CN106251924A - Supercritical water oxidation processes the method for PVA polymeric material - Google Patents

Supercritical water oxidation processes the method for PVA polymeric material Download PDF

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Publication number
CN106251924A
CN106251924A CN201610039905.9A CN201610039905A CN106251924A CN 106251924 A CN106251924 A CN 106251924A CN 201610039905 A CN201610039905 A CN 201610039905A CN 106251924 A CN106251924 A CN 106251924A
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pva
polymeric material
solution
water
supercritical
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CN201610039905.9A
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CN106251924B (en
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赵师普
李田宇
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Qingdao Tianhe Qingyuan Technology Co Ltd
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Qingdao Tianhe Qingyuan Technology Co Ltd
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    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/28Treating solids
    • G21F9/30Processing

Abstract

The invention discloses a kind of method that supercritical water oxidation processes PVA polymeric material, first pretreated PVA polymeric material is put in dissolving tank, in dissolving tank, be then passed through distilled water, and heating makes distilled water seethe with excitement, and forms PVA solution;First filtration, filters the particulate matter in PVA solution;Adding sodium citrate solution in PVA solution after filtering, pH is at 3.8-4.3 in control, is added thereto to the copperas solution that mass fraction is 1%, is uniformly mixed, obtains reactant liquor one;Gained reactant liquor one is passed through in supercritical reaction still, carry out supercritical oxidation, control reaction temperature 400 DEG C, reaction pressure 22MPa, obtaining product carbon dioxide and water after first supercritical processing, wherein, carbon dioxide is directly through discharge of pipes, water flow to around dissolving tank through back of pipeline, for heating dissolving tank.The inventive method can reach more than 99.99% to organic clearance, and environmentally safe.

Description

Supercritical water oxidation processes the method for PVA polymeric material
Technical field
The present invention relates to the processing technology field of PVA polymeric material, be specifically related to a kind of supercritical water oxidation and process PVA polymerization material The method of material.
Background technology
Due to nuclear power plant, to deposit saturated and disposal of wastes the cost of the memory space of radwaste quite big, and therefore, exploitation subtracts The technology of few amount of waste produced by nuclear power plant is increasingly paid close attention to by people, needs to seek a kind of new technology and fundamentally subtracts Few radioactive solid waste percentage ratio in combustible waste.
The investigation report of the parties concerned shows at present, and at the U.S. and Mexican nuclear power station, the factory of more than 85% is devoted to by making With the various water solublity Protection Products prepared by PVA, such as working clothing, purify paper, overshoes etc., reduce the various behaviour of laundry room Making the amount of waste of expense and generation, the technology reducing the combustible waste amount produced by nuclear power station can be divided into for blocking generation source Technology and for processing the technology of refuse of generation.On the whole, it is possible to the technology processing combustible waste most effectively is to burn, But due to the reason such as place, transport, this technology is not particularly suited for final disposal radwaste, and, volatility Spent Radioactive Thing is discharged in environment, can cause long-term environmental pollution.
In sum, it is desirable to provide a kind of basic solution carries out the disposal of oil-containing PVA refuse.
Summary of the invention
It is an object of the invention to provide a kind of method that supercritical water oxidation processes PVA polymeric material, the method is with supercritical water Carry out oxidation Decomposition PVA polymeric material as reaction medium, the C in PVA polymeric material, H element are finally changed into carbon dioxide And water, after testing, the organic clearance of the method can reach more than 99.99%, and environmentally safe.
Its technical solution includes:
The processing method of a kind of PVA polymeric material, comprises the following steps successively:
A dissolves, and puts in dissolving tank by pretreated PVA polymeric material, is then passed through distilled water in described dissolving tank, And heating makes distilled water seethe with excitement, forming PVA solution, wherein, the mass fraction of PVA is 8%;
B filters for the first time, is filtered by the particulate matter in PVA solution;
C adds acid in the PVA solution after filtering, pH is at 3.8-4.3 in control, is added thereto to the sulphuric acid that mass fraction is 1% Ferrous iron solution, is uniformly mixed, and obtains reactant liquor one;
D first supercritical processing, is passed through step c gained reactant liquor one in supercritical reaction still, carries out supercritical oxidation, controls anti- Answer temperature 400 DEG C, reaction pressure 22MPa, after first supercritical processing, obtain product carbon dioxide and water, wherein, titanium dioxide Carbon is directly through discharge of pipes, and water flow to around dissolving tank through back of pipeline, for heating dissolving tank.
In technique scheme, being first dissolved in dissolving tank by PVA polymeric material, the character of PVA determines it can be molten Solution is more conducive to follow-up biochemical treatment in the water of 100 DEG C, the PVA after dissolving;
Under normal circumstances, water exists with steam, liquid and three kinds of common states of ice, and is polar solvent, can dissolve and include Salt is at interior most of electrolyte, and to gas and most of Organic substance then slightly soluble or insoluble, the density of aqueous water is little with pressure Raise and change;If but the temperature and pressure of water is increased to more than critical point (Tc=374.3 DEG C, Pc=22.1MPa), The character of water there occurs greatly change, and its density, dielectric constant, viscosity, diffusion coefficient, thermal conductivity and dissolubility etc. are all different In light water, i.e. reactant liquor one is passed through in supercritical reaction still by such scheme and processes, outstanding due to supercritical water Solvability, compressibility and mass transfer characteristic, make it a kind of and have the most active thundering reaction medium, instead Answer pressure 22MPa, under the conditions of 22.1MPa, carry out oxidation Decomposition Organic substance using supercritical water as reaction medium.
During supercritical water oxidation, owing to supercritical water is all fabulous solvent to Organic substance and oxygen, the most organic Oxidation can be carried out in oxygen-enriched homogeneous phase, and reaction will not be restricted because of alternate transfer;The highest reaction temperature also makes Reaction rate is accelerated, and in the shortest reaction time, organic clearance can reach more than 99.99%.
In oxidizing process, C, H element in organic pollution finally change into carbon dioxide and water;N, S, P and halogen etc. Hetero atom oxidation generates gas, oxyacid or salt;In supercritical water, salt or is formed solid presented in concentrated salt solution Body granule and separate out, the water in supercritical fluid becomes clean water after supercooling.
As a preferred version of the present invention, above-mentioned PVA polymeric material is in water solublity Protection Product, first to water solublity Protection Product carries out prerinse, removes the nucleic wherein adhered to.
Above-mentioned water solublity Protection Product such as working clothing, purify paper, overshoes etc., the most all oil-containing PVA polymeric material, certainly, Wherein possibly together with nucleic, therefore the nucleic of attachment is carried out prerinse.
As another preferred version of the present invention, in step c, PVA solution is 100:1, PVA with the volume ratio of sodium citrate Solution is 100:1 with the volume ratio of copperas solution.
Preferably, described acid is sulphuric acid or mass fraction is the sodium citrate solution of 10%.
Preferably, described acid be mass fraction be the sodium citrate solution of 10%.
Compared with prior art, the reaction of dissolving in present invention dissolving tank replaces the Fenton's reaction in common PVA processing method, It is to say, be by PVA thermosol rather than to utilize hydrogen peroxide and Fe2+So that it is oxidation.
Supercritical water oxidation processes PVA polymeric material, and it is organic dirt of the most effectively degrading in the case of not producing harmful side product A kind of new method of dye thing.
Accompanying drawing explanation
The present invention will be further described below in conjunction with the accompanying drawings:
Fig. 1 is processing technological flow figure of the present invention.
Detailed description of the invention
The present invention proposes a kind of method that supercritical water oxidation processes PVA polymeric material, in order to make advantages of the present invention, technology Scheme is clearer, clear and definite, elaborates the present invention below in conjunction with specific embodiment.
PVA polymeric material handled by the present invention, essentially from nuclear power station use PVA product from the working clothing of primary stage, To purifying paper, vinyl, overshoes, glove etc., therefore, before PVA polymeric material is processed, especially it is entered Row prerinse step, the nucleic etc. wherein adhered to removing.
D reagent and E reagent employed in following embodiment are purchased from Lian Hua scientific & technical corporation.
As above-mentioned background technology is introduced, prior art is typically to burn for the processing method of PVA polyester material, And on the one hand incinerating method needs place, on the other hand pollute environment;The method of the present invention, carries out pretreatment by dissolving, then Processing in conjunction with supercritical water oxidation, end product carbon dioxide and water, carbon dioxide directly discharges, water and then recycling.
Elaborate below in conjunction with specific embodiment.
Embodiment 1:
Collect the working clothing of nuclear power station, these working clothing are cleaned, remove the nucleic of attachment.
Step 1, will clean after working clothing carry out preliminary treatment, will its shear or be processed into 1cm × 1cm by other method Fractionlet, weigh 80g, and place it in dissolving tank, in dissolving tank, add 920mL distilled water, heat this dissolving tank, And to make the temperature of wherein distilled water be 100 DEG C, observe the PVA polymeric material in dissolving tank, by stirring, if seeing dissolving tank Stop when the most all becoming white viscous liquid;
Step 2, the particulate matter in PVA solution is filtered, the thick liquid in step 1 adds acid for adjusting pH, preferably adds Entering the sodium citrate that mass fraction is 10%, thick liquid is 100:1 with the volume ratio of sodium citrate, and stirring and adjusting pH is about 3.8;
Step 3, being subsequently added into the copperas solution that mass fraction is 1%, copperas solution with the volume ratio of thick liquid is 1:100, obtains reactant liquor one;
Step 4, reactant liquor one are passed through in supercritical reaction still, carry out supercritical oxidation, and controlling reaction temperature is 420 DEG C, reaction Pressure is 22.1MPa, obtains product carbon dioxide, water and end reaction liquid after first supercritical processing, and wherein, carbon dioxide is direct Through discharge of pipes, water flow to around dissolving tank through back of pipeline, for heating dissolving tank, it is achieved making full use of of thermal source.
COD concentration in end reaction liquid is measured by following method:
Utilize the even China Tech special consumptive material of skill water quality detection to measure reaction liquid C OD concentration, measure process approximately as: measure reactant liquor 2.5ml adds D reagent (the special consumable reagent of COD) 0.7ml and adds E reagent (the anti-high chlorine consumable reagent of COD) 4.8ml 165 Degree Celsius constant temperature digestion air cools down 2min add distilled water 2.5ml cold water cooling 2min luminosity colorimetric detection and go out value, Calculate the COD concentration of end reaction liquid.
Calculated COD concentration directly discharges national grade one discharge standard less than sewage: COD concentration is less than 100mg/L.
Embodiment 2:
Difference from Example 1 is, adds sodium citrate and control pH 4.3 in step 2.
Comparative example 1:
Selecting the method that prior art is conventional, process PVA polymeric material, its processing method is:
Membrane separation technique: by the separation of Pollutants in Wastewater, concentrate, reclaim reach purify sewage purpose, mainly have micro- Filter, ultrafiltration, nanofiltration and reverse osmosis.Under the operating condition that temperature is 50-80 degree Celsius and maximum pressure is 0.6MPa, PVA The response rate is below 95%.
Electrochemical process: be directly or indirectly to utilize electrolysis, the contaminants removal in water or be converted into nontoxic, low toxicity material. Tank voltage be 6V, sodium chloride consumption be 2000mg/L, be electrolysed 3h at 45 DEG C, the clearance of COD is reached 29%, and PVA turns Rate, below 95%, significantly reduces the burden of subsequent treatment.

Claims (5)

1. the processing method of a PVA polymeric material, it is characterised in that comprise the following steps successively:
A dissolves, and puts in dissolving tank by pretreated PVA polymeric material, is then passed through distilled water in described dissolving tank, And heating makes distilled water seethe with excitement, forming PVA solution, wherein, the mass fraction of PVA is 8%;
B filters for the first time, is filtered by the particulate matter in PVA solution;
C adds acid in the PVA solution after filtering, pH is at 3.8-4.3 in control, is added thereto to the sulphuric acid that mass fraction is 1% Ferrous iron solution, is uniformly mixed, and obtains reactant liquor one;
D first supercritical processing, is passed through step c gained reactant liquor one in supercritical reaction still, carries out supercritical oxidation, controls anti- Answer temperature 400 DEG C, reaction pressure 22MPa, after first supercritical processing, obtain product carbon dioxide and water, wherein, titanium dioxide Carbon is directly through discharge of pipes, and water flow to around dissolving tank through back of pipeline, for heating dissolving tank.
The processing method of PVA polymeric material the most according to claim 1, it is characterised in that: described PVA polymeric material is selected from water In dissolubility Protection Product, first water solublity Protection Product is carried out prerinse, remove the nucleic wherein adhered to.
3. according to the processing method of the PVA polymeric material described in right 1, it is characterised in that: in step c, PVA solution and citric acid The volume ratio of sodium is 100:1, and PVA solution is 100:1 with the volume ratio of copperas solution.
The processing method of PVA polymeric material the most according to claim 1, it is characterised in that: in step c, described acid is sulphuric acid Or mass fraction is the sodium citrate solution of 10%.
The processing method of PVA polymeric material the most according to claim 4, it is characterised in that: described acid be mass fraction be 10% Sodium citrate solution.
CN201610039905.9A 2016-01-21 2016-01-21 The method of supercritical water oxidation processing PVA polymeric material Expired - Fee Related CN106251924B (en)

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CN106847358A (en) * 2017-03-07 2017-06-13 中国科学技术大学 A kind of supercritical water oxidation processes the device and method of Radioactive myocardial damage
CN106875995A (en) * 2017-01-20 2017-06-20 魏家奎 A kind of method for purifying the degradable PVA products of low-activity in disposal
CN107552547A (en) * 2017-10-24 2018-01-09 深圳市厚植复材科技工程有限公司 The degradation technique and device systems of polyvinyl alcohol product
CN107658038A (en) * 2017-08-30 2018-02-02 广东核电合营有限公司 Radiological techniques treatment of wastes produced method
CN109036611A (en) * 2018-06-30 2018-12-18 天津市德信成环保科技有限公司 Nuclear steam generator cleans the processing method of waste liquid and Spent Radioactive organic solvent
CN111560196A (en) * 2020-05-19 2020-08-21 兴核科学研究(福建)有限责任公司 Strippable film solutions for radionuclide decontamination, methods of making and using
CN112820438A (en) * 2020-04-30 2021-05-18 东部技术公司 Chemical oxidation treatment process of PVA waste treatment system

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
CN106875995A (en) * 2017-01-20 2017-06-20 魏家奎 A kind of method for purifying the degradable PVA products of low-activity in disposal
CN106847358A (en) * 2017-03-07 2017-06-13 中国科学技术大学 A kind of supercritical water oxidation processes the device and method of Radioactive myocardial damage
CN107658038A (en) * 2017-08-30 2018-02-02 广东核电合营有限公司 Radiological techniques treatment of wastes produced method
CN107658038B (en) * 2017-08-30 2019-11-01 广东核电合营有限公司 Radiological techniques treatment of wastes produced method
CN107552547A (en) * 2017-10-24 2018-01-09 深圳市厚植复材科技工程有限公司 The degradation technique and device systems of polyvinyl alcohol product
CN109036611A (en) * 2018-06-30 2018-12-18 天津市德信成环保科技有限公司 Nuclear steam generator cleans the processing method of waste liquid and Spent Radioactive organic solvent
CN109036611B (en) * 2018-06-30 2022-03-01 天津市德信成环保科技有限公司 Method for treating nuclear power steam generator cleaning waste liquid and radioactive waste organic solvent
CN112820438A (en) * 2020-04-30 2021-05-18 东部技术公司 Chemical oxidation treatment process of PVA waste treatment system
CN111560196A (en) * 2020-05-19 2020-08-21 兴核科学研究(福建)有限责任公司 Strippable film solutions for radionuclide decontamination, methods of making and using

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