CN111925669A - Surface treatment method of special titanium dioxide for high-covering-power papermaking - Google Patents
Surface treatment method of special titanium dioxide for high-covering-power papermaking Download PDFInfo
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/043—Drying, calcination
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- 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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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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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
- D21H17/675—Oxides, hydroxides or carbonates
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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
Abstract
The invention belongs to the technical field of titanium dioxide production, and particularly relates to a surface treatment method of special titanium dioxide for high-covering-power papermaking, which comprises the following steps: taking rutile type titanium dioxide as a raw material, sequentially adopting cerium phosphate, aluminum phosphate and hydrated alumina to carry out inorganic coating on the rutile type titanium dioxide, and then adopting trimethylolpropane to carry out organic coating on the rutile type titanium dioxide; the coating amount of the inorganic coating is 4.0-9.0% of the weight of the titanium dioxide; the coating amount of the organic coating is 0.1-1.0% of the weight of the titanium dioxide. The special titanium dioxide for papermaking prepared by the method has excellent covering performance, can reduce the addition of the titanium dioxide, saves the cost, and can be used in the fields of laminated paper and decorative paper.
Description
Technical Field
The invention relates to the technical field of titanium dioxide production, in particular to a surface treatment method of special titanium dioxide for high-covering-power papermaking.
Background
Titanium dioxide is a nontoxic and tasteless white inorganic pigment, has the characteristics of good whiteness, opacity (covering power), photochromic and the like, and is a white pigment which has no substitution and optimal performance so far. Because of its outstanding pigment performance and optical performance, it is widely used in the fields of paint, plastics, printing ink, paper making, etc. Papermaking is the third application field of titanium dioxide, and the titanium dioxide is used as a filler in papermaking, so that the whiteness, light resistance, covering power and other properties of paper can be improved. In the field of papermaking, the most titanium dioxide is used as the decorative base paper, the decorative base paper is a new fashionable environment-friendly material, high-quality wood pulp, titanium dioxide and the like are used as main raw materials, and the decorative base paper is used for artificial boards such as fiber boards, shaving boards and the like after being printed and impregnated with melamine resin. The base decorative paper is generally printed and gummed, and then pressed with the panel, and the base layer is required to be impermeable, and therefore, the base decorative paper has good covering power (opacity).
Hiding power refers to the ability of a pigment to hide the undertone of the surface of a substrate when the pigment is applied to the surface of another material, and is also called opacity. The hiding power of pigments is influenced by the crystal structure, refractive index and scattering power for light and absorption power for light. Because the titanium dioxide is a white pigment, the absorption capacity of the titanium dioxide to light is very small and can be ignored, and the covering power of the titanium dioxide is mainly influenced by the scattering force of light. The covering power is an important economic index, and the stronger the covering power of the titanium dioxide is, the less the amount of the titanium dioxide required for completely covering the ground color is.
CN105199434A describes a surface treatment method of special titanium dioxide for papermaking, and the prepared titanium dioxide has good dispersibility, high covering power and good color fastness to light by forming a cerium phosphate and aluminum phosphate mixed film and a boehmite alumina coating film.
Disclosure of Invention
The invention aims to provide a surface treatment method of special titanium dioxide for papermaking with high covering power.
The invention firstly provides a surface treatment method of special titanium dioxide for high-covering power papermaking, which comprises the following steps: taking rutile type titanium dioxide as a raw material, sequentially adopting cerium phosphate, aluminum phosphate and hydrated alumina to carry out inorganic coating on the rutile type titanium dioxide, and then adopting trimethylolpropane to carry out organic coating on the rutile type titanium dioxide; the coating amount of the inorganic coating is 4.0-9.0% of the weight of the titanium dioxide; the coating amount of the organic coating is 0.1-1.0% of the weight of the titanium dioxide.
The surface treatment method of the special titanium dioxide for papermaking with high covering power comprises the following steps:
s1, adding water and a dispersing agent into rutile type titanium dioxide serving as a raw material to prepare titanium dioxide slurry with the concentration of 260-500 g/L;
s2, heating to 50-80 ℃, adding a water-soluble cerium salt solution, adding a phosphate solution in parallel, maintaining the pH value at 8-10, and curing for 30-60 min;
s3, adjusting the pH value to 5-6 by using phosphoric acid, adding a phosphoric acid solution and a sodium metaaluminate solution in a concurrent flow manner, maintaining the pH value to 5-6, and curing for 45-90 min;
s4, adding an aluminum salt solution, controlling the pH to be 6-7.5, and curing for 120-240 min;
and S5, performing solid-liquid separation, performing organic coating on the solid by adopting trimethylolpropane, drying and crushing to obtain the special titanium dioxide for papermaking with high covering power.
In the surface treatment method of the special titanium dioxide for papermaking with high covering power, in S1, the dispersant is sodium silicate or sodium hexametaphosphate; the adding amount is 0.1-0.5% of the mass of the titanium dioxide.
In the surface treatment method of the special titanium dioxide for papermaking with high covering power, in S2, the cerium salt is cerium nitrate or ammonium cerium nitrate; the concentration of the cerium salt solution is 50-100 g/L; the addition time of the cerium salt solution is 30-60 min.
In the surface treatment method of the titanium dioxide special for papermaking with high covering power, in S2, the cerium salt solution is added with CeO2Calculated as 0.2-1.0% of the mass of the titanium dioxide.
In the surface treatment method of the special titanium dioxide for papermaking with high covering power, in S2, the concentration of the phosphate solution is 20-50 g/L; the phosphate is disodium hydrogen phosphate and/or trisodium phosphate; preferably, the phosphate is disodium hydrogen phosphate and trisodium phosphate; more preferably, the mass ratio of the trisodium phosphate to the disodium hydrogen phosphate is 2: 1.
in the surface treatment method of the special titanium dioxide for papermaking with high covering power, in S3, the concentration of the phosphoric acid solution is 90-150 g/L; the concentration of the sodium metaaluminate solution is 50-150 g/L; the phosphoric acid solution is added in an amount of P2O5Calculated as 1.0-3.0% of the mass of titanium dioxide; the addition amount of the sodium metaaluminate solution is Al2O3Calculated as 0.3-0.8% of the mass of the titanium dioxide; the adding time of the phosphoric acid solution and the sodium metaaluminate solution is 60-120 min.
In the surface treatment method of the special titanium dioxide for papermaking with high covering power, in S4, the aluminum salt is sodium metaaluminate and/or aluminum sulfate; the concentration of the aluminum salt solution is 50-150 g/L; the addition amount of the aluminum salt solution is Al2O3The mass of the titanium dioxide accounts for 3-6 percent; the addition time of the aluminum salt solution is 120-240 min.
In the surface treatment method of the special titanium dioxide for papermaking with high covering power, the aluminum salt is sodium metaaluminate and aluminum sulfate; preferably, the mass ratio of the sodium metaaluminate to the aluminum sulfate is 1.4: 1.6.
compared with the prior art, the invention has the beneficial effects that:
according to the invention, through carrying out inorganic coating and organic coating on the titanium dioxide particles, the special titanium dioxide for papermaking prepared by the method has excellent covering performance, can reduce the addition of the titanium dioxide, saves the cost, and can be used in the fields of laminated paper and decorative paper.
Detailed Description
Specifically, the surface treatment method of the special titanium dioxide for high-covering-power papermaking comprises the following steps:
s1, adding water and a dispersing agent into rutile type titanium dioxide serving as a raw material to prepare titanium dioxide slurry with the concentration of 260-500 g/L;
s2, heating to 50-80 ℃, adding a water-soluble cerium salt solution, adding a phosphate solution in parallel, maintaining the pH value at 8-10, and curing for 30-60 min;
s3, adjusting the pH value to 5-6 by using phosphoric acid, adding a phosphoric acid solution and a sodium metaaluminate solution in a concurrent flow manner, maintaining the pH value to 5-6, and curing for 45-90 min;
s4, adding an aluminum salt solution, controlling the pH to be 6-7.5, and curing for 120-240 min;
and S5, performing solid-liquid separation, performing organic coating on the solid by adopting trimethylolpropane, drying and crushing to obtain the special titanium dioxide for papermaking with high covering power.
In the method S2 of the present invention, the pH is adjusted to 8-10 because this pH range is the optimum condition for forming cerium phosphate; in the method S3 of the present invention, the pH is adjusted to 5 to 6 because this pH range is the optimum condition for phosphoric acid and sodium metaaluminate to form aluminum phosphate precipitate on the surface of titanium dioxide; in the method S4 of the present invention, the pH is adjusted to 6-7.5 because the amorphous hydrated alumina formed in this pH range is advantageous in improving the weather resistance of the product and making the slurry filtration performance good.
In the method S2, the cerium salt is cerium nitrate or ammonium cerium nitrate; the concentration of the cerium salt solution is 50-100 g/L; the adding time of the cerium salt solution is 30-60 min; the cerium salt solution is added with CeO2Calculated as 0.2-1.0% of the mass of titanium dioxide; the phosphate is disodium hydrogen phosphate and/or trisodium phosphate; the concentration of the phosphate solution is 20-50 g/L.
In the method S3, the concentration of the phosphoric acid solution is 90-150 g/L; the concentration of the sodium metaaluminate solution is 50-150 g/L; the phosphoric acid solution is added in an amount of P2O5Calculated as 1.0-3.0% of the mass of titanium dioxide; the adding time of the phosphoric acid solution and the sodium metaaluminate solution is 60-120 min.
In the method S4, the aluminum salt is sodium metaaluminate and/or aluminum sulfate; the concentration of the aluminum salt solution is 50-150 g/L; the addition amount of the aluminum salt solution is Al2O3The mass of the titanium dioxide accounts for 3-6 percent; the addition time of the aluminum salt solution is 120-240 min.
In the method S4, when the aluminum salt is sodium metaaluminate, dilute acid needs to be added in parallel to maintain the pH of the slurry; when the aluminum salt is aluminum sulfate, a dilute base needs to be added in parallel to maintain the pH of the slurry; when the aluminum salt is sodium metaaluminate and aluminum sulfate, no acid or alkali is required to be additionally added.
In the method, the comprehensive solubility is considered, the concentration of a cerium salt solution is set to be 50-100g/L, and the concentration of a phosphate solution is set to be 20-50 g/L; the concentration of the phosphoric acid solution is set to be 90-150 g/L; the concentration of the sodium metaaluminate solution is set to be 50-150 g/L; the concentration of the aluminum salt solution is set to 50-150 g/L. And if the concentration is too high, the local reaction will be too violent, and if the concentration is too low, the envelope will not be stored too much, which affects the yield.
The amount of phosphate solution added in step S2 is determined by pH.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The raw materials are not indicated by manufacturers, and are all conventional products which can be obtained commercially.
Example 1
Deionized water is added into the rutile type titanium dioxide primary product, and sodium silicate with the mass of 0.1 percent of that of the titanium dioxide is added for dispersion, so as to prepare titanium dioxide slurry with the concentration of 260 g/L. Adding the slurry into a four-mouth round-bottom flask, starting stirring, starting a heating device, and heating to 50-80 ℃; 100g/L of ammonium ceric nitrate solution (added in CeO) is added into the slurry in a concurrent flow manner within 30min20.3% of the mass of the titanium dioxide), and 35g/L of a compound liquid of trisodium phosphate and disodium hydrogen phosphate (the mass ratio of the trisodium phosphate to the disodium hydrogen phosphate is 2: 1) maintaining the pH value of the slurry at 9.5-10.0, and curing for 60 min; the pH value is adjusted to 5.7 by phosphoric acid, and the phosphoric acid solution is added in a concurrent flow manner within 60min (the adding amount is P)2O51.5 percent of the mass of the titanium dioxide) and sodium metaaluminate solution (the addition amount is Al2O3Calculated as 0.5 percent of the mass of the titanium dioxide), maintaining the pH value of the slurry at 5.5-6.0, and curing for 60 min; adding sodium metaaluminate solution (the addition amount is Al) in a concurrent flow manner within 120min2O3Calculated as dioxy3 percent of titanium oxide by mass) and dilute acid, maintaining the pH value of the slurry at 6.0-6.5, and curing for 120 min; washing and filtering with deionized water, adding 100g/L trimethylolpropane solution (the addition amount is 0.1 percent of the mass of titanium dioxide) into the filter cake, uniformly mixing, finally drying at 105 ℃, and carrying out jet milling to obtain a sample.
Example 2
Deionized water is added into the rutile type titanium dioxide primary product, and sodium silicate with the mass of 0.1 percent of that of the titanium dioxide is added for dispersion, so as to prepare titanium dioxide slurry with the concentration of 260 g/L. Adding the slurry into a four-mouth round-bottom flask, starting stirring, starting a heating device, and heating to 50-80 ℃; 30min, 100g/L cerium ammonium nitrate solution (added in CeO)20.3% of the mass of the titanium dioxide), and 35g/L of a compound liquid of trisodium phosphate and disodium hydrogen phosphate (the mass ratio of the trisodium phosphate to the disodium hydrogen phosphate is 2: 1) maintaining the pH value of the slurry at 9.5-10.0, and curing for 60 min; the pH is adjusted to 5.7 with phosphoric acid, and the phosphoric acid solution is added concurrently (the addition is in P)2O51.5 percent of the mass of the titanium dioxide) and sodium metaaluminate solution (the addition amount is Al2O3Calculated as 0.5 percent of the mass of the titanium dioxide), maintaining the pH value of the slurry at 5.5-6.0, and curing for 60 min; adding aluminum sulfate solution (the addition amount is Al) in parallel flow for 120min2O33 percent of the weight of the titanium dioxide) and dilute alkali, maintaining the pH value of the slurry at 6.0-6.5, and curing for 120 min; washing and filtering with deionized water, adding 100g/L trimethylolpropane solution (the addition amount is 0.1 percent of the mass of titanium dioxide) into the filter cake, uniformly mixing, and finally drying and carrying out air flow crushing at 105 ℃ to obtain a sample.
Example 3
Deionized water is added into the rutile type titanium dioxide primary product, and sodium silicate with the mass of 0.1 percent of that of the titanium dioxide is added for dispersion, so as to prepare titanium dioxide slurry with the concentration of 260 g/L. Adding the slurry into a four-mouth round-bottom flask, starting stirring, starting a heating device, and heating to 50-80 ℃; 30min, 100g/L cerium ammonium nitrate solution (added in CeO)20.3% of the mass of the titanium dioxide), and 35g/L of a compound liquid of trisodium phosphate and disodium hydrogen phosphate (the mass ratio of the trisodium phosphate to the disodium hydrogen phosphate is 2: 1) maintenance of slurry pHAging for 60min at 9.5-10.0; the pH is adjusted to 5.7 with phosphoric acid, and the phosphoric acid solution is added concurrently (the addition is in P)2O51.5 percent of the mass of the titanium dioxide) and sodium metaaluminate solution (the addition amount is Al2O3Calculated as 0.5 percent of the mass of the titanium dioxide), maintaining the pH value of the slurry at 5.5-6.0, and curing for 60 min; adding sodium metaaluminate and aluminum sulfate compound solution in parallel for 120min (the total aluminum addition is Al2O3The mass ratio of sodium metaaluminate to aluminum sulfate is 1.4: 1.6), maintaining the pH value of the slurry at 6.0-6.5, and curing for 120 min; washing and filtering with deionized water, adding 100g/L trimethylolpropane solution (the addition amount is 0.1 percent of the mass of titanium dioxide) into the filter cake, uniformly mixing, and finally drying and carrying out air flow crushing at 105 ℃ to obtain a sample.
The application performance test is carried out on the examples 1 to 3, and the detection method comprises the following steps: adding the prepared titanium dioxide into deionized water and melamine resin, uniformly mixing, coating to prepare a sample wafer, and detecting the opacity on a whiteness meter to judge the covering power of the sample. The greater the opacity, the better the hiding power.
TABLE 1 opacity of different samples
Note: the comparative sample 1 is titanium white special for domestic sulfuric acid process paper making; the comparative sample 2 is titanium white special for foreign chlorination papermaking.
Claims (9)
1. The surface treatment method of the special titanium dioxide for high-covering power papermaking is characterized by comprising the following steps: taking rutile type titanium dioxide as a raw material, sequentially adopting cerium phosphate, aluminum phosphate and hydrated alumina to carry out inorganic coating on the rutile type titanium dioxide, and then adopting trimethylolpropane to carry out organic coating on the rutile type titanium dioxide; the coating amount of the inorganic coating is 4.0-9.0% of the weight of the titanium dioxide; the coating amount of the organic coating is 0.1-1.0% of the weight of the titanium dioxide.
2. The surface treatment method of the special titanium dioxide for high-covering-power papermaking according to claim 1, characterized by comprising the following steps:
s1, adding water and a dispersing agent into rutile type titanium dioxide serving as a raw material to prepare titanium dioxide slurry with the concentration of 260-500 g/L;
s2, heating to 50-80 ℃, adding a water-soluble cerium salt solution, adding a phosphate solution in parallel, maintaining the pH value at 8-10, and curing for 30-60 min;
s3, adjusting the pH value to 5-6 by using phosphoric acid, adding a phosphoric acid solution and a sodium metaaluminate solution in a concurrent flow manner, maintaining the pH value to 5-6, and curing for 45-90 min;
s4, adding an aluminum salt solution, controlling the pH to be 6-7.5, and curing for 120-240 min;
and S5, performing solid-liquid separation, performing organic coating on the solid by adopting trimethylolpropane, drying and crushing to obtain the special titanium dioxide for papermaking with high covering power.
3. The surface treatment method of the special titanium dioxide for high-covering-power papermaking according to claim 2, wherein in S1, the dispersant is sodium silicate or sodium hexametaphosphate; the adding amount is 0.1-0.5% of the mass of the titanium dioxide.
4. The surface treatment method of the special titanium dioxide for high hiding power papermaking according to claim 2, wherein in S2, the cerium salt is cerium nitrate or ammonium cerium nitrate; the concentration of the cerium salt solution is 50-100 g/L; the addition time of the cerium salt solution is 30-60 min.
5. The surface treatment method of the special titanium dioxide for high hiding power papermaking according to claim 2 or 4, wherein in S2, the cerium salt solution is added in CeO2Calculated as 0.2-1.0% of the mass of the titanium dioxide.
6. The surface treatment method of the special titanium dioxide for high-covering-power papermaking according to claim 2, wherein in S2, the concentration of the phosphate solution is 20-50 g/L; the phosphate is disodium hydrogen phosphate and/or trisodium phosphate; preferably, the phosphate is disodium hydrogen phosphate and trisodium phosphate; more preferably, the mass ratio of the trisodium phosphate to the disodium hydrogen phosphate is 2: 1.
7. the surface treatment method of the special titanium dioxide for high-covering-power papermaking according to claim 2, wherein in S3, the concentration of the phosphoric acid solution is 90-150 g/L; the concentration of the sodium metaaluminate solution is 50-150 g/L; the phosphoric acid solution is added in an amount of P2O5Calculated as 1.0-3.0% of the mass of titanium dioxide; the addition amount of the sodium metaaluminate solution is Al2O3Calculated as 0.3-0.8% of the mass of the titanium dioxide; the adding time of the phosphoric acid solution and the sodium metaaluminate solution is 60-120 min.
8. The surface treatment method of the titanium pigment specially used for high covering power papermaking according to claim 2, wherein in S4, the aluminum salt is sodium metaaluminate and/or aluminum sulfate; the concentration of the aluminum salt solution is 50-150 g/L; the addition amount of the aluminum salt solution is Al2O3The mass of the titanium dioxide accounts for 3-6 percent; the addition time of the aluminum salt solution is 120-240 min.
9. The surface treatment method of the titanium dioxide special for high hiding power paper making according to claim 8, wherein the aluminum salt is sodium metaaluminate and aluminum sulfate; preferably, the mass ratio of the sodium metaaluminate to the aluminum sulfate is 1.4: 1.6.
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