CN108455665A - The method that successive reaction prepares rutile type nano titanic oxide - Google Patents
The method that successive reaction prepares rutile type nano titanic oxide Download PDFInfo
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- CN108455665A CN108455665A CN201810307119.1A CN201810307119A CN108455665A CN 108455665 A CN108455665 A CN 108455665A CN 201810307119 A CN201810307119 A CN 201810307119A CN 108455665 A CN108455665 A CN 108455665A
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Abstract
The invention discloses a kind of methods that successive reaction prepares rutile type nano titanic oxide, belong to field of inorganic nano material.Present invention solves the technical problem that the production process for being existing rutile type nano titanic oxide is intermittent reaction, low production efficiency.The step of this method is：A, titanium tetrachloride solution, which is reacted with sodium hydroxide solution in continuous neutralizing tank, generates white slurry, flows into and neutralizes material storage tank；B, and then in batches enter peptization tank, reacted by peptization and red schorl phase titanium dioxide slurry is made, through plate-frame filtering, washing, then through drying, grinding obtains rutile type nano titanic oxide powder；C, present lot red schorl phase titanium dioxide slurry flows into sheet frame, i.e., puts next batch white slurry into peptization tank, repeats the operation of b, continuously prepares rutile type nano titanic oxide powder.The present invention improves the production efficiency of rutile type nano titanic oxide by successive reaction, and product cut size narrowly distributing, favorable dispersibility is made.
Description
Technical field
The invention belongs to field of inorganic nano material, and in particular to a kind of successive reaction prepares rutile type nano titanium dioxide
The method of titanium.
Background technology
Rutile type nano titanic oxide has good ultraviolet shielded ability, down flop property, light resistance and heat-resisting
Property, it is widely used in the fields such as automobile coating industry and cosmetics, coating, ceramics.The method for preparing nano-titanium dioxide at present
Have very much, including liquid phase method, vapor phase method, sol-gal process, pyrohydrolytic method, microemulsion method, wherein liquid phase method and vapor phase method exist
The shortcomings that energy consumption is big, of high cost, to equipment requirement height, products obtained therefrom poor dispersion, sol-gal process and microemulsion method need
Using organic matter as raw material, process treatment process is more complicated, is difficult to control, industrial enforcement difficulty is larger, and hot water
Solution usually requires to carry out in autoclave, it is more than a hour to need to keep the temperature more than ten in autoclave, the reaction time is longer.
The raw material for preparing nano-titanium dioxide usually has metatitanic acid, titanium tetrachloride and titanium organic matter.Metatitanic acid contains miscellaneous
Matter is more, is not suitable for preparing high performance nano-titanium dioxide；The usual higher price of titanium organic matter, and easy to produce organic by-product
Object is not suitable as the raw material of industrial production nano-titanium dioxide, and the titanium tetrachloride impurity content after refining is extremely low, and price is suitable
In, it is suitable for the high performance nanometer titanium dioxide titanium products of preparation of industrialization.
Application publication number has been the patent disclosure of CN103073058A, and a kind of heating hydrolysis prepares rutile type nano dioxy
Change the method for titanium, this method is carried out using titanium tetrachloride as raw material under conditions of strong acid, and hydrolysis time was controlled at 3-8h hours,
Reaction time is longer, reacts for intermittent reaction, and hydrolyzes the hydrochloric acid vapour generated and can cause to corrode to equipment；Authorization Notice No.
It discloses for the patent of CN1398924 and a kind of reacted with alkali using titanium tetrachloride as raw material using liquid phase method and prepare rutile type nano
The method of titanium dioxide powder, preparation method include titanium tetrachloride with liquid, neutralization, refined processing, secondary neutralization, washing, surface
Processing, drying and other steps, this method, which is dried by technique after powder obtained has to pass through calcining, can just obtain rutile-type
The titanium dioxide of structure, calcination time are 2-6 hours, and calcination time is long, and it is intermittent reaction to react, and step is complicated, production
Efficiency is low.
Invention content
It is intermittent it is an object of the invention to overcome the production process of rutile type nano titanic oxide in the prior art
Reaction, low production efficiency provide a kind of method that successive reaction may be implemented and prepares rutile type nano titanic oxide.
The technical solution adopted by the present invention to solve the technical problems, which is to provide a kind of successive reaction and prepares rutile-type, to be received
The method of rice titanium dioxide, this method specifically include following steps：
A, titanium tetrachloride solution continuous neutralizing tank is added in the environment of lye B is as bottom material with lye A to react generation white
The white slurry of mill base material, generation continuously flows into neutralization material storage tank；
B, the white slurry in neutralization material storage tank is made to enter peptization tank in batches, to present lot white slurry in peptization tank
Middle addition peptizing agent controls H+A concentration of 0.01~3.16mol/L, at 80-100 DEG C, heat preservation to titanium dioxide crystal form is converted into
It when the content of rutile titanium dioxide is more than 98%, is cooled to room temperature, adjusts pH value to 6.8-8.5, obtain Rutile Type two
Titania slurry makes the red schorl phase titanium dioxide slurry of present lot in peptization tank enter plate-frame filtering, washing, then through dry
Dry, grinding obtains rutile type nano titanic oxide powder；
C, after the red schorl phase titanium dioxide slurry of the present lot obtained in peptization tank flows into sheet frame, i.e., expect from neutralization
Storage tank puts next batch white slurry into peptization tank, repeats the operation of step b, continuously prepares rutile type nano titanic oxide
Powder.
Wherein, in above method step a, the purity ＞ 99.9% of the titanium tetrachloride used in titanium tetrachloride solution is prepared, it is miscellaneous
Matter limitation Fe ＜ 50ppm, V ＜ 50ppm, Cr ＜ 50ppm.
Wherein, in above method step a, the reaction temperature of titanium tetrachloride solution and lye A are 10-100 DEG C.
Wherein, in above method step a, the molar ratio that titanium tetrachloride solution is reacted with lye A is 1:4.
Wherein, in above method step a, titanium dioxide meter, titanium tetrachloride solution is that the clarification of a concentration of 2-4mol/L is molten
Liquid.
Wherein, in above method step a, titanium tetrachloride solution is to prepare to obtain under the conditions of 45 DEG C below.
Wherein, in above method step a, lye A is the sodium hydroxide solution that mass fraction is 10%-15%.
Wherein, in above method step a, lye B is the sodium hydroxide solution that mass fraction is 3%-15%.
Wherein, in above method step b, peptizing agent is titanium tetrachloride solution, hydrochloric acid or nitric acid.Preferably, four chlorination
A concentration of 2mol/L of titanium solution.Preferably, hydrochloric acid is the hydrochloric acid solution of mass fraction ＞ 20%.Preferably, nitric acid is quality
The salpeter solution of score ＞ 20%.
Wherein, it in above method step b, keeps the temperature in program, soaking time 60-180min.
Wherein, in above method step b, the temperature of drying program is 100-600 DEG C.
Wherein, in above method step b, with pure water to 150 μ s/cm of wash water conductivity ＜.
Wherein, in above method step b, drying to sample moisture is less than 2%.
The beneficial effects of the invention are as follows：(1) the method for the present invention is reacted by continuous charging, continuous overflow discharging, instead
The white slurry that should be generated enters peptization tank and carries out peptization reaction in batches, the rutile titanium dioxide slurry that successive reaction generates
Material is through plate-frame filtering, washing, then through dry, pulverize to obtain finished product, entire reaction system is continuously to prepare production, used time
Short, compared with other preparation processes, the present invention greatly accelerates the production efficiency of nano-titanium dioxide, is easy to large-scale industry metaplasia
Production.(2) titanium dioxide that the method for the present invention can be prepared by having Rutile structure by two-step reaction needs not move through high temperature and forges
It burns to realize transformation of crystal, simplifies processing step, saved the energy, reduce cost.(3) the method for the present invention can be according to not
Demand with grain size prepares the nanometer two that different grains pass through by the adjustment of the reaction temperature and drying program of titanium tetrachloride and lye
Titanium oxide, and the particle diameter distribution that product is prepared is narrow, and favorable dispersibility can be widely applied to high-grade paint, chemical fibre, ceramics
Equal fields.
Description of the drawings
Fig. 1 is the process flow chart that successive reaction prepares rutile type nano titanic oxide.
In figure label for：Titanium tetrachloride solution storage tank 1, sig water storage tank 2, aqueous solution regulating valve 3, sig water regulating valve 4,
Continuous neutralizing tank 5, neutralizes material storage tank 7, neutralizes bottom valve 8, transfering material pump 9, peptizing agent storage tank 10, peptizing agent regulating valve overflow pipe 6
11, peptization tank 12, baiting valve 13, sheet frame 14, drier 15, blender 16.
Specific implementation mode
Find improve production efficiency prepare rutile type nano titanic oxide method during, inventor by pair plus
The processing etc. of material mode, intermediate product improves, and the production efficiency for preparing rutile type nano titanic oxide is made to have been improved,
And the preparation method of the present invention is two-step reaction, uses titanium tetrachloride solution with lye to carry out that positive metatitanic acid is obtained by the reaction first,
It is secondary, peptization is carried out to positive metatitanic acid, rutile titanium dioxide slurry is obtained by the reaction, entire processing step is simple, has saved the energy,
Cost is reduced, the particle diameter distribution that product is prepared is narrow, favorable dispersibility, passes through specific implementation mode below with reference to attached drawing
Further the process of preparation method of the present invention is illustrated.
As shown in Figure 1：The outlet of titanium tetrachloride solution storage tank 1 is by piping connection in the import of continuous neutralizing tank 5, pipeline
On be provided with aqueous solution regulating valve 3, the outlet of sig water storage tank 2 is by piping connection in the import of continuous neutralizing tank 5, pipeline
It is provided with sig water regulating valve 4, blender 16 is provided in continuous neutralizing tank 5, one end of overflow pipe 6 connects continuous neutralizing tank 5
Outlet, the other end connection neutralize material storage tank 7 import, neutralize material storage tank 7 outlet and the import of peptization tank 12 between pass through
Pipeline, which is connected in turn, neutralizes bottom valve 8 and transfering material pump 9, neutralizes and is provided with blender 16 in material storage tank 7, and peptizing agent storage tank 10 is logical
Piping connection is crossed in being provided with peptizing agent regulating valve 11 on the top of peptization tank 12, pipeline, blender is provided in peptization tank 12
16,12 lower exit port of peptization tank is connected with baiting valve 13, and 13 lower end of baiting valve passes through the entrance of piping connection sheet frame 14, sheet frame 14
Outlet pass through piping connection drier 15.
It is 3m in capacity first in conjunction with Fig. 13Continuous neutralizing tank 5 in be added 50L-200L mass fractions be 3%-15%
Sodium hydroxide solution as bottom material, titanium tetrachloride is added into deionized water under the conditions of 45 DEG C are below, be configured to
Prepared titanium tetrachloride solution is placed titanium tetrachloride solution storage tank by the clear solution of a concentration of 2-4mol/L of titanium dioxide meter
In 1, the sodium hydroxide solution of 10%-15% is positioned in sig water storage tank 2.
Then, aqueous solution regulating valve 3 and sig water regulating valve 4 are opened, the flow velocity of titanium tetrachloride solution is 150-300L/h,
The flow velocity of sodium hydroxide solution is 276-1746L/h, and titanium tetrachloride solution is with sodium hydroxide solution with molar ratio for 1:4 ratio
Into in continuous neutralizing tank 5, under the stirring of blender 16 reaction generate white slurry, successive reaction generate white slurry from
Outflux flows out, and it is 10m to enter capacity by overflow pipe 63Neutralization material storage tank 7 in, open neutralize bottom valve 8, so that neutralization is expected
It is 3m that white slurry in storage tank 7 enters capacity in batches by transfering material pump 93Peptization tank 12, per a batch of white slurry
Amount into peptization tank 12 is about 2.5m3。
Next, opening peptizing agent regulating valve 11, peptizing agent is added in the white slurry of present lot into peptization tank 12,
Control H+A concentration of 0.01~3.16mol/L keeps the temperature 60-180min, is cooled to room temperature, uses hydroxide then at 80-100 DEG C
Sodium solution adjusts pH value to 7, obtains red schorl phase titanium dioxide slurry.Baiting valve 13 is opened, is made in present lot peptization tank 12
After obtained red schorl phase titanium dioxide slurry flows into sheet frame 14, i.e., from neutralizing in material storage tank 7 by the white slurry of next batch
It puts peptization tank 12 into, repeats the operation of peptization reaction, the rutile titanium dioxide slurry being continuously prepared enters sheet frame 14
Filtering, washing, is then dried through drier 15 at 100-600 DEG C, drying time>It is 2 hours, dry to sample moisture
Less than 2%, final grinding obtains rutile type nano titanic oxide powder.
Wherein, continuous neutralizing tank 5 is the continuous reaction apparatus of titanium tetrachloride solution and lye A.
Wherein, the temperature that titanium tetrachloride solution is reacted with lye A is 10-100 DEG C.Reaction can be carried out at 10-100 DEG C,
The reaction is exothermic reaction, and reaction temperature is not easy to realize less than 10 DEG C, in liquid-phase system, if the case where not using high-tension apparatus
Under, system only has 100 DEG C when boiling, and can not further increase temperature and be reacted.
Wherein, the molar ratio of titanium tetrachloride solution and lye A are 1:4.According to chemical reaction chemical equation, titanium tetrachloride is molten
It is 1 that liquid reacts required molar ratio with lye A completely:4.
Wherein, in terms of titanium dioxide, titanium tetrachloride solution is the clear solution of a concentration of 2-4mol/L.Titanium tetrachloride solution
Concentration it is too low, make low production efficiency, excessive concentration, reaction speed so that particle is easily reunited soon, at the same plant process viscosity compared with
Greatly.
Wherein, it is in order to avoid titanium tetrachloride hydrolyzes titanium tetrachloride solution to be prepared under the conditions of 45 DEG C below.
Wherein, the purity ＞ 99.9% of titanium tetrachloride, Light absorbing impurty Fe ＜ 50ppm, V ＜ 50ppm, Cr ＜ 50ppm.To miscellaneous
The restriction of matter is the nano-titanium dioxide being prepared in order to prevent influences whiteness because of foreign pigment.
Wherein, lye A is the sodium hydroxide solution that mass fraction is 10%-15%.When the concentration is too low, make production efficiency
It is low；When the concentration is too high, reaction speed makes particle easily reunite soon, while plant process viscosity is larger.
Wherein, lye B is added in continuous neutralizing tank 5 and is to provide for reacting required alkaline environment as bottom material, inhibit
Generate the possibility of anatase titanium dioxide.
Wherein, lye B is the sodium hydroxide solution that mass fraction is 3%-15%.When the concentration is too low, reactant solution
It is easy to form local acidic environment when concentration is larger or flow velocity is very fast, leads to the generation of anatase titanium dioxide；When concentration is excessive
When, reaction speed is fast, and particle is made easily to reunite, while plant process viscosity is larger.
Wherein, peptizing agent is titanium tetrachloride solution, hydrochloric acid or nitric acid.Preferably, titanium tetrachloride solution is a concentration of
2mol/L.Preferably, hydrochloric acid is the hydrochloric acid solution of mass fraction ＞ 20%.Preferably, nitric acid is the nitre of mass fraction ＞ 20%
Acid solution.
Wherein, in peptization tank 12 carries out heat preservation program, the intermediate material of generation keeps the temperature 60-180min at 80-100 DEG C.
At 80-100 DEG C, heat preservation can promote titanium dioxide crystal form to change to rutile crystal type and promote particle growth, when temperature is less than 80 DEG C
When, conversion is very slow, and required time is longer, and when temperature is excessively high, conversion is faster, and at 80-100 DEG C, heat preservation 60-180min, which can guarantee, turns
Metaplasia is more than 98% at the content of rutile titanium dioxide, when the content of rutile titanium dioxide can be cold more than 98%
But.
Wherein, the temperature of drying program is 100-600 DEG C, drying time>2 hours, drying to sample moisture was less than
2%.
When drying temperature is less than 100 DEG C, moisture evaporation is slow, and drying efficiency is low, and drying temperature is more than 600 DEG C, and crystal grain is quick
Increase, is difficult to control its grain size.
Wherein, it is titanic that titanium tetrachloride solution reacts the white slurry generated with sodium hydroxide solution in continuous neutralizing tank 5
Acid, white slurry expect that storage tank 7 enters peptization tank 12 in batches by neutralization, peptizing agent be added, the hydrogen ion in peptizing agent with just
Metatitanic acid reaction dehydration obtains rutile-phase nano-titanium dioxide and water.
Wherein, while peptization reaction occurs in peptization tank 12, white slurry is continuously generated in continuous neutralizing tank 5, in vain
Mill base material, which flows into, neutralizes material storage tank 7, and the time that the production quantity of 7 white slurry of neutralization material storage tank is reacted with peptization matches, makes
Entire reaction process is able to continuously.
Wherein, in washing step, the main purpose of washing is the objectionable impurities such as removal sodium chloride, with pure water to washing
150 μ s/cm of water conductivity ＜, keep charged impurity in slurry fewer, its dispersion is conducive to during preparing nano-titanium dioxide.
Description below by way of specific embodiment does further detailed description to the present invention.
Embodiment 1
Titanium tetrachloride is add to deionized water under the conditions of 45 DEG C below, is configured to a concentration of in terms of titanium dioxide
The clear solution of 2mol/L, is added sodium hydroxide solution that 200L mass fractions are 3% as bottom material in continuous neutralizing tank 5,
Temperature in continuous neutralizing tank 5 is warming up to 10 DEG C, by titanium tetrachloride solution with the flow velocity of 300L/h and 10% under stirring
Sodium hydroxide solution with the flow velocity of 873L/h in molar ratio 1:4 ratio is added in continuous neutralizing tank 5, and successive reaction generates
White slurry outflow, by overflow pipe 6 enter neutralize material storage tank 7, by neutralize material storage tank 7 in white slurry be put into batches
Peptization tank 12 is added the titanium tetrachloride solution of 2mol/L as peptizing agent, controls H+A concentration of 0.01~0.1mol/L, adds glue
Temperature is raised to 100 DEG C after solvent, keeps the temperature 60min, is cooled to room temperature, pH value is adjusted to 7 with sodium hydroxide solution, obtains golden red
Stone phase titanic oxide slurry will neutralize the white slurry in material storage tank 7 after red schorl phase titanium dioxide slurry flows into sheet frame 14
It is put into peptization tank 12, repeats the operation of above-mentioned peptization reaction, filter red schorl phase titanium dioxide slurry and with pure water to washing
Water conductivity is less than 150 μ s/cm, and filter cake is placed in drier 15, is dried to moisture at 100 DEG C and is less than 2%, grinding obtains
The nano titanium dioxide powder for all batches that the secondary response generates is blended in one by rutile type nano titanic oxide powder
It rises, it is about 5-8nm, yield about 96.8% repeatedly to sample the average grain diameter measured at random.
Embodiment 2
Titanium tetrachloride is add to deionized water under the conditions of 45 DEG C below, is configured to a concentration of in terms of titanium dioxide
The clear solution of 2mol/L, is added sodium hydroxide solution that 200L mass fractions are 3% as bottom material in continuous neutralizing tank 5,
Temperature in continuous neutralizing tank 5 is warming up to 30 DEG C, by titanium tetrachloride solution with the flow velocity of 300L/h and 10% under stirring
Sodium hydroxide solution with the flow velocity of 873L/h in molar ratio 1:4 ratio is added in continuous neutralizing tank 5, and successive reaction generates
White slurry outflow, by overflow pipe 6 enter neutralize material storage tank 7, by neutralize material storage tank 7 in white slurry be put into batches
Peptization tank 12 is added the titanium tetrachloride solution of 2mol/L as peptizing agent, controls H+A concentration of 0.01~0.1mol/L, adds glue
Temperature is raised to 100 DEG C after solvent, keeps the temperature 60min, is cooled to room temperature, pH value is adjusted to 7 with sodium hydroxide solution, obtains golden red
Stone phase titanic oxide slurry will neutralize the white slurry in material storage tank 7 after red schorl phase titanium dioxide slurry flows into sheet frame 14
It is put into peptization tank 12, repeats the operation of above-mentioned peptization reaction, filter red schorl phase titanium dioxide slurry and with pure water to washing
Water conductivity is less than 150 μ s/cm, and filter cake is placed in drier 15, is dried to moisture at 100 DEG C and is less than 2%, grinding obtains
The nano titanium dioxide powder for all batches that the secondary response generates is blended in one by rutile type nano titanic oxide powder
It rises, it is about 8-12nm, yield about 97% repeatedly to sample the average grain diameter measured at random.
Embodiment 3
Titanium tetrachloride is add to deionized water under the conditions of 45 DEG C below, is configured to a concentration of in terms of titanium dioxide
The clear solution of 3mol/L, is added sodium hydroxide solution that 100L mass fractions are 8% as bottom material in continuous neutralizing tank 5,
Temperature in continuous neutralizing tank 5 is warming up to 50 DEG C, by titanium tetrachloride solution with the flow velocity of 200L/h and 10% under stirring
Sodium hydroxide solution with the flow velocity of 873L/h in molar ratio 1:4 ratio is added in continuous neutralizing tank 5, and successive reaction generates
White slurry outflow, by overflow pipe 6 enter neutralize material storage tank 7, by neutralize material storage tank 7 in white slurry be put into batches
Peptization tank 12 is added the hydrochloric acid solution of mass fraction ＞ 20% as peptizing agent, controls H+A concentration of 1~3.16mol/L, adds
Temperature is raised to 80 DEG C after peptizing agent, keeps the temperature 180min, is cooled to room temperature, pH value is adjusted to 7 with sodium hydroxide solution, obtains gold
Red stone phase titanic oxide slurry will neutralize the stock white in material storage tank 7 after red schorl phase titanium dioxide slurry flows into sheet frame 14
Material is put into peptization tank 12, repeats the operation of above-mentioned peptization reaction, filter red schorl phase titanium dioxide slurry and with pure water extremely
Wash water conductivity is less than 150 μ s/cm, and filter cake is placed in drier 15, is dried to moisture at 300 DEG C and is less than 2%, ground
To rutile type nano titanic oxide powder, the nano titanium dioxide powder for all batches which generates is blended in one
It rises, it is about 10-15nm, yield about 96.6% repeatedly to sample the average grain diameter measured at random.
Embodiment 4
Titanium tetrachloride is add to deionized water under the conditions of 45 DEG C below, is configured to a concentration of in terms of titanium dioxide
The clear solution of 3mol/L, is added sodium hydroxide solution that 100L mass fractions are 8% as bottom material in continuous neutralizing tank 5,
Temperature in continuous neutralizing tank 5 is warming up to 60 DEG C, by titanium tetrachloride solution with the flow velocity of 200L/h and 10% under stirring
Sodium hydroxide solution with the flow velocity of 873L/h in molar ratio 1:4 ratio is added in continuous neutralizing tank 5, and successive reaction generates
White slurry outflow, by overflow pipe 6 enter neutralize material storage tank 7, by neutralize material storage tank 7 in white slurry be put into batches
Peptization tank 12 is added the hydrochloric acid solution of mass fraction ＞ 20% as peptizing agent, controls H+A concentration of 1~3.16mol/L, adds
Temperature is raised to 80 DEG C after peptizing agent, keeps the temperature 180min, is cooled to room temperature, pH value is adjusted to 7 with sodium hydroxide solution, obtains gold
Red stone phase titanic oxide slurry will neutralize the stock white in material storage tank 7 after red schorl phase titanium dioxide slurry flows into sheet frame 14
Material is put into peptization tank 12, repeats the operation of above-mentioned peptization reaction, filter red schorl phase titanium dioxide slurry and with pure water extremely
Wash water conductivity is less than 150 μ s/cm, and filter cake is placed in drier 15, is dried to moisture at 600 DEG C and is less than 2%, ground
To rutile type nano titanic oxide powder, the nano titanium dioxide powder for all batches which generates is blended in one
It rises, it is about 20-30nm, yield about 96.8% repeatedly to sample the average grain diameter measured at random.
Embodiment 5
Titanium tetrachloride is add to deionized water under the conditions of 45 DEG C below, is configured to a concentration of in terms of titanium dioxide
The clear solution of 3.5mol/L, the sodium hydroxide solution that addition 100L mass fractions are 8% in continuous neutralizing tank 5 is the bottom of as
Material, temperature in continuous neutralizing tank 5 is warming up to 75 DEG C, under stirring by titanium tetrachloride solution with the flow velocity of 171L/h with
10% sodium hydroxide solution is with the flow velocity of 871L/h in molar ratio 1:4 ratio is added in continuous neutralizing tank 5, successive reaction
The white slurry of generation flows out, and is entered by overflow pipe 6 and neutralizes material storage tank 7, will neutralize the white slurry in material storage tank 7 in batches
It is put into peptization tank 12, the hydrochloric acid solution of mass fraction ＞ 20% is added as peptizing agent, controls H+A concentration of 1~3.16mol/L,
Temperature is raised to 80 DEG C after adding peptizing agent, keeps the temperature 180min, is cooled to room temperature, pH value is adjusted to 7 with sodium hydroxide solution, is obtained
It is white in material storage tank 7 by neutralizing after red schorl phase titanium dioxide slurry flows into sheet frame 14 to red schorl phase titanium dioxide slurry
Mill base material is put into peptization tank 12, repeats the operation of above-mentioned peptization reaction, filters red schorl phase titanium dioxide slurry and washed with pure water
It washs to wash water conductivity and is less than 150 μ s/cm, filter cake is placed in drier 15, dried to moisture at 500 DEG C and be less than 2%, ground
Mill obtains rutile type nano titanic oxide powder, the nano titanium dioxide powder mixing for all batches which is generated
Together, it is about 25-35nm, yield about 96.8% repeatedly to sample the average grain diameter measured at random.
Embodiment 6
Titanium tetrachloride is add to deionized water under the conditions of 45 DEG C below, is configured to a concentration of in terms of titanium dioxide
The clear solution of 4mol/L, is added sodium hydroxide solution that 50L mass fractions are 15% as bottom material in continuous neutralizing tank 5,
Temperature in continuous neutralizing tank 5 is warming up to 90 DEG C, by titanium tetrachloride solution with the flow velocity of 150L/h and 15% under stirring
Sodium hydroxide solution with the flow velocity of 552L/h in molar ratio 1:4 ratio is added in continuous neutralizing tank 5, and successive reaction generates
White slurry outflow, by overflow pipe 6 enter neutralize material storage tank 7, by neutralize material storage tank 7 in white slurry be put into batches
Peptization tank 12 is added the salpeter solution of mass fraction ＞ 20% as peptizing agent, controls H+A concentration of 0.1~1mol/L, adds
Temperature is raised to 90 DEG C after peptizing agent, keeps the temperature 120min, is cooled to room temperature, pH value is adjusted to 7 with sodium hydroxide solution, obtains gold
Red stone phase titanic oxide slurry will neutralize the stock white in material storage tank 7 after red schorl phase titanium dioxide slurry flows into sheet frame 14
Material is put into peptization tank 12, repeats the operation of above-mentioned peptization reaction, filter red schorl phase titanium dioxide slurry and with pure water extremely
Wash water conductivity is less than 150 μ s/cm, and filter cake is placed in drier 15, is dried to moisture at 200 DEG C and is less than 2%, ground
To rutile type nano titanic oxide powder, the nano titanium dioxide powder for all batches which generates is blended in one
It rises, it is about 10-20nm, yield about 97.5% repeatedly to sample the average grain diameter measured at random.
Claims (10)
1. the method that successive reaction prepares rutile type nano titanic oxide, it is characterised in that include the following steps：
A, titanium tetrachloride solution, which continuous neutralizing tank is added in the environment of lye B is as bottom material with lye A is reacted, generates stock white
The white slurry of material, generation continuously flows into neutralization material storage tank；
B, so that the white slurry in neutralization material storage tank is entered peptization tank in batches, add into present lot white slurry in peptization tank
Enter peptizing agent control H+A concentration of 0.01~3.16mol/L, at 80-100 DEG C, heat preservation to titanium dioxide crystal form is converted into golden red
It when the content of stone-type titanium dioxide is more than 98%, is cooled to room temperature, adjusts pH value to 6.8-8.5, obtain Rutile Type titanium dioxide
Titanium slurry makes the red schorl phase titanium dioxide slurry of present lot in peptization tank enter plate-frame filtering, washing, then through drying,
Grinding obtains rutile type nano titanic oxide powder；
C, after the red schorl phase titanium dioxide slurry of the present lot obtained in peptization tank flows into sheet frame, i.e., expect storage tank from neutralization
It puts next batch white slurry into peptization tank, repeats the operation of step b, continuously prepare rutile type nano titanic oxide powder
End.
2. the method that successive reaction according to claim 1 prepares rutile type nano titanic oxide, it is characterised in that：Step
In rapid a, the temperature that titanium tetrachloride solution is reacted with lye A is 10-100 DEG C.
3. the method that successive reaction according to claim 1 or 2 prepares rutile type nano titanic oxide, feature exist
In：In step a, the molar ratio that titanium tetrachloride solution is reacted with lye A is 1:4.
4. special according to the method that claim 1-3 any one of them successive reactions prepare rutile type nano titanic oxide
Sign is：In step a, in terms of titanium dioxide, the titanium tetrachloride solution is the clear solution of a concentration of 2-4mol/L.
5. special according to the method that claim 1-4 any one of them successive reactions prepare rutile type nano titanic oxide
Sign is：In step a, the titanium tetrachloride solution is to prepare to obtain under the conditions of 45 DEG C below.
6. special according to the method that claim 1-5 any one of them successive reactions prepare rutile type nano titanic oxide
Sign is：In step a, the lye A is the sodium hydroxide solution that mass fraction is 10%-15%.
7. special according to the method that claim 1-6 any one of them successive reactions prepare rutile type nano titanic oxide
Sign is：In step a, the lye B is the sodium hydroxide solution that mass fraction is 3%-15%.
8. special according to the method that claim 1-7 any one of them successive reactions prepare rutile type nano titanic oxide
Sign is：In step b, the peptizing agent is titanium tetrachloride solution, hydrochloric acid or nitric acid.
9. special according to the method that claim 1-8 any one of them successive reactions prepare rutile type nano titanic oxide
Sign is：In step b, in the heat preservation program, soaking time 60-180min.
10. special according to the method that claim 1-9 any one of them successive reactions prepare rutile type nano titanic oxide
Sign is：In step b, the temperature of the drying program is 100-600 DEG C.
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| CN115806313A (en) * | 2022-12-26 | 2023-03-17 | 常州纳欧新材料科技有限公司 | Preparation method of micron-sized rutile type titanium dioxide nanocrystal aggregate |
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