The cement solidification material of waste phosphoric acid tributyl/kerosene and its preparation of solidified cement body
Method
Technical field
The present invention relates to a kind of Radwastes treatment technical field, more particularly to a kind of waste phosphoric acid tributyl/kerosene
Cement solidification material and its solidified cement body preparation method.
Background technology
Waste phosphoric acid tributyl/kerosene (TBP/OK) is extraction processing spentnuclear fuel and actinium series and lanthanide series in high activity liquid waste
During produce, be nuclear industry produce important radioactive liquid waste, according to GB9133-1995《Radwaste contingency table
It is accurate》Regulation, during it belongs to, low radioactive waste liquid.After tributyl phosphate (TBP) is recycled for multiple times as extractant, by chemistry and
, there is degradation reaction degradation in the effect of radiation, needs are disposed as radwaste.Because of the change of its radionuclide
Learn composition complicated and inflammable, volatile, process and reorganize and outfit and be required for special consideration.
At present, both at home and abroad to the method for disposal of waste phosphoric acid tributyl/kerosene mainly have burning or be pyrolyzed, hydrolysis solidification,
Connect electrochemical oxidation, plastics solidification and cement solidification etc..Wherein, burning or being pyrolyzed needs to run in high temperature environments, in waste liquid
Phosphorus, sulphur and chlorine is serious to equipment corrosion and tail gas clean-up is complicated, make the construction of facility and difficult in maintenance.Hydrolysis solidification, indirectly
Waste still needs to carry out later stage cement solidification disposal after electrochemicial oxidation, and complex process, processing cost is also higher.Plastics
Firming body chance naked light easily burns, non-refractory, easily causes radioactive release.The N910 polymer that Nochar companies of the U.S. develop
It is used to solidify organic liquid waste Deng N series of products, firming body stability is preferable, but same non-refractory, and Nochar prices are high
Expensive, it is loose particle or fritter that it absorbs the firming body after waste liquid, domestic at present to receive mark without related waste body
It is accurate.Cement solidification method is widely used in solidification, cool waste, but due to cement and waste phosphoric acid tributyl/kerosene compatibility
Difference, causes waste phosphoric acid tributyl/kerosene volume inclusion quantity in solidified cement body low (less than 24%), firming body intensity difference, unit
Volume increase-volume is big, and solidification disposal efficiency, security and economy be not good.
The content of the invention
Present invention is primarily targeted at, there is provided a kind of cement solidification material of new waste phosphoric acid tributyl/kerosene and
The preparation method of its solidified cement body, technical problem to be solved is to make its cement-based solidified material have nuclear waste inclusion quantity
Greatly, nuclear waste disposal process is simple, processing cost is low, processing procedure without chemical contamination, thus more suitable for practicality.
The object of the invention to solve the technical problems employs the following technical solutions to realize.According to present invention proposition
A kind of waste phosphoric acid tributyl/kerosene cement solidification material, by weight percentage, it includes:
Portland cement:45.0-65.0%;
Flyash:17.0-38.0%;
Silicon ash:4.0-6.0%;
Swelling agent:4.0-6.0%;
Powdery water-reducing agent:0.8-1.2%;
Compatibility improvement agent:5.0-6.0%;
Gu light wood material:2.5-3.0%.
The object of the invention to solve the technical problems can also be applied to the following technical measures to achieve further.
Preferably, the cement solidification material of aforesaid waste phosphoric acid tributyl/kerosene, wherein described portland cement is height
Alite silicate cement;Described flyash is the fine heavy pearl of flyash;Described swelling agent is calcium sulphoaluminate-calcium oxide
Cement expansive material;Described powdery water-reducing agent is polycarboxylic acid series high-performance powdery water-reducing agent;Described Compatibility improvement agent is
Sodium matter montmorillonite;Described solid light wood material is organobentonite modified cyclodextrin base high oil-absorbing resin.
The object of the invention to solve the technical problems is also realized using following technical scheme.According to present invention proposition
A kind of waste phosphoric acid tributyl/kerosene solidified cement body preparation method, it includes:
1) will solid light wood material and waste phosphoric acid tributyl/kerosene by weight 1:14-16 mixing stands, and adds Compatibility improvement
Agent, stirring, obtains solid light wood material-waste phosphoric acid tributyl/kerosene compound;
2) by cement-based solidified paste materials and water by weight 1:0.16-0.20 mixes, stirring, is obtained cement-based solidified
Slurry;Wherein, cement-based solidified paste materials include portland cement, flyash, silicon ash, swelling agent, powdery water-reducing agent;
3) described cement-based solidified slurry is mixed with solid light wood material-waste phosphoric acid tributyl/kerosene compound, is stirred,
Obtain the solidified cement body of waste phosphoric acid tributyl/kerosene;
Wherein, portland cement, flyash, silicon ash, swelling agent, powdery water-reducing agent, Compatibility improvement agent and solid light wood material
For the cement solidification material of waste phosphoric acid tributyl/kerosene, its percentage by weight is:
Portland cement:45.0-65.0%;
Flyash:17.0-38.0%;
Silicon ash:4.0-6.0%;
Swelling agent:4.0-6.0%;
Powdery water-reducing agent:0.8-1.2%;
Compatibility improvement agent:5.0-6.0%;
Gu light wood material:2.5-3.0%.
The object of the invention to solve the technical problems can also be applied to the following technical measures to achieve further.
Preferably, the preparation method of the solidified cement body of aforesaid waste phosphoric acid tributyl/kerosene, wherein described silicate
Cement is high alite silicate cement;Described flyash is the fine heavy pearl of flyash;Described swelling agent be calcium sulphoaluminate-
Calcium oxide cement expansive material;Described powdery water-reducing agent is polycarboxylic acid series high-performance powdery water-reducing agent;Described compatibility
Improver is sodium matter montmorillonite;Described solid light wood material is organobentonite modified cyclodextrin base high oil-absorbing resin.
Preferably, the preparation method of the solidified cement body of aforesaid waste phosphoric acid tributyl/kerosene, wherein step 1) described in
Stirring speed be 6-8m/s.
Preferably, the preparation method of the solidified cement body of aforesaid waste phosphoric acid tributyl/kerosene, wherein step 2) described in
Stirring speed be 14-18m/s.
Preferably, the preparation method of the solidified cement body of aforesaid waste phosphoric acid tributyl/kerosene, wherein step 3) described in
Stirring speed be 9-12m/s.
Preferably, the preparation method of the solidified cement body of aforesaid waste phosphoric acid tributyl/kerosene, wherein described waste phosphoric acid
The volume inclusion quantity of the solidified cement body of tributyl/kerosene is 42-50%.
By above-mentioned technical proposal, the cement solidification material and its solidified cement body of waste phosphoric acid tributyl/kerosene of the present invention
Preparation method at least have following advantages:
1) present invention improves the phase of waste phosphoric acid tributyl/kerosene and cement using solid light wood material and Compatibility improvement agent
Capacitive, inclusion quantity rises to 42-50%, greatly reduces the volume increase-volume in solidification process, reduces shared by later stage process
Space and expense, with great economic benefit;
2) solidified cement body radionuclide ion leaching rate of the invention is low, and Cs (42d) leaching rate is 1.5-4.9 × 10-4Cm/d,
Ce (42d) leaching rate is 0.76-4.5 × 10-6cm/d;Compression strength is 13.2-17.2MPa;It is impact resistance, anti-immersion, anti-
Freeze thawing performance meets GB14569.1-2011《Low, middle level radioactive waste firming body performance requirement-solidified cement body》With GB
7023-86《The long-term leaching test of solidification of radwaste body》Indices, with excellent performance;
3) preparation method of the invention is simple, process without chemical contamination, it is "dead", without light pollution, low noise, it is adaptable to
Actual production process.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, described in detail as after with presently preferred embodiments of the present invention below.
Specific embodiment
Further to illustrate the present invention to reach technological means and effect that predetermined goal of the invention is taken, below in conjunction with
Preferred embodiment, to the cement solidification material according to waste phosphoric acid tributyl/kerosene proposed by the present invention and its solidified cement body
Preparation method its specific embodiment, structure, feature and its effect, describe in detail as after.In the following description, different " one
What embodiment " or " embodiment " referred to is not necessarily same embodiment.Additionally, special characteristic, structure in one or more embodiments,
Or feature can be combined by any suitable form.
The cement solidification material of a kind of waste phosphoric acid tributyl/kerosene that one embodiment of the present of invention is proposed, with weight hundred
Divide than meter, it includes:
Portland cement:45.0-65.0%;
Flyash:17.0-38.0%;
Silicon ash:4.0-6.0%;
Swelling agent:4.0-6.0%;
Powdery water-reducing agent:0.8-1.2%;
Compatibility improvement agent:5.0-6.0%;
Gu light wood material:2.5-3.0%.
Wherein, portland cement, flyash, silicon ash, swelling agent, powdery water-reducing agent are cement-based solidified paste materials;Water
Mud base solidification paste materials, Compatibility improvement agent and the big component of solid light wood material three are individually packed.
Preferably, portland cement be the high alite silicate cement of P I 52.5, tricalcium silicate weight content 68-
71%, tricalcium aluminate weight content 6-7%, free calcium oxide weight content is less than 0.8%, and magnesia weight content is less than
3.5%, Blain specific surface is (420 ± 10) m2/kg。
Preferably, flyash be the fine heavy pearl of flyash, fineness d50≤ 3 μm, d95≤ 10 μm, water requirement is less than 90%, 28
Its activity index is more than 110%, and activity index is more than 120% within 90 days.
Preferably, silicon ash meets the requirement of GB/T 27690-2011 standards, SiO2Weight content is not less than 96%, loss on ignition
Less than 1.0wt%, specific surface area (BET method) (23 ± 2) m2/ g, water requirement is less than 115%, 28d activity indexs 97-98%.
Preferably, swelling agent is the calcium sulphoaluminate-calcium oxide concrete expansion for meeting the requirement of GB 23439-2009 standards
Agent, main mineral constituent is:(by weight percentage) f-CaO:40-45%;CaSO4:15-20%,
Waterproof expands, 7 days limited expansion rate 0.08-0.12% in water, and preferably 0.10%.The waterproof for making full use of the swelling agent expands spy
Property, for solving the volume contraction of solidified cement body, prevent solidified cement body from departing from disposal barrel.
Preferably, powdery water-reducing agent is polycarboxylic acid series high-performance powdery water-reducing agent, preferably reduces-early strong compound poly- carboxylic
Sour based water reducer, water-reducing rate weight content is more than 35%, reduces concrete shrinkage and is more than or equal to 30%, room temperature maintenance 12h resistance to compressions
Strength ratio is more than or equal to 300%.
Compatibility improvement agent is sodium matter montmorillonite, and Absorbance ratio-derivative method 42-43, silica weight content is not low by 60%, three oxidations
Aluminium weight content is not less than 15%, fineness 600-800 mesh, preferably 700 mesh.Sodium matter montmorillonite is improving solid light wood material, waste phosphoric acid
Tributyl/kerosene with cement compatibility simultaneously, has stronger selective physical absorption ability to radionuclide ion Cs, Ce, increases
The radionuclide ion ability to cure of cement-based solidified material.
Gu light wood material is organobentonite modified cyclodextrin base high oil-absorbing resin, particle diameter distribution 0.3-0.6mm, semi-transparent jewel
Shape, to the oil suction multiplying power of kerosene and tributyl phosphate 22 gram grams and 16 gram grams are respectively, and (weight contains to protect oil cut rate more than 95%
Amount).It is modified by organobentonite, in addition to increasing solid oil ability, radionuclide ion Cs, Ce are equally inhaled with stronger physics
Attached ability.
Another embodiment of the present invention proposes a kind of preparation method of the solidified cement body of waste phosphoric acid tributyl/kerosene, its
Including:
1) will solid light wood material and waste phosphoric acid tributyl/kerosene by weight 1:14-16 adds mixing in disposal barrel to stand 3h,
Compatibility improvement agent is added, 4-6min is stirred, solid light wood material-waste phosphoric acid tributyl/kerosene compound is obtained;
2) by cement-based solidified paste materials and water by weight 1:0.16-0.20 mixes, and in being placed in high-speed pulping machine, stirs
4-6min is mixed, cement-based solidified slurry is obtained;Wherein, cement-based solidified paste materials include portland cement, flyash, silicon
Ash, swelling agent, powdery water-reducing agent;
3) described cement-based solidified slurry is added into disposal barrel, with solid light wood material-waste phosphoric acid tributyl/kerosene compound
Mixing, stirs 3-5min, obtains the solidified cement body of waste phosphoric acid tributyl/kerosene;
Portland cement, flyash, silicon ash, swelling agent, powdery water-reducing agent, Compatibility improvement agent and solid light wood material are useless phosphorus
The cement solidification material of sour tributyl/kerosene, its percentage by weight is:
Portland cement:45.0-65.0%;
Flyash:17.0-38.0%;
Silicon ash:4.0-6.0%;
Swelling agent:4.0-6.0%;
Powdery water-reducing agent:0.8-1.2%;
Compatibility improvement agent:5.0-6.0%;
Gu light wood material:2.5-3.0%.
Preferably, step 1) in paddle linear velocity 6-8m/s, preferably 7m/s.
Preferably, step 2) high speed pulper paddle linear velocity 14-18m/s, preferably 16m/s.
Preferably, step 3) in mixer rotating speed 600-800 turn/min, paddle linear velocity 9-12m/s, preferably 10m/
s。
In the present embodiment waste phosphoric acid tributyl/kerosene be on-radiation simulation in, it is low put waste phosphoric acid tributyl/kerosene, by
AR tributyl phosphate and anhydrous kerosene by volume 3:7 are mixed, and are 10 mixed with activity equivalent5-6Bq's
Cs and Ce, wherein Ce are used to simulate nucleic239Pu。
One embodiment of the present of invention proposes a kind of cement solidification material of waste phosphoric acid tributyl/kerosene, embodiment 1-12
The cement solidification material component of waste phosphoric acid tributyl/kerosene is as shown in table 1.
The component (percentage by weight %) of the cement solidification material of the waste phosphoric acid tributyl of table 1/kerosene
Embodiment 1
One embodiment of the present of invention proposes a kind of preparation method of the solidified cement body of waste phosphoric acid tributyl/kerosene, its
Including:
1) the solid light wood material high oil-absorbing resins of 2.5kg and 35.0kg waste phosphoric acids tributyl/kerosene are added in disposal barrel and is mixed
3h is stood, 5.0kg Compatibility improvement agent sodium matter montmorillonites are added, 5min is stirred, paddle linear velocity 8m/s obtains solid light wood
Material-waste phosphoric acid tributyl/kerosene compound;
2) 45.0kg portland cements, 35.7kg flyash, 6.0kg silicon ashes, 5.0kg swelling agents and 0.8kg powderies are subtracted
Aqua is well mixed makes the cement-based solidified paste materials of 92.5kg, and 18.5kg water is placed in high-speed pulping machine, stirs 4min,
High-speed pulping machine paddle linear velocity 18m/s, is obtained cement-based solidified slurry;
3) described cement-based solidified slurry is added into disposal barrel, with solid light wood material-waste phosphoric acid tributyl/kerosene compound
Mixing, paddle linear velocity 10m/s stirs 4min, the curing solidified cement body for obtaining waste phosphoric acid tributyl/kerosene.
Φ 50mm × 50mm samples are prepared, is conserved to corresponding age in the environment of temperature is for 25 ± 5 DEG C, according to
GB14569.1-2011《Low, middle level radioactive waste firming body performance requirement-solidified cement body》With GB 7023-86《Radiation
The property long-term leaching test of solidification of waste body》Carry out properties test.Under 42% volume inclusion quantity, compression strength 16.5MPa,
Impact resistance, freeze-thaw resistance and anti-immersion are qualified, Cs (42d) leaching rate 2.5 × 10-4Cm/d, Ce (42d) leaching rate 7.6 ×
10-7cm/d。
Embodiment 2
One embodiment of the present of invention proposes a kind of preparation method of the solidified cement body of waste phosphoric acid tributyl/kerosene, its
Including:
1) the solid light wood material high oil-absorbing resins of 2.6kg and 39.0kg waste phosphoric acids tributyl/kerosene are added in disposal barrel and is mixed
3h is stood, 5.2kg Compatibility improvement agent sodium matter montmorillonites are added, 4min is stirred, paddle linear velocity 7m/s obtains solid light wood
Material-waste phosphoric acid tributyl/kerosene compound;
2) 50.0kg portland cements, 32.3kg flyash, 5.0kg silicon ashes, 4.0kg swelling agents and 0.9kg powderies are subtracted
Aqua is well mixed makes the cement-based solidified paste materials of 92.2kg, and 17.5kg water is placed in high-speed pulping machine, stirs 4min,
High-speed pulping machine paddle linear velocity 16m/s, is obtained cement-based solidified slurry;
3) described cement-based solidified slurry is added into disposal barrel, with solid light wood material-waste phosphoric acid tributyl/kerosene compound
Mixing, paddle linear velocity 12m/s stirs 3min, the curing solidified cement body for obtaining waste phosphoric acid tributyl/kerosene.
Φ 50mm × 50mm samples are prepared into, are conserved to corresponding age in the environment of temperature is for 25 ± 5 DEG C, according to
GB14569.1-2011《Low, middle level radioactive waste firming body performance requirement-solidified cement body》With GB 7023-86《Radiation
The property long-term leaching test of solidification of waste body》Carry out properties test.Under 44% volume inclusion quantity, compression strength 14.5MPa,
Impact resistance, freeze-thaw resistance and anti-immersion are qualified, Cs (42d) leaching rate 2.7 × 10-4Cm/d, Ce (42d) leaching rate 8.6 ×
10-7cm/d。
Embodiment 3
One embodiment of the present of invention proposes a kind of preparation method of the solidified cement body of waste phosphoric acid tributyl/kerosene, its
Including:
1) the solid light wood material high oil-absorbing resins of 2.7kg and 43.2kg waste phosphoric acids tributyl/kerosene are added in disposal barrel and is mixed
3h is stood, 5.4kg Compatibility improvement agent sodium matter montmorillonites are added, 4min is stirred, paddle linear velocity 7m/s obtains solid light wood
Material-waste phosphoric acid tributyl/kerosene compound;
2) 55.0kg portland cements, 25.9kg flyash, 4.0kg silicon ashes, 6.0kg swelling agents and 1.0kg powderies are subtracted
Aqua is well mixed makes the cement-based solidified paste materials of 91.9kg, and 17.5kg water is placed in high-speed pulping machine, stirs 6min,
High-speed pulping machine paddle linear velocity 18m/s, is obtained cement-based solidified slurry;
3) described cement-based solidified slurry is added into disposal barrel, with solid light wood material-waste phosphoric acid tributyl/kerosene compound
Mixing, paddle linear velocity 9m/s stirs 5min, the curing solidified cement body for obtaining waste phosphoric acid tributyl/kerosene.
Φ 50mm × 50mm samples are prepared, is conserved to corresponding age in the environment of temperature is for 25 ± 5 DEG C, according to
GB14569.1-2011《Low, middle level radioactive waste firming body performance requirement-solidified cement body》With GB 7023-86《Radiation
The property long-term leaching test of solidification of waste body》Carry out properties test.Under 47% volume inclusion quantity, compression strength 16.2MPa,
Impact resistance, freeze-thaw resistance and anti-immersion are qualified, Cs (42d) leaching rate 3.8 × 10-4Cm/d, Ce (42d) leaching rate 1.1 ×
10-6cm/d。
Embodiment 4
One embodiment of the present of invention proposes a kind of preparation method of the solidified cement body of waste phosphoric acid tributyl/kerosene, its
Including:
1) the solid light wood material high oil-absorbing resins of 2.8kg and 44.8kg waste phosphoric acids tributyl/kerosene are added in disposal barrel and is mixed
3h is stood, 5.6kg Compatibility improvement agent sodium matter montmorillonites are added, 5min is stirred, paddle linear velocity 7m/s obtains solid light wood
Material-waste phosphoric acid tributyl/kerosene compound;
2) 60.0kg portland cements, 20.0kg flyash, 5.5kg silicon ashes, 5.0kg swelling agents and 1.1kg powderies are subtracted
Aqua is well mixed makes the cement-based solidified paste materials of 91.6kg, and 15.6kg water is placed in high-speed pulping machine, stirs 5min,
High-speed pulping machine paddle linear velocity 15m/s, is obtained cement-based solidified slurry;
3) described cement-based solidified slurry is added into disposal barrel, with solid light wood material-waste phosphoric acid tributyl/kerosene compound
Mixing, paddle linear velocity 10m/s stirs 4min, the curing solidified cement body for obtaining waste phosphoric acid tributyl/kerosene.
Φ 50mm × 50mm samples are prepared, is conserved to corresponding age in the environment of temperature is for 25 ± 5 DEG C, according to
GB14569.1-2011《Low, middle level radioactive waste firming body performance requirement-solidified cement body》With GB 7023-86《Radiation
The property long-term leaching test of solidification of waste body》Carry out properties test.Under 48% volume inclusion quantity, compression strength 13.9MPa,
Impact resistance, freeze-thaw resistance and anti-immersion are qualified, Cs (42d) leaching rate 4.9 × 10-4Cm/d, Ce (42d) leaching rate 4.5 ×
10-6cm/d。
Embodiment 5
One embodiment of the present of invention proposes a kind of preparation method of the solidified cement body of waste phosphoric acid tributyl/kerosene, its
Including:
1) the solid light wood material high oil-absorbing resins of 3.0kg and 48.0kg waste phosphoric acids tributyl/kerosene are added in disposal barrel and is mixed
3h is stood, 5.8kg Compatibility improvement agent sodium matter montmorillonites are added, 5min is stirred, paddle linear velocity 7m/s obtains solid light wood
Material-waste phosphoric acid tributyl/kerosene compound;
2) 65.0kg portland cements, 17.0kg flyash, 4.0kg silicon ashes, 4.0kg swelling agents and 1.2kg powderies are subtracted
Aqua is well mixed makes the cement-based solidified paste materials of 91.2kg, and 14.6kg water is placed in high-speed pulping machine, stirs 6min,
High-speed pulping machine paddle linear velocity 16m/s, is obtained cement-based solidified slurry;
3) described cement-based solidified slurry is added into disposal barrel, with solid light wood material-waste phosphoric acid tributyl/kerosene compound
Mixing, paddle linear velocity 10m/s stirs 4min, the curing solidified cement body for obtaining waste phosphoric acid tributyl/kerosene.
Φ 50mm × 50mm samples are prepared, is conserved to corresponding age in the environment of temperature is for 25 ± 5 DEG C, according to
GB14569.1-2011《Low, middle level radioactive waste firming body performance requirement-solidified cement body》With GB 7023-86《Radiation
The property long-term leaching test of solidification of waste body》Carry out properties test.Under 50% volume inclusion quantity, compression strength 17.8MPa,
Impact resistance, freeze-thaw resistance and anti-immersion are qualified, Cs (42d) leaching rate 4.4 × 10-4Cm/d, Ce (42d) leaching rate 3.8 ×
10-6cm/d。
Preparation method step such as embodiment 1-5 of the solidified cement body of the waste phosphoric acid tributyl/kerosene of embodiment 6-12, gives up
As shown in table 1, the preparation technology parameter of solidified cement body is as shown in table 2 for the cement solidification material component of tributyl phosphate/kerosene.
The preparation technology parameter of the waste phosphoric acid tributyl of table 2/kerosene solidified cement body
According to GB14569.1-2011《Low, middle level radioactive waste firming body performance requirement-solidified cement body》With GB
7023-86《The long-term leaching test of solidification of radwaste body》Carry out properties test, embodiment 1-12 waste phosphoric acid tri butyl ester/
The solidified cement body test result of kerosene is shown in Table 3.
The solidified cement body test result of the waste phosphoric acid tri butyl ester of table 3/kerosene
The above, is only presently preferred embodiments of the present invention, and any pro forma restriction is not made to the present invention, according to
According to any simple modification, equivalent variations and modification that the technical spirit of the present invention is made to above example, this is still fallen within
In the range of bright technical scheme.