CN114671447B - Treatment method of sodium tetrachloroaluminate solid waste residue generated in production process of methyl phosphorus dichloride - Google Patents
Treatment method of sodium tetrachloroaluminate solid waste residue generated in production process of methyl phosphorus dichloride Download PDFInfo
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- 229910001538 sodium tetrachloroaluminate Inorganic materials 0.000 title claims abstract description 124
- -1 sodium tetrachloroaluminate Chemical compound 0.000 title claims abstract description 123
- 239000002910 solid waste Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 56
- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 81
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 74
- 239000000243 solution Substances 0.000 claims abstract description 56
- 239000011780 sodium chloride Substances 0.000 claims abstract description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 239000012266 salt solution Substances 0.000 claims abstract description 24
- 238000002844 melting Methods 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- 238000000605 extraction Methods 0.000 claims description 26
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims description 20
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 16
- 230000018044 dehydration Effects 0.000 claims description 15
- 238000006297 dehydration reaction Methods 0.000 claims description 15
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 14
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000004434 industrial solvent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 56
- 239000011574 phosphorus Substances 0.000 abstract description 56
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 56
- 239000012535 impurity Substances 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000012824 chemical production Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910052918 calcium silicate Inorganic materials 0.000 abstract 1
- 239000000378 calcium silicate Substances 0.000 abstract 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 40
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 238000011084 recovery Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004064 recycling Methods 0.000 description 8
- 239000003651 drinking water Substances 0.000 description 7
- 235000020188 drinking water Nutrition 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004939 coking Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010923 batch production Methods 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005561 Glufosinate Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PKVYRMYNUBUIJI-UHFFFAOYSA-N butoxy(methyl)phosphinous acid Chemical compound CCCCOP(C)O PKVYRMYNUBUIJI-UHFFFAOYSA-N 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- ZLVVDNKTHWEIOG-UHFFFAOYSA-N chloro(dimethyl)phosphane Chemical compound CP(C)Cl ZLVVDNKTHWEIOG-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NSSMTQDEWVTEKN-UHFFFAOYSA-N diethoxy(methyl)phosphane Chemical compound CCOP(C)OCC NSSMTQDEWVTEKN-UHFFFAOYSA-N 0.000 description 1
- UTZAXPKCGJZGLB-UHFFFAOYSA-N diethyl methyl phosphite Chemical compound CCOP(OC)OCC UTZAXPKCGJZGLB-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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- 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 Table
- 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 Table
- 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
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- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of chemical production, and in particular 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 extractant, extracting most of organic phosphorus impurities in the melted sodium tetrachloroaluminate waste residues into an extract, and completely removing a small amount of organic phosphorus impurities remained in the melted sodium tetrachloroaluminate waste residues through burning treatment; adding the burned 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 to react to obtain the polyaluminum chloride. The invention not only reduces the generation of solid dangerous waste, but also realizes the resource utilization of sodium tetrachloroaluminate in solid waste residues, and obtains high-quality sodium chloride products and polyaluminium chloride products, thereby having higher economic benefit and environmental protection benefit and having 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 diethyl methylphosphonite and mono-n-butyl methylphosphonite which are key intermediates of glufosinate at present. The main synthesis processes for preparing the methyl phosphorus dichloride at home are a ternary complex method and an alkyl aluminum method. The two synthesis processes can generate a large amount of solid waste after separating the product methyl phosphorus dichloride, and the main component of the synthesis process is sodium tetrachloroaluminate, and the synthesis process also contains a small amount of impurities such as organic phosphorus and the like. Because sodium tetrachloroaluminate is easy to dissolve in water, the existing sodium tetrachloroaluminate solid waste residues are directly discharged after being dissolved by adding water, so that the environment is polluted greatly, and the resource waste is caused. How to reasonably treat the sodium tetrachloroaluminate solid waste is a problem to be solved in the industrialization of the glufosinate.
At present, the following processes for treating sodium tetrachloroaluminate solid waste residues are reported in the literature: firstly adding an alcohol and ether solution agent into sodium tetrachloroaluminate solid waste residue, separating out sodium chloride obtained by solution, dissolving aluminum trichloride obtained by solution in the solution agent, filtering to obtain sodium chloride solid, cooling and crystallizing the filtrate to obtain aluminum trichloride solid, purifying the aluminum trichloride to reach the raw material standard, recycling the aluminum trichloride for synthesizing methyl phosphorus dichloride, and adding sodium hydroxide into the aluminum trichloride to synthesize polyaluminum chloride after the complexing capacity is reduced. The process is complex in operation, 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 organic impurity content and cannot be directly used in the field of industrial sewage treatment. Therefore, development of an effective treatment method for sodium tetrachloroaluminate solid waste residues is needed at present, and the aim of recycling the sodium tetrachloroaluminate solid waste residues is fulfilled with low cost, high efficiency and thoroughly.
Disclosure of Invention
Aiming at the problems that the existing treatment method of the sodium tetrachloroaluminate solid waste is complex in process and cannot realize thorough recycling of the sodium tetrachloroaluminate solid waste, the invention provides the treatment method of the sodium tetrachloroaluminate solid waste generated in the production process of methyl phosphorus dichloride.
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 residue generated in the production process of methyl phosphorus dichloride comprises the following steps:
step a, melting sodium tetrachloroaluminate solid waste residues, adding an extracting agent under the condition of isolating air, uniformly mixing, standing, and separating liquid to obtain an extraction solution and molten sodium tetrachloroaluminate; wherein the extractant is at least one of n-hexadecane, pseudocumene, industrial solvent oil or tributyl phosphate;
step b, burning the molten sodium tetrachloroaluminate under the aerobic condition, adding the burnt sodium tetrachloroaluminate into water, and filtering to obtain a mixed salt solution;
step 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 polyaluminium chloride product.
The most difficult point of recycling sodium tetrachloroaluminate in sodium tetrachloroaluminate solid waste residues is that organic impurities such as methyl phosphorus dichloride, a small amount of dimethyl phosphorus chloride and the like exist in the sodium tetrachloroaluminate solid waste residues. In the prior art, the polyaluminum chloride product or the byproduct salt product obtained by recycling the sodium tetrachloroaluminate solid waste residues contains organic impurities, the purity of the polyaluminum chloride product or the byproduct salt product does not reach the standard, and secondary treatment is needed.
Compared with the prior art, the method for treating the sodium tetrachloroaluminate solid waste generated in the production process of the methyl phosphorus dichloride comprises the steps of firstly melting the solid waste, adding a specific extractant, extracting most of organic phosphorus impurities in the molten sodium tetrachloroaluminate into an extract, and completely removing a small amount of organic phosphorus impurities remained in the molten sodium tetrachloroaluminate through burning treatment; then adding 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, thereby not only reducing the generation of solid hazardous waste, but also realizing the recycling utilization of sodium tetrachloroaluminate in solid waste residues, and obtaining a high-quality sodium chloride product and polyaluminum chloride product, thereby having higher economic benefit and environmental protection benefit and broad market prospect.
Preferably, in step a, the melting temperature is 150 ℃ to 200 ℃.
Preferably, in the step a, the extractant is trimellitic benzene and tributyl phosphate with the mass ratio of 2-3:1.
Preferably, in the step a, the mass ratio of the extractant to the sodium tetrachloroaluminate solid waste residue is 1-5:1.
The optimized extractant and the addition amount of the extractant can fully extract the organic phosphorus impurities in the sodium tetrachloroaluminate solid waste residue into the extract, especially can extract most of methyl phosphorus dichloride into the extract, and is favorable for fully recycling the methyl phosphorus dichloride in the solid waste residue, and also favorable for obtaining high-quality sodium chloride and polyaluminium chloride products, thereby being favorable for realizing thorough recycling of the sodium tetrachloroaluminate solid waste residue.
Preferably, the 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 cause a small amount of organic phosphorus in the sodium tetrachloroaluminate to spontaneously combust.
Further, in the step b, the temperature of the high-temperature air is 150-180 ℃.
The preferable process can fully burn a small amount of residual organic phosphorus impurities in the molten sodium tetrachloroaluminate and 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 burnt sodium tetrachloroaluminate is added into room-temperature water.
The preferable temperature and the adding amount of water are beneficial to improving the hydrolysis efficiency of the sodium tetrachloroaluminate.
Optionally, in the step b, molten sodium tetrachloroaluminate is added into water in a fed-batch mode, wherein the feeding rate is based on the control of the temperature of the water to be 80-100 ℃.
Optionally, in step b, the filtration temperature is controlled to be 50 ℃ to 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-20KPa, and the dehydration temperature is 80-100 ℃.
The optimized dehydration amount is favorable for fully precipitating sodium chloride and improving the yield of 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 ℃ to 100 ℃.
Preferably, in 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 aluminum chloride in the aluminum chloride solution.
Preferably, rectifying the extraction solution obtained in the step a to obtain a recovered solvent and methyl phosphorus dichloride; and c, returning the recovered solvent to the step a to serve as an extracting agent for extracting the sodium tetrachloroaluminate solid waste residue of the next batch.
Rectifying the extraction solution, recovering methyl phosphorus dichloride with the content of more than 99% from the tower top, and continuously extracting sodium tetrachloroaluminate in the next batch for the recovered extractant at the tower bottom.
Further, the rectification is negative pressure rectification, the absolute pressure of the rectification is 5KPa-20KPa, and the temperature of the tower kettle is controlled to be 80-100 ℃.
The preferential rectification condition is favorable for improving the recovery rate of the methyl phosphorus dichloride.
According to the method for treating the sodium tetrachloroaluminate solid waste generated in the production process of the methyl phosphorus dichloride, the recovery of the methyl phosphorus dichloride in the solid waste can be realized, the purity of the obtained methyl phosphorus dichloride product can reach more than 99%, the full recovery and the utilization of sodium tetrachloroaluminate are realized, the sodium chloride product with the purity of more than 99.9% and the polyaluminum chloride product reaching the standard for domestic drinking water are obtained, and the extractant added in the treatment process is not directly discharged out of the system, but is continuously recycled back to the system to serve as the extractant of the sodium tetrachloroaluminate of the next batch, so that no liquid hazardous waste is generated in the whole system, and the method for treating the sodium tetrachloroaluminate solid waste is green, resource-saving and low-cost, meets the current trend of clean production, and has higher popularization and application values.
Drawings
FIG. 1 is a process route diagram of a method for treating sodium tetrachloroaluminate solid waste in an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The sodium tetrachloroaluminate solid waste residue in the following examples and comparative examples is derived from the 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 residue generated in the production process of methyl phosphorus dichloride, wherein the sodium tetrachloroaluminate solid waste residue contains 2.55% of organic phosphorus substances, and the method specifically comprises the following steps:
step a, adding 200g of sodium tetrachloroaluminate solid waste residues 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 isolating air, stirring for 0.5h, standing for 0.5h, separating the solution, 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 extraction solution is measured to be 2.8g, and the organic phosphorus accounts for 54.9 percent of the total amount of the organic phosphorus;
transferring the lower layer of molten sodium tetrachloroaluminate into a high-temperature oxidation kettle, heating to 260 ℃, introducing 160 ℃ high-temperature air into the molten sodium tetrachloroaluminate, burning a small amount of organic phosphorus in the sodium tetrachloroaluminate, stopping introducing air when no open fire is generated, then adding the molten sodium tetrachloroaluminate into 400g of water, controlling the water temperature to 80 ℃ in a fed-batch process, 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 0.5ppm;
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 ℃, filtering at 80 ℃ to obtain 439.2g of aluminum chloride solution and 48g of sodium chloride product, wherein the content of the sodium chloride product is 99.9%, and detecting that the sodium chloride product does not contain organic phosphorus;
step 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, carrying out heat preservation reaction for 6 hours at 100 ℃, and drying to obtain a polyaluminium chloride product;
step e, carrying out negative pressure rectification on the extraction solution obtained in the step a under the condition that the absolute pressure of the system is 10-15KPa, controlling the temperature of a tower bottom to be 80 ℃, and recovering methyl phosphorus dichloride from the tower top, wherein the content of the methyl phosphorus dichloride is 99.14%; 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%, and the loss rate of the n-hexadecane extractant is 1%.
The polyaluminum chloride product prepared by the embodiment meets the standard of GB15892-2009 domestic drinking water polyaluminum chloride.
Example 2
The embodiment provides a method for treating sodium tetrachloroaluminate solid waste residue generated in the production process of methyl phosphorus dichloride, wherein the sodium tetrachloroaluminate solid waste residue contains 2.55% of organic phosphorus substances, and the method specifically comprises the following steps:
step a, adding 200g of sodium tetrachloroaluminate solid waste residues into a 160 ℃ high-temperature melting kettle for melting, adding 400g of industrial solvent oil into the high-temperature melting kettle under the condition of isolating air, stirring for 1h, standing for 1h, separating the solution, 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 extraction solution is 3.5g, which accounts for 68.6% of the total organic phosphorus;
transferring the lower layer of molten sodium tetrachloroaluminate into a high-temperature oxidation kettle, heating to 260 ℃, introducing high-temperature air of 150 ℃ into the molten sodium tetrachloroaluminate, burning a small amount of organic phosphorus in the sodium tetrachloroaluminate, stopping introducing 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 90 ℃, filtering at 50 ℃, and filtering out phosphorus coking black slag insoluble in water 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 0.2ppm;
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 90 ℃, 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%, and detecting that the sodium chloride product does not contain organic phosphorus;
step 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 for 4 hours at 130 ℃, and drying to obtain a polyaluminum chloride product;
step e, carrying out negative pressure rectification on the extraction solution obtained in the step a under the condition that the absolute pressure of the system is 5-10KPa, controlling the temperature of a tower bottom to be 80 ℃, and recovering methyl phosphorus dichloride from the tower top, wherein the content of the methyl phosphorus dichloride is 99.19%; 393g of industrial solvent oil was extracted from the bottom of the column and was used for the next batch of sodium tetrachloroaluminate extraction. The recovery rate of the methyl phosphorus dichloride is 100%, and the loss rate of the industrial solvent oil is 1.75%.
The polyaluminum chloride product prepared by the embodiment meets the standard of GB15892-2009 domestic drinking water polyaluminum chloride.
Example 3
The embodiment provides a method for treating sodium tetrachloroaluminate solid waste residue generated in the production process of methyl phosphorus dichloride, wherein the sodium tetrachloroaluminate solid waste residue contains 2.55% of organic phosphorus substances, and the method specifically comprises the following steps:
step a, adding 200g of sodium tetrachloroaluminate solid waste residues into a high-temperature melting kettle at 200 ℃ for melting, adding 400g of pseudocumene into the high-temperature melting kettle under the condition of isolating air, stirring for 2 hours, standing for 1 hour, separating the solution, 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 extraction solution is measured to be 4.0g, and the organic phosphorus accounts for 78.4 percent of the total amount;
transferring the lower layer of molten sodium tetrachloroaluminate 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 air when no open fire is generated, then adding the molten sodium tetrachloroaluminate into 500g of water, controlling the water temperature at 90 ℃ in a fed-batch process, filtering at 50 ℃, and filtering out phosphorus coking black slag insoluble in water 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 0.15ppm;
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 ℃, filtering at 90 ℃ to obtain 434g of aluminum chloride solution and 49g of sodium chloride product, wherein the content of the sodium chloride product is 99.9%, and detecting that the sodium chloride product does not contain organic phosphorus;
step 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, carrying out heat preservation reaction for 4.5 hours at 110 ℃, and drying to obtain a polyaluminum chloride product;
step e, carrying out negative pressure rectification on the extraction solution obtained in the step a under the condition that the absolute pressure of the system is 15-20KPa, controlling the temperature of a tower bottom to be 90 ℃, and recovering methyl phosphorus dichloride from the tower top, wherein the content is 99.03%; 397g of pseudocumene is extracted from the tower bottom and is continuously used for extracting the sodium tetrachloroaluminate of the next batch. The recovery rate of the methyl phosphorus dichloride is 100%, and the loss rate of the pseudocumene extractant is 0.75%.
The polyaluminum chloride product prepared by the embodiment meets the standard of GB15892-2009 domestic drinking water polyaluminum chloride.
Example 4
The embodiment provides a method for treating sodium tetrachloroaluminate solid waste residue generated in the production process of methyl phosphorus dichloride, wherein the sodium tetrachloroaluminate solid waste residue contains 2.55% of organic phosphorus substances, and the method specifically comprises the following steps:
step a, adding 200g of sodium tetrachloroaluminate solid waste 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 isolating air, stirring for 2.5h, standing for 2h, separating the solution, 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 extraction solution is 3.97g, which occupies 77.8 percent of the total organic phosphorus;
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, burning a small amount of organic phosphorus in the sodium tetrachloroaluminate, stopping introducing air when no open fire is generated, then adding the molten sodium tetrachloroaluminate into 600g of water, controlling the water temperature to 90 ℃ in a feeding process, filtering at 80 ℃, and filtering out phosphorus coking black slag insoluble in water 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 0.1ppm;
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 ℃, filtering at 90 ℃ to obtain 462g of aluminum chloride solution and 45g of sodium chloride product, wherein the content of the sodium chloride product is 99.9%, and detecting that the sodium chloride product does not contain organic phosphorus;
step 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, carrying out heat preservation reaction for 5 hours at 120 ℃, and drying to obtain a polyaluminium chloride product;
step e, carrying out negative pressure rectification on the extraction solution obtained in the step a under the condition that the absolute pressure of the system is 5-10KPa, controlling the temperature of a tower bottom to be 90 ℃, and recovering methyl phosphorus dichloride from the tower top, wherein the content of the methyl phosphorus dichloride is 99.08%; 598g of tributyl phosphate is extracted from the tower bottom and is continuously used for extracting the next batch of sodium tetrachloroaluminate. The recovery rate of the methyl phosphorus dichloride is 100%, and the loss rate of the tributyl phosphate extractant is 0.33%.
The polyaluminum chloride product prepared by the embodiment meets the standard of GB15892-2009 domestic drinking water polyaluminum chloride.
Example 5
The embodiment provides a method for treating sodium tetrachloroaluminate solid waste residue generated in the production process of methyl phosphorus dichloride, wherein the sodium tetrachloroaluminate solid waste residue contains 2.55% of organic phosphorus substances, and the method specifically comprises the following steps:
step a, adding 200g of sodium tetrachloroaluminate solid waste 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 isolating air, stirring for 2.5h, standing for 2h, separating the solution, 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 extraction solution is 4.6g, which accounts for 90.2% of the total organic phosphorus;
transferring the lower layer of molten sodium tetrachloroaluminate into a high-temperature oxidation kettle, heating to 260 ℃, introducing 160 ℃ high-temperature air into the molten sodium tetrachloroaluminate, burning a small amount of organic phosphorus in the sodium tetrachloroaluminate, stopping introducing air when no open fire is generated, then adding the molten sodium tetrachloroaluminate into 500g of water, controlling the water temperature to 80 ℃ in a fed-batch process, 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 0.05ppm;
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 ℃, filtering at 80 ℃ to obtain 434g of aluminum chloride solution and 49g of sodium chloride product, wherein the content of the sodium chloride product is 99.9%, and detecting that the sodium chloride product does not contain organic phosphorus;
step 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, carrying out heat preservation reaction for 5 hours at 120 ℃, and drying to obtain a polyaluminium chloride product;
step e, carrying out negative pressure rectification on the extraction solution obtained in the step a under the condition that the absolute pressure of the system is 10-15KPa, controlling the temperature of a tower bottom to be 80 ℃, and recovering methyl phosphorus dichloride from the tower top, wherein the content of the methyl phosphorus dichloride is 99.3%; 598g of mixed solvent of trimellitic benzene and tributyl phosphate 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%, and the total loss rate of the trimellitic benzene and tributyl phosphate extractant is 0.33%.
The polyaluminum chloride product prepared by the embodiment meets the standard of GB15892-2009 domestic drinking water polyaluminum chloride.
Comparative example 1
The comparative example provides a method for treating 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 of the example 5, and the difference is that the mixed solvent of the trimellitic benzene and the tributyl phosphate in the step a is replaced by the equivalent glycerol.
The mass of the organic phosphorus in the lower extraction solution in step a was found to be 0.2g, accounting for 3.92% of the total organic phosphorus. And 250g of glycerol obtained by rectification recovery in the step e has the loss rate of the glycerol close to 58.3 percent.
The above comparative examples demonstrate that the residual amount of glycerol in sodium tetrachloroaluminate is large and that efficient extraction of organic phosphorus in sodium tetrachloroaluminate cannot be achieved.
Comparative example 2
The comparative example provides a method for treating 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 of the example 5, and the difference is that the mixed solvent of the trimellitic benzene and the tributyl phosphate in the step a is replaced by equal amount of phenol.
The lower extraction solution in step a was measured to be free of organic phosphorus species.
The above comparative examples demonstrate that phenol does not allow extraction of the organic phosphorus in sodium tetra-chloroaluminate.
Comparative example 3
The comparative example provides a method for treating 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 of the example 5, except that the mixed solvent of the pseudocumene and tributyl phosphate in the step a is replaced by the same amount of the pseudocumene and 1, 4-butyrolactone (the mass ratio of the pseudocumene to the 1, 4-butyrolactone is 2:1).
The mass of the organic phosphorus in the lower extraction solution in step a was found to be 1.52g, accounting for 29.8% of the total organic phosphorus. And the total content of the trimellitic benzene and the 1, 4-butyrolactone obtained by rectification and recovery in the step e is 540g, and the loss rate of the solvent is close to 10%.
The technical effect equivalent to that of example 5 can be achieved by replacing the mixed solvent of the trimellitic benzene and the tributyl phosphate in the step a of example 1 with the mixed solvent of the trimellitic benzene and the tributyl phosphate in other proportions defined by the invention.
In summary, the treatment method of the sodium tetrachloroaluminate solid waste generated in the production process of the methyl phosphorus dichloride can not only realize the full recovery of the methyl phosphorus dichloride in the solid waste, but also fully remove the organic phosphorus impurities in the sodium tetrachloroaluminate solid waste to obtain a high-quality sodium chloride product and polyaluminium chloride meeting the standard for drinking water, and the whole process does not generate liquid hazardous waste, meets the trend of clean production, and has wide application prospect.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (8)
1. The method for treating the sodium tetrachloroaluminate solid waste residue generated in the production process of the methyl phosphorus dichloride is characterized by comprising the following steps of:
step a, melting sodium tetrachloroaluminate solid waste residues, adding an extracting agent under the condition of isolating air, uniformly mixing, standing, and separating liquid to obtain an extraction solution and molten sodium tetrachloroaluminate; wherein the extractant is at least one of n-hexadecane, pseudocumene, industrial solvent oil or tributyl phosphate; the melting temperature is 150-200 ℃; the mass ratio of the extractant to the sodium tetrachloroaluminate solid waste residue is 1-5:1;
step b, burning the molten sodium tetrachloroaluminate under the aerobic condition, adding the burnt sodium tetrachloroaluminate into water, and filtering to obtain a mixed salt solution;
step 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 polyaluminium chloride product.
2. The method for treating sodium tetrachloroaluminate solid waste produced in the production process of methyl phosphorus dichloride according to claim 1, wherein in the step a, the extractant is trimellitic benzene and tributyl phosphate in a mass ratio of 2-3:1.
3. The method for treating sodium tetrachloroaluminate solid waste produced in the production process of methyl phosphorus dichloride according to claim 1, wherein step b comprises the following steps: heating the molten sodium tetrachloroaluminate to 250-300 ℃, and then introducing high-temperature air into the molten sodium tetrachloroaluminate for burning.
4. The method for treating sodium tetrachloroaluminate solid waste produced in the production process of methyl phosphorus dichloride according to claim 3, wherein in step b, the temperature of the high temperature air is 150 ℃ to 180 ℃.
5. The method for treating sodium tetrachloroaluminate solid waste produced in the production process of methyl phosphorus dichloride according to claim 1, wherein in the step b, the mass ratio of water to sodium tetrachloroaluminate solid waste is 1-5:1; and/or
In the step c, the dehydration amount is 15-40% of the mass of the mixed salt solution.
6. The method for treating sodium tetrachloroaluminate solid waste produced in the production process of methyl phosphorus dichloride according to claim 1 or 5, wherein in step c, a negative pressure dehydration mode is adopted, the absolute pressure of dehydration is 5KPa-20KPa, and the dehydration temperature is 80 ℃ to 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 adding amount of the calcium aluminate powder is 1 to 1.1 times of the mass of aluminum chloride in the aluminum chloride solution.
7. The method for treating sodium tetrachloroaluminate solid waste residue produced in the production process of methyl phosphorus dichloride according to claim 1, wherein the extraction solution obtained in step a is rectified to obtain a recovered solvent and methyl phosphorus dichloride; and c, returning the recovered solvent to the step a to serve as an extracting agent for extracting the sodium tetrachloroaluminate solid waste residue of the next batch.
8. The method for treating sodium tetrachloroaluminate solid waste produced in the process of producing phosphorus oxychloride as defined in claim 7, wherein the rectification is negative pressure rectification, the absolute pressure of the rectification is 5KPa-20KPa, and the temperature of the tower bottom is controlled to be 80 ℃ to 100 ℃.
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