CN116421924A - Method for degrading tributyl phosphate and recovering phosphorus element by using alkali-assisted trimanganese tetroxide - Google Patents
Method for degrading tributyl phosphate and recovering phosphorus element by using alkali-assisted trimanganese tetroxide Download PDFInfo
- Publication number
- CN116421924A CN116421924A CN202310454446.0A CN202310454446A CN116421924A CN 116421924 A CN116421924 A CN 116421924A CN 202310454446 A CN202310454446 A CN 202310454446A CN 116421924 A CN116421924 A CN 116421924A
- Authority
- CN
- China
- Prior art keywords
- tributyl phosphate
- reaction
- phosphate
- degrading
- alkali
- 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.)
- Pending
Links
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 title claims abstract description 53
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 36
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 35
- 239000011574 phosphorus Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000003513 alkali Substances 0.000 title claims abstract description 16
- 230000000593 degrading effect Effects 0.000 title claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 18
- 239000012071 phase Substances 0.000 claims abstract description 17
- 239000006228 supernatant Substances 0.000 claims abstract description 16
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims abstract description 11
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 6
- 239000010935 stainless steel Substances 0.000 claims abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- -1 methane hydrocarbon Chemical class 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 235000019983 sodium metaphosphate Nutrition 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- GSQTXLAHEVFYSA-UHFFFAOYSA-K trisodium;phosphate;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O GSQTXLAHEVFYSA-UHFFFAOYSA-K 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 238000005904 alkaline hydrolysis reaction Methods 0.000 abstract description 6
- 239000002920 hazardous waste Substances 0.000 abstract description 6
- 238000012869 ethanol precipitation Methods 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005119 centrifugation Methods 0.000 abstract description 2
- 239000007857 degradation product Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010029350 Neurotoxicity Diseases 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000007135 neurotoxicity Effects 0.000 description 1
- 231100000228 neurotoxicity Toxicity 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 230000033458 reproduction Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000155 toxicity by organ Toxicity 0.000 description 1
- 230000007675 toxicity by organ Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/35—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/26—Organic substances containing nitrogen or phosphorus
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a method for degrading tributyl phosphate and recovering phosphorus elements by using alkali-assisted trimanganese tetroxide. The method comprises the following steps: tributyl phosphate, sodium hydroxide and manganous oxide are uniformly mixed in a stainless steel high-pressure stirring reactor according to a certain proportion. Setting the stirring speed, the reaction temperature and the reaction time of the reactor. After the reaction was completed and cooled to room temperature, the gas phase product in the reactor was detected. The solid phase mixture was washed with 50% ethanol and the supernatant was collected by centrifugation, and the phosphorus element in the tributyl phosphate degradation product was recovered in the form of phosphate-like salt by ethanol precipitation. According to the invention, the characteristic that the manganous oxide rapidly releases oxygen and generates active oxygen at high temperature is utilized as an oxygen carrier to treat tributyl phosphate, and meanwhile, the alkaline hydrolysis reaction is coupled to strengthen the degradation effect of the tributyl phosphate, so that the efficient degradation treatment of the tributyl phosphate is realized, and meanwhile, the phosphorus element is recovered by a convenient ethanol precipitation method, so that the purposes of hazardous waste management and resource recovery are achieved.
Description
Technical Field
The invention belongs to the technical field of organic hazardous waste treatment, and particularly relates to a method for degrading tributyl phosphate and recovering phosphorus elements by using alkali-assisted trimanganese tetroxide.
Background
Tributyl phosphate is an artificially synthesized organic phosphate compound and is widely used in the production and manufacture of industrial products. Tributyl phosphate is also commonly used in extraction of pharmaceutical wastewater and nuclear fuel due to its strong chemical stability and high partition coefficient for most organics and metals. However, since the components of industrial wastewater are very complex, various toxic, harmful and radioactive substances are contained in the extract liquid, so that new high-concentration organic hazardous wastes are formed, and further treatment and disposal are required. Tributyl phosphate is easy to gather in sediment, soil and water, is difficult to decompose through natural pyrolysis and hydrolysis for a long time, causes serious threat to life health of animals, plants and human beings, and the biotoxicity effect of the tributyl phosphate is mainly expressed in aspects of acute toxicity, neurotoxicity, organ toxicity, reproduction and development toxicity, carcinogenesis and teratogenicity and the like. Therefore, developing effective harmless treatment technology to reduce or eliminate the harm of tributyl phosphate to natural environment and life health has been unprecedented.
The currently reported tributyl phosphate dangerous waste treatment methods include a direct incineration method, a wet oxidation method, an alkaline hydrolysis method, an absorption method, a solidification method and the like. However, these methods have the disadvantages that if the generated tail gas and secondary waste are required to be treated or the method does not have ideal economical efficiency, the industrialized application is difficult to realize, and the recycling of the phosphorus element contained in tributyl phosphate is not considered. Chemical looping combustion technology is a pyrolysis technology commonly used for capturing carbon dioxide in fuels, but in practice, the technology has a non-negligible application potential in the field of environmental protection. There are few reports of treating solid waste by using the technology, but there is no systematic study on the treatment of liquid waste.
The oxygen carrier is an important factor for determining the efficient operation of the whole chemical looping combustion system, and manganese oxide can deoxidize to generate active oxygen with strong oxidation performance under the high-temperature condition. Alkaline hydrolysis is a mature method for treating tributyl phosphate, but in view of the complexity of actual waste liquid, the alkaline hydrolysis treatment cannot be generally directly carried out on tributyl phosphate hazardous waste (such as radioactive tributyl phosphate/kerosene organic hazardous waste) in actual production, so that the capacity and environmental risk of radioactive waste are prevented from being increased. Therefore, the invention introduces the manganous oxide as an oxygen carrier into a pyrolysis system of tributyl phosphate based on the principle of chemical chain combustion reaction, simultaneously couples alkaline hydrolysis reaction to strengthen the degradation efficiency of tributyl phosphate, and utilizes an ethanol precipitation method to recover phosphorus element in tributyl phosphate degradation products, thereby achieving the harmless and recycling disposal targets of tributyl phosphate. In addition, compared with the traditional chemical looping combustion process, the reaction system constructed by the invention can obviously reduce the reaction temperature and reduce the energy requirement of the treatment process.
Disclosure of Invention
In view of the defects and shortcomings of the prior art, the invention provides a method for degrading tributyl phosphate and recycling phosphorus elements by using alkali to assist in manganous oxide.
The aim of the invention is achieved by the following technical scheme.
The method for degrading tributyl phosphate and recycling phosphorus element by using alkali-assisted trimanganese tetroxide comprises the following specific operations:
(1) Uniformly mixing tributyl phosphate, sodium hydroxide and manganous oxide in a certain proportion in a stainless steel high-pressure stirring reactor to obtain a mixture;
(2) After the stirring and sealing assembly of the reactor is installed, setting stirring rotation speed, reaction temperature and reaction time, and starting the reaction;
(3) After the reaction is finished, cooling the reactor to room temperature, collecting a gas phase product formed after the reaction by using a gas sampling bag, and detecting the composition of the gas phase product and the total non-methane hydrocarbon content by using gas chromatography-mass spectrometry;
(4) After the reaction is finished, cooling the reactor to room temperature, washing the residual solid phase materials in the reactor by using 50% ethanol water solution (volume ratio), centrifugally separating and collecting supernatant, adding absolute ethanol into the supernatant, standing, and collecting white precipitate after the precipitation is complete.
In the step (1), the proportion of tributyl phosphate, sodium hydroxide and manganous oxide is 1 mL:2-10 g:13 g.
In the step (2), the stirring speed is 300-600 rpm,the reaction temperature is 100-260 deg.f o C, the reaction time is 1-5 h.
In the step (3), the gas phase product formed after the reaction contains carbon monoxide and methane.
In the step (4), the ratio of the solid phase material to the 50% ethanol aqueous solution in the washing process is 13 g:1-3L, the volume ratio of the supernatant to the absolute ethanol is 1:0.5-1, and the standing time is 0.5-2 h.
In the step (4), the recovered phosphorus element exists in the solid of phosphate such as sodium phosphate, sodium phosphate octahydrate, sodium metaphosphate, disodium hydrogen phosphate and the like.
The innovation and beneficial effects of the invention are as follows: based on the principle of chemical chain combustion reaction, the trimanganese tetroxide is firstly introduced into a pyrolysis system of tributyl phosphate as an oxygen carrier, and simultaneously, the degradation effect of the tributyl phosphate is enhanced by coupling alkaline hydrolysis reaction, so that the inorganic mineralization of the tributyl phosphate is realized, and meanwhile, phosphorus element is extracted by an ethanol precipitation method, thereby realizing harmless and recycling treatment of the hazardous waste of the tributyl phosphate. Compared with the traditional chemical looping combustion process, the reaction system constructed by the invention can obviously reduce the reaction temperature and reduce the energy requirement of the treatment process.
Drawings
FIG. 1 is a schematic flow chart of a method for degrading tributyl phosphate and recovering phosphorus element by using alkali-assisted trimanganese tetroxide.
FIG. 2 is a graph showing the experimental results of the effect of the addition amount of sodium hydroxide on the conversion rate of phosphorus and the total non-methane hydrocarbons in the gas phase product in the method for degrading tributyl phosphate and recovering phosphorus by using alkali-assisted trimanganese tetroxide.
FIG. 3 is an X-ray diffraction analysis chart of the extracted phosphorus-containing product in the method for degrading tributyl phosphate and recovering phosphorus by using alkali-assisted trimanganese tetroxide.
Detailed Description
For a better understanding of the present invention, the present invention will be described in further detail with reference to the accompanying drawings and examples.
As shown in FIG. 1, the method for degrading tributyl phosphate and recovering phosphorus by using alkali-assisted trimanganese tetroxide comprises the following steps:
(1) Uniformly mixing tributyl phosphate, sodium hydroxide and manganous oxide in a certain proportion in a stainless steel high-pressure stirring reactor to obtain a mixture;
(2) After the stirring and sealing assembly of the reactor is installed, setting stirring rotation speed, reaction temperature and reaction time, and starting the reaction;
(3) After the reaction is finished, cooling the reactor to room temperature, collecting a gas phase product formed after the reaction by using a gas sampling bag, and detecting the composition of the gas phase product and the total non-methane hydrocarbon content by using gas chromatography-mass spectrometry;
(4) After the reaction is finished, cooling the reactor to room temperature, washing the residual solid phase materials in the reactor by using 50% ethanol water solution (volume ratio), centrifugally separating and collecting supernatant, adding absolute ethanol into the supernatant, standing, and collecting white precipitate after the precipitation is complete.
In the step (1), the proportion of tributyl phosphate, sodium hydroxide and manganous oxide is 1 mL:2-10 g:13 g.
In the step (2), the stirring speed is 300-600 rpm, and the reaction temperature is 100-260 o C, the reaction time is 1-5 h.
In the step (4), the ratio of the solid phase material to the 50% ethanol aqueous solution in the washing process is 13 g:1-3L, the volume ratio of the supernatant to the absolute ethanol is 1:0.5-1, and the standing time is 0.5-2 h.
Implementation example 1: adding 13 g manganous oxide and 6 g sodium hydroxide into a stainless steel high-pressure stirring reactor, dropwise adding 1 mL tributyl phosphate, setting the stirring speed of the reactor to be 500 rpm, and stirring at 220 o Reaction 3 h under C. After the reaction is finished, cooling the reactor to room temperature, collecting gas phase products, and detecting the concentration of non-methane total hydrocarbons of the gas phase products by adopting a gas chromatography method for measuring the total hydrocarbons of waste gas, methane and non-methane of the fixed pollution sources of HJ 38-2017. The solid product after the reaction was washed with 50% ethanol several times, and the precipitate and supernatant were collected by centrifugation, respectively. After the ethanol in the supernatant is completely volatilized, separating residual liquid phase organic matters possibly existing in the supernatant by using a separating funnel with normal hexane as an extracting agentAnd collecting water phase liquid, measuring the phosphorus content in the water phase liquid by using an ammonium molybdate spectrophotometry for measuring total phosphorus in GB 11893-89 water quality, and calculating the conversion rate of phosphorus element from tributyl phosphate to water phase product.
The process is used for treating tributyl phosphate dangerous waste, the conversion rate of phosphorus element can reach 77.47 percent, and the concentration of non-methane total hydrocarbon in gas phase products is 27.28 mg m -3 Is lower than the maximum allowable emission concentration of 120 mg m of non-methane total hydrocarbon in GB 16297-1996 comprehensive emission standard of atmospheric pollutants -3 。
The amount of the manganous oxide in the fixed reaction system is 13 g, the amount of the tributyl phosphate is 1 mL, and the influence of the addition amount of the sodium hydroxide on the reaction is studied. As shown in figure 2, the conversion rate of the phosphorus element from tributyl phosphate to the aqueous phase product is increased along with the increase of the addition amount of sodium hydroxideC P ) Gradually increasing, but as the amount of sodium hydroxide increased to 6 g mL -1 Above TBP, the phosphorus conversion hardly increases. Meanwhile, with the increase of the addition amount of sodium hydroxide, the concentration of non-methane total hydrocarbon (NMHC) in the gas phase product is obviously reduced, and the dosage of sodium hydroxide is 10 g mL -1 At TBP, NMHC concentration after the reaction was as low as 16.54 mg m -3 。
Implementation example 2: adding 13 g manganous manganic oxide and 5 g sodium hydroxide into a stainless steel high-pressure stirring reactor, uniformly dripping 1 mL tributyl phosphate, setting the stirring speed of the reactor to be 500 rpm, and stirring at 220 o Reaction 3 h under C. After the reaction is finished, the reactor is naturally cooled to room temperature, and the solid product is washed by 50 percent ethanol (volume ratio) for a plurality of times and is centrifugally collected to precipitate and supernatant. Absolute ethyl alcohol is added into the supernatant according to the volume ratio of 1:0.5, and the phosphate-like substance is easily dissolved in water and is insoluble in ethanol, so that the phosphorus-containing substance in the supernatant is extracted by an ethanol precipitation method. The suspension is kept stand for 30 min at room temperature, and after the precipitation of the phosphorus-containing product is completed, the solid phosphorus-containing material is collected by filtration and ethanol washing. As shown in fig. 3, the main components of the phosphorus-containing material were sodium phosphate, sodium phosphate octahydrate, sodium metaphosphate and disodium hydrogen phosphate according to the X-ray crystal diffraction analysis of the product.
Claims (6)
1. The method for degrading tributyl phosphate and recycling phosphorus by using alkali-assisted trimanganese tetroxide is characterized by comprising the following steps:
(1) Uniformly mixing tributyl phosphate, sodium hydroxide and manganous oxide in a certain proportion in a stainless steel high-pressure stirring reactor to obtain a mixture;
(2) After the stirring and sealing assembly of the reactor is installed, setting stirring rotation speed, reaction temperature and reaction time, and starting the reaction;
(3) After the reaction is finished, cooling the reactor to room temperature, collecting a gas phase product formed after the reaction by using a gas sampling bag, and detecting the composition of the gas phase product and the total non-methane hydrocarbon content by using gas chromatography-mass spectrometry;
(4) After the reaction is finished, cooling the reactor to room temperature, washing the residual solid phase materials in the reactor by using 50% ethanol water solution (volume ratio), centrifugally separating and collecting supernatant, adding absolute ethanol into the supernatant, standing, and collecting white precipitate after the precipitation is complete.
2. The method for degrading tributyl phosphate and recovering phosphorus by using alkali-assisted trimanganese tetroxide according to claim 1, wherein in the step (1), the ratio of tributyl phosphate, sodium hydroxide and trimanganese tetroxide is 1 mL:2-10 g:13 g.
3. The method for degrading tributyl phosphate and recovering phosphorus element by using alkali-assisted trimanganese tetroxide as claimed in claim 1, wherein the stirring speed in the step (2) is 300-600 rpm, and the reaction temperature is 100-260 o C, the reaction time is 1-5 h.
4. The method for degrading tributyl phosphate and recovering phosphorus by using alkali-assisted trimanganese tetroxide according to claim 1, wherein in the step (3), the gas phase product formed after the reaction contains carbon monoxide and methane.
5. The method for degrading tributyl phosphate and recovering phosphorus element by using alkali-assisted trimanganese tetroxide according to claim 1, wherein in the step (4), the ratio of solid phase material to 50% ethanol aqueous solution in the washing process is 13 g:1-3L, the volume ratio of supernatant to absolute ethanol is 1:0.5-1, and the standing time is 0.5-2 h.
6. The method for degrading tributyl phosphate and recovering phosphorus element by using alkali-assisted trimanganese tetroxide according to claim 1, wherein in the step (4), the recovered phosphorus element exists in the solid of phosphate such as sodium phosphate, sodium phosphate octahydrate, sodium metaphosphate and disodium hydrogen phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310454446.0A CN116421924A (en) | 2023-04-25 | 2023-04-25 | Method for degrading tributyl phosphate and recovering phosphorus element by using alkali-assisted trimanganese tetroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310454446.0A CN116421924A (en) | 2023-04-25 | 2023-04-25 | Method for degrading tributyl phosphate and recovering phosphorus element by using alkali-assisted trimanganese tetroxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116421924A true CN116421924A (en) | 2023-07-14 |
Family
ID=87085295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310454446.0A Pending CN116421924A (en) | 2023-04-25 | 2023-04-25 | Method for degrading tributyl phosphate and recovering phosphorus element by using alkali-assisted trimanganese tetroxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116421924A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100010283A1 (en) * | 2005-05-09 | 2010-01-14 | Vempati R K | Method for degrading chemical warfare agents using Mn(VII) oxide with-and-without solid support |
| WO2012036560A1 (en) * | 2010-09-17 | 2012-03-22 | Elkem As | Slurry comprising manganomanganic oxide particles and dispersant and method for the production of such slurries |
| US9907988B1 (en) * | 2015-02-13 | 2018-03-06 | The United States Of America As Represented By The Secretary Of The Army | Porous metal hydroxides for decontaminating toxic agents |
| DE102019006084A1 (en) * | 2019-02-12 | 2020-08-13 | Elke Münch | Mechanochemical process |
| CN116748285A (en) * | 2023-06-21 | 2023-09-15 | 四川大学 | Method for treating hazardous waste of organic phosphate |
-
2023
- 2023-04-25 CN CN202310454446.0A patent/CN116421924A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100010283A1 (en) * | 2005-05-09 | 2010-01-14 | Vempati R K | Method for degrading chemical warfare agents using Mn(VII) oxide with-and-without solid support |
| WO2012036560A1 (en) * | 2010-09-17 | 2012-03-22 | Elkem As | Slurry comprising manganomanganic oxide particles and dispersant and method for the production of such slurries |
| US9907988B1 (en) * | 2015-02-13 | 2018-03-06 | The United States Of America As Represented By The Secretary Of The Army | Porous metal hydroxides for decontaminating toxic agents |
| DE102019006084A1 (en) * | 2019-02-12 | 2020-08-13 | Elke Münch | Mechanochemical process |
| CN116748285A (en) * | 2023-06-21 | 2023-09-15 | 四川大学 | Method for treating hazardous waste of organic phosphate |
Non-Patent Citations (3)
| Title |
|---|
| WENHUA TONG: "Tributyl phosphate degradation and phosphorus immobilization by MnO2: Reaction condition optimization and mechanism exploration", JOURNAL OF HAZARDOUS MATERIALS, vol. 432, 17 March 2022 (2022-03-17), pages 128725 * |
| 丁欢: "磷酸三丁酯在碱中的降解研究", 化学工程师, vol. 29, no. 11, 25 November 2015 (2015-11-25), pages 51 - 53 * |
| 童文华: "碱辅助四氧化三锰降解磷酸三丁酯及磷元素回收研究", 化工学报, vol. 74, no. 10, 14 August 2023 (2023-08-14), pages 4277 - 4285 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Treatment of urban sludge by hydrothermal carbonization | |
| CN104858229B (en) | A kind of soil-repairing agent and preparation method thereof | |
| Wang et al. | Catalytic degradation of sulfamethoxazole by peroxymonosulfate activation system composed of nitrogen-doped biochar from pomelo peel: Important roles of defects and nitrogen, and detoxification of intermediates | |
| CN110655243A (en) | By using TiO2Method for treating uranium-containing wastewater by adsorption-photocatalytic reduction | |
| Guo et al. | Photochemical alkylation of inorganic arsenic Part 1. Identification of volatile arsenic species | |
| Wu et al. | Facile fabrication of Bi2WO6/biochar composites with enhanced charge carrier separation for photodecomposition of dyes | |
| CN104930518B (en) | A kind of low-carbon processing solid refuse and the method for suppressing bioxin generation | |
| Zheng et al. | Enhanced photocatalytic activity of Bi24O31Br10 microsheets constructing heterojunction with AgI for Hg0 removal | |
| CN103170501A (en) | Preparation method of in-situ repair material for soil polluted by heavy metal chromium and application of material | |
| CN110624566A (en) | CuInS2Preparation method and application of quantum dot/NiAl-LDH composite photocatalyst | |
| Luo et al. | Hydrochar effectively removes aqueous Cr (VI) through synergistic adsorption and photoreduction | |
| Hou et al. | Migration and transformation of heavy metals in Chinese medicine residues during the process of traditional pyrolysis and solar pyrolysis | |
| Sun et al. | Enhanced photocatalyst with TiO2-anchored iron tailings structure for highly efficient degradation of doxycycline hydrochloride | |
| Zhang et al. | Two birds, one stone: rational design of Bi-MOF/g-C3N4 photocatalyst for effective nitrogen fixation and pollutants degradation | |
| CN116421924A (en) | Method for degrading tributyl phosphate and recovering phosphorus element by using alkali-assisted trimanganese tetroxide | |
| CN106753504B (en) | A kind of method of biomass liquefying production liquid fuel | |
| Xiong et al. | Visible-light driven Tetracycline hydrochloride degradation by Nano-lanthanum hydroxide modified carbon nitride: performance, mechanism, and application in real wastewater treatment | |
| Li et al. | Hydrothermal liquefaction of sewage sludge and model compound: Heavy metals distribution and behaviors | |
| CN103949221B (en) | A kind of synthetic method of the Chitosan-crown Ethers material for adsorption uranium | |
| CN104438285B (en) | Method for innocent treatment of waste mercury catalyst by mechanical ball milling with sulfur as additive | |
| CN116748285A (en) | Method for treating hazardous waste of organic phosphate | |
| Pan et al. | Distribution and transformation behaviors of heavy metals during liquefaction process of sewage sludge in ethanol-water mixed solvents | |
| JP2013036825A (en) | Method for reducing radioactive substances to safety level in living environment | |
| CN113351623A (en) | Kitchen waste treatment process method | |
| CN112076429B (en) | Microwave treatment method for chemical waste |
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 |