CN102391399A - Preparation method for chelating ion exchange resin using inorganic substance as matrix - Google Patents
Preparation method for chelating ion exchange resin using inorganic substance as matrix Download PDFInfo
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Abstract
The invention belongs to the technical field of macromolecular ion exchange resin, and relates to a preparation method for chelating ion exchange resin. The preparation method comprises the following steps of: acidizing a matrix by using acid under the heating condition; washing the matrix by using deionized water until the matrix is neutral; allowing damp air in a sodium bromide or potassium bromide saturated solution reaction kettle to enter the matrix which is treated in the previous steps, so that a water molecule single layer is generated on the surface of the matrix; performing silanization reaction on the hydrated matrix, alkane and a silane coupling agent to obtain a silanized matrix; performing grafting reaction on the silanized matrix and multi-amino polymer to obtain a functional resin material; and performing Mannick reaction on the functional resin material, formaldehyde and phosphorous acid so as to obtain the final chelating ion exchange resin using an inorganic substance as the matrix. The method has the advantages that the operation process is short and the method is convenient to operate. A reagent is not required to be added into an ion exchange column when noble metal ions are adsorbed, so pollution and wastes are avoided.
Description
Technical field
The invention belongs to macroion exchange resin technical field, relate to a kind of preparation method of chelating ion exchange resin.
Background technology
Polymer huge legendary turtle resin is as a kind of functional high molecule material; Have synthetic easy, loading capacity big, be prone to wash-out, do not produce advantages such as secondary pollution and good stability, receive widely in organic chemical waste water, the fields such as waste water treatment that contain heavy metal ion and paying close attention to.Compare with ion exchange resin, the binding ability of huge legendary turtle resin and metals ion is stronger, and selectivity is higher, is widely used in aspects such as enrichment, separation, analysis, recovery metals ion.Development novel high polymer huge legendary turtle resin also is used for metal recovery and aspect such as environment protection is the focus of Recent study always.
The main kind, functional group with ligating atom to the chelating ability of precious metal ion of resin is relevant with the physique of the bonding state of high polymer main chain, resin matrix, so generally according to this resin is classified.
Classifying by the kind of the ligating atom of resin or functional group is modal sorting technique, because be easy to predict the adsorption selectivity of resin to metals ion from the kind of ligating atom and functional group, instructs the design of resin synthetic.By the kind of ligating atom resin is divided into and contains oxygen type, nitrogenous type, sulfur-type, phosphorous type, contain arsenic type and mixed type resin; Can be divided into carboxylic acid type (COOH), polyester type (COOR), polyether-type (ROR '-), polyamine type (NH-), guanidine radicals type [N (C=N) NH by functional group
2], schiff's base type (C=N-), acid amide type (CONH
2), aminocarboxylic acid type [NCH
2(COOH)
2], thioalcohol type (SH), polythioether type (RSR '-), dithiocarboxylic acid type (CSSH), thiocarbamide type [N (C=S) NH
2] etc.
The compound method of resin is similar basically with ion exchange resin, and the one, contain the monomeric polymerization of functional group, the one, the macromolecular scaffold modification.Latter preparation method is simple, and that adopts at present is more, but the content of functional group receives the restriction of parent physics and chemical structure in its reaction efficiency and the product; The resin functional group of monomer polymerization method preparation be evenly distributed and content high, the key that adopts this legal system to be equipped with resin is to select the appropriate resin moulding process, the preparation particle diameter is even, specific surface area big, swelling behavior and the good resin of physical strength.In addition, the means that adopt physically modified or chemical graft are arranged also, compound new resin phase on matrix, the report of preparation composite adsorbing material, this method provides a kind of new way for the use properties that improves resin.
The mechanism of resin adsorbing metal ions mainly is function atom and the metals ion generation coordination reaction on the resin, forms the rock steady structure of similar small molecules inner complex, and the mechanism of ion exchange resin absorption is electrostatic interaction.Therefore, compare with ion exchange resin, the bonding force of resin and metals ion is stronger, and selectivity is also higher, can be widely used in aspects such as the recovery separation of each metal ion species, amino acid whose fractionation and hydrometallurgy, public pollution control.Resin separating metal ionic principle is as shown in Figure 1.
Among Fig. 1, ch is a functional group, and some metals ion is had specific complex ability, therefore can these metals ions and other separation of metal ions be come.Resin is owing to having the special selected separation function, and is therefore rising, studied the successful 30 polytype products that have.The chelating ion exchange resin of relevant organic polymer/inorganic mineral material hydridization is seen also being difficult on the market.
In recent years, utilize chemical process at immobilized specific function polymer of solid surface or group, being used for enriching noble metals or selectively removing heavy metal ion has become the focus that people pay close attention to.Adopt the resin method from waste water, to reclaim or remove metals ion, this method has a lot of advantages, as resin can repeatedly reuse, production cost is low etc.The resin major part of using at present is preparing carriers with synthetic macromolecule; Because it exists that mechanical property is lower, thermostability is relatively poor, with the metallochemistry linkage force more weak and adsorption time shortcomings such as length, cost height, so scientists is still at the continuous better sorbent material of searching.Wherein silica gel and many inorganic mineral nano materials, vesicular structure high with its Heat stability is good, physical strength or multilayered structure and surface area ratio are easier to advantage such as control and by broad research; Particularly a large amount of activated silica hydroxyls are contained on the silica gel surface; Can carry out surface chemistry bonding or modification at an easy rate, thereby receive increasing concern.
Got into since 21 century, nano material is because its good characteristic is widely used in the productive life field.Most important components is exactly an inorganic nano material in the nano material; And non-metallic minerals (silica gel, natural mineral kaolin-halloysite nanotubes, attapulgite, kaolin, zeyssatite etc.) nano material is the main body of inorganic nano material; Because its raw material is easy to get; Processing and preparing technology is simple relatively, has low production cost, is easy to many advantages such as large-scale production; So it will become in the nanosecond science and technology such as nano material and nano composite material and have suitability most, and the agent technology product of development potentiality is arranged most.
Summary of the invention
The object of the present invention is to provide a kind of inorganics is the preparation method of the chelating ion exchange resin of matrix, and this method operating process is brief, when adsorbing precious metal ion, need not in ion exchange column, to add any reagent, pollution-free.
To achieve these goals, the technical scheme that the present invention taked is: a kind of inorganics is the preparation method of the chelating ion exchange resin of matrix, it is characterized in that it comprises the steps:
1) be 5kg: 25～30L by matrix with sour proportioning, choose matrix and acid, subsequent use; Described matrix is silica gel, natural mineral kaolin-halloysite nanotubes, attapulgite, kaolin or zeyssatite etc.;
Under 60～120 ℃ of conditions; With acid matrix is carried out acidification (acid and matrix mix stirring); Acidification 12～24h; Be cooled to room temperature then; Obtain the matrix after the acidification by filtration; Be neutral with the matrix washing of deionized water after until it again, be dried to constant weight, obtain pretreated matrix acidification;
2) damp atmosphere that bromizates sodium saturated solution or Potassium Bromide saturated solution reaction kettle gets into and to be equipped with in the pretreated matrix, makes matrix surface generate the water molecules individual layer, and obtaining water ratio is the hydration matrix of 6～10wt%;
3) proportioning by matrix, alkane, silane coupling agent is 5kg: 9～10L: 2～2.5kg, chooses alkane and silane coupling agent;
Hydration matrix and alkane and silane coupling agent are mixed, after reacting 18～24h under the room temperature, filter, washing, dry (to recording matrix rate of body weight gain 10～16% o'clock taking-up), obtain the silylanization matrix;
4) proportioning by matrix, polyamines based polyalcohol is 5kg: 5～6kg, chooses the polyamines based polyalcohol; Proportioning by matrix, deionized water, methyl alcohol is 5kg: 10～11L: 5～6L, chooses deionized water and methyl alcohol; The adding of silylanization matrix is equipped with in the reaction kettle of stirring, in reaction kettle, adds the polyamines based polyalcohol, in reaction kettle, add deionized water and methyl alcohol; In whipping process, vacuumize 15min; Vacuum tightness in the reaction kettle is 20～60mm Hg, then at 50～100 ℃ of following graft reaction 24～48h, after graft reaction finishes; Filter, wash, be dried to constant weight, obtain the grafting matrix;
5) proportioning by matrix, HCl, phosphorous acid, formaldehyde is 5kg: 20～25L: 2.5～3kg: 3.5～4L, chooses HCl, phosphorous acid and formaldehyde;
The adding of grafting matrix being equipped with in the reaction kettle of stirring, adding HCl and phosphorous acid, is under 80～100 ℃ in temperature, adds formaldehyde, behind 80～100 ℃ of reaction 24h, washs, is dried to constant weight, obtains the chelating ion exchange resin that inorganics is a matrix.
Press such scheme, described natural mineral kaolin-halloysite nanotubes obtains through following treatment process: after getting the washing of kaolin raw material process, filtration, oven dry, ball milling, obtain kaolin powder; Solid-liquid weight ratio according to the sodium hexametaphosphate solution of kaolin powder and 0.2-1mol/L is 1: 5, adds the sodium hexametaphosphate solution of 0.2-1mol/L in the kaolin powder, mixes, and 80-100 ℃ is stirred 4-6h, filters, washing and dry, obtains the s.t. sample; According to s.t. sample and concentration is that the weight ratio of the polyacrylic acid solution of 1-5wt% is 1: 1; Adding concentration in the s.t. sample is the polyacrylic acid solution of 1-5wt%; Mix; 90-100 ℃ is stirred 10-15h, passes through filtration, washing, drying and ball milling again, obtains natural mineral kaolin-halloysite nanotubes (or claiming halloysite nanotubes).Commercially available halloysite nanotubes also can be used among the present invention.Described halloysite nanotubes is natural many walls nanotube that a kind of kaolinite lamella curls and forms under natural condition, and chemical formula is Al
4[Si
4O
10] (OH)
8.nH
2O, external diameter is about 10-60nm, and internal diameter is about 5-20nm, and length is about 2-40 μ m.
Described silica gel, attapulgite, kaolin, zeyssatite etc. have Heat stability is good, physical strength height, pore structure and surface area ratio and are easier to advantages such as control; Particularly a large amount of activated silica hydroxyls are contained on the silica gel surface; Can carry out surface chemistry bonding or modification at an easy rate, thereby receive increasing concern.
Press such scheme, the said acid of step 1) is any one or any mixture more than two kinds in hydrochloric acid, nitric acid, the sulfuric acid, and any is any proportioning when mixing more than two kinds.
Press such scheme, described alkane is any one or any mixture more than two kinds in butane, pentane, hexane, heptane, the octane, and any is any proportioning when mixing more than two kinds.
Press such scheme; Described silane coupling agent is any one or any mixture more than two kinds in γ-(methacryloxy) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, chloropropyl trichloro-silane, r-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane, the 3-epoxypropyl Trimethoxy silane, and any is any proportioning when mixing more than two kinds.
Press such scheme, described polyamines based polyalcohol is any one the perhaps two kinds of mixing in polyallylamine, the polymine, is any proportioning during two kinds of mixing.The molecular weight of polymkeric substance (weight-average molecular weight) does not wait from 1000-1000000 and all can be used for the present invention.
The invention has the beneficial effects as follows: compare with existing chelating ion exchange resin; The present invention with derive from natural cheapness, be easy to get, stable silica gel, halloysite nanotubes, attapulgite, kaolin, zeyssatite etc. is matrix; Can make full use of their microcosmic nano effect; Improve its ion exchange capacity, effectively improve the usefulness of ion exchange resin; After the polyamines based polyalcohol modification through the differing mol quality, the usefulness of carrying out the ion exchange resin of Mannich reaction gained with formaldehyde and phosphorous acid again can be effectively improved.
It is brief that this method has operating process, and easy to operate advantage when adsorbing precious metal ion such as rare earth, nickel, cobalt, copper or gold, need not in ion exchange column, to add any reagent, pollution-free and do not produce any waste.
Description of drawings
Fig. 1 is a resin separating metal ion principle schematic.
Fig. 2 is a synthesis process flow diagram of the present invention.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with accompanying drawing, embodiment, but content of the present invention not only is confined to following embodiment; Should not be regarded as limitation of the present invention yet.
Through embodiment the present invention is elaborated below, but should not be regarded as limitation of the present invention.Wherein, Experimental example 1-6 synthetic is that silica gel is the chelating ion exchange resin of matrix; Experimental example 7-12 synthetic is that halloysite nanotubes is the chelating ion exchange resin of matrix; Experimental example 13 synthetic are that attapulgite is the chelating ion exchange resin of matrix, and experimental example 14 synthetic are that kaolin is the chelating ion exchange resin of matrix, and embodiment 15 synthetic are that zeyssatite is the chelating ion exchange resin of matrix.
Embodiment 1:
The adding of 5kg silica gel is equipped with in the corrosion resistant reaction kettle of stirring, adds 30L, 1MHCl then, vacuumizing 15min final vacuum degree is 40mm Hg, the beginning heated and boiled, and stirring velocity is unsuitable too fast, is controlled at below 70 rev/mins, in order to avoid damage silica gel.In 80 ℃ of following stirring and pickling 12h of bubble point temperature, logical then cooling water temperature is emitted silica gel when temperature of charge is reduced to room temperature.The silica gel of emitting is through filtering elimination filtrating; Respectively wash 2 times with deionized water and methyl alcohol successively again, when washing water show neutrality, stop washing, carry out separating of silica gel and water; Dry silica gel then to constant weight, obtain through pickling and be dried to the silica gel (pretreated matrix) of constant weight.Being placed on the sand formula funnel through pickling and the silica gel that is dried to constant weight; The damp atmosphere that bromizates the sodium saturated solution gets in the sand formula funnel through rubber tubing; Make the silica gel surface generate the water molecules individual layer; When the water ratio that records hydrated silica gel was 7wt%, hydration was accomplished, and obtains the hydrated silica gel that water ratio is 7wt% (being the hydration matrix).
Hydrated silica gel is put into the corrosion resistant reaction kettle that another is equipped with stirring, in reaction kettle, add the heptane of 10L and 2.5 kilograms chloropropyl triethoxysilane respectively, slowly mix then.Behind reaction 18h under the room temperature; Carry out separating of silica gel and solution; Use normal hexane and methanol wash more successively; The silica gel of washing is put in the moisture eliminator and dries, and taking-up when recording silica gel rate of body weight gain 16% [{ (silanized silica gel-hydrated silica gel)/hydrated silica gel * 100%=16%] promptly obtains silanized silica gel.
The silanized silica gel adding is equipped with in the corrosion resistant reaction kettle of stirring; In reaction kettle, add 6 kilograms of polyallylamine (PAA respectively; Mw=1.7 ten thousand), 10L deionized water and 5L methyl alcohol, slowly vacuumizing 15min in the whipping process, vacuum tightness be 30mmHg then in reacting kettle jacketing logical hot water make that temperature of charge is 65 ℃ in the reaction kettle; Stir 36h, the silica gel to recording grafting after be former silica gel quality more than 1.0 times the time grafting completion.After graft reaction finishes, grafting silica gel through filtering and solution separating, is washed 2 times with deionized water wash 4 times, one normal caustic wash(ing) 1 time, de-ionized washing 3 times and methyl alcohol successively, then with drying materials to constant weight, promptly get middle resin-1.
Resin-1 in the middle of this added be equipped with in the corrosion resistant reaction kettle of stirring, add 25L, 2MHCl and 3 kilograms of phosphorous acid respectively, logical hot water makes that temperature of charge is 95 ℃ in the reaction kettle in reacting kettle jacketing; Stir and slowly add 4L, 37.7wt% formaldehyde simultaneously; Behind 95 ℃ of reaction 24h, wash 2 times with deionized water successively, 1 mole of every liter of NaOH washes 1 time; De-ionized is washed 3 times, 1MH
2SO
4Wash 1 time, methyl alcohol is washed 3 times, then with drying materials to constant weight, obtain the chelating ion exchange resin that silica gel of the present invention is matrix (being that inorganics is the chelating ion exchange resin of matrix).
Embodiment 2:
5 kilograms of silica gel addings are equipped with in the corrosion resistant reaction kettle of stirring, add 30L, 1MHNO then
3, vacuumize 15min after, vacuum tightness is 30mm Hg, begins to be heated to 100 ℃ and boils, stirring velocity is unsuitable too fast, is controlled at below 70 rev/mins, in order to avoid damage silica gel.In 80 ℃ of following stirring and pickling 12h of bubble point temperature, logical then cooling water temperature is emitted silica gel when temperature of charge is reduced to room temperature.The silica gel of emitting is respectively washed 2 times with deionized water and methyl alcohol through filtering elimination filtrating more successively, when washing water show neutrality, stops washing, carries out separating of silica gel and water, dries silica gel then to constant weight.Being placed on the sand formula funnel through pickling and the silica gel that is dried to constant weight; The damp atmosphere that bromizates the potassium saturated solution gets in the sand formula funnel through rubber tubing; Make the silica gel surface generate the water molecules individual layer; To the water ratio that records hydrated silica gel is 7% o'clock, and hydration is accomplished, and obtains the hydrated silica gel that water ratio is 7wt%.
Hydrated silica gel is put into the corrosion resistant reaction kettle that another is equipped with stirring, in reaction kettle, add the normal hexane of 10L and γ-(methacryloxy) propyl trimethoxy silicane of 2.5 kilograms respectively, slowly mix then.Behind reaction 18h under the room temperature, carry out separating of silica gel and solution, wash with normal hexane and methyl alcohol successively again, the silica gel that washs is put in the moisture eliminator dries, taking-up when recording silica gel rate of body weight gain 16% promptly obtains silanized silica gel.
The silanized silica gel adding is equipped with in the corrosion resistant reaction kettle of stirring; In reaction kettle, add 6 kilograms of polymines (PEI, Mw=3 ten thousand), 10L deionized water and 5L methyl alcohol respectively, slowly vacuumizing 15min in the whipping process; Vacuum tightness is 20mmHg; Logical hot water makes that temperature of charge is 65 ℃ in the reaction kettle in reacting kettle jacketing then, stirs 36h, the silica gel to recording grafting after be former silica gel quality more than 1.0 times the time grafting completion.After graft reaction finishes, grafting silica gel through filtering and solution separating, is washed 2 times with deionized water wash 4 times, one normal caustic wash(ing) 1 time, de-ionized washing 3 times and methyl alcohol successively, then with drying materials to constant weight, promptly get middle resin-1.
Resin-1 in the middle of this added be equipped with in the corrosion resistant reaction kettle of stirring, add 25L, 2MHCl and 3 kilograms of phosphorous acid respectively, logical hot water makes that temperature of charge is 95 ℃ in the reaction kettle in reacting kettle jacketing; Stir and slowly add 4L, 37.7wt% formaldehyde simultaneously; Behind 95 ℃ of reaction 24h, wash 2 times with deionized water successively, 1 mole of every liter of NaOH washes 1 time; De-ionized is washed 3 times, 1MH
2SO
4Wash 1 time, methyl alcohol is washed 3 times, then with drying materials to constant weight, obtain the chelating ion exchange resin that silica gel of the present invention is matrix.
Embodiment 3:
Using weight-average molecular weight instead except the polyallylamine molecular weight is 50,000, and other conditions are identical with embodiment 1.
Embodiment 4:
Except silane coupling agent γ-(methacryloxy) propyl trimethoxy silicane changes into the 3-epoxypropyl Trimethoxy silane, other conditions are identical with embodiment 2.
Embodiment 5:
Except polyallylamine changed polymine into, other conditions were identical with embodiment 1.
Embodiment 6:
Except polymine changed polyallylamine into, other conditions were identical with embodiment 2.
Embodiment 7:
5 kilograms of natural mineral kaolin-halloysite nanotubes (or claim halloysite nanotubes) are added be equipped with in the corrosion resistant reaction kettle of stirring, then the 1MH of adding 25L in the reaction kettle
2SO
4After vacuumizing 15min, vacuum tightness is 45mm Hg, begins to be heated to boiling.At 100 ℃ of following stirring and pickling 24h of boiling temperature, when reducing to normal temperature, temperature emits material.The material of emitting is respectively washed 2 times with deionized water and methyl alcohol through filtering back elimination acid solution more successively, when washing water show neutrality, stops washing, carries out separating of halloysite and water, and the oven dry halloysite is to constant weight.Being placed on the sand formula funnel through pickling and the halloysite that is dried to constant weight; The damp atmosphere that bromizates the potassium saturated solution gets in the sand formula funnel through rubber tubing, makes the halloysite surface generate the water molecules individual layer, is 6% o'clock to the water ratio that records hydration silicon halloysite; Hydration is accomplished, and obtains hydrated halloysite.
Described natural mineral kaolin-halloysite nanotubes obtains through following treatment process: after getting the washing of kaolin raw material process, filtration, oven dry, ball milling, obtain kaolin powder; Solid-liquid weight ratio according to the sodium hexametaphosphate solution of kaolin powder and 0.2-1mol/L is 1: 5, adds the sodium hexametaphosphate solution of 0.2-1mol/L in the kaolin powder, mixes, and 80-100 ℃ is stirred 4-6h, filters, washing and dry, obtains the s.t. sample; According to s.t. sample and concentration is that the weight ratio of the polyacrylic acid solution of 1-5wt% is 1: 1; Adding concentration in the s.t. sample is the polyacrylic acid solution of 1-5wt%; Mix; 90-100 ℃ is stirred 10-15h, passes through filtration, washing, drying and ball milling again, obtains natural mineral kaolin-halloysite nanotubes (or claiming halloysite nanotubes).
Hydrated halloysite is put into the corrosion resistant reaction kettle that another is equipped with stirring, in reaction kettle, add the normal heptane of 9L and 2.0 kilograms 3-epoxypropyl Trimethoxy silane respectively, slowly mix then.Behind reaction 24h under the room temperature, carry out separating of halloysite and solution, wash with normal hexane and methyl alcohol successively again, the halloysite that washs is put in the moisture eliminator dries, taking-up when recording halloysite rate of body weight gain 16% promptly obtains the silylanization halloysite.
The adding of silylanization halloysite is equipped with in the corrosion resistant reaction kettle of stirring; In reaction kettle, add 5 kilograms of polyallylamines (PAA, Mw=1.5 ten thousand), 11L deionized water and 6L methyl alcohol respectively, slowly vacuumizing 15min in the whipping process; Vacuum tightness is 25mm Hg; Logical hot water makes that temperature of charge is 65 ℃ in the reaction kettle in reacting kettle jacketing then, stirs 36h, the halloysite to recording grafting after be former halloysite quality more than 1.0 times the time grafting completion.After graft reaction finishes, the grafting halloysite through filtering and solution separating, is washed 2 times with deionized water wash 4 times, one normal caustic wash(ing) 1 time, de-ionized washing 3 times and methyl alcohol successively, then with drying materials to constant weight, promptly get middle resin-1.
Resin-1 in the middle of this added be equipped with in the corrosion resistant reaction kettle of stirring, add 20L, 2MHCl and 2.5 kilograms of phosphorous acid respectively, logical hot water makes that temperature of charge is 95 ℃ in the reaction kettle in reacting kettle jacketing; Stir and slowly add 3.5L, 37.7wt% formaldehyde simultaneously; Behind 95 ℃ of reaction 24h, wash 2 times with deionized water successively, 1 mole of every liter of NaOH washes 1 time; De-ionized is washed 3 times, 1MH
2SO
4Wash 1 time, methyl alcohol is washed 3 times, then with drying materials to constant weight, obtain the chelating ion exchange resin that halloysite nanotubes of the present invention is a matrix.
Embodiment 8:
5 kilograms of halloysite nanotubes (commercially available halloysite nanotubes) are added be equipped with in the corrosion resistant reaction kettle of stirring, then the 1MH of adding 25L in the reaction kettle
2SO
4After vacuumizing 15min, vacuum tightness is 60mm Hg, begins to be heated to boiling.At 90 ℃ of following stirring and pickling 24h of boiling temperature, when reducing to normal temperature, temperature emits material.The material of emitting is respectively washed 2 times with deionized water and methyl alcohol through filtering back elimination acid solution more successively, when washing water show neutrality, stops washing, carries out separating of halloysite and water, and the oven dry halloysite is to constant weight.Being placed on the sand formula funnel through pickling and the halloysite that is dried to constant weight; The damp atmosphere that bromizates the sodium saturated solution gets in the sand formula funnel through rubber tubing, makes the halloysite surface generate the water molecules individual layer, is 6% o'clock to the water ratio that records hydration silicon halloysite; Hydration is accomplished, and obtains hydrated halloysite.
Hydrated halloysite is put into the corrosion resistant reaction kettle that another is equipped with stirring, in reaction kettle, add the octane of 9L and γ-(methacryloxy) propyl trimethoxy silicane of 2.0 kilograms respectively, slowly mix then.Behind reaction 24h under the room temperature, carry out separate (filtering separation) of halloysite and solution, wash with normal hexane and methyl alcohol successively again, the halloysite that washs is put in the moisture eliminator dries, taking-up when recording halloysite rate of body weight gain 16% promptly obtains the silylanization halloysite.
The adding of silylanization halloysite is equipped with in the corrosion resistant reaction kettle of stirring; In reaction kettle, add 5 kilograms of polyallylamines (PAA, Mw=5 ten thousand), 11L deionized water and 6L methyl alcohol respectively, slowly vacuumizing 15min in the whipping process; Vacuum tightness is 30mmHg; Logical hot water makes that temperature of charge is 65 ℃ in the reaction kettle in reacting kettle jacketing then, stirs 36h, the halloysite to recording grafting after be former halloysite quality more than 1.0 times the time grafting completion.After graft reaction finishes, the grafting halloysite through filtering and solution separating, is washed 2 times with deionized water wash 4 times, one normal caustic wash(ing) 1 time, de-ionized washing 3 times and methyl alcohol successively, then with drying materials to constant weight, promptly get middle resin-1.
Resin-1 in the middle of this added be equipped with in the corrosion resistant reaction kettle of stirring, add 20L, 2MHCl and 2.5 kilograms of phosphorous acid respectively, logical hot water makes that temperature of charge is 95 ℃ in the reaction kettle in reacting kettle jacketing; Stir and slowly add 3.5L, 37.7wt% formaldehyde simultaneously; Behind 95 ℃ of reaction 24h, wash 2 times with deionized water successively, 1 mole of every liter of NaOH washes 1 time; De-ionized is washed 3 times, 1MH
2SO
4Wash 1 time, methyl alcohol is washed 3 times, then with drying materials to constant weight, obtain the chelating ion exchange resin that halloysite nanotubes of the present invention is a matrix.
Embodiment 9:
Except normal heptane changed normal hexane into, other conditions were identical with embodiment 7.
Embodiment 10:
Except 3-epoxypropyl Trimethoxy silane changes chloropropyl trichloro-silane into, other conditions are identical with embodiment 7.
Embodiment 11:
Using weight-average molecular weight instead except the polyallylamine molecular weight is 10,000, and other conditions are identical with embodiment 8.
Embodiment 12:
Except polyallylamine substitutes for the polymine, other conditions are identical with embodiment 7.
Embodiment 13:
5 kilograms of attapulgites addings are equipped with in the corrosion resistant reaction kettle of stirring, add 30L, 1MH then
2SO
4, vacuumize 15min after, vacuum tightness is 20mm Hg, vigorous stirring pickling 12h under 80 ℃ of conditions, logical then cooling water temperature is emitted attapulgite when temperature of charge is reduced to room temperature.The attapulgite of emitting is respectively washed 2 times with deionized water and methyl alcohol through filtering elimination filtrating more successively, when washing water show neutrality, stops washing, carries out separating of attapulgite and water, dries attapulgite then to constant weight.Being placed on the sand formula funnel through pickling and the attapulgite that is dried to constant weight; The damp atmosphere that bromizates the sodium saturated solution gets in the sand formula funnel through rubber tubing; Make the attapulgite surface generate the water molecules individual layer; To the water ratio that records the hydration attapulgite is 10% o'clock, and hydration is accomplished, and obtains the hydration attapulgite.
The hydration attapulgite is put into the corrosion resistant reaction kettle that another is equipped with stirring, add the chloropropyl trichloro-silane of 5L heptane, 5L hexane and 2.5 kilograms respectively in the reaction kettle, slowly mix then.Behind reaction 18h under the room temperature, carry out separating of attapulgite and solution, wash with normal hexane and methyl alcohol successively again, the attapulgite that washs is put in the moisture eliminator dries, taking-up when recording attapulgite rate of body weight gain 10% promptly obtains the silylanization attapulgite.
The adding of silylanization attapulgite is equipped with in the corrosion resistant reaction kettle of stirring; In reaction kettle, add 6 kilograms of polymines (PEI, Mw=1.7 ten thousand), 10L deionized water and 5L methyl alcohol respectively, slowly vacuumizing 15min in the whipping process; Vacuum tightness is 30mm Hg; Logical hot water makes that temperature of charge is 65 ℃ in the reaction kettle in reacting kettle jacketing then, stirs 36h, the attapulgite to recording grafting after be former attapulgite quality more than 1.0 times the time grafting completion.After graft reaction finishes; The grafting attapulgite is passed through to filter and solution separating; Wash 2 times with deionized water wash 4 times, one normal caustic wash(ing) 1 time, de-ionized washing 3 times and methyl alcohol successively, then with drying materials to constant weight, promptly get centre resin-2 (being the grafting matrix).
Resin-2 in the middle of this added be equipped with in the corrosion resistant reaction kettle of stirring, add 25L, 2MHCl and 3 kilograms of phosphorous acid respectively, logical hot water makes that temperature of charge is 95 ℃ in the reaction kettle in reacting kettle jacketing; Stir and slowly add 4L, 37.7wt% formaldehyde simultaneously; Behind 95 ℃ of reaction 24h, wash 2 times with deionized water successively, 1 mole of every liter of NaOH washes 1 time; De-ionized is washed 3 times, 1MH
2SO
4Wash 1 time, methyl alcohol is washed 3 times, then with drying materials to constant weight, obtain the chelating ion exchange resin that attapulgite of the present invention is a matrix.
Embodiment 14:
5 kilograms of kaolin are added be equipped with in the corrosion resistant reaction kettle of stirring, then the 1MH of adding 25L in the reaction kettle
2SO
4After vacuumizing 15min, vacuum tightness is 30mm Hg, begins to be heated to boiling.At 95 ℃ of following stirring and pickling 18h of boiling temperature, when reducing to normal temperature, temperature emits material.The material of emitting is respectively washed 2 times with deionized water and methyl alcohol through filtering back elimination acid solution more successively, when washing water show neutrality, stops washing, carries out separating of kaolin and water, and oven dry kaolin is to constant weight.Being placed on the sand formula funnel through pickling and the kaolin that is dried to constant weight; The damp atmosphere that bromizates the potassium saturated solution gets in the sand formula funnel through rubber tubing, makes the kaolin surface generate the water molecules individual layer, is 6% o'clock to the water ratio that records hydrous kaolin; Hydration is accomplished, and obtains hydrous kaolin.
Hydrous kaolin is put into the corrosion resistant reaction kettle that another is equipped with stirring, in reaction kettle, add the octane of 9L and γ-(methacryloxy) propyl trimethoxy silicane of 2.0 kilograms respectively, slowly mix then.Behind reaction 24h under the room temperature, carry out separating of kaolin and solution, wash with normal hexane and methyl alcohol successively again, the kaolin that washs is put in the moisture eliminator dries, taking-up when recording kaolin rate of body weight gain 16% promptly obtains silylanization kaolin.
The adding of silylanization kaolin is equipped with in the corrosion resistant reaction kettle of stirring; In reaction kettle, add 5 kilograms of polyallylamines (PAA, Mw=5 ten thousand), 11L deionized water and 6L methyl alcohol respectively, slowly vacuumizing 15min in the whipping process; Vacuum tightness is 50mmHg; Logical hot water makes that temperature of charge is 65 ℃ in the reaction kettle in reacting kettle jacketing then, stirs 36h, the kaolin to recording grafting after be the protokaolin quality more than 1.0 times the time grafting completion.After graft reaction finishes, grafting kaolin through filtering and solution separating, is washed 2 times with deionized water wash 4 times, one normal caustic wash(ing) 1 time, de-ionized washing 3 times and methyl alcohol successively, then with drying materials to constant weight, promptly get middle resin-1.
Resin-1 in the middle of this added be equipped with in the corrosion resistant reaction kettle of stirring, add 20L, 2MHCl and 2.5 kilograms of phosphorous acid respectively, logical hot water makes that temperature of charge is 95 ℃ in the reaction kettle in reacting kettle jacketing; Stir and slowly add 3.5L, 37.7wt% formaldehyde simultaneously; Behind 95 ℃ of reaction 24h, wash 2 times with deionized water successively, 1 mole of every liter of NaOH washes 1 time; De-ionized is washed 3 times, 1MH
2SO
4Wash 1 time, methyl alcohol is washed 3 times, then with drying materials to constant weight, obtain the chelating ion exchange resin that kaolin of the present invention is matrix.
Embodiment 15:
5 kilograms of zeyssatite addings are equipped with in the corrosion resistant reaction kettle of stirring, add 30L, 1MH then
2SO
4, vacuumize 15min after, vacuum tightness is 30mm Hg, vigorous stirring pickling 24h under 60 ℃ of conditions, logical then cooling water temperature is emitted zeyssatite when temperature of charge is reduced to room temperature.The attapulgite of emitting is respectively washed 2 times with deionized water and methyl alcohol through filtering elimination filtrating more successively, when washing water show neutrality, stops washing, carries out separating of zeyssatite and water, dries zeyssatite then to constant weight.Being placed on the sand formula funnel through pickling and the zeyssatite that is dried to constant weight; The damp atmosphere that bromizates the potassium saturated solution gets in the sand formula funnel through rubber tubing, makes the zeyssatite surface generate the water molecules individual layer, is 7% o'clock to recording the diatomaceous water ratio of hydration; Hydration is accomplished, and obtains hydration zeyssatite.
Hydration zeyssatite is put into the corrosion resistant reaction kettle that another is equipped with stirring, in reaction kettle, add the heptane of 10L and 2.5 kilograms chloropropyl triethoxysilane respectively, slowly mix then.Behind reaction 18h under the room temperature, carry out separating of zeyssatite and solution, wash with normal hexane and methyl alcohol successively again, the zeyssatite that washs is put in the moisture eliminator dries, taking-up when recording zeyssatite rate of body weight gain 10% promptly obtains the silylanization attapulgite.
The adding of silylanization zeyssatite is equipped with in the corrosion resistant reaction kettle of stirring; In reaction kettle, add 6 kilograms of polymines (PEI, Mw=1.7 ten thousand), 10L deionized water and 5L methyl alcohol respectively, slowly vacuumizing 15min in the whipping process; Vacuum tightness is 40mm Hg; Logical hot water makes that temperature of charge is 65 ℃ in the reaction kettle in reacting kettle jacketing then, stirs 36h, the zeyssatite to recording grafting after be former zeyssatite quality more than 0.5 times the time grafting completion.After graft reaction finishes, grafting zeyssatite through filtering and solution separating, is washed 2 times with deionized water wash 4 times, one normal caustic wash(ing) 1 time, de-ionized washing 3 times and methyl alcohol successively, then with drying materials to constant weight, promptly get middle resin-2.
Middle resin-2 added be equipped with in the corrosion resistant reaction kettle of stirring, add 25L, 2MHCl and 3 kilograms of phosphorous acid respectively, logical hot water makes that temperature of charge is 95 ℃ in the reaction kettle in reacting kettle jacketing; Stir and slowly add 4L, 37.7wt% formaldehyde simultaneously; Behind 95 ℃ of reaction 24h, wash 2 times with deionized water successively, 1 mole of every liter of NaOH washes 1 time; De-ionized is washed 3 times, 1MH
2SO
4Wash 1 time, methyl alcohol is washed 3 times, then with drying materials to constant weight, obtain the chelating ion exchange resin that zeyssatite of the present invention is matrix.
Embodiment 16:
Basic identical with embodiment 15, difference is: after vacuumizing 15min, and vigorous stirring pickling 24h under 120 ℃ of conditions.
Embodiment 17:
Basic identical with embodiment 15; Difference is: heptane is replaced by butane; Chloropropyl triethoxysilane is replaced by γ-glycidyl ether oxygen propyl trimethoxy silicane, and polymine is replaced by polyallylamine, polymine, and the weight of polyallylamine, polymine respectively accounts for 1/2.
Embodiment 18:
Basic identical with embodiment 15, difference is: heptane is replaced by pentane, and chloropropyl triethoxysilane is replaced by r-chloropropyl trimethoxyl silane and chloropropyl trichloro-silane, and the weight of r-chloropropyl trimethoxyl silane and chloropropyl trichloro-silane respectively accounts for 1/2.
Embodiment 19:
Basic identical with embodiment 15, difference is: the molecular weight of polymine (weight-average molecular weight) is 1000.
Embodiment 20:
Basic identical with embodiment 15, difference is: the molecular weight of polymine (weight-average molecular weight) is 1000000.
Embodiment 21:
Basic identical with embodiment 15, difference is: the graft reaction temperature changes 50 ℃ into for 65 ℃, and the graft reaction time, 36h changed 24h into; " behind 95 ℃ of reaction 24h " changes " behind 80 ℃ of reaction 24h " into.
Embodiment 22:
Basic identical with embodiment 15, difference is: the graft reaction temperature changes 100 ℃ into for 65 ℃, and the graft reaction time, 36h changed 48h into; " behind 95 ℃ of reaction 24h " changes " behind 100 ℃ of reaction 24h " into.
Embodiment 1-22 when adsorbing precious metal ion, need not in ion exchange column, to add any reagent, pollution-free.
Each raw material that the present invention is cited, and the bound value of each raw material, with and interval value, can both realize the present invention; And the bound value of each processing parameter (like temperature, time etc.), with and interval value, can both realize the present invention, do not enumerate embodiment one by one at this.
Main performance index of the present invention and measuring method:
The outward appearance of the foregoing description 1-6,13,14 products: range estimation, the white solid powder is qualified, the outward appearance of embodiment 7-12 product: the chocolate pressed powder is qualified, the outward appearance of embodiment 15 products: the light yellow solid powder is qualified.
Following through performance is measured example the present invention is elaborated, but should not be regarded as limitation of the present invention.Wherein performance measurement example 1 is for silica gel being the detection that the chelating ion exchange resin of matrix is used to adsorb rare earth ion cerium (III); Performance measurement example 2 is for the halloysite nanotubes being the detection that the chelating ion exchange resin of matrix is used for Adsorption of Heavy Metal Ions nickel (II); Performance measurement example 3 is for the attapulgite being the detection that the chelating ion exchange resin of matrix is used to adsorb rare earth ion lanthanum (III); Performance measurement example 4 is for kaolin being the detection that the chelating ion exchange resin of matrix is used to adsorb rare earth ion europium (III), and performance measurement example 5 is for zeyssatite being the detection that the chelating ion exchange resin of matrix is used to adsorb rare earth ion yttrium (III).Performance measurement example 6 is for kaolin being the detection that the chelating ion exchange resin of matrix is used for Adsorption of Heavy Metal Ions cobalt (II).Performance measurement example 7 is for silica gel being the detection that the chelating ion exchange resin of matrix is used for Adsorption of Heavy Metal Ions copper (II).Performance measurement example 8 is the detection that the chelating ion exchange resin of matrix is used for Adsorption of Heavy Metal Ions gold (III) for attapulgite.
1.1 with silica gel is the test that the chelating ion exchange resin of matrix is used to adsorb rare earth ion, is example with rare earth cerium (III).
Cerium (III) standardized solution is by spectroscopically pure Ce (NO
3)
36H
2The O preparation; Oxalic acid-CPA-mA mixing solutions: 4 parts of 17.6g/L oxalic acid solutions mix with a 0.15g/LCPA-mA solution and are made into, the mixed once amount press the sample analyzed what and decide; Other reagent are analytical pure.
1.2 adsorption equilibrium test and analytical procedure
Adsorption equilibrium test is carried out on HZ9212S type digital display constant temperature water bath vibrator, accurately takes by weighing a certain amount of resin of anticipating in the round-bottomed flask that has a mouth of pipe, adds zero(ppm) water and a certain amount of cerium (III) reference liquid of certain volume; Vacuumize 15min, at room temperature vibrate, pipette the filtrating of 1ml after resin absorption to adsorption equilibrium; Add oxalic acid-CPA-mA solution 20ml; Shake up,, survey its absorbancy in the 669nm wavelength with the absorption vessel of 3cm light path; Substitution equation of linear regression: A=0.0285C-0.0092 (ug/ml) then, R
2=0.9998, try to achieve the equilibrium concentration Ce (mg/mL) of aqueous phase cerium (III).
Be calculated as follows adsorptive capacity Q
R(mg/g), partition ratio D and adsorption rate E%.
Q
R＝(C
0-Ce)V/W
D＝Q
R/Ce
E(％)＝(C
0-Ce)/C
0*100％
Initial concentration and equilibrium concentration (mg/mL); W is dried resin weight (g); V is water volume (mL).
1.3 desorption experiment
Take by weighing the 15.0mg dried resin, add HAc-NaAc damping fluid and a certain amount of cerium (III) standardized solution of pH=5.70, measure water cerium (III) concentration after the balance, try to achieve resin cerium (III) ionic adsorptive capacity.Tell the residue water, wash resin three times with damping fluid then, add strippant again, vibration records water cerium (III) after the balance) content, try to achieve desorption efficiency.
Accurately take by weighing the 1.0g resin, at T=298K, [Ce
3+]
0Under=17.0mg/mL the condition; Undertaken by above-mentioned adsorption experiment method; Trying to achieve every gram resin (embodiment 2) is 196mg to the loading capacity of cerium (III); Every gram resin (embodiment 3) is 182mg to the loading capacity of cerium (III), and every gram resin (embodiment 4) is 167mg to the loading capacity of cerium (III), and every gram resin (embodiment 5) is 154mg to the loading capacity of cerium (III).
Performance measurement instance 2
2.1 with halloysite nanotubes is the test that the chelating ion exchange resin of matrix is used for Adsorption of Heavy Metal Ions, is example with metallic nickel (II).
The nickel standardized solution is by spectroscopically pure NiCl
26H
2The O preparation; PH 2.6～6.2 damping fluids are by HAc-NaAc; Colour developing liquid: 8g EDTA disodium salt and 7g ammonium chloride are dissolved in the 57mL strong aqua, add water to 100mL; Other reagent are analytical pure.
2.2 adsorption equilibrium test and analytical procedure
The adsorption equilibrium test is carried out on HZ9212S type digital display constant temperature water bath vibrator; Accurately take by weighing a certain amount of resin of anticipating in the round-bottomed flask that has a mouth of pipe, add 1mol/LHCl and a certain amount of nickel ion reference liquid of certain volume, vacuumize 15min; At room temperature vibrate to adsorption equilibrium; Pipette 5.00mL through the filtrating after the resin absorption in the 50mL volumetric flask, add 10mL colour developing liquid, add water to scale and shake up.Measure Ax value, substitution equation of linear regression A=0.2889C+0.0087, R in the 374nm place with spectrophotometry
2=0.9989, try to achieve the equilibrium concentration Ce (mg/mL) of aqueous phase nickel ion, make reference with the de-ionized pure water.
Be calculated as follows adsorptive capacity Q
R(mg/g), partition ratio D and adsorption rate E%.
Q
R＝(C
0-Ce)V/W
D＝Q
R/Ce
E(％)＝(C
0-Ce)/C
0*100％
In the formula: Q
RAdsorptive capacity (mg/g dried resin) for every gram resin under the equilibrium state; C
0, Ce is respectively aqueous phase ionic initial concentration and equilibrium concentration (mg/mL); W is dried resin weight (g); V is water volume (mL).
2.3 desorption experiment
Take by weighing the 15.0mg dried resin, add HAc-NaAc damping fluid and a certain amount of nickel (II) standardized solution of pH=5.70, measure water nickel (II) concentration after the balance, try to achieve resin nickel (II) ionic adsorptive capacity.Tell the residue water, wash resin three times with damping fluid then, add strippant again, record the content of water nickel (II) after the vibration balance, try to achieve desorption efficiency.
Accurately take by weighing the 1.0g resin, at T=298K, [Ni
2+]
0Under=13.0mg/mL the condition; Undertaken by above-mentioned adsorption experiment method; Trying to achieve every gram resin (embodiment 8) is 156mg to the loading capacity of nickel ion; Every gram resin (embodiment 10) is 148mg to the loading capacity of nickel ion, and every gram resin (embodiment 11) is 139mg to the loading capacity of nickel ion, and every gram resin (embodiment 12) is 130mg to the loading capacity of nickel ion.
3.1 with attapulgite is the test that the chelating ion exchange resin of matrix is used to adsorb rare earth ion, is example with lanthanoid metal (III).
The lanthanum standardized solution is by spectroscopically pure La
2O
3Preparation; PH 2.6 ∽ 6.2 damping fluids are by HAc-NaAc; Colour developing liquid: trolamine-HNO of 0.1% arsenazo I solution and pH=7.2
3Buffered soln adds water to 100mL; Other reagent are analytical pure.
3.2 adsorption equilibrium test and analytical procedure
The adsorption equilibrium test is carried out on HZ9212S type digital display constant temperature water bath vibrator; Accurately take by weighing a certain amount of resin of anticipating in the round-bottomed flask that has a mouth of pipe, add 1mol/LHCl and a certain amount of lanthanum ion reference liquid of certain volume, vacuumize 15min; At room temperature vibrate to adsorption equilibrium; Pipette 5.00mL through the filtrating after the resin absorption in the 50mL volumetric flask, add 10mL colour developing liquid, add water to scale and shake up.Measure Ax value, substitution equation of linear regression A=8.86C+0.037, R in the 656nm place with spectrophotometry
2=0.9981, try to achieve the equilibrium concentration Ce (mg/mL) of aqueous phase lanthanum ion, make reference with the de-ionized pure water.
Be calculated as follows adsorptive capacity Q
R(mg/g), partition ratio D and adsorption rate E%.
Q
R＝(C
0-Ce)V/W
D＝Q
R/Ce
E(％)＝(C
0-Ce)/C
0*100％
In the formula: Q
RAdsorptive capacity (mg/g dried resin) for every gram resin under the equilibrium state; C
0, Ce is respectively aqueous phase ionic initial concentration and equilibrium concentration (mg/mL); W is dried resin weight (g); V is water volume (mL).
3.3 desorption experiment
Take by weighing the 15.0mg dried resin, add HAc-NaAc damping fluid and a certain amount of lanthanum standardized solution of pH=5.70, measure the water la concn after the balance, try to achieve the adsorptive capacity of resin lanthanum ion.Tell the residue water, wash resin three times with damping fluid then, add strippant again, record the content of water lanthanum after the vibration balance, try to achieve desorption efficiency.
Accurately take by weighing the 15mg.0g resin, at T=298K, [La
3+]
0Under=133.0mg/L the condition, undertaken by above-mentioned adsorption experiment method, trying to achieve every gram resin (embodiment 13) is 188mg to the loading capacity of lanthanum ion.
Performance measurement instance 4
4.1 with kaolin is the test that the chelating ion exchange resin of matrix is used to adsorb rare earth ion, is example with metal europium (III).
The europium standardized solution is by spectroscopically pure Eu
2O
3Preparation; PH 2.6 ∽ 6.2 damping fluids are by HAc-NaAc; Colour developing liquid: trolamine-HNO of 0.1% arsenazo I solution and pH=7.2
3Buffered soln adds water to 100mL; Other reagent are analytical pure.
4.2 adsorption equilibrium test and analytical procedure
The adsorption equilibrium test is carried out on HZ9212S type digital display constant temperature water bath vibrator; Accurately take by weighing a certain amount of resin of anticipating in the round-bottomed flask that has a mouth of pipe, add 1mol/LHCl and a certain amount of europium ion reference liquid of certain volume, vacuumize 15min; At room temperature vibrate to adsorption equilibrium; Pipette 5.00mL through the filtrating after the resin absorption in the 50mL volumetric flask, add 10mL colour developing liquid, add water to scale and shake up.Measure Ax value, substitution equation of linear regression A=0.0012C+0.00254, R in the 570nm place with spectrophotometry
2=0.9999, try to achieve the equilibrium concentration Ce (mg/mL) of aqueous phase europium ion, make reference with the de-ionized pure water.
Be calculated as follows adsorptive capacity Q
R(mg/g), partition ratio D and adsorption rate E%.
Q
R＝(C
0-Ce)V/W
D＝Q
R/Ce
E(％)＝(C
0-Ce)/C
0*100％
In the formula: Q
RAdsorptive capacity (mg/g dried resin) for every gram resin under the equilibrium state; C
0, Ce is respectively aqueous phase ionic initial concentration and equilibrium concentration (mg/mL); W is dried resin weight (g); V is water volume (mL).
4.3 desorption experiment
Take by weighing the 15.0mg dried resin, add HAc-NaAc damping fluid and a certain amount of europium standardized solution of pH=5.70, measure water europium concentration after the balance, try to achieve the adsorptive capacity of resin europium ion.Tell the residue water, wash resin three times with damping fluid then, add strippant again, record the content of water europium after the vibration balance, try to achieve desorption efficiency.
Accurately take by weighing the 15mg.0g resin, at T=298K, [Eu
3+]
0Under=4.0mg/25mL the condition, undertaken by above-mentioned adsorption experiment method, trying to achieve every gram resin (embodiment 14) is 195mg to the loading capacity of europium ion.
Performance measurement instance 5
5.1 with zeyssatite is the test that the chelating ion exchange resin of matrix is used to adsorb rare earth ion, is example with metallic yttrium (III).
The yttrium standardized solution is by spectroscopically pure Y
2O
3Preparation; PH 2.6 ∽ 6.2 damping fluids are by HAc-NaAc; Colour developing liquid: trolamine-HNO of 0.1% arsenazo I solution and pH=7.2
3Buffered soln adds water to 100mL; Other reagent are analytical pure.
5.2 adsorption equilibrium test and analytical procedure
The adsorption equilibrium test is carried out on HZ9212S type digital display constant temperature water bath vibrator; Accurately take by weighing a certain amount of resin of anticipating in the round-bottomed flask that has a mouth of pipe, add 1mol/LHCl and a certain amount of ruthenium ion reference liquid of certain volume, vacuumize 15min; At room temperature vibrate to adsorption equilibrium; Pipette 5.00mL through the filtrating after the resin absorption in the 50mL volumetric flask, add 10mL colour developing liquid, add water to scale and shake up.Measure Ax value, substitution equation of linear regression A=2.81C+0.00184, R in the 570nm place with spectrophotometry
2=0.9689, try to achieve the equilibrium concentration Ce (mg/mL) of aqueous phase ruthenium ion, make reference with the de-ionized pure water.
Be calculated as follows adsorptive capacity Q
R(mg/g), partition ratio D and adsorption rate E%.
Q
R＝(C
0-Ce)V/W
D＝Q
R/Ce
E(％)＝(C
0-Ce)/C
0*100％
In the formula: Q
RAdsorptive capacity (mg/g dried resin) for every gram resin under the equilibrium state; C
0, Ce is respectively aqueous phase ionic initial concentration and equilibrium concentration (mg/mL); W is dried resin weight (g); V is water volume (mL).
5.3 desorption experiment
Take by weighing the 15.0mg dried resin, add HAc-NaAc damping fluid and a certain amount of yttrium standardized solution of pH=5.70, measure water yttrium concentration after the balance, try to achieve the adsorptive capacity of resin ruthenium ion.Tell the residue water, wash resin three times with damping fluid then, add strippant again, record the content of water yttrium after the vibration balance, try to achieve desorption efficiency.
Accurately take by weighing the 15mg.0g resin, at T=298K, [Y
3+]
0Under=4.0mg/30mL the condition, undertaken by above-mentioned adsorption experiment method, trying to achieve every gram resin (embodiment 15) is 140mg to the loading capacity of ruthenium ion.
Performance measurement instance 6
4.1 with kaolin is the test that the chelating ion exchange resin of matrix is used for Adsorption of Heavy Metal Ions, is example with cobalt metal (II).
Cobalt standard solution is by spectroscopically pure CoCl
26H
2The O preparation; PH 2.6 ∽ 6.2 damping fluids are by HAc-NaAc; Colour developing liquid: 0.5% xylenol orange developer adds water to 100mL; Other reagent are analytical pure.
4.2 adsorption equilibrium test and analytical procedure
The adsorption equilibrium test is carried out on HZ9212S type digital display constant temperature water bath vibrator; Accurately take by weighing a certain amount of resin of anticipating in the round-bottomed flask that has a mouth of pipe, add 1mol/LHCl and a certain amount of cobalt ion reference liquid of certain volume, vacuumize 15min; At room temperature vibrate to adsorption equilibrium; Pipette 5.00mL through the filtrating after the resin absorption in the 50mL volumetric flask, add 10mL colour developing liquid, add water to scale and shake up.Measure Ax value, substitution equation of linear regression A=0.294C+2.36, R in the 570nm place with spectrophotometry
2=0.9912, try to achieve the equilibrium concentration Co (mg/mL) of aqueous phase cobalt ion, make reference with the de-ionized pure water.
Be calculated as follows adsorptive capacity Q
R(mg/g), partition ratio D and adsorption rate E%.
Q
R＝(C
0-Ce)V/W
D＝Q
R/Ce
E(％)＝(C
0-Ce)/C
0*100％
In the formula: Q
RAdsorptive capacity (mg/g dried resin) for every gram resin under the equilibrium state; C
0, Ce is respectively aqueous phase ionic initial concentration and equilibrium concentration (mg/mL); W is dried resin weight (g); V is water volume (mL).
4.3 desorption experiment
Take by weighing the 15.0mg dried resin, add HAc-NaAc damping fluid and a certain amount of europium standardized solution of pH=5.70, measure the water cobalt concentration after the balance, try to achieve the adsorptive capacity of resin cobalt ion.Tell the residue water, wash resin three times with damping fluid then, add strippant again, record the content of water europium after the vibration balance, try to achieve desorption efficiency.
Accurately take by weighing the 15mg.0g resin, at T=298K, [Co
2+]
0Under=100 μ g/mL conditions, undertaken by above-mentioned adsorption experiment method, trying to achieve every gram resin (embodiment 8) is 127mg to the loading capacity of cobalt ion.
Performance measurement instance 7
1.1 with silica gel is the test that the chelating ion exchange resin of matrix is used for Adsorption of Heavy Metal Ions, is example with metallic copper (II).
Copper (II) standardized solution is by spectroscopically pure Cu (SO
4)
35H
2The O preparation; PH 3.6 ∽ 6.2 damping fluids are by HAc-NaAc; Colour developing liquid: 0.5% xylenol orange developer adds water to 100mL; Other reagent are analytical pure.
1.2 adsorption equilibrium test and analytical procedure
Adsorption equilibrium test is carried out on HZ9212S type digital display constant temperature water bath vibrator, accurately takes by weighing a certain amount of resin of anticipating in the round-bottomed flask that has a mouth of pipe, adds zero(ppm) water and a certain amount of cupric ion reference liquid of certain volume; Vacuumize 15min, at room temperature vibrate, pipette the filtrating of 1ml after resin absorption to adsorption equilibrium; The xylenol orange solution 20ml of adding 0.5%; Shake up,, survey its absorbancy in the 576.3nm wavelength with the absorption vessel of 3cm light path; Substitution equation of linear regression: A=0.005015C-0.0059 (ug/ml) then, R
2=0.9882, try to achieve the equilibrium concentration Ce (mg/mL) of aqueous phase copper.
Be calculated as follows adsorptive capacity Q
R(mg/g), partition ratio D and adsorption rate E%.
Q
R＝(C
0-Ce)V/W
D＝Q
R/Ce
E(％)＝(C
0-Ce)/C
0*100％
Initial concentration and equilibrium concentration (mg/mL); W is dried resin weight (g); V is water volume (mL).
1.3 desorption experiment
Take by weighing the 15.0mg dried resin, add HAc-NaAc damping fluid and a certain amount of copper standardized solution of pH=5.70, measure water copper concentration after the balance, try to achieve the adsorptive capacity of resin cupric ion.Tell the residue water, wash resin three times with damping fluid then, add strippant again, record the content of water copper after the vibration balance, try to achieve desorption efficiency.
Accurately take by weighing the 1.0g resin, at T=298K, [Cu
2+]
0Under=267 μ g/mL conditions; Undertaken by above-mentioned adsorption experiment method; Trying to achieve every gram resin (embodiment 2) is 238mg to the loading capacity of copper, and every gram resin (embodiment 3) is 245mg to the loading capacity of copper, and every gram resin (embodiment 11) is 257mg to the loading capacity of copper.
Performance measurement instance 8
3.1 with attapulgite is the test that the chelating ion exchange resin of matrix is used for adsorbing metal ions, is example with metallic gold (III).
The proof gold of gold (III) standardized solution 99.99%, chloroazotic acid, KCl preparation; PH 2.0 ∽ 6.0 damping fluids are by HAc-NaAc; Colour developing liquid: the ethanolic soln of 0.02% sulfo-Michler's keton adds water to 100mL; Other reagent are analytical pure.
3.2 adsorption equilibrium test and analytical procedure
The adsorption equilibrium test is carried out on HZ9212S type digital display constant temperature water bath vibrator; Accurately take by weighing a certain amount of resin of anticipating in the round-bottomed flask that has a mouth of pipe, add 1mol/LHCl and a certain amount of gold (III) ion reference liquid of certain volume, vacuumize 15min; At room temperature vibrate to adsorption equilibrium; Pipette 5.00mL through the filtrating after the resin absorption in the 50mL volumetric flask, add 10mL colour developing liquid, add water to scale and shake up.Measure Ax value, substitution equation of linear regression A=0.0000194C-0.492, R in the 540nm place with spectrophotometry
2=0.9992, try to achieve aqueous phase gold (III) ionic equilibrium concentration Ce (mg/mL), make reference with the de-ionized pure water.
Be calculated as follows adsorptive capacity Q
R(mg/g), partition ratio D and adsorption rate E%.
Q
R＝(C
0-Ce)V/W
D＝Q
R/Ce
E(％)＝(C
0-Ce)/C
0*100％
In the formula: Q
RAdsorptive capacity (mg/g dried resin) for every gram resin under the equilibrium state; C
0, Ce is respectively aqueous phase ionic initial concentration and equilibrium concentration (mg/mL); W is dried resin weight (g); V is water volume (mL).
3.3 desorption experiment
Take by weighing the 15.0mg dried resin, add HAc-NaAc damping fluid and a certain amount of gold (III) standardized solution of pH=5.70, measure water gold (III) concentration after the balance, try to achieve resin gold (III) ionic adsorptive capacity.Tell the residue water, wash resin three times with damping fluid then, add strippant again, record the content of water gold (III) after the vibration balance, try to achieve desorption efficiency.
Accurately take by weighing the 15mg.0g resin, at T=298K, [Au
3+]=600mg/L is undertaken by above-mentioned adsorption experiment method, and trying to achieve every gram resin (embodiment 15) is 828.36mg to gold (III) ionic loading capacity.
The product of this invention of above-mentioned performance measurement instance explanation has good adsorption effect to rare earth and precious metal ion, and flow process is simple, easy to operate, need not in IX firmly, to add any reagent, pollution-free and do not produce any waste.
Chelating resin according to the invention can be used for equally other metals ions absorption (like rare earth, nickel, cobalt, copper, gold, silver, etc.), explanation no longer one by one here.
Claims (6)
1. the preparation method that inorganics is the chelating ion exchange resin of matrix is characterized in that it comprises the steps:
1) be 5kg: 25～30L by matrix with sour proportioning, choose matrix and acid, subsequent use; Described matrix is silica gel, natural mineral kaolin-halloysite nanotubes, attapulgite, kaolin or zeyssatite etc.;
Under 60～120 ℃ of conditions, matrix is carried out acidification, acidification 12～24h with acid; Be cooled to room temperature then, obtain the matrix after the acidification, be neutral with the matrix washing of deionized water after until it again acidification through filtration; Be dried to constant weight, obtain pretreated matrix;
2) damp atmosphere that bromizates sodium saturated solution or Potassium Bromide saturated solution reaction kettle gets into and to be equipped with in the pretreated matrix, makes matrix surface generate the water molecules individual layer, and obtaining water ratio is the hydration matrix of 6～10wt%;
3) proportioning by matrix, alkane, silane coupling agent is 5kg: 9～10L: 2～2.5kg, chooses alkane and silane coupling agent;
Hydration matrix and alkane and silane coupling agent are mixed, after reacting 18～24h under the room temperature, filter, washing, dry (to recording matrix rate of body weight gain 10～16% o'clock taking-up), obtain the silylanization matrix;
4) proportioning by matrix, polyamines based polyalcohol is 5kg: 5～6kg, chooses the polyamines based polyalcohol; Proportioning by matrix, deionized water, methyl alcohol is 5kg: 10～11L: 5～6L, chooses deionized water and methyl alcohol; The adding of silylanization matrix is equipped with in the reaction kettle of stirring, in reaction kettle, adds the polyamines based polyalcohol, in reaction kettle, add deionized water and methyl alcohol; In whipping process, vacuumize 15min; Vacuum tightness in the reaction kettle is 20～60mm Hg, then at 50～100 ℃ of following graft reaction 24～48h, after graft reaction finishes; Filter, wash, be dried to constant weight, obtain the grafting matrix;
5) proportioning by matrix, HCl, phosphorous acid, formaldehyde is 5kg: 20～25L: 2.5～3kg: 3.5～4L, chooses HCl, phosphorous acid and formaldehyde;
The adding of grafting matrix being equipped with in the reaction kettle of stirring, adding HCl and phosphorous acid, is under 80～100 ℃ in temperature, adds formaldehyde, behind 80～100 ℃ of reaction 24h, washs, is dried to constant weight, obtains the chelating ion exchange resin that inorganics is a matrix.
2. a kind of inorganics according to claim 1 is the preparation method of the chelating ion exchange resin of matrix; It is characterized in that: described natural mineral kaolin-halloysite nanotubes obtains through following treatment process: after getting the washing of kaolin raw material process, filtration, oven dry, ball milling, obtain kaolin powder; Solid-liquid weight ratio according to the sodium hexametaphosphate solution of kaolin powder and 0.2-1mol/L is 1: 5, adds the sodium hexametaphosphate solution of 0.2-1mol/L in the kaolin powder, mixes, and 80-100 ℃ is stirred 4-6h, filters, washing and dry, obtains the s.t. sample; According to s.t. sample and concentration is that the weight ratio of the polyacrylic acid solution of 1-5wt% is 1: 1; Adding concentration in the s.t. sample is the polyacrylic acid solution of 1-5wt%; Mix; 90-100 ℃ is stirred 10-15h, passes through filtration, washing, drying and ball milling again, obtains natural mineral kaolin-halloysite nanotubes.
3. a kind of inorganics according to claim 1 is the preparation method of the chelating ion exchange resin of matrix; It is characterized in that: the said acid of step 1) is any one or any mixture more than two kinds in hydrochloric acid, nitric acid, the sulfuric acid, and any is any proportioning when mixing more than two kinds.
4. a kind of inorganics according to claim 1 is the preparation method of the chelating ion exchange resin of matrix; It is characterized in that: described alkane is any one or any mixture more than two kinds in butane, pentane, hexane, heptane, the octane, and any is any proportioning when mixing more than two kinds.
5. a kind of inorganics according to claim 1 is the preparation method of the chelating ion exchange resin of matrix; It is characterized in that: described silane coupling agent is any one or any mixture more than two kinds in γ-(methacryloxy) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, chloropropyl trichloro-silane, r-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane, the 3-epoxypropyl Trimethoxy silane, and any is any proportioning when mixing more than two kinds.
6. a kind of inorganics according to claim 1 is the preparation method of the chelating ion exchange resin of matrix; It is characterized in that: described polyamines based polyalcohol is any one the perhaps two kinds of mixing in polyallylamine, the polymine, is any proportioning during two kinds of mixing.
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Effective date of registration: 20171122 Address after: 341100 Ganzhou, Ganzhou, Jiangxi Province, Ganxian District, Meilin Town, Gan Xin Avenue, No. 127, No. 1, No. 1 Oasis New Town, room 132 Patentee after: Ganzhou Rare Earth Mining Industry Co., Ltd. Address before: 430074 Wuhan Road, Hongshan, Shandong Province, Lu Lu Road, No. 388, No. Patentee before: China University of Geosciences (Wuhan) |