CN101693757B - Hydrophilous porous phenolic resin as well as preparation method and application thereof - Google Patents
Hydrophilous porous phenolic resin as well as preparation method and application thereof Download PDFInfo
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- CN101693757B CN101693757B CN2009101746969A CN200910174696A CN101693757B CN 101693757 B CN101693757 B CN 101693757B CN 2009101746969 A CN2009101746969 A CN 2009101746969A CN 200910174696 A CN200910174696 A CN 200910174696A CN 101693757 B CN101693757 B CN 101693757B
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Abstract
The invention relates to hydrophilous porous phenolic resin as well as a preparation method and the application thereof, belonging to the technical field of porous polymer materials. The hydrophilous porous phenolic resin comprises a phenol monomer and an aldehyde monomer, wherein the mole ratio of the phenol monomer to the aldehyde monomer is 1 to 1-5; structures of the phenol monomer and the aldehyde monomer are formed by micropores of 0.4-1 nanometer and mesopores of 2-50 nanometers. The hydrophilous porous phenolic resin can absorb and selectively reduce partial noble metal ions and respectively achieve the large absorption amount of gold and silver ions of 700-1500 mg/g and 1000-3000 mg/g. The preparation method of the hydrophilous porous phenolic resin has the characteristics of simple, convenient and easy technology, easy sequential processing, and the like; and in addition, the hydrophilous porous phenolic resin has large absorption amount, high selectivity for the noble metal ions and extensive application prospect in the fields of noble metal smelting and recovery, and the like.
Description
Technical field
The invention belongs to the porous polymer material technical field, be specifically related to a kind of Hydrophilous porous phenolic resin and its production and application.
Background technology
Since 20th century, the highly crosslinked polystyrene porous polymer appearred in the seventies, highly cross-linked porous polymer had caused great concern in fields such as catalysis, ion-exchange, absorption, separation, chromatograms, and good several materials are suitability for industrialized production all.Compare traditional gac and zeolite molecular sieve, polymkeric substance is because its distinctive snappiness and might be made into separatory membrane and be used for divided gas flow or liquid, and this is the advantage of a highly significant of polymer porous material.But because the polystyrene type material all is hydrophobic, thereby limited its application in the aqueous solution greatly, known its hydrophilic method of improving all is to utilize hydrophilic monomer and styrene monomer copolymerization or direct hydrophilic radical in the crosslinked polystyrene finishing, as sulfonic group, amido or hydroxyl.
Traditional method for preparing hydrophilic polymer has two kinds: the one, and utilize polymerizable hydrophilic monomer to obtain, the hydrophilic monomer of using in the report generally all is to obtain with acrylate, acrylic acid amides and derivative thereof and cross-linking monomer copolymerization.As Shea[K.J.Shea, G.J.Stoddard, D.M.Shavelle, F.Wakui, R.M.Choate, Macromolecules, 1990,23,4497-4507] etc. the people prepared the hydrophilic polymer of a large amount of acrylic acid amides and diacrylamine, wherein the diacrylate acid amides is as crosslinked body.CN1389296 discloses and has utilized polyacrylic ester and crosslinked body copolymerization posthydrolysis to obtain weakly acidic cation-exchange resin.The 2nd, by crosslinked polystyrene is carried out finishing, hydrophilic radicals such as sulfonic group, amido, hydroxyl in the modification, wherein sulfonic group is modified and is commonly used to do storng-acid cation exchange resin, as disclosing the highly acidic resin that a kind of crosslinked polystyrene sulfonation prepares high-exchange-capacity among the CN1389297.But, if will directly modify phenolic hydroxyl group on the crosslinked polystyrene surface, it is very loaded down with trivial details that its technology becomes, will be through nitrated, reduction, diazotization hydrolysis again, if have the organism of phenolic hydroxyl group on modifying, because organic molecule can account for the part pore volume of crouching, cause its pore volume to reduce and the exchange capacity reduction.Relevant phenolic resinoid has disclosed pnenolic aldehyde type adsorption resin among the CN101062969A, but because its specific surface area is lower, usually less than 250m
2/ g is difficult to practicability.
Porous resin adsorbents adsorb precious metal ion (Au, Ag, Pt, Pd, Ru, Rh, Os, Ir) and other toxic heavy metal ions (Hg, Cd) done commonly used.Precious metal is because its huge using value and serious day by day scarcity make that reclaiming precious metal from waste has huge economic.Because precious metal ion general form with complex anion in solution exists, so anionite-exchange resin is widely used for adsorbing precious metal ion, but such resin is undesirable to the fractionation by adsorption of precious metal, because they can adsorb most of precious metal ion, thus not too high to the selectivity of a certain precious metal ion.In addition, the sorbent material that contains sulfydryl, imidazoles and other chelation groups also is developed [R.X.Liu, Y.Li, H.X.Tang, Journal of Applied Polymer Science, 2002,83,1608-1616; T.Kang, Y.Park, K.Choi, J.S.Lee, J.Yi, Journal of Materials Chemistry, 2004,14,1043-1049; W.S.W.Ngah, K.H.Liang, Industrial ﹠amp; Engineering Chemistry Research, 1999,38,1411-1414; M.A.Hassanien, K.S.Abou-El-Sherbini, Talanta, 2006,68,1550-1559], CN86103557 discloses the method for a kind of AP of utilization resin isolation enrichment gold, palladium, platinum, and the AP resin utilizes its nitrogen-containing group bonding absorption precious metal ion.CN101091908 discloses the method for a kind of amido thiourea-formaldehyde resin ADSORPTION OF GOLD, silver ions, wherein mainly utilizes sulfur-containing group and nitrogen-containing group bonding absorption precious metal ion, and its adsorptive capacity to silver reaches as high as 10.8mmol/g.But because the reactive force between such sorbent material and metal ion is general acid-base function, so its selectivity is not ideal enough equally.
Because the precious metal ion electrode potential is usually greater than base-metal ion, so can utilize the adsorbents adsorb with suitable reductibility also optionally reduces precious metal ion and does not reduce base-metal ion, good several sorbent materials can both reductibility adsorb precious metal ion, as Pittman[Z.R.Yue, W.Jiang, L.Wang, H.Toghiani, S.D.Gardner, C.U.Pittman, Carbon, 1999,37,1607-1618], Chen[S.X.Chen, H.M.Zeng, Carbon, 2003,41,1265-1271] etc. the people studied activated carbon reduction absorption precious metal ion (Ag
+, Au
3+, Pt
2+, Pd
2+) phenomenon, find that activated carbon fiber is handled through 9540 electrooxidation after, in silver ammino solution, soak after 30 days, the adsorptive capacity of its silver ions is up to 1.36g/g.But, prepare this carbon fiber and need pass through long electro-oxidation process, can not suitability for industrialized production.Huang[X.G.Li, M.R.Huang, S.X.Li, Acta Materialia, 2004,52,5363-5374; X.G.Li, R.Liu, M.R.Huang, Chemistry of Materials, 2005,17,5411-5419] etc. the people studied poly-1,8-naphthylene diamine, pentanoic-4-sulfonic acid and 1, the multipolymer of 8-naphthylene diamine is to the absorbing and reducing of silver ions, find that the latter adsorb after 48 hours the silver ions adsorptive capacity up to 2.0g/g when PH=7, but silver ions can generate precipitation during owing to PH=7, so its actual adsorptive capacity should be less than 2.0g/g.And the monomer of these polymkeric substance is relatively more expensive, does not also possess the ability of large-scale industrial production in a short time.In addition, the sorbent material [R.X.Liu, Y.Li, H.X.Tang, Journalof Applied Polymer Science, 2002,83, the 1608-1616 that contain sulfydryl; C.C.Zhang, X.Li, J.X.Pang, Journal of Applied Polymer Science 2001,82,1587; S.A.Simanova, A.V.Shukarev, A.A.Lysenko, S.F.Grebennikov, O.V.Astashkina, Fibre Chemistry 2008,40,365; S.Q.Tang, Y.Lu, H.M.Zeng, Journal of Applied Polymer Science 2001,81,1985.] also can its absorption of selective reduction the part gold ion.But these all reductibility sorbent materials all do not have renovation process.Therefore it is very high to cause adsorbing cost, is unfavorable for large-scale industrial utilization and popularization.
Summary of the invention
The objective of the invention is to solve problems of the prior art, a kind of Hydrophilous porous phenolic resin and its production and application is provided.
The present invention adopts following technical scheme to solve the problems of the technologies described above:
A kind of Hydrophilous porous phenolic resin, this Hydrophilous porous phenolic resin is made up of phenol monomer and aldehyde monomer, the monomeric mol ratio of phenol monomer and aldehyde is between 1: 1 to 1: 5, and this Hydrophilous porous phenolic resin structure is made up of micropore and the mesoporous of 2～50nm of a kind of 0.4～1nm.
The implication that term " is made up of phenol monomer and aldehyde monomer " is: Hydrophilous porous phenolic resin of the present invention is to be made through the phenol formaldehyde condensation reaction by phenol monomer and aldehyde monomer.
Preferable, described phenol monomer is selected from phenol, 2,2-two (4-hydroxy phenyl) propane (claiming dihydroxyphenyl propane again), pyrocatechol, Resorcinol or 4, one or more in 4 '-dihydroxybiphenyl.
Preferable, described aldehyde monomer is selected from one or more in acetaldehyde, formaldehyde or the phenyl aldehyde.
Preferably, described Hydrophilous porous phenolic resin has following general structure:
Wherein A represents the phenol structural unit, and phenol is by the ortho para and the aldehyde generation dehydration reaction of hydroxyl, and each phenol all has four active sites, so each phenol unit can link to each other with four aldehyde unit at most; R represents hydrogen atom, methyl or phenyl, corresponds respectively to aldehyde monomers such as formaldehyde, acetaldehyde and phenyl aldehyde.The cavity that polymer chain surrounded (among the figure shown in the broken circle) has just constituted the hole in the polymkeric substance.Wherein, the A of different positions can be identical, also can be different; The R of different positions can be identical, also can be different.
In the said structure general formula, other phenol structural units that the part phenol units replaces in the above general structure also can obtain porous resin, and by pyrocatechol, 2, in the non-porous polymkeric substance that 2-two (4-hydroxy phenyl) propane, 4,4 '-dihydroxybiphenyl and oxymethylene polymerization obtain then is not included in.
Preferably, the BET specific surface area of described Hydrophilous porous phenolic resin is greater than 460m
2g
-1, be preferably 460～1060m
2g
-1Pore volume is 0.2～2.4cm
3g
-1
The preparation method of Hydrophilous porous phenolic resin of the present invention comprises the steps:
1) phenol monomer and aldehyde monomer are dissolved in the solvent, at room temperature stir it is dissolved fully, add acid or alkali then and make catalyzer and obtain reaction system;
2) step 1) gained reaction system is packed into seal in the reactor, carry out the constant temperature insulation reaction under a certain temperature of reaction between 30～180 ℃, the reaction times is 0.5 hour to 30 days;
3) with step 2) smash alcohol immersion after-filtration, washing with alcohol to pieces behind the gel naturally cooling that makes;
4) the filter cake seasoning that step 3) is made is approximately at 10～90% o'clock to the ethanol massfraction, and filter cake is clayed into power, and is under 50～150 ℃ drying temperature, dry in atmosphere of inert gases then, promptly makes Hydrophilous porous phenolic resin.
Preferable, the phenol monomer in the described step 1) is selected from phenol, 2,2-two (4-hydroxy phenyl) propane (claiming dihydroxyphenyl propane again), pyrocatechol, Resorcinol or 4, one or more in 4 '-dihydroxybiphenyl.
Preferable, the aldehyde monomer in the described step 1) is selected from one or more in acetaldehyde, formaldehyde or the phenyl aldehyde.
Preferable, phenol monomer in the described step 1) and the monomeric mol ratio of aldehyde are 1: 1～5.
Preferable, the acid in the described step 1) is mineral acid, further preferred hydrochloric acid, sulfuric acid or phosphoric acid, and further preferably sulfuric acid and hydrochloric acid, and the concentration of described acid in reaction system is 0.1～5mol/L.
Preferable, the alkali in the described step 1) is sodium hydroxide or potassium hydroxide, and the concentration of described alkali in reaction system is 0.1～2mol/L.
Preferable, the solvent in the described step 1) is ethanol or water.
Preferable, in the described step 1), in the total mass of described reaction system, the monomeric mass percent of described phenol is 1%～50%.
Term " reaction system " is meant the total reaction system that comprises phenol monomer, aldehyde monomer, solvent and catalyzer.
Preferable, described step 2) temperature of reaction in is 30～120 ℃.
Described step 2) reaction times and temperature of reaction in are inversely proportional to, that is: the low more then required reaction times of temperature of reaction is long more.
Preferable, the concrete steps of the usefulness washing with alcohol in the described step 3) are: if make catalyzer with acid, then need add 6 hours after-filtration of ethanol agitator treating in powder, add 1～4ml ethanol in wherein every gram powder; If make catalyzer with alkali, then need in powder, add in the excess acid and residual alkali, add 6 hours after-filtration of ethanol agitator treating then, add 1～4ml ethanol in wherein every gram powder.
Preferable, the drying temperature in the described step 4) is 120 ℃.
Preferable, the rare gas element in the described step 4) is a nitrogen.
Preferably, when using acid as catalyzer, the preparation method's of described Hydrophilous porous phenolic resin concrete steps are:
1) one or more in one or more in the phenol monomer of selecting for use and the aldehyde monomer selected for use, the monomeric mol ratio of phenol monomer and aldehyde is between 1: 1 to 1: 5;
When selecting several phenol monomer for use, can adopt arbitrary proportion between several phenol monomers;
When selecting several aldehyde monomer for use, can adopt arbitrary proportion between several aldehyde monomers;
Described phenol monomer is phenol, Resorcinol, pyrocatechol or 2,2-two (4-hydroxy phenyl) propane (claiming dihydroxyphenyl propane again);
Described aldehyde monomer is acetaldehyde, formaldehyde or phenyl aldehyde;
2) phenol monomer and aldehyde monomer are dissolved in water or the ethanol, the mass content of phenol in solution is 1%-50%, adds acid and makees catalyzer;
The concentration of described acid is at 0.1～5mol/L;
The preferred mineral acid of described acid, further preferred hydrochloric acid, sulfuric acid or phosphoric acid;
3) with step 2) in products therefrom between 30～120 ℃ the reaction more than 0.5 hour;
4) with products therefrom in the step 3) after washing with alcohol is dried to ethanol content 10%-90%, dry under 50～150 ℃ of rare gas elementes.
Preferably, when using alkali as catalyzer, the preparation method's of described Hydrophilous porous phenolic resin concrete steps are:
1) one or more in one or more in the phenol monomer of selecting for use and the aldehyde monomer selected for use, the monomeric mol ratio of phenol monomer and aldehyde is between 1: 1 to 1: 5;
When selecting several phenol monomer for use, can adopt arbitrary proportion between several phenol monomers;
When selecting several aldehyde monomer for use, can adopt arbitrary proportion between several aldehyde monomers;
Described phenol monomer is phenol, Resorcinol, pyrocatechol or 2,2-two (4-hydroxy phenyl) propane (claiming dihydroxyphenyl propane again);
Described aldehyde monomer is acetaldehyde, formaldehyde or phenyl aldehyde;
2) phenol monomer and aldehyde monomer are dissolved in water or the ethanol, the mass content of phenol in solution is 1%-50%, adds alkali and makees catalyzer;
The concentration of described alkali is at 0.1-2mol/L;
Preferred sodium hydroxide of described alkali or potassium hydroxide;
3) with step 2) in products therefrom between 30～120 ℃ the reaction more than 0.5 hour;
4) with products therefrom in the step 3) through washing with alcohol and add excess acid neutralization bases catalyzer, be dried to ethanol content 10%-90% after, dry under 50～150 ℃ of rare gas elementes.
The concentration of described acid is at 0.1-5mol/L;
The preferred mineral acid of described acid, further preferred hydrochloric acid, nitric acid or sulfuric acid.
Hydrophilous porous phenolic resin of the present invention can be used for fields such as precious metal Separation and Recovery, purification of waste water and gas adsorption storage.
The know-why of Hydrophilous porous phenolic resin of the present invention in the application in precious metal Separation and Recovery field is: by phenolic hydroxyl group absorption and selective reduction part precious metal ion.
Owing to contain a large amount of phenolic hydroxyl groups in this Hydrophilous porous phenolic resin, these phenolic hydroxyl groups have not only improved the wetting ability of resin greatly, can also be as reductibility group selectivity reduction precious metal ion, with 4,4 '-dihydroxybiphenyl formaldehyde resin absorbing and reducing precious metal ion is an example, and its reaction is as follows:
Wherein oval and circle is represented the hole in the Hydrophilous porous phenolic resin.The porous phenolic resinoid utilizes its huge specific surface adsorbing metal ions earlier, and then optionally the part precious metal ion (Au ion or Ag ion etc.) of its absorption being carried out in-situ reducing, the formed metallic particles that reduces just is deposited in the inside, hole of polymkeric substance.
Resin reductive agent (NaHSO after the absorption precious metal reaches capacity
3Solution or Fe+ hydrochloric acid) soak after, the two keys of carbon oxygen in the resin are reduced into hydroxyl (this moment, precious metal simple substance was still stayed in the duct of resin) again, reductibility is adsorbed precious metal once more, and then regenerate with reductive agent, so repeat, till can not effectively adsorbing precious metal again, can adopt the incendiary method to burn resin this moment, stays precious metal simple substance.
The invention discloses the method for this porous phenolic resinoid absorption of a kind of application and selective reduction precious metal ion, comprise the steps: the porous phenolic resinoid is placed precious metal ion solution, whip attachment is 0.1～100 hour under 0～100 ℃ temperature condition, filtering separation solid-liquid two-phase.
Preferable, described precious metal is selected from gold and silver, palladium, ruthenium, rhodium, platinum, iridium or osmium.
Preferable, in the described precious metal ion solution, the content of precious metal ion is greater than 0.002ppm.
Preferable, the solid-to-liquid ratio of described porous phenolic resinoid and precious metal ion solution is 1: 10～1: 10000 (W/V).
The concrete operations step of the method for the Hydrophilous porous phenolic resin adsorbing metal ions among the present invention is:
Adsorption method 1: precious metal ion solution is joined in the resin, the constant temperature whip attachment is 6～72 hours under a certain fixed temperature condition between 0～100 ℃, filtering separation solid-liquid two-phase then, the original solution of precious metal ion solution and filtrate solution use inductively coupled plasma atomic emission spectrometer to measure its ionic concn, and calculate adsorptive capacity according to following formula:
Q＝(C
0-C)V/W
Q is the adsorptive capacity (mg/g) of unit mass sorbent material in the formula, C
0For adsorbing preceding concentration of metal ions (mg/L), C is absorption back concentration of metal ions (mg/L), and V is precious metal solution volume (L), and W is sorbent material dry weight (g).
Preferably, the resinoid add-on of described porous phenolic is relevant with precious metal ion concentration in the precious metal ion solution, and its concrete ratio is: the resinoid weight ratio of gold ion and porous phenolic is 0.1～1: 1; The resinoid weight ratio of silver ions and porous phenolic is 0.5～2.5: 1.
Adsorption method 2: will contain metal ion solution and adsorb by the adsorption column of being filled by expanded phenol-formaldehyde resin, in adsorption process, the temperature of expanded phenol-formaldehyde resin packed column remains on a certain fixed temperature condition between 0～100 ℃.
The invention also discloses this porous phenolic resinoid of a kind of application and from precious metal ion solution, reclaim the method for precious metal simple substance, comprise the steps: the porous phenolic resinoid placed and contain metal ion solution, 0～100 ℃ of following whip attachment 0.1～100 hour, filtering separation solid-liquid two-phase, remove with ionic state with hydrochloric acid lotion washing and to be adsorbed on base-metal ion on the resin, obtain the precious metal of metallic state and the mixture of resin, remove resin by burning and promptly obtain the mixture that precious metal simple substance or multiple precious metal simple substance are formed.
Preferable, described temperature of combustion is 250～1000 ℃.
The invention also discloses the saturated later renovation process of this Hydrophilous porous phenolic resin absorption precious metal, comprise the steps: that the Hydrophilous porous phenolic resin that will adsorb after precious metal reaches capacity is immersed in the reductive agent, soak back taking-up washing and just obtain the regenerated resin.
Preferable, described reductive agent is selected from the mixed solution of sodium sulfite solution or iron and hydrochloric acid.
Preferably, the molecular volume concentration of sodium bisulfite is 0.01～10mol/L in the described sodium sulfite solution.
Preferably, in the mixed solution of described iron and hydrochloric acid, the concentration range 1～12mol/L of hydrochloric acid, the mol ratio of iron and hydrochloric acid is 1: 2～4, more preferably 1: 2.
Preferable, the part by weight of described sodium sulfite solution and Hydrophilous porous phenolic resin is 0.1～50: 1, more preferably 0.5～10: 1.
Preferable, the mass ratio of described iron and Hydrophilous porous phenolic resin is 0.2～10: 1.
Preferable, described soak time is 0.1～100 hour, 0.1～72h more preferably, and soaking temperature is 0～100 ℃.
Compare and other precious metals, the Hydrophilous porous phenolic resin among the present invention is very high to the selectivity of gold ion and silver ions, therefore can be used for gold ion and silver ions are carried out selective adsorption.
Hydrophilous porous phenolic resin among the present invention selects the performance test procedure as follows to precious metal: (is example with the gold ion)
Gold ion and other metal ions (as copper, cadmium, nickel, iron, platinum, palladium ion) are made into mixing solutions by a certain percentage, (ratio of the volumetric molar concentration of gold ion and the volumetric molar concentration of other foreign ions is 1: 10), GOLD FROM PLATING SOLUTION belongs to ionic concn before and after surveying absorption according to the step of adsorption method 1 then, and it is many more that the metal ion explanation that change in concentration is big more is adsorbed.Hydrophilous porous phenolic resin of the present invention is up to ten thousand times of other ionic to the adsorptive capacity of gold ion, illustrates that Hydrophilous porous phenolic resin of the present invention is very high to the selectivity of gold ion.
Hydrophilous porous phenolic resin of the present invention is the phenolic resinoid that is made by phenol monomer and aldehyde dehydration polymerization.Resin of the present invention is a kind of porous polymer, and this polymkeric substance is made of micropore and the mesoporous of 2～50nm of a kind of 0.4～1nm, and pore volume can be up to 2.4cm
3g
-1, specific surface is up to 1100m
2g
-1During resin absorption precious metal ion of the present invention (Au, Ag), the selectivity height, adsorptive capacity is big, and (adsorptive capacity of gold and silver is respectively up to 700～1500,1000～3000mg/g), the organic efficiency height.Hydrophilous porous phenolic resin of the present invention to precious metal ion have selectivity high and loading capacity big and rate of adsorption fast and under without the prerequisite of wash-out precious metal simple substance with characteristics such as reductive agent regeneration, suitable industrial applications.In addition, Hydrophilous porous phenolic resin of the present invention also has broad application prospects in fields such as purification of waste water, gas adsorption storage, separation, gel chromatographies.
Simultaneously, the present invention's method of directly adopting hydrophilic phenol monomer and formaldehyde direct condensation in suitable solvent to obtain the crosslinked resol of porous highly has following advantage: raw material is easy to get, synthesis technique simple, need not to add any template; The productive rate height, and solvent and catalyzer can reuse.
Preparation is simple for porous resin of the present invention, starting material all are the heavy industrialization products, the porous material of preparation has very big pore volume and specific surface area, has three grades of pore structures of micropore-mesopore-macropore, helps metal ion transmission effectively in the duct; And its inherent phenolic hydroxyl group has not only improved the wetting ability of polymkeric substance, also simultaneously as the precious metal ion in the reductibility group selectivity reducing solution, (adsorptive capacity of gold and silver all is that existing polymeric adsorbent is unapproachable up to 700～1580,1000～3480mg/g) respectively to this resin to the highly selective of precious metal ion (Au, Ag) and high-adsorption-capacity.These character have determined the present invention that wide industrial prospect is arranged.
Description of drawings
Fig. 1 is the stereoscan photograph of the Hydrophilous porous phenolic resin that makes among the embodiment 1.
Fig. 2 is the nitrogen adsorption-desorption isotherm of the Hydrophilous porous phenolic resin that makes among embodiment 1, embodiment 2, the embodiment 4.
Fig. 3 is that the micropore size of the Hydrophilous porous phenolic resin that makes among embodiment 1, embodiment 2, the embodiment 4 distributes.
Fig. 4 is the infrared spectrogram of the Hydrophilous porous phenolic resin that makes among embodiment 1, embodiment 2, embodiment 3, the embodiment 4 from top to bottom successively.
Fig. 5 is the stereoscan photograph behind the Hydrophilous porous phenolic resin absorption silver ions that makes among the embodiment 3.
Fig. 6 is the backscattered electron image in zone shown in Figure 5.
Behind the Hydrophilous porous phenolic resin that makes among Fig. 7 embodiment 3 absorption gold and silver, the palladium ion the wide-angle XRD figure.
Infrared spectrogram before and after the Hydrophilous porous phenolic resin absorption silver ions that makes among Fig. 8 embodiment 3.
Fig. 9 is the thermogravimetric curve figure behind the Hydrophilous porous phenolic resin absorption silver ions that makes among the embodiment 3.
Embodiment
The present invention is further described below in conjunction with example, and these examples are not limitation of the scope of the invention.
Embodiment 1: the preparation of porous pyrocatechol formaldehyde resin
2.20g pyrocatechol, 2ml formaldehyde (37wt%) and 5ml concentrated hydrochloric acid are added in the 10ml ethanol together, stirring is dissolved it fully, with the above-mentioned solution reactor of packing into, 100 ℃ of insulations 5 hours, the gained gel was smashed to pieces, adding 50g ethanol stirred 6 hours, filter, washing with alcohol, the filter cake seasoning is about at 80% o'clock to ethanol content it is ground, the dry lightweight black powder that gets under 120 ℃ of nitrogen atmospheres, the pore volume of gained material is 2.4cm
3g
-1, specific surface area is 1008m
2g
-1
The stereoscan photograph of the porous pyrocatechol formaldehyde resin that makes in the present embodiment has shown the macroporous structure and the granule-morphology thereof of material as shown in Figure 1 intuitively among Fig. 1.Nitrogen adsorption-the desorption isotherm of this resin as shown in Figure 2, Fig. 2 shows that this material has high specific surface area and pore volume and hierarchical porous structure, wherein phenol formaldehyde resin is mainly micropore.The micropore size distribution plan of this resin shows among Fig. 3 that this material demonstrates very sharp-pointed micropore size and distributes as shown in Figure 3.The infrared spectrogram of this resin material shows among Fig. 4 that material is the phenolic resinoid that phenol and aldehyde dehydrating condensation obtain as shown in Figure 4.
Accurately take by weighing a certain amount of this kind resin, place 100ml tool plug Erlenmeyer flask, add certain density precious metal ion solution, whip attachment is 24 hours in thermostat container, Thermostat Temperature Control is at 0～100 degree, filtering separation solid-liquid two-phase, original solution and filter liquor concentration record with inductively coupled plasma atomic emission spectrometer, and calculate adsorptive capacity according to following formula:
Q＝(C
0-C)V/W
Q is adsorptive capacity (mg/g) in the formula, C
0For adsorbing preceding concentration of metal ions (mg/L), C is absorption back concentration of metal ions (mg/L), and V is precious metal solution volume (L), and W is sorbent material dry weight (g).The saturated extent of adsorption that records the gold ion of this resin is 1200mg/g, and the saturated extent of adsorption of silver ions is 2500mg/g.This resin to Pd, Pt, Ru, Rh, Os, Ir, Hg, Cd ionic saturated extent of adsorption be respectively 170,65,47,45,63,56,41,34mg/g.
Regenerability test: after this resin absorption gold reaches capacity, use excessive N aHSO
3Solution soaking 24 hours is surveyed resin after the regeneration to the adsorptive capacity of gold by above method afterwards again, finds secondary adsorptive capacity up to 958mg/g, for the first time adsorptive capacity 80%.As seen resin has good regenerability.
Competitive adsorption (weighing the selection performance of resin) to gold
Gold ion and copper, cadmium, nickel, iron, platinum, the isoionic muriate of palladium ion are made into mixing solutions, the concentration of gold ion is 200mg/L, other ionic volumetric molar concentrations are about 10 times of volumetric molar concentration of gold ion, in a certain amount of mixed solution, added above-mentioned resin stirring 25 degree 24 hours then, measure every kind of ionic change in concentration with inductively coupled plasma atomic emission spectrometer afterwards, calculate every kind of ionic adsorptive capacity (the big more explanation resin of adsorptive capacity is good more to this ionic selectivity, and the big more explanation selectivity of partition ratio Kd is good more) in view of the above.Various resin choice data see Table 1.
Embodiment 2: porous pyrocatechol acetaldehyde resin (base catalysis)
2.20g pyrocatechol, 3ml acetaldehyde (37wt%) and 0.5g NaOH are added in the 10ml ethanol together, stirring is dissolved it fully, with the above-mentioned solution reactor of packing into, 100 ℃ of insulations 10 hours, the gained gel was smashed to pieces, the ethanol solution hydrochloride that adds 50g 5wt% stirred 6 hours, filter, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry lightweight black powder that gets under 120 ℃ of nitrogen atmospheres, the pore volume of gained material is 1.4cm
3g
-1, specific surface area is 807m
2g
-1Nitrogen adsorption-the desorption isotherm of this resin as shown in Figure 2, Fig. 2 shows that this material has high specific surface area and pore volume and hierarchical porous structure, wherein phenol formaldehyde resin is mainly micropore.The micropore size distribution plan of this resin shows among Fig. 3 that this material demonstrates very sharp-pointed micropore size and distributes as shown in Figure 3.The infrared spectrogram of this resin material shows among Fig. 4 that material is the phenolic resinoid that phenol and aldehyde dehydrating condensation obtain as shown in Figure 4.
The adsorptive capacity that the gained material records its gold and silver by the method for embodiment 1 is respectively 978,2350mg/g.
Embodiment 3: porous pyrocatechol acetaldehyde resin (acid catalysis)
2.20g pyrocatechol, 3ml acetaldehyde (37wt%) and 5ml concentrated hydrochloric acid are added in the 10ml ethanol together, stirring is dissolved it fully, with the above-mentioned solution reactor of packing into, 100 ℃ of insulations 10 hours, the gained gel was smashed to pieces, adding 50g ethanol stirred 6 hours, filter, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry lightweight black powder that gets under 120 ℃ of nitrogen atmospheres, the pore volume of gained material is 1.6cm
3g
-1, specific surface area is 879m
2g
-1The infrared spectrogram of this resin material shows among Fig. 4 that material is the phenolic resinoid that phenol and aldehyde dehydrating condensation obtain as shown in Figure 4.
The adsorptive capacity that the gained material records its gold and silver by the method for embodiment 1 is respectively 958,2250mg/g.Stereoscan photograph behind the resin absorption silver ions that makes in the present embodiment has shown among Fig. 5 that the not obviously change of silver ions post polymerization thing pattern is adsorbed in resin pattern and Fig. 1 contrast behind the absorption silver ions as can be known as shown in Figure 5.The backscattered electron image in zone shown in Figure 5 has shown clearly among Fig. 6 that argent is evenly distributed in the resin as shown in Figure 6.The resin material ADSORPTION OF GOLD that makes in the present embodiment, silver, behind the palladium ion the wide-angle XRD figure as shown in Figure 7, be followed successively by the resin absorption gold that makes in the present embodiment among Fig. 7 from top to bottom, silver, behind the palladium ion the wide-angle XRD figure, diffraction peak among the figure corresponds respectively to gold, silver, the diffraction peak of palladium, shown that clearly resin is reduced into simple substance precious metal (golden simple substance and silver-colored simple substance) with precious metal ion (gold ion and silver ions) in absorption, prove that simultaneously the resin material that present embodiment makes not only has adsorption to gold ion and silver ions, also has the effect of selective reduction simultaneously.Infrared spectrogram before and after resin material that present embodiment the makes absorption silver ions as shown in Figure 8, both differences at the 1243cm-1 place show that the process of selective reduction precious metal ion mainly is that phenolic hydroxyl group is oxidized.Thermogravimetric behind the resin material absorption silver ions that makes in the present embodiment as shown in Figure 9, Fig. 9 shows that the resin of absorption behind the silver ions can remove wherein resin through burning disposal, obtain pure precious metal simple substance, the adsorptive capacity of silver is calculated by the ablation residual volume, and this result is consistent with the silver adsorption that inductance coupled plasma atomic absorption spectrum records.
Embodiment 4: porous pyrocatechol phenyl aldehyde resin
2.20g pyrocatechol, 2ml phenyl aldehyde and 5ml concentrated hydrochloric acid are added in the 10ml ethanol together, stirring is dissolved it fully, with the above-mentioned solution reactor of packing into, 120 ℃ of insulations 10 hours, the gained gel was smashed to pieces, adding 50g ethanol stirred 6 hours, filter, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry lightweight black powder that gets under 120 ℃ of nitrogen atmospheres, the pore volume of gained material is 0.4cm
3g
-1, specific surface area is 477m
2g
-1Nitrogen adsorption-the desorption isotherm of this resin as shown in Figure 2, Fig. 2 shows that this material has high specific surface area and pore volume and hierarchical porous structure, wherein phenol formaldehyde resin is mainly micropore.The micropore size distribution plan of this resin shows among Fig. 3 that this material demonstrates very sharp-pointed micropore size and distributes as shown in Figure 3.The infrared spectrogram of this resin material shows among Fig. 4 that material is the phenolic resinoid that phenol and aldehyde dehydrating condensation obtain as shown in Figure 4.
The adsorptive capacity that the gained material records its gold and silver by the method for embodiment 1 is respectively 357,650mg/g.
Embodiment 5: porous 2,2-two (4-hydroxy phenyl) propane formaldehyde resin
With 2.28g 2,2-two (4-hydroxy phenyl) propane, 2ml formaldehyde (37wt%) and 5ml concentrated hydrochloric acid add in the 10ml ethanol together, stir it is dissolved fully, with the above-mentioned solution reactor of packing into, 100 ℃ of insulations 5 hours, the gained gel is smashed to pieces, adds 50g ethanol and stirs 6 hours, filters, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry brown powder of lightweight that gets under 120 ℃ of nitrogen atmospheres, and the pore volume of gained material is 0.5cm
3g
-1, specific surface area is 560m
2g
-1
Embodiment 6: porous 2,2-two (4-hydroxy phenyl) propane acetaldehyde resin (base catalysis)
With 2.28g 2,2-two (4-hydroxy phenyl) propane, 3ml acetaldehyde (37wt%) and 0.5g NaOH add in the 10ml ethanol together, stir it is dissolved fully, with the above-mentioned solution reactor of packing into, 140 ℃ of insulations 5 hours, the gained gel is smashed to pieces, and the ethanol solution hydrochloride that adds 50g 5wt% stirred 6 hours, filtered, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry brown powder of lightweight that gets under 120 ℃ of nitrogen atmospheres, and the pore volume of gained material is 0.45cm
3g
-1, specific surface area is 487m
2g
-1
Embodiment 7: porous 2,2-two (4-hydroxy phenyl) propane acetaldehyde resin (acid catalysis)
With 2.28g 2,2-two (4-hydroxy phenyl) propane, 3ml acetaldehyde (37wt%) and 2.5ml concentrated hydrochloric acid add in the 10ml ethanol together, stir it is dissolved fully, with the above-mentioned solution reactor of packing into, 100 ℃ of insulations 5 hours, the gained gel is smashed to pieces, adds 50g ethanol and stirs 6 hours, filters, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry brown powder of lightweight that gets under 120 ℃ of nitrogen atmospheres, and the pore volume of gained material is 0.67cm
3g
-1, specific surface area is 756m
2g
-1
Embodiment 8: porous 2, the preparation of 2-two (4-hydroxy phenyl) propane phenyl aldehyde resin
With 2.28g 2,2-two (4-hydroxy phenyl) propane, 2ml phenyl aldehyde and 5ml concentrated hydrochloric acid add in the 10ml ethanol together, stir it is dissolved fully, with the above-mentioned solution reactor of packing into, 100 ℃ of insulations 5 hours, the gained gel is smashed to pieces, adds 50g ethanol and stirs 6 hours, filters, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry brown powder of lightweight that gets under 120 ℃ of nitrogen atmospheres, and the pore volume of gained material is 1.1cm
3g
-1, specific surface area is 460m
2g
-1
Embodiment 9: the preparation of porous Resorcinol phenyl aldehyde resin
2.20g Resorcinol, 2ml phenyl aldehyde and 5ml concentrated hydrochloric acid are added in the 10ml ethanol together, stirring is dissolved it fully, with the above-mentioned solution reactor of packing into, 150 ℃ of insulations 5 hours, the gained gel was smashed to pieces, adding 50g ethanol stirred 6 hours, filter, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry lightweight reddish-brown powder that gets under 120 ℃ of nitrogen atmospheres, the pore volume of gained material is 2.0cm
3g
-1, specific surface area is 1060m
2g
-1The adsorptive capacity that the gained material records its gold and silver by the method for embodiment 1 is respectively 481,804mg/g.
Embodiment 10: porous Resorcinol acetaldehyde resin
2.20g Resorcinol, 3ml acetaldehyde and 5ml concentrated hydrochloric acid are added in the 10ml ethanol together, stirring is dissolved it fully, with the above-mentioned solution reactor of packing into, 120 ℃ of insulations 5 hours, the gained gel was smashed to pieces, adding 50g ethanol stirred 6 hours, filter, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry lightweight reddish-brown powder that gets under 120 ℃ of nitrogen atmospheres, the pore volume of gained material is 1.0cm
3g
-1, specific surface area is 960m
2g
-1The adsorptive capacity that the gained material records its gold and silver by the method for embodiment 1 is respectively 656,1310mg/g.
Embodiment 11: porous Resorcinol formaldehyde resin (acid catalysis)
2.20g Resorcinol, 2ml formaldehyde and 5ml concentrated hydrochloric acid are added in the 10ml ethanol together, stirring is dissolved it fully, with the above-mentioned solution reactor of packing into, 120 ℃ of insulations 5 hours, the gained gel was smashed to pieces, adding 50g ethanol stirred 6 hours, filter, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry lightweight reddish-brown powder that gets under 120 ℃ of nitrogen atmospheres, the pore volume of gained material is 1.7cm
3g
-1, specific surface area is 865m
2g
-1The adsorptive capacity that the gained material records its gold and silver by the method for embodiment 1 is respectively 781,1530mg/g.After this resin absorption gold reached capacity, with iron and regeneration of hydrochloric acid, the saturated extent of adsorption to gold was 400mg/g for the second time, is primary 51%.This resin to Pd, Pt, Ru, Rh, Os, Ir, Hg, Cd ionic saturated extent of adsorption be respectively 102,97,70,57,87,76,75,55mg/g.This embodiment gained resin sees Table 1. to the selectivity of gold
Embodiment 12: porous Resorcinol formaldehyde resin (base catalysis)
2.20g Resorcinol, 2ml formaldehyde and 0.25g KOH are added in the 10ml ethanol together, stirring is dissolved it fully, with the above-mentioned solution reactor of packing into, 120 ℃ of insulations 5 hours, the gained gel was smashed to pieces, the ethanol solution hydrochloride that adds 50g 5wt% stirred 6 hours, filter, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry lightweight reddish-brown powder that gets under 120 ℃ of nitrogen atmospheres, the pore volume of gained material is 1.2cm
3g
-1, specific surface area is 665m
2g
-1The adsorptive capacity that the gained material records its gold and silver by the method for embodiment 1 is respectively 761,1480mg/g.
Embodiment 13: porous Resorcinol formaldehyde resin (room temperature preparation)
2.20g Resorcinol, 2ml formaldehyde and 5ml concentrated hydrochloric acid are added in the 10ml ethanol together, stirring is dissolved it fully, (about 30 ℃) reaction is 30 days under the room temperature, the gained gel is smashed to pieces, adds 50g ethanol and stirs 6 hours, filters, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry lightweight reddish-brown powder that gets under 120 ℃ of nitrogen atmospheres, and the pore volume of gained material is 0.2cm
3g
-1, specific surface area is 465m
2g
-1The adsorptive capacity that the gained material records its gold and silver by the method for embodiment 1 is respectively 560,1180mg/g.
Embodiment 14: porous 4,4 '-dihydroxybiphenyl formaldehyde resin
With 1.86 grams 4,4 '-dihydroxybiphenyl, 2ml formaldehyde and 5ml 5mol/L sulfuric acid join in the 10ml distilled water together, stir it is dissolved fully, with the above-mentioned solution reactor of packing into, 100 ℃ of insulations 5 hours, the gained gel is smashed to pieces, adds 50g ethanol and stirs 6 hours, filters, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry yellow powder of lightweight that gets under 120 ℃ of nitrogen atmospheres, and the pore volume of gained material is 0.5cm
3g
-1, specific surface area is 678m
2g
-1The adsorptive capacity that the gained material records its gold and silver by the method for embodiment 1 is respectively 330,580mg/g.
Embodiment 15: porous 4,4 '-dihydroxybiphenyl acetaldehyde resin
With 1.86 grams 4,4 '-dihydroxybiphenyl, 2ml acetaldehyde and 1g sodium hydroxide join in the 10ml distilled water together, stir it is dissolved fully, with the above-mentioned solution reactor of packing into, 100 ℃ of insulations 5 hours, the gained gel is smashed to pieces, and the ethanol solution hydrochloride that adds 50g 5wt% stirred 6 hours, filtered, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry yellow powder of lightweight that gets under 120 ℃ of nitrogen atmospheres, and the pore volume of gained material is 0.3cm
3g
-1, specific surface area is 568m
2g
-1The adsorptive capacity that the gained material records its gold and silver by the method for embodiment 1 is respectively 320,530mg/g.
Embodiment 16: porous 4,4 '-dihydroxybiphenyl phenyl aldehyde resin
With 1.86 grams 4,4 '-dihydroxybiphenyl, 2ml phenyl aldehyde and 1g sodium hydroxide join in the 10ml ethanol together, stir it is dissolved fully, with the above-mentioned solution reactor of packing into, 180 ℃ of insulations 5 hours, the gained gel is smashed to pieces, adds 50g ethanol and stirs 6 hours, filters, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry yellow powder of lightweight that gets under 120 ℃ of nitrogen atmospheres, and the pore volume of gained material is 0.6cm
3g
-1, specific surface area is 878m
2g
-1The adsorptive capacity that the gained material records its gold and silver by the method for embodiment 1 is respectively 220,370mg/g.
Embodiment 17: the preparation of porous phenol pyrocatechol formaldehyde resin
1.88g phenol, 1.1g pyrocatechol, 2ml formaldehyde and 5ml concentrated hydrochloric acid are added in the 10ml ethanol together, stirring is dissolved it fully, with the above-mentioned solution reactor of packing into, 150 ℃ of insulations 5 hours, the gained gel was smashed to pieces, adding 50g ethanol stirred 6 hours, filter, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry yellow powder of lightweight that gets under 120 ℃ of nitrogen atmospheres, the pore volume of gained material is 0.7cm
3g
-1, specific surface area is 558m
2g
-1The adsorptive capacity that the gained material records its gold and silver by the method for embodiment 1 is respectively 620,1170mg/g.
Table 1, resin are to the adsorptive capacity (mg/g) of each metal ion species
Embodiment 18
With 1.08g 2,2-two (4-hydroxy phenyl) propane (claiming dihydroxyphenyl propane again), 1g pyrocatechol, 2ml phenyl aldehyde and 5ml concentrated hydrochloric acid add in the 10ml ethanol together, stir it is dissolved fully, with the above-mentioned solution reactor of packing into, 100 ℃ of insulations 5 hours, the gained gel is smashed to pieces, adds 50g ethanol and stirs 6 hours, filters, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry brown powder of lightweight that gets under 120 ℃ of nitrogen atmospheres, and the pore volume of gained material is 1.1cm
3g
-1, specific surface area is 460m
2g
-1
Embodiment 19
2.20g Resorcinol, 2ml phenyl aldehyde and 5ml concentrated hydrochloric acid are added in the 10ml ethanol together, stirring is dissolved it fully, with the above-mentioned solution reactor of packing into, 100 ℃ of insulations 5 hours, the gained gel was smashed to pieces, adding 50g ethanol stirred 6 hours, filter, washing with alcohol, the filter cake seasoning is about at 20% o'clock to ethanol content it is ground, the dry lightweight reddish-brown powder that gets under 120 ℃ of nitrogen atmospheres, the pore volume of gained material is 2.0cm
3g
-1, specific surface area is 1060m
2g
-1
1.88g phenol, 2ml formaldehyde and 5ml concentrated nitric acid are added in the 10ml ethanol together, stirring is dissolved it fully, with the above-mentioned solution reactor of packing into, 100 ℃ of insulations 5 hours, the gained gel was smashed to pieces, adding 50g ethanol stirred 6 hours, filter, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry yellow powder of lightweight that gets under 120 ℃ of nitrogen atmospheres, the pore volume of gained material is 0.4cm
3g
-1, specific surface area is 518m
2g
-1
Embodiment 21
With 2.28g 2,2-two (4-hydroxy phenyl) propane (claiming dihydroxyphenyl propane again), 0.1ml acetaldehyde, 1.9ml formaldehyde and 1g sodium hydroxide add in the 10ml water together, stirring is dissolved it fully, with the above-mentioned solution reactor of packing into, 100 ℃ of insulations 5 hours, the gained gel is smashed to pieces, adding 50g 1mol/L hydrochloric acid stirred 6 hours, filter, washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry yellow powder of lightweight that gets under 120 ℃ of nitrogen atmospheres, and the pore volume of gained material is 0.3cm
3g
-1, specific surface area is 560m
2g
-1
Embodiment 22
With 2.28g 2,2-two (4-hydroxy phenyl) propane (claiming dihydroxyphenyl propane again), 2ml acetaldehyde and 0.8g potassium hydroxide add in the 10ml water together, stirring is dissolved it fully, with the above-mentioned solution reactor of packing into, 100 ℃ of insulations 5 hours, the gained gel is smashed to pieces, add 50g 1mol/L hydrochloric acid and stirred 6 hours, filter washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry light powder that gets under 120 ℃ of nitrogen atmospheres.
Embodiment 23
With 2.28g 2,2-two (4-hydroxy phenyl) propane (claiming dihydroxyphenyl propane again), 2ml acetaldehyde, 1ml formaldehyde and 1g sodium hydroxide add in the 10ml water together, stirring is dissolved it fully, with the above-mentioned solution reactor of packing into, 100 ℃ of insulations 5 hours, the gained gel is smashed to pieces, add 50g 1mol/L hydrochloric acid and stirred 6 hours, filter washing with alcohol, the filter cake seasoning is about at 40% o'clock to ethanol content it is ground, the dry yellow powder of lightweight that gets under 120 ℃ of nitrogen atmospheres.
Embodiment 24
With 0.2g 2,2-two (4-hydroxy phenyl) propane (claiming dihydroxyphenyl propane again), 1.6g pyrocatechol, 2ml phenyl aldehyde and 5ml concentrated hydrochloric acid add in the 10ml ethanol together, stirring is dissolved it fully, with the above-mentioned solution reactor of packing into, 100 ℃ of insulations 5 hours, the gained gel is smashed to pieces, add 50g ethanol and stirred 6 hours, filter washing with alcohol, the filter cake seasoning is about at 50% o'clock to ethanol content it is ground, the dry brown powder of lightweight that gets under 120 ℃ of nitrogen atmospheres.
Claims (8)
1. a Hydrophilous porous phenolic resin is made up of phenol monomer and aldehyde monomer, and the monomeric mol ratio of phenol monomer and aldehyde is between 1: 1 to 1: 5, and its structure is made up of micropore and the mesoporous of 2～50nm of a kind of 0.4～1nm; The BET specific surface area of described Hydrophilous porous phenolic resin is 460～1060m
2g
-1Pore volume is 0.2～2.4cm
3g
-1
Described phenol monomer is selected from phenol, 2,2-two (4-hydroxy phenyl) propane, pyrocatechol, Resorcinol or 4, one or more in 4 '-dihydroxybiphenyl; Described aldehyde monomer is selected from one or more in acetaldehyde, formaldehyde or the phenyl aldehyde; Described Hydrophilous porous phenolic resin has following general structure:
Wherein A represents the phenol structural unit; R represents hydrogen atom, methyl or phenyl; Broken circle is represented the hole in the polymkeric substance.
2. the preparation method of the described Hydrophilous porous phenolic resin of claim 1 comprises the steps:
1) phenol monomer and aldehyde monomer are dissolved in the solvent, at room temperature stir it is dissolved fully, add acid or alkali then and make catalyzer and obtain reaction system;
2) step 1) gained reaction system is packed into seal in the reactor, carry out the constant temperature insulation reaction under a certain temperature of reaction between 30～180 ℃, the reaction times is 0.5 hour to 30 days;
3) with step 2) smash alcohol immersion after-filtration, washing with alcohol to pieces behind the gel naturally cooling that makes;
4) the filter cake seasoning that step 3) is made is 10～90% o'clock to the ethanol massfraction, and filter cake is clayed into power, and is under 50～150 ℃ drying temperature, dry in atmosphere of inert gases then, promptly makes Hydrophilous porous phenolic resin.
3. the preparation method of Hydrophilous porous phenolic resin described in claim 2 is characterized in that, the acid in the described step 1) is mineral acid, and the concentration of described acid in reaction system is 0.1～5mol/L; Described alkali is sodium hydroxide or potassium hydroxide, and the concentration of described alkali in reaction system is 0.1～2mol/L.
4. the preparation method of Hydrophilous porous phenolic resin described in claim 2, it is characterized in that, the concrete steps of washing with alcohol are in the described step 3): when making catalyzer with acid, then need add 6 hours after-filtration of ethanol agitator treating in the product of smashing to pieces, wherein every gram product adds 1～4ml ethanol; When making catalyzer with alkali, then need in the product of smashing to pieces, add in the excess acid and residual alkali, add 6 hours after-filtration of ethanol agitator treating then, wherein every gram product adds 1～4ml ethanol.
5. the application of the described Hydrophilous porous phenolic resin of claim 1 is characterized in that, described Hydrophilous porous phenolic resin is used to adsorb precious metal ion or absorption and selective reduction precious metal ion.
6. the application of Hydrophilous porous phenolic resin as claimed in claim 5 is characterized in that, the precious metal ion of described absorption is selected from one or more in gold and silver, palladium, ruthenium, rhodium, platinum, iridium and the osmium ion; The precious metal ion of described absorption and selective reduction is selected from one or both in gold ion and the silver ions.
7. method of adsorbing precious metal ion, comprise the steps: the described Hydrophilous porous phenolic resin of arbitrary claim in the claim 1～2 is placed precious metal ion solution, 0～100 ℃ of following whip attachment 0.1～100 hour, filtering separation solid-liquid two-phase then.
8. the renovation process of a Hydrophilous porous phenolic resin, arbitrary described Hydrophilous porous phenolic resin soaks the back and takes out and wash with reductive agent sodium sulfite solution or iron+salt acid soak in the claim 1～2 that comprises the steps: to adsorb after precious metal reaches capacity.
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| CN102255079B (en) * | 2011-05-17 | 2013-12-18 | 奇瑞汽车股份有限公司 | Stannum-carbon composite material used for lithium ion battery cathode, preparation method thereof and lithium ion battery |
| CN102513069B (en) * | 2011-12-16 | 2013-07-17 | 浙江农林大学 | Method for producing hierarchically structured porous coordination polymer absorbent material |
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| CN105013452B (en) * | 2014-04-17 | 2017-08-22 | 宁波大学 | High-molecular bone frame material of formaldehyde and preparation method thereof in a kind of energy absorption air |
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| CN109939657B (en) * | 2019-03-28 | 2022-03-04 | 广东工业大学 | Macroporous phenolic resin, preparation method thereof and application thereof in adsorption of 5-hydroxymethylfurfural |
| CN113333021A (en) * | 2021-04-07 | 2021-09-03 | 贵研铂业股份有限公司 | Porous polymer supported palladium catalyst with high catalytic activity and application thereof in catalyzing Suzuki-Miyaura reaction |
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