CN114446506A - Method for treating radioactive TBP/OK organic waste liquid - Google Patents
Method for treating radioactive TBP/OK organic waste liquid Download PDFInfo
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- CN114446506A CN114446506A CN202111662390.5A CN202111662390A CN114446506A CN 114446506 A CN114446506 A CN 114446506A CN 202111662390 A CN202111662390 A CN 202111662390A CN 114446506 A CN114446506 A CN 114446506A
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- 239000007788 liquid Substances 0.000 title claims abstract description 85
- 239000010815 organic waste Substances 0.000 title claims abstract description 49
- 230000002285 radioactive effect Effects 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002699 waste material Substances 0.000 claims abstract description 40
- 239000000839 emulsion Substances 0.000 claims abstract description 31
- 238000000197 pyrolysis Methods 0.000 claims abstract description 24
- 238000002485 combustion reaction Methods 0.000 claims abstract description 19
- 238000005336 cracking Methods 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- 239000005416 organic matter Substances 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 238000004088 simulation Methods 0.000 claims abstract description 8
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 63
- 238000003756 stirring Methods 0.000 claims description 16
- 239000003995 emulsifying agent Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 10
- 239000003350 kerosene Substances 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 239000001095 magnesium carbonate Substances 0.000 claims description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 5
- 230000014759 maintenance of location Effects 0.000 claims description 5
- 150000003254 radicals Chemical class 0.000 claims description 5
- 239000006194 liquid suspension Substances 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000010891 electric arc Methods 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000002956 ash Substances 0.000 description 4
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910000393 dicalcium diphosphate Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000009284 supercritical water oxidation Methods 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/14—Processing by incineration; by calcination, e.g. desiccation
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention belongs to the field of radioactive organic waste liquid treatment, and particularly relates to a method for treating radioactive TBP/OK organic waste liquid, which comprises the following steps: step 1, preparing radioactive TBP/OK organic waste liquid into suspension or emulsion; step 2, carrying out organic matter cracking on TBP/OK simulation waste liquid emulsion in a plasma torch; and 3, settling and separating the cracked product in the pyrolysis combustion chamber to remove the micromolecular hydrocarbon substances. The invention can safely and efficiently utilize the plasma technology to realize the cracking of the radioactive TBP/OK organic waste liquid, realize the complete pyrolysis combustion of organic matters, fix the radioactive nuclide and the corrosive P in the ash, and reduce the influence of the large volatilization of the volatile nuclide caused by high-temperature pyrolysis.
Description
Technical Field
The invention belongs to the field of radioactive organic waste liquid treatment, and particularly relates to a method for treating radioactive TBP/OK organic waste liquid.
Background
30% TBP-70% kerosene is used as an extracting agent in a PUREX flow adopted by uranium purification and spent fuel aftertreatment, and radioactive TBP/OK organic waste liquid is formed after repeated utilization for many times. The radioactive TBP/OK organic waste liquid belongs to flammable and explosive substances, has the characteristics of complex components, high heat value, high heat release rate and the like, is multiphase, and reserves a small amount of U, Pu, Am, Cm, trace fission products (niobium, zirconium, ruthenium, Sr, Cs and the like), DBP, MDP and the like generated by degradation.
At present, no ideal method is available at home and abroad for treating the waste liquid, and the waste liquid can only be temporarily stored in a special stainless steel barrel. With the continuous operation and accumulation of a plurality of related enterprise nuclear facilities, the total amount is considerable, and the stainless steel storage tank has quality and service life problems, so that the temporary storage pressure and the potential safety hazard are increased day by day.
At present, a plurality of research methods for TBP waste organic phases are internationally carried out, and the conventional method for burning TBP waste organic phases or the like are frequently used or researched. The traditional air burning method has simple process, but insufficient burning causes large burden of a tail gas treatment system; the supercritical water oxidation method has the characteristics of high temperature and high pressure, harsh operating conditions and severe equipment corrosion in the reaction process; the steam reforming method has the disadvantages that the reactor is extremely corroded, polyphosphoric acid is generated in the reaction process, and the polyphosphoric acid is adhered to a filter and a pyrolysis furnace wall after being evaporated, so that the operation performance of the pyrolysis furnace is reduced, and the steam reforming method is not applied to commercial engineering at present.
Therefore, it is desired to develop a method for treating radioactive TBP/OK organic waste liquid to effectively solve the existing problems.
Disclosure of Invention
The invention aims to provide a method for treating radioactive TBP/OK organic waste liquid, which can safely and efficiently realize the cracking of the radioactive TBP/OK organic waste liquid by using a plasma technology, realize the complete pyrolysis combustion of organic matters, fix radionuclide and corrosive P in ash, and reduce the influence of large-amount volatilization of volatile nuclide caused by high-temperature pyrolysis.
The technical scheme for realizing the purpose of the invention is as follows:
a method of treating radioactive TBP/OK organic waste streams, the method comprising the steps of:
step 1, preparing radioactive TBP/OK organic waste liquid into suspension or emulsion;
step 2, carrying out organic matter cracking on TBP/OK simulation waste liquid emulsion in a plasma torch;
and 3, settling and separating the cracked product in the pyrolysis combustion chamber to remove the micromolecular hydrocarbon substances.
The step 1 comprises the following steps:
step 1.1, preparing simulated radioactive TBP/OK organic waste liquid;
and 1.2, preparing radioactive TBP/OK organic waste liquid suspension or emulsion.
The step 1.1 specifically comprises the following steps: pouring kerosene, tributyl phosphate (TBP) and dibutyl phosphate into a pneumatic lifting dispersion stirrer for stirring, and preparing simulated radioactive TBP/OK organic waste liquid.
The mass ratio of tributyl phosphate, kerosene and dibutyl phosphate in the step 1.1 is as follows: m (TBP), m (OK), m (DBP), 30:70: 0.63.
The step 1.2 comprises the following steps:
and step 1.2.1, adding a phosphorus fixing agent into the stirred simulated waste liquid for stirring.
Step 1.2.2, add mixed emulsifier and water to stir, then pause stirring afterwards.
And step 1.2.3, adding a stabilizer, and stirring to obtain a radioactive TBP/OK organic waste liquid suspension or emulsion.
In the step 1.2.1, the phosphorus fixing agent is calcium hydroxide or magnesium hydroxide.
In the step 1.2.2, the emulsifier is cetyl trimethyl ammonium bromide.
In the step 1.2.2, the mass ratio of the emulsifier to the water is m (emulsifier)/m (water) ═ 0.045-0.07.
In the step 1.2.3, the stabilizing agent is magnesium carbonate.
The step 2 comprises the following steps:
step 2.1, operating the plasma torch to a steady state
2.2, directly spraying the prepared TBP/OK simulation waste liquid emulsion into a plasma jet high-temperature area in a jet mode through a plasma torch feed inlet to perform organic matter cracking;
the step 2.1 is specifically as follows: when the plasma torch electrode rises to 8kV-10kV, high-temperature and high-concentration free radical arc jet flow is generated between the electrodes. The electric arc current intensity is 100A-140A; the voltage is about 270V-300V.
The step 2.2 specifically comprises the following steps: directly spraying the prepared TBP/OK simulated waste liquid emulsion into a plasma jet high-temperature area through a plasma torch feed inlet in a jet flow mode, wherein the gas flow rate of the plasma jet high-temperature area is 200-250 m/s, the pressure of a pressure inlet is 100000-120000 Pa, the pressure of a pressure outlet is 99500-99900 Pa, and the retention time of the simulated organic waste liquid in a jet flow cracking section pipeline is 1.2-2 ms.
The step 3 specifically comprises the following steps: after the gas enters the pyrolysis combustion chamber, the temperature is instantly reduced to below 300 ℃ from the thousands of high temperature, so that volatile nuclides such as Cs and the like contained in the organic waste liquid which is volatilized in a large amount under the high-temperature atmosphere are settled, and incompletely-reacted small molecular hydrocarbon substances existing in the cracking products are subjected to combustion reaction in the pyrolysis combustion chamber to generate H2O and CO2。
The invention has the beneficial technical effects that:
1. the method pretreats the waste liquid before feeding the waste liquid, adds a phosphorus fixing agent, an emulsifying agent and the like into the waste liquid for emulsification, and prepares the radioactive TBP/OK organic waste liquid into suspension or emulsion to reduce the corrosion in the running process of equipment, is easy to convey, is suitable for feeding of a plasma treatment system, and effectively avoids P generated in the decomposition process of the radioactive TBP/OK waste liquid2O5Phosphoric acid is generated when meeting water, and serious corrosion is caused to equipment.
2. When preparing radioactive TBP/OK organic waste liquid emulsion, the invention adds a phosphorus fixing agent Ca (OH)2P in the pyrolysis products is fixed in the ash, so that the corrosion of equipment is reduced; the organic waste liquid is emulsified by using cetyl trimethyl ammonium bromide as an emulsifier, and the liquid is stable; by adding stabilizer MgCO3The emulsion is stabilized for a longer time; the milk formation is facilitated by suspending stirring after adding the stabilizer and stirring uniformly.
3. The plasma torch adopted by the invention has the characteristics of high temperature, high enthalpy, high energy density and the like, the central temperature of the plasma torch can reach more than 5000K, and the jet heat energy is highly concentrated, so that the plasma torch can carry out high-efficiency geothermal conversion in a relatively small space, thereby achieving the cracking effect.
4. The invention has the advantages of small secondary waste yield and high reaction process speed; the method has the advantages of less tail gas, cleanness, high volume reduction and weight reduction ratio, good operability and the like, and can effectively inhibit the generation of toxic and harmful substances such as dioxin, furan and the like due to more complete organic matter cracking.
5. The plasma technology of the invention can safely and efficiently pyrolyze the waste liquid, realize the complete pyrolysis combustion of organic matters, fix the radioactive nuclide and the corrosive P into the ash, reduce the influence of large volatilization of the volatile nuclide caused by high-temperature pyrolysis, realize the high volume reduction and weight reduction ratio of waste, and easily treat the generated product. And the miniaturization of the apparatus can be realized due to the characteristics of the heat source (plasma torch).
6. The plasma temperature of the method is high, TBP can be cracked instantly, and cracked products immediately enter an environment lower than 300 ℃, so that volatilization of nuclides such as Cs can be reduced; the plasma jet temperature is independent of the chemical composition of the input waste; the time for completely oxidizing the substances is reduced, so that the equipment structure is more compact and the miniaturization is easy under the same feeding rate.
Detailed Description
The present invention will be described in further detail with reference to examples.
The invention provides a method for treating radioactive TBP/OK organic waste liquid, which comprises the following steps:
step 1, preparing radioactive TBP/OK organic waste liquid into suspension or emulsion
Step 1.1, preparing simulated radioactive TBP/OK organic waste liquid (namely simulated waste liquid)
121.5g of kerosene (OK), 52.1g of tributyl phosphate (TBP) and 1g of dibutyl phosphate (DBP) are poured into a pneumatic lifting dispersion stirrer and stirred for 5min to prepare simulated radioactive TBP/OK organic waste liquid (namely simulated waste liquid).
The mass ratio of tributyl phosphate (TBP), kerosene (OK) and dibutyl phosphate (DBP) is as follows: m (TBP), m (OK), m (DBP), 30:70: 0.63.
And 1.2, adding a phosphorus fixing agent, an emulsifying agent and a stabilizing agent into the simulated waste liquid, and preparing the radioactive TBP/OK organic waste liquid into uniform and stable suspension or emulsion.
And step 1.2.1, adding a phosphorus fixing agent into the stirred simulated waste liquid, and continuously stirring for 5-15 min.
The phosphorus fixing agent is calcium hydroxide or magnesium hydroxide.
And step 1.2.2, adding the emulsifier and the water which are mixed according to the proportion, stirring for 25-45 min, and then suspending stirring for a plurality of minutes.
The mass ratio of the emulsifier to the water is 0.045-0.07.
The emulsifier is cetyl trimethyl ammonium bromide.
And step 1.2.3, adding a stabilizer, stirring for 30-60 min, observing whether bubbles exist in the emulsion or not by naked eyes, whether layering occurs or not, maintaining no bubbles, obtaining uniform and stable emulsion after the layering state exceeds 12h, turning off a stirrer after the uniform and stable emulsion is obtained, and filling the prepared feed liquid into a simulated waste liquid storage tank for later use.
The stabilizer is magnesium carbonate.
In the prepared suspension or emulsion, the mass percentages of the components are as follows: TBP: 22.63% -23.30%; kerosene: 52.75% -54.32%; DBP: 0.52-0.65%; calcium hydroxide: 8.15% -8.45%; cetyl trimethylammonium bromide: 0.52% -0.71%; MgCO3: 0% -0.4%; water: 12.5 to 15.2 percent.
According to the steps, 5 groups of simulated waste liquid emulsion (or suspension) are prepared, the time length before layering is taken as the stable time of the feed liquid to measure the stable time, and meanwhile, the viscosity is measured. The contents of the components in each simulated waste liquid emulsion (or suspension) and the measurement results thereof are shown in table 1.
TABLE 1 content of each component in simulated waste liquid emulsion (or suspension) and measurement results thereof
In addition, the phosphorus fixation rate of the mixed solution of the contents of the components in table 1 can reach more than 99.5%.
As can be seen from Table 1, the viscosity of the emulsion (or suspension) obtained by the above 5 groups of test schemes is less than or equal to 850mPa · s, the feed liquid stabilization time t is more than or equal to 16h, and the phosphorus fixation rate is more than 99.5 percent, so that the method is suitable for treating radioactive TBP/OK organic waste liquid by using the plasma technology, effectively prolongs the service life of equipment, and reduces the process cost of the plasma technology. And the stabilization time of the 2 nd group of test schemes is longest, and the emulsion state can be recovered by mixing the feed liquid after the feed liquid is layered.
Step 2, carrying out organic matter cracking on TBP/OK simulation waste liquid emulsion in a plasma torch
Step 2.1, operating the plasma torch to a steady state
The plasma torch in the embodiment is a 50kw direct current non-transfer hollow cathode plasma torch, the highest pressure value of the inlet position of nitrogen filled in the torch is 1.2 times atmospheric pressure, the torch mainly comprises a cathode and an anode, the cathode and the anode are made of red copper, the inside of the cathode is of a hollow structure, insulating materials between the electrodes are polytetrafluoroethylene obliquely, and a water cooling channel of the electrode is of a spiral structure and is used for increasing the heat exchange area. When the plasma torch is ignited, electrode cooling circulating water is opened, a tangential gas inlet mode is adopted, nitrogen is supplied by a nitrogen making machine to serve as working gas of the plasma torch, and the working gas is punctured by high-voltage pulses to generate stable plasma arc jet.
When the plasma torch electrode rises to 8kV-10kV, high-temperature and high-concentration free radical arc jet flow is generated between the electrodes. The electric arc current intensity is 100A-140A; the voltage is about 270V-300V; under the above operating conditions, the torch thermal efficiency is about 60% to 72%. The cathode is nitrogen gas with gas delivery volume of 9-12m3H) the total system injected air amount is 270m3/h-300m3H is used as the reference value. The plasma torch steady state operating parameters in this example are shown in table 2.
TABLE 2 stable operating parameters of the plasma torch
| Numbering | Name (R) | Parameter(s) |
| 1 | Electric current | 140A |
| 2 | Voltage of | 300V |
| 3 | Working gas | Nitrogen gas |
| 4 | Pyrolysis chamber air flow | 28m3/h |
| 5 | Electrode form | Hollow cathode |
| 6 | Feed rate | 5L/h |
| 7 | Plasma generation method | Direct current arc |
Step 2.2, directly spraying the prepared TBP/OK simulation waste liquid emulsion into a plasma jet high-temperature area in a jet mode through a plasma torch feed inlet to perform organic matter cracking
Directly spraying the prepared TBP/OK simulated waste liquid emulsion into a plasma jet high-temperature area through a plasma torch feed inlet in a jet flow mode, wherein the gas flow speed of the plasma jet high-temperature area is 200-250 m/s, the pressure of a pressure inlet is 100000-120000 Pa, the pressure of a pressure outlet is 99500-99900 Pa, the retention time of the simulated organic waste liquid in a jet flow cracking section pipeline is 1.2-2 ms, and the complete cracking of organic matters is ensured.
After the pyrolysis chamber is preheated to 150 ℃, the organic waste liquid is directly injected into the stable section of the plasma arc jet zone, and the feeding rate is controlled at 3-5L/h by using a peristaltic pump.
In the plasma jet high-temperature region, pyrolysis of the waste TBP at 500 ℃ generates phosphoric acid, butylene fractions and water, and various volatile hydrocarbons, including the following reactions:
(C4H9O)3PO+Ca(OH)2→Ca2P2O7+C4H8+H2O
(C4H9O)3PO→P2O5+C4H8O+3C4H10
2Ca(OH)2+P2O5→Ca2P2O7+H2O
3Ca(OH)2+P2O5→Ca3(PO4)2+3H2O
C12H26+O2→CO2+H2O
step 3, settling and separating the cracked product in a pyrolysis combustion chamber to remove small molecular hydrocarbon substances
The completely cracked gas enters the pyrolysis combustion chamber from the plasma torch and passes through an exhaust gas volume of 282m3Controlling the residence time t of the gas in the pyrolysis combustion chamberThe time is more than or equal to 2 s. After the gas enters the pyrolysis combustion chamber, the temperature is instantly reduced to below 300 ℃ from thousands of high temperature, so that rapid quenching is realized, volatile nuclides such as Cs contained in the organic waste liquid which is volatilized in a large amount under the high-temperature atmosphere are settled, and the amount of the volatile nuclides entering a tail gas treatment system is reduced.
The incompletely reacted small molecular hydrocarbon substances in the cracked product can be further completely combusted in a combustion chamber (the gas retention time is more than or equal to 2s) to generate H2O and CO2。
The working principle of the invention is as follows:
adding a phosphorus fixing agent Ca (OH) into the simulated waste liquid in the preparation process of the feed liquid2P formed by TBP cleavage2O5Will immediately react with Ca (OH)2Neutralization reaction is carried out to generate calcium phosphate and calcium pyrophosphate, P and inorganic substances in the waste liquid are fixed in the ash together, so that equipment corrosion can be prevented, and the reaction equation is as follows:
P2O5+2Ca(OH)2→Ca2P2O7+2H2O
P2O5+3Ca(OH)2→Ca3(PO4)2+3H2O
therefore, before feeding the waste liquid, the waste liquid is pretreated, and the phosphorus fixing agent, the emulsifying agent and the stabilizing agent are added into the waste liquid to emulsify the waste liquid, so that the corrosion of the equipment in the operation process is reduced, and the method is suitable for feeding of a plasma treatment system.
And directly spraying the prepared TBP simulation waste liquid into a plasma jet high-temperature area through a feed inlet in a jet flow mode to perform organic matter cracking.
The parameter range that the plasma can have is unusually wide, because the plasma contains extremely active chemical reaction species such as ions, electrons, excited state atoms, molecules, free radicals, etc., the energy level of the plasma chemical reaction is high. The plasma contains high concentration of oxidizing radicals (HO, ON, O)+Etc.) and strong ultraviolet radiation, to realize the high-efficiency cracking combustion of the radioactive TBP/OK organic waste liquid.
As the organic waste liquid contains Cs, the nuclide is volatilized in a large amount under the high-temperature atmosphere to form radioactive gas to the tail gas, the rapid quenching is realized by the plasma technology, the temperature is instantly reduced to below 300 ℃ from the high temperature of thousands of DEG C, and the fly ash can be settled and separated by rapid cooling from a high-temperature area to a low-temperature area, so that the volatile nuclide is quenched and settled, and the volatilization amount of the nuclide is reduced.
The organic waste liquid is cracked in a plasma high-temperature area, rapidly cooled, fly ash is settled and separated, small molecular hydrocarbon substances which are not completely reacted and possibly exist in cracked products can further realize complete combustion in a pyrolysis chamber (the gas retention time is more than or equal to 2s) to generate H2O and CO2。
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. The prior art can be adopted in the content which is not described in detail in the invention.
Claims (13)
1. A method for treating radioactive TBP/OK organic waste liquid, which is characterized by comprising the following steps:
step 1, preparing radioactive TBP/OK organic waste liquid into suspension or emulsion;
step 2, carrying out organic matter cracking on TBP/OK simulation waste liquid emulsion in a plasma torch;
and 3, settling and separating the cracked product in the pyrolysis combustion chamber to remove the micromolecular hydrocarbon substances.
2. The method of claim 1, wherein the step 1 comprises:
step 1.1, preparing simulated radioactive TBP/OK organic waste liquid;
and 1.2, preparing radioactive TBP/OK organic waste liquid suspension or emulsion.
3. The method for treating radioactive TBP/OK organic waste liquid as claimed in claim 2, wherein the step 1.1 is specifically as follows: pouring kerosene, tributyl phosphate (TBP) and dibutyl phosphate into a pneumatic lifting dispersion stirrer for stirring, and preparing simulated radioactive TBP/OK organic waste liquid.
4. The method for treating radioactive TBP/OK organic waste liquid according to claim 3, wherein the mass ratio of tributyl phosphate to kerosene and dibutyl phosphate in the step 1.1 is as follows: m (TBP), m (OK), m (DBP), 30:70: 0.63.
5. The method of claim 4, wherein the step 1.2 comprises:
step 1.2.1, adding a phosphorus fixing agent into the stirred simulated waste liquid for stirring;
step 1.2.2, adding the mixed emulsifier and water for stirring, and then suspending stirring;
and step 1.2.3, adding a stabilizer, and stirring to obtain a radioactive TBP/OK organic waste liquid suspension or emulsion.
6. The method of claim 5, wherein the phosphorus-fixing agent in step 1.2.1 is calcium hydroxide or magnesium hydroxide.
7. The method of claim 5, wherein the emulsifying agent in step 1.2.2 is cetyltrimethylammonium bromide.
8. The method of claim 5, wherein the mass ratio of the emulsifier to the water in step 1.2.2 is 0.045-0.07 m (emulsifier)/m (water).
9. The method of claim 5, wherein the stabilizing agent in step 1.2.3 is magnesium carbonate.
10. The method of claim 5, wherein the step 2 comprises:
step 2.1, operating the plasma torch to a stable state;
and 2.2, directly spraying the prepared TBP/OK simulation waste liquid emulsion into a plasma jet high-temperature area through a plasma torch feed inlet in a jet flow mode to perform organic matter cracking.
11. The method for treating radioactive TBP/OK organic waste liquid as claimed in claim 10, wherein said step 2.1 is specifically as follows: when the plasma torch electrode rises to 8kV-10kV, high-temperature and high-concentration free radical arc jet flow is generated between the electrodes; the electric arc current intensity is 100A-140A; the voltage is about 270V-300V.
12. The method for treating radioactive TBP/OK organic waste liquid as claimed in claim 11, wherein said step 2.2 is specifically as follows: directly spraying the prepared TBP/OK simulated waste liquid emulsion into a plasma jet high-temperature area through a plasma torch feed inlet in a jet flow mode, wherein the gas flow speed of the plasma jet high-temperature area is 200-250 m/s, the pressure of a pressure inlet is 100000-120000 Pa, the pressure of a pressure outlet is 99500-99900 Pa, and the retention time of the simulated organic waste liquid in a jet flow cracking section pipeline is 1.2-2 ms.
13. The method for treating radioactive TBP/OK organic waste liquid of claim 12, wherein said step 3 is specifically: after the gas enters the pyrolysis combustion chamber, the temperature is instantly reduced to below 300 ℃ from the thousands of high temperature, so that volatile nuclides such as Cs and the like contained in the organic waste liquid which is volatilized in a large amount under the high-temperature atmosphere are settled, and incompletely-reacted small molecular hydrocarbon substances existing in the cracking products are subjected to combustion reaction in the pyrolysis combustion chamber to generate H2O and CO2。
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