CN102391399B - 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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- CN102391399B CN102391399B CN 201110304590 CN201110304590A CN102391399B CN 102391399 B CN102391399 B CN 102391399B CN 201110304590 CN201110304590 CN 201110304590 CN 201110304590 A CN201110304590 A CN 201110304590A CN 102391399 B CN102391399 B CN 102391399B
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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
The polymer chelate resin is as a kind of functional high molecule material, have synthetic easy, loading capacity large, easily wash-out, do not produce the advantages such as secondary pollution and good stability, paid close attention to widely in organic chemical waste water, the fields such as waste water treatment that contain heavy metal ion.With the Ion Exchange Resin Phase ratio, the binding ability of chelate resin and metal ion is stronger, and selectivity is higher, is widely used in the aspects such as enrichment, separation, analysis, recovery metal ion.It is the focus of Recent study that development of new polymer chelate resin also is used for the aspects such as metal recovery and environment protection always.
Resin kind, function base with ligating atom main to the chelating ability of precious metal ion 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 resin to the metal biosorption selectivity 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), Thiourea Type [N (C=S) NH
2] etc.
The synthetic method of resin is substantially similar to ion exchange resin, and the one, contain the polymerization of functional group monomer, the one, the macromolecular scaffold modification.Latter preparation method is simple, and that adopts at present is more, but in its reaction efficiency and product, the content of function base is subject to the restriction of parent physics and chemistry structure; The resin function base of monomer polymerization method preparation be evenly distributed and content high, the key that adopts the standby resin of this legal system is to select suitable resin forming technique, the preparation particle diameter is even, specific surface area large, 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 is mainly function atom and the metal ion generation coordination reaction on resin, forms the rock steady structure of similar small molecules inner complex, and the mechanism of ion exchange resin absorption is electrostatic interaction.Therefore, with the Ion Exchange Resin Phase ratio, the bonding force of resin and metal ion is stronger, and selectivity is also higher, can be widely used in the aspects such as the recovery separation of each metal ion species, amino acid whose fractionation and hydrometallurgy, public pollution control.The principle of resin separating metal ion as shown in Figure 1.
In Fig. 1, ch is functional group, and some metal ion is had specific complex ability, therefore these metal ions and other separation of metal ions can be come.Resin is owing to having special selection 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 the 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 to reclaim or remove metal ion from waste water, this method has advantages of a lot, as resin can repeatedly reuse, production cost is low etc.The resin major part of using at present prepares as carrier with synthetic macromolecule, due to its have that mechanical property is lower, thermostability is relatively poor, weak and adsorption time is long, the high in cost of production shortcoming with the metallochemistry linkage force, so scientists is still constantly being sought better sorbent material.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 the advantages such as control and are widely studied, particularly Silica Surface contains a large amount of activated silica hydroxyls, can carry out at an easy rate surface chemistry bonding or modification, thereby receive increasing concern.
Since entering 21 century, nano material is because its good characteristic is widely used in the productive life field.In nano material, most important components is exactly inorganic nano material; and non-metallic minerals (silica gel, natural mineral kaolin-halloysite nanotubes, attapulgite, kaolin, diatomite etc.) nano material is the main body of inorganic nano material; because its raw material is easy to get; preparation technology is relatively simple in processing; has low production cost; be easy to the many advantages such as large-scale production; have most suitability therefore it will become in the nanosecond science and technology such as nano material and nano composite material, 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 the method operating process is brief, when adsorbing precious metal ion, need not to add any reagent, pollution-free in ion exchange column.
To achieve these goals, the technical solution used in the present invention 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) proportioning by matrix and acid is 5kg: 25～30L, chooses matrix and acid, and is standby; Described matrix is silica gel, natural mineral kaolin-halloysite nanotubes, attapulgite, kaolin or diatomite etc.;
Under 60～120 ℃ of conditions, with acid, matrix is carried out acidification (acid and matrix mix and blend), acidification 12～24h, then be cooled to room temperature, obtain matrix after acidification by filtration, the washing of matrix after to acidification until it is neutral, is dried to constant weight with deionized water again, obtains pretreated matrix;
2) damp atmosphere that bromizates sodium saturated solution or Potassium Bromide saturated solution reactor enters and is equipped with in 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 room temperature, filter, washing, dry (taking-up when recording matrix rate of body weight gain 10～16%), obtain the silanization 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 silanization matrix is added in the reactor that stirring is housed, add the polyamines based polyalcohol in reactor, add deionized water and methyl alcohol in reactor, vacuumize 15min in whipping process, vacuum tightness in reactor is 20～60mm Hg, then at 50～100 ℃ of lower 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 grafting matrix being added in the reactor that stirring is housed, add HCl and phosphorous acid, is under 80～100 ℃ in temperature, adds formaldehyde, after 80～100 ℃ of reaction 24h, washs, is dried to constant weight, obtains the chelating ion exchange resin that inorganics is 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 kaolin powder, mixes, and 80-100 ℃ is stirred 4-6h, filters, washing and dry, obtains the acid treatment sample; The weight ratio that is the polyacrylic acid solution of 1-5wt% according to acid treatment sample and concentration is 1: 1, adding concentration in the acid treatment sample is the polyacrylic acid solution of 1-5wt%, mix, 90-100 ℃ is stirred 10-15h, pass through again filtration, washing, drying and ball milling, obtain natural mineral kaolin-halloysite nanotubes (or claiming halloysite nanotubes).Commercially available halloysite nanotubes also can be used in the present invention.Described halloysite nanotubes is a kind of kaolinite lamella curling natural many walls nanotube that 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, diatomite etc. have that Heat stability is good, physical strength are high, pore structure and surface area ratio are easier to the advantages such as control, particularly Silica Surface contains a large amount of activated silica hydroxyls, can carry out at an easy rate surface chemistry bonding or modification, thereby receive increasing concern.
Press such scheme, step 1) described acid is the above mixture of any one or any two in hydrochloric acid, nitric acid, sulfuric acid, is any proportioning during any two above mixing.
Press such scheme, described alkane is the above mixture of any one or any two in butane, pentane, hexane, heptane, octane, is any proportioning during any two above mixing.
Press such scheme, described silane coupling agent is the above mixture of any one or any two in γ-(methacryloxy) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, chloropropyl trichloro-silane, r-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane, 3-epoxypropyl Trimethoxy silane, is any proportioning during any two above mixing.
Press such scheme, described polyamines based polyalcohol is any one or the two kinds of mixing in polyallylamine, polymine, and two kinds is any proportioning when 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 take derive from natural cheapness, be easy to get, stable silica gel, halloysite nanotubes, attapulgite, kaolin, diatomite etc. is as matrix, can take full advantage of their microcosmic nano effect, improve its ion exchange capacity, effectively improve the usefulness of ion exchange resin; After polyamines based polyalcohol modification by the differing molecular quality, then can be effectively improved with usefulness that formaldehyde and phosphorous acid carry out the ion exchange resin of Mannich reaction gained.
It is brief that the 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 to add any reagent, pollution-free and do not produce any waste in ion exchange column.
Description of drawings
Fig. 1 is resin separating metal ion principle schematic.
Fig. 2 is synthesis process flow diagram of the present invention.
Embodiment
In order to understand better the present invention, 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 the following examples; Should not be considered as limitation of the present invention yet.
Below by embodiment, the present invention is elaborated, but should not be considered as limitation of the present invention.Wherein, what experimental example 1-6 was synthetic is that silica gel is the chelating ion exchange resin of matrix, what experimental example 7-12 was synthetic is that halloysite nanotubes is the chelating ion exchange resin of matrix, what experimental example 13 was synthetic is that attapulgite is the chelating ion exchange resin of matrix, what experimental example 14 was synthetic is that kaolin is the chelating ion exchange resin of matrix, and what embodiment 15 was synthetic is that diatomite is the chelating ion exchange resin of matrix.
Embodiment 1:
5kg silica gel is added in the corrosion resistant reactor that stirring is housed, then add 30L, 1MHCl, 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 lower stirring and pickling 12h of bubble point temperature, then logical cooling water temperature, emit silica gel when temperature of charge is down to room temperature.The silica gel of emitting is by filtering elimination filtrate, respectively wash 2 times with deionized water and methyl alcohol successively again, stop washing when washing water show neutrality, carry out separating of silica gel and water, then dry silica gel to constant weight, obtain through pickling and be dried to the silica gel (pretreated matrix) of constant weight.Being placed on sand formula funnel through pickling and the silica gel that is dried to constant weight, the damp atmosphere that bromizates the sodium saturated solution enters in sand formula funnel through rubber tubing, make Silica Surface generate the water molecules individual layer, when being 7wt% to the water ratio that records hydrated silica gel, hydration is completed, and obtains the hydrated silica gel that water ratio is 7wt% (being the hydration matrix).
Hydrated silica gel is put into the corrosion resistant reactor that another is equipped with stirring, add the heptane of 10L and the chloropropyl triethoxysilane of 2.5 kilograms respectively in reactor, then slowly mix.After reaction 18h under room temperature, carry out separating of silica gel and solution, use successively again normal hexane and methanol wash, the silica gel that washs is put in moisture eliminator dries, to recording silica gel rate of body weight gain 16%[{ (silanized silica gel-hydrated silica gel)/hydrated silica gel * 100%=16%] time takes out, and namely obtains silanized silica gel.
Silanized silica gel is added in the corrosion resistant reactor that stirring is housed, add 6 kilograms of polyallylamine (PAA respectively in reactor, Mw=1.7 ten thousand), 10L deionized water and 5L methyl alcohol, slowly vacuumizing 15min in whipping process, vacuum tightness be 30mmHg then in the reacting kettle jacketing logical hot water make that in reactor, temperature of charge is 65 ℃, stir 36h, to record silica gel after grafting be former silica gel quality more than 1.0 times the time grafting complete.After graft reaction finished, by filtering and solution separating, caustic wash(ing) 1 time, deionization washing 3 times and the methyl alcohol of washing 4 times, one equivalents with deionized water were successively washed 2 times with grafting silica gel, then with drying materials to constant weight, resin-1 in the middle of namely getting.
Resin-1 in the middle of this is added in the corrosion resistant reactor that stirring is housed, add respectively 25L, 2MHCl and 3 kilograms of phosphorous acid, logical hot water makes that in reactor, temperature of charge is 95 ℃ in the reacting kettle jacketing, stir and slowly add 4L, 37.7wt% formaldehyde simultaneously, after 95 ℃ of reaction 24h, wash 2 times with deionized water successively, 1 mole of every liter of NaOH washes 1 time, deionization is washed 3 times, 1MH
2SO
4Wash 1 time, methyl alcohol is washed 3 times, then with drying materials to constant weight, obtaining silica gel of the present invention is the chelating ion exchange resin (being that inorganics is the chelating ion exchange resin of matrix) of matrix.
Embodiment 2:
5 kilograms of silica gel are added in the corrosion resistant reactor that stirring is housed, then add 30L, 1MHNO
3, after vacuumizing 15min, 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 lower stirring and pickling 12h of bubble point temperature, then logical cooling water temperature, emit silica gel when temperature of charge is down to room temperature.The silica gel of emitting passes through to filter elimination filtrate, respectively washes 2 times with deionized water and methyl alcohol successively, stops washing when washing water show neutrality, carries out separating of silica gel and water, then dries silica gel to constant weight.Being placed on sand formula funnel through pickling and the silica gel that is dried to constant weight, the damp atmosphere that bromizates the potassium saturated solution enters in sand formula funnel through rubber tubing, make Silica Surface generate the water molecules individual layer, when being 7% to the water ratio that records hydrated silica gel, hydration is completed, and obtains the hydrated silica gel that water ratio is 7wt%.
Hydrated silica gel is put into the corrosion resistant reactor that another is equipped with stirring, add the normal hexane of 10L and the γ of 2.5 kilograms-(methacryloxy) propyl trimethoxy silicane respectively in reactor, then slowly mix.After reaction 18h under room temperature, carry out separating of silica gel and solution, then wash with normal hexane and methyl alcohol successively, the silica gel of washing is put in moisture eliminator and dries, taking-up when recording silica gel rate of body weight gain 16% namely obtains silanized silica gel.
Silanized silica gel is added in the corrosion resistant reactor that stirring is housed, add 6 kilograms of polymine (PEI respectively in reactor, Mw=3 ten thousand), 10L deionized water and 5L methyl alcohol, slowly vacuumizing 15min in whipping process, vacuum tightness is 20mmHg, then logical hot water makes that in reactor, temperature of charge is 65 ℃ in the reacting kettle jacketing, stirs 36h, to record silica gel after grafting be former silica gel quality more than 1.0 times the time grafting complete.After graft reaction finished, by filtering and solution separating, caustic wash(ing) 1 time, deionization washing 3 times and the methyl alcohol of washing 4 times, one equivalents with deionized water were successively washed 2 times with grafting silica gel, then with drying materials to constant weight, resin-1 in the middle of namely getting.
Resin-1 in the middle of this is added in the corrosion resistant reactor that stirring is housed, add respectively 25L, 2MHCl and 3 kilograms of phosphorous acid, logical hot water makes that in reactor, temperature of charge is 95 ℃ in the reacting kettle jacketing, stir and slowly add 4L, 37.7wt% formaldehyde simultaneously, after 95 ℃ of reaction 24h, wash 2 times with deionized water successively, 1 mole of every liter of NaOH washes 1 time, deionization is washed 3 times, 1MH
2SO
4Wash 1 time, methyl alcohol is washed 3 times, then with drying materials to constant weight, obtaining silica gel of the present invention is the chelating ion exchange resin of 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 changed 3-epoxypropyl Trimethoxy silane into, other conditions were 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 in the corrosion resistant reactor that stirring is housed, then add the 1MH of 25L in the reactor
2SO
4After vacuumizing 15min, vacuum tightness is 45mm Hg, begins to be heated to boiling.At 100 ℃ of lower stirring and pickling 24h of boiling temperature, when being down to normal temperature, temperature emits material.Elimination acid solution after the material of emitting passes through to filter, respectively wash 2 times with deionized water and methyl alcohol successively, when showing neutrality, washing water stop washing, carry out separating of halloysite and water, and the oven dry halloysite is to constant weight.Being placed on sand formula funnel through pickling and the halloysite that is dried to constant weight, the damp atmosphere that bromizates the potassium saturated solution enters in sand formula funnel through rubber tubing, makes halloysite Surface Creation water molecules individual layer, when being 6% to the water ratio that records hydration silicon halloysite, hydration is completed, 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 kaolin powder, mixes, and 80-100 ℃ is stirred 4-6h, filters, washing and dry, obtains the acid treatment sample; The weight ratio that is the polyacrylic acid solution of 1-5wt% according to acid treatment sample and concentration is 1: 1, adding concentration in the acid treatment sample is the polyacrylic acid solution of 1-5wt%, mix, 90-100 ℃ is stirred 10-15h, pass through again filtration, washing, drying and ball milling, obtain natural mineral kaolin-halloysite nanotubes (or claiming halloysite nanotubes).
Hydrated halloysite is put into the corrosion resistant reactor that another is equipped with stirring, add the normal heptane of 9L and the 3-epoxypropyl Trimethoxy silane of 2.0 kilograms respectively in reactor, then slowly mix.After reaction 24h under room temperature, carry out separating of halloysite and solution, then wash with normal hexane and methyl alcohol successively, the halloysite of washing is put in moisture eliminator and dries, taking-up when recording halloysite rate of body weight gain 16% namely obtains the silanization halloysite.
The silanization halloysite is added in the corrosion resistant reactor that stirring is housed, add 5 kilograms of polyallylamine (PAA respectively in reactor, Mw=1.5 ten thousand), 11L deionized water and 6L methyl alcohol, slowly vacuumizing 15min in whipping process, vacuum tightness is 25mm Hg, then logical hot water makes that in reactor, temperature of charge is 65 ℃ in the reacting kettle jacketing, stirs 36h, to record halloysite after grafting be former halloysite quality more than 1.0 times the time grafting complete.After graft reaction finished, by filtering and solution separating, caustic wash(ing) 1 time, deionization washing 3 times and the methyl alcohol of washing 4 times, one equivalents with deionized water were successively washed 2 times with the grafting halloysite, then with drying materials to constant weight, resin-1 in the middle of namely getting.
Resin-1 in the middle of this is added in the corrosion resistant reactor that stirring is housed, add respectively 20L, 2MHCl and 2.5 kilograms of phosphorous acid, logical hot water makes that in reactor, temperature of charge is 95 ℃ in the reacting kettle jacketing, stir and slowly add 3.5L, 37.7wt% formaldehyde simultaneously, after 95 ℃ of reaction 24h, wash 2 times with deionized water successively, 1 mole of every liter of NaOH washes 1 time, deionization is washed 3 times, 1MH
2SO
4Wash 1 time, methyl alcohol is washed 3 times, then with drying materials to constant weight, obtaining halloysite nanotubes of the present invention is the chelating ion exchange resin of matrix.
Embodiment 8:
5 kilograms of halloysite nanotubes (commercially available halloysite nanotubes) are added in the corrosion resistant reactor that stirring is housed, then add the 1MH of 25L in the reactor
2SO
4After vacuumizing 15min, vacuum tightness is 60mm Hg, begins to be heated to boiling.At 90 ℃ of lower stirring and pickling 24h of boiling temperature, when being down to normal temperature, temperature emits material.Elimination acid solution after the material of emitting passes through to filter, respectively wash 2 times with deionized water and methyl alcohol successively, when showing neutrality, washing water stop washing, carry out separating of halloysite and water, and the oven dry halloysite is to constant weight.Being placed on sand formula funnel through pickling and the halloysite that is dried to constant weight, the damp atmosphere that bromizates the sodium saturated solution enters in sand formula funnel through rubber tubing, makes halloysite Surface Creation water molecules individual layer, when being 6% to the water ratio that records hydration silicon halloysite, hydration is completed, and obtains hydrated halloysite.
Hydrated halloysite is put into the corrosion resistant reactor that another is equipped with stirring, add the octane of 9L and the γ of 2.0 kilograms-(methacryloxy) propyl trimethoxy silicane respectively in reactor, then slowly mix.After reaction 24h under room temperature, carry out separate (filtering separation) of halloysite and solution, then wash with normal hexane and methyl alcohol successively, the halloysite of washing is put in moisture eliminator and dries, taking-up when recording halloysite rate of body weight gain 16% namely obtains the silanization halloysite.
The silanization halloysite is added in the corrosion resistant reactor that stirring is housed, add 5 kilograms of polyallylamine (PAA respectively in reactor, Mw=5 ten thousand), 11L deionized water and 6L methyl alcohol, slowly vacuumizing 15min in whipping process, vacuum tightness is 30mmHg, then logical hot water makes that in reactor, temperature of charge is 65 ℃ in the reacting kettle jacketing, stirs 36h, to record halloysite after grafting be former halloysite quality more than 1.0 times the time grafting complete.After graft reaction finished, by filtering and solution separating, caustic wash(ing) 1 time, deionization washing 3 times and the methyl alcohol of washing 4 times, one equivalents with deionized water were successively washed 2 times with the grafting halloysite, then with drying materials to constant weight, resin-1 in the middle of namely getting.
Resin-1 in the middle of this is added in the corrosion resistant reactor that stirring is housed, add respectively 20L, 2MHCl and 2.5 kilograms of phosphorous acid, logical hot water makes that in reactor, temperature of charge is 95 ℃ in the reacting kettle jacketing, stir and slowly add 3.5L, 37.7wt% formaldehyde simultaneously, after 95 ℃ of reaction 24h, wash 2 times with deionized water successively, 1 mole of every liter of NaOH washes 1 time, deionization is washed 3 times, 1MH
2SO
4Wash 1 time, methyl alcohol is washed 3 times, then with drying materials to constant weight, obtaining halloysite nanotubes of the present invention is the chelating ion exchange resin of 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 polymine, other conditions are identical with embodiment 7.
Embodiment 13:
5 kilograms of attapulgites are added in the corrosion resistant reactor that stirring is housed, then add 30L, 1MH
2SO
4, after vacuumizing 15min, vacuum tightness is 20mm Hg, vigorous stirring pickling 12h under 80 ℃ of conditions, and then logical cooling water temperature, emit attapulgite when temperature of charge is down to room temperature.The attapulgite of emitting passes through to filter elimination filtrate, respectively washes 2 times with deionized water and methyl alcohol successively, stops washing when washing water show neutrality, carries out separating of attapulgite and water, then dries attapulgite to constant weight.Being placed on sand formula funnel through pickling and the attapulgite that is dried to constant weight, the damp atmosphere that bromizates the sodium saturated solution enters in sand formula funnel through rubber tubing, make attapulgite Surface Creation water molecules individual layer, when being 10% to the water ratio that records the hydration attapulgite, hydration is completed, and obtains the hydration attapulgite.
The hydration attapulgite is put into the corrosion resistant reactor that another is equipped with stirring, add respectively the chloropropyl trichloro-silane of 5L heptane, 5L hexane and 2.5 kilograms in the reactor, then slowly mix.After reaction 18h under room temperature, carry out separating of attapulgite and solution, then wash with normal hexane and methyl alcohol successively, the attapulgite of washing is put in moisture eliminator and dries, taking-up when recording attapulgite rate of body weight gain 10% namely obtains the silanization attapulgite.
The silanization attapulgite is added in the corrosion resistant reactor that stirring is housed, add 6 kilograms of polymine (PEI respectively in reactor, Mw=1.7 ten thousand), 10L deionized water and 5L methyl alcohol, slowly vacuumizing 15min in whipping process, vacuum tightness is 30mm Hg, then logical hot water makes that in reactor, temperature of charge is 65 ℃ in the reacting kettle jacketing, stirs 36h, to record attapulgite after grafting be former attapulgite quality more than 1.0 times the time grafting complete.After graft reaction finishes, the grafting attapulgite is passed through to filter and solution separating, caustic wash(ing) 1 time, deionization washing 3 times and the methyl alcohol of washing 4 times, one equivalents with deionized water are successively washed 2 times, then with drying materials to constant weight, resin-2 (being the grafting matrix) in the middle of namely getting.
Resin-2 in the middle of this is added in the corrosion resistant reactor that stirring is housed, add respectively 25L, 2MHCl and 3 kilograms of phosphorous acid, logical hot water makes that in reactor, temperature of charge is 95 ℃ in the reacting kettle jacketing, stir and slowly add 4L, 37.7wt% formaldehyde simultaneously, after 95 ℃ of reaction 24h, wash 2 times with deionized water successively, 1 mole of every liter of NaOH washes 1 time, deionization is washed 3 times, 1MH
2SO
4Wash 1 time, methyl alcohol is washed 3 times, then with drying materials to constant weight, obtaining attapulgite of the present invention is the chelating ion exchange resin of matrix.
Embodiment 14:
5 kilograms of kaolin are added in the corrosion resistant reactor that stirring is housed, then add the 1MH of 25L in the reactor
2SO
4After vacuumizing 15min, vacuum tightness is 30mm Hg, begins to be heated to boiling.At 95 ℃ of lower stirring and pickling 18h of boiling temperature, when being down to normal temperature, temperature emits material.Elimination acid solution after the material of emitting passes through to filter, respectively wash 2 times with deionized water and methyl alcohol successively, when showing neutrality, washing water stop washing, carry out separating of kaolin and water, and oven dry kaolin is to constant weight.Being placed on sand formula funnel through pickling and the kaolin that is dried to constant weight, the damp atmosphere that bromizates the potassium saturated solution enters in sand formula funnel through rubber tubing, makes kaolin Surface Creation water molecules individual layer, when being 6% to the water ratio that records hydrous kaolin, hydration is completed, and obtains hydrous kaolin.
Hydrous kaolin is put into the corrosion resistant reactor that another is equipped with stirring, add the octane of 9L and the γ of 2.0 kilograms-(methacryloxy) propyl trimethoxy silicane respectively in reactor, then slowly mix.After reaction 24h under room temperature, carry out separating of kaolin and solution, then wash with normal hexane and methyl alcohol successively, the kaolin of washing is put in moisture eliminator and dries, taking-up when recording kaolin rate of body weight gain 16% namely obtains silanization kaolin.
Silanization kaolin is added in the corrosion resistant reactor that stirring is housed, add 5 kilograms of polyallylamine (PAA respectively in reactor, Mw=5 ten thousand), 11L deionized water and 6L methyl alcohol, slowly vacuumizing 15min in whipping process, vacuum tightness is 50mmHg, then logical hot water makes that in reactor, temperature of charge is 65 ℃ in the reacting kettle jacketing, stirs 36h, to record kaolin after grafting be the protokaolin quality more than 1.0 times the time grafting complete.After graft reaction finished, by filtering and solution separating, caustic wash(ing) 1 time, deionization washing 3 times and the methyl alcohol of washing 4 times, one equivalents with deionized water were successively washed 2 times with grafting kaolin, then with drying materials to constant weight, resin-1 in the middle of namely getting.
Resin-1 in the middle of this is added in the corrosion resistant reactor that stirring is housed, add respectively 20L, 2MHCl and 2.5 kilograms of phosphorous acid, logical hot water makes that in reactor, temperature of charge is 95 ℃ in the reacting kettle jacketing, stir and slowly add 3.5L, 37.7wt% formaldehyde simultaneously, after 95 ℃ of reaction 24h, wash 2 times with deionized water successively, 1 mole of every liter of NaOH washes 1 time, deionization is washed 3 times, 1MH
2SO
4Wash 1 time, methyl alcohol is washed 3 times, then with drying materials to constant weight, obtaining kaolin of the present invention is the chelating ion exchange resin of matrix.
Embodiment 15:
5 kilograms of diatomite are added in the corrosion resistant reactor that stirring is housed, then add 30L, 1MH
2SO
4, after vacuumizing 15min, vacuum tightness is 30mm Hg, vigorous stirring pickling 24h under 60 ℃ of conditions, and then logical cooling water temperature, emit diatomite when temperature of charge is down to room temperature.The attapulgite of emitting passes through to filter elimination filtrate, respectively washes 2 times with deionized water and methyl alcohol successively, stops washing when washing water show neutrality, carries out separating of diatomite and water, then dries diatomite to constant weight.Being placed on sand formula funnel through pickling and the diatomite that is dried to constant weight, the damp atmosphere that bromizates the potassium saturated solution enters in sand formula funnel through rubber tubing, makes diatomite Surface Creation water molecules individual layer, when recording the diatomaceous water ratio of hydration and be 7%, hydration is completed, and obtains hydration diatomite.
Hydration diatomite is put into the corrosion resistant reactor that another is equipped with stirring, add the heptane of 10L and the chloropropyl triethoxysilane of 2.5 kilograms respectively in reactor, then slowly mix.After reaction 18h under room temperature, carry out separating of diatomite and solution, then wash with normal hexane and methyl alcohol successively, the diatomite of washing is put in moisture eliminator and dries, taking-up when recording diatomite rate of body weight gain 10% namely obtains the silanization attapulgite.
Silanization diatomite is added in the corrosion resistant reactor that stirring is housed, add 6 kilograms of polymine (PEI respectively in reactor, Mw=1.7 ten thousand), 10L deionized water and 5L methyl alcohol, slowly vacuumizing 15min in whipping process, vacuum tightness is 40mm Hg, then logical hot water makes that in reactor, temperature of charge is 65 ℃ in the reacting kettle jacketing, stirs 36h, to record diatomite after grafting be former diatomite quality more than 0.5 times the time grafting complete.After graft reaction finished, by filtering and solution separating, caustic wash(ing) 1 time, deionization washing 3 times and the methyl alcohol of washing 4 times, one equivalents with deionized water were successively washed 2 times with grafting diatomite, then with drying materials to constant weight, resin-2 in the middle of namely getting.
Middle resin-2 are added in the corrosion resistant reactor that stirring is housed, add respectively 25L, 2MHCl and 3 kilograms of phosphorous acid, logical hot water makes that in reactor, temperature of charge is 95 ℃ in the reacting kettle jacketing, stir and slowly add 4L, 37.7wt% formaldehyde simultaneously, after 95 ℃ of reaction 24h, wash 2 times with deionized water successively, 1 mole of every liter of NaOH washes 1 time, deionization is washed 3 times, 1MH
2SO
4Wash 1 time, methyl alcohol is washed 3 times, then with drying materials to constant weight, obtaining diatomite of the present invention is the chelating ion exchange resin of matrix.
Embodiment 16:
Substantially the same manner as Example 15, difference is: after vacuumizing 15min, and vigorous stirring pickling 24h under 120 ℃ of conditions.
Embodiment 17:
Substantially the same manner as Example 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:
Substantially the same manner as Example 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:
Substantially the same manner as Example 15, difference is: the molecular weight of polymine (weight-average molecular weight) is 1000.
Embodiment 20:
Substantially the same manner as Example 15, difference is: the molecular weight of polymine (weight-average molecular weight) is 1000000.
Embodiment 21:
Substantially the same manner as Example 15, difference is: 65 ℃ of graft reaction temperature change 50 ℃ into, and the graft reaction time, 36h changed 24h into; " after 95 ℃ of reaction 24h " changes " after 80 ℃ of reaction 24h " into.
Embodiment 22:
Substantially the same manner as Example 15, difference is: 65 ℃ of graft reaction temperature change 100 ℃ into, and the graft reaction time, 36h changed 48h into; " after 95 ℃ of reaction 24h " changes " after 100 ℃ of reaction 24h " into.
Embodiment 1-22 when adsorbing precious metal ion, need not to add any reagent, pollution-free in ion exchange column.
Each raw material that the present invention is cited, and the bound value of each raw material, with and interval value, can realize the present invention; And the bound value of each processing parameter (as temperature, time etc.), with and interval value, can realize the present invention, do not enumerate embodiment at this.
Main performance index of the present invention and measuring method:
The outward appearance of above-described embodiment 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.
Below by the performance measurement example, the present invention is elaborated, but should not be considered as limitation of the present invention.wherein performance measurement example 1 is used for the detection of absorption rare earth ion cerium (III) for the chelating ion exchange resin take silica gel as matrix, performance measurement example 2 is used for the detection of Adsorption of Heavy Metal Ions nickel (II) for the chelating ion exchange resin take halloysite nanotubes as matrix, performance measurement example 3 is used for the detection of absorption rare earth ion lanthanum (III) for the chelating ion exchange resin take attapulgite as matrix, performance measurement example 4 is used for the detection of absorption rare earth ion europium (III) for the chelating ion exchange resin take kaolin as matrix, performance measurement example 5 is used for the detection of absorption rare earth ion yttrium (III) for the chelating ion exchange resin take diatomite as matrix.Performance measurement example 6 is used for the detection of Adsorption of Heavy Metal Ions cobalt (II) for the chelating ion exchange resin take kaolin as matrix.Performance measurement example 7 is used for the detection of Adsorption of Heavy Metal Ions copper (II) for the chelating ion exchange resin take silica gel as matrix.The chelating ion exchange resin that performance measurement example 8 is matrix for attapulgite is used for the detection of Adsorption of Heavy Metal Ions gold (III).
Performance measurement example 1
1.1 the test that the chelating ion exchange resin that is matrix with silica gel is used for adsorbing rare earth ion is take cerium (III) as example.
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
The adsorption equilibrium test is carried out on HZ9212S type digital display water-bath constant temperature oscillator, accurately take a certain amount of resin of anticipating in the round-bottomed flask with a mouth of pipe, the distilled water and a certain amount of cerium (III) reference liquid that add certain volume, vacuumize 15min, at room temperature vibrate to adsorption equilibrium, pipette the filtrate of 1ml after resin absorption, add oxalic acid-CPA-mA solution 20ml, shake up, absorption vessel with the 3cm light path, the place surveys its absorbancy at the 669nm wavelength, 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 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 balance, try to achieve resin to the adsorptive capacity of cerium (III) ion.Tell the residue water, then wash resin three times with damping fluid, then add strippant, vibration records water cerium (III) after balance) content, try to achieve desorption efficiency.
Accurately take the 1.0g resin, at T=298K, [Ce
3+]
0Under=17.0mg/mL 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), 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 example 2
2.1 be that the chelating ion exchange resin of matrix is for the test of Adsorption of Heavy Metal Ions, take metallic nickel (II) as example with halloysite nanotubes.
The nickel standardized solution is by spectroscopically pure NiCl
26H
2The O preparation; PH 2.6～6.2 damping fluids are by HAc-NaAc; Nitrite ion: 8g EDETATE DISODIUM 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 water-bath constant temperature oscillator, accurately take a certain amount of resin of anticipating in the round-bottomed flask with a mouth of pipe, the 1mol/LHCl and a certain amount of nickel ion reference liquid that add certain volume, vacuumize 15min, at room temperature vibrate to adsorption equilibrium, pipette 5.00mL through the filtrate after resin absorption in the 50mL volumetric flask, add the 10mL nitrite ion, 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 deionization 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 formula: Q
RAdsorptive capacity (mg/g dried resin) for every gram resin under equilibrium state; C
0, Ce is respectively initial concentration and the equilibrium concentration (mg/mL) of aqueous phase ion; W is dried resin weight (g); V is water volume (mL).
2.3 desorption experiment
Take 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 balance, try to achieve resin to the adsorptive capacity of nickel (II) ion.Tell the residue water, then wash resin three times with damping fluid, then add strippant, record the content of water nickel (II) after the vibration balance, try to achieve desorption efficiency.
Accurately take the 1.0g resin, at T=298K, [Ni
2+]
0Under=13.0mg/mL 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, 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.
Performance measurement example 3
3.1 the test that the chelating ion exchange resin that is matrix with attapulgite is used for adsorbing rare earth ion is take lanthanoid metal (III) as example.
The lanthanum standardized solution is by spectroscopically pure La
2O
3Preparation; PH 2.6 ∽ 6.2 damping fluids are by HAc-NaAc; Nitrite ion: 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 water-bath constant temperature oscillator, accurately take a certain amount of resin of anticipating in the round-bottomed flask with a mouth of pipe, the 1mol/LHCl and a certain amount of lanthanum ion reference liquid that add certain volume, vacuumize 15min, at room temperature vibrate to adsorption equilibrium, pipette 5.00mL through the filtrate after resin absorption in the 50mL volumetric flask, add the 10mL nitrite ion, 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 deionization 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 formula: Q
RAdsorptive capacity (mg/g dried resin) for every gram resin under equilibrium state; C
0, Ce is respectively initial concentration and the equilibrium concentration (mg/mL) of aqueous phase ion; W is dried resin weight (g); V is water volume (mL).
3.3 desorption experiment
Take 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 balance, try to achieve resin to the adsorptive capacity of lanthanum ion.Tell the residue water, then wash resin three times with damping fluid, then add strippant, record the content of water lanthanum after the vibration balance, try to achieve desorption efficiency.
Accurately take the 15mg.0g resin, at T=298K, [La
3+]
0Under=133.0mg/L 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 example 4
4.1 the test that the chelating ion exchange resin that is matrix with kaolin is used for adsorbing rare earth ion is take Europium Metal (III) as example.
The europium standardized solution is by spectroscopically pure Eu
2O
3Preparation; PH 2.6 ∽ 6.2 damping fluids are by HAc-NaAc; Nitrite ion: 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 water-bath constant temperature oscillator, accurately take a certain amount of resin of anticipating in the round-bottomed flask with a mouth of pipe, the 1mol/LHCl and a certain amount of europium ion reference liquid that add certain volume, vacuumize 15min, at room temperature vibrate to adsorption equilibrium, pipette 5.00mL through the filtrate after resin absorption in the 50mL volumetric flask, add the 10mL nitrite ion, 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 deionization 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 formula: Q
RAdsorptive capacity (mg/g dried resin) for every gram resin under equilibrium state; C
0, Ce is respectively initial concentration and the equilibrium concentration (mg/mL) of aqueous phase ion; W is dried resin weight (g); V is water volume (mL).
4.3 desorption experiment
Take 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 balance, try to achieve resin to the adsorptive capacity of europium ion.Tell the residue water, then wash resin three times with damping fluid, then add strippant, record the content of water europium after the vibration balance, try to achieve desorption efficiency.
Accurately take the 15mg.0g resin, at T=298K, [Eu
3+]
0Under=4.0mg/25mL 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 example 5
5.1 the test that the chelating ion exchange resin that is matrix with diatomite is used for adsorbing rare earth ion is take metallic yttrium (III) as example.
The yttrium standardized solution is by spectroscopically pure Y
2O
3Preparation; PH 2.6 ∽ 6.2 damping fluids are by HAc-NaAc; Nitrite ion: 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 water-bath constant temperature oscillator, accurately take a certain amount of resin of anticipating in the round-bottomed flask with a mouth of pipe, the 1mol/LHCl and a certain amount of ruthenium ion reference liquid that add certain volume, vacuumize 15min, at room temperature vibrate to adsorption equilibrium, pipette 5.00mL through the filtrate after resin absorption in the 50mL volumetric flask, add the 10mL nitrite ion, 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 deionization 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 formula: Q
RAdsorptive capacity (mg/g dried resin) for every gram resin under equilibrium state; C
0, Ce is respectively initial concentration and the equilibrium concentration (mg/mL) of aqueous phase ion; W is dried resin weight (g); V is water volume (mL).
5.3 desorption experiment
Take 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 balance, try to achieve resin to the adsorptive capacity of ruthenium ion.Tell the residue water, then wash resin three times with damping fluid, then add strippant, record the content of water yttrium after the vibration balance, try to achieve desorption efficiency.
Accurately take the 15mg.0g resin, at T=298K, [Y
3+]
0Under=4.0mg/30mL 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 example 6
4.1 be that the chelating ion exchange resin of matrix is for the test of Adsorption of Heavy Metal Ions, take cobalt metal (II) as example with kaolin.
Cobalt standard solution is by spectroscopically pure CoCl
26H
2The O preparation; PH 2.6 ∽ 6.2 damping fluids are by HAc-NaAc; Nitrite ion: 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 water-bath constant temperature oscillator, accurately take a certain amount of resin of anticipating in the round-bottomed flask with a mouth of pipe, the 1mol/LHCl and a certain amount of cobalt ion reference liquid that add certain volume, vacuumize 15min, at room temperature vibrate to adsorption equilibrium, pipette 5.00mL through the filtrate after resin absorption in the 50mL volumetric flask, add the 10mL nitrite ion, 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 deionization 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 formula: Q
RAdsorptive capacity (mg/g dried resin) for every gram resin under equilibrium state; C
0, Ce is respectively initial concentration and the equilibrium concentration (mg/mL) of aqueous phase ion; W is dried resin weight (g); V is water volume (mL).
4.3 desorption experiment
Take 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 balance, try to achieve resin to the adsorptive capacity of cobalt ion.Tell the residue water, then wash resin three times with damping fluid, then add strippant, record the content of water europium after the vibration balance, try to achieve desorption efficiency.
Accurately take 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 example 7
1.1 be that the chelating ion exchange resin of matrix is for the test of Adsorption of Heavy Metal Ions, take metallic copper (II) as example with silica gel.
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; Nitrite ion: 0.5% xylenol orange developer adds water to 100mL; Other reagent are analytical pure.
1.2 adsorption equilibrium test and analytical procedure
The adsorption equilibrium test is carried out on HZ9212S type digital display water-bath constant temperature oscillator, accurately take a certain amount of resin of anticipating in the round-bottomed flask with a mouth of pipe, the distilled water and a certain amount of cupric ion reference liquid that add certain volume, vacuumize 15min, at room temperature vibrate to adsorption equilibrium, pipette the filtrate of 1ml after resin absorption, add 0.5% xylenol orange solution 20ml, shake up, absorption vessel with the 3cm light path, the place surveys its absorbancy at the 576.3nm wavelength, 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 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 balance, try to achieve resin to the adsorptive capacity of cupric ion.Tell the residue water, then wash resin three times with damping fluid, then add strippant, record the content of water copper after the vibration balance, try to achieve desorption efficiency.
Accurately take 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 example 8
3.1 be that the chelating ion exchange resin of matrix is for the test of adsorbing metal ions, take metallic gold (III) as example with attapulgite.
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; Nitrite ion: the ethanolic soln of 0.02% michler's 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 water-bath constant temperature oscillator, accurately take a certain amount of resin of anticipating in the round-bottomed flask with a mouth of pipe, the 1mol/LHCl and a certain amount of gold (III) ion reference liquid that add certain volume, vacuumize 15min, at room temperature vibrate to adsorption equilibrium, pipette 5.00mL through the filtrate after resin absorption in the 50mL volumetric flask, add the 10mL nitrite ion, 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 the equilibrium concentration Ce (mg/mL) of aqueous phase gold (III) ion, make reference with the deionization 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 formula: Q
RAdsorptive capacity (mg/g dried resin) for every gram resin under equilibrium state; C
0, Ce is respectively initial concentration and the equilibrium concentration (mg/mL) of aqueous phase ion; W is dried resin weight (g); V is water volume (mL).
3.3 desorption experiment
Take 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 balance, try to achieve resin to the adsorptive capacity of gold (III) ion.Tell the residue water, then wash resin three times with damping fluid, then add strippant, record the content of water gold (III) after the vibration balance, try to achieve desorption efficiency.
Accurately take the 15mg.0g resin, at T=298K, [Au
3+]=600mg/L is undertaken by above-mentioned adsorption experiment method, try to achieve every gram resin (embodiment 15) to the gold (III) ion loading capacity be 828.36mg.
Above-mentioned performance measurement example illustrates that the product of this invention has good adsorption effect to rare earth and precious metal ion, and flow process is simple, easy to operate, need not toward adding any reagent, pollution-free and do not produce any waste during ion-exchange is lived.
Chelating resin of the present invention can be used for equally other metal biosorptions (as rare earth, nickel, cobalt, copper, gold, silver, etc.), explanation no longer one by one here.
Claims (3)
1. the preparation method that inorganics is the chelating ion exchange resin of matrix, is characterized in that it comprises the steps:
1) proportioning by matrix and acid is 5kg: 25～30L, chooses matrix and acid, and is standby; Described matrix is silica gel, natural mineral kaolin-halloysite nanotubes, attapulgite, kaolin or diatomite;
Under 60～120 ℃ of conditions, matrix is carried out acidification, acidification 12～24h with acid, then be cooled to room temperature, obtain matrix after acidification by filtration, then with deionized water the matrix washing after to acidification until it is neutral, be dried to constant weight, obtain pretreated matrix;
Described acid is that concentration is any one or any two the above mixture in the hydrochloric acid, nitric acid, sulfuric acid of 1M, is any proportioning during any two above mixing;
2) damp atmosphere that bromizates sodium saturated solution or Potassium Bromide saturated solution reactor enters and is equipped with in 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 room temperature, filter, wash, be dried to when recording matrix rate of body weight gain 10～16% and take out, obtain the silanization matrix;
Described alkane is the above mixture of any one or any two in pentane, hexane, heptane, octane, is any proportioning during any two above mixing;
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 silanization matrix is added in the reactor that stirring is housed, add the polyamines based polyalcohol in reactor, add deionized water and methyl alcohol in reactor, vacuumize 15min in whipping process, vacuum tightness in reactor is 20～60mm Hg, then at 50～100 ℃ of lower graft reaction 24～48h, after graft reaction finishes, filter, wash, be dried to constant weight, obtain the grafting matrix;
Described polyamines based polyalcohol is any one or the two kinds of mixing in polyallylamine, polymine, and two kinds is any proportioning when mixing;
5) proportioning by matrix, 2MHCl, phosphorous acid, 37.7wt% formaldehyde is 5kg: 20～25L: 2.5～3kg: 3.5～4L, chooses HCl, phosphorous acid and formaldehyde;
The grafting matrix being added in the reactor that stirring is housed, add HCl and phosphorous acid, is under 80～100 ℃ in temperature, adds formaldehyde, after 80～100 ℃ of reaction 24h, washs, is dried to constant weight, obtains the chelating ion exchange resin that inorganics is matrix.
2. a kind of inorganics according to claim 1 preparation method that is 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 kaolin powder, mixes, and 80-100 ℃ is stirred 4-6h, filters, washing and dry, obtains the acid treatment sample; The weight ratio that is the polyacrylic acid solution of 1-5wt% according to acid treatment sample and concentration is 1:1, adding concentration in the acid treatment sample is the polyacrylic acid solution of 1-5wt%, mix, 90-100 ℃ is stirred 10-15h, pass through again filtration, washing, drying and ball milling, obtain natural mineral kaolin-halloysite nanotubes.
3. a kind of inorganics according to claim 1 preparation method that is the chelating ion exchange resin of matrix, it is characterized in that: described silane coupling agent is the above mixture of any one or any two in γ-(methacryloxy) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, chloropropyl trichloro-silane, r-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane, 3-epoxypropyl Trimethoxy silane, is any proportioning during any two above 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) |