic phosphorus in the sodium tetrachloroaluminate, stopping introducing the air when no open fire is generated, then adding the molten sodium tetrachloroaluminate into 400g of water, controlling the water temperature in the feeding process to be 80 ℃, filtering at 50 ℃, and filtering out water-insoluble phosphorus coking black slag to obtain a mixed salt solution of sodium chloride and aluminum chloride; detecting the content of organic phosphorus in the mixed salt solution to be 0.5 ppm;
step c, carrying out negative pressure dehydration on the mixed salt solution under the conditions that the absolute pressure of the system is 5-10KPa and the temperature is 80 ℃, wherein the dehydration amount is 16 percent of the total amount of the mixed salt solution, filtering at 80 ℃ to obtain 439.2g of aluminum chloride solution and 48g of sodium chloride product, the content of the sodium chloride product is 99.9 percent, and the sodium chloride product does not contain organic phosphorus through detection;
d, adding calcium aluminate powder into the aluminum chloride solution, wherein the adding amount of the calcium aluminate powder is 1 time of the mass of aluminum chloride contained in the aluminum chloride solution, reacting for 6 hours at the temperature of 100 ℃, and drying to obtain a polyaluminum chloride product;
step e, performing negative pressure rectification on the extraction solution obtained in the step a under the condition that the absolute pressure of a system is 10-15KPa, controlling the temperature of a tower kettle to be 80 ℃, and recovering methyl phosphorus dichloride with the content of 99.14% from the top of the tower; 198g of n-hexadecane is extracted from the tower kettle and is continuously used for extracting the next batch of sodium tetrachloroaluminate. The recovery rate of the methyl phosphorus dichloride is 100 percent, and the loss rate of the n-hexadecane extracting agent is 1 percent.
The polyaluminium chloride product prepared by the embodiment meets the standard of GB15892-2009 drinking water polyaluminium chloride.
Example 2
The embodiment provides a method for treating sodium tetrachloroaluminate solid waste residues generated in a methyl phosphorus dichloride production process, wherein the sodium tetrachloroaluminate solid waste residues contain 2.55% of organic phosphorus substances, and the treatment method specifically comprises the following steps:
step a, adding 200g of sodium tetrachloroaluminate solid waste residue into a high-temperature melting kettle at 160 ℃ for melting, adding 400g of industrial solvent oil into the high-temperature melting kettle under the condition of air isolation, stirring for 1h, standing for 1h, and then separating liquid, wherein the lower layer is molten sodium tetrachloroaluminate, and the upper layer is an extraction solution; the mass of the organic phosphorus in the lower layer extraction solution is 3.5g, which accounts for 68.6 percent of the total amount of the organic phosphorus;
b, transferring the molten sodium tetrachloroaluminate at the lower layer into a high-temperature oxidation kettle, heating to 260 ℃, introducing high-temperature air at 150 ℃ into the molten sodium tetrachloroaluminate, burning a small amount of organic phosphorus in the sodium tetrachloroaluminate, stopping introducing the air when no open fire is generated, then adding the molten sodium tetrachloroaluminate into 400g of water, controlling the temperature of the fed-in process to be 90 ℃, filtering at 50 ℃, and filtering out water-insoluble phosphorus coking black slag to obtain a mixed salt solution of sodium chloride and aluminum chloride; detecting the content of organic phosphorus in the mixed salt solution to be 0.2 ppm;
step c, performing negative pressure dehydration on the mixed salt solution under the conditions that the absolute pressure of the system is 10-15KPa and the temperature is 90 ℃, wherein the dehydration amount is 15 percent of the total amount of the mixed salt solution, filtering at 90 ℃ to obtain 446g of aluminum chloride solution and 47g of sodium chloride product, wherein the content of the sodium chloride product is 99.9 percent, and the sodium chloride product does not contain organic phosphorus through detection;
d, adding calcium aluminate powder into the aluminum chloride solution, wherein the adding amount of the calcium aluminate powder is 1.1 times of the mass of aluminum chloride contained in the aluminum chloride solution, carrying out heat preservation reaction at 130 ℃ for 4 hours, and drying to obtain a polyaluminum chloride product;
step e, performing negative pressure rectification on the extraction solution obtained in the step a under the condition that the absolute pressure of a system is 5-10KPa, controlling the temperature of a tower kettle to be 80 ℃, and recovering methyl phosphorus dichloride with the content of 99.19% from the top of the tower; 393g of industrial solvent oil is extracted from the tower kettle and is continuously used for extracting the next batch of sodium tetrachloroaluminate. The recovery rate of the methyl phosphorus dichloride is 100 percent, and the loss rate of the industrial solvent oil is 1.75 percent.
The polyaluminium chloride product prepared by the embodiment meets the standard of GB15892-2009 drinking water polyaluminium chloride.
Example 3
The embodiment provides a method for treating sodium tetrachloroaluminate solid waste residues generated in a methyl phosphorus dichloride production process, wherein the sodium tetrachloroaluminate solid waste residues contain 2.55% of organic phosphorus substances, and the treatment method specifically comprises the following steps:
step a, adding 200g of sodium tetrachloroaluminate solid waste residue into a high-temperature melting kettle at 200 ℃ for melting, adding 400g of pseudocumene into the high-temperature melting kettle under the condition of air isolation, stirring for 2h, standing for 1h, and then separating liquid, wherein the lower layer is molten sodium tetrachloroaluminate, and the upper layer is an extraction solution; the mass of the organic phosphorus in the lower layer extraction solution is 4.0g, which accounts for 78.4% of the total amount of the organic phosphorus;
b, transferring the molten sodium tetrachloroaluminate at the lower layer into a high-temperature oxidation kettle, heating to 280 ℃, introducing high-temperature air at 170 ℃ into the molten sodium tetrachloroaluminate, burning a small amount of organic phosphorus in the sodium tetrachloroaluminate, stopping introducing the air when no open fire is generated, then adding the molten sodium tetrachloroaluminate into 500g of water, controlling the temperature of the fed-in process to be 90 ℃, filtering at 50 ℃, and filtering out water-insoluble phosphorus coking black slag to obtain a mixed salt solution of sodium chloride and aluminum chloride; detecting the content of organic phosphorus in the mixed salt solution to be 0.15 ppm;
step c, carrying out negative pressure dehydration on the mixed salt solution under the conditions that the absolute pressure of the system is 15-20KPa and the temperature is 90 ℃, wherein the dehydration amount is 29 percent of the total amount of the mixed salt solution, filtering at 90 ℃ to obtain 434g of aluminum chloride solution and 49g of sodium chloride products, the content of the sodium chloride products is 99.9 percent, and the sodium chloride products do not contain organic phosphorus through detection;
d, adding calcium aluminate powder into the aluminum chloride solution, wherein the adding amount of the calcium aluminate powder is 1 time of the mass of aluminum chloride in the aluminum chloride solution, reacting for 4.5 hours at the temperature of 110 ℃, and drying to obtain a polyaluminum chloride product;
step e, performing negative pressure rectification on the extraction solution obtained in the step a under the condition that the absolute pressure of a system is 15-20KPa, controlling the temperature of a tower kettle to be 90 ℃, and recovering methyl phosphorus dichloride with the content of 99.03% from the top of the tower; 397g of pseudocumene are extracted from the tower bottom and are continuously used for extracting sodium tetrachloroaluminate in the next batch. The recovery rate of the methyl phosphorus dichloride is 100 percent, and the loss rate of the pseudocumene extractant is 0.75 percent.
The polyaluminium chloride product prepared by the embodiment meets the standard of GB15892-2009 drinking water polyaluminium chloride.
Example 4
The embodiment provides a method for treating sodium tetrachloroaluminate solid waste residues generated in a methyl phosphorus dichloride production process, wherein the sodium tetrachloroaluminate solid waste residues contain 2.55% of organic phosphorus substances, and the treatment method specifically comprises the following steps:
step a, adding 200g of sodium tetrachloroaluminate solid waste residue into a high-temperature melting kettle at 180 ℃ for melting, adding 600g of tributyl phosphate into the high-temperature melting kettle under the condition of air isolation, stirring for 2.5h, standing for 2h, and then separating liquid, wherein the lower layer is molten sodium tetrachloroaluminate, and the upper layer is an extraction solution; the mass of the organic phosphorus in the lower layer extraction solution is 3.97g, which accounts for 77.8% of the total amount of the organic phosphorus;
b, transferring the lower layer of molten sodium tetrachloroaluminate into a high-temperature oxidation kettle, heating to 300 ℃, introducing high-temperature air of 180 ℃ into the molten sodium tetrachloroaluminate to burn a small amount of organic phosphorus in the sodium tetrachloroaluminate, stopping introducing the air when no open fire is generated, then adding the molten sodium tetrachloroaluminate into 600g of water, controlling the water temperature in the feeding process to be 90 ℃, filtering at 80 ℃, and filtering out water-insoluble phosphorus coking black slag to obtain a mixed salt solution of sodium chloride and aluminum chloride; detecting the content of organic phosphorus in the mixed salt solution to be 0.1 ppm;
step c, carrying out negative pressure dehydration on the mixed salt solution under the conditions that the absolute pressure of the system is 15-20KPa and the temperature is 90 ℃, wherein the dehydration amount is 35 percent of the total amount of the mixed salt solution, filtering at 90 ℃ to obtain 462g of aluminum chloride solution and 45g of sodium chloride product, the content of the sodium chloride product is 99.9 percent, and the sodium chloride product does not contain organic phosphorus through detection;
d, adding calcium aluminate powder into the aluminum chloride solution, wherein the adding amount of the calcium aluminate powder is 1 time of the mass of aluminum chloride contained in the aluminum chloride solution, reacting for 5 hours at the temperature of 120 ℃, and drying to obtain a polyaluminum chloride product;
step e, performing negative pressure rectification on the extraction solution obtained in the step a under the condition that the absolute pressure of a system is 5-10KPa, controlling the temperature of a tower kettle to be 90 ℃, and recovering methyl phosphorus dichloride with the content of 99.08% from the top of the tower; 598g of tributyl phosphate is extracted from the tower kettle and is continuously used for extracting the sodium tetrachloroaluminate of the next batch. The recovery rate of the methyl phosphorus dichloride is 100 percent, and the loss rate of the tributyl phosphate extractant is 0.33 percent.
The polyaluminium chloride product prepared by the embodiment meets the standard of GB15892-2009 drinking water polyaluminium chloride.
Example 5
The embodiment provides a method for treating sodium tetrachloroaluminate solid waste residues generated in a methyl phosphorus dichloride production process, wherein the sodium tetrachloroaluminate solid waste residues contain 2.55% of organic phosphorus substances, and the treatment method specifically comprises the following steps:
step a, adding 200g of sodium tetrachloroaluminate solid waste residue into a high-temperature melting kettle at 180 ℃ for melting, adding 600g of mixed solvent of pseudocumene and tributyl phosphate (the mass ratio of the pseudocumene to the tributyl phosphate is 2:1) into the high-temperature melting kettle under the condition of air isolation, stirring for 2.5h, standing for 2h, and then separating liquid, wherein the lower layer is molten sodium tetrachloroaluminate, and the upper layer is an extraction solution; the mass of the organic phosphorus in the lower layer of extraction solution is measured to be 4.6g, which accounts for 90.2 percent of the total amount of the organic phosphorus;
b, transferring the molten sodium tetrachloroaluminate at the lower layer into a high-temperature oxidation kettle, heating to 260 ℃, introducing high-temperature air at 160 ℃ into the molten sodium tetrachloroaluminate, burning a small amount of organic phosphorus in the sodium tetrachloroaluminate, stopping introducing the air when no open fire is generated, then adding the molten sodium tetrachloroaluminate into 500g of water, controlling the temperature of the fed-in process to be 80 ℃, filtering at 50 ℃, and filtering out water-insoluble phosphorus coking black slag to obtain a mixed salt solution of sodium chloride and aluminum chloride; detecting the content of organic phosphorus in the mixed salt solution to be 0.05 ppm;
step c, carrying out negative pressure dehydration on the mixed salt solution under the conditions that the absolute pressure of the system is 10-15KPa and the temperature is 80 ℃, wherein the dehydration amount is 29 percent of the total amount of the mixed salt solution, filtering at 80 ℃ to obtain 434g of aluminum chloride solution and 49g of sodium chloride products, the content of the sodium chloride products is 99.9 percent, and the sodium chloride products do not contain organic phosphorus through detection;
d, adding calcium aluminate powder into the aluminum chloride solution, wherein the adding amount of the calcium aluminate powder is 1 time of the mass of aluminum chloride in the aluminum chloride solution, reacting for 5 hours at the temperature of 120 ℃, and drying to obtain a polyaluminum chloride product;
step e, performing negative pressure rectification on the extraction solution obtained in the step a under the condition that the absolute pressure of a system is 10-15KPa, controlling the temperature of a tower kettle to be 80 ℃, and recovering methyl phosphorus dichloride with the content of 99.3% from the top of the tower; 598g of mixed solvent of pseudocumene and tributyl phosphate is extracted from the tower kettle and is continuously used for extracting the sodium tetrachloroaluminate in the next batch. The recovery rate of the methyl phosphorus dichloride is 100 percent, and the total loss rate of the pseudocumene and the tributyl phosphate extractant is 0.33 percent.
The polyaluminum chloride product prepared by the embodiment meets the standard of GB15892-2009 drinking water polyaluminum chloride.
Comparative example 1
The comparative example provides a method for treating sodium tetrachloroaluminate solid waste slag generated in the production process of methyl phosphorus dichloride, the treatment process and the process parameters are completely the same as those of the example 5, and the difference is that the mixed solvent of the pseudocumene and the tributyl phosphate in the step a is replaced by the same amount of glycerol.
The weight of organic phosphorus in the lower extraction solution in step a was found to be 0.2g, accounting for 3.92% of the total amount of organic phosphorus. And the total amount of the glycerol obtained by rectifying and recovering in the step e is 250g, and the loss rate of the glycerol is close to 58.3 percent.
The above comparative example illustrates that glycerol has a relatively large residual amount in sodium tetrachloroaluminate and does not allow for effective extraction of organic phosphorus from sodium tetrachloroaluminate.
Comparative example 2
The comparative example provides a method for treating sodium tetrachloroaluminate solid waste slag generated in the production process of methyl phosphorus dichloride, the treatment process and the process parameters are completely the same as those of the example 5, and the difference is that the mixed solvent of the pseudocumene and the tributyl phosphate in the step a is replaced by the same amount of phenol.
The lower extraction solution in step a was found to be free of organic phosphorus species.
The above comparative example illustrates that phenol does not achieve extraction of organic phosphorus in sodium tetrachloroaluminate.
Comparative example 3
The comparative example provides a treatment method of sodium tetrachloroaluminate solid waste residue generated in the production process of methyl phosphorus dichloride, the treatment process and the process parameters are completely the same as those in the example 5, except that the mixed solvent of pseudocumene and tributyl phosphate in the step a is replaced by pseudocumene and 1, 4-butyrolactone in equal amount (the mass ratio of the pseudocumene to the 1, 4-butyrolactone is 2: 1).
The weight of organic phosphorus in the lower extraction solution in step a was found to be 1.52g, which accounted for 29.8% of the total organic phosphorus. And the total amount of the pseudocumene and the 1, 4-butyrolactone recovered by rectification in the step e is 540g, and the loss rate of the solvent is close to 10%.
The technical effect equivalent to that of the embodiment 5 can be achieved by replacing the mixed solvent of the pseudocumene and the tributyl phosphate in the step a of the embodiment 1 with the mixed solvent of the pseudocumene and the tributyl phosphate in other proportions defined by the invention.
In conclusion, the method for treating the tetrachloro sodium aluminate solid waste residues generated in the production process of the methyl phosphorus dichloride provided by the invention can not only realize the full recovery of the methyl phosphorus dichloride in the solid waste residues, but also fully remove the organic phosphorus impurities in the tetrachloro sodium aluminate solid waste residues to obtain high-quality sodium chloride products and polyaluminium chloride which meets the drinking water standard, and the whole process does not generate liquid hazardous waste, meets the trend of clean production, and has wide application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for treating sodium tetrachloroaluminate solid waste residues generated in the production process of methyl phosphorus dichloride is characterized by comprising the following steps:
melting the sodium tetrachloroaluminate solid waste residue, adding an extracting agent under the condition of air isolation, uniformly mixing, standing, and separating liquid to obtain an extraction solution and molten sodium tetrachloroaluminate; wherein the extracting agent is at least one of n-hexadecane, pseudocumene, industrial solvent oil or tributyl phosphate;
b, burning the molten sodium tetrachloroaluminate under an aerobic condition, then adding the burnt sodium tetrachloroaluminate into water, and filtering to obtain a mixed salt solution;
c, removing part of water from the mixed salt solution, and filtering to obtain an aluminum chloride solution and a sodium chloride product;
and d, adding calcium aluminate powder into the aluminum chloride solution, and reacting to obtain a polyaluminum chloride product.
2. The method for treating sodium tetrachloroaluminate solid waste residue generated in the production process of methyl phosphorus dichloride as claimed in claim 1, wherein in step a, the melting temperature is 150-200 ℃.
3. The method for treating sodium tetrachloroaluminate solid waste residue generated in the production process of methyl phosphorus dichloride as claimed in claim 1, wherein in step a, the extractant is pseudocumene and tributyl phosphate in a mass ratio of 2-3: 1.
4. The method for treating the sodium tetrachloroaluminate solid waste residue generated in the production process of methyl phosphorus dichloride as claimed in claim 1 or 3, wherein in the step a, the mass ratio of the extracting agent to the sodium tetrachloroaluminate solid waste residue is 1-5: 1.
5. The method for treating sodium tetrachloroaluminate solid waste residue generated in the production process of methyl phosphorus dichloride as claimed in claim 1, wherein the step b specifically comprises: and heating the molten sodium tetrachloroaluminate to 250-300 ℃, and introducing high-temperature air into the molten sodium tetrachloroaluminate to burn.
6. The method for treating sodium tetrachloroaluminate solid waste residue generated in the production process of methyl phosphorus dichloride as claimed in claim 5, wherein in step b, the temperature of the high temperature air is 150-180 ℃.
7. The method for treating sodium tetrachloroaluminate solid waste residues generated in the production process of methyl phosphorus dichloride as claimed in claim 1, wherein in the step b, the mass ratio of the water to the sodium tetrachloroaluminate solid waste residues is 1-5: 1; and/or
In the step c, the dehydration amount is 15-40% of the mass of the mixed salt solution.
8. The method for treating sodium tetrachloroaluminate solid waste residue generated in the production process of methyl phosphorus dichloride as claimed in claim 1 or 7, wherein in the step c, a negative pressure dehydration mode is adopted, the absolute pressure of dehydration is 5KPa-20KPa, and the dehydration temperature is 80-100 ℃; and/or
In the step d, the reaction temperature is 100-130 ℃, and the reaction time is 4-6 h; and/or
In the step d, the addition amount of the calcium aluminate powder is 1-1.1 times of the mass of the aluminum chloride in the aluminum chloride solution.
9. The method for treating sodium tetrachloroaluminate solid waste residue generated in the production process of methyl phosphorus dichloride as claimed in claim 1, wherein the extraction solution obtained in step a is rectified to obtain the recovered solvent and methyl phosphorus dichloride; and (c) the recovered solvent is recycled to the step (a) to be used as an extracting agent for extracting the next batch of sodium tetrachloroaluminate solid waste residue.
10. The method for treating sodium tetrachloroaluminate solid waste residue generated in the production process of methyl phosphorus dichloride as claimed in claim 9, wherein the rectification is negative pressure rectification, the absolute pressure of rectification is 5KPa-20KPa, and the temperature of the tower kettle is controlled to be 80 ℃ to 100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210316255.3A CN114671447B (en) | 2022-03-28 | 2022-03-28 | Treatment method of sodium tetrachloroaluminate solid waste residue generated in production process of methyl phosphorus dichloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210316255.3A CN114671447B (en) | 2022-03-28 | 2022-03-28 | Treatment method of sodium tetrachloroaluminate solid waste residue generated in production process of methyl phosphorus dichloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114671447A true CN114671447A (en) | 2022-06-28 |
| CN114671447B CN114671447B (en) | 2023-05-30 |
Family
ID=82076862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210316255.3A Active CN114671447B (en) | 2022-03-28 | 2022-03-28 | Treatment method of sodium tetrachloroaluminate solid waste residue generated in production process of methyl phosphorus dichloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114671447B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115253915A (en) * | 2022-08-22 | 2022-11-01 | 山东滨农科技有限公司 | Device and method for treating sodium tetrachloroaluminate in glufosinate-ammonium production |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH061607A (en) * | 1992-06-22 | 1994-01-11 | Mitsubishi Materials Corp | Production of aluminum chloride of high purity |
| CN105217667A (en) * | 2015-10-22 | 2016-01-06 | 安徽国星生物化学有限公司 | In a kind of glufosinates production, sodium terachloroaluminate recycles technique |
| CN109052444A (en) * | 2018-10-17 | 2018-12-21 | 浙江新安化工集团股份有限公司 | The method for preparing aluminium polychloride using the by-product generated in the production of methylisothiouronium methylphosphite diethylester |
| CN111689508A (en) * | 2020-06-15 | 2020-09-22 | 浙江新安化工集团股份有限公司 | Method for treating tetrachloro sodium aluminate solid slag |
| CN111804704A (en) * | 2020-07-15 | 2020-10-23 | 浙江新安化工集团股份有限公司 | Method for treating tetrachloro sodium aluminate solid slag |
| CN111921153A (en) * | 2020-04-15 | 2020-11-13 | 浙江安力能源有限公司 | Method for treating sodium tetrachloroaluminate |
| CN112456462A (en) * | 2019-09-09 | 2021-03-09 | 江苏优士化学有限公司 | Recovery processing method of sodium tetrachloroaluminate catalyst composition |
| CN112794868A (en) * | 2020-12-15 | 2021-05-14 | 洪湖市一泰科技有限公司 | Method for treating sodium tetrachloroaluminate generated in methyl dichlorophosphine production process |
-
2022
- 2022-03-28 CN CN202210316255.3A patent/CN114671447B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH061607A (en) * | 1992-06-22 | 1994-01-11 | Mitsubishi Materials Corp | Production of aluminum chloride of high purity |
| CN105217667A (en) * | 2015-10-22 | 2016-01-06 | 安徽国星生物化学有限公司 | In a kind of glufosinates production, sodium terachloroaluminate recycles technique |
| CN109052444A (en) * | 2018-10-17 | 2018-12-21 | 浙江新安化工集团股份有限公司 | The method for preparing aluminium polychloride using the by-product generated in the production of methylisothiouronium methylphosphite diethylester |
| CN112456462A (en) * | 2019-09-09 | 2021-03-09 | 江苏优士化学有限公司 | Recovery processing method of sodium tetrachloroaluminate catalyst composition |
| CN111921153A (en) * | 2020-04-15 | 2020-11-13 | 浙江安力能源有限公司 | Method for treating sodium tetrachloroaluminate |
| CN111689508A (en) * | 2020-06-15 | 2020-09-22 | 浙江新安化工集团股份有限公司 | Method for treating tetrachloro sodium aluminate solid slag |
| CN111804704A (en) * | 2020-07-15 | 2020-10-23 | 浙江新安化工集团股份有限公司 | Method for treating tetrachloro sodium aluminate solid slag |
| CN112794868A (en) * | 2020-12-15 | 2021-05-14 | 洪湖市一泰科技有限公司 | Method for treating sodium tetrachloroaluminate generated in methyl dichlorophosphine production process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115253915A (en) * | 2022-08-22 | 2022-11-01 | 山东滨农科技有限公司 | Device and method for treating sodium tetrachloroaluminate in glufosinate-ammonium production |
| CN115253915B (en) * | 2022-08-22 | 2024-04-05 | 山东滨农科技有限公司 | Treatment device and treatment method for sodium tetrachloroaluminate in glufosinate production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114671447B (en) | 2023-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106848472B (en) | Method for recycling lithium from waste lithium iron phosphate batteries | |
| CN110482511B (en) | Method for recovering anode material of waste lithium iron phosphate battery | |
| CN101824530A (en) | Process for roasting chromite resources in ring kiln through pure oxygen by using low-temperature method and harmlessly and deeply utilizing chromium residue | |
| CN114671447A (en) | Method for treating sodium tetrachloroaluminate solid waste residues generated in methyl phosphorus dichloride production process | |
| CN104693009A (en) | Method for cooperatively producing 1-naphthol and 2-naphthol from naphthalene sulfonation product by virtue of direct alkali fusion | |
| CN111689508A (en) | Method for treating tetrachloro sodium aluminate solid slag | |
| CN109911909B (en) | Recovery processing method of waste sagger in preparation process of lithium cobaltate positive electrode material | |
| CN101063184A (en) | Process for reclaiming chromium and aluminum by comprehensive treatment of sludge containing chromium-aluminium | |
| CN115140719B (en) | Method for full recycling of secondary aluminum ash | |
| CN102020300B (en) | Method for producing metallurgical-grade aluminum oxide by coal ash | |
| CN113716591A (en) | Aluminum ash recycling method | |
| CN113072089B (en) | Method for recovering cryolite by combined treatment of aluminum electrolysis overhaul slag and aluminum ash | |
| CN113955753A (en) | Method for recovering waste lithium iron phosphate battery powder | |
| CN101712482A (en) | Method for preparing crystallized aluminum chloride and soluble glass by waste aluminum ash | |
| CN113697834B (en) | Method for preparing friedel-crafts salt from titanium extraction slag and friedel-crafts salt | |
| CN110735048A (en) | Method for removing magnesium and fluorine from zinc-containing solution of wet-method zinc smelting | |
| CN108588424B (en) | Method for separating manganese and lead in electrolytic manganese anode slag | |
| CN115028151B (en) | Comprehensive utilization method of secondary aluminum ash | |
| CN111690266B (en) | Production method of dye disperse blue B56# | |
| CN109179361B (en) | Method for synthesizing aluminum metaphosphate by using glufosinate-ammonium production byproduct | |
| CN108675325B (en) | Method for separating manganese from magnesium chloride | |
| CN103183384A (en) | Method for preroasting and intensifying chromite decomposed by sub-molten salt | |
| CN106631651A (en) | Preparation method of benzyl methylbenzene | |
| CN113149044A (en) | Method for preparing magnesium salt by adopting boric sludge | |
| CN110438341A (en) | A kind of preparation method of the carbonated rare earth salt of the low COD of the low ammonia nitrogen of environmental protection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |