CN107652714A - A kind of method of titanium dioxide densification sial coating - Google Patents

A kind of method of titanium dioxide densification sial coating Download PDF

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Publication number
CN107652714A
CN107652714A CN201711046193.4A CN201711046193A CN107652714A CN 107652714 A CN107652714 A CN 107652714A CN 201711046193 A CN201711046193 A CN 201711046193A CN 107652714 A CN107652714 A CN 107652714A
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slurry
titanium dioxide
densification
acid
control
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吕波
伍良英
陆平
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3653—Treatment with inorganic compounds
    • C09C1/3661—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C09C3/063—Coating

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

The invention discloses a kind of method of titanium dioxide densification sial coating, belong to field of titanium.Present invention solves the technical problem that it is to provide a kind of method of new titanium dioxide densification coating.The method of titanium dioxide densification sial coating, comprises the following steps：A, titanium white first product is beaten, control beating consistency is with TiO2150~350g/L is calculated as, inorganic base is added and controls slurry pH value to 9.0~11.0；B, 60~90 DEG C are heated to, orthosilicic acid and inorganic base is added, control slurry pH value to 8.0~11.0, cures 1~3h；C, slurry temperature is adjusted to 50~90 DEG C, adds inorganic acid and sodium metaaluminate, or adds inorganic acid, sodium metaaluminate, aluminum sulfate and inorganic base, and control terminal slurry pH value to 6.0~10.0 cures 1~3h, and coating is completed.The inventive method covered effect even compact, the weatherability of TiO 2 pigment is significantly improved, a kind of new way is provided for titanium dioxide surface cladding.

Description

A kind of method of titanium dioxide densification sial coating
Technical field
The invention belongs to field of titanium, and in particular to a kind of method of titanium dioxide densification sial coating.
Background technology
Titanium dioxide has stronger photocatalytic activity, shone in sunshine especially ultraviolet due to its semiconductor property Penetrate it is lower can the organic matter that contacts of degraded, phenomena such as causing coating xanthochromia, efflorescence.In order to improve the weather-proof of TiO 2 pigment Property, appropriate surface treatment is very necessary." homogeneous nucleation " theory is better than according to " heterogeneous nucleation ", easily in TiO2Particle surface Precipitated hydrated silica film.But because the main component of hydrated SiO 2 film is the polymer of orthosilicic acid or metasilicic acid； This polymer has the characteristics such as molecular weight is big, short texture, settling rate are fast, to allow it uniformly and densely by TiO2Particle Surface all coats, and difficulty is very big：Too fast settling rate is on the one hand easily in TiO2Particle surface locally coats, i.e., only wraps Cover certain point or certain is a piece of, on the other hand easily itself is nucleated without being deposited in TiO2Particle surface, the dosage increase of silicon reach again Purpose is coated less than even compact.
At present, it is silicate or silicon tetrachloride with the silicon raw material of the silicon oxide coated process selection of document report in production. United States Patent (USP) US2885366, US3928057, US4125412, US5041162, US7682441B2 are original using silicate Material, passes through wet-treating coated silica.United States Patent (USP) US6852306B2, US7029648B2 are raw material using silicon tetrachloride Pass through vapor phase method bag silicon.Chinese patent CN100506923C and CN100506922C are also that raw material coats titanium dioxide using silicate Titanium pigment.It yet there are no the public affairs for the TiO 2 pigment that sial coating is prepared using orthosilicic acid, low alkalinity sodium metaaluminate as raw material Open patent.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of method of new titanium dioxide densification coating.
The present invention solves the technical scheme that above-mentioned technical problem uses and there is provided a kind of titanium dioxide densification sial coating Method, this method comprise the following steps：
A, titanium white first product is beaten, control beating consistency is with TiO2150~350g/L is calculated as, adds inorganic base control slurry PH value obtains slurry a to 9.0~11.0；
B, slurry a is heated to 60~90 DEG C, adds orthosilicic acid and inorganic base, control slurry pH value is ripe to 8.0~11.0 Change 1~3h, obtain slurry b；
C, slurry b temperature is adjusted to 50~90 DEG C, adds inorganic acid and sodium metaaluminate, or add inorganic acid, meta-aluminic acid Sodium, aluminum sulfate and inorganic base, control terminal slurry pH value to 6.0~10.0 cure 1~3h, and coating is completed.
Wherein, in the above method, in step B, slurry a is heated to 75-90 DEG C；The addition of the orthosilicic acid is with SiO2 It is calculated as TiO in titanium white first product2The 1~5% of weight；The addition of the inorganic base is control slurry pH value to 8.0~11.0；Add The total time for entering orthosilicic acid and inorganic base is 2~4h.
Wherein, in the above method, in step C, regulation slurry b temperature is to 60-80 DEG C；Feed and regulation pH total time is 1~4h.
Wherein, in the above method, in step C, when adding inorganic acid and during sodium metaaluminate, the addition of sodium metaaluminate with Al2O3It is calculated as TiO in titanium white first product2The 1~5% of weight, the addition of inorganic acid is control slurry pH value to 6.0~10.0.
Wherein, in the above method, in step C, when adding inorganic acid, sodium metaaluminate, aluminum sulfate and inorganic base, charging step Rapid is to add inorganic acid, controls slurry pH to 2.5~3.5, adds sodium metaaluminate, controls slurry pH to 9.5~10.5, then Aluminum sulfate is added, controls slurry pH to 4.5~5.5, is preferably added inorganic base, controls terminal slurry pH to 6.0~10.0.
Wherein, in the above method, in step C, total addition of sodium metaaluminate and aluminum sulfate is with Al2O3It is calculated as titanium white first product Middle TiO2The 1~5% of weight.
Wherein, in the above method, in step C, the inorganic acid is at least one of sulfuric acid, hydrochloric acid；Preferred mass is dense Spend the hydrochloric acid for 5~10%.
Wherein, in the above method, in step C, the concentration of the sodium metaaluminate is 100~300g/L low alkalinity meta-aluminic acid Sodium.
Wherein, in the above method, the inorganic base is at least one of ammoniacal liquor, sodium hydroxide；Preferred mass concentration is 10~20% sodium hydroxide solution.
Wherein, in the above method, in addition to step D, the titania slurry that coating is completed is filtered, washed, done Dry and air-flow crushing.
Beneficial effects of the present invention：
The inventive method it is creative using orthosilicic acid as silicon source, with low alkalinity sodium metaaluminate, or with low alkalinity meta-aluminic acid Sodium and aluminum sulfate are alclad raw material, and fine and close sial cladding is carried out to titanium dioxide, are included in titanium dioxide granule Surface coating the Layer of silicon dioxide clad and second layer alumina-coated layer, covered effect even compact, significantly improve titanium dioxide face The weatherability of material, a kind of new way is provided for titanium dioxide surface cladding；The inventive method is simple to operate, production technology work Low intensity, cost is low, is worthy of popularization.
Embodiment
Specifically, a kind of method of titanium dioxide densification sial coating, this method comprise the following steps：
A, titanium white first product is beaten, control beating consistency is with TiO2150~350g/L is calculated as, adds inorganic base control slurry PH value obtains slurry a to 9.0~11.0；
B, slurry a is heated to 60~90 DEG C, adds orthosilicic acid and inorganic base, control slurry pH value is ripe to 8.0~11.0 Change 1~3h, obtain slurry b；
C, slurry b temperature is adjusted to 50~90 DEG C, adds inorganic acid and sodium metaaluminate, or add inorganic acid, meta-aluminic acid Sodium, aluminum sulfate and inorganic base, control terminal slurry pH value to 6.0~10.0 cure 1~3h, and coating is completed.
Titanium white first product can use the rutile titanium dioxide of chloridising production, in order to improve coating efficiency, avoid impurity Element is not brought into, is added into water and is beaten to concentration with TiO2150~350g/L is calculated as, adds inorganic base control slurry pH value To 9.0~11.0, make sample dispersed, avoid sodium metasilicate settling rate too fast；Preferably, the purity of water is not less than deionization Water.
In step B, slurry a is heated to 60~90 DEG C, orthosilicic acid and inorganic base, charging are added into titania slurry Mode can use downstream feeding：First all required orthosilicic acid are disposably added in titania slurry, then are gradually added Inorganic base, on the contrary also may be used；Also cocurrent adding material can be used：Orthosilicic acid and inorganic base are added in titania slurry simultaneously；Add The total time for entering orthosilicic acid and inorganic base is 2~4h；The addition of the orthosilicic acid is with SiO2It is calculated as TiO in titanium white first product2Weight 1~5%；The addition of the inorganic base is control slurry pH value to 8.0~11.0；Preferably, slurry is heated to 75-85 ℃。
In step C, by slurry b temperature adjustments to after 60~80 DEG C, there are two kinds of different feed way：First, add simultaneously Enter inorganic acid and sodium metaaluminate, the addition of sodium metaaluminate is with Al2O3It is calculated as TiO in titanium white first product2The 1~5% of weight, it is inorganic The addition of acid is control slurry pH value to 6.0~10.0；Second, adding inorganic acid, slurry pH is to 2.5~3.5 for control, then adds Enter sodium metaaluminate, control slurry pH to 9.5~10.5, then add aluminum sulfate, control slurry pH to 4.5~5.5, be preferably added Inorganic base, control terminal slurry pH to 6.0~10.0；In step C, charging and regulation pH total time are 1~4h；Sodium metaaluminate Total addition with aluminum sulfate is with Al2O3It is calculated as TiO in titanium white first product2The 1~5% of weight；The concentration of the sodium metaaluminate is 100~300g/L low alkalinity sodium metaaluminate.
In the inventive method, used inorganic acid is at least one of sulfuric acid, hydrochloric acid；Preferred mass concentration be 5~ 10% hydrochloric acid；Used inorganic base is at least one of ammoniacal liquor, sodium hydroxide；Preferred mass concentration is 10~20% Sodium hydroxide solution.
In actual production, the inventive method can also include step D：The titania slurry that coating is completed was carried out Filter, washing, dry and air-flow crushing.
Embodiment 1
A, 150g titanium white first products are added in deionized water, high-speed stirred mashing, slurry concentration control 300g/L (with TiO2Meter), the NaOH solution of 10% (mass fraction) is added, controls slurry pH value to control addition amount of sodium hydroxide in 9.5, pH, Obtain slurry a；
B, slurry a is warming up to 90 DEG C, while adds the NaOH solution of orthosilicic acid and 10% (mass fraction), orthosilicic acid Addition is (with SiO2Meter) it is TiO in titanium white first product2The 3% of weight, control slurry pH value add in 9.5, pH control sodium hydroxides Amount, feed time 120min, adds post curing 120min, obtains slurry b；
C, slurry b temperature is adjusted to 70 DEG C, and into slurry b, cocurrent adds 200g/L low alkalinity sodium metaaluminate and 6% Hydrochloric acid, the addition of sodium metaaluminate is (with Al2O3Meter) it is TiO in titanium white first product2The 2.5% of weight, slurry pH is 9.0, pH for control Hydrochloric acid addition is controlled, is added in 90min, cures 120min, coating is completed；
D, the titania slurry that coating is completed filtered, washed, dried, air-flow crushing.
Embodiment 2
A, 150g titanium white first products are added in deionized water, high-speed stirred mashing, slurry concentration control 300g/L (with TiO2Meter), the NaOH solution of 10% (mass fraction) is added, controls slurry pH value to control addition amount of sodium hydroxide in 9.5, pH, Obtain slurry a；
B, slurry a is warming up to 90 DEG C, adds orthosilicic acid, the addition of orthosilicic acid is (with SiO2Meter) it is in titanium white first product TiO2The 3% of weight, the feed time of orthosilicic acid is 30min；Then the NaOH solution of 10% (mass fraction) is added, NaOH adds The material time is 120min, and control slurry pH controls sodium hydroxide dosage in 9.5, pH, adds post curing 120min, obtains slurry b；
C, slurry b temperature is adjusted to 65 DEG C, and into slurry b, cocurrent adds 200g/L low alkalinity sodium metaaluminate and 6% Hydrochloric acid, the addition of sodium metaaluminate is added (with Al2O3Meter) it is TiO in titanium white first product2The 2.5% of weight, control slurry pH exist 9.0, pH control hydrochloric acid additions, feed time 90min cure 120min, and coating is completed；
D, the titania slurry that coating is completed filtered, washed, dried, air-flow crushing.
Embodiment 3
A, 150g titanium white first products are added in deionized water, high-speed stirred mashing, slurry concentration control 300g/L (with TiO2Meter), the NaOH solution of 10% (mass fraction) is added, controls slurry pH value to control sodium hydroxide dosage in 9.5, pH, obtains Slurry a；
B, slurry a is warming up to 90 DEG C, adds orthosilicic acid, the addition of orthosilicic acid is (with SiO2Meter) it is in titanium white first product TiO2The 3% of weight, the feed time of orthosilicic acid is 30min；Then the NaOH solution of 10% (mass fraction) is added, during charging Between be 120min, control slurry pH 9.5, pH control sodium hydroxide dosage, add post curing 120min, obtain slurry b；
C, slurry b temperature is adjusted to 80 DEG C, 6% hydrochloric acid is added into slurry b, and control slurry pH controls salt in 3.0, pH Sour dosage, the feed time of hydrochloric acid is 30min；200g/L low alkalinity sodium metaaluminate is added, slurry pH is 10.0, pH for control Sodium metaaluminate dosage is controlled, the feed time of sodium metaaluminate is 60min；Aluminum sulfate is added, control slurry pH is controlled in 5.0, pH Sulphuric acid aluminium dosage, the feed time of aluminum sulfate is 60min；10%NaOH solution is eventually adding, control slurry terminal pH exists 7.0, pH control sodium hydroxide dosages, the feed time of NaOH solution is 30min；Finish, cure 120min, coating is completed；
D, the titania slurry that coating is completed is filtered, washed, dried, air-flow crushing.
Embodiment 4
Commercially available titanium dioxide with following characteristics：
Contrast 1：E.I.Du Pont Company R706 sial coated products
Contrast 2：Certain domestic manufacturer's sial coated product
With reference to GB/T1706-2006 method, titanium dioxide obtained by test above-described embodiment 1-3 and the acid for contrasting 1,2 products Molten rate, the film layer consistency of TiO 2 pigment is characterized by oil absorption, as a result such as table one：
The titanium dioxide oil absorption of table one is tested
Sample Embodiment 1 Embodiment 2 Embodiment 3 Contrast 1 Contrast 2
Oil absorption/g/100g 16.47 16.50 16.88 22.45 17.19
As shown in Table 1, the TiO 2 pigment oil absorption relatively contrast 1,2 prepared by the inventive method is all low, reaches domestic Outer main product is horizontal, shows that titanium dioxide dense has coated sial film layer.

Claims (10)

1. the method for titanium dioxide densification sial coating, it is characterised in that：Comprise the following steps：
A, titanium white first product is beaten, control beating consistency is with TiO2150~350g/L is calculated as, adds inorganic base control slurry pH value To 9.0~11.0, slurry a is obtained；
B, slurry a is heated to 60~90 DEG C, adds orthosilicic acid and inorganic base, control slurry pH value to 8.0~11.0, curing 1 ~3h, obtain slurry b；
C, slurry b temperature is adjusted to 50~90 DEG C, adds inorganic acid and sodium metaaluminate, or add inorganic acid, sodium metaaluminate, sulphur Sour aluminium and inorganic base, control terminal slurry pH value to 6.0~10.0 cure 1~3h, and coating is completed.
2. the method for titanium dioxide densification sial coating according to claim 1, it is characterised in that：In step B, by slurry a It is heated to 75~90 DEG C；The addition of the orthosilicic acid is with SiO2It is calculated as TiO in titanium white first product2The 1~5% of weight；It is described inorganic The addition of alkali is control slurry pH value to 8.0~11.0；The total time for adding orthosilicic acid and inorganic base is 2~4h.
3. the method for titanium dioxide densification sial coating according to claim 1, it is characterised in that：In step C, slurry is adjusted B temperature is to 60~80 DEG C；Charging and regulation pH total time are 1~4h.
4. the method for the titanium dioxide densification sial coating according to any one of claims 1 to 3, it is characterised in that：Step C In, when adding inorganic acid and sodium metaaluminate, the addition of sodium metaaluminate is with Al2O3It is calculated as TiO in titanium white first product2The 1 of weight~ 5%, the addition of inorganic acid is control slurry pH value to 6.0~10.0.
5. the method for the titanium dioxide densification sial coating according to any one of claims 1 to 3, it is characterised in that：Step C In, when adding inorganic acid, sodium metaaluminate, aluminum sulfate and inorganic base, addition step is adds inorganic acid, and control slurry pH is extremely 2.5~3.5, sodium metaaluminate is added, controls slurry pH to 9.5~10.5, then adds aluminum sulfate, controls slurry pH to 4.5 ~5.5, inorganic base is preferably added, controls terminal slurry pH to 6.0~10.0.
6. the method for titanium dioxide densification sial coating according to claim 5, it is characterised in that：In step C, the inclined aluminium Total addition of sour sodium and aluminum sulfate is with Al2O3It is calculated as TiO in titanium white first product2The 1~5% of weight.
7. the method for titanium dioxide densification sial coating according to claim 5, it is characterised in that：It is described inorganic in step C Acid is at least one of sulfuric acid, hydrochloric acid；Preferred mass concentration is 5~10% hydrochloric acid.
8. the method for the titanium dioxide densification sial coating according to any one of claim 1~7, it is characterised in that：Step C In, the sodium metaaluminate is the low alkalinity sodium metaaluminate that concentration is 100~300g/L.
9. the method for the titanium dioxide densification sial coating according to any one of claim 1~8, it is characterised in that：The nothing Machine alkali is at least one of ammoniacal liquor, sodium hydroxide；Preferred mass concentration is 10~20% sodium hydroxide solution.
10. the method for titanium dioxide densification sial coating according to claims 1 to 9, it is characterised in that：Also include step D, The titania slurry that coating is completed is filtered, washed, dry and air-flow crushing.
CN201711046193.4A 2017-10-31 2017-10-31 A kind of method of titanium dioxide densification sial coating Pending CN107652714A (en)

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CN108329719A (en) * 2018-04-25 2018-07-27 四川龙蟒钛业股份有限公司 A kind of titanium white production method with high glaze low oil absorption ferric
CN108822583A (en) * 2018-07-31 2018-11-16 湖南工业大学 A kind of preparation method of the inorganic and organic coated rutile type titanium white in surface
CN109266049A (en) * 2018-11-22 2019-01-25 中信钛业股份有限公司 A kind of preparation method of coatings with high weatherability titanium dioxide pigment special
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CN108329719A (en) * 2018-04-25 2018-07-27 四川龙蟒钛业股份有限公司 A kind of titanium white production method with high glaze low oil absorption ferric
CN109989265A (en) * 2018-07-04 2019-07-09 河北惠尔信新材料有限公司 A kind of the inorganic coating treatment process and delustering agent of polyamide fibre delustering agent
CN109989265B (en) * 2018-07-04 2022-04-12 河北惠尔信新材料有限公司 Inorganic coating treatment process of chinlon delustering agent and delustering agent
CN108822583A (en) * 2018-07-31 2018-11-16 湖南工业大学 A kind of preparation method of the inorganic and organic coated rutile type titanium white in surface
CN109401572A (en) * 2018-11-13 2019-03-01 安徽桑瑞斯环保新材料有限公司 A kind of concrete mixing tank car weather-resistant powder paint
CN109266049A (en) * 2018-11-22 2019-01-25 中信钛业股份有限公司 A kind of preparation method of coatings with high weatherability titanium dioxide pigment special
CN109913088A (en) * 2019-02-23 2019-06-21 廊坊艾格玛新立材料科技有限公司 The compound high heat-dissipation powder paint of acrylic acid sial and its preparation process
CN110079129A (en) * 2019-05-31 2019-08-02 龙蟒佰利联集团股份有限公司 A kind of preparation method of extra-weather-proof titanium dioxide
CN111234567B (en) * 2020-03-18 2021-11-05 中南大学 Inorganic coating process for preparing high-weather-resistance titanium dioxide
CN111410880A (en) * 2020-04-03 2020-07-14 沪宝新材料科技（上海）股份有限公司 Environment-friendly heat-insulating middle-layer paint, and preparation method and construction process thereof
CN112375402A (en) * 2020-11-27 2021-02-19 安徽盈锐优材科技有限公司 Preparation method of novel thermal spraying chromium oxide powder
CN112408991A (en) * 2020-11-27 2021-02-26 安徽盈锐优材科技有限公司 Preparation method of novel thermal spraying silicon nitride powder
CN114367260A (en) * 2021-12-29 2022-04-19 龙佰禄丰钛业有限公司 Titanium white powder coating production system
CN116023806A (en) * 2022-09-22 2023-04-28 攀枝花东方钛业有限公司 Titanium dioxide for environment-friendly paint and preparation method thereof
CN115491052A (en) * 2022-10-20 2022-12-20 福建乐钛科技有限公司 Titanium dioxide for termite-repelling chemical fiber and preparation method thereof
CN115491052B (en) * 2022-10-20 2023-08-18 福建乐钛科技有限公司 Titanium dioxide for termite-expelling chemical fiber and preparation method thereof
CN115772337A (en) * 2022-11-30 2023-03-10 攀钢集团研究院有限公司 Special high-weather-resistance titanium dioxide enveloping method for wind power blade coating
CN118460028A (en) * 2024-07-10 2024-08-09 成都彩星化工有限公司 Water-based air-curing fluorocarbon coating and preparation method thereof

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Application publication date: 20180202