CN102915783B - Flocculation adsorption treatment method of waste liquid of nuclear power plant and flocculating agent - Google Patents

Flocculation adsorption treatment method of waste liquid of nuclear power plant and flocculating agent Download PDF

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CN102915783B
CN102915783B CN201210410024.5A CN201210410024A CN102915783B CN 102915783 B CN102915783 B CN 102915783B CN 201210410024 A CN201210410024 A CN 201210410024A CN 102915783 B CN102915783 B CN 102915783B
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power plant
nuclear power
waste liquid
component
flocculating agent
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CN102915783A (en
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刘杰安
陈斌
王鑫
柳丹
朱来叶
翁明辉
谈遗海
储志军
刘兵
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JIANGSU BAOCHEN PURIFYING EQUIPMENT CO Ltd
Shanghai Nuclear Engineering Research and Design Institute Co Ltd
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JIANGSU BAOCHEN PURIFICATION EQUIPMENT CO Ltd
Shanghai Nuclear Engineering Research and Design Institute Co Ltd
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Abstract

The invention provides a flocculation adsorption treatment method of waste liquid of a nuclear power plant and a flocculating agent. The flocculation adsorption treatment method includes the steps of adding flocculating agent into the waste liquid of the nuclear power plant, keeping a pH (potential of hydrogen) value within 7-9, performing mixed reaction to obtain colloid flocculation; and subjecting the colloid flocculation to activated carbon adsorption column for adsorption, wherein Fe, Co, Mn and Ag nuclides are absorbed and intercepted by the activated carbon adsorption column. The flocculating agent comprises a component A including NaOH or KOH, a component B which is polyacrylamide, a component C which is sodium polyacrylate or potassium polyacrylate. Coagulation capacity of corrosion product colloids is improved by adding the flocculating agent, and decontamination factor of activated carbon to Fe, Co, Mn, Ag is increased by 5 times. The flocculation adsorption treatment method is stable in eliminating effect, good in repeatability, low in running energy consumption and less in secondary pollution output.

Description

The flocculation adsorption disposal route of a kind of nuclear power plant waste liquid and flocculating agent
Technical field
The present invention relates to nuclear power plant's liquid waste disposal technique, particularly relate to flocculation adsorption disposal route and the flocculating agent of a kind of nuclear power plant waste liquid.
Background technology
Nuclear power plant runs and inevitably produces radioactive liquid waste.Along with the development of China's nuclear power, the impact of nuclear power plant construction on water environment more and more receives publicity.In order on the environmental radiation protection of new period China's Construction of Nuclear Electricity and affect, there is provided safer, reasonable, effectively, value disciplines accurately, a collection of new liter version nuclear power waste discharge administrative standard that it is representative that national environmental protection portion has taken the lead in official approval in 2011 with " regulation of protection of GB 6249-2011 nuclear power plant environmental radiation ".Standard regulation Coastal Nuclear Power Plant (detritiation and C14 are outward) liquid radiation effluent total radioactivity concentration limit value is decided to be 1000Bq/L, and this concentration limit of inland nuclear power plant is then decided to be 100Bq/L.
The existing operation of China and building nuclear power plant's majority for pressurized water reactor type.For PWR nuclear power plant, the source of radioactive liquid waste mainly contains chemical waste fluid, process waste liquor, miscellaneous waste liquid, scrub raffinate and potential radioactive liquid waste.Wherein process waste liquor activity concentration is the highest, can reach 107Bq/L.Process waste liquor mainly comprises reactor coolant efflux, also comprise that equipment is hydrophobic, refuelling pool and spentnuclear fuel pond hydrophobic etc.Liquid radiomaterial contained by it mainly comprises fission product that Cs, Sr etc. exist with ionic forms and the corrosion product that Co, Mn etc. exist with colloid, particle shape.
The disposal route of current radioactive liquid waste mainly contains chemical precipitation, evaporation, ion-exchange, film process, chemical flocculation, charcoal absorption, continuous electric desalination etc.
Chemical precipitation is widely used in the process of early stage nuclear facilities radioactive liquid waste, but the decontamination factor of chemical precipitation process compared with low, equipment is huge and need more chemical reagent, secondary refuse generation large, at present when processing nuclear power plant's waste liquid, be generally only used as pre-service.
In the nuclear power plant that China has run at present, liquid waste system nearly all have employed evaporation treatment process, but evaporation treatment process is not suitable for process containing waste liquid that is easy to foaming, volatile component, and operation energy consumption is high, maintenance, repair are more complicated, and concentrate also needs process further or disposes.
Ion-exchange is the most frequently used treatment process of nuclear power plant's active-effluent system, general employing multiple stage ion exchange bed series connection (or in parallel) is run, but resin bed is not suitable for process salt content or the higher waste liquid of solid content: when in waste liquid, salinity is more, resin will soon saturatedly lose efficacy; When in waste liquid, solid content is higher, resin bed easily causes runner to block.
Membrane technology is that the process of radioactive liquid waste provides new selection, but film process exists certain shortcoming, still needs process further etc. as limited, high to maintenance requirement in: detergent power, the concentrate that produces.Wherein the most frequently used reverse-osmosis treated, require higher to influent quality, the upstream of reverse-osmosis treated need adopt filtration etc. to carry out pre-service to waste liquid.
At present, the treatment process of many advanced persons is also developed in radioactive liquid waste process, comprising: adopt novel sorbing material to adsorb, continuous electric desalination, electrochemical ion exchange etc.But these treatment technologies are also in conceptual phase, be seldom applied to the process of radioactive liquid waste in nuclear power plant.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, meeting the emission limit requirement of GB 6249-2011 new standard simultaneously, the invention provides flocculation adsorption disposal route and the flocculating agent of a kind of nuclear power plant waste liquid.
Realize the technical scheme of the object of the invention: the flocculation adsorption disposal route of a kind of nuclear power plant waste liquid, it comprises the steps:
(1) in nuclear power plant's waste liquid, add flocculating agent, Mei Sheng nuclear power plant waste liquid adds flocculating agent 1.1mg ~ 14.2mg, makes pH value remain on 7 ~ 9, and hybrid reaction obtains colloid flco;
Described nuclear power plant's waste liquid comprises one or more in Fe, Co, Mn, Ag corrosion product; Wherein, Fe, Co, Mn or Ag nuclide concentration is at 0.01ng/L ~ 10mg/L;
Described flocculating agent comprises following component; Component A: NaOH or KOH; B component: polyacrylamide; Component C: sodium polyacrylate or polyacrylic acid potassium; Wherein, component A, B component and component C mass ratio are (0.1 ~ 12.3): 1:(0.5 ~ 2);
(2) by the colloid flco of step (1) gained by active carbon adsorption column, wherein Fe, Co, Mn, Ag nucleic is tightly held by activated carbon post absorption and retains; Described activated carbon granule is of a size of 20 ~ 50 orders, and iodine number is >=900mg/g.
The chemical flocculation disposal route of a kind of nuclear power plant as above waste liquid, in the step (2) described in it, colloid flco passes through active carbon adsorption column with the flow velocity of 10m/h ~ 25m/h.
The chemical flocculation disposal route of a kind of nuclear power plant as above waste liquid, the active carbon adsorption column loading height described in it is 0.2m ~ 0.85m.
The chemical flocculation disposal route of a kind of nuclear power plant as above waste liquid, in the last gained waste liquid of its step (2), the average decontamination factor of Fe, Co, Mn, Ag nucleic colloid reaches more than 50.
The chemical flocculation disposal route of a kind of nuclear power plant as above waste liquid, the polyacrylamide described in it is cationic, its solid content>=90%, molecular weight>=3 × 10 6.
The chemical flocculation disposal route of a kind of nuclear power plant as above waste liquid, solid content>=40% of the sodium polyacrylate described in it, molecular weight>=3 × 10 7.
A kind of flocculating agent for nuclear power plant's liquid waste processing of the present invention, it is the aqueous solution comprising following component; Component A: NaOH or KOH; B component: polyacrylamide; Component C: sodium polyacrylate or polyacrylic acid potassium; Wherein, the mass concentration ratio of component A, B component and component C is (0.1 ~ 12.3): 1:(0.5 ~ 2).
As above for a flocculating agent for nuclear power plant's liquid waste processing, the polyacrylamide described in it is cationic, its solid content>=90%, molecular weight>=3 × 10 6.
As above for a flocculating agent for nuclear power plant's liquid waste processing, solid content>=40% of the sodium polyacrylate described in it, molecular weight>=3 × 10 7.
Effect of the present invention is:
(1) traditional flocculation precipitation method is for the higher liquid waste processing of salt content, and decontamination factor lower (usually about 10).The flocculation adsorption method that the present invention proposes is applicable to nuclear power plant's low concentration liquid waste processing, effectively can improve the dirt-removing power of nuclear power plant's liquid waste system, the removal of the corrosion product existed in colloidal form for Fe, Co, Mn, Ag has significant effect (average decontamination factor reaches more than 50).
(2) compared to charcoal absorption method, the flocculation adsorption method that the present invention proposes improves the coagulation ability of corrosion product colloid by adding flocculating agent, make the decontamination factor of activated charcoal to Fe, Co, Mn, Ag improve more than 5 times.
(3) the flocculation adsorption method removal effect that the present invention proposes is stablized, and favorable reproducibility, operation energy consumption is low, and secondary refuse generation is few.
(4) the flocculating agent safety and environmental protection of the present invention's proposition, preparation method is simple, and economical, in nuclear power plant, field of waste liquid treatment has popularizing application prospect.
Embodiment
Below in conjunction with specific embodiment, the flocculation adsorption disposal route of a kind of nuclear power plant of the present invention waste liquid and flocculating agent are described in further detail.
Embodiment 1
(1) in nuclear power plant's waste liquid, add flocculating agent, Mei Sheng nuclear power plant waste liquid adds flocculating agent 12.4mg, makes pH value remain on 9, and hybrid reaction 15s obtains colloid flco;
Described nuclear power plant's waste liquid comprises 4.5mg/L Fe, 7.2mg/L Co, 1.8mg/L Mn;
Described flocculating agent comprises following component; Component A: NaOH; B component: polyacrylamide; Component C: sodium polyacrylate; Wherein, component A, B component and component C mass ratio are 1.1:1:1;
(2) the colloid flco of step (1) gained is passed through active carbon adsorption column with the flow velocity of 20m/h, wherein flco be tightly held by activated carbon post absorption retain, in gained waste liquid, the decontamination factor of Fe, Co, Mn nucleic colloid is respectively: 150,82,67, and average decontamination factor is 93;
Described active carbon adsorption column loading height is 0.2m; Described activated carbon granule is of a size of 20-50 order, and iodine number is >=900mg/g.
Embodiment 2
(1) in nuclear power plant's waste liquid, add flocculating agent, Mei Sheng nuclear power plant waste liquid adds flocculating agent 10mg, makes pH value remain on 7, and hybrid reaction 15s obtains colloid flco;
Described nuclear power plant's waste liquid comprises 3.1mg/L Fe, 4.4mg/L Co, 1.1mg/L Mn;
Described flocculating agent comprises following component; Component A: NaOH; B component: polyacrylamide; Component C: sodium polyacrylate; Wherein, component A, B component and component C mass ratio are 8:1:1;
(2) the colloid flco of step (1) gained is passed through active carbon adsorption column with the flow velocity of 10m/h, wherein flco be tightly held by activated carbon post absorption retain, in gained waste liquid, the decontamination factor of Fe, Co, Mn nucleic colloid is respectively: 104,102,16, and comprehensive decontamination factor is 61;
Described active carbon adsorption column loading height is 0.85m; Described activated carbon granule is of a size of 20-50 order, and iodine number is >=900mg/g.
Embodiment 3
(1) in nuclear power plant's waste liquid, add flocculating agent, Mei Sheng nuclear power plant waste liquid adds flocculating agent 8.4mg, makes pH value remain on 9, and hybrid reaction 15s obtains colloid flco;
Described nuclear power plant's waste liquid comprises 1.5mg/LAg;
Described flocculating agent comprises following component; Component A: NaOH; B component: polyacrylamide; Component C: sodium polyacrylate; Wherein, component A, B component and component C mass ratio are 2.2:1:1;
(2) by the colloid flco of step (1) gained with the flow velocity of 20m/h by active carbon adsorption column, wherein flco is tightly held by activated carbon post absorption and retains, and in gained waste liquid, the decontamination factor of Ag nucleic colloid is 91;
Described active carbon adsorption column loading height is 0.2m; Described activated carbon granule is of a size of 20-50 order, and iodine number is >=900mg/g.
Embodiment 4
(1) in nuclear power plant's waste liquid, add flocculating agent, Mei Sheng nuclear power plant waste liquid adds flocculating agent 14.2mg, makes pH value remain on 9, and hybrid reaction 15s obtains colloid flco;
Described nuclear power plant's waste liquid comprises 3.1mg/L Fe, 4.0mg/L Co, 1.0mg/L Mn;
Described flocculating agent comprises following component; Component A: KOH; B component: polyacrylamide; Component C: polyacrylic acid potassium; Wherein, component A, B component and component C mass ratio are 1.55:1:1;
(2) the colloid flco of step (1) gained is passed through active carbon adsorption column with the flow velocity of 25m/h, wherein flco be tightly held by activated carbon post absorption retain, in gained waste liquid, the decontamination factor of Fe, Co, Mn nucleic colloid is respectively: 102,85,101, and average decontamination factor is 93;
Described active carbon adsorption column loading height is 0.2m; Described activated carbon granule is of a size of 20-50 order, and iodine number is >=900mg/g.
Embodiment 5
(1) in nuclear power plant's waste liquid, add flocculating agent, Mei Sheng nuclear power plant waste liquid adds flocculating agent 7.65mg, makes pH value remain on 9, and hybrid reaction 15s obtains colloid flco;
Described nuclear power plant's waste liquid comprises 3.1mg/L Fe, 4.0mg/L Co, 1.0mg/L Mn;
Described flocculating agent comprises following component; Component A: KOH; B component: polyacrylamide; Component C: sodium polyacrylate; Wherein, component A, B component and component C mass ratio are 12.3:1:2;
(2) the colloid flco of step (1) gained is passed through active carbon adsorption column with the flow velocity of 20m/h, wherein flco be tightly held by activated carbon post absorption retain, in gained waste liquid, the decontamination factor of Fe, Co, Mn nucleic colloid is respectively: 102,60,90, and average decontamination factor is 75;
Described active carbon adsorption column loading height is 0.2m; Described activated carbon granule is of a size of 20-50 order, and iodine number is >=900mg/g.
Embodiment 6
(1) in nuclear power plant's waste liquid, add flocculating agent, Mei Sheng nuclear power plant waste liquid adds flocculating agent 6.4mg, makes pH value remain on 7, and hybrid reaction 15s obtains colloid flco;
Described nuclear power plant's waste liquid comprises 4.4mg/L Fe, 6.4mg/L Co, 1.7mg/L Mn;
Described flocculating agent comprises following component; Component A: NaOH; B component: polyacrylamide; Component C: sodium polyacrylate; Wherein, component A, B component and component C mass ratio are 0.1:1:0.5;
(2) the colloid flco of step (1) gained is passed through active carbon adsorption column with the flow velocity of 20m/h, wherein flco be tightly held by activated carbon post absorption retain, in gained waste liquid, the decontamination factor of Fe, Co, Mn nucleic colloid is respectively: 55,49,56, and comprehensive decontamination factor is 52;
Described active carbon adsorption column loading height is 0.2m; Described activated carbon granule is of a size of 20-50 order, and iodine number is >=900mg/g.

Claims (5)

1. a flocculation adsorption disposal route for nuclear power plant's waste liquid, is characterized in that: the method comprises the steps:
(1) in nuclear power plant's waste liquid, add flocculating agent, Mei Sheng nuclear power plant waste liquid adds flocculating agent 1.1mg ~ 14.2mg, makes pH value remain on 7 ~ 9, and hybrid reaction obtains colloid flco;
Described nuclear power plant's waste liquid comprises one or more in Fe, Co, Mn, Ag corrosion product; Wherein, Fe, Co, Mn or Ag nuclide concentration is at 0.01ng/L ~ 10mg/L;
Described flocculating agent comprises following component; Component A: NaOH or KOH; B component: polyacrylamide; Component C: sodium polyacrylate or polyacrylic acid potassium; Wherein, component A, B component and component C mass ratio are (0.1 ~ 12.3): 1:(0.5 ~ 2);
(2) by the colloid flco of step (1) gained with the flow velocity of 10m/h ~ 25m/h by active carbon adsorption column, wherein Fe, Co, Mn, Ag nucleic is tightly held by activated carbon post absorption and retains; Described activated carbon granule is of a size of 20 ~ 50 orders, and iodine number is >=900mg/g.
2. the flocculation adsorption disposal route of a kind of nuclear power plant according to claim 1 waste liquid, is characterized in that: described active carbon adsorption column loading height is 0.2m ~ 0.85m.
3. the flocculation adsorption disposal route of a kind of nuclear power plant according to claim 1 waste liquid, is characterized in that: in the last gained waste liquid of step (2), the average decontamination factor of Fe, Co, Mn, Ag nucleic colloid reaches more than 50.
4. the flocculation adsorption disposal route of a kind of nuclear power plant according to claim 1 waste liquid, is characterized in that: described polyacrylamide is cationic, its solid content>=90%, molecular weight>=3 × 10 6.
5. the flocculation adsorption disposal route of a kind of nuclear power plant according to claim 1 waste liquid, is characterized in that: solid content>=40% of described sodium polyacrylate, molecular weight>=3 × 10 7.
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CN104538077A (en) * 2013-12-06 2015-04-22 东华理工大学 Method for treating acidic uranium-bearing wastewater with bone-based adsorbent
CN103714875B (en) * 2013-12-30 2016-06-22 中国原子能科学研究院 Ag colloid removal device in a kind of nuclear waste water
CN104867528A (en) * 2015-03-31 2015-08-26 湖南桃花江核电有限公司 Treatment method of process wastewater in nuclear power plant
CN107140721A (en) * 2017-04-21 2017-09-08 中铁四局集团有限公司 A kind of discarded slurry mud-water separation preparation and its application process
CN110467179A (en) * 2018-05-09 2019-11-19 上海核工程研究设计院有限公司 A method of active carbon is handled with nuclear facilities radioactive liquid waste chemical flocculation
CN109493988A (en) * 2018-12-14 2019-03-19 核工业理化工程研究院 Core biochemical decontamination waste liquid pretreatment unit and processing method
CN112970764B (en) * 2021-04-21 2022-11-18 北京科奥明生物技术有限公司 Microbial waste liquid treatment agent and microbial waste liquid treatment bag

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