CN103351029B - Method for processing waste liquid of titanium dioxide factory - Google Patents
Method for processing waste liquid of titanium dioxide factory Download PDFInfo
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- CN103351029B CN103351029B CN201310212046.5A CN201310212046A CN103351029B CN 103351029 B CN103351029 B CN 103351029B CN 201310212046 A CN201310212046 A CN 201310212046A CN 103351029 B CN103351029 B CN 103351029B
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Abstract
The invention discloses a method for processing the waste liquid of a titanium dioxide factory. The method comprises the steps of aggregating for residue removal, crystallizing ferrous sulfate, filtering and washing with water, carrying out vacuum concentrating, bleaching, and further removing impurities. The method has the advantages of less consumption of sulfuric acid, less consumption of a reducing agent, low operating temperature, short bleaching time, no residue pollution, and good bleaching effect. Regular metatitanic acid can be prepared through adopting the method, and can be easily washed by water, so the output and quality are improved; and high-quality ferrous sulfate can also be produced, and the quality of titanium dioxide is also obviously improved.
Description
Technical field
The present invention relates to titanium white production technique, especially a kind of method of processing titanium powder plant waste liquid.
Background technology
Ilmenite carries out after acid decomposition at acidolysis pot, and the solution obtaining through leaching, is a kind of muddy complex system.This solution had both had the character of true solution; There is again the character of colloidal solution.Both contained the soluble salt as leading taking titanium and iron; Contain again the mechanical impurity of the suspension insoluble, particle is larger and particle less, the colloidal impurity with higher stability.The insoluble solid impurity of latter two, is referred to as titanium liquid residue.The mechanical impurity that particle is larger is mainly the compound of indissoluble or undecomposed ilmenite, rutile, monazite, zircon, gangue, mud and carbon, lead, calcium etc.The colloidal impurity that particle is less is mainly silicic acid, aluminate and metatitanic acid.The filter press that the separating and filtering of ferrous sulfate crystal and titanium liquid and titanium liquid further purify, can make filtering layer stop up, and filtration is difficult to carry out, to such an extent as to greatly affects the output of titanium dioxide.Some metal ion finally can be sneaked into finished product, reduce the purity of finished product, and sneaking into of the harmful metal ions such as some colored iron, vanadium, chromium, manganese, lead and cobalt also can have influence on the whiteness of product.
In addition, above-mentioned impurity comprises a large amount of callable resources, the not only contaminate environment of directly waste liquid being drained, and cause the wasting of resources, prior art provides the whole bag of tricks, but does not have a set of complete, efficient and cheap treatment process.
Summary of the invention
Goal of the invention: the present invention will provide a kind of method of processing titanium powder plant waste liquid, to address the above problem.
Technical scheme: a kind of method of processing titanium powder plant waste liquid, comprises the steps:
S1, the titanium liquid after acidolysis is added to amphiprotic polyacrylamide, establish sloping settling bowl bottom pumping into 3-5 through the mixing tank on pipeline, sedimentation 3-5h, imports impeller pump by siphon pipe by clear liquid; In the time that the slag mud in settling bowl exceedes 60 centimetres, the muddy top titanium liquid suspending is imported to another settling bowl by impeller pump, and to add weight be the sodium alkyl benzene sulfonate of titanium liquid weight 10～15%, clean the slag mud of the lowest layer with water blast gun, by clean mud suspension send into pressure filter by pond bottom valve slush pump and carry out press filtration;
S2, supernatant liquor is pumped in the sealing crystallizer of bottom with agitator, to vacuumizing in crystallizer, titanium liquid temp is declined with water-ring vacuum pump; In the time that temperature is 37-39 DEG C, open steam injector, strengthen cooling water flow, secondary steam and uperize are cooled to water of condensation, noncondensable gas is discharged by vacuum pump; Only open water-ring pump 45-65min; When opening water-ring pump, increase injector 3h, make temperature reach 15-20 DEG C; Steam off injector, is adjusted to emptying position by water-ring pump valve, makes to return in crystallizer normal pressure; Suspension is discharged from crystallizer bottom valve, separate through whizzer, obtain iron vitriol, and collect extracting solution;
S3, before filter press, flocculating aids is made into suspension and adds in sheet frame press, make filter cloth stick flocculating aids, and then add the collection liquid of titanium liquid to carry out filter press; Described auxiliary agent is charcoal, diatomite and paper pulp, part by weight between them is 1-3:2-3:1:5, the weight burning decrement of charcoal is 90%, fineness is 150-200 order, every square metre of filtration area is used 0.5-1.0kg, pressure filter drainage layer laying depth is 3-5mm, and diatomaceous granularity is 30-80ptm, and relative density is 2.3-2.7;
S4, by the collection liquid vacuum concentration of press filtration, obtain metatitanic acid crystal; In the enamel reactor of the chuck heating with stirring, add metatitanic acid and water, stir and adjust concentration of slurry between 180-220g/l, under agitation adding weight is the technical grade sulfuric acid of titanium dioxide weight 32-35%, make the sulfuric acid concentration of slurries between 78-88g/l, lead to and be steam heated to 75-85 DEG C, make ironic hydroxide be transformed into ferric sulphate; Make a part of metatitanic acid dissolve simultaneously and generate titanium sulfate, by after aluminium powder water furnishing pulpous state, it is the aluminium powder of titanium dioxide weight 0.5-1.0% that gradation adds weight, continues heating, make temperature be incubated 1.8-2.8h at 90-95 DEG C, sampling and measuring titanous content is 0.3～0.5g/l; After insulation finishes, change logical water coolant material is cooled to below 45 DEG C, obtain metatitanic acid slurry;
S5, described metatitanic acid slurry is filtered with leaf filter after, with contain 0.1%～2.0wt% sour water, temperature is the deionized water wash metatitanic acid of 50-65 DEG C, further washes away ferrous sulfate, until metatitanic acid containing ferric oxide lower than 2 × 10
-5.
In step S1, maintenance solution temperature is 60-70 DEG C, every 1m
3titanium liquid to add mass concentration be the amphiprotic polyacrylamide 5-8L of 1.5%-2.5%, and point add for 3-5 time.
In step S4, the flow process that has of vacuum concentration is: titanium liquid is collected to liquid Implanted Titanium liquid header tank, and the titanium liquid injecting in water seal tank makes it to keep fluid-tight; Start vacuum pump, open water coolant, and mix up the flow of water coolant and mix up vacuum tightness 9 × 10
4above; Open valve, allows titanium liquid enter in titanium pipe evaporator, and concentrator feed amount is controlled at 1.5-2.5m
3/ l, the heat interchanging area of titanium liquid vaporizer is 260～300m
2; Open steam valve, and remain on 4.9～8.5 × 10
4under the vapor pressure of Pa, carry out vacuum concentration, control titanium liquid temp at 75-80 DEG C; Measure titanium concentration on time; When concentrated stopping, steam off valve, allows titanium liquid continue charging, closes feed valve, water coolant and vacuum pump.
In step S5, metatitanic acid slurry temperature remains on 25-40 DEG C; The vacuum keep of leaf filter is in 5.3-5.5 × 10
4pA; Washing is divided into pressurization washing and normal pressure washing, pressurized water pulp washing material 8-12h, water at atmospheric pressure pulp washing material 3-6h.
In step S2, the vapor pressure of injector is greater than 0.8MPa, and the steam flow of injector is 2-2.5 ton/h, and circulating cooling water flow is 30-50m
3/ h.
Step S5 also comprises: after washing with deionized water, after washing with deionized water, add oxygenant, ferrous ion is oxidized to ferric ion, then adjust pH value higher than 5.2, the cotton-shaped ferric hydroxide precipitate that ferric ion hydrolysis is generated, filters.
Beneficial effect: treatment process of the present invention can be separated various resources in order, improved the utilization ratio of resource and the quality of titanium dioxide, and the method cost is lower, is easy to promote.
Embodiment
Embodiment 1
A method of processing titanium powder plant waste liquid, comprises the steps:
S1, the titanium liquid after acidolysis is added to amphiprotic polyacrylamide, establish sloping settling bowl bottom pumping into 3-5 through the mixing tank on pipeline, sedimentation 3h, imports impeller pump by siphon pipe by clear liquid; In the time that the slag mud in settling bowl exceedes 60 centimetres, the muddy top titanium liquid suspending is imported to another settling bowl by impeller pump, and to add weight be the sodium alkyl benzene sulfonate of titanium liquid weight 10%, clean the slag mud of the lowest layer with water blast gun, by clean mud suspension send into pressure filter by pond bottom valve slush pump and carry out press filtration; Keeping solution temperature is 62 DEG C, every 1m
3titanium liquid to add mass concentration be 1.5% amphiprotic polyacrylamide 6L, and point add for 3 times;
S2, supernatant liquor is pumped in the sealing crystallizer of bottom with agitator, to vacuumizing in crystallizer, titanium liquid temp is declined with water-ring vacuum pump; In the time that temperature is 37 DEG C, open steam injector, strengthen cooling water flow, secondary steam and uperize are cooled to water of condensation, noncondensable gas is discharged by vacuum pump; Only open water-ring pump 55min; When opening water-ring pump, increase injector 3h, make temperature reach 20 DEG C; Steam off injector, is adjusted to emptying position by water-ring pump valve, makes to return in crystallizer normal pressure; Suspension is discharged from crystallizer bottom valve, separate through whizzer, obtain iron vitriol, and collect extracting solution; The vapor pressure of injector is greater than 0.8MPa, and the steam flow of injector is 2 tons/h, and circulating cooling water flow is 50m
3/ h;
S3, before filter press, flocculating aids is made into suspension and adds in sheet frame press, make filter cloth stick flocculating aids, and then add the collection liquid of titanium liquid to carry out filter press; Described auxiliary agent is charcoal, diatomite and paper pulp, part by weight between them is 1:2:1, the weight burning decrement of charcoal is 90%, fineness is approximately 150 orders, every square metre of filtration area is used 1.0kg, pressure filter drainage layer laying depth is 5mm, and diatomaceous granularity is 70ptm, and relative density is 2.4;
S4, by the collection liquid vacuum concentration of press filtration, obtain metatitanic acid crystal; In the enamel reactor of the chuck heating with stirring, add metatitanic acid and water, stir and adjust concentration of slurry between 180g/l, under agitation adding weight is the technical grade sulfuric acid of titanium dioxide weight 35%, the sulfuric acid concentration that makes slurries is 80g/l, lead to and be steam heated to 85 DEG C, make ironic hydroxide be transformed into ferric sulphate; Make a part of metatitanic acid dissolve simultaneously and generate titanium sulfate, by after aluminium powder water furnishing pulpous state, it is the aluminium powder of titanium dioxide weight 1.0% that gradation adds weight, due to aluminium powder can with slurry in ferric sulphate effect, again can be with the effect of sulfuric acid of slurry and releasing hydrogen gas, make to produce a large amount of bubbles in slurry, must slowly add for this reason, to avoid reaction too acutely cause slurry to splash or emit pot.Add after aluminium powder, continue heating, make temperature be incubated 2.0h at 95 DEG C, sampling and measuring titanous content is 0.4g/l; After insulation finishes, change logical water coolant material is cooled to below 45 DEG C, obtain metatitanic acid slurry;
The flow process that has of vacuum concentration is: titanium liquid is collected to liquid Implanted Titanium liquid header tank, and the titanium liquid injecting in water seal tank makes it to keep fluid-tight; Start vacuum pump, open water coolant, and mix up the flow of water coolant and mix up vacuum tightness 9 × 10
4above; Open valve, allows titanium liquid enter in titanium pipe evaporator, and concentrator feed amount is controlled at 1.5m
3/ l, the heat interchanging area of titanium liquid vaporizer is 260m
2; Open steam valve, and remain on 8.5 × 10
4under the vapor pressure of Pa, carry out vacuum concentration, control titanium liquid temp at 76 DEG C; Measure titanium concentration on time; When concentrated stopping, steam off valve, allows titanium liquid continue charging, closes feed valve, water coolant and vacuum pump.
S5, described metatitanic acid slurry is filtered with leaf filter after, with contain 0.5wt% sour water, temperature is the deionized water wash metatitanic acid of 55 DEG C, further washes away ferrous sulfate, until metatitanic acid containing ferric oxide lower than 2 × 10
-5; After washing with deionized water, add oxygenant, ferrous ion is oxidized to ferric ion, then adjust pH value, the cotton-shaped ferric hydroxide precipitate that ferric ion hydrolysis is generated, filters; Metatitanic acid slurry temperature remains on 40 DEG C; The vacuum keep of leaf filter is 5.5 × 10
4pA; Washing is divided into pressurization washing and normal pressure washing, pressurized water pulp washing material 12h, water at atmospheric pressure pulp washing material 5h.
Embodiment 2
A method of processing titanium powder plant waste liquid, comprises the steps:
S1, the titanium liquid after acidolysis is added to amphiprotic polyacrylamide, establish sloping settling bowl bottom pumping into 3-5 through the mixing tank on pipeline, sedimentation 4h, imports impeller pump by siphon pipe by clear liquid; In the time that the slag mud in settling bowl exceedes 60 centimetres, the muddy top titanium liquid suspending is imported to another settling bowl by impeller pump, and to add weight be the sodium alkyl benzene sulfonate of titanium liquid weight 12%, clean the slag mud of the lowest layer with water blast gun, by clean mud suspension send into pressure filter by pond bottom valve slush pump and carry out press filtration; Keeping solution temperature is 60 DEG C, every 1m
3titanium liquid to add mass concentration be 2.0% amphiprotic polyacrylamide 6L, and point add for 4 times;
S2, supernatant liquor is pumped in the sealing crystallizer of bottom with agitator, to vacuumizing in crystallizer, titanium liquid temp is declined with water-ring vacuum pump; In the time that temperature is 39 DEG C, open steam injector, strengthen cooling water flow, secondary steam and uperize are cooled to water of condensation, noncondensable gas is discharged by vacuum pump; Only open water-ring pump 45min; When opening water-ring pump, increase injector 3h, make temperature reach 18 DEG C; Steam off injector, is adjusted to emptying position by water-ring pump valve, makes to return in crystallizer normal pressure; Suspension is discharged from crystallizer bottom valve, separate through whizzer, obtain iron vitriol, and collect extracting solution; The vapor pressure of injector is greater than 0.8MPa, and the steam flow of injector is 2.2 tons/h, and circulating cooling water flow is 35m
3/ h;
S3, before filter press, flocculating aids is made into suspension and adds in sheet frame press, make filter cloth stick flocculating aids, and then add the collection liquid of titanium liquid to carry out filter press; Described auxiliary agent is charcoal, diatomite and paper pulp, part by weight between them is 2:3:3, the weight burning decrement of charcoal is 90%, fineness is about 200 orders, every square metre of filtration area is used 0.8kg, pressure filter drainage layer laying depth is 4mm, and diatomaceous granularity is 70ptm, and relative density is 2.5;
S4, by the collection liquid vacuum concentration of press filtration, obtain metatitanic acid crystal; In the enamel reactor of the chuck heating with stirring, add metatitanic acid and water, stir and adjust concentration of slurry between 200g/l, under agitation adding weight is the technical grade sulfuric acid of titanium dioxide weight 33%, make the sulfuric acid concentration of slurries between 85g/l, lead to and be steam heated to 76 DEG C, make ironic hydroxide be transformed into ferric sulphate; Make a part of metatitanic acid dissolve simultaneously and generate titanium sulfate, by after aluminium powder water furnishing pulpous state, it is the aluminium powder of titanium dioxide weight 0.6% that gradation adds weight, due to aluminium powder can with slurry in ferric sulphate effect, again can be with the effect of sulfuric acid of slurry and releasing hydrogen gas, make to produce a large amount of bubbles in slurry, must slowly add for this reason, to avoid reaction too acutely cause slurry to splash or emit pot.Add after aluminium powder, continue heating, make temperature be incubated 2.3h at 90 DEG C, sampling and measuring titanous content is 0.3g/l; After insulation finishes, change logical water coolant material is cooled to below 45 DEG C, obtain metatitanic acid slurry;
The flow process that has of vacuum concentration is: titanium liquid is collected to liquid Implanted Titanium liquid header tank, and the titanium liquid injecting in water seal tank makes it to keep fluid-tight; Start vacuum pump, open water coolant, and mix up the flow of water coolant and mix up vacuum tightness 9 × 10
4above; Open valve, allows titanium liquid enter in titanium pipe evaporator, and concentrator feed amount is controlled at 2.0m
3/ l, the heat interchanging area of titanium liquid vaporizer is 280m
2; Open steam valve, and remain on 5.2 × 10
4under the vapor pressure of Pa, carry out vacuum concentration, control titanium liquid temp at 80 DEG C; Measure titanium concentration on time; When concentrated stopping, steam off valve, allows titanium liquid continue charging, closes feed valve, water coolant and vacuum pump.
S5, described metatitanic acid slurry is filtered with leaf filter after, with contain 1.7wt% sour water, temperature is the deionized water wash metatitanic acid of 58 DEG C, further washes away ferrous sulfate, until metatitanic acid containing ferric oxide lower than 2 × 10
-5; After washing with deionized water, add oxygenant, ferrous ion is oxidized to ferric ion, then adjust pH value, the cotton-shaped ferric hydroxide precipitate that ferric ion hydrolysis is generated, filters; Metatitanic acid slurry temperature remains on 30 DEG C; The vacuum keep of leaf filter is 5.3 × 10
4pA; Washing is divided into pressurization washing and normal pressure washing, pressurized water pulp washing material 10h, water at atmospheric pressure pulp washing material 4h.
Embodiment 3
A method of processing titanium powder plant waste liquid, comprises the steps:
S1, the titanium liquid after acidolysis is added to amphiprotic polyacrylamide, establish sloping settling bowl bottom pumping into 3-5 through the mixing tank on pipeline, sedimentation 5h, imports impeller pump by siphon pipe by clear liquid; In the time that the slag mud in settling bowl exceedes 60 centimetres, the muddy top titanium liquid suspending is imported to another settling bowl by impeller pump, and to add weight be the sodium alkyl benzene sulfonate of titanium liquid weight 15%, clean the slag mud of the lowest layer with water blast gun, by clean mud suspension send into pressure filter by pond bottom valve slush pump and carry out press filtration; Keeping solution temperature is 71 DEG C, every 1m
3titanium liquid to add mass concentration be 1.7% amphiprotic polyacrylamide 5L, and point add for 3 times;
S2, supernatant liquor is pumped in the sealing crystallizer of bottom with agitator, to vacuumizing in crystallizer, titanium liquid temp is declined with water-ring vacuum pump; In the time that temperature is 38 DEG C, open steam injector, strengthen cooling water flow, secondary steam and uperize are cooled to water of condensation, noncondensable gas is discharged by vacuum pump; Only open water-ring pump 65min; When opening water-ring pump, increase injector 3h, make temperature reach 19 DEG C; Steam off injector, is adjusted to emptying position by water-ring pump valve, makes to return in crystallizer normal pressure; Suspension is discharged from crystallizer bottom valve, separate through whizzer, obtain iron vitriol, and collect extracting solution; The vapor pressure of injector is greater than 0.8MPa, and the steam flow of injector is 2.4 tons/h, and circulating cooling water flow is 40m
3/ h;
S3, before filter press, flocculating aids is made into suspension and adds in sheet frame press, make filter cloth stick flocculating aids, and then add the collection liquid of titanium liquid to carry out filter press; Described auxiliary agent is charcoal, diatomite and paper pulp, part by weight between them is 3:2:5, the weight burning decrement of charcoal is 90%, fineness is about 190 orders, every square metre of filtration area is used 0.9kg, pressure filter drainage layer laying depth is 5mm, and diatomaceous granularity is 75ptm, and relative density is 2.6;
S4, by the collection liquid vacuum concentration of press filtration, obtain metatitanic acid crystal; In the enamel reactor of the chuck heating with stirring, add metatitanic acid and water, stirring and adjust concentration of slurry is 225g/l, under agitation adding weight is the technical grade sulfuric acid of titanium dioxide weight 34%, the sulfuric acid concentration that makes slurries is 88g/l, lead to and be steam heated to 84 DEG C, make ironic hydroxide be transformed into ferric sulphate; Make a part of metatitanic acid dissolve simultaneously and generate titanium sulfate, by after aluminium powder water furnishing pulpous state, it is the aluminium powder of titanium dioxide weight 0.9% that gradation adds weight, due to aluminium powder can with slurry in ferric sulphate effect, again can be with the effect of sulfuric acid of slurry and releasing hydrogen gas, make to produce a large amount of bubbles in slurry, must slowly add for this reason, to avoid reaction too acutely cause slurry to splash or emit pot.Add after aluminium powder, continue heating, make temperature be incubated 2.5h at 93 DEG C, sampling and measuring titanous content is 0.5g/l; After insulation finishes, change logical water coolant material is cooled to below 45 DEG C, obtain metatitanic acid slurry;
The flow process that has of vacuum concentration is: titanium liquid is collected to liquid Implanted Titanium liquid header tank, and the titanium liquid injecting in water seal tank makes it to keep fluid-tight; Start vacuum pump, open water coolant, and mix up the flow of water coolant and mix up vacuum tightness 9 × 10
4above; Open valve, allows titanium liquid enter in titanium pipe evaporator, and concentrator feed amount is controlled at 2.4m
3/ l, the heat interchanging area of titanium liquid vaporizer is 300m
2; Open steam valve, and remain on 6.5 × 10
4under the vapor pressure of Pa, carry out vacuum concentration, control titanium liquid temp at 74 DEG C; Measure titanium concentration on time; When concentrated stopping, steam off valve, allows titanium liquid continue charging, closes feed valve, water coolant and vacuum pump.
S5, described metatitanic acid slurry is filtered with leaf filter after, with contain 0.3wt% sour water, temperature is the deionized water wash metatitanic acid of 65 DEG C, further washes away ferrous sulfate, until metatitanic acid containing ferric oxide lower than 2 × 10
-5; After washing with deionized water, add oxygenant, ferrous ion is oxidized to ferric ion, then adjust pH value, the cotton-shaped ferric hydroxide precipitate that ferric ion hydrolysis is generated, filters; Metatitanic acid slurry temperature remains on 37 DEG C; The vacuum keep of leaf filter is 5.4 × 10
4pA; Washing is divided into pressurization washing and normal pressure washing, pressurized water pulp washing material 12h, water at atmospheric pressure pulp washing material 6h.
Embodiment 4
A method of processing titanium powder plant waste liquid, comprises the steps:
S1, the titanium liquid after acidolysis is added to amphiprotic polyacrylamide, establish sloping settling bowl bottom pumping into 3-5 through the mixing tank on pipeline, sedimentation 4.5h, imports impeller pump by siphon pipe by clear liquid; In the time that the slag mud in settling bowl exceedes 60 centimetres, the muddy top titanium liquid suspending is imported to another settling bowl by impeller pump, and to add weight be the sodium alkyl benzene sulfonate of titanium liquid weight 14%, clean the slag mud of the lowest layer with water blast gun, by clean mud suspension send into pressure filter by pond bottom valve slush pump and carry out press filtration; Keeping solution temperature is 62 DEG C, every 1m
3titanium liquid to add mass concentration be 1.9% amphiprotic polyacrylamide 7.5L, and point add for 4 times;
S2, supernatant liquor is pumped in the sealing crystallizer of bottom with agitator, to vacuumizing in crystallizer, titanium liquid temp is declined with water-ring vacuum pump; In the time that temperature is 39 DEG C, open steam injector, strengthen cooling water flow, secondary steam and uperize are cooled to water of condensation, noncondensable gas is discharged by vacuum pump; Only open water-ring pump 57min; When opening water-ring pump, increase injector 3h, make temperature reach 15 DEG C; Steam off injector, is adjusted to emptying position by water-ring pump valve, makes to return in crystallizer normal pressure; Suspension is discharged from crystallizer bottom valve, separate through whizzer, obtain iron vitriol, and collect extracting solution; The vapor pressure of injector is greater than 0.8MPa, and the steam flow of injector is 2.1 tons/h, and circulating cooling water flow is 30m
3/ h;
S3, before filter press, flocculating aids is made into suspension and adds in sheet frame press, make filter cloth stick flocculating aids, and then add the collection liquid of titanium liquid to carry out filter press; Described auxiliary agent is charcoal, diatomite and paper pulp, part by weight between them is 3:3:1, the weight burning decrement of charcoal is 90%, fineness is about 175 orders, every square metre of filtration area is used 0.65kg, pressure filter drainage layer laying depth is 4mm, and diatomaceous granularity is 35ptm, and relative density is 2.65;
S4, by the collection liquid vacuum concentration of press filtration, obtain metatitanic acid crystal; In the enamel reactor of the chuck heating with stirring, add metatitanic acid and water, stirring and adjust concentration of slurry is 185g/l, under agitation adding weight is the technical grade sulfuric acid of titanium dioxide weight 32-35%, the sulfuric acid concentration that makes slurries is 84g/l, lead to and be steam heated to 78 DEG C, make ironic hydroxide be transformed into ferric sulphate; Make a part of metatitanic acid dissolve simultaneously and generate titanium sulfate, by after aluminium powder water furnishing pulpous state, it is the aluminium powder of titanium dioxide weight 0.65wt% that gradation adds weight, due to aluminium powder can with slurry in ferric sulphate effect, again can be with the effect of sulfuric acid of slurry and releasing hydrogen gas, make to produce a large amount of bubbles in slurry, must slowly add for this reason, to avoid reaction too acutely cause slurry to splash or emit pot.Add after aluminium powder, continue heating, make temperature be incubated 2.6h at 90-95 DEG C, sampling and measuring titanous content is 0.45g/l; After insulation finishes, change logical water coolant material is cooled to below 45 DEG C, obtain metatitanic acid slurry;
The flow process that has of vacuum concentration is: titanium liquid is collected to liquid Implanted Titanium liquid header tank, and the titanium liquid injecting in water seal tank makes it to keep fluid-tight; Start vacuum pump, open water coolant, and mix up the flow of water coolant and mix up vacuum tightness 9 × 10
4above; Open valve, allows titanium liquid enter in titanium pipe evaporator, and concentrator feed amount is controlled at 2.35m
3/ l, the heat interchanging area of titanium liquid vaporizer is 285m
2; Open steam valve, and remain on 7.3 × 10
4under the vapor pressure of Pa, carry out vacuum concentration, control titanium liquid temp at 79 DEG C; Measure titanium concentration on time; When concentrated stopping, steam off valve, allows titanium liquid continue charging, closes feed valve, water coolant and vacuum pump.
S5, described metatitanic acid slurry is filtered with leaf filter after, with contain 0.7wt% sour water, temperature is the deionized water wash metatitanic acid of 50-65 DEG C, further washes away ferrous sulfate, until metatitanic acid containing ferric oxide lower than 2 × 10
-5; After washing with deionized water, add oxygenant, ferrous ion is oxidized to ferric ion, then adjust pH value, the cotton-shaped ferric hydroxide precipitate that ferric ion hydrolysis is generated, filters; Metatitanic acid slurry temperature remains on 38 DEG C; The vacuum keep of leaf filter is 5.5 × 10
4pA; Washing is divided into pressurization washing and normal pressure washing, pressurized water pulp washing material 11h, water at atmospheric pressure pulp washing material 3.5h.
Embodiment 5
A method of processing titanium powder plant waste liquid, comprises the steps:
S1, the titanium liquid after acidolysis is added to amphiprotic polyacrylamide, establish sloping settling bowl bottom pumping into 3-5 through the mixing tank on pipeline, sedimentation 3.8h, imports impeller pump by siphon pipe by clear liquid; In the time that the slag mud in settling bowl exceedes 60 centimetres, the muddy top titanium liquid suspending is imported to another settling bowl by impeller pump, and to add weight be the sodium alkyl benzene sulfonate of titanium liquid weight 10%, clean the slag mud of the lowest layer with water blast gun, by clean mud suspension send into pressure filter by pond bottom valve slush pump and carry out press filtration; Keeping solution temperature is 66 DEG C, every 1m
3titanium liquid to add mass concentration be 1.65% amphiprotic polyacrylamide 8L, and point add for 5 times;
S2, supernatant liquor is pumped in the sealing crystallizer of bottom with agitator, to vacuumizing in crystallizer, titanium liquid temp is declined with water-ring vacuum pump; In the time that temperature is 38.5 DEG C, open steam injector, strengthen cooling water flow, secondary steam and uperize are cooled to water of condensation, noncondensable gas is discharged by vacuum pump; Only open water-ring pump 56min; When opening water-ring pump, increase injector 3h, make temperature reach 19 DEG C; Steam off injector, is adjusted to emptying position by water-ring pump valve, makes to return in crystallizer normal pressure; Suspension is discharged from crystallizer bottom valve, separate through whizzer, obtain iron vitriol, and collect extracting solution; The vapor pressure of injector is greater than 0.8MPa, and the steam flow of injector is 2.48 tons/h, and circulating cooling water flow is 48m
3/ h;
S3, before filter press, flocculating aids is made into suspension and adds in sheet frame press, make filter cloth stick flocculating aids, and then add the collection liquid of titanium liquid to carry out filter press; Described auxiliary agent is charcoal, diatomite and paper pulp, part by weight between them is 1:3:5, the weight burning decrement of charcoal is 90%, fineness is about 200 orders, every square metre of filtration area is used 0.85kg, pressure filter drainage layer laying depth is 5mm, and diatomaceous granularity is 45ptm, and relative density is 2.3;
S4, by the collection liquid vacuum concentration of press filtration, obtain metatitanic acid crystal; In the enamel reactor of the chuck heating with stirring, add metatitanic acid and water, stirring and adjust concentration of slurry is 195g/l, under agitation adding weight is the technical grade sulfuric acid of titanium dioxide weight 34%, the sulfuric acid concentration that makes slurries is 83g/l, lead to and be steam heated to 77 DEG C, make ironic hydroxide be transformed into ferric sulphate; Make a part of metatitanic acid dissolve simultaneously and generate titanium sulfate, by after aluminium powder water furnishing pulpous state, it is the aluminium powder of titanium dioxide weight 1.0wt% that gradation adds weight, due to aluminium powder can with slurry in ferric sulphate effect, again can be with the effect of sulfuric acid of slurry and releasing hydrogen gas, make to produce a large amount of bubbles in slurry, must slowly add for this reason, to avoid reaction too acutely cause slurry to splash or emit pot.Add after aluminium powder, continue heating, make temperature be incubated 1.85h at 95 DEG C, sampling and measuring titanous content is 0.32g/l; After insulation finishes, change logical water coolant material is cooled to below 45 DEG C, obtain metatitanic acid slurry;
The flow process that has of vacuum concentration is: titanium liquid is collected to liquid Implanted Titanium liquid header tank, and the titanium liquid injecting in water seal tank makes it to keep fluid-tight; Start vacuum pump, open water coolant, and mix up the flow of water coolant and mix up vacuum tightness 9 × 10
4above; Open valve, allows titanium liquid enter in titanium pipe evaporator, and concentrator feed amount is controlled at 1.7m
3/ l, the heat interchanging area of titanium liquid vaporizer is 290m
2; Open steam valve, and remain on 5.3 × 10
4under the vapor pressure of Pa, carry out vacuum concentration, control titanium liquid temp at 78 DEG C; Measure titanium concentration on time; When concentrated stopping, steam off valve, allows titanium liquid continue charging, closes feed valve, water coolant and vacuum pump.
S5, described metatitanic acid slurry is filtered with leaf filter after, with contain 1.8wt% sour water, temperature is the deionized water wash metatitanic acid of 63 DEG C, further washes away ferrous sulfate, until metatitanic acid containing ferric oxide lower than 2 × 10
-5; After washing with deionized water, add oxygenant, ferrous ion is oxidized to ferric ion, then adjust pH value, the cotton-shaped ferric hydroxide precipitate that ferric ion hydrolysis is generated, filters; Metatitanic acid slurry temperature remains on 35 DEG C; The vacuum keep of leaf filter is 5.35 × 10
4pA; Washing is divided into pressurization washing and normal pressure washing, pressurized water pulp washing material 10h, water at atmospheric pressure pulp washing material 5h.
Embodiment 6
A method of processing titanium powder plant waste liquid, comprises the steps:
S1, the titanium liquid after acidolysis is added to amphiprotic polyacrylamide, establish sloping settling bowl bottom pumping into 3-5 through the mixing tank on pipeline, sedimentation 4.6h, imports impeller pump by siphon pipe by clear liquid; In the time that the slag mud in settling bowl exceedes 60 centimetres, the muddy top titanium liquid suspending is imported to another settling bowl by impeller pump, and to add weight be the sodium alkyl benzene sulfonate of titanium liquid weight 13%, clean the slag mud of the lowest layer with water blast gun, by clean mud suspension send into pressure filter by pond bottom valve slush pump and carry out press filtration; Keeping solution temperature is 70 DEG C, every 1m
3titanium liquid to add mass concentration be 1.75% amphiprotic polyacrylamide 8L, and point add for 5 times;
S2, supernatant liquor is pumped in the sealing crystallizer of bottom with agitator, to vacuumizing in crystallizer, titanium liquid temp is declined with water-ring vacuum pump; In the time that temperature is 39 DEG C, open steam injector, strengthen cooling water flow, secondary steam and uperize are cooled to water of condensation, noncondensable gas is discharged by vacuum pump; Only open water-ring pump 50min; When opening water-ring pump, increase injector 3h, make temperature reach 16 DEG C; Steam off injector, is adjusted to emptying position by water-ring pump valve, makes to return in crystallizer normal pressure; Suspension is discharged from crystallizer bottom valve, separate through whizzer, obtain iron vitriol, and collect extracting solution; The vapor pressure of injector is greater than 0.8MPa, and the steam flow of injector is 2.2 tons/h, and circulating cooling water flow is 36m
3/ h;
S3, before filter press, flocculating aids is made into suspension and adds in sheet frame press, make filter cloth stick flocculating aids, and then add the collection liquid of titanium liquid to carry out filter press; Described auxiliary agent is charcoal, diatomite and paper pulp, part by weight between them is 1:2:3, the weight burning decrement of charcoal is 90%, fineness is about 195 orders, every square metre of filtration area is used 0.75kg, pressure filter drainage layer laying depth is 3.8mm, and diatomaceous granularity is 45ptm, and relative density is 2.6;
S4, by the collection liquid vacuum concentration of press filtration, obtain metatitanic acid crystal; In the enamel reactor of the chuck heating with stirring, add metatitanic acid and water, stirring and adjust concentration of slurry is 215g/l, under agitation adding weight is the technical grade sulfuric acid of titanium dioxide weight 32-35%, the sulfuric acid concentration that makes slurries is 80g/l, lead to and be steam heated to 79 DEG C, make ironic hydroxide be transformed into ferric sulphate; Make a part of metatitanic acid dissolve simultaneously and generate titanium sulfate, by after aluminium powder water furnishing pulpous state, it is the aluminium powder of titanium dioxide weight 0.6wt% that gradation adds weight, due to aluminium powder can with slurry in ferric sulphate effect, again can be with the effect of sulfuric acid of slurry and releasing hydrogen gas, make to produce a large amount of bubbles in slurry, must slowly add for this reason, to avoid reaction too acutely cause slurry to splash or emit pot.Add after aluminium powder, continue heating, make temperature be incubated 2.0h at 95 DEG C, sampling and measuring titanous content is 0.32g/l; After insulation finishes, change logical water coolant material is cooled to below 45 DEG C, obtain metatitanic acid slurry;
The flow process that has of vacuum concentration is: titanium liquid is collected to liquid Implanted Titanium liquid header tank, and the titanium liquid injecting in water seal tank makes it to keep fluid-tight; Start vacuum pump, open water coolant, and mix up the flow of water coolant and mix up vacuum tightness 9 × 10
4above; Open valve, allows titanium liquid enter in titanium pipe evaporator, and concentrator feed amount is controlled at 2.4m
3/ l, the heat interchanging area of titanium liquid vaporizer is 295m
2; Open steam valve, and remain on 8.45 × 10
4under the vapor pressure of Pa, carry out vacuum concentration, control titanium liquid temp at 76 DEG C; Measure titanium concentration on time; When concentrated stopping, steam off valve, allows titanium liquid continue charging, closes feed valve, water coolant and vacuum pump.
S5, described metatitanic acid slurry is filtered with leaf filter after, with contain 1.75wt% sour water, temperature is the deionized water wash metatitanic acid of 53 DEG C, further washes away ferrous sulfate, until metatitanic acid containing ferric oxide lower than 2 × 10
-5; After washing with deionized water, add oxygenant, ferrous ion is oxidized to ferric ion, then adjust pH value, the cotton-shaped ferric hydroxide precipitate that ferric ion hydrolysis is generated, filters; Metatitanic acid slurry temperature remains on 35 DEG C; The vacuum keep of leaf filter is 5.4 × 10
4pA; Washing is divided into pressurization washing and normal pressure washing, pressurized water pulp washing material 8h, water at atmospheric pressure pulp washing material 6h.
The present invention has that sulfuric acid consumption is few, reductive agent consumption is few, service temperature is low, bleaching time is short, the advantage such as noresidue pollution, bleaching effect are good.Adopt method of the present invention can make regular metatitanic acid and be easy to washing, having improved output and quality, and produced the ferrous sulfate of high-quality, the quality of titanium dioxide also obviously improves simultaneously.
Claims (6)
1. a method of processing titanium powder plant waste liquid, is characterized in that, comprises the steps:
S1, the titanium liquid after acidolysis is added to amphiprotic polyacrylamide, establish sloping settling bowl bottom pumping into 3-5 through the mixing tank on pipeline, sedimentation 3-5h, imports impeller pump by siphon pipe by clear liquid; In the time that the slag mud in settling bowl exceedes 60 centimetres, the muddy top titanium liquid suspending is imported to another settling bowl by impeller pump, and to add weight be the sodium alkyl benzene sulfonate of titanium liquid weight 10 ~ 15%, clean the slag mud of the lowest layer with water blast gun, by clean mud suspension send into pressure filter by pond bottom valve slush pump and carry out press filtration;
S2, supernatant liquor is pumped in the sealing crystallizer of bottom with agitator, to vacuumizing in crystallizer, titanium liquid temp is declined with water-ring vacuum pump; In the time that temperature is 37-39 DEG C, open steam injector, strengthen cooling water flow, secondary steam and uperize are cooled to water of condensation, noncondensable gas is discharged by vacuum pump; Only open water-ring pump 45-65min; When opening water-ring pump, increase
steaminjector 3h, makes temperature reach 15-20 DEG C; Steam off injector, is adjusted to emptying position by water-ring pump valve, makes to return in crystallizer normal pressure; Suspension is discharged from crystallizer bottom valve, separate through whizzer, obtain iron vitriol, and collect extracting solution;
S3, before filter press, flocculating aids is made into suspension and adds in sheet frame press, make filter cloth stick flocculating aids, and then add the collection liquid of titanium liquid to carry out filter press; Described helping
filteragent is charcoal, diatomite and paper pulp, part by weight between them is 1-3:2-3:1:5, the weight burning decrement of charcoal is 90%, fineness is 150-200 order, every square metre of filtration area is used 0.5-1.0kg, pressure filter drainage layer laying depth is 3-5mm, and diatomaceous granularity is 30-80ptm, and relative density is 2.3-2.7;
S4, by the collection liquid vacuum concentration of press filtration, obtain metatitanic acid crystal; In the enamel reactor of the chuck heating with stirring, add metatitanic acid and water, stir and adjust concentration of slurry between 180-220g/l, under agitation adding weight is the technical grade sulfuric acid of titanium dioxide weight 32-35%, make the sulfuric acid concentration of slurries between 78-88g/l, lead to and be steam heated to 75-85 DEG C, make ironic hydroxide be transformed into ferric sulphate; Make a part of metatitanic acid dissolve simultaneously and generate titanium sulfate, by after aluminium powder water furnishing pulpous state, it is the aluminium powder of titanium dioxide weight 0.5-1.0% that gradation adds weight, continues heating, make temperature be incubated 1.8-2.8h at 90-95 DEG C, sampling and measuring titanous content is 0.3 ~ 0.5g/l; After insulation finishes, change logical water coolant material is cooled to below 45 DEG C, obtain metatitanic acid slurry;
S5, described metatitanic acid slurry is filtered with leaf filter after, with contain 0.1% ~ 2.0wt% sour water, temperature is the deionized water wash metatitanic acid of 50-65 DEG C, further washes away ferrous sulfate, until metatitanic acid containing ferric oxide lower than 2 × 10
-5.
2. the method for processing titanium powder plant waste liquid as claimed in claim 1, is characterized in that, in step S1, maintenance solution temperature is 60-70 DEG C, and it is the amphiprotic polyacrylamide 5-8L of 1.5%-2.5% that the titanium liquid of every 1m3 adds mass concentration, and point adds for 3-5 time.
3. the method for processing titanium powder plant waste liquid as claimed in claim 1, is characterized in that, in step S4, vacuum concentration
specificallyflow process is: titanium liquid is collected to liquid Implanted Titanium liquid header tank, and in water seal tank
implanted Titanium liquidmake it to keep fluid-tight; Start vacuum pump, open water coolant, and mix up the flow of water coolant and mix up vacuum tightness 9 × 10
4 paabove; Open valve, allows titanium liquid enter in titanium pipe evaporator, and concentrator feed amount is controlled at 1.5-2.5m
3/ l, the heat interchanging area of titanium liquid vaporizer is 260 ~ 300m
2; Open steam valve, and remain on 4.9 ~ 8.5 × 10
4under the vapor pressure of Pa, carry out vacuum concentration, control titanium liquid temp at 75-80 DEG C; Measure titanium concentration on time; When concentrated stopping, steam off valve, allows titanium liquid continue charging, closes feed valve, water coolant and vacuum pump.
4. the method for processing titanium powder plant waste liquid as claimed in claim 1, is characterized in that, in step S5, metatitanic acid slurry temperature remains on 25-40 DEG C; The vacuum keep of leaf filter is in 5.3-5.5 × 10
4 pa; Washing is divided into pressurization washing and normal pressure
washing, pressurization
washingslurry 8-12h, normal pressure
washingslurry 3-6h.
5. the method for processing titanium powder plant waste liquid as claimed in claim 1, is characterized in that, in step S2, the vapor pressure of steam injector is greater than 0.8MPa, and the steam flow of injector is 2-2.5 ton/h, and circulating cooling water flow is 30-50m
3/ h.
6. the method for processing titanium powder plant waste liquid as claimed in claim 1, it is characterized in that, step S5 also comprises: after washing with deionized water, add oxygenant, ferrous ion is oxidized to ferric ion, then adjust pH value higher than 5.2, the cotton-shaped ferric hydroxide precipitate that ferric ion hydrolysis is generated, filters.
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| CN112723410B (en) * | 2021-01-15 | 2022-12-16 | 安徽金龙机械有限公司 | Continuous crystallization process of titanium dioxide |
| CN115028207A (en) * | 2022-06-24 | 2022-09-09 | 杭州安永环保科技有限公司 | Method for concentrating titanium dioxide waste acid by sulfuric acid process |
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| CN1171777C (en) * | 2002-01-25 | 2004-10-20 | 吉林市吉研高新技术开发公司 | Process for recovering waste acid in producing titanium white powder by sulfuric acid method |
| CN101792187B (en) * | 2009-12-30 | 2012-03-21 | 四川龙蟒钛业股份有限公司 | Method for producing feed grade ferrous sulfate monohydrate from titanium pigment waste acid condensed slag |
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