CN116748285A - Method for treating hazardous waste of organic phosphate - Google Patents
Method for treating hazardous waste of organic phosphate Download PDFInfo
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- CN116748285A CN116748285A CN202310735585.0A CN202310735585A CN116748285A CN 116748285 A CN116748285 A CN 116748285A CN 202310735585 A CN202310735585 A CN 202310735585A CN 116748285 A CN116748285 A CN 116748285A
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- organic phosphate
- reaction
- phosphate
- cerium oxide
- phase product
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 40
- 239000010452 phosphate Substances 0.000 title claims abstract description 40
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000002920 hazardous waste Substances 0.000 title abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 45
- 239000011574 phosphorus Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 22
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 230000015556 catabolic process Effects 0.000 claims abstract description 17
- 238000006731 degradation reaction Methods 0.000 claims abstract description 17
- 239000007790 solid phase Substances 0.000 claims abstract description 16
- 230000035484 reaction time Effects 0.000 claims abstract description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 13
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 11
- 239000012071 phase Substances 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 9
- 239000010935 stainless steel Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 25
- 238000000498 ball milling Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 230000029087 digestion Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 6
- YYQRGCZGSFRBAM-UHFFFAOYSA-N Triclofos Chemical compound OP(O)(=O)OCC(Cl)(Cl)Cl YYQRGCZGSFRBAM-UHFFFAOYSA-N 0.000 claims description 6
- -1 phosphate ester Chemical class 0.000 claims description 6
- 229960001147 triclofos Drugs 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- 231100001261 hazardous Toxicity 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000012265 solid product Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000002798 spectrophotometry method Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AFINAILKDBCXMX-PBHICJAKSA-N (2s,3r)-2-amino-3-hydroxy-n-(4-octylphenyl)butanamide Chemical compound CCCCCCCCC1=CC=C(NC(=O)[C@@H](N)[C@@H](C)O)C=C1 AFINAILKDBCXMX-PBHICJAKSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/38—Stirring or kneading
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Abstract
The invention provides a method for treating hazardous waste of organic phosphate, which comprises the following steps: mixing organic phosphate and cerium dioxide uniformly in a stainless steel high-pressure stirring reactor according to a certain proportion; setting the stirring rotation speed of the reactor to be 500 revolutions per minute, the reaction temperature to be 100-260 ℃ and the reaction time to be 1-5 hours; after the reaction is finished, after the reactor is cooled to room temperature, the phosphorus content in the solid-phase product, the chemical oxygen demand of the liquid-phase product and the total hydrocarbon and methane content in the gas-phase product are respectively detected, and the degradation, mineralization and phosphorus immobilization efficiency of the organic phosphate are evaluated. The invention uses the reaction principle of chemical-looping combustion, utilizes the characteristics of releasing oxygen and generating active oxygen species at high temperature of cerium oxide, realizes the efficient degradation, high mineralization and phosphorus immobilization of the hazardous waste of organic phosphate, and avoids the environmental pollution risk caused by the release of a large amount of secondary products.
Description
Technical Field
The invention belongs to the technical field of organic hazardous waste treatment, and particularly relates to a method for treating organic phosphate hazardous waste.
Background
The organic phosphate is a kind of artificially synthesized phosphoric acid derivative containing organic groups, wherein phosphorus is taken as a central atom, and a phosphoric acid group is taken as a framework, and can be divided into three types of alkyl phosphate, aromatic phosphate and halogenated phosphate according to different substituents. Along with the wide application of organic phosphate esters in the industries of pharmacy, agriculture, nuclear energy, power industry, chemical product production and the like, the harm to the ecological environment is gradually revealed. Thus, safe disposal of hazardous organic phosphate wastes is becoming urgent.
The existing method for treating the hazardous waste of the organic phosphate has the defects of direct incineration, wet oxidation, alkali hydrolysis, absorption, solidification, biodegradation and the like, but the methods have certain defects such as low degradation efficiency, long degradation time, and the need of treating the generated tail gas and secondary waste or the non-ideal economical efficiency, and most of the treatment methods do not consider the reasonable and safe treatment of the phosphorus element in the organic phosphate.
Based on the method, a novel efficient disposal technology is developed, so that efficient degradation, high mineralization and synchronous immobilization of phosphorus elements of the organic phosphate are realized, and the method is very important for harmless disposal of hazardous organic phosphate wastes.
Disclosure of Invention
In view of the above-mentioned drawbacks, an object of the present invention is to propose a method for treating hazardous organic phosphate waste, which can achieve high degradation rate (about 100%), high mineralization rate (90%), excellent phosphorus immobilization efficiency (about 100%), low total non-methane hydrocarbon emissions, etc. of organic phosphate.
The invention is realized by the following technical scheme:
a method of disposing of hazardous organic phosphate waste comprising:
(1) Adding organic phosphate and cerium dioxide into a stainless steel high-pressure stirring reactor, sealing the reactor, setting stirring rotation speed, reaction temperature and reaction time, and starting the reaction;
(2) After the reaction is finished, cooling the reactor to room temperature, collecting a gas phase product formed after the reaction, detecting the composition of the gas phase product, quantitatively analyzing the total hydrocarbon and methane, and further calculating the total non-methane hydrocarbon content;
(3) After the reaction is finished, cooling the reactor to room temperature, washing the solid-phase product, collecting the liquid-phase product deposited in the solid-phase product after the reaction, detecting the chemical oxygen demand of the liquid-phase product, and further calculating the mineralization rate of the organic phosphate degradation;
(4) After the reaction is finished, cooling the reactor to room temperature, collecting a solid-phase product, digesting the solid-phase product, detecting the content of phosphorus element in the digestion solution, and further calculating the immobilization efficiency of phosphorus element after the organic phosphate is degraded.
Further, the organic phosphate of step (1) comprises: tributyl phosphate, tricresyl phosphate, and trichloroethyl phosphate.
Further, the ratio of the organic phosphate to the cerium oxide in the step (1) is 1mL (4.8-24.8) g.
Further, the ratio of the organic phosphate to cerium oxide was 1 mL/19.8 g.
Further, the stirring speed in the step (1) is 500 revolutions per minute, the reaction temperature is 100-260 ℃, and the reaction time is 1-5 hours.
Further, the reaction temperature is 180 ℃ and the reaction time is 3 hours.
Further, the total non-methane hydrocarbon content in the gas phase product formed after the reaction in the step (2) meets the requirement of the emission limit of the new pollution source atmospheric pollutants in the integrated emission standard of the atmospheric pollutants of GB 16297-1996.
Further, the mineralization rate of the organic phosphate in the step (3) after degradation is not less than 90%.
Further, the phosphorus immobilization efficiency after the organic phosphate is degraded in the step (4) is not lower than 90%.
The invention has the beneficial effects that:
the method for treating hazardous waste of organic phosphate is based on the principle of chemical chain combustion, oxygen in cerium dioxide is released at high temperature to form active oxygen species, the organic phosphate is efficiently decomposed under the combined action of flameless combustion and the active oxygen species, carbon chains in the organic phosphate are further oxidized and decomposed and finally mineralized into small molecular substances such as carbon dioxide, water and the like, and meanwhile, phosphorus element in the organic phosphate is combined with cerium element on the surface of cerium dioxide to form insoluble solid-phase products including cerium phosphate after being released, so that the purpose of phosphorus immobilization is achieved.
The degradation rates of tributyl phosphate, tricresyl phosphate and trichloroethyl phosphate are all close to 100% after the treatment by the technology of the invention, and the mineralization rate is close to 100% after the treatment>90 percent of the phosphorus immobilization efficiency is close to 100 percent, and simultaneously, the total non-methane hydrocarbon content in the gas phase product meets the emission limit value of the new pollution source atmospheric pollutant in the integrated emission standard of the atmospheric pollutant of GB 16297-1996<120mg m -3 Is not limited.
Drawings
FIG. 1 is a comparative schematic diagram of phosphorus immobilization efficiency after the catalytic degradation of tributyl phosphate by ball milling of cerium oxide under different reaction temperature conditions in example 2 of the present invention.
FIG. 2 is a graph showing the comparison of the phosphorus immobilization efficiency after the catalytic degradation of tributyl phosphate by ball milling of cerium oxide under different reaction time conditions in example 3 of the present invention.
FIG. 3 is a graph showing the comparison of phosphorus immobilization efficiency after the catalytic degradation of tributyl phosphate by ball milling of cerium oxide under the condition of different catalyst dosage in example 4 of the present invention.
FIG. 4 is a transmission electron microscope image and a surface element distribution image of a solid phase product obtained after the catalytic degradation of tributyl phosphate by ball milling of cerium oxide in example 5 of the present invention.
FIG. 5 is a graph showing the comparative efficiency of phosphorus immobilization, chemical oxygen demand removal, total hydrocarbon/methane/non-methane total hydrocarbon content in gas phase products for ball-milling ceria-catalyzed degradation of tributyl phosphate, tricresyl phosphate and trichloroethyl phosphate in example 6 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following examples and drawings, but it should be understood that the examples and drawings are only for illustrative purposes and are not intended to limit the scope of the present invention in any way. All reasonable variations and combinations that are included within the scope of the inventive concept fall within the scope of the present invention.
Example 1:
19.8g of original cerium oxide was added to a stainless steel high-pressure stirred reactor, 1mL of tributyl phosphate was added dropwise thereto, and after the reactor was installed, the reaction temperature was set at 220℃and the stirring speed was 500 rpm, and the reaction time was 3 hours. After the reaction was completed and after the reactor was naturally cooled to room temperature, the solid product was washed 3 times with n-hexane. And (3) drying the collected solid product in a 60 ℃ oven, taking a certain amount of solid product, digesting the solid product by using strong acid, and measuring the phosphorus content in the digestion liquid by adopting an ammonium molybdate spectrophotometry for measuring total phosphorus of GB 11893-89 water quality, wherein the phosphorus immobilization efficiency of the tributyl phosphate, which is obtained by calculating the phosphorus element transferred into the solid product after the tributyl phosphate is degraded by ceria, is up to 95.6%.
Similarly, the above reaction is carried out by using the ball-milled cerium dioxide, and the phosphorus immobilization efficiency of the tributyl phosphate, which is obtained by calculating and transferring phosphorus elements into a solid-phase product after the degradation of the ball-milled cerium dioxide, reaches more than 99.9 percent.
Example 2:
19.8g of ball-milled ceria was added to a stainless steel high-pressure stirring reactor, 1mL of tributyl phosphate was added dropwise thereto, and after the reactor was installed, the stirring speed was set at 500 rpm and the reaction time was set at 100, 140, 180, 220 or 260℃for 3 hours. After the reaction was completed and after the reactor was naturally cooled to room temperature, the solid product was washed 3 times with n-hexane. And (3) drying the collected solid product in a 60 ℃ oven, taking a certain amount of solid product, digesting the solid product by using strong acid, and measuring the phosphorus content in the digestion liquid by adopting an ammonium molybdate spectrophotometry for measuring total phosphorus of GB 11893-89 water quality. As shown in FIG. 1, as the reaction temperature increases, the phosphorus immobilization efficiency of the phosphorus element transferred into the solid-phase product after the tributyl phosphate is degraded by ball milling of cerium oxide increases from 62.3% (100 ℃) to nearly 100% (180-260 ℃). Therefore, a reaction temperature of 180℃was selected as the preferred treatment temperature.
Example 3:
19.8g of ball-milled ceria was added to a stainless steel high-pressure stirring reactor, 1mL of tributyl phosphate was added dropwise thereto, and after the reactor was installed, the stirring speed was set at 500 rpm, the reaction temperature was 180℃and the reaction time was 1, 2, 3, 4 or 5 hours. After the reaction was completed and after the reactor was naturally cooled to room temperature, the solid product was washed 3 times with n-hexane. And (3) drying the collected solid product in a 60 ℃ oven, taking a certain amount of solid product, digesting the solid product by using strong acid, and measuring the phosphorus content in the digestion liquid by adopting an ammonium molybdate spectrophotometry for measuring total phosphorus of GB 11893-89 water quality. As shown in FIG. 2, the phosphorus immobilization efficiency of the phosphorus element transferred into the solid-phase product after the tributyl phosphate is degraded by ball milling of cerium oxide is improved from 93.2 percent (1 h) to nearly 100 percent (3-5 h) along with the extension of the reaction time. Therefore, a reaction time of 3 hours was chosen as the preferred treatment time.
Example 4:
4.8, 9.8, 14.8, 19.8 or 24.8g of ball-milled cerium oxide is added into a stainless steel high-pressure stirring reactor, 1mL of tributyl phosphate is added dropwise and dispersed into the reactor, and after the reactor is installed, the stirring speed is 500 revolutions per minute, the reaction temperature is 180 ℃ and the reaction time is 3 hours. After the reaction was completed and after the reactor was naturally cooled to room temperature, the solid product was washed 3 times with n-hexane. And (3) drying the collected solid product in a 60 ℃ oven, taking a certain amount of solid product, digesting the solid product by using strong acid, and measuring the phosphorus content in the digestion liquid by adopting an ammonium molybdate spectrophotometry for measuring total phosphorus of GB 11893-89 water quality. As shown in FIG. 3, the phosphorus immobilization efficiency of the phosphorus element transferred to the solid-phase product after the tributyl phosphate is degraded by the ball-milled ceria is improved from 74.8% (4.8 g) to nearly 100% (19.8-24.8 g) with the increase of the ball-milled ceria. Thus, 19.8g CeO was selected 2 Each mLTBP is used as a better catalyst.
Example 5:
adding 19.8 ball-milled cerium oxide into a stainless steel high-pressure stirring reactor, dispersing and dripping 1mL of tributyl phosphate into the reactor, and setting the stirring speed to 500 revolutions per minute, the reaction temperature to 180 ℃ and the reaction time to 3 hours after the reactor is installed. After the reaction was completed and after the reactor was naturally cooled to room temperature, the solid product was washed 3 times with n-hexane. After the collected solid product was dried in an oven at 60 ℃, the morphology and surface element distribution of the solid product were observed using a transmission electron microscope. As shown in FIG. 4, the solid product after the reaction is in a form of nano particle accumulation, signals of cerium, oxygen and phosphorus elements are detected on the surface of the solid product, and the elements are distributed uniformly, which means that the phosphorus elements are transferred and fixed into the solid product after tributyl phosphate is degraded.
Example 6:
adding 19.8 ball-milled cerium oxide into a stainless steel high-pressure stirring reactor, dispersing and dropwise adding 1mL of tributyl phosphate, tricresyl phosphate or trichloroethyl phosphate into the reactor, and setting the stirring speed to 500 revolutions per minute, the reaction temperature to 180 ℃ and the reaction time to 3 hours after the reactor is installed. After the reaction is finished and the reactor is naturally cooled to room temperature, washing the solid product for 3 times by using normal hexane, drying the collected solid product in a 60 ℃ oven, taking a certain amount of solid product, digesting the solid product by using strong acid, and measuring the phosphorus content in the digestion liquid by using an ammonium molybdate spectrophotometry for measuring total phosphorus of GB 11893-89 water quality. And washing the solid-phase product by using normal hexane, collecting washing liquid and completely volatilizing normal hexane, then digesting liquid-phase residues, and determining the chemical oxygen demand of the digestion liquid by referring to the bichromate method for determining the chemical oxygen demand of the water quality of HJ 828-2017. The gas phase product is collected, and the non-methane total hydrocarbon concentration of the gas phase product is detected by adopting a gas chromatography method for measuring the total hydrocarbon of waste gas, methane and non-methane of the fixed pollution source of HJ 38-2017. As shown in fig. 5, after tributyl phosphate (abbreviated as TBP), tricresyl phosphate (abbreviated as TCP) and trichloroethyl phosphate (abbreviated as TCEP) are degraded by ball milling of ceria, the phosphorus immobilization efficiency of transferring phosphorus elements into solid phase products reaches 99.9%, 97.9% and 97.6%, respectively; the mineralization rate of a liquid phase product generated after the TBP, TCP, TCEP is degraded by ball milling of cerium oxide can reach 98.3 percent, 98.5 percent and 95.8 percent respectively; the concentration of non-methane total hydrocarbon (NMHC for short) in the gas phase product produced by the degradation of TBP, TCP, TCEP by ball milling cerium oxide is respectively 0.58, 37.79 and 27.52mg m -3 Is lower than the emission limit value of the atmospheric pollutant for a new pollution source in the integrated emission standard of the atmospheric pollutant of GB 16297-1996<120mg m -3 Is not limited. The method for treating the hazardous waste of the organic phosphate has the advantages of high efficiency, high mineralization degree and high phosphorus immobilization efficiency.
Claims (10)
1. A method of disposing of hazardous organic phosphate waste comprising:
(1) Adding organic phosphate and cerium dioxide into a stainless steel high-pressure stirring reactor, mixing and then sealing for reaction;
(2) Cooling to room temperature after the reaction is finished, collecting gas phase products formed after the reaction, detecting the composition of the gas phase products, quantitatively analyzing the total hydrocarbon and methane, and further calculating the content of non-methane total hydrocarbon;
(3) Washing a solid-phase product in the reactor, collecting a liquid-phase product deposited in the solid-phase product after the reaction, detecting the chemical oxygen demand of the liquid-phase product, and further calculating the mineralization rate of the organic phosphate degradation;
(4) And (3) digesting the washed solid-phase product, detecting the content of phosphorus element in the digestion solution, and further calculating the immobilization efficiency of phosphorus element after the organic phosphate is degraded.
2. The method according to claim 1, wherein:
the organic phosphate ester of step (1) is selected from: tributyl phosphate, tricresyl phosphate, and trichloroethyl phosphate.
3. The method according to claim 1, wherein:
the ratio of the organic phosphate to the cerium oxide in the step (1) is 1mL (4.8-24.8) g.
4. A method according to claim 3, wherein:
the ratio of the organic phosphate to cerium oxide was 1 mL/19.8 g.
5. The method according to claim 1, wherein:
the cerium oxide in the step (1) is untreated original cerium oxide or cerium oxide treated by ball milling.
6. The method according to claim 5, wherein:
the ball-milled cerium oxide is prepared by the following method:
adding 5 times of water into cerium oxide, and ball milling for 2 hours under the condition of 600 r/min.
7. The method according to claim 1, wherein:
the sealed reaction conditions after mixing in the step (1) are as follows: the stirring speed is 500 rpm, the reaction temperature is 100-260 ℃ and the reaction time is 1-5h.
8. The method of claim 7, wherein:
the reaction temperature is 180 ℃ and the reaction time is 3 hours.
9. The method according to claim 1, wherein:
and (3) degrading the organic phosphate, wherein the mineralization rate is not less than 90%.
10. The method according to claim 1, wherein:
and (3) after the organic phosphate is degraded, the phosphorus immobilization efficiency is not lower than 90%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310735585.0A CN116748285A (en) | 2023-06-21 | 2023-06-21 | Method for treating hazardous waste of organic phosphate |
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| CN202310735585.0A CN116748285A (en) | 2023-06-21 | 2023-06-21 | Method for treating hazardous waste of organic phosphate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116421924A (en) * | 2023-04-25 | 2023-07-14 | 四川大学 | Method for degrading tributyl phosphate and recovering phosphorus element by using alkali-assisted trimanganese tetroxide |
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2023
- 2023-06-21 CN CN202310735585.0A patent/CN116748285A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116421924A (en) * | 2023-04-25 | 2023-07-14 | 四川大学 | Method for degrading tributyl phosphate and recovering phosphorus element by using alkali-assisted trimanganese tetroxide |
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