CN105949354A - Preparation method of weak basic anion exchange resin, product of preparation method and application of product - Google Patents
Preparation method of weak basic anion exchange resin, product of preparation method and application of product Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/02—Column or bed processes
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
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- C08F2810/00—Chemical modification of a polymer
- C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
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Abstract
The invention provides a preparation method of weak basic anion exchange resin, the weak basic anion exchange resin prepared by the preparation method, and application of the weak basic anion exchange resin. The preparation method provided by the invention reasonably adopts a micro-channel fluidic device; meanwhile, a tube type reaction system is also used for implementing suspension polymerization, so that synthesized resin grains are uniform, and the quantity of functional groups is more under the same volume; a certain amount of pore-forming agent is added, so that the surfaces and inner parts of grain balls have pore channel connection structures, and the specific surface area of whole resin balls is increased, so that the aim of improving the reaction rate of an ion exchange reaction is realized; an auxiliary cross-linking agent is additionally arranged and an acrylic acid framework is introduced to accelerate the formation of an auxiliary cross-linked net-shaped structure, so that the anti-deformation capability and osmotic pressure resisting capability of the resin balls are greatly improved. The weak basic anion exchange resin is high in ion exchange rate and low in production cost, and has excellent application prospect and market potential.
Description
Technical field
The present invention relates to a kind of anion exchange resin, be specifically related to the preparation side of a kind of weak-base anion-exchange resin
Method and the weak-base anion-exchange resin prepared by this preparation method, and the purposes of this weak-base anion-exchange resin.
Background technology
Ending for the end of the year 2015, the whole world has at fortune nuclear power generating sets 438, is building nuclear power generating sets 70, nuclear energy power generation amount
Account for the 12% of whole world gross generation.Whole world nuclear power operating experience surpassed for 15660 heap years, in the mean age of fortune nuclear power generating sets
Exceed " 28 years old ".
According to China " nuclear power Long-and Medium-term Development is planned: 2005～2020 ", to the year two thousand twenty, nuclear power runs installed capacity and strives for
Reach 40,000,000 kilowatts；Nuclear power annual electricity generating capacity reaches 2600～280,000,000,000 kilowatt hours.Building and running nuclear power capacity at present
On the basis of 1696.8 ten thousand kilowatts, new operation nuclear power installed capacity about 23,000,000 kilowatts.Simultaneously, it is considered to the follow-up developments of nuclear power,
About 18,000,000 kilowatts should be kept building nuclear power capacity at the end of 2020.According to newly-started construction and the nuclear power of operation in 15 years
Construction scale is substantially estimated, nuclear power projects construction fund total demand is about 450,000,000,000 RMB, wherein, project money in 15 years
Capital demand is 90,000,000,000 yuan, funds at ther disposal of autonomy to be put into more than 5,400,000,000 yuan.
Uranium is the main nuclear fuel of nuclear power station.The rare chemical element of one that uranium is present in nature, has radiation
Property.Uranium is mainly containing three kinds of isotopes, and i.e. uranium 238, uranium 235 and uranium 234, the most only uranium 235 are fissionable nucleus elements, at neutron
Chain type nuclear fission can be occurred under Hong Ji to react, can be used as core charging and the fuel of nuclear power plant reactor of atomic bomb.Acquisition uranium is
Extremely complex series of processes, through prospect, open a mine, ore dressing, leaching ore deposit, refine the flow process such as ore deposit, refine, and concentrating and separating is wherein
Last flow process, needs the highest scientific and technological level.Obtain 1 kilogram of weapongrade uranium 235 and need 200 tons of uranium ores.
Poorer in uranium resources in China, along with developing rapidly of national economy, the development and utilization of the energy seems more to come
The most important.Nuclear energy is as one of clean energy resource, and in the whole world, particularly developed country is most popular, French, German nuclear energy profit
With accounting for more than the 70% of main energy sources.China builds up at present and is 8,700,000 kilowatts in the nuclear power station total installation of generating capacity built, it is contemplated that arrive
The year two thousand twenty is about 40,000,000 kilowatts.Greatly develop nuclear power and not only solution Chinese energy anxiety is had positive effect, and be to protect
Hold the desirable route of strategy in China deterrent capability.In China " 12 " plans, using nuclear energy as one of clean energy resource, will again
Build more than 20 nuclear power stations, enter the development epoch that the peaceful utilization of atomic energy is new.
In China, the ion exchange resin being used for extracting uranium in early days relies primarily on import, afterwards, and Ministry of Nuclear Industry's Beijing smelting
Institute takes the lead in developing the extraction process of corresponding ion exchange resin and uranium.
Total well known, when ion exchange resin being used for nuclear fuel uranium and extracting, ion-exchange reactions is reversible reaction, tree
Fat is when absorption, and forward reaction speed is more than backward reaction speed, and complexation uranium ion shows as being adsorbed, and salt ion then shows
For desorbing；During regeneration, backward reaction speed is more than forward reaction speed, and salt ion shows as being adsorbed, complexation uranium ion table
Now for desorbing.Whenever, positive reaction and back reaction are simultaneous, are only sufficiently above back reaction speed when positive reaction speed
During rate, exchanger water just meets complexation uranium ion and is adsorbed and is less than leakage index request.
But, traditional weak-base anion-exchange resin of synthesis remains in following defect at present:
(A) granularity of resin Archon is the most uniform: at present, domestic resin producer uses traditional stirring-type to suspend mostly
Polymerization is with synthetic resin Archon skeleton, due to stirring action, causes Archon granule to be linearly distributed, and granularity is uneven, and this is just
Cause to obtain specified particle size Archon then must be by means of mechanical grading.
(B) deficiency of functional group quantity: current domestic resin industry is when chlorination and amination function base are reacted, due to general
Store-through is in spheroid situation bigger than normal, and amine used when chloromethyl ether used when this causes chlorination reaction and aminating reaction cannot be a large amount of
Be rapidly introduced into ball interior, and if expect ball interior access more functional group, then generally require prolongation reaction time
Between or need to add methanol or dimethoxym ethane as extender, in order to close Archon skeleton is carried out swelling after expand, allow
Chloromethyl ether and amine enter in the micropore of skeleton, fully react with the phenyl ring of skeletal internal, thus access more function base
Group；The exchange capacity that functional group represents resin the most at most is the strongest, and cycle throughput strengthens, and regenerative agent consumes and just reduces, from
And reduce environmental pollution further.
(C) ion-exchange reactions speed is relatively low: use the resin particle of conventional suspension polymerization technique synthesis relatively slightly and to compare table
Area is less, thus when carrying out ion exchange, reaction rate is relatively low, and the ion in part water body has little time and the merit on resin
Energy radical reaction, causes Ion-leakage bigger.
(D) impermeabilisation pressure scarce capacity: after resin strip has functional group, the functional group on resin is carrying out ion exchange
With in regenerative process, spheroid the most repeatedly shrinks and expands；But traditional acrylic acid-divinylbenzene copolymer is a kind of firm
Property skeleton, ability of anti-deformation is poor, affects the fatigue strength of resin itself, thus broken；And broken resin will result in pressure
Fall is big, causes ion-exchange process to realize, affects the safety in utilization of equipment simultaneously.
Therefore, in order to overcome above-mentioned technological deficiency present in prior art, develop a kind of New-type weak alkali anion
The preparation method of exchanger resin, is one of current research emphasis of this area research staff.
Summary of the invention
For above-mentioned technical problem, particularly granularity present in prior art are uneven and velocity of ion exchange is the fastest
Technical problem, inventor intends devising a kind of preparation side of weak-base anion-exchange resin extracted for nuclear fuel uranium
Method: for drawbacks described above (A) and (B), this preparation method reasonably have employed microchannel mjector, the most also utilizes tubular type anti-
System is answered to implement suspension polymerisation, uniform to guarantee the resin particle of synthesis, and owing to introducing acrylic backbone, can protect further
Card functional group in the case of same volume is more；For drawbacks described above (C), this preparation method is utilizing microchannel fluidic cartridge
Put with tubular reactor system while, be also added with a certain amount of porogen, to ensure that particle spheres surface and inside have duct
Attachment structure, improves the specific surface area of whole resin spheroid, thus realizes improving the purpose of ion-exchange reactions speed；For upper
Stating defect (D), this preparation method not only with the addition of auxiliary crosslinking agent, also introduces acrylic backbone, to promote to form auxiliary friendship
The network structure of connection, is greatly improved resin spheroid ability of anti-deformation and impermeabilisation pressure energy power.
Therefore, a first aspect of the present invention, it is provided that the preparation method of a kind of weak-base anion-exchange resin, it includes
Following steps:
(1) at normal temperatures, acrylic acid-divinyl benzene copolymer Archon is placed in reaction vessel, immerses chloromethyl ether and carry out swollen
Swollen 2 ~ 6 hours, wherein, the quality of described chloromethyl ether was 4 ~ 6 times of described acrylic acid-divinyl benzene copolymer Archon quality；
Then, at 30 DEG C ~ 45 DEG C, reaction 9 ~ 18 hours is stirred；
(2) then, at normal temperatures, in this reaction vessel, the aqueous solution of dimethylethanolamine or polyethylene polyamine is added, heating
To 110 DEG C ~ 120 DEG C, it is gradually heating to 160 DEG C ~ 180 DEG C the most again, and maintains reaction 6 ~ 12 hours at 160 DEG C ~ 180 DEG C；
After reaction completely, it is cooled to 50 ~ 80 DEG C, drains mother solution, with pure water to pH=5 ~ 7, again drain, i.e. prepare described weak base
Property anion exchange resin；
Wherein, the quality of the aqueous solution of described dimethylethanolamine or polyethylene polyamine is that described acrylic acid-divinylbenzene is common
2 ~ 6 times of polymers Archon quality.
Preferably, in above-mentioned preparation method, described acrylic acid-divinyl benzene copolymer Archon is gel-type or macropore
Type, and the degree of cross linking is 8% ~ 16%.
Preferably, in above-mentioned preparation method, described acrylic acid-divinyl benzene copolymer Archon is according to following steps system
:
Acrylic acid, divinylbenzene are added to the mjector of microchannel with initiator, is then sent to tubular reactor system
In, and add pure water, organic dispersing agent, auxiliary crosslinking agent and porogen, fully carry out suspension polymerisation；After completing polymerization, regulation
PH, washing product, to neutral, i.e. obtains described acrylic acid-divinyl benzene copolymer Archon.
It is further preferred that in above-mentioned preparation method, described tubular reactor system includes: compressor, material preparation still,
Tubular reactor A, tubular reactor B, equipment for separating liquid from solid, collection still, aqueous phase injection device, circulating pump, and if dry pipe valve；
Acrylic acid, divinylbenzene are delivered in described material preparation still by described microchannel mjector with initiator；Further, pure
Water, organic dispersing agent, auxiliary crosslinking agent and porogen are also added respectively to described material preparation still；
Wherein, tubular reactor A and tubular reactor B series connection, on the outer wall of described tubular reactor A and tubular reactor B all
Steam heating equipment or heat tape are set, and are correspondingly provided with insulation jacket；Wherein, described compressor, for compressing
Air or compressed nitrogen are delivered in described material preparation still, and by this compressed air or compressed nitrogen, material are prepared still
The various reaction raw materials of middle storage inject tubular type reactor A, and maintaining the temperature in tubular reactor A is 80 ~ 86 DEG C, obtain required
The reaction microsphere of particle diameter；Then, reaction microsphere is pressed into tubular reactor B, and maintaining the temperature in tubular reactor B is 80 ~ 86
DEG C, carrying out sizing and solidifying, cured product microsphere slowly declines；Then, products therefrom microsphere enters described with aqueous phase
Equipment for separating liquid from solid, isolates product microsphere and aqueous phase, by collect product microsphere in described collection still the most aging, adjust
Joint pH, washing product, to neutral, prepares described acrylic acid-divinyl benzene copolymer Archon；The aqueous phase separated then flow to institute
State aqueous phase injection device, after be back to described tubular reactor B through described circulating pump；Wherein, the two of described tubular reactor A
End is provided with AND DEWATERING FOR ORIFICE STRUCTURE I and II.
A second aspect of the present invention, it is provided that a kind of weak-base anion-exchange resin, it is by first aspect present invention institute
The preparation method stated prepares, and, the structural formula of described weak-base anion-exchange resin is as follows:
Wherein, R is the alkyl of C1 ~ C30, and n is amount of monomer.
Preferably, under drying regime, weak base base >=9.0 mmol/g that described weak-base anion-exchange resin has, its
Weak acid base≤0.5 mmol/g having.
Preferably, described weak-base anion-exchange resin mass exchange capacity in the dry state is 9.0 ~ 11.0
Mmol/g, volume-exchange capacity is 2.8 ~ 4.3 mmol/ml.
A third aspect of the present invention, it is provided that the weak-base anion-exchange resin described in second aspect present invention is continuously
Purposes in bed process.
A fourth aspect of the present invention, it is provided that the weak-base anion-exchange resin described in second aspect present invention is extracting
Purposes in uranium.
The invention provides the preparation method of a kind of weak-base anion-exchange resin, solve this area research staff difficult
Following technological difficulties to solve: how to improve the functional group quantity in the case of same volume；How to improve when skeleton is polymerized
Mechanical strength of resin；How to improve the specific surface area of spheroid, thus improve reaction rate；How to synthesize uniform resin particle.
Common process for suspension polymerization, during stirring, the speed of axial line is zero, and axoplasm edge line speed is maximum, thus causes
The linear distribution on a large scale that granularity is ascending, causes granularity the most irregular；And technical scheme provided by the present invention, by closing
Reason uses microchannel mjector to implement suspension polymerisation with tubular reactor system, improves linear velocity homogenization so that granularity and
The distribution of narrow particle size becomes to be controlled, thus obtains fine size and even resin particle.Secondly, provided by the present invention
Technical scheme with the addition of auxiliary crosslinking agent when skeleton is polymerized, and has been simultaneously introduced acrylic backbone, oozes improving the antiacid alkali of resin
Pressure and the consistency of structure thoroughly, thus improve wear-resistant mechanical strength and antiacid alkali osmotic pressure intensity.Further, institute of the present invention
The technical scheme provided also with the addition of porogen when skeleton is polymerized, thus ensures that particle spheres surface and inside have duct knot
Structure, improves the specific surface area of whole spheroid, shortens ion diffusion length, reaches to improve the purpose of reaction rate, increases simultaneously
The ability of anti-deformation of spheroid.Additionally, in preparation method of the present invention, in the case of improve same volume during aminating reaction
Functional group quantity, beneficially organic amine rapidly diffuses into and carries out aminating reaction inside copolymer, and reaction fully, thus carries
High period treatment amount.
Compared with prior art, technical solutions according to the invention have following useful technique effect: (1) improves white
Ball yield, shortens the aminating reaction production cycle, improves yield, reduce production cost；The introducing of pore passage structure, it is ensured that resin
Spherome surface and inside have pore passage structure, improve the specific surface area of whole spheroid, reach to improve the purpose of reaction rate, simultaneously
Increase the ability of anti-deformation of spheroid, shorten the response time so that manufacturing cost reduces, energy-saving and cost-reducing, beneficially ecological environment；
Therefore, preparation method of the present invention and products thereof has superior application prospect and market potential.
Accompanying drawing explanation
Fig. 1 is the technique stream synthesizing described acrylic acid-divinyl benzene copolymer Archon in one embodiment of the present of invention
Journey schematic diagram；
Fig. 2 is that in one embodiment of the present of invention, the technological process of acrylic acid described in amination-divinyl benzene copolymer Archon is shown
It is intended to；
Fig. 3 is continuous bed schematic diagram；
Fig. 4 is the micropore figure of the weak-base anion-exchange resin under ultramicroscope；
Fig. 5 is the schematic flow sheet forming auxiliary crosslinking in prior art；
Fig. 6 is tubular reactor system structural representation；Wherein, 1-reaction raw materials；2-compressor；3-material preparation still；4-tubular type
Reactor A；5-tubular reactor B；41,51-insulation jacket；42,52-heat tapes；6-equipment for separating liquid from solid；61-is by army cap；
7-collects still；8-aqueous phase injection device；9-circulating pump；I-AND DEWATERING FOR ORIFICE STRUCTURE I, II-AND DEWATERING FOR ORIFICE STRUCTURE II.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further elaborated, but the present invention is not limited to following embodiment party
Formula.
A first aspect of the present invention, it is provided that the preparation method of a kind of weak-base anion-exchange resin, it includes following
Step:
(1) at normal temperatures, acrylic acid-divinyl benzene copolymer Archon is placed in reaction vessel, immerses chloromethyl ether and carry out swollen
Swollen 2 ~ 6 hours, wherein, the quality of described chloromethyl ether was 4 ~ 6 times of described acrylic acid-divinyl benzene copolymer Archon quality；
Then, at 30 DEG C ~ 45 DEG C, reaction 9 ~ 18 hours is stirred；
(2) then, at normal temperatures, in this reaction vessel, the aqueous solution of dimethylethanolamine or polyethylene polyamine is added, heating
To 110 DEG C ~ 120 DEG C, it is gradually heating to 160 DEG C ~ 180 DEG C the most again, and maintains reaction 6 ~ 12 hours at 160 DEG C ~ 180 DEG C；
After reaction completely, it is cooled to 50 ~ 80 DEG C, drains mother solution, with pure water to pH=5 ~ 7, again drain, i.e. prepare described weak base
Property anion exchange resin；
Wherein, the quality of the aqueous solution of described dimethylethanolamine or polyethylene polyamine is that described acrylic acid-divinylbenzene is common
2 ~ 6 times of polymers Archon quality.
In a preferred embodiment, described acrylic acid-divinyl benzene copolymer Archon is gel-type or macroporous type, and
The degree of cross linking is 8% ~ 16%.
In a preferred embodiment, described acrylic acid-divinyl benzene copolymer Archon prepares according to following steps:
Acrylic acid, divinylbenzene are added to the mjector of microchannel with initiator, is then sent to tubular reactor system
In, and add pure water, organic dispersing agent, auxiliary crosslinking agent and porogen, fully carry out suspension polymerisation；After completing polymerization, regulation
PH, washing product, to neutral, i.e. obtains described acrylic acid-divinyl benzene copolymer Archon.
In a further preferred embodiment, described tubular reactor system includes: compressor, material preparation still, pipe
Formula reactor A, tubular reactor B, equipment for separating liquid from solid, collection still, aqueous phase injection device, circulating pump, and if dry pipe valve；Institute
State microchannel mjector acrylic acid, divinylbenzene to be delivered in described material preparation still with initiator；Further, pure water,
Organic dispersing agent, auxiliary crosslinking agent and porogen are also added respectively to described material preparation still；
Wherein, tubular reactor A and tubular reactor B series connection, on the outer wall of described tubular reactor A and tubular reactor B all
Steam heating equipment or heat tape are set, and are correspondingly provided with insulation jacket；Wherein, described compressor, for compressing
Air or compressed nitrogen are delivered in described material preparation still, and by this compressed air or compressed nitrogen, material are prepared still
The various reaction raw materials of middle storage inject tubular type reactor A, and maintaining the temperature in tubular reactor A is 80 ~ 86 DEG C, obtain required
The reaction microsphere of particle diameter；Then, reaction microsphere is pressed into tubular reactor B, and maintaining the temperature in tubular reactor B is 80 ~ 86
DEG C, carrying out sizing and solidifying, cured product microsphere slowly declines；Then, products therefrom microsphere enters described with aqueous phase
Equipment for separating liquid from solid, isolates product microsphere and aqueous phase, by collect product microsphere in described collection still the most aging, adjust
Joint pH, washing product, to neutral, prepares described acrylic acid-divinyl benzene copolymer Archon；The aqueous phase separated then flow to institute
State aqueous phase injection device, after be back to described tubular reactor B through described circulating pump；Wherein, the two of described tubular reactor A
End is provided with AND DEWATERING FOR ORIFICE STRUCTURE I and II.
A second aspect of the present invention, it is provided that a kind of weak-base anion-exchange resin, it is by first aspect present invention institute
The preparation method stated prepares, and, the structural formula of described weak-base anion-exchange resin is as follows:
Wherein, R is the alkyl of C1 ~ C30, and n is amount of monomer.
In a preferred embodiment, under drying regime, the weak base base that described weak-base anion-exchange resin has >=
9.0 mmol/g, weak acid base≤0.5 mmol/g that it has.
In a preferred embodiment, described weak-base anion-exchange resin mass exchange in the dry state is held
Amount is 9.0 ~ 11.0 mmol/g, and volume-exchange capacity is 2.8 ~ 4.3 mmol/ml.
See Fig. 3, a third aspect of the present invention, it is provided that the weakly-basic anion exchange tree described in second aspect present invention
Fat purposes in continuous bed technique.
A fourth aspect of the present invention, it is provided that the weak-base anion-exchange resin described in second aspect present invention is extracting
Purposes in uranium.
Embodiment 1
See Fig. 1 and Fig. 6, acrylic acid, divinylbenzene are added to the mjector of microchannel with benzoyl peroxide, then
It is delivered in material preparation still 3, and is added thereto to pure water, organic dispersing agent, auxiliary crosslinking agent and porogen；Inject to aqueous phase
Device 8 adds hot water and appropriate benzoyl peroxide, pumps into tubular reactor B by circulating pump 9 and be circulated；At material
Preparation still 3 carries out mechanical agitation, by compressed nitrogen, each reaction raw materials 1(is included acrylic acid, divinylbenzene, peroxidating
Benzoyl, pure water, organic dispersing agent, auxiliary crosslinking agent and porogen) in press-in hole plate structure II, through orifice plate effect, dispersion
Become the reaction microsphere of appropriate particle size；, heated by heat tape 42 meanwhile, and keep tubular reactor A by insulation jacket 41
Interior temperature is 80 ~ 86 DEG C；Then, reaction microsphere rises, and through AND DEWATERING FOR ORIFICE STRUCTURE I, leaves described tubular reactor A, thus obtains
The microspherulite diameter of regulation；Then, heated by heat tape 52, and kept the temperature in tubular reactor B by insulation jacket 51
Degree is 80 ~ 86 DEG C, and described reaction microsphere enters tubular reactor B, and sizing and solidifying wherein, under cured microsphere is slow
Fall；Then, products therefrom microsphere enters equipment for separating liquid from solid 6 with aqueous phase, isolates solid phase acrylic acid-divinylbenzene copolymerization
Thing microsphere and aqueous phase, by collect solid phase acrylic acid-divinylbenzene copolymer microsphere in described collection still 7 the most aging,
Regulation pH, washing product, to neutral, prepares described acrylic acid-divinyl benzene copolymer Archon；The aqueous phase separated then flow to
Described aqueous phase injection device 8, after be back to described tubular reactor B through described circulating pump 9；By continuous feed, this suspension
Polyreaction can be implemented the most repeatedly.
Seeing Fig. 2, gel-type acrylic acid-divinyl benzene copolymer Archon that the degree of cross linking is 9% at normal temperatures, is put by (1)
In reaction vessel, immersing chloromethyl ether and carry out expanding 3 hours, wherein, the quality of described chloromethyl ether is described acrylic acid-divinyl
5 times of base benzene copolymer Archon quality；Then, stirring reaction 16 hours at 45 DEG C；(2) then, at normal temperatures, to this reaction
Container adds dimethylethanolamine water-soluble of 4 times that quality is described acrylic acid-divinyl benzene copolymer Archon quality
Liquid, is heated to 120 DEG C, is gradually heating to 170 DEG C the most again, and maintains reaction 8 hours at 170 DEG C；Monitoring reaction, until instead
Should be complete, it is cooled to 60 DEG C afterwards, drains mother solution, with pure water to pH=5 ~ 7, again drain, i.e. prepare described alkalescence cloudy
Ion exchange resin；Recording this weak-base anion-exchange resin mass exchange capacity in the dry state is 11.0 mmol/
G, volume-exchange capacity is 3.71 mmol/ml；The water content additionally recording this weak-base anion-exchange resin is 53.80%；
Using Particle Size Analyzer to record its mean diameter is 300 μm (seeing Fig. 4).
Embodiment 2
See Fig. 1 and Fig. 6, acrylic acid, divinylbenzene are added to the mjector of microchannel with benzoyl peroxide, then
It is delivered in material preparation still 3, and is added thereto to pure water, organic dispersing agent, auxiliary crosslinking agent and porogen；Inject to aqueous phase
Device 8 adds hot water and appropriate benzoyl peroxide, pumps into tubular reactor B by circulating pump 9 and be circulated；At material
Preparation still 3 carries out mechanical agitation, by compressed nitrogen, each reaction raw materials 1(is included acrylic acid, divinylbenzene, peroxidating
Benzoyl, pure water, organic dispersing agent, auxiliary crosslinking agent and porogen) in press-in hole plate structure II, through orifice plate effect, dispersion
Become the reaction microsphere of appropriate particle size；, heated by heat tape 42 meanwhile, and keep tubular reactor A by insulation jacket 41
Interior temperature is 80 ~ 86 DEG C；Then, reaction microsphere rises, and through AND DEWATERING FOR ORIFICE STRUCTURE I, leaves described tubular reactor A, thus obtains
The microspherulite diameter of regulation；Then, heated by heat tape 52, and kept the temperature in tubular reactor B by insulation jacket 51
Degree is 80 ~ 86 DEG C, and described reaction microsphere enters tubular reactor B, and sizing and solidifying wherein, under cured microsphere is slow
Fall；Then, products therefrom microsphere enters equipment for separating liquid from solid 6 with aqueous phase, isolates solid phase acrylic acid-divinylbenzene copolymerization
Thing microsphere and aqueous phase, by collect solid phase acrylic acid-divinylbenzene copolymer microsphere in described collection still 7 the most aging,
Regulation pH, washing product, to neutral, prepares described acrylic acid-divinyl benzene copolymer Archon；The aqueous phase separated then flow to
Described aqueous phase injection device 8, after be back to described tubular reactor B through described circulating pump 9；By continuous feed, this suspension
Polyreaction can be implemented the most repeatedly.
See Fig. 2, (1) at normal temperatures, by macroporous type acrylic acid-divinyl benzene copolymer Archon that the degree of cross linking is 12%
Being placed in reaction vessel, immerse chloromethyl ether and carry out expanding 5 hours, wherein, the quality of described chloromethyl ether is described acrylic acid-diethyl
4 times of alkenyl benzene copolymer Archon quality；Then, stirring reaction 14 hours at 35 DEG C；(2) then, at normal temperatures, anti-to this
Answer polyethylene polyamine water-soluble adding 6 times that quality is described acrylic acid-divinyl benzene copolymer Archon quality in container
Liquid, is heated to 115 DEG C, is gradually heating to 165 DEG C the most again, and maintains reaction 7 hours at 165 DEG C；Monitoring reaction, until instead
Should be complete, it is cooled to 80 DEG C afterwards, drains mother solution, with pure water to pH=5 ~ 7, again drain, i.e. prepare described alkalescence cloudy
Ion exchange resin；Recording this weak-base anion-exchange resin mass exchange capacity in the dry state is 10.83
Mmol/g, volume-exchange capacity is 3.72 mmol/ml；The water content additionally recording this weak-base anion-exchange resin is
52.93 %；Using Particle Size Analyzer to record its mean diameter is 330 μm (seeing Fig. 4).
In the above-described embodiments, effectively use auxiliary crosslinking agent and porogen, in Archon polymerization process, rely on auxiliary
Cross-linking agent forms resilient, crosslinked framework with acrylic acid-divinylbenzene copolymer rigid structure, thus ensures that spheroid is suffering the external world
Do not crush when mechanical presses and chemosmosis pressure, even if deformation also can recover deformation at short notice；So, it is ensured that bone
Frame spheroid meets the ability of anti-deformation of special processing needs under complex environment system.Additionally, auxiliary crosslinking agent and porogen, third
The use in conjunction of olefin(e) acid skeleton, advantageously forms the network structure of auxiliary crosslinking, is greatly improved spheroid ability of anti-deformation and impervious
Pressure energy power, improves the exchange capacity of product in actual production and substantially reduces the response time, thus improve yield thoroughly,
Save again the input of equipment simultaneously, save fund, energy-saving and cost-reducing, significantly improve production efficiency.
Being described in detail the specific embodiment of the present invention above, but it is intended only as example, the present invention does not limit
It is formed on particular embodiments described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and
Substitute the most all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Amendment, all should contain within the scope of the invention.
Claims (9)
1. the preparation method of a weak-base anion-exchange resin, it is characterised in that comprise the following steps:
(1) at normal temperatures, acrylic acid-divinyl benzene copolymer Archon is placed in reaction vessel, immerses chloromethyl ether and carry out swollen
Swollen 2 ~ 6 hours, wherein, the quality of described chloromethyl ether was 4 ~ 6 times of described acrylic acid-divinyl benzene copolymer Archon quality；
Then, at 30 DEG C ~ 45 DEG C, reaction 9 ~ 18 hours is stirred；
(2) then, at normal temperatures, in this reaction vessel, the aqueous solution of dimethylethanolamine or polyethylene polyamine is added, heating
To 110 DEG C ~ 120 DEG C, it is gradually heating to 160 DEG C ~ 180 DEG C the most again, and maintains reaction 6 ~ 12 hours at 160 DEG C ~ 180 DEG C；
After reaction completely, it is cooled to 50 ~ 80 DEG C, drains mother solution, with pure water to pH=5 ~ 7, again drain, i.e. prepare described weak base
Property anion exchange resin；
Wherein, the quality of the aqueous solution of described dimethylethanolamine or polyethylene polyamine is that described acrylic acid-divinylbenzene is common
2 ~ 6 times of polymers Archon quality.
Preparation method the most according to claim 1, it is characterised in that described acrylic acid-divinyl benzene copolymer Archon
For gel-type or macroporous type, and the degree of cross linking is 8% ~ 16%.
Preparation method the most according to claim 1, it is characterised in that described acrylic acid-divinyl benzene copolymer Archon
Prepare according to following steps:
Acrylic acid, divinylbenzene are added to the mjector of microchannel with initiator, is then sent to tubular reactor system
In, and add pure water, organic dispersing agent, auxiliary crosslinking agent and porogen, fully carry out suspension polymerisation；After completing polymerization, regulation
PH, washing product, to neutral, i.e. obtains described acrylic acid-divinyl benzene copolymer Archon.
Preparation method the most according to claim 3, it is characterised in that described tubular reactor system includes: compressor, material
Preparation still, tubular reactor A, tubular reactor B, equipment for separating liquid from solid, collect still, aqueous phase injection device, circulating pump, Yi Jiruo
Dry pipe valve；Acrylic acid, divinylbenzene are delivered in described material preparation still by described microchannel mjector with initiator；And
And, pure water, organic dispersing agent, auxiliary crosslinking agent and porogen are also added respectively to described material preparation still；
Wherein, tubular reactor A and tubular reactor B series connection, on the outer wall of described tubular reactor A and tubular reactor B all
Steam heating equipment or heat tape are set, and are correspondingly provided with insulation jacket；Wherein, described compressor, for compressing
Air or compressed nitrogen are delivered in described material preparation still, and by this compressed air or compressed nitrogen, material are prepared still
The various reaction raw materials of middle storage inject tubular type reactor A, and maintaining the temperature in tubular reactor A is 80 ~ 86 DEG C, obtain required
The reaction microsphere of particle diameter；Then, reaction microsphere is pressed into tubular reactor B, and maintaining the temperature in tubular reactor B is 80 ~ 86
DEG C, carrying out sizing and solidifying, cured product microsphere slowly declines；Then, products therefrom microsphere enters described with aqueous phase
Equipment for separating liquid from solid, isolates product microsphere and aqueous phase, by collect product microsphere in described collection still the most aging, adjust
Joint pH, washing product, to neutral, prepares described acrylic acid-divinyl benzene copolymer Archon；The aqueous phase separated then flow to institute
State aqueous phase injection device, after be back to described tubular reactor B through described circulating pump；Wherein, the two of described tubular reactor A
End is provided with AND DEWATERING FOR ORIFICE STRUCTURE I and II.
5. a weak-base anion-exchange resin, it is characterised in that it is by the preparation side according to any one of claim 1 ~ 4
Method prepares, and, the structural formula of described weak-base anion-exchange resin is as follows:
Wherein, R is the alkyl of C1 ~ C30, and n is amount of monomer.
Weak-base anion-exchange resin the most according to claim 5, it is characterised in that under drying regime, it has
Weak base base >=9.0 mmol/g, weak acid base≤0.5 mmol/g that it has.
Weak-base anion-exchange resin the most according to claim 5, it is characterised in that the quality under its drying regime is handed over
Changing capacity is 9.0 ~ 11.0 mmol/g, and volume-exchange capacity is 2.8 ~ 4.3 mmol/ml.
8. according to the purposes in continuous bed technique of the weak-base anion-exchange resin according to any one of claim 5 ~ 7.
9. according to the weak-base anion-exchange resin according to any one of claim 5 ~ 7 in the purposes extracted in uranium.
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| CN106378212A (en) * | 2016-09-27 | 2017-02-08 | 南京工程学院 | Branched-structure-containing weakly-acidic cation exchange resin and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85104153A (en) * | 1985-06-03 | 1986-12-03 | 核工业部北京第五研究所 | The synthetic method of acrylate type weakly basic anionic ionexchange resin |
| CN101954299A (en) * | 2009-07-15 | 2011-01-26 | 中国船舶重工集团公司第七一八研究所 | Method for preparing anion exchange resin |
| CN102372812A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Macroporous strong alkaline carbon nanotube composite ion exchange resin and preparation method thereof |
| EP2564925A1 (en) * | 2011-08-31 | 2013-03-06 | Dow Global Technologies LLC | Shell functionalized ion exchange resins |
| CN103755846A (en) * | 2013-12-27 | 2014-04-30 | 宁波争光树脂有限公司 | Synthetic method of high temperature-resistant strongly basic anion exchange resin |
-
2016
- 2016-07-07 CN CN201610531159.5A patent/CN105949354B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85104153A (en) * | 1985-06-03 | 1986-12-03 | 核工业部北京第五研究所 | The synthetic method of acrylate type weakly basic anionic ionexchange resin |
| CN101954299A (en) * | 2009-07-15 | 2011-01-26 | 中国船舶重工集团公司第七一八研究所 | Method for preparing anion exchange resin |
| CN102372812A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Macroporous strong alkaline carbon nanotube composite ion exchange resin and preparation method thereof |
| EP2564925A1 (en) * | 2011-08-31 | 2013-03-06 | Dow Global Technologies LLC | Shell functionalized ion exchange resins |
| CN103755846A (en) * | 2013-12-27 | 2014-04-30 | 宁波争光树脂有限公司 | Synthetic method of high temperature-resistant strongly basic anion exchange resin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106378212A (en) * | 2016-09-27 | 2017-02-08 | 南京工程学院 | Branched-structure-containing weakly-acidic cation exchange resin and preparation method thereof |
| CN106378212B (en) * | 2016-09-27 | 2018-11-23 | 南京工程学院 | A kind of weak-acid cation-exchange resin and preparation method thereof containing branched structure |
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