CN107325588A - A kind of preparation method for the pigment for coating high gorgeous degree iron oxide - Google Patents
A kind of preparation method for the pigment for coating high gorgeous degree iron oxide Download PDFInfo
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- CN107325588A CN107325588A CN201710557721.6A CN201710557721A CN107325588A CN 107325588 A CN107325588 A CN 107325588A CN 201710557721 A CN201710557721 A CN 201710557721A CN 107325588 A CN107325588 A CN 107325588A
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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
- C09C1/22—Compounds of iron
- C09C1/24—Oxides of iron
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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
- 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
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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
- 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
Abstract
The present invention relates to a kind of preparation method for the pigment for coating high gorgeous degree iron oxide, the method comprising the steps of：(1) base material is scattered according to solid-liquid weight than 1/4 1/20 in the mixed liquor of water or water and alcohol, control system temperature is at 0 120 DEG C, and adjustment system pH is 5 13, and controls to add Fe (II) salting liquid under the pH value, stirring condition；(2) control system temperature is at 0 120 DEG C, and adjustment system pH is 15, and controls in the pH value, and stirring is lower to add Fe (II) salting liquid, and its feeding quantity is (with Fe2O3Meter) it is the 0.01 200% of substrate weight；(3) filtering, washing, 80 120 DEG C of dryings, further in 300 900 DEG C of calcinings, obtain the pigment of bright red iron oxide cladding, wherein step (1) and (2) are carried out in the presence of an oxidizer.The gorgeous degree of iron oxide coated pigment prepared by the method for the present invention is high, can apply to the cosmetics such as lipstick, and have the advantages that nontoxic, non-volatile thing.
Description
Technical field
The present invention relates to a kind of preparation method of pigment, face is coated more specifically to the iron oxide of Gao Yandu a kind of
The preparation method of material.
Background technology
Iron oxide is the second largest inorganic pigment for being only second to titanium dioxide, is also the first big colored organic pigments.Iron oxide red
It is a very important class in iron oxide pigment, has purposes widely, be widely used in ink, plastics, coating, rubber
The various fields such as glue, ceramics, building materials, papermaking.Iron oxide red is also known as that iron oxide red, iron oxygen are red, is a kind of traditional and important inorganic
Pigment, its chemical formula is α-Fe2O3, it is red or dark red powder, because preparation approach is different, produces particle size and shape
Also different, iron oxide red has different form and aspect.Reunion is had when iron oxide red individually makes, is difficult to disperse, iron oxide can be caused to make
Used time is a bit darkish in color, and influences its application.And iron oxide pigment is coated on carrier, scattered, the group of powder can be solved
Poly- problem.
The preparation method of iron oxide red is a lot, divides according to reaction mass state, is broadly divided into 2 kinds of dry and wet：
Dry method mainly includes roasting method, thermal decomposition method etc., but dry method is unsuitable for cladding of the iron oxide red on base material；Wet method is mainly wrapped
Include sol-gal process, air oxidation process, Hydrolyze method, precipitation method etc..[Wang Yunhua, Guan Xiaowei, He Dewu are produced with ferrous sulfate
Method [P] Chinese patents of iron oxide red:CN200610021578.0,2006-08-10.] and [the preparation work of nano-sized iron oxide
Skill research [J] models Jing Lian, Cheng Huichao, Liu Tao, Ma Yunzhu, Li Zhixi.PM technique, 2005 (05)] for collosol and gel
Method, main technique is to contain Fe3+Solution in add certain growth-regulating agent and OH-, Fe (OH) is made3Precipitation suspends
Filter and be washed with deionized repeatedly after liquid, heating, finally dry obtained α-Fe2O3Particle.Gel method is unsuitable in base material
Upper uniform coated iron oxide；The precipitation method are the methods that liquid-phase chemical reaction synthesis of metal oxide nanoparticle is used earliest, are led to
It is often, by the material mixing of different chemical composition, appropriate precipitating reagent to be added in mixed solution and prepares nanometer under solution state
The presoma sediment of particle, then this sediment is dried or calcined, so that corresponding nanometer particle is made.The method can
Be divided into direct precipitation method and sluggish precipitation [molysite basic hydrolysis it is prepared by liquid phase method nanometer iron oxide red influence [J] Gong Liang,
Chen Yanjun, Mo Baicheng, Li Meng, Jia Zhenbin, Guangdong chemical industry, 2010 (04)].For the pearlescent pigment of substrate surface coated iron oxide
Generally it is to be prepared using hydrolysis methods.But this method is applied to preparing spherical SiO 2 such as and uses iron chloride liquid-phase precipitation
Pigment is brown during coated iron oxide pigment, and gorgeous degree is very poor.Hydro-thermal method refers in closed pressure vessel, with water or water vapour
It is solvent Deng fluid, under high-temperature and high-pressure conditions, precursor is reacted and is crystallized.This method can prepare tens nanometers cube and
The superfine iron oxide of ellipse, is carried out due to reacting under high-temperature and high-pressure conditions, therefore higher to equipment requirement, while also uncomfortable
It is suitable for the production of mass product.
With FeSO4The liquid phase oxidation precipitation method prepared for raw material are that to prepare iron oxide pigment be also conventional method, [Wang Yun
China, Guan Xiaowei, He Dewu, a kind of method [P] Chinese patents that iron oxide red is produced with ferrous sulfate:CN101172663,
2008-05-07.], [Zhou Shuhua, copperas solution prepare iron oxide red production technology [P] Chinese patents:
CN201410671153.9,2014.11.21] and [research of the full liquid phase oxygenerating iron oxide yellow of sulfate process titanium dioxide ferrous sulfate by-product
The tertiary refined, Wang little Mei of [J] Wus, modern coatings and application, 1996 (01)] its technique generally use alkali neutralisation of sulphuric acid ferrous iron generation hydrogen
Ferrous oxide, in the basic conditions with air oxidation ferrous hydroxide combinations kind, the iron red crystal seed formation solution into oxidation tank is added
Iron sheet and/or iron powder；And the oxide for depositing generation is deposited on crystal seed in the presence of ferrous sulfate with air, and gradually oxygen
Iron oxide red is melted into, filtration drying can obtain iron oxide red.But this method is directly to prepare iron oxide pigment, and given birth to without calcining
Into be exactly iron oxide red.
In a word, the pigment or filler color obtained according to existing method coated iron oxide is partially dark, and red phase is not enough, particularly makees
Such case is more obvious during the fine grain substrate product used for filler.And as wished in lipstick in many cosmetic formulations
Obtain gorgeous red effect, and common iron oxide pigment can not obtain conveniently, satisfied scattered effect, and must not be without using
Organic red pigment, but this can cause the worry that people influence on organic matter on people.
Therefore coating out pigment or filler with gorgeous red effect using nontoxic, harmless iron oxide turns into when business
It is anxious.
The content of the invention
It is an object of the invention to provide a kind of preparation method for the pigment for coating high gorgeous degree iron oxide.
In order to reach our bright purpose, using following technological means.
A kind of preparation method for the pigment for coating high gorgeous degree iron oxide, this method comprises the following steps：
(1) base material is scattered according to solid-liquid weight than 1/4-1/20 in the mixed liquor of water or water and alcohol, control system temperature
Degree is at 0-120 DEG C, and adjustment system pH is 5-13, and controls to add Fe (II) salting liquid under the pH value, stirring condition；
(2) control system temperature is at 0-120 DEG C, and adjustment system pH is 1-5, and controls in the pH value, and stirring is lower to be added
Fe (II) salting liquid；
(3) filtering, washing, 80-120 DEG C of drying, further in 300-900 DEG C of calcining, obtain bright red iron oxide cladding
Pigment,
Wherein step (1) and (2) are carried out in the presence of an oxidizer.
In a preferred embodiment of the invention, this method further comprises repeating 1-10 times before step (3)
(step (1)+step (2)).
In a more preferred embodiment of the present invention, this method further comprises repeating (step (1)+step
(2) before), individually step (2) is carried out once.
In a preferred embodiment of the invention, before this method further comprises step (1) and/or step (2)
Or afterwards, adjustment system pH is 2-4, adds Fe (III) salting liquid and is coated, the feeding quantity of Fe (III) salt is (with Fe2O3
Meter) be substrate weight 0%-100%.
In a preferred embodiment of the invention, Fe (II) salting liquid is molten selected from copperas solution, frerrous chloride
One or more in liquid and ferrous oxalate solution.
In a more preferred embodiment of the present invention, the concentration of Fe (II) salting liquid choosing is 0.1M-6M.
In a preferred embodiment of the invention, in step (1) total feeding quantity of Fe (II) salt (with Fe2O3Meter) be
The 0.01-200% of substrate weight, more preferably 0.01% to 60%, further preferred 0.1%-40%, still more preferably 1-
30%.
Total feeding quantity of Fe (II) salt is added in another preferred embodiment of the present invention, in step (2) (with Fe2O3
Meter) be substrate weight 0.01-200%, more preferably 0.01% to 60%, further preferred 0.1%-40%, it is further excellent
Select 1-30%.
In a more preferred embodiment of the present invention, the addition speed of Fe (II) salting liquid in step (1) and step (2)
Spend for 8ml/h-200ml/h, addition stirs 0-2h after finishing.
In a preferred embodiment of the invention, the oxidant is oxygen, hydrogen peroxide, potassium chlorate and potassium pyrosulfate
In one or more, preferably oxygen, hydrogen peroxide or its mixture, more preferably oxygen.
In a preferred embodiment of the invention, Fe (III) salting liquid is selected from liquor ferri trichloridi, ferrum sulfuricum oxydatum solutum
With the one or more in oxalic acid ferrous solution.
In a more preferred embodiment of the present invention, the feeding quantity of Fe (III) salt is (with Fe2O3Meter) it is substrate weight
0%-40%, preferably 0-20%.In another more preferred of the present invention, the concentration of Fe (III) salting liquid is
0.1M-6M。
In a preferred embodiment of the invention, this method further comprises adding Fe (II) salting liquid process every time
In, before or after add oxidant.
In the present invention, for open reaction system, the oxygen in air can be as most cheap oxidant, can be each
Add Fe (II) salting liquid during, before or after add other oxidants, other oxidants can not also be added；It is right
In confined reaction system, it is necessary to every time add Fe (II) salting liquid during, before or after add oxidant.
In a more preferred embodiment of the present invention, the consumption of oxidant is addition Fe (II) salt mole in system
1.5-4 times.
In a preferred embodiment of the invention, base material is non-flat substrates or flat substrates；The non-sheet material
Material is selected from：Kaolin, calcium carbonate, barium sulfate, diatomite, magnesium carbonate, magnesium silicate, barium carbonate, boron nitride, hydroxyapatite, oxygen
Change the mixture of zirconium, calcium borosilicate, borsal, spherical silica, glass dust or a variety of above materials, or coated thereon
The kaolin of metal and/or nonmetallic and/or metal oxide and/or nonmetal oxide, calcium carbonate, barium sulfate, diatomite,
Magnesium carbonate, magnesium silicate, barium carbonate, boron nitride, hydroxyapatite, zirconium oxide, calcium borosilicate, borsal, spherical silica,
The pigment or a variety of mixtures with paint of glass dust formation；The flaky material is selected from natural mica, synthetic mica, glass
Piece, titanium dioxide silicon chip, alumina wafer, flake ferric oxide or bismuth oxychloride crystals, borosilicate, platelet boron nitride or it is a variety of more than
The mixture of material, or coating metal thereon and/or nonmetallic and/or metal oxide and/or nonmetal oxide from
Natural mica, synthetic mica, sheet glass, titanium dioxide silicon chip, alumina wafer, flake ferric oxide or bismuth oxychloride crystals, borosilicic acid
Salt, the pigment or a variety of mixtures with paint of platelet boron nitride formation.
In a more preferred embodiment of the present invention, the non-flat substrates are selected from the powder that radius-thickness ratio is less than 10；
Further preferred radius-thickness ratio is less than 5 powder, bead, hollow glass still more preferably with above radius-thickness ratio feature
Pearl, spherical silica, ball-type hollow silicon dioxide, particle diameter D50 are less than 10 μm of synthetic mica；Further optimize particle diameter
D50 is less than 5 μm of synthetic mica.
In a preferred embodiment of the invention, 300-900 DEG C of calcination time is 1-300 minutes in step (3).
In a preferred embodiment of the invention, alkali used in adjustment system pH is inorganic in step (1) and step (2)
Alkali, it is preferable that the inorganic base is in sodium hydroxide and potassium hydroxide, one or two kinds of mixtures of ammoniacal liquor.
In a preferred embodiment of the invention, acid used in adjustment system pH is inorganic in step (1) and step (2)
Acid, it is preferable that one or more mixtures of the inorganic acid in hydrochloric acid, sulfuric acid, acetic acid and oxalic acid.
In a more preferred embodiment of the present invention, adjustment system pH uses the Fe (II) for adding acid in step (2)
Salting liquid, wherein the acid is inorganic acid, it is preferable that the one kind or many of the inorganic acid in hydrochloric acid, sulfuric acid, acetic acid and oxalic acid
The mixture planted.
In a more preferred embodiment of the present invention, control system temperature is at 25-80 DEG C in step (1), more preferably
65-78℃。
In a more preferred embodiment of the present invention, control system temperature is at 25-80 DEG C in step (2), more preferably
65-78℃。
In a more preferred embodiment of the present invention, the content of the mixed liquor reclaimed water of step (1) reclaimed water and alcohol is many
In 30% (by weight).In another more preferred of the present invention, alcohol used is ethanol or/or methanol, more excellent
Select ethanol.
In a more preferred embodiment of the present invention, adjustment system pH is 7-10 in step (1), further preferably
System pH is 8-9.
In a more preferred embodiment of the present invention, adjustment system pH is 2-4 in step (2), further preferably
System pH is 2-3.
It is a further object of the present invention to provide the pigment of the high gorgeous degree iron oxide of the cladding prepared by the method for the present invention.
The pigment of the high gorgeous degree iron oxide of present invention cladding can apply to the industries such as cosmetics, coating, plastics, be preferred for
Cosmetic industry, its consumption is calculated as 0.1-80%, preferably 2-20% with the weight of composition.It need not be ground when using, can be with
Directly apply in formula.
The reason for can obtaining gorgeous color on this method, may be from carrying out being coated with for divalent iron salt under different pH
Close, the crystalline form and granular size of the iron oxide coated under possible this condition of different pH are different, so as to cause to give birth to after firing
Into gorgeous iron oxide.
Although the principle of the present invention has similar part with the ferrous sulfate crystal seed oxidizing process that background technology is mentioned, also have
Obvious different, [Zhou Shuhua, copperas solution prepares production technology [P] Chinese patents of iron oxide red to literature method:
CN201410671153.9,2014.11.21] principle generally in copperas solution, add alkali adjustment system pH=
8.5-9.5, generates iron red crystal seed formation under conditions of air is blasted, and iron sheet and/or iron powder are added afterwards, and it is molten to add ferrous sulfate
Liquid；And be passed through air oxidation ferrous ion and obtain iron ion, iron ion is combined with the hydroxyl in water and is deposited on iron red crystal seed formation
On surface, iron oxide red is gradually formed, the hydrogen ion produced while oxidation reaction reacts with iron sheet and/or iron powder, and generation is sub-
Iron ion is simultaneously oxidized to iron ion again, until oxidation reaction terminates.This method can directly generate iron oxide red.
And be also, in pH=5-10, preferably under 8.5-9.5 alkalescence condition, to add during beginning for the method for the present invention
Copperas solution, generates Fe (III), with (FeO.nH in the presence of air by part Fe (II)2O+Fe2O3.mH2O shape)
Formula is deposited on substrate surface, but and continue further clad of the oxidation generation with specific structure, in further addition Fe2+
During, cladding is further completed on above-mentioned burden layer, now powder is yellow, the iron oxide red generated with literature method is not
Together.If but after now being calcined, color is in brown, and without gorgeous red.If but according to the method described above in pH
=8.5-9.5 coats a certain amount of iron oxide, then adjusts pH to 1-5, continues to coat, and its coating is in then yellow, with document side
Method, which directly generates iron oxide red, significant difference, only can just become deep red by calcining.If being coated entirely under the conditions of pH=1-5,
Although with coating orange red phase, the still difference with adjustment pH claddings under the conditions of pH=5-10.Its reason be probably at high temperature,
The two kinds of crystal structures coated under the conditions of two kinds interact, and may produce interaction with base material, produce bright red form and aspect.Together
If sample directly carries out high-temperature calcination using iron oxide yellow, although can mutually turn to red phase from Huang, but deep red can not be obtained, therefore should
The technique that method prepares iron oxide yellow from tradition is also different.
The advantage of the pigment of the high gorgeous degree iron oxide of cladding of the present invention is can to obtain the iron oxide cladding with Gao Yandu
Pigment, can apply to the cosmetics such as lipstick and obtains gorgeous red, and have the advantages that nontoxic, non-volatile thing.
" a variety of " refer to two or more in the present invention.
" solution " unless otherwise specified, refers to the aqueous solution in the present invention.
In the present invention, " D50 " refers to the average grain diameter or median of powder, further refers in size distribution curve and tires out
Accumulate the equivalent diameter of the largest particles when being distributed as 50%.For example, the particle diameter in the present invention is swashed using America and Europe gram LS-POP (6) type
Light Particle Size Analyzer is measured.In the present invention " maintenance system pH stable " generally refer to maintenance system target ph ±
0.1 unit, such as maintenance system pH are stable between 2.5 finger 2.4-2.6.Refer to 2.4-2.7 if pH=2.5-2.6.For temperature
It is then design temperature ± 3 DEG C.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.The experimental method of unreceipted actual conditions in example below, generally according to conventional strip
Part, or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise percentage is calculated by weight.In example below
" solution " unreceipted specific solvent refers to the aqueous solution.
Blade coating detection is specific as follows in the following example：It is well mixed according to 0.2g powder pigments with 2g polyurethane resins,
Using 100um swipe device swipe wet film, 1min is dried at 105 DEG C afterwards, afterwards using Ai Seli X-Rite MA68II types point
Light color difference meter is measured, and uses D65/10 ° of light source, 45 ° of detection angles.Use CIELab color model.Wherein：L represents shading value
(black and white), a represents red (+), green (-) color, and b represents yellow (+) blue (-) color, and c represents chroma, and (degree of color saturation is pure
Degree), h represents hue angle.
Embodiment 1
In open reactor, spherical silica of the 60g average grain diameters at 3 μm is added, compares 1/10 according to solid-liquid weight
Add 600mL water and be configured to slurry, system pH is adjusted to 8.5 with sodium hydroxide solution, made afterwards by heating stirring to 78 DEG C
With the ferrous sulfate aqueous solution for the 1M that 200mL is added in sodium hydroxide and under conditions of maintenance system pH stabilizations, charging rate
20mL/h, about 10h are added；It is 3 that system pH is adjusted to pH by charging after finishing with hydrochloric acid, is neutralized afterwards using sodium hydroxide
250mL 1M ferrous sulfate aqueous solution is added under conditions of maintenance system pH is stable, temperature maintains 78 DEG C, charging rate
20mL/h, is about added in 12.5h；Yellow powder is obtained after filtering, washing, 100 DEG C of dryings after charging is finished, at 600 DEG C
Lower calcining 10min, obtains the preparing spherical SiO 2 of deep red iron oxide cladding.Swipe detects a=26.8, b=15.61, c=
30.99。
Comparative example 1
In open reactor, spherical silica of the 60g average grain diameters at 3 μm is added, compares 1/10 according to solid-liquid weight
Add 600mL water and be configured to slurry, heating stirring is to 78 DEG C, and it is 3.0 that system pH is adjusted into pH with hydrochloric acid, afterwards using hydrogen
450mL 1M ferrous sulfate aqueous solution is added in sodium oxide molybdena and under conditions of maintenance system pH stabilizations, range temperature is maintained
78 DEG C, charging rate 20mL/h is about added in 22.5h, obtains orange after filtering, washing, 100 DEG C of dryings after charging is finished
Powder, calcines 10min at 600 DEG C, obtains the preparing spherical SiO 2 of bronzing iron oxide cladding.Swipe detects a=17.8, b
=7.9, c=19.53.
Comparative example 2
In open reactor, spherical silica of the 60g average grain diameters at 3 μm is added, compares 1/10 according to solid-liquid weight
Add 600mL water and be configured to slurry, heating stirring is to 78 DEG C, and it is 8.5 that system pH is adjusted into pH with sodium hydroxide, is made afterwards
With the ferrous sulfate aqueous solution for the 1M that 450mL is added in sodium hydroxide and under conditions of maintenance system pH stabilizations, range temperature dimension
Hold at 78 DEG C, charging rate 20mL/h is about added in 22.5h；Obtained after charging is finished after filtering, washing, 100 DEG C of dryings
Orange powder, calcines 10min at 600 DEG C, obtains the spherical silica of brown iron oxide cladding.Swipe detection a=16.1,
B=13.0, c=20.7.
Comparative example 3
In open reactor, spherical silica of the 60g average grain diameters at 3 μm is added, compares 1/10 according to solid-liquid weight
Add 600mL water and be configured to slurry, system pH is adjusted to 3.0, afterwards using hydroxide by heating stirring to 78 DEG C with hydrochloric acid
In sodium and maintenance system pH it is stable under conditions of add 450mL 1M ferric chloride in aqueous solution, range temperature maintains 78 DEG C, plus
Expect speed 20mL/h, about added in 22.5h；Filtering, washing, 100 DEG C of dryings, are calcined at 600 DEG C after charging is finished
10min, obtains the preparing spherical SiO 2 of orange red iron oxide cladding.Swipe detects a=11.9, b=5.1, c=13.0.
Comparative example 4
In open reactor, spherical silica of the 60g average grain diameters at 3 μm is added, compares 1/10 according to solid-liquid weight
Add 600mL water and be configured to slurry, system pH is adjusted to 3.0 with hydrochloric acid solution, is using hydrogen afterwards by heating stirring to 78 DEG C
With the ferrous sulfate aqueous solution for the 1M for maintaining to add 200mL under conditions of pH is stable in sodium oxide molybdena, charging rate 20mL/h, about
10h is added；It is 8.5 that system pH is adjusted to pH by charging after finishing with sodium hydroxide, uses in sodium hydroxide and ties up afterwards
The ferrous sulfate aqueous solution for the 1M that 250mL is added under conditions of system pH stablizes is held, range temperature maintains 78 DEG C, charging rate
20mL/h, is about added in 12.5h；Filtering, washing, 100 DEG C of dryings, calcine 10min at 600 DEG C, obtain after charging is finished
Obtain the preparing spherical SiO 2 of brown iron oxide cladding.Swipe detects a=15.8, b=13.2, c=20.6.
Comparative example 5
In closed reactor, spherical silica of the 60g average grain diameters at 3 μm is added, compares 1/10 according to solid-liquid weight
Add 600g water and be configured to slurry, system pH is adjusted to 8.5 with sodium hydroxide solution, made afterwards by heating stirring to 78 DEG C
With the ferrous sulfate aqueous solution for the 1M that 200mL is added in sodium hydroxide and under conditions of maintenance system pH stabilizations, charging rate
20mL/h, about 10h are added；It is 3 that system pH is adjusted to pH by charging after finishing with hydrochloric acid, uses in sodium hydroxide and ties up afterwards
The ferrous sulfate aqueous solution for the 1M that 250mL is added under conditions of system pH stablizes is held, range temperature maintains 78 DEG C, charging rate
20mL/h, is about added in 12.5h；After charging is finished brownish black powder is obtained after filtering, washing, 100 DEG C of dryings；At 600 DEG C
Lower calcining 10min, obtains the preparing spherical SiO 2 of brown iron oxide cladding.Swipe detects a=12.4, b=9.8, c=15.8.
The ABC values that can be seen that the sample prepared using this method from embodiment 1 and comparative example 1-5 are higher, special
It is not that A values are high, it is in red phase to illustrate sample.
Embodiment 2
In open reactor, spherical silica of the 60g average grain diameters at 3 μm is added, compares 1/20 according to solid-liquid weight
1000mL water and 200 ethanol are added, system pH is adjusted to 8.0 with potassium hydroxide solution, made afterwards by heating stirring to 70 DEG C
With the ferrous sulfate aqueous solution for the 2M that 50mL is added in potassium hydroxide and under conditions of maintenance system pH stabilizations, charging rate
10mL/h, about 5h are added, and continue to stir 1h after adding；System pH is adjusted to pH by charging after finishing with sulfuric acid
2.8, afterwards using the ferrous sulfate aqueous solution for the 1M that 350mL is added in potassium hydroxide and under conditions of maintenance system pH stabilizations,
Reaction temperature maintains 70 DEG C, and charging rate 35mL/h, about 10h are added；Filtering, washing, 100 DEG C of dryings after charging is finished
After obtain calcining 60min at yellow powder, 500 DEG C, obtain the preparing spherical SiO 2 of deep red iron oxide cladding.Swipe detects a
=26.8, b=16.9, c=31.7.
Embodiment 3
In open reactor, synthetic mica of the 60g average grain diameters at 5 μm is added, is added according to solid-liquid weight than 1/8
480mL water is configured to slurry, and system pH is adjusted to 9.0 with sodium hydroxide, uses hydrogen at 85 DEG C afterwards by heating stirring to 85 DEG C
With maintenance system pH addition 200mL 2M under conditions of stable ferrous sulfate aqueous solution in sodium oxide molybdena, charging rate 10mL/h,
About 20h is added；Charging is added after finishing to be added in 5mL30% hydrogen peroxide, 0.5h, continues to stir 0.5h afterwards；Afterwards
It is 2.5 that pH value is adjusted into pH in 2h using the solution containing 1M ferrous sulfate, 1M sulfuric acid, uses hydroxide at 85 DEG C afterwards
50mL 1M ferrous sulfate aqueous solution, about charging rate 20mL/h, 2.5h are added in potassium and under conditions of maintenance pH stabilizations
Add；Yellow powder is obtained after filtering, washing, 110 DEG C of dryings after charging is finished, 180min is calcined at 400 DEG C, is obtained gorgeous
The spherical synthetic mica of red iron oxide cladding.
Embodiment 4
In open reactor, spherical silica of the 60g average grain diameters at 3 μm is added, is added according to solid-liquid weight 1/10
Enter 600g water and be configured to slurry, heating stirring is to 78 DEG C；System pH is adjusted to 8.5 by (step one) with sodium hydroxide solution, it
50mL 1M ferrous sulfate aqueous solution, charging rate are added in using sodium hydroxide and under conditions of maintenance pH stabilizations afterwards
20mL/h, about 2.5h are added；It is 3 that system pH is adjusted to pH by (step 2) with hydrochloric acid, uses in sodium hydroxide and ties up afterwards
The ferrous sulfate aqueous solution for the 1M that 50mL is added under conditions of system pH stablizes is held, range temperature maintains 78 DEG C, charging rate
20mL/h, is about added in 2.5h；Repeat (step one+step 2) 5 times；Yellow powder is obtained after filtering, washing, 100 DEG C of dryings
Body；10min is calcined at 600 DEG C, the preparing spherical SiO 2 of deep red iron oxide cladding is obtained.
Embodiment 5
In open reactor, add 60g average grain diameters has red interference in 30 μm of natural mica cladding titanium dioxide
Pearlescent pigment, according to solid-liquid weight than 1/12 add 720mL water, heating stirring to 25 DEG C, afterwards with ammoniacal liquor value adjust system
PH to 8.5, adds 20mL 1M ferrous sulfate aqueous solution afterwards in using ammoniacal liquor and under conditions of maintenance system pH stabilizations,
Charging rate 10mL/h, about 2h are added；System pH is adjusted to 3.0 by charging after finishing with hydrochloric acid, and is warming up to 78 DEG C, is stirred
Mix the ferrous sulfate aqueous solution for the 1M that 20mL is added in lower use ammoniacal liquor and under conditions of maintenance system pH stabilizations, charging rate
10mL/h, about 1h are added；Feed and stir 0.5h at 78 DEG C after finishing；Calcined after filtering, washing, 100 DEG C of dryings at 700 DEG C
5min, obtains the red pearlescent pigment of deep red iron oxide cladding.
Embodiment 6
In open reactor, 60g average grain diameters cladding titanium dioxide, titanium dioxide on 30 μm of natural mica are added
The chameleon pearlescent pigment with golden red discoloration of silicon, titanium dioxide, according to the ratio of solid-liquid weight 1/20, adds 1200mL water and matches somebody with somebody
Slurry is set to, system pH is adjusted to 9.0 to 78 DEG C, using sodium hydroxide afterwards by heating stirring by sodium hydroxide afterwards
15mL 1M ferrous sulfate aqueous solution is added under conditions of neutralization maintenance system pH is stable, 1h is added；Charging finish after
0.5h is stirred at 78 DEG C；System pH is adjusted to 3.0 with hydrochloric acid, stablized afterwards in use sodium hydroxide with maintenance system pH
Under the conditions of add 15mL 1M ferrous sulfate aqueous solution, 1h adds, and charging stirs 0.5h after finishing at 78 DEG C；Filtering,
13min is calcined after washing, 100 DEG C of dryings at 600 DEG C, the chameleon powder of the golden red discoloration of deep red iron oxide cladding is obtained
Body.
Embodiment 7
In open reactor, kaolin of the 60g average grain diameters at 3 μm is added, water is added than 1/20 according to solid-liquid weight
1200mL is configured to slurry, and system pH is adjusted to 8.8, used afterwards to 78 DEG C by heating stirring with sodium hydroxide afterwards
150mL 1M ferrous sulfate aqueous solution, charging rate 30mL/ are added in sodium hydroxide and under conditions of maintenance system pH stabilizations
H, 5h are added；Charging stirs 1h after finishing at 78 DEG C；System pH is adjusted to 2.9 with hydrochloric acid, afterwards using sodium hydroxide
Neutralize maintenance system pH it is stable under conditions of add 350mL 1M ferrous sulfate aqueous solution, charging rate 35mL/h, 10h adds
Complete, charging stirs 0.5h after finishing at 78 DEG C；Afterwards at 78 DEG C, under the conditions of pH=3,100mL 0.5M iron chloride is added,
Charging rate 35mL/h, 10h are added；30min is calcined at 600 DEG C after filtering afterwards, washing, 100 DEG C of dryings, deep red is obtained
The kaolin of iron oxide cladding.
Embodiment 8
In open reactor, kaolin of the 60g average grain diameters at 3 μm is added, water is added than 1/20 according to solid-liquid weight
1200mL is configured to slurry, and system pH is adjusted to 3.0 with sodium hydroxide afterwards, adds 100mL0.5M by heating stirring to 78 DEG C
Iron chloride, charging rate 10mL/h about adds in 10h；Afterwards by system with sodium hydroxide by system pH adjust to
8.8, the ferrous sulfate for the 1M for adding 150mL in using sodium hydroxide and under conditions of maintenance system pH stabilizations afterwards is water-soluble
Liquid, charging rate 10mL/h, is about added in 15h；System pH is adjusted to 2.9 by charging after finishing with hydrochloric acid, is made afterwards
With the ferrous sulfate aqueous solution for the 1M that 350mL is added in sodium hydroxide and under conditions of maintenance system pH stabilizations, charging rate
20mL/h, is about added in 17.5h；5min is calcined at 800 DEG C after filtering, washing, 100 DEG C of dryings after charging is finished, is obtained
The kaolin of red iron oxide cladding.
Embodiment 9
In open reactor, titanium dioxide of the 60g average grain diameters at 2 μm is added, is added according to solid-liquid weight than 1/18
1080mL water, heating stirring is to 78 DEG C, and potassium hydroxide adjusts system pH to 8.7, afterwards in using sodium hydroxide afterwards
150mL 1M ferrous sulfate aqueous solution is added under conditions of stable with maintenance system pH, charging rate 30mL/h, about 5h add
Complete, charging adds potassium chlorate 2.0g after finishing, and 1h is stirred at 78 DEG C；System pH is adjusted to 2.9 with hydrochloric acid afterwards, it
Afterwards using the ferrous sulfate aqueous solution for the 1M that 350mL is added in sodium hydroxide and under conditions of maintenance pH stabilizations, feed express delivery
20mL/h, about 17.5h charging are finished；200min is calcined at 300 DEG C after filtering, washing, 100 DEG C of dryings, deep red oxygen is obtained
Change the titanium dioxide of iron cladding.
Embodiment 10
In open reactor, spherical silica of the 1Kg average grain diameters at 3 μm is added, is added according to solid-liquid weight 1/12
Enter 12Kg water and be configured to slurry, system pH is adjusted to 8.5 with sodium hydroxide solution, used afterwards by heating stirring to 78 DEG C
With maintenance system pH addition 2L 1M under conditions of stable ferrous sulfate aqueous solution in sodium hydroxide, charging rate 0.2L/h,
About 10h is added；System pH is adjusted to 3.0 by charging after finishing with hydrochloric acid, afterwards using in sodium hydroxide and maintenance system
Add 2.5L 1M ferrous sulfate aqueous solution under conditions of pH is stable, range temperature maintains 78 DEG C, charging rate 0.2L/h,
About added in 12.5h；After charging is finished yellow powder is obtained after filtering, washing, 100 DEG C of dryings；Calcined at 600 DEG C
10min, obtains the preparing spherical SiO 2 of deep red iron oxide cladding.
Carry out not having conditional description to the present invention by example according to the preferred form of production of the present invention, still
It should be appreciated that in the range of appended claims definition, those skilled in the art can make any change and/or change
Type, without departing from related protection domain.
Claims (10)
1. a kind of preparation method for the pigment for coating high gorgeous degree iron oxide, this method comprises the following steps：
(1) base material is scattered according to solid-liquid weight than 1/4-1/20 in the mixed liquor of water or water and alcohol, control system temperature exists
0-120 DEG C, adjustment system pH is 5-13, and controls to add Fe (II) salting liquid under the pH value, stirring condition；
(2) control system temperature is at 0-120 DEG C, and adjustment system pH is 1-5, and controls in the pH value, and stirring is lower to add Fe
(II) salting liquid；
(3) filtering, washing, 80-120 DEG C of drying, further in 300-900 DEG C of calcining, obtain the pigment of bright red iron oxide cladding,
Wherein step (1) and (2) are carried out in the presence of an oxidizer.
2. preparation method according to claim 1, this method further comprises repeating 1-10 (step before step (3)
Suddenly (1)+step (2)).
3. preparation method according to claim 2, this method further comprise repeat (step (1)+step (2)) it
Before, individually carry out step (2) once.
4. the preparation method according to claim any one of 1-3, this method further comprises step (1) and/or step (2)
Before or after, adjustment system pH is 2-4, adds Fe (III) salting liquid and is coated, the feeding quantity of Fe (III) salt (with
Fe2O3Meter) be substrate weight 0%-100%.
5. Fe (II) salting liquid in the preparation method according to claim any one of 1-3, wherein step (1) and step (2)
One or more in copperas solution, solution of ferrous chloride and ferrous oxalate solution.
Preparation method according to claim 4, wherein Fe 6. (III) salting liquid is selected from liquor ferri trichloridi, ferric sulfate solution
One or more in liquid, oxalic acid ferrous solution.
7. in the preparation method according to claim any one of 1-3, wherein step (1) Fe (II) salt total feeding quantity (with
Fe2O3Meter) be substrate weight 0.01-200%.
8. in the preparation method according to claim any one of 1-3, wherein step (2) Fe (II) salt total feeding quantity (with
Fe2O3Meter) be substrate weight 0.01-200%.
9. the preparation method according to claim any one of 1-3, wherein the oxidant is preferably：Air, oxygen, dioxygen
One or more in water, potassium chlorate and potassium pyrosulfate.
10. the preparation method according to claim any one of 1-3, wherein the base material is non-flat substrates or sheet base
Material；The non-flaky material is selected from：Kaolin, calcium carbonate, barium sulfate, diatomite, magnesium carbonate, magnesium silicate, barium carbonate, nitridation
Boron, hydroxyapatite, zirconium oxide, calcium borosilicate, borsal, spherical silica, glass dust or a variety of above materials it is mixed
Compound, or in kaolin, the carbonic acid of coating metal and/or nonmetallic and/or metal oxide and/or nonmetal oxide thereon
Calcium, barium sulfate, diatomite, magnesium carbonate, magnesium silicate, barium carbonate, boron nitride, hydroxyapatite, zirconium oxide, calcium borosilicate, borosilicate
Sour sodium, spherical silica, the pigment or a variety of mixtures with paint of glass dust formation；The flaky material is selected from natural
Mica, synthetic mica, sheet glass, titanium dioxide silicon chip, alumina wafer, flake ferric oxide or bismuth oxychloride crystals, borosilicate, piece
The mixture of shape boron nitride or a variety of above materials, or thereon coating metal and/or nonmetallic and/or metal oxide and/
Or nonmetal oxide from natural mica, synthetic mica, sheet glass, titanium dioxide silicon chip, alumina wafer, flake ferric oxide or chlorine
Bismuth oxide crystal, borosilicate, the pigment or a variety of mixtures with paint of platelet boron nitride formation.
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| CN109705625A (en) * | 2019-02-25 | 2019-05-03 | 华东理工大学 | A kind of preparation method of the red pearlescent pigment of wine |
| CN115044231A (en) * | 2022-06-10 | 2022-09-13 | 湖州师范学院 | Heat-resistant iron oxide yellow pigment with multilayer coating structure and preparation method thereof |
| CN115806745A (en) * | 2022-11-22 | 2023-03-17 | 云浮鸿志新材料有限公司 | Composite nano transparent iron oxide red and preparation method thereof |
| CN115895294A (en) * | 2022-11-22 | 2023-04-04 | 云浮鸿志新材料有限公司 | Composite nano transparent iron oxide yellow and preparation method thereof |
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Application publication date: 20171107 |