CN104785226B - Glass powder enhanced Zr modification montmorillonite honeycomb block chromium sorbent and preparation method thereof - Google Patents
Glass powder enhanced Zr modification montmorillonite honeycomb block chromium sorbent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a glass powder enhanced Zr modification montmorillonite honeycomb block chromium sorbent and a preparation method thereof. The preparation method comprises the following steps: dissolving a monomer, a cross-linking agent and a dispersant, which are used for gel polymerization, in water to form a mixed solution; adding Zr modification montmorillonite powder, polystyrene spheres with particle diameters of 1-1.5 mm and glass powder into the mixed solution, and carrying out uniform mixing to obtain a slurry; adding a foaming agent, an initiating agent and a catalyst which are used for gel polymerization, carrying out uniform mixing for a polymerization reaction, and obtain a dry blank after the polymerization reaction is completed; conducting heat preservation on the dry blank at 330-440 DEG C and 550-700 DEG C respectively, and then obtain the glass powder enhanced Zr modification montmorillonite honeycomb block chromium sorbent. Through the polymerization reaction, the Zr modification montmorillonite powder, the polystyrene spheres and the glass powder are uniformly embedded in a polymer chain to form a regular block porous material which is high in water permeability; when being utilized for treating low-concentration chromium-containing wastewater, the formed regular block porous material has the advantages that the adsorption effect is good, and the Zr modification montmorillonite powder is effectively prevented from being lost along with wastewater discharge.
Description
Technical field
The present invention relates to field of waste water treatment, more particularly to the cellular block chromium suction of glass powder enhancing Zr modified montmorillonoids
Attached dose and preparation method thereof.
Background technology
Montmorillonite (MMT) becomes current sorbent material and grinds with larger specific surface area and cation exchange capacity
The emphasis studied carefully.Used as a kind of efficient natural adsorbent, the adsorption of montmorillonite is mainly ion exchange and surface complexation suction
Attached effect, montmorillonite are the stratum water aluminium silicate minerals of 2: 1 or TOT types, generally white or faint yellow.Construction unit layer
For one layer of Al-O of folder in two panels drift angle Si-O tetrahedrons (T layers) inwardly4(OH)2Octahedral sheet (O layers).Between montmorillonite lattice by
In there is aliovalent isomorphous replacement, the part aluminium atom in alumina octahedral is easily replaced by low price atom, such as Mg2+、Fe2+
Deng so that crystal interlayer carries certain negative charge, in order to keep electric neutrality, has adsorbed the cation such as Na of large radius between crystal+、K+、Mg2+、Ca2+、Li+、H+, these cationes occur with hydration status, and can be exchanged with each other.
Adsorbance of the montmorillonite to chromium can be improved using the modified sodio nano imvite of zirconates, but obtained Zr-MMT mostly is
Powder body, in actual waste water process, powder body is easily lost in water outlet, separates difficulty, and the little quick grade (200910091394.5) of bean also studied
The absorbent powder of arsenic removal, fluorine is made by granule by the esterification of polyethylene alcohol and carboxylic acid, the intensity of adsorbent is improve,
But no loose structure.
The content of the invention
It is an object of the present invention to provide one kind is not easily runed off and facilitates detached glass powder to strengthen Zr modified montmorillonoids
Cellular block chromium adsorbent and preparation method thereof.
To solve the above problems, the technical scheme of preparation method of the present invention is：
Monomer Ag, cross-linking agent and the dispersant for taking gel polymerisation is dissolved in water formation mixed solution, adds in the mixed solution
Enter the Zr modified montmorillonoid powder body of Bg, the polystyrene spheres that CmL particle diameters are 1～1.5mm and be 1 with the mass ratio of monomer:(5
～glass powder 20), wherein A：B：C=(10～15)：(21～29)：(90～120), mix homogeneously obtains slurry, in slurry
Foaming agent, initiator and the catalyst of gel polymerisation, mix homogeneously is added to carry out polyreaction, done after the completion of reaction in material
Base substrate, dry body body is incubated respectively at 330～440 DEG C and 550～700 DEG C, is obtained glass powder modified illiteracies of enhancing Zr and is taken off
The cellular block chromium adsorbent of soil.
Further, the present invention includes step in detail below：
1) by monomer Ag, cross-linking agent Rg and dispersant SmL obtains mixed solution in being dissolved in TmL water, wherein monomer is propylene
Amide or N,N-DMAA, and A：R：S：T=(10～15)：(1～1.5)：(1.2～1.7)：15；
2) in step 1) obtained by Zr modified montmorillonoid powder body Dg are added in mixed solution, be stirring evenly and then adding into particle diameter for 1
The polystyrene spheres CmL of～1.5mm, A：D：C=(10～15)：(3～7)：(90～120), obtain slurry I；
3) Zr modified montmorillonoid powder body Eg are added in FmL water with glass powder, wherein A：E：F=(10～15)：(18～
22)：35, and D+E=B；The quality of glass powder and step 1) in the mass ratio of monomer be 1:(5～20), fully mix, obtain
The suspension of Zr modified montmorillonoids, and add step 2) obtained by slurry I, mix homogeneously obtains slurry II；
4) in step 3) obtained by foaming agent Xg, initiator Yg and catalyst Z mL, wherein A are added in slurry II：X：Y：Z=
(10～15)：(2.0～4.0)：(0.01～1.0)：(0.4～2), stirs and injects mould after irritant abnormal smells from the patient is produced,
Molding；
5) dry body body is obtained after 40～60 DEG C of 50～70h of drying；
6) dry body body is incubated respectively at 330～440 DEG C and 550～700 DEG C, furnace cooling obtains glass powder
Strengthen the cellular block chromium adsorbent of Zr modified montmorillonoids.
Further, the preparation process of described Zr modified montmorillonoid powder body includes：
A) take the montmorillonite suspension that mass concentration is 10%；
B) under 30～80 DEG C of stirring conditions, sulphuric acid zirconium solution is added drop-wise in montmorillonite suspension, wherein Disulfatozirconic acid. with
The mass ratio of montmorillonite is (1～2):5, continue 1～1.5h of stirring after completion of dropping, it is 2 to adjust pH value with sodium hydroxide solution
～8, it is centrifuged after dipping, takes out the filter cake after centrifugation；
C) grinding after filtration cakes torrefaction is sieved, at 200～500 DEG C, 3～4 hours of roasting obtain Zr modified montmorillonoid powder
Body.
Further, it is centrifuged after 6～8h of dipping in the step b), step is into being dried in c) at 70～90 DEG C, and mistake
Screen cloth used by sieve is 200 mesh.
Further, montmorillonite adopts sodio nano imvite.
Further, described glass powder is B2O3-Na2O-Bi2O3, wherein by mass percentage, B2O3For 30～
60%, Na2O：30～60%, Bi2O3：10～20%.
Further, described cross-linking agent is N, and N '-methylene-bisacrylamide, dispersant are ammonium polyacrylate salt or lemon
Lemon acid ammonium, foaming agent are Laurel alcohol sulfuric ester TEA salt, and initiator is Ammonium persulfate. or azo [2- amidine propanes] hydrochlorate, is urged
Agent is N, N, N, ' N, '-tetramethylethylenediamine.
Further, described catalyst concn is 0.35g/100mL.
Further, dry body body insulating process is specially：330～440 are increased to the speed of 5 DEG C/min from room temperature first
DEG C insulation 5～7h, then with the speed of 2 DEG C/min be increased to 550～700 DEG C insulation 1～3h.
The technical scheme of chromium adsorbent of the present invention is：Described glass powder strengthens the cellular block chromium of Zr modified montmorillonoids
Adsorbent is the porous material of rule, and aperture is 1.0～1.5mm.
Compared with prior art, the present invention has following beneficial technique effect：
By the present invention in that increasing the layer of montmorillonite as adsorbent, zirconates pillared montmorillonite with the montmorillonite of modified zirconia
Spacing and specific surface area, so as to increase the adsorbance of montmorillonite；And by by Zr modified montmorillonoid powder body, polystyrene spheres
In the raw material that glass powder adds polyreaction, polyreaction is carried out under conditions of montmorillonite fundamental property is not changed by Zr
Modified montmorillonoid powder body molding, makes Zr modified montmorillonoid powder body, polystyrene spheres and glass powder be uniformly embedded in polymer chain,
The base substrate with regular texture, and glass powder are formed beneficial to the intensity for improving base substrate, then by Discrete control heat preservation sintering
Temperature, in 330～440 DEG C of low-temperature sinterings, cracks polystyrene spheres, so as to space occurs in its position being located, forms honeybee
The loose structure of nest shape；In 550～700 DEG C of high temperature sinterings, Zr modified montmorillonoids are made to keep original interlamellar spacing, while increasing
Intensity, is finally made cellular block Zr-MMT chromium adsorbents.
The present invention by the Zr-MMT of powder body make rule block body stephanoporate material, and made by porous adsorbent aperture be about
1.0～1.5mm, good water permeability, for processing the chromate waste water of low concentration, waste water is bigger with the contact area of adsorbent, more sharp
In absorption, measured with GB/T 7466-87, the present invention is at least up to 5.4mg/g, advantages of good adsorption effect to the adsorbance of Cr (III)；And
The block body stephanoporate material of formation, the problem that effectively solving powder body is easy to run off in application process are easily separated.
Description of the drawings
Fig. 1 is the scanning electron microscope image of the cellular block Zr-MMT chromium adsorbents obtained by the embodiment of the present invention 1.
Specific embodiment
The concrete preparation process of the present invention includes：
1) sodio nano imvite is configured to into the montmorillonite suspension that mass concentration is 10%, room temperature high-speed stirred
30min is standby.
2) high-speed stirred at 30～80 DEG C, sulphuric acid zirconium solution is added drop-wise in montmorillonite suspension, and Disulfatozirconic acid. is taken off with covering
The mass ratio of soil is (1～2):5, continue 1～1.5h of stirring after completion of dropping, pH=2～8, leaching are adjusted with sodium hydroxide solution
6～8h of stain, centrifugation take out the filter cake after centrifugation and are placed in beaker.
3) filter cake is dried at 70～90 DEG C, ground 200 mesh sieve after being dried, roasting 3～4 at 200～500 DEG C
Hour obtains Zr modified montmorillonoid powder body, i.e. Zr-MMT nano adsorbers, hereinafter referred to as Zr-MMT powder body.
4) by the monomeric acrylamide (AM) or N,N-DMAA Ag of gel polymerisation, cross-linking agent N, N '-methylene
Base bisacrylamide (MBAM) Rg, is dissolved in TmL water, adds dispersants ammonium polyacrylate salt or ammonium citrate SmL, stir after dissolving
Mix uniform, obtain mixed solution, wherein A：R：S：T=(10～15)：(1～1.5)：(1.2～1.7)：15.
5) in step 4) obtained by be slowly added to step 3 in mixed solution) the Zr-MMT powder body Dg that obtain, after stirring plus
Enter the polystyrene spheres CmL that particle diameter is 1～1.5mm, A：D：C=(10～15)：(3～7)：(90～120), obtain slurry I.
6) by step 3) the Zr-MMT powder body Eg that obtains added in FmL water with glass powder, wherein A：E：F=(10～
15)：(18～22)：35, and D+E=B, B are the Zr-MMT powder body total amounts added in the present invention, so A：B：C=(10～15)：
(21～29)：(90～120)；The quality of glass powder and step 4) in the mass ratio of monomer be 1:(5～20), fully mix,
Obtain the suspension of Zr-MMT, and add step 5) obtained by slurry I, mix homogeneously obtains slurry II；The glass powder of addition
For B2O3-Na2O-Bi2O3, and by mass percentage, B2O3For 30～60%, Na2O：30～60%, Bi2O3：10～20%.
7) in step 6) obtained by foaming agent Laurel alcohol sulfuric ester TEA (triethanolamine) salt Xg is added in slurry II, be stirred to
Fully bubble, it was observed that slurry bleaches, soften, add initiator ammonium persulfate (APS) or azo [2- amidine propanes] hydrochloric acid
Salt Yg, catalyst n of the concentration for 0.35g/100mL, N, N, ' N, '-tetramethylethylenediamine (TEMED) ZmL, wherein A：X：Y：Z=
(10～15)：(2.0～4.0)：(0.01～1.0)：(0.4～2), stirs and injects mould after irritant abnormal smells from the patient is produced,
Molding；
8) in 40～60 DEG C of 50～70h of drying, obtain dry body body.
9) dry body body is increased to into 330～440 DEG C with the speed of 5 DEG C/min from room temperature, is incubated 5～7h, with 2 DEG C/min's
Speed is increased to 550～700 DEG C of 1～3h of insulation, and furnace cooling obtains the cellular block of glass powder enhancing Zr modified montmorillonoids
Chromium adsorbent.
By by sodio nano imvite modified zirconia, zirconates is increased with the pillared MMT of zirconic form in the present invention
The interlamellar spacing and specific surface area of MMT, so as to increase the adsorbance of montmorillonite, by being added separately to Zr-MMT powder body and Zr-MMT
Suspension, be in order that polystyrene spheres and Zr-MMT powder body mix in the slurry it is more uniform；The polystyrene of addition
Ball, the ground that bead is located after low-temperature sintering will form macropore, then carry out high temperature sintering, lift the intensity of product, by Zr-
MMT powder body is prepared into certain volume, shape the cellular block Zr-MMT chromium adsorbents with glass powder increase intensity.
To make the technical problem to be solved in the present invention clearer, it is more to the detailed description purpose of instantiation below
Good understanding present disclosure, rather than limit the scope of the invention.
Embodiment 1
1) take the montmorillonite suspension that finely dispersed mass concentration is 10%.
2) high-speed stirred at 40 DEG C, sulphuric acid zirconium solution is added drop-wise in montmorillonite suspension, Disulfatozirconic acid. and montmorillonite
Mass ratio is 1:5, continue stirring 1h after completion of dropping, it is 3 to adjust pH value with the sodium hydroxide solution of 1mol/L, impregnates 7h, from
The heart, takes out the filter cake after centrifugation and is placed in beaker.
3) filter cake is dried at 80 DEG C, ground 200 mesh sieve after being dried, at 400 DEG C, 3 hours of roasting obtain Zr-
MMT powder body.
4) by monomeric acrylamide (AM) 12.5g, cross-linking agent N, N '-methylene-bisacrylamide (MBAM) 1.25g is dissolved in
In 15mL water, 1.25mL dispersants ammonium polyacrylate salt is added after dissolving, is stirred, is obtained mixed solution, now A：R：S：T
=12.5：1.25：1.25：15.
5) in step 4) obtained by be slowly added to step 3 in mixed solution) the Zr-MMT powder body 5g that obtain, after stirring plus
Enter the polystyrene spheres 100mL that particle diameter is 1～1.5mm, now A：D：C=12.5：5：100, obtain slurry I.
6) by step 3) the Zr-MMT powder body 20g that obtains added in 35mL water with glass powder, then A：E：F=12.5：20：
35, and A：B：C=12.5：25：100；The quality of glass powder and step 4) in the mass ratio of monomer be 1:20, fully mix,
Obtain the suspension of Zr-MMT, and add step 5) obtained by slurry I, mix homogeneously obtains slurry II.
7) in step 6) obtained by foaming agent Laurel alcohol sulfuric ester TEA (triethanolamine) salt 2.65g, stirring are added in slurry II
To fully foaming, the catalyst n of initiator ammonium persulfate (APS) 0.0287g and concentration for 0.35g/100mL is added, N, N, '
N, '-tetramethylethylenediamine (TEMED) 0.88mL, then A：X：Y：Z=12.5：2.65：0.0287：0.88, stir until there is stimulation
Property abnormal smells from the patient produce, slurry preparation completes, and reinjects die for molding.
8) 50h is dried at 60 DEG C, completes polyreaction, obtain dry body body.
9) dry body body is increased to into 330 DEG C with the speed of 5 DEG C/min from room temperature, is incubated 7h, raised with the speed of 2 DEG C/min
To 600 DEG C of insulation 2h, furnace cooling, obtaining glass powder strengthens the cellular block chromium adsorbent of Zr modified montmorillonoids.
From Fig. 1, it is evident that Zr modified honeycombs shape block montmorillonite chromium adsorbent obtained in the present embodiment is rule
Loose structure, pore size is about 1～1.5mm, equal with the particle diameter of polystyrene spheres, and pore size distribution is uniform, good water permeability,
Increase the contact area of waste water and adsorbent.
It is that 10mg/L (III) containing Cr is molten that prepared cellular block chromium adsorbent is used for adsorption treatment initial concentration
Liquid, adsorption test condition：60 DEG C, pH=4.5, adsorbent dosage are 1g/L, adsorption reaction absorption 60min.Use GB/T
7466-87 surveys total chromium change.The adsorbance for measuring Cr (III) is 5.8mg/g.
Embodiment 2
1) take the montmorillonite suspension that finely dispersed mass concentration is 10%.
2) high-speed stirred at 60 DEG C, sulphuric acid zirconium solution is added drop-wise in montmorillonite suspension, Disulfatozirconic acid. and montmorillonite
Mass ratio is 2:5, continue stirring 1h after completion of dropping, it is 7 to adjust pH value with the sodium hydroxide solution of 1mol/L, after dipping 8h from
The heart, takes out the filter cake after centrifugation and is placed in beaker.
3) filter cake is dried at 80 DEG C, ground 200 mesh sieve after being dried, at 500 DEG C, 3 hours of roasting obtain Zr-
MMT powder body.
4) by monomeric acrylamide (AM) 11.5g, cross-linking agent N, N '-methylene-bisacrylamide (MBAM) 1.35g is dissolved in
In 15mL water, 1.35mL dispersants ammonium polyacrylate salt is added after dissolving, is stirred, is obtained mixed solution, now A：R：S：T
=11.5：1.35：1.35：15.
5) in step 4) obtained by be slowly added to step 3 in mixed solution) the Zr-MMT powder body 3g that obtain, after stirring plus
Enter the polystyrene spheres 115mL that particle diameter is 1～1.5mm, now A：D：C=11.5：3：115, obtain slurry I.
6) by step 3) the Zr-MMT powder body 22g that obtains added in 35mL water with glass powder, then A：E：F=11.5：22：
35, and A：B：C=11.5：25：115；The quality of glass powder and step 4) in the mass ratio of monomer be 1:10, fully mix,
Obtain the suspension of Zr-MMT, and add step 5) obtained by slurry I, mix homogeneously obtains slurry II.
7) foaming agent Laurel alcohol sulfuric ester TEA (triethanolamine) salt 2.40g is added in slurry II obtained by step (6), stir
Fully foaming is mixed, the catalyst n of initiator ammonium persulfate (APS) 0.0210g and concentration for 0.35g/100mL is added, N,
N, ' N, '-tetramethylethylenediamine (TEMED) 1.0mL, then A：X：Y：Z=11.5：2.40：0.0210：1.0, stir until spinosity
Sharp property abnormal smells from the patient is produced, and slurry preparation is completed, and reinjects die for molding；
8) 50h is dried at 50 DEG C, completes polyreaction, obtain dry body body.
9) dry body body is increased to into 360 DEG C with the speed of 5 DEG C/min from room temperature, is incubated 6.5h, with the speed liter of 2 DEG C/min
High to 650 DEG C insulation 1.4h, furnace cooling, obtaining glass powder strengthens the cellular block chromium adsorbent of Zr modified montmorillonoids.
It is that 10mg/L contains Cr (III) solution that prepared cellular block Zr-MMT is used for adsorption treatment initial concentration,
Adsorption test condition：60 DEG C, pH=4.5, adsorbent dosage are 1g/L, adsorption reaction absorption 60min.Measure to Cr (III)
Adsorbance be 6.1mg/g.
Embodiment 3
1) take the montmorillonite suspension that finely dispersed mass concentration is 10%.
2) high-speed stirred at 80 DEG C, sulphuric acid zirconium solution is added drop-wise in montmorillonite suspension, Disulfatozirconic acid. and montmorillonite
Mass ratio is 1.2:5, continue stirring 1h after completion of dropping, it is 2 to adjust pH value with the sodium hydroxide solution of 1mol/L, after dipping 6h
Centrifugation, takes out the filter cake after centrifugation and is placed in beaker.
3) filter cake is dried at 80 DEG C, ground 200 mesh sieve after being dried, at 500 DEG C, 3 hours of roasting obtain Zr-
MMT powder body.
4) by monomeric acrylamide (AM) 13.5g, cross-linking agent N, N '-methylene-bisacrylamide (MBAM) 1.15g is dissolved in
In 15mL water, 1.25mL dispersant ammonium citrates are added after dissolving, is stirred, is obtained mixed solution, now A：R：S：T=
13.5：1.15：1.25：15.
5) in step 4) obtained by be slowly added to step 3 in mixed solution) the Zr-MMT powder body 4g that obtain, after stirring plus
Enter the polystyrene spheres 120mL that particle diameter is 1～1.5mm, now A：D：C=13.5：4：120, obtain slurry I.
6) by step 3) the Zr-MMT powder body 19g that obtains added in 35mL water with glass powder, then A：E：F=13.5：19：
35, and A：B：C=13.5：23：120；The quality of glass powder and step 4) in the mass ratio of monomer be 1:5, fully mix, obtain
To the suspension of Zr-MMT, and add step 5) obtained by slurry I, mix homogeneously obtains slurry II.
7) in step 6) obtained by foaming agent Laurel alcohol sulfuric ester TEA (triethanolamine) salt 3.15g, stirring are added in slurry II
To fully foaming, the catalyst n of initiator ammonium persulfate (APS) 0.0450g and concentration for 0.35g/100mL is added, N, N, '
N, '-tetramethylethylenediamine (TEMED) 1.2mL, then A：X：Y：Z=13.5：3.15：0.045：1.2, stir until irritant
Abnormal smells from the patient is produced, and slurry preparation is completed, and reinjects die for molding；
8) 70h is dried at 50 DEG C, completes polyreaction, obtain dry body body.
9) dry body body is increased to into 380 DEG C with the speed of 5 DEG C/min from room temperature, is incubated 6h, raised with the speed of 2 DEG C/min
To 680 DEG C of insulation 1.6h, furnace cooling, obtaining glass powder strengthens the cellular block chromium adsorbent of Zr modified montmorillonoids.
It is that 10mg/L contains Cr (III) solution that prepared cellular block Zr-MMT is used for adsorption treatment initial concentration,
Adsorption test condition：60 DEG C, pH=4.3, adsorbent dosage are 1g/L, adsorption reaction absorption 60min.Measure to Cr (III)
Adsorbance be 5.4mg/g.
Embodiment 4
1) take the montmorillonite suspension that finely dispersed mass concentration is 10%.
2) high-speed stirred at 30 DEG C, sulphuric acid zirconium solution is added drop-wise in montmorillonite suspension, Disulfatozirconic acid. and montmorillonite
Mass ratio is 1.4:5, continue stirring 1.5h after completion of dropping, it is 4 to adjust pH value with the sodium hydroxide solution of 1mol/L, dipping 6
It is centrifuged after～8h, takes out the filter cake after centrifugation and be placed in beaker.
3) filter cake is dried at 70 DEG C, ground 200 mesh sieve after being dried, at 300 DEG C, 3.5 hours of roasting are obtained
Zr-MMT powder body.
4) by monomer N,N-DMAA Ag, cross-linking agent N, N '-methylene-bisacrylamide (MBAM) Rg is dissolved in
In TmL water, SmL dispersants ammonium polyacrylate salt is added after dissolving, is stirred, is obtained mixed solution, wherein A：R：S：T=
10：1：1.2：15.
5) in step 4) obtained by be slowly added to step 3 in mixed solution) the Zr-MMT powder body Dg that obtain, after stirring plus
Enter the polystyrene spheres CmL that particle diameter is 1～1.5mm, wherein A：D：C=10：6：90, obtain slurry I.
6) by step 3) the Zr-MMT powder body Eg that obtains added in FmL water with glass powder, wherein A：E：F=10：21：
35, and A：B：C=10：27：90；The quality of glass powder and step 4) in the mass ratio of monomer be 1:8, fully mix, obtain
The suspension of Zr-MMT, and add step 5) obtained by slurry I, mix homogeneously obtains slurry II.
7) in step 6) obtained by foaming agent Laurel alcohol sulfuric ester TEA (triethanolamine) salt Xg is added in slurry II, be stirred to
Fully bubble, add the catalyst n of initiator azo [2- amidine propanes] hydrochlorate Yg and concentration for 0.35g/100mL, N,
N, ' N, '-tetramethylethylenediamine (TEMED) ZmL, wherein A：X：Y：Z=10：2：0.5：0.4, stir until irritant abnormal smells from the patient
Produce, slurry preparation is completed, and reinjects die for molding；
8) 55h is dried at 40 DEG C, completes polyreaction, obtain dry body body.
9) dry body body is increased to into 400 DEG C with the speed of 5 DEG C/min from room temperature, is incubated 5h, raised with the speed of 2 DEG C/min
To 700 DEG C of insulation 1h, furnace cooling, obtaining glass powder strengthens the cellular block chromium adsorbent of Zr modified montmorillonoids.
Embodiment 5
1) take the montmorillonite suspension that finely dispersed mass concentration is 10%.
2) high-speed stirred at 50 DEG C, sulphuric acid zirconium solution is added drop-wise in montmorillonite suspension, Disulfatozirconic acid. and montmorillonite
Mass ratio is 1.6:5, continue stirring 1.2h after completion of dropping, it is 5 to adjust pH value with the sodium hydroxide solution of 1mol/L, dipping 6
It is centrifuged after～8h, takes out the filter cake after centrifugation and be placed in beaker.
3) filter cake is dried at 90 DEG C, ground 200 mesh sieve after being dried, at 200 DEG C, 4 hours of roasting obtain Zr-
MMT powder body.
4) by monomer N,N-DMAA Ag, cross-linking agent N, N '-methylene-bisacrylamide (MBAM) Rg is dissolved in
In TmL water, SmL dispersant ammonium citrates are added after dissolving, is stirred, is obtained mixed solution, wherein A：R：S：T=11：
1.1：1.4：15.
5) in step 4) obtained by be slowly added to step 3 in mixed solution) the Zr-MMT powder body Dg that obtain, after stirring plus
Enter the polystyrene spheres CmL that particle diameter is 1～1.5mm, wherein A：D：C=11：7：95, obtain slurry I.
6) by step 3) the Zr-MMT powder body Eg that obtains added in FmL water with glass powder, wherein A：E：F=11：22：
35, and A：B：C=11：29：95；The quality of glass powder and step 4) in the mass ratio of monomer be 1:15, fully mix, obtain
The suspension of Zr-MMT, and add step 5) obtained by slurry I, mix homogeneously obtains slurry II.
7) in step 6) obtained by foaming agent Laurel alcohol sulfuric ester TEA (triethanolamine) salt Xg is added in slurry II, be stirred to
Fully bubble, add the catalyst n of initiator ammonium persulfate (APS) Yg and concentration for 0.35g/100mL, N, N, ' N, '-four
Methyl ethylenediamine (TEMED) ZmL, wherein A：X：Y：Z=11：3：0.01：1.6, stir and produce until irritant abnormal smells from the patient, slurry
Preparation is completed, and reinjects die for molding；
8) 60h is dried at 45 DEG C, completes polyreaction, obtain dry body body.
9) dry body body is increased to into 420 DEG C with the speed of 5 DEG C/min from room temperature, is incubated 5.5h, with the speed liter of 2 DEG C/min
High to 580 DEG C insulation 2.5h, furnace cooling, obtaining glass powder strengthens the cellular block chromium adsorbent of Zr modified montmorillonoids.
Embodiment 6
1) take the montmorillonite suspension that finely dispersed mass concentration is 10%.
2) high-speed stirred at 70 DEG C, sulphuric acid zirconium solution is added drop-wise in montmorillonite suspension, Disulfatozirconic acid. and montmorillonite
Mass ratio is 1.8:5, continue 1～1.5h of stirring after completion of dropping, it is 8 to adjust pH value with the sodium hydroxide solution of 1mol/L, leaching
It is centrifuged after 6～8h of stain, takes out the filter cake after centrifugation and be placed in beaker.
3) filter cake is dried at 85 DEG C, ground 200 mesh sieve after being dried, at 450 DEG C, 3.5 hours of roasting are obtained
Zr-MMT powder body.
4) by monomeric acrylamide (AM) Ag, cross-linking agent N, N '-methylene-bisacrylamide (MBAM) Rg is dissolved in TmL water
In, SmL dispersant ammonium citrates are added after dissolving, is stirred, is obtained mixed solution, wherein A：R：S：T=15：1.5：1.7：
15。
5) in step 4) obtained by be slowly added to step 3 in mixed solution) the Zr-MMT powder body Dg that obtain, after stirring plus
Enter the polystyrene spheres CmL that particle diameter is 1～1.5mm, wherein A：D：C=15：3：110, obtain slurry I.
6) by step 3) the Zr-MMT powder body Eg that obtains added in FmL water with glass powder, wherein A：E：F=15：18：
35, and A：B：C=15：21：110；The quality of glass powder and step 4) in the mass ratio of monomer be 1:16, fully mix, obtain
To the suspension of Zr-MMT, and add step 5) obtained by slurry I, mix homogeneously obtains slurry II.
7) in step 6) obtained by foaming agent Laurel alcohol sulfuric ester TEA (triethanolamine) salt Xg is added in slurry II, be stirred to
Fully bubble, add the catalyst n of initiator azo [2- amidine propanes] hydrochlorate Yg and concentration for 0.35g/100mL, N,
N, ' N, '-tetramethylethylenediamine (TEMED) ZmL, wherein A：X：Y：Z=15：4：1：2, stir and produce until irritant abnormal smells from the patient,
Slurry preparation is completed, and reinjects die for molding；
8) 65h is dried at 55 DEG C, completes polyreaction, obtain dry body body.
9) dry body body is increased to into 440 DEG C with the speed of 5 DEG C/min from room temperature, is incubated 5h, raised with the speed of 2 DEG C/min
To 550 DEG C of insulation 3h, furnace cooling, obtaining glass powder strengthens the cellular block chromium adsorbent of Zr modified montmorillonoids.
Embodiment 7
1) take the montmorillonite suspension that finely dispersed mass concentration is 10%.
2) high-speed stirred at 55 DEG C, sulphuric acid zirconium solution is added drop-wise in montmorillonite suspension, Disulfatozirconic acid. and montmorillonite
Mass ratio is 1.5:5, continue 1～1.5h of stirring after completion of dropping, it is 6 to adjust pH value with the sodium hydroxide solution of 1mol/L, leaching
It is centrifuged after 6～8h of stain, takes out the filter cake after centrifugation and be placed in beaker.
3) filter cake is dried at 75 DEG C, ground 200 mesh sieve after being dried, at 350 DEG C, 3.2 hours of roasting are obtained
Zr-MMT powder body.
4) by monomer N,N-DMAA Ag, cross-linking agent N, N '-methylene-bisacrylamide (MBAM) Rg is dissolved in
In TmL water, SmL dispersants ammonium polyacrylate salt is added after dissolving, is stirred, is obtained mixed solution, now A：R：S：T=
12：1.2：1.5：15.
5) in step 4) obtained by be slowly added to step 3 in mixed solution) the Zr-MMT powder body Dg that obtain, after stirring plus
Enter the polystyrene spheres CmL that particle diameter is 1～1.5mm, wherein A：D：C=12：5：105, obtain slurry I.
6) by step 3) the Zr-MMT powder body Eg that obtains added in FmL water with glass powder, wherein A：E：F=15：21：
35, and A：B：C=12：26：105；The quality of glass powder and step 4) in the mass ratio of monomer be 1:12, fully mix, obtain
To the suspension of Zr-MMT, and add step 5) obtained by slurry I, mix homogeneously obtains slurry II.
7) in step 6) obtained by foaming agent Laurel alcohol sulfuric ester TEA (triethanolamine) salt Xg is added in slurry II, be stirred to
Fully bubble, add the catalyst n of initiator azo [2- amidine propanes] hydrochlorate Yg and concentration for 0.35g/100mL, N,
N, ' N, '-tetramethylethylenediamine (TEMED) ZmL, wherein A：X：Y：Z=12：3.5：0.7：1.4, stir until irritant gas
Taste is produced, and slurry preparation is completed, and reinjects die for molding；
8) 58h is dried at 58 DEG C, completes polyreaction, obtain dry body body.
9) dry body body is increased to into 350 DEG C with the speed of 5 DEG C/min from room temperature, is incubated 6.3h, with the speed liter of 2 DEG C/min
High to 630 DEG C insulation 2.8h, furnace cooling, obtaining glass powder strengthens the cellular block chromium adsorbent of Zr modified montmorillonoids.
Claims (9)
1. glass powder strengthens the preparation method of the cellular block chromium adsorbent of Zr modified montmorillonoids, it is characterised in that：Take gel
The monomer Ag of polymerization, cross-linking agent and dispersant are dissolved in water and form mixed solution, add the Zr of Bg modified to cover in the mixed solution
De- soil powder body, the polystyrene spheres that CmL particle diameters are 1～1.5mm and be 1 with the mass ratio of monomer:（5~20）Glass powder,
Wherein A：B：C=（10～15）：（21～29）：（90～120）, mix homogeneously obtains slurry, adds gel polymerisation in the slurry
Foaming agent, initiator and catalyst, mix homogeneously carry out polyreaction, and dry body body is obtained after the completion of reaction, by dry body body 330
～440 DEG C and 550～700 DEG C are incubated respectively, and obtaining glass powder strengthens the cellular block chromium absorption of Zr modified montmorillonoids
Agent；Monomer is acrylamide or N, N- DMAA；Described cross-linking agent is N, N '-methylene-bisacrylamide, is divided
Powder is ammonium polyacrylate salt or ammonium citrate, and foaming agent is Laurel alcohol sulfuric ester TEA salt, and initiator is Ammonium persulfate. or azo
[2- amidine propanes] hydrochlorate, catalyst is N, N, N, ' N, '-tetramethylethylenediamine.
2. glass powder according to claim 1 strengthens the preparation side of the cellular block chromium adsorbent of Zr modified montmorillonoids
Method, it is characterised in that：Including step in detail below：
1）Mixed solution, and A are obtained during monomer Ag, cross-linking agent Rg and dispersant SmL are dissolved in TmL water：R：S：T=（10～15）：
（1～1.5）：（1.2～1.7）：15；
2）In step 1）Zr modified montmorillonoid powder body Dg are added in gained mixed solution, be stirring evenly and then adding into particle diameter for 1～
The polystyrene spheres CmL of 1.5mm, A：D：C=（10～15）：（3～7）：（90～120）, obtain slurry I；
3）Zr modified montmorillonoid powder body Eg are added in FmL water with glass powder, wherein A：E：F=（10～15）：（18～22）：
35, and D+E=B；The quality of glass powder and step 1）The mass ratio of middle monomer is 1:（5～20）, fully mix, obtain Zr and change
The suspension of property montmorillonite, and add step 2）In gained slurry I, mix homogeneously obtains slurry II；
4）In step 3）Foaming agent Xg, initiator Yg and catalyst Z mL, wherein A are added in gained slurry II：X：Y：Z=（10～
15）：（2.0～4.0）：（0.01～1.0）：（0.4～2）, stir mould, molding are injected after irritant abnormal smells from the patient is produced；
5）Dry body body is obtained after 40～60 DEG C of 50～70h of drying；
6）Dry body body is incubated respectively at 330～440 DEG C and 550～700 DEG C, furnace cooling, is obtained glass powder enhancing
The cellular block chromium adsorbent of Zr modified montmorillonoids.
3. glass powder according to claim 1 and 2 strengthens the preparation of the cellular block chromium adsorbent of Zr modified montmorillonoids
Method, it is characterised in that：The preparation process of described Zr modified montmorillonoid powder body includes：
a）Take the montmorillonite suspension that mass concentration is 10%；
b）Under 30 ~ 80 DEG C of stirring conditions, sulphuric acid zirconium solution is added drop-wise in montmorillonite suspension, wherein Disulfatozirconic acid. and montmorillonite
Mass ratio be（1~2）:5, continue 1～1.5h of stirring after completion of dropping, it is 2 ~ 8 to adjust pH value with sodium hydroxide solution, dipping
After be centrifuged, take out centrifugation after filter cake；
c）Grinding after filtration cakes torrefaction is sieved, at 200 ~ 500 DEG C, 3～4 hours of roasting obtain Zr modified montmorillonoid powder body.
4. glass powder according to claim 3 strengthens the preparation side of the cellular block chromium adsorbent of Zr modified montmorillonoids
Method, it is characterised in that：Step b）It is centrifuged after 6 ~ 8h of middle dipping, step c）In be dried at 70～90 DEG C, and it is used to sieve
Screen cloth is 200 mesh.
5. glass powder according to claim 3 strengthens the preparation side of the cellular block chromium adsorbent of Zr modified montmorillonoids
Method, it is characterised in that：Montmorillonite adopts sodio nano imvite.
6. glass powder according to claim 1 and 2 strengthens the preparation of the cellular block chromium adsorbent of Zr modified montmorillonoids
Method, it is characterised in that：Described glass powder is B2O3-Na2O-Bi2O3, wherein by mass percentage, B2O3For 30～
60%, Na2O：30～60%, Bi2O3：10～20%.
7. glass powder according to claim 1 and 2 strengthens the preparation of the cellular block chromium adsorbent of Zr modified montmorillonoids
Method, it is characterised in that：Described catalyst concn is 0.35g/100mL.
8. glass powder according to claim 1 and 2 strengthens the preparation of the cellular block chromium adsorbent of Zr modified montmorillonoids
Method, it is characterised in that：Dry body body insulating process is specially：330～440 are increased to the speed of 5 DEG C/min from room temperature first
DEG C insulation 5～7h, then with the speed of 2 DEG C/min be increased to 550～700 DEG C insulation 1～3h.
9. the cellular block chromium of Zr modified montmorillonoids is strengthened based on glass powder prepared by preparation method described in claim 1 or 2
Adsorbent, it is characterised in that：It is many of rule that described glass powder strengthens the cellular block chromium adsorbent of Zr modified montmorillonoids
Porous materials, and aperture is 1.0～1.5mm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324761A (en) * | 2000-05-24 | 2001-12-05 | 中国石油化工集团公司 | Prepn. of layered molecular sieve |
| CN1375516A (en) * | 2001-03-21 | 2002-10-23 | 中国科学院化学研究所 | Nano composite polymer-montmorillonoid material and its prepn. |
| CN1803610A (en) * | 2005-09-15 | 2006-07-19 | 浙江大学 | Method for preparing rare earth-compounded Zr cross-linked montmorillonite material |
| CN1837043A (en) * | 2006-04-14 | 2006-09-27 | 西北师范大学 | Rare earth particle and montmorillonite nano composite materials and process for preparing same |
| CN103406973A (en) * | 2013-07-25 | 2013-11-27 | 中南大学 | Formation technology for preparation of porous or compact material with gel-casting of alcohol-water basic material slurry |
-
2015
- 2015-04-15 CN CN201510177759.1A patent/CN104785226B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324761A (en) * | 2000-05-24 | 2001-12-05 | 中国石油化工集团公司 | Prepn. of layered molecular sieve |
| CN1375516A (en) * | 2001-03-21 | 2002-10-23 | 中国科学院化学研究所 | Nano composite polymer-montmorillonoid material and its prepn. |
| CN1803610A (en) * | 2005-09-15 | 2006-07-19 | 浙江大学 | Method for preparing rare earth-compounded Zr cross-linked montmorillonite material |
| CN1837043A (en) * | 2006-04-14 | 2006-09-27 | 西北师范大学 | Rare earth particle and montmorillonite nano composite materials and process for preparing same |
| CN103406973A (en) * | 2013-07-25 | 2013-11-27 | 中南大学 | Formation technology for preparation of porous or compact material with gel-casting of alcohol-water basic material slurry |
Non-Patent Citations (2)
| Title |
|---|
| Alumina Heat Insulator Through Composite Poring Mechanisms;Haibo Wu et al.;《Int. J. Appl. Ceram. Technol.》;20141130;第11卷(第6期);1061-1067 * |
| 凝胶注模成形法制备多孔铝及其性能研究;张秀丽等;《功能材料》;20101231;第41卷;401-404 * |
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