CN103540950B - A kind of preparation method of porous silica lead material - Google Patents
A kind of preparation method of porous silica lead material Download PDFInfo
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- CN103540950B CN103540950B CN201310542693.2A CN201310542693A CN103540950B CN 103540950 B CN103540950 B CN 103540950B CN 201310542693 A CN201310542693 A CN 201310542693A CN 103540950 B CN103540950 B CN 103540950B
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- polyurethane sponge
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Abstract
The invention discloses a kind of preparation method of porous silica lead material.Comprise and carrying out successively as anode after oil removing, alligatoring, neutralization, preimpregnation and chemical oxidation treatment polyurethane sponge substrate, carry out electrochemicial oxidation with pure stereotype as negative electrode, final curing, drying obtains porous silica lead material; Described electrochemical oxidation process adds o-benzoic sulfimide sodium; Described polyurethane sponge substrate perforate is 2 ~ 5mm, the diameter of spongin fiber at 0.1 ~ 0.25mm, porosity 85 ~ 95%; Described electrochemicial oxidation adopts the acidic mixed solution of lead nitrate, o-benzoic sulfimide sodium; Anodic current density is with the surface area 8 ~ 20A/dm of polyurethane sponge
2, temperature controls at 45 DEG C.Adding of o-benzoic sulfimide sodium makes the microscopic appearance of titanium dioxide lead layer more coarse, and hardness is high, is desirable insoluble anode material.
Description
Technical field
The present invention relates to a kind of preparation method of porous silica lead material.
Background technology
Plumbic oxide material has good form, structure, optics and mechanical property, its stable chemical nature, and resistant to many strong acid corrodes.Plumbic oxide, as insoluble anode material, in aqueous during electrolysis, has the advantages such as higher oxygen evolution potential, resistance of oxidation is strong, solidity to corrosion is good, causes the extensive concern of domestic and international researcher.Plumbic oxide material, as insoluble anode material, is widely used in the fields such as chemical industry production, hydrometallurgy, wastewater treatment.The preparation of traditional plumbic oxide material, adopts metal titanium as matrix (coefficient of expansion of metal titanium is close with plumbic oxide material), and after special chemical solution process, in the acidic solution containing lead ion, electrolysis obtains plumbic oxide material.In recent years adopt iron and steel, stainless steel as plumbic oxide material metal body material in addition; By pottery, ABS plastic as the report of plumbic oxide material non-metallic matrix material.But the plumbic oxide material prepared on above-mentioned body material is bar-shaped or tabular, specific surface area is less, can not meet the needs of electrolysis production completely.
Summary of the invention
The object of the invention is the preparation method providing a kind of porous silica lead material, and the porous silica lead material of preparation has certain physical strength, and specific volume is large, and specific surface area is large, and through-hole rate is high.
For achieving the above object, the technical scheme of employing is as follows:
A kind of preparation method of porous silica lead material, comprise and polyurethane sponge substrate is carried out after oil removing, alligatoring, neutralization, preimpregnation and chemical oxidation treatment successively as anode, carry out electrochemicial oxidation with pure stereotype as negative electrode, final curing, drying obtains porous silica lead material; Described electrochemical oxidation process adds o-benzoic sulfimide sodium; Described polyurethane sponge substrate perforate is 2 ~ 5mm, the diameter of spongin fiber at 0.1 ~ 0.25mm, porosity 85 ~ 95%.
By such scheme, described electrochemicial oxidation adopts the acidic mixed solution of lead nitrate 180-330g/L, o-benzoic sulfimide sodium 2-4g/L; Anodic current density 8 ~ 20A/dm2, temperature controls at 45 DEG C.
By such scheme, described oil removal treatment is soaked in the mixed aqueous solution of sodium hydroxide, sodium carbonate, polyoxyethylene octylphenol ether polyurethane sponge substrate.
By such scheme, described roughening treatment is soaked in strongly acidic solution by polyurethane sponge; Strongly acidic solution is the mixed aqueous solution of sulfuric acid, potassium bichromate two kinds of materials; Or sulfuric acid, chromic anhydride two kinds of materials mixed aqueous solution.
By such scheme, described neutralizing treatment be by alligatoring after polyurethane sponge be placed in sodium carbonate solution and soak.
By such scheme, described pre-preg is that polyurethane sponge neutralizing treatment crossed soaks in predip solution; Described presoak is the mixed solution of ammonium thiosulfate and ammoniacal liquor.
By such scheme, described chemical oxidation treatment be by preimpregnation after polyurethane sponge soak in chemical oxidation solution; Described chemical oxidation solution is the mixing solutions of plumbic acetate, ammonium thiosulfate, ammoniacal liquor.
Deoiling step process, the greasy dirt on removing polyurethane sponge surface, makes the coarsening process of next step more even; Roughening step process, makes the surface microroughness of polyurethane sponge, increases its surface-area, increases the bonding strength of matrix and titanium dioxide lead layer; In and the acidic solution that may not clean up of polyurethane sponge surface, avoid hexavalent chromium or sulfate ion to bring predip solution into, cause predip solution to decompose, lost efficacy; Adopt the method for chemical oxidation on polyurethane sponge surface, obtain the titanium dioxide lead layer with conducting function; Then in electrochemical oxidation solution, the polyurethane sponge of aforesaid method process is used to make anode, pure stereotype carries out electrochemical oxidation as negative electrode, obtains the plumbic oxide material with three-dimensional porous structure, and the electrochemical oxidation time determines according to the thickness of required titanium dioxide lead layer.
Beneficial effect of the present invention:
Electrochemical oxidation solution composition is simple, is easy to allotment; Adding of special chemical additive o-benzoic sulfimide sodium, make the microscopic appearance of titanium dioxide lead layer more coarse, surface-area strengthens further; The porous silica lead material prepared with aforesaid method, hardness is high, and specific surface area is huge, is desirable insoluble anode material.
Accompanying drawing explanation
Fig. 1: the porous lead dioxide material sample (with the addition of o-benzoic sulfimide sodium) of preparation in example 1.
Fig. 2: the porous lead dioxide material sample (not adding o-benzoic sulfimide sodium) of preparation in example 1.
Fig. 3: the porous lead dioxide material sample surface topography (400 times) of preparation in example 2.
Embodiment
Following examples as the further explanation of technical solution of the present invention, but not as limiting the scope of the invention.
Embodiment 1
Prepared by sample: choosing perforate is 3 ~ 5mm, and the diameter of spongin fiber is at 0.15 ~ 0.25mm, and the polyurethane sponge of porosity 90 ~ 95% is matrix, and the rectangular parallelepiped being cut to 150 × 50 × 5mm is for subsequent use.
Oil removing: by sample shaping for cutting, is soaked in the mixing solutions of sodium hydroxide 8g/L, sodium carbonate 45g/L, polyoxyethylene octylphenol ether 1g/L, temperature 25 DEG C, soak time 20 minutes.
Alligatoring: by the sample after oil removing, is soaked in the mixing solutions of sulfuric acid 100ml/L and chromic acid 80g/L, and temperature is 25 DEG C, soak time 10 minutes.
Neutralization: soaked 15 minutes in the sodium carbonate solution of 10g/L by the polyurethane sponge after alligatoring, temperature is 30 DEG C.
Preimpregnation: by the polyurethane sponge after neutralization, be placed in predip solution and soak 10 minutes, temperature 25 DEG C is consisting of of described presoak: ammonium thiosulfate 50g/L and ammoniacal liquor 20ml/L.
Chemical oxidation: taken out from predip solution by the polyurethane sponge after preimpregnation, without washing, be directly soaked in chemical oxidation solution, temperature controls at 40 DEG C, and soak time is 8 hours, and omnidistance pressurized air stirs (maintenance dissolution homogeneity).Chemical oxidation solution formula is plumbic acetate 38g/L, ammonium thiosulfate 45g/L, ammoniacal liquor 30ml/L.
Electrochemical oxidation: get the polyurethane sponge after chemical oxidation and make anode, negative electrode made by pure stereotype, in the acidic solution containing lead nitrate 180g/L, (pH=1.5, the salpeter solution with 50% or lead oxide powder adjust ph) carries out two groups of electrochemical oxidations contrasts.Wherein add o-benzoic sulfimide sodium 2g/L in one group of electrochemical oxidation liquor sample, in another group, do not add o-benzoic sulfimide sodium; Solution temperature all controls at 45 DEG C, initial anodic current density (surface area with polyurethane sponge) 18A/dm
2, be oxidized after 30 minutes, transfer 10A/dm to
2anodization current density, continue oxidation 8 hours.
Be cured as: by the plumbic oxide material of preparation, be soaked in the deionized water of 60 ± 5 DEG C, soak time 45 minutes.
Drying is: by the plumbic oxide material after solidification, be placed in the air dry oven of 60 ± 5 DEG C, 60 minutes time of drying.
The photo of porous lead dioxide material sample prepared by this example is with reference to shown in accompanying drawing 1,2; with the addition of o-benzoic sulfimide sodium in the electrochemical oxidation solution that sample shown in Fig. 1 adopts, in the electrochemical oxidation solution that the sample shown in Fig. 2 adopts, do not add o-benzoic sulfimide sodium.From Fig. 1,2 contrast, can observe: with the addition of porous lead dioxide material structure prepared by o-benzoic sulfimide sodium tight, specific surface area is huge, is excellent insoluble anode material.
Embodiment 2
Prepared by sample: taking away hole is 2 ~ 3mm, and the diameter of spongin fiber is at 0.1 ~ 0.15mm, and the polyurethane sponge of porosity 85 ~ 90% is matrix, and the rectangular parallelepiped being cut to 150 × 50 × 5mm is for subsequent use.
Oil removing: by sample shaping for cutting, is soaked in the mixing solutions of sodium hydroxide 15g/L, sodium carbonate 20g/L, polyoxyethylene octylphenol ether 0.5g/L, temperature 25 DEG C, soak time 10 minutes.
Alligatoring: by sample shaping for cutting, is soaked in the mixing solutions of sulfuric acid 180ml/L and potassium bichromate 50g/L, and temperature is 25 DEG C, soak time 15 minutes.
Neutralization: soaked 10 minutes in the sodium carbonate solution of 50g/L by the polyurethane sponge after alligatoring, temperature is 25 DEG C.
Preimpregnation: by the polyurethane sponge after neutralization, is placed in predip solution 20 DEG C and soaks 30 minutes, consisting of of described presoak: ammonium thiosulfate 10g/L and ammoniacal liquor 50ml/L.
Chemical oxidation: taken out from predip solution by the polyurethane sponge after preimpregnation, without washing, be directly soaked in chemical oxidation solution, temperature 50 C, soak time is 6 hours, and omnidistance pressurized air stirs, and makes dissolution homogeneity.Chemical oxidation solution formula is plumbic acetate 80g/L, ammonium thiosulfate 25g/L, ammoniacal liquor 60ml/L.
Electrochemical oxidation: the polyurethane sponge through chemical oxidation is made anode; negative electrode made by pure stereotype; containing lead nitrate 330g/L; the acidic solution of o-benzoic sulfimide sodium 4g/L (pH=1.0 with 50% salpeter solution or lead oxide powder adjust ph) in; solution temperature 45 DEG C, initial anodic current density (surface area with polyurethane sponge) 20A/dm
2, be oxidized after 45 minutes, transfer 8A/dm to
2oxidation current density, oxidization time 5 hours.
Solidification: by the plumbic oxide material of preparation, be soaked in the deionized water of 60 ± 5 DEG C, soak time 45 minutes.
Dry: by the plumbic oxide material after solidification, to be placed in the air dry oven of 60 ± 5 DEG C, 45 minutes time of drying.
Porous silica lead material prepared by example 2, the picture under 400 power microscopes as shown in Figure 3.Can observe from picture, porous lead dioxide material structure prepared by example 3 is tight, and its surface is that convex-concave is irregularly shaped, further increases the surface-area of porous silica lead material.
Claims (6)
1. the preparation method of a porous silica lead material, it is characterized in that comprising and polyurethane sponge substrate is carried out after oil removing, alligatoring, neutralization, preimpregnation and chemical oxidation treatment successively as anode, electrochemicial oxidation is carried out as negative electrode with pure stereotype, final curing, drying obtains porous silica lead material;
Described electrochemical oxidation process adds o-benzoic sulfimide sodium; Described polyurethane sponge substrate perforate is 2 ~ 5mm, the diameter of spongin fiber at 0.1 ~ 0.25mm, porosity 85 ~ 95%;
Described electrochemicial oxidation adopts the acidic mixed solution of lead nitrate 180-330g/L, o-benzoic sulfimide sodium 2-4g/L; Anodic current density 8 ~ 20A/dm
2, temperature controls at 45 DEG C.
2. the preparation method of porous silica lead material as claimed in claim 1, is characterized in that described oil removal treatment is soaked in the mixed aqueous solution of sodium hydroxide, sodium carbonate, polyoxyethylene octylphenol ether polyurethane sponge substrate.
3. the preparation method of porous silica lead material as claimed in claim 1, is characterized in that described roughening treatment is soaked in strongly acidic solution by polyurethane sponge; Strongly acidic solution is the mixed aqueous solution of sulfuric acid, potassium bichromate two kinds of materials; Or sulfuric acid, chromic anhydride two kinds of materials mixed aqueous solution.
4. the preparation method of porous silica lead material as claimed in claim 1, it is characterized in that described neutralizing treatment be by alligatoring after polyurethane sponge be placed in sodium carbonate solution and soak.
5. the preparation method of porous silica lead material as claimed in claim 1, is characterized in that described pre-preg is that polyurethane sponge neutralizing treatment crossed soaks in predip solution; Described presoak is the mixed solution of ammonium thiosulfate and ammoniacal liquor.
6. the preparation method of porous silica lead material as claimed in claim 1, it is characterized in that described chemical oxidation treatment be by preimpregnation after polyurethane sponge soak in chemical oxidation solution; Described chemical oxidation solution is the mixing solutions of plumbic acetate, ammonium thiosulfate, ammoniacal liquor.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6972078B1 (en) * | 1999-10-20 | 2005-12-06 | The Dow Chemical Company | Catalytic powder and electrode made therewith |
| CN1924102A (en) * | 2006-09-05 | 2007-03-07 | 陕西科技大学 | Preparation method of lead dioxide porous electrode |
| CN101555051A (en) * | 2009-05-05 | 2009-10-14 | 苏州科技学院 | Production method for powder porous lead dioxide electrode used for treating organics in water |
| CN101824619A (en) * | 2010-06-01 | 2010-09-08 | 武汉银泰科技电源股份有限公司 | Preparation method of foam tin material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6972078B1 (en) * | 1999-10-20 | 2005-12-06 | The Dow Chemical Company | Catalytic powder and electrode made therewith |
| CN1924102A (en) * | 2006-09-05 | 2007-03-07 | 陕西科技大学 | Preparation method of lead dioxide porous electrode |
| CN101555051A (en) * | 2009-05-05 | 2009-10-14 | 苏州科技学院 | Production method for powder porous lead dioxide electrode used for treating organics in water |
| CN101824619A (en) * | 2010-06-01 | 2010-09-08 | 武汉银泰科技电源股份有限公司 | Preparation method of foam tin material |
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