CN109183497A - A kind of paper grade (stock) nano-TiO2The preparation method of/wollastonite compound - Google Patents
A kind of paper grade (stock) nano-TiO2The preparation method of/wollastonite compound Download PDFInfo
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- CN109183497A CN109183497A CN201811087287.0A CN201811087287A CN109183497A CN 109183497 A CN109183497 A CN 109183497A CN 201811087287 A CN201811087287 A CN 201811087287A CN 109183497 A CN109183497 A CN 109183497A
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- wollastonite
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- tio
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Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
-
- 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
- C09C1/28—Compounds of silicon
-
- 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
Abstract
A kind of paper grade (stock) nano-TiO2The preparation method of/wollastonite compound belongs to Inorganic synthese technical field.The invention discloses a kind of new methods having not been reported, and successfully synthesize one kind and are evenly coated, each side's surface properties nano-TiO up to standard2/ wollastonite compound new product.It is plate structure using preparation method of the present invention composite product obtained, has whiteness high, be evenly coated, the characteristics of good weatherability.It is close when the properties of paper are with titanium dioxide as filler when resulting composite product is used as papermaking filler.Simple production process of the invention, the additive amount of the controllable rate for being passed through gas and titanium dioxide, so as to adjust the size of titanium dioxide granule and the clad ratio of wollastonite, and wollastonite surface is evenly coated, yield is high, and reaction condition is mild, it is easy to accomplish industrialized production.
Description
Technical field
The invention belongs to Inorganic synthese technical fields, especially relate to a kind of paper grade (stock) nano-TiO2/ wollastonite is compound
The preparation method of object.
Background technique
TiO2Have the characteristics that high whiteness, high diopter, high covering power, be a kind of pigment with very high optical property,
Play a significant role in field of papermaking.By TiO2Applied to the physical strength that paper not only can be enhanced in paper, additionally it is possible to mention
Whiteness, the opacity of high paper, enhance the pliability of paper, are a kind of advanced papermaking fillers, but due to titanium dioxide price
Valuableness only uses in fine paper.It is attempted to find the substitute products of titanium dioxide thus.And wollastonite belongs to one kind is in
Fibrous, needle-shaped, plate metasilicate, special crystal habit and structure determine its property.Wollastonite has good
Insulating properties, while there is very high whiteness, good dielectric properties and higher heat-resisting, weather resistance, widely apply
In field of papermaking.Nano-TiO2Specific grain surface product is big, easy to reunite, is not easy to disperse in paper；Micron silicon limestone particles are not
It is easy to reunite but poor to the modified effect of paper.The advantages of the two, is combined, the modified effect and solution that can have been obtained
Certainly the dispersion.Therefore in one layer of nano-TiO of wollastonite coated with uniform2Composite product come into being.Investigate golden red
Stone-type nano-TiO2The all aspects of the parameters of the compound of wollastonite are coated, the performance for whether meeting rutile titanium dioxide is wanted
The application for compound in paper is asked to be even more important.
At present about TiO2The related patents of/wollastonite compound synthesis are not yet found, only in a small amount of document
There is relevant report.The pre-prepared TiO by the way of Chemical assembly such as Yang Shaofeng, prince's sincere feeling of Jilin University2/ wollastonite complex
Presoma forms the complex structure of anatase or rutile-type by calcining.The fourth of China Mining University's Materials Academy
The big, Geng Deying of family, fourth have just reported the technical study of rutile titanium dioxide cladding wollastonite.With SnO2For nucleating agent,
TiCl4For titanium source, the composite particles of coated by titanium dioxide wollastonite have been prepared, have been roasted by 500 DEG C, the crystal form of clad is more
It adds whole.But above two method operating process is complicated, using presoma hydrolysis and calcine technology higher cost, is unsuitable for work
Industry application.
Therefore there is an urgent need for a kind of novel technical solutions in the prior art to solve the problems, such as this.
Summary of the invention
The technical problems to be solved by the present invention are: providing a kind of paper grade (stock) nano-TiO2The preparation of/wollastonite compound
Nm-class rutile-type TiO 2 when method is used to solve to prepare the composite particles of coated by titanium dioxide wollastonite in the prior art
It is easy to reunite in cladding and covered effect is bad；Coated by titanium dioxide wollastonite is prepared using presoma hydrolysis and calcine technology
Composite particles higher cost the technical issues of being unsuitable for industrial applications.
A kind of paper grade (stock) nano-TiO2The preparation method of/wollastonite compound, it is characterized in that: include the following steps, and
Following steps sequentially carry out,
Step 1: weighing wollastonite and distilled water respectively, the two is mixed to the wollastonite slurry for obtaining that mass fraction is 10%
Liquid；
Step 2: 200 mesh net filtrations of the wollastonite slurries obtained in step 1 are sequentially added in the filtrate of acquisition
Commerical grade rutile titanium dioxide, dispersing agent PEG and sodium hydroxide, 30~80 DEG C stirring in water bath 1 hour；
Step 3: the slurries after stirring in water bath in step 2 are transferred in quartz glass carbonized tube, 50 DEG C of water bath conditions
Under be passed through air and CO2Volume ratio is the mixed gas of 2:1 to the pH=7 of slurries, obtains white slurries；
Step 4: drying 12h for being placed in 80 DEG C of baking ovens after the white slurries vacuum filtration in step 3, papermaking is obtained
Use nano-TiO2/ wollastonite compound.
The additive amount of commerical grade rutile titanium dioxide is the 5%~20% of wollastonite quality in the step 2.
The commerical grade rutile titanium dioxide partial size is 200nm~300nm.
The mass ratio of the additive amount of dispersing agent PEG and wollastonite is 1:3000 in the step 2.
The mass ratio of the additive amount of sodium hydroxide and wollastonite is 1:6 in the step 2.
The dispersing agent PEG is PEG-400, PEG-1000 or PEG-6000.
Through the above design, the present invention can be brought the following benefits:
The invention discloses a kind of new methods having not been reported, and successfully synthesize one kind and are evenly coated, each side's surface properties
Nano-TiO up to standard2/ wollastonite compound new product.
It is plate structure using preparation method of the present invention composite product obtained, has whiteness high, be evenly coated, it is resistance to
The good feature of time property.By resulting composite product be used as papermaking filler when, the properties of paper with titanium dioxide conduct
It is close when filler.
Simple production process of the invention, the additive amount of the controllable rate for being passed through gas and titanium dioxide, so as to
The size of titanium dioxide granule and the clad ratio of wollastonite are adjusted, and wollastonite surface is evenly coated, yield is high, reaction condition temperature
With, it is easy to accomplish industrialized production.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is further illustrated:
Fig. 1 is the TiO in the embodiment of the present invention 22The scanning electron microscopic picture of/wollastonite compound.
Fig. 2 is the scanning electron microscope (SEM) photograph of natural wollastonite.
Fig. 3 is rutile TiO2Scanning electron microscope (SEM) photograph.
Fig. 4 is natural wollastonite, rutile TiO2With the TiO of embodiment 42The UV absorption of/wollastonite compound compares
Figure.
Specific embodiment
The nano-TiO that the present invention obtains2/ wollastonite composite product, structure are evenly coated at for titanium dioxide granule
Wollastonite surface.It is that the present invention uses the specific technical proposal is:
30g wollastonite is added in 270ml distilled water and is configured to the slurries that mass fraction is 10%, with 200 mesh screen mistakes
Filter, the quality that rutile titanium dioxide is added is 5%~20%, 0.01g dispersing agent PEG, the 5g hydroxide of wollastonite quality
Slurries, are then transferred in quartz glass carbonized tube by sodium, 50 DEG C of stirring in water bath 30min, are passed through air under 50 DEG C of water bath conditions
And CO2Volume ratio is the mixed gas of 2:1 to pH=7, finally obtains white slurries, is placed in 80 DEG C of baking ovens after vacuum filtration
Composite product can be obtained in drying 12h.
The titanium dioxide partial size preferably 200~300nm.
The dispersing agent is PEG, and dispersing method used is to be passed through CO2With air gas mixture bubble shearing force work
Keep fully dispersed with lower.
The additive amount of the rutile titanium dioxide is the 5%~20% of wollastonite quality, and reaction temperature is 50 DEG C.
The reaction end is slurries pH=7.
Preferably, the optimum flow rate for the mixed gas being passed through is 300l/h.
Preferably, the additive amount of rutile titanium dioxide is the 20% of wollastonite quality.
Preferably, the optimum weight of PEG is 1000.
Preferably, optimal reaction temperature is 50 DEG C.
Embodiment 1
30g wollastonite addition 270ml distilled water is configured to 10% slurries, with 200 mesh net filtrations, 1.5g gold is added
Then red stone-type titanium dioxide, 0.01g dispersing agent PEG-1000,5g sodium hydroxide, 50 DEG C of stirring in water bath 30min turn slurries
It moves in quartz glass carbonized tube, is passed through air and CO under 50 DEG C of water bath conditions2Volume ratio is the mixed gas of 2:1 to pH=7,
White slurries are obtained, drying 12h in 80 DEG C of baking ovens is placed after vacuum filtration can be obtained nano-TiO2The compound produce of/wollastonite
Product.The whiteness value of products obtained therefrom is 92.2, yield 88.49%.It is applied to gained compound as the main stuffing of paper
In papermaking, the whiteness of gained paper is 81.3, covering power 90.5, tearability 16mN.
Embodiment 2
3g golden red is added with 200 mesh net filtrations in the slurries that 30g wollastonite addition 270ml distilled water is configured to 10%
Then stone-type titanium dioxide, 0.01g dispersing agent PEG-1000,5g sodium hydroxide, 50 DEG C of stirring in water bath 30min shift slurries
Into quartz glass carbonized tube, air and CO are passed through under 50 DEG C of water bath conditions2Volume ratio is the mixed gas of 2:1 to pH=7, is obtained
Drying 12h in 80 DEG C of baking ovens is placed to white slurries, after vacuum filtration can be obtained nano-TiO2/ wollastonite composite product.
The whiteness value of products obtained therefrom is 92.8, yield 90.66%.It is applied to papermaking for gained compound as the main stuffing of paper
In, the whiteness of gained paper is 82.1, covering power 91.2, tearability 40mN.
Embodiment 3
30g wollastonite addition 270ml distilled water is configured to 10% slurries, with 200 mesh net filtrations, 4.5g gold is added
Then red stone-type titanium dioxide, 0.01g dispersing agent PEG-1000,5g sodium hydroxide, 50 DEG C of stirring in water bath 30min turn slurries
It moves in quartz glass carbonized tube, is passed through air and CO under 50 DEG C of water bath conditions2Volume ratio is the mixed gas of 2:1 to pH=7,
White slurries are obtained, drying 12h in 80 DEG C of baking ovens is placed after vacuum filtration can be obtained nano-TiO2The compound produce of/wollastonite
Product.The whiteness value of products obtained therefrom is 93.3, yield 91.85%.It is applied to gained compound as the main stuffing of paper
In papermaking, the whiteness of gained paper is 86.4, covering power 91.8, tearability 48mN.
Embodiment 4
6g golden red is added with 200 mesh net filtrations in the slurries that 30g wollastonite addition 270ml distilled water is configured to 10%
Then stone-type titanium dioxide, 0.01g dispersing agent PEG-1000,5g sodium hydroxide, 50 DEG C of stirring in water bath 30min shift slurries
Into quartz glass carbonized tube, air and CO are passed through under 50 DEG C of water bath conditions2Volume ratio is the mixed gas of 2:1 to pH=7, is obtained
Drying 12h in 80 DEG C of baking ovens is placed to white slurries, after vacuum filtration can be obtained nano-TiO2/ wollastonite composite product.
The whiteness value of products obtained therefrom is 94.1, yield 92.58%.It is applied to papermaking for gained compound as the main stuffing of paper
In, the whiteness of gained paper is 88.2, covering power 92.6, tearability 64mN.
By embodiment 1 to embodiment 4 it is found that when the additive amount of rutile titanium dioxide is wollastonite quality
20%, it is passed through air and CO2Volume ratio is 2:1, and when reaction temperature is 50 DEG C, resulting composite product covered effect is best
, whiteness and yield are also best.
Embodiment 5
6g golden red is added with 200 mesh net filtrations in the slurries that 30g wollastonite addition 270ml distilled water is configured to 10%
Then slurries are transferred to by stone-type titanium dioxide, 0.01g dispersing agent PEG-400,5g sodium hydroxide, 50 DEG C of stirring in water bath 30min
In quartz glass carbonized tube, air and CO are passed through under 50 DEG C of water bath conditions2Volume ratio is the mixed gas of 2:1 to pH=7, is obtained
White slurries, drying 12h in 80 DEG C of baking ovens is placed after vacuum filtration can be obtained nano-TiO2/ wollastonite composite product.Institute
The whiteness value for obtaining product is 93.8, yield 92.27%.It is applied to papermaking for gained compound as the main stuffing of paper
In, the whiteness of gained paper is 87.2, covering power 92.0, tearability 58mN.
Embodiment 6
6g golden red is added with 200 mesh net filtrations in the slurries that 30g wollastonite addition 270ml distilled water is configured to 10%
Then stone-type titanium dioxide, 0.01g dispersing agent PEG-6000,5g sodium hydroxide, 50 DEG C of stirring in water bath 30min shift slurries
Into quartz glass carbonized tube, air and CO are passed through under 50 DEG C of water bath conditions2Volume ratio is the mixed gas of 2:1 to pH=7, is obtained
Drying 12h in 80 DEG C of baking ovens is placed to white slurries, after vacuum filtration can be obtained nano-TiO2/ wollastonite composite product.
The whiteness value of products obtained therefrom is 93.4, yield 91.76%.It is applied to papermaking for gained compound as the main stuffing of paper
In, the whiteness of gained paper is 87.8, covering power 91.8, tearability 60mN.
TiO in 1~embodiment of embodiment 62/ wollastonite compound is applied to every property of paper in papermaking
By comparing above embodiments it is found that when the additive amount of rutile titanium dioxide is the 20% of wollastonite quality,
Dispersing agent used is PEG-1000, is passed through air and CO2Volume ratio be 2:1, reaction temperature be 50 DEG C when, resulting nanometer
TiO2/ wollastonite composite product covered effect be it is best, whiteness and yield are also best.Using gained compound as paper
Main stuffing be applied in papermaking, every property of paper be improved significantly.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, it cannot be assumed that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art, it can be according to the present invention
Technical solution and inventive concept, make it is corresponding change and substitution, and performance or use is identical, all should be considered as of the invention
Protection scope.
Claims (6)
1. a kind of paper grade (stock) nano-TiO2The preparation method of/wollastonite compound, it is characterized in that: including the following steps, and following
Step sequentially carries out,
Step 1: weighing wollastonite and distilled water respectively, the two is mixed to the wollastonite slurries for obtaining that mass fraction is 10%；
Step 2: 200 mesh net filtrations of the wollastonite slurries obtained in step 1 are sequentially added commodity in the filtrate of acquisition
Rutile type titanium dioxide, dispersing agent PEG and sodium hydroxide, 30~80 DEG C stirring in water bath 1 hour；
Step 3: the slurries after stirring in water bath in step 2 are transferred in quartz glass carbonized tube, lead under 50 DEG C of water bath conditions
Enter air and CO2Volume ratio is the mixed gas of 2:1 to the pH=7 of slurries, obtains white slurries；
Step 4: drying 12h for being placed in 80 DEG C of baking ovens after the white slurries vacuum filtration in step 3, obtains paper grade (stock) and receive
Rice TiO2/ wollastonite compound.
2. a kind of paper grade (stock) nano-TiO according to claim 12The preparation method of/wollastonite compound, it is characterized in that: institute
The additive amount for stating commerical grade rutile titanium dioxide in step 2 is the 5%~20% of wollastonite quality.
3. a kind of paper grade (stock) nano-TiO according to claim 1 or 22The preparation method of/wollastonite compound, feature
Be: the commerical grade rutile titanium dioxide partial size is 200nm~300nm.
4. a kind of paper grade (stock) nano-TiO according to claim 12The preparation method of/wollastonite compound, it is characterized in that: institute
Stating the mass ratio of the additive amount of dispersing agent PEG and wollastonite in step 2 is 1:3000.
5. a kind of paper grade (stock) nano-TiO according to claim 12The preparation method of/wollastonite compound, it is characterized in that: institute
Stating the mass ratio of the additive amount of sodium hydroxide and wollastonite in step 2 is 1:6.
6. a kind of paper grade (stock) nano-TiO according to claim 12The preparation method of/wollastonite compound, it is characterized in that: institute
Stating dispersing agent PEG is PEG-400, PEG-1000 or PEG-6000.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248942A (en) * | 2021-03-12 | 2021-08-13 | 吉林大学 | Nano TiO for improving paper performance2Preparation method and application of opal compound |
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| CN103897438A (en) * | 2014-04-17 | 2014-07-02 | 长春天成高新纳米复合材料有限公司 | Preparation method of composite calcium carbonate |
| CN104098932A (en) * | 2013-04-15 | 2014-10-15 | 中国地质大学（北京） | Preparation method for white mineral-titanium dioxide composite powder pigment |
| CN106590062A (en) * | 2016-12-06 | 2017-04-26 | 大连环球矿产股份有限公司 | Preparation method of composite titanium dioxide pigment with wollastonite coated with titanium dioxide |
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| CN101302359A (en) * | 2008-06-30 | 2008-11-12 | 攀枝花学院 | Composite titanium pigment and preparation thereof |
| CN103194098A (en) * | 2013-04-07 | 2013-07-10 | 攀枝花学院 | Preparation method of composite titanium dioxide |
| CN104098932A (en) * | 2013-04-15 | 2014-10-15 | 中国地质大学（北京） | Preparation method for white mineral-titanium dioxide composite powder pigment |
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| CN106590062A (en) * | 2016-12-06 | 2017-04-26 | 大连环球矿产股份有限公司 | Preparation method of composite titanium dioxide pigment with wollastonite coated with titanium dioxide |
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| CN113248942A (en) * | 2021-03-12 | 2021-08-13 | 吉林大学 | Nano TiO for improving paper performance2Preparation method and application of opal compound |
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