CN108212225A - A kind of inorganic type silica gel chelating ion exchange resin and preparation method thereof - Google Patents
A kind of inorganic type silica gel chelating ion exchange resin and preparation method thereof Download PDFInfo
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- B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
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Abstract
The invention belongs to macroion exchanger resin technical fields, are related to a kind of inorganic type silica gel chelating ion exchange resin and preparation method thereof：In a heated condition, acidification is carried out to silica gel matrix with acid, deionized water is washed to neutrality；The humid air of sodium bromide or potassium bromide saturated solution is made to contact silica gel matrix, silica gel matrix surface is made to generate hydrone individual layer；Hydrated silica gel matrix and alkane and silane coupling agent are subjected to Silanization reaction, obtain silanization matrix；Functional resin material is obtained after silanization matrix and polyamines based polyalcohol are carried out graft reaction, then Mannich reaction is carried out with formaldehyde and phosphorous acid, so as to obtain final inorganic type silica gel chelating ion exchange resin.When carrying out mineral products wet-process metallurgy leachate absorbing copper, nickel, cobalt, precious metal, rare earth plasma using the resin, without adding any reagent, energy saving, pollution-free and do not generate any waste into ion exchange column, sheerly environment-friendly type sci-tech product.
Description
Technical field
The invention belongs to macroion exchanger resin technical fields, are related to inorganic type silica gel chelating ion exchange resin
A kind of preparation method, and in particular to preparation method of inorganic type silica gel chelating ion exchange resin.
Background technology
Nickel is widely used in alloy manufacture, plating, Ni-MH battery and the fields such as catalyst is big-eared as a kind of strategy metal.Though
Right 65% nickel resources are stored in oxide ore (laterite), but more than 70% nickel product both from sulphide ore.At present,
The hydrometallurgy of laterite is more and more concerned, specifically includes the leaching, the extraction of nickel leachate and the electrodeposition of nickel of laterite
Three big processes.Leaching mainly has ammonia leaching, one Roasting And Leaching of sulphation, normal pressure acidleach and high pressure acidleach etc..Acid leaching solution extracts
Usually hydroximic species of extractants is then commonly used with carboxylic acid extractant or organic sulfur generation phosphoric acid extraction agent ammonia leachate.
Due to containing a large amount of iron ion, carboxylic acid extractant and organic sulfur generation phosphoric acid extraction in lateritic nickel ore pickle liquor
Agent is difficult to effectively extract nickel ion therein, unless being removed iron ion in advance by chemical precipitation.In addition, organic extraction
Agent and related diluent is inflammable and explosive and toxicity is larger, can adversely affect environment, hence it is imperative that developing a kind of ring
The laterite nickel ore hydrometallurgical technique of border close friend.
One of which consideration be using inorganic type ion exchange resin substitute solvent extraction technology come realize the separation of nickel with
Enrichment.However, due to the entropic elasticity of polymer, this kind of ion exchange resin is inevitably sent out in regenerative processes are adsorbed
Raw periodically expansion is shunk, and not only resin life is caused to shorten, it is also necessary to reserve certain hollow body when exchanging post design
Product.
Macromolecule chelate resin as a kind of functional high molecule material, have convieniently synthesized, adsorption capacity is big, easily elution,
The advantages that not generating secondary pollution and good stability, the fields such as organic chemical waste water, waste water treatment containing heavy metal ion by
To extensive concern.Compared with ion exchange resin, the binding ability of chelate resin and metal ion is stronger, selective higher,
It is widely used in being enriched with, separates, analyzes, recycles metal ion etc..Development of new macromolecule chelate resin is simultaneously used for metal
Recycling and environmental protection etc. are always the hot spot of Recent study.
Chelating resin to the chelating ability of precious metal ion mainly with the type of coordination atom, the same high polymer main chain of function base
Bonding state, the physique of resin matrix it is related, therefore generally classify according to this to chelating resin.
By the coordination atom of chelating resin or the type of functional group carry out classification be most common sorting technique because from
The type of position atom and functional group is easy to prediction resin to the adsorptive selectivity of metal ion, and the design of chelating resin is instructed to close
Into.By coordination atom type by chelating resin be divided into oxygen-containing type, nitrogenous type, sulfur-type, containing phosphorous, type containing arsenic and mixed type
Chelating resin；By functional group can be divided into carboxylic acid type (- COOH), polyester-type (- COOR), polyether-type (- ROR ' -), polyamine type (-
NH-), guanidine radicals type [- N (C=N) NH2], schiff's base type (- C=N-), acid amide type (- CONH2), aminocarboxylic acid type [- NCH2
(COOH) 2], thioalcohol type (- SH), polysulfide ether type (- RSR ' -), dithiocarboxylic acid type (- CSSH), Thiourea Type [- N (C=S) NH2]
Deng.
The synthetic method of chelating resin is substantially similar to ion exchange resin, when the polymerization containing functional group monomer,
First, macromolecular scaffold is modified.The latter's preparation method is simple, and what is used at present is more, but function base in its reaction efficiency and product
Content limited by parent physics and chemical constitution；Resin function base prepared by monomer polymerization method is evenly distributed and content
Height, the key that resin is prepared using the method is the suitable resin forming technique of selection, prepares uniform particle sizes, large specific surface area, molten
Swollen performance and the good resin of mechanical strength.In addition, also have the means using physical modification or chemical graft, it is compound new on matrix
Resin phase, the mechanism of chelating resin adsorbing metal ions processed is mainly that the function atom on resin is coordinated with metal ion
Reaction forms the rock-steady structure of similar small molecule chelate, and the mechanism of ion exchange resin absorption is electrostatic interaction.Therefore,
Compared with ion exchange resin, the binding force of chelating resin and metal ion is stronger, and selective also higher can be widely applied to each
Metal ion species recycle separation, the fractionation of amino acid and hydrometallurgy, public hazards prevention etc..
In recent years, using chemical method in the immobilized specific function macromolecule of the surface of solids or group, for enriching noble metals
Or selectively removing heavy metal ion is had become as people's focus of attention.Gold is recycled or removed from waste water using chelating resin method
Belong to ion, this method has the advantages that very much, such as resin can be used repeatedly, production cost is low.The chelating tree used at present
Fat is largely to be prepared using synthesizing macromolecule as carrier, and due to it, there are mechanical performance is relatively low, thermal stability is poor and metal
Chemical bonding is weaker and the shortcomings of adsorption time is longer, of high cost, so scientists still are constantly looking for preferably inhaling
Attached dose.Wherein silica gel and many inorganic mineral nano materials are with its thermal stability is good, high mechanical strength, porous structure or multilayer knot
Structure and surface area ratio are easier to the advantages that control and are widely studied, and particularly Silica Surface contains a large amount of active silicone hydroxyls, can
Easily to carry out surface chemistry bonding or modification, thus receive more and more attention.But how to obtain comprehensive performance
Better silica column is still that researcher needs to put into a large amount of energy and studied.
Invention content
To solve the above-mentioned problems, the purpose of the present invention is to provide a kind of inorganic type silica gel chelating ion exchange resins
Iminodiacetic acid is attached on silica gel microball skeleton by preparation method, this method, forms one kind and expansion-contraction phenomenon is not present
Novel lateritic nickel ore adsorbent.
Another object of the present invention is to provide a kind of inorganic type silica gel chelating ion exchange resin, the chelating resin into
When row adsorbing metal, precious metal, rare earth ion, without into ion exchange column plus any reagent, pollution-free.
To achieve these goals, the present invention provides a kind of preparation method of inorganic type silica gel chelating ion exchange resin,
Include the following steps：
1) 10~20h of acidification is carried out to silica gel matrix with acid solution under the conditions of 80~100 DEG C, is subsequently cooled to room
The matrix after acidification is obtained by filtration in temperature, then with deionized water the matrix after acidification is washed until it is in neutrality, and does
It is dry to constant weight, obtain pretreated silica gel matrix；
Acidification is that acid solution and silica gel matrix are mixed.
2) enter the humid air of sodium bromide saturated solution or the reaction kettle containing potassium bromide saturated solution and be equipped with pretreatment
In matrix afterwards, matrix surface is made to generate hydrone individual layer, obtain the hydration matrix that moisture content is 4~12wt%；
3) hydration matrix, alkane and silane coupling agent are stirred, reacted at room temperature (preferably 20 after 12~36h
~28h), it is filtered, washed, is dried to when measuring matrix rate of body weight gain 12~14% and takes out, obtain silanization matrix；
4) silanization matrix is added in the reaction kettle equipped with blender, polyamines based polyalcohol is added in into reaction kettle, then
Deionized water and methanol are added in, vacuumizes 10~20min in whipping process, the vacuum degree in reaction kettle is 30~60mm Hg,
Then 36~72h of graft reaction at 60~90 DEG C after graft reaction, is filtered, washed, dries to constant weight, be grafted
Silica gel matrix；
5) it will be grafted silica gel matrix again to add in the reaction kettle equipped with blender, adds in HCl and phosphorous acid, be 70 in temperature
At~120 DEG C, formaldehyde is added in, after 70~120 DEG C are reacted for 24 hours~36h, washing, drying obtain inorganic type silica gel base to constant weight
The chelating resin of body.
Preferably, any one in the step 1) acid solution is a concentration of 1M hydrochloric acid, nitric acid, sulfuric acid or arbitrary two
Kind or more mixture, when any two is mixed above be arbitrary proportioning.
Preferably, step 1) the silica gel matrix and the amount ratio of acid solution are silica gel matrix：Acid solution=10kg: 50~60L.
Preferably, the consumption proportion of hydration matrix, alkane and silane coupling agent is described in step 3：It is hydrated matrix：Alkane
Hydrocarbon：Silane coupling agent=10kg: 18~20L: 4~5kg.
Preferably, the alkane be pentane, hexane, heptane, in octane any one or any two more than it is mixed
Object is closed, is arbitrary proportioning when any two is mixed above.
Preferably, the silane coupling agent is γ-(methacryloxy) propyl trimethoxy silicane, γ-shrink
Glycerine ether oxygen propyl trimethoxy silicane, chloropropyl trichloro-silane, r-chloropropyl trimethoxyl silane, chloropropyl triethoxy silicon
In alkane, 3- glycidyl trimethoxy silanes any one or any two more than mixture, any two is above mixed
It is arbitrary proportioning during conjunction.
Preferably, step 4) the silanization matrix and the proportioning of polyamines based polyalcohol are：Silica gel matrix：Polyamines base polymerize
Object=10kg: 10~12kg.
Preferably, the proportioning of step 4) the silanization matrix, deionized water and methanol is：Silanization matrix：Deionization
Water：Methanol=10kg: 20~22L: 10~12L.
Preferably, any one or two kind of the polyamines based polyalcohol for polyallylamine, in polyethyleneimine are mixed
It closes, two kinds are arbitrary proportioning when mixing, and the weight average molecular weight of polyamines based polyalcohol is 1,000-1,000,000.
Preferably, a concentration of 1M of HCl described in step 5, concentration of formaldehyde 37.7wt%, grafting silica gel matrix, HCl, phosphorous
Sour, formaldehyde proportioning is branch silica gel matrix：HCl：Phosphorous acid：Formaldehyde=10kg: 40~50L: 5~6kg: 7~8L.
Silica gel has many advantages, such as that good thermal stability, high mechanical strength, pore structure and surface area ratio are easier to control, particularly
Silica Surface contains a large amount of active silicone hydroxyls, can easily carry out surface chemistry bonding or modification.
Inorganic type silica gel chelating ion exchange resin and traditional polystyrene and acrylic acid series provided by the invention are organic
Type ion exchange resin is compared, and has the advantages that uniqueness：
(1) for hydrophobic polystyrene and acrylic acid series organic polymer backbones, silica gel/polymer composite
Material is big with strongly hydrophilic, functional group grafting density, and thus obtained inorganic type silica gel chelating ion exchange resin is water-soluble
In liquid to the exchange velocity of metal ion faster, more thorough, the removal particularly to trace heavy metal ion in aqueous solution is handled
Ability is stronger.
(2) during use unlike organic polymer backbones ion exchange resin can generating period expansion-contraction,
Thus service life greatly improves, and it is 10 times higher than organic polymer backbones ion exchange resin to recycle number.
(3) chemical bond of silica gel matrix skeleton is mainly silicon-oxygen key (Si-O), bond energy 422.5KJ/mol, than organic bone
Carbon-carbon bond (C-C bond energy 347KJ/mol) in frame ion exchange resin is much higher.
(4) even if high temperature, ultraviolet light or radiation exposure, strong oxidizer effect are not easy to cause silicon-oxygen bond rupture or decomposition,
Thermal stability, radiation hardness, resistance to oxidation and the mechanical and physical performance for having organic polymer material incomparable.
(5) using silica gel matrix as framework material, oil is not depended on, is derived from a wealth of sources and cheap, can save largely can not be again
Raw fossil resources, it appears it is both economically and environmentally beneficial, meet the thinking of development of national green manufacture.
Inorganic type silica gel chelating ion exchange resin provided by the invention is the oriented attachment tree of nickelous, cobalt, copper ion
Fat.(or depth removal) nickelous, cobalt, copper ion can be effectively enriched in complicated solution system, available for hydrometallurgy,
Related valuable metal recovery, waste water control, deep impurity-removing etc. in medical separation, electroplating wastewater.
The beneficial effects of the present invention are：
The present invention provides a kind of inorganic type silica gel chelating ion exchange resin and preparation method thereof, with existing chelating type from
Sub-exchange resin is compared, the chelating resin for preparing of the present invention to derive from the natural cheap, silica gel that is easy to get, stablizes as matrix,
Their microcosmic nano effect can be made full use of, improves its ion exchange capacity, effectively improves the efficiency of ion exchange resin；It is logical
The polyamines based polyalcohol for crossing different molecular quality is modified, then the ion friendship obtained by Mannich reaction is carried out with formaldehyde and phosphorous acid
Changing the efficiency of resin can be effectively improved, and preparation method.It is carrying out adsorbing each metal ion species such as：Nickel, cobalt,
Whens copper, gold or rare earth etc., without into ion exchange column plus any reagent, pollution-free and do not generate any waste.
Description of the drawings
Fig. 1 is the synthesis technology schematic diagram of the inorganic type silica gel chelating ion exchange resin of the present invention.
Specific embodiment
For a better understanding of the present invention, below in conjunction with the accompanying drawings, the embodiment content that the present invention is furture elucidated, but this hair
Bright content is not limited solely to the following examples；Also it is not construed as limitation of the present invention.
Embodiment 1：
As shown in Figure 1, by 10kg silica gel matrix add in equipped with blender corrosion resistant reaction kettle in, then add in 60L,
1M HCl, after vacuumizing 10min, vacuum degree 30mmHg begins to warm up and boils (100 DEG C), and mixing speed is unsuitable too fast, control
At 70 revs/min, in order to avoid damage silica gel.Then the stirring and pickling 14h at 100 DEG C of bubble point temperature leads to cooling water temperature, when material temperature
Degree releases silica gel matrix when being down to room temperature.The silica gel matrix filtering of releasing filters off filtrate, then is washed with deionized water, to washing
Stop washing when washing water display neutrality, carry out the separation of silica gel matrix and water, then dry silica gel matrix to constant weight, obtain through acid
It washes and dries to the pretreated silica gel matrix of constant weight.
Being placed on sand formula funnel through pickling and the dry silica gel matrix to constant weight, make the humid air of sodium bromide saturated solution
Enter in sand formula funnel by rubber tube, Silica Surface made to generate hydrone individual layer, to measure the moisture content of silica gel matrix for 6~
During 8wt%, hydration is completed, and obtains the hydration matrix that moisture content is 6~8wt%.
Matrix will be hydrated to be put into another corrosion resistant reaction kettle equipped with blender, then add in into reaction kettle respectively
Then the heptane of 40L and 10 kilograms of chloropropyl triethoxysilane carry out being slowly stirred mixing (70 revs/min).At room temperature
After reaction 24, separation of solid and liquid is carried out, the hydration matrix through silanization is to neutrality using n-hexane and the isometric mixing, washing of methanol
Stop, being put into drier drying to measure rate of body weight gain 12~17% i.e. (silanization matrix-hydrated silica gel)/hydrated silica gel ×
During 100%=12~17% } it takes out to get to silanization matrix.
Silanization matrix is added in the corrosion resistant reaction kettle equipped with blender, adds in 12 kilograms into reaction kettle respectively
Polyallylamine (PAA, Mw=1.7 ten thousand), 20L deionized waters and 10L methanol vacuumize 15min, vacuum during being slowly stirred
It spends for 40mmHg and then leads to hot water into reacting kettle jacketing so that temperature of charge is 60 DEG C in reaction kettle, stirring 36h connects to measuring
Grafting is completed when silica gel after branch is 1~1.5 times or more of former silica gel quality).After graft reaction, grafting silica gel is passed through
Filtering is detached with solution, and caustic washing 1 time, deionization washing 3 times and the first of 4 times, one equivalents are washed with deionized water successively
Alcohol is washed 2 times, then by drying materials to constant weight to get grafting silica gel matrix.
This grafting silica gel matrix is added in equipped in corrosion resistant reaction kettle, is separately added into 100L, 1MHCl and 12 kilograms of Asias
Phosphoric acid leads to hot water into reacting kettle jacketing and so that temperature of charge is 100 DEG C in reaction kettle, stir while be slowly added to 16L,
37.7wt% formaldehyde after 100 DEG C of reactions for 24 hours, is washed with deionized water 2 times, 1 mole of every liter of NaOH is washed 1 time, and deionization is washed successively
3 times, 1M H2SO4It washes 1 time, methanol is washed 3 times, then by drying materials to constant weight, is obtained inorganic type silica gel chelating ion and is exchanged tree
Fat.
Embodiment 2：
As shown in Figure 1, by 10 kilograms of silica gel matrixes add in equipped in corrosion resistant reaction kettle, then add in 60L,
1MHNO3, after vacuumizing 20min, vacuum degree 40mmHg is begun to warm up to 90 DEG C, and mixing speed is unsuitable too fast, controls 75
Rev/min, in order to avoid damage silica gel.Then 6~18h of stirring and pickling at 90 DEG C of bubble point temperature leads to cooling water temperature, works as temperature of charge
Stop washing when the silica gel matrix after acidification being obtained by filtration when being down to room temperature, then being washed with deionized to its display neutrality
It washs, then drying to constant weight, obtain pretreated silica gel matrix.
Being placed on sand formula funnel through pickling and the dry silica gel matrix to constant weight, make the humid air of potassium bromide saturated solution
Enter in sand formula funnel by rubber tube, make Silica Surface generate hydrone individual layer, to measure hydrated silica gel moisture content be 6.5
When~7.5%, hydration is completed, and obtains the hydrated silica gel that moisture content is 6.5~7.5wt%.
By hydrated silica gel be put into another equipped in corrosion resistant reaction kettle, added in respectively into reaction kettle 20L just oneself
Alkane and 5 kilograms of γ-(methacryloxy) propyl trimethoxy silicane, then carry out being slowly stirred mixing.At room temperature
After reacting 18h, filtering is washed to neutrality with n-hexane and the isometric mixed liquor of methanol and stopped, being put into drier and be dried to survey
Silica gel rate of body weight gain 15~17% when take out to get to silanization matrix.
Silanization matrix is added in the corrosion resistant reaction kettle equipped with blender, adds in 12 kilograms into reaction kettle respectively
Polyethyleneimine (PEI, Mw=3 ten thousand), 20L deionized waters and 10L methanol vacuumize 10~20min during being slowly stirred,
Vacuum degree is 30mmHg, and hot water is then led into reacting kettle jacketing and so that temperature of charge is 70 DEG C in reaction kettle, stirs 48h, arrives
Grafting is completed when measuring 1.0~1.5 times or more that the silica gel after grafting is former silica gel quality.After graft reaction, it will be grafted
Silica gel is detached by filtering with solution, the caustic washing 1 time of 4 times, one equivalents is washed with deionized water successively, deionization is washed
3 times and methanol are washed 2 times, then by drying materials to constant weight to get grafting silica gel matrix.
This grafting silica gel matrix is added in equipped in corrosion resistant reaction kettle, is separately added into 50L, 1M HCl and 6 kilogram of Asia
Phosphoric acid leads to hot water into reacting kettle jacketing and so that temperature of charge is 90 DEG C in reaction kettle, stir while be slowly added to 8L,
37.7wt% formaldehyde after 90 DEG C are reacted 30h, is washed with deionized water 2 times, 1 mole of every liter of NaOH is washed 1 time, and deionization washes 3 successively
It is secondary, 1M H2SO4It washes 1 time, methanol is washed 3 times, then by drying materials to constant weight, is obtained inorganic type silica gel chelating ion and is exchanged tree
Fat.
The inorganic type silica gel chelating ion exchange resin technical indicator of acquisition：
Skeleton：Inorganic silicon dioxide
Functional group：-(NH)n-COOH
Appearance：White or light yellow spheric granules, no black impurity
Manufacture pattern：H+
Granularity：100-400 microns, main Li Du≤80%
Moisture content：≤ 20% (GB 5757)
Exchange capacity (Ni2+)：≧0.82mmol/g(GB8144)
Apparent density：0.65-0.75g/mL(GB1191)
Temperature in use：≦120℃
It shrinks and expands：≤ 1% (GB1191)
PH use scopes：≦12
Compressive resistance：≦1.2MPa
Service life：It recycles 5000 times, exchange capacity Jiang Di≤15%
Embodiment 3
Chelating resin prepared by embodiment 1 and embodiment 2 carries out the absorption verification of nickel respectively.
Method is：Chelating resin is respectively charged into resin column, packed column volume 1m3, then washed using 25% sulfuric acid solution
Resin, then rinsed resin to pH5 with water, column absorption, nickel in lateritic nickel ore pickle liquor are crossed into lateritic nickel ore pickle liquor (stoste)
Iron content is as shown in table 1.
Ferronickel content in 1 lateritic nickel ore pickle liquor stoste of table
| Serial number | Nickel (g/L) | Iron (g/L) | Flow velocity (m3/h) | |
| 1 | 0.7984 | 13.4 | 1.9 |
The chelating resin prepared using embodiment 1 relationship of ferronickel adsorbance and volume in adsorption process is as shown in table 2：
The record that chelating resin prepared by embodiment 1 is cleaned using water as cleaning solution is as shown in table 3：
| Serial number | Cleaning solution cumulative volume (m3) | Nickel (g/L) | Iron (g/L) | Flow velocity (m3/h) |
| 1 | 0.475 | 0.7675 | 13.000 | 1.9 |
| 2 | 0.950 | 0.2675 | 5.6451 | 1.9 |
| 3 | 1.425 | 0.0006 | 3.4664 | 1.9 |
| 4 | 1.900 | 0.0004 | 2.5640 | 1.9 |
| 5 | 2.375 | 0.0001 | 1.1644 | 1.9 |
| 6 | 2.850 | 0.0000 | 0.7390 | 1.9 |
| 7 | 3.325 | 0.0000 | 0.1518 | 1.9 |
| 8 | 3.800 | 0.0000 | 0.0006 | 1.9 |
| 9 | 4.275 | 0.0000 | 0.0000 | 1.9 |
It is as shown in table 4 that desorption data is carried out using sulfuric acid as stripping liquid：
| Serial number | Stripping liquid cumulative volume (m3) | Nickel (g/L) | Iron (g/L) | Flow velocity (m3/h) |
| 1 | 0.150 | 2.1820 | 0.6586 | 1.9 |
| 2 | 0.300 | 28.000 | 0.8854 | 1.9 |
| 3 | 0.600 | 0.6375 | 0.6381 | 1.9 |
The chelating resin prepared using embodiment 2 relationship of ferronickel adsorbance and volume in adsorption process is as shown in table 5：
The record that chelating resin prepared by embodiment 2 is cleaned using water as cleaning solution is as shown in table 6：
| Serial number | Cleaning solution cumulative volume (m3) | Nickel (g/L) | Iron (g/L) | Flow velocity (m3/h) |
| 1 | 0.475 | 0.7787 | 12.98 | 1.9 |
| 2 | 0.950 | 0.2368 | 6.375 | 1.9 |
| 3 | 1.425 | 0.0006 | 3.112 | 1.9 |
| 4 | 1.900 | 0.0005 | 1.5640 | 1.9 |
| 5 | 2.375 | 0.0002 | 0.9653 | 1.9 |
| 6 | 2.850 | 0.0000 | 0.7268 | 1.9 |
| 7 | 3.325 | 0.0000 | 0.1345 | 1.9 |
| 8 | 3.800 | 0.0000 | 0.0005 | 1.9 |
| 9 | 4.275 | 0.0000 | 0.0000 | 1.9 |
It is as shown in table 7 that desorption data is carried out using sulfuric acid as stripping liquid：
| Serial number | Stripping liquid cumulative volume (m3) | Nickel (g/L) | Iron (g/L) | Flow velocity (m3/h) |
| 1 | 0.150 | 2.1820 | 0.5668 | 1.9 |
| 2 | 0.300 | 28.210 | 0.7874 | 1.9 |
| 3 | 0.600 | 0.8467 | 0.6182 | 1.9 |
It can be seen that, the inorganic type silica gel chelating ion exchange resin of preparation can be adsorbed effectively from above-mentioned data
Nickel, from table 1 and table 4 as can be seen that when the amount of stoste is less than 6m3When (be equivalent to 6 times of column volumes), nickel is all adsorbed in resin,
Illustrate to reach adsorption saturation in 6 times or so column volumes.As table 2 and table 5 wash away the stoste retained in resin when washing with water.Make
When sulfuric acid amount is 3m when being desorbed with sulfuric acid3When, the desorption concentration of nickel reaches maximum value, more than 30 times of a concentration of stoste of nickel, together
The concentration of Shi Tie is only 5% of stoste or so, and the adsorbance of iron is very low.Therefore the present invention is to provide it is a kind of it is extraordinary can
For the resin of nickel Adsorption Concentration.
From the above it can be seen that method provided by the invention has the precious metal and rare earth ion using nickel as representative
There is good adsorption effect, flow is simple and convenient to operate, without in being lived toward ion exchange plus any reagent, pollution-free and do not produce
Raw any waste.A kind of inorganic type silica gel chelating ion exchange resin of the present invention can be equally used for other metals from
The absorption (such as nickel, cobalt, copper, gold, silver, rare earth etc.) of son, no longer illustrates one by one here.
Claims (10)
1. a kind of preparation method of inorganic type silica gel chelating ion exchange resin, which is characterized in that include the following steps：
1) silica gel matrix is added in equipped in corrosion resistant reaction kettle, adds in acid solution, after vacuumizing 10~20min, vacuum degree is
20~50mmHg is mixed, and to 80~100 DEG C, mixing speed is 60~80 revs/min for warming while stirring, and acidification 6~
20h is subsequently cooled to room temperature, the silica gel matrix after acidification is obtained by filtration, then with deionized water to the silicon after acidification
For the washing of matrix body until it is in neutrality, drying obtains pretreated silica gel matrix to constant weight；
2) humid air containing sodium bromide saturated solution or containing potassium bromide saturated solution is made to contact pretreated silica gel matrix,
Silica gel matrix surface is made to generate hydrone individual layer, obtains the hydration matrix that moisture content is 4~12wt%；
3) hydration matrix, alkane and silane coupling agent are stirred, mixing speed is 60~80 revs/min, is reacted at room temperature
After 12~36h, filtering is washed to neutrality using n-hexane and the isometric mixed liquor of methanol and stops, being dried to and measure through silanization
Hydration matrix rate of body weight gain 12~17% when take out, obtain silanization matrix；
4) silanization matrix is added in the reaction kettle equipped with blender, polyamines based polyalcohol is added in into reaction kettle, is stirred
It mixes, mixing speed is 60~80 revs/min, and deionized water and methanol are added in stirring, vacuumize 10 in whipping process~
20min, until the vacuum degree in reaction kettle is 20~60mm Hg, then 24~72h of graft reaction at 50~90 DEG C, grafting are anti-
Should after, filter, be washed with deionized water the caustic washing 1 time of 4 times, one equivalents, deionization is washed 3 times and methanol washes 2
Secondary, drying to constant weight obtains grafting silica gel matrix；
5) it being grafted silica gel matrix again to add in the reaction kettle equipped with blender, adds in HCl and phosphorous acid, stirring is warming up to 70~
120 DEG C, mixing speed is 60~80 revs/min, and the stirring of another side is slowly added to the formaldehyde of a concentration of 37.7wt% on one side, 70~
After 120 DEG C of reaction 12h~36h, deionization is washed 2 times, and 1 mole of every liter of NaOH is washed 1 time, and deionization is washed 3 times, 1M H2SO4Wash 1
Secondary, methanol washes 3 times, is dry to constant weight, obtains inorganic type silica gel chelating ion exchange resin.
2. preparation method as described in claim 1, which is characterized in that the step 1) acid solution is hydrochloric acid, the nitre of a concentration of 1M
Acid, in sulfuric acid any one or any two more than mixture, be arbitrary proportioning when any two is mixed above.
3. preparation method as described in claim 1, which is characterized in that step 1) the silica gel matrix and the amount ratio of acid solution are
Silica gel matrix：Acid solution=10kg: 50~60L.
4. preparation method as described in claim 1, which is characterized in that matrix, alkane and silane coupling agent are hydrated described in step 3
Consumption proportion be：It is hydrated matrix：Alkane：Silane coupling agent=10kg: 18~20L: 4~5kg.
5. preparation method as described in claim 1 or 4, which is characterized in that the alkane is pentane, in hexane, heptane, octane
Any one or any two more than mixture, when any two is mixed above be arbitrary proportioning.
6. preparation method as described in claim 1 or 4, which is characterized in that the silane coupling agent is γ-(metering system
Acyloxy) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, chloropropyl trichloro-silane, chloropropyl
Any one in trimethoxy silane, chloropropyl triethoxysilane, 3- glycidyl trimethoxy silanes or arbitrary two
Kind or more mixture, when any two is mixed above be arbitrary proportioning.
7. preparation method as described in claim 1, which is characterized in that step 4) the silanization matrix, polyamines based polyalcohol,
Deionized water and the proportioning of methanol are：Silica gel matrix：Polyamines based polyalcohol：Deionized water：Methanol=10kg: 10~12kg: 20
~22L: 8~16L.
8. the preparation method as described in claim 1 or 7, which is characterized in that the polyamines based polyalcohol is polyallylamine, gathers
The mixing of any one or two kinds in aziridine is arbitrary proportioning, the Weight-average molecular of polyamines based polyalcohol during two kinds of mixing
It measures as 1,000-1,000,000.
9. preparation method as described in claim 1, which is characterized in that a concentration of 1M of HCl described in step 5, concentration of formaldehyde are
37.7wt%, grafting silica gel matrix, HCl, phosphorous acid, formaldehyde proportioning be branch silica gel matrix：HCl：Phosphorous acid：Formaldehyde=10kg
: 40~50L: 5~6kg: 7~8L.
10. a kind of inorganic type silica gel chelating ion exchange resin prepared such as claim 1-9 any one of them method.
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