3/9/2019 CN101774595B - Process for enhanced reduction and bleaching of kaolin by using thiocarbamide - Google Patents

 Patents

Process for enhanced reduction and bleaching of kaolin by using thiocarbamide

Abstract
CN101774595B
The invention relates to a process for enhanced reduction bleaching of kaolin by using
China
thiocarbamide, which uses sodium dithionite as a main reducing agent and the thiocarbamide as an
auxiliary reducing agent to perform combined enhanced bleaching on the kaolin under a Zn/gamma-
Al2O3 catalyzed condition with the pH value of 3.0 to 6.5 at the normal temperature, and Download PDF Find Prior Art Similar
simultaneously perform a shielding reaction and a complex reaction. The process solves the
problem that the kaolin is yellowed after bleaching, and has the characteristics of low cost, good Other languages: Chinese
bleaching effect and small environmental pollution; besides, a kaolin powder product has the natural
Inventor: 夏光华, 朱永杰, 李晓鸣, 苏小丽, 邓元臣, 陈强
whiteness of over 85 percent and the calcination whiteness of over 90 percent, has high brightness,
stability and dispersity, and can be widely used in the industries of high-grade ne ceramics,
coatings, papermaking and the like. Worldwide applications

2010 CN

Application CN 201010004271 events

2010-01-16 Application led by 兖矿北海高岭土有限公司, 景

德镇陶瓷学院

2010-01-16 Priority to CN 201010004271

2010-07-14 Publication of CN101774595A

2011-11-09 Application granted

2011-11-09 Publication of CN101774595B

Info: Cited by (5), Legal events, Similar documents, Priority and

Related Applications

External links: Espacenet, Global Dossier, Discuss

Claims (2) translated from Chinese

A reinforced thiourea reductive bleaching process kaolin, kaolin comprising after hydraulic classi cation, sedimentation dispersed puri ed bleaching reaction, then washed,
pressure ltration, and drying, to obtain the nished product, characterized in that said bleaching reaction -Al2O3 under catalytic conditions at normal temperature, PH value 3.
0~6. 5 Zn / y, to sodium dithionite as the reducing agent and thiourea main joint kaolin bleach boosting auxiliary reducing agent, sodium dithionite wherein was added in an
amount of 0.2% ~ 0 7% by weight of kaolin, thiourea is added in an amount of 0.05% by weight of kaolin 5% ~ 0;. after reduction bleaching reaction, the reaction reintroduction
as aluminum shield shielding agent to prevent iron ions recombine to clay, wherein the masking agent is added in an amount of 0.2% by weight of kaolin _1.5% of complexing
agent is then added reduced iron ions, added in an amount of 0.3% by weight of kaolin 0.6%; the complexing agent is a humic acid, oxalic acid, citric acid and EDTA or the
combination of any two of them.

2. The thiourea of claim 1 reinforced kaolin reductive bleaching process, wherein the aluminum salt is aluminum chloride.

Description translated from Chinese

Thiourea strengthening process reductive bleaching kaolin

FIELD

[0001] The present invention relates to a production process for bleaching kaolin, kaolin particularly strengthen reductive bleaching process, widely used in the bleaching
of clay mineral as a thiourea.

Background technique

[0002] Kaolin is an inorganic non-metallic mineral raw materials, mainly composed of kaolinite, mica, quartz and feldspar residue, easily dispersed or suspended in water,
having a good plasticity, adhesion and high ion exchange capacity, and other unique properties So it is widely used in ceramics, paper, chemicals and pharmaceuticals
and other important industries. Pure white kaolin, kaolin nature but often some of the dark color associated minerals such as hematite, magnetite, goethite and other
iron-containing mica; Further kaolinite itself adsorbs some of the coloring matter, to the kaolin partial participation the lattice structure is formed among the minerals iron
(aluminum substituted trioctahedral), the yellow and the gray kaolin presents other colors, making it di cult to use directly as industrial raw materials, are generally
physical and chemical methods must be used to remove impurities in kaolin, enhance the whiteness of kaolin, to improve its value. Therefore, the whiteness of kaolin is
an important indicator to determine its uses and economic value, whiteness kaolin for each percentage point increase in its value will be greatly improved, however, from
a technical and economic considerations to improve the overall balance kaolin whiteness has become di cult in the present technical eld.

[0003] At present, at home and abroad have otation method of purifying bleaching kaolin, oxidative bleaching, bleaching reduction, oxidation - reduction joint bleaching
agents, chelating agents bleach boosting method. The above methods for improving the whiteness of a certain effect, but the level of increase is limited, it is di cult to
calcine whiteness above 90%. Foreign of newborn liquid dithionite reduction bleaching intensive hydrogenation boride, although whiteness can be close to 90%, but the

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3/9/2019 CN101774595B - Process for enhanced reduction and bleaching of kaolin by using thiocarbamide - Google Patents
borohydride reducing agent is expensive, di cult to industrially practical use, and yellowing of bleached kaolin phenomenon is di cult to control, i.e. iron in solution is
easy to return to the clay mineral; reduction prior hydrosul te bleaching, the bleaching reaction is performed under strongly acidic conditions, severe corrosion of the
equipment, pollution of the environment, and a limited bleaching effect.

SUMMARY

[0004] The object of the present invention is to provide a low cost, good bleaching effect, environmental pollution kaolin new bleaching process.

[0005] To achieve the above object, the present invention is a process scheme: kaolin ore through the hydrocyclone separator to more than 325 mesh formulated solids
content of 20% -25% of well dispersed slurry, adjusting the slurry pH to 7 . 0-8. settling afforded the 5 volume concentration of about 20% pulp, and adjust the slurry pH to
3. 0-6.5 to sodium dithionite as the reducing agent and thiourea as the main auxiliary reducing agent in Zn / y -Al2O3 under catalytic conditions, kaolin bleach boosting
joint, wherein sodium dithionite is added in an amount of 0.2% ~ 0. 7% by weight of kaolin, thiourea is added in an amount of 0.05% ~ 0. 5% by weight of kaolin ; higher
valence state is then introduced into a metal salt as a colorless shielding agent prevents iron ions recombine with the clay, wherein the masking agent is added in an
amount of 0.2% -15 wt% kaolin;. complexing agent added is reduced iron ions, added in an amount of 0.3% by weight of kaolin 6% ~ 0; then washed, pressure ltration,
and drying, to obtain the natural whiteness of greater than 85.0 percent, greater than the whiteness of the calcined kaolin 90.0% concentrate product.

[0006] In the above process, the bleach boosting joint using sodium dithionite surfaces of the particles of kaolin, dog structural boundary portion is reduced to 3+ 2+
dogs, and use of a reducing agent thiourea auxiliary reinforcing reduction performed. Bleaching reaction of the present invention is carried out at ambient temperature,
weakly acidic slurry, and thiourea is usually only a reducing under heating or basic conditions to produce strengthening thiourea reduction under the above conditions, the
studies showed that Zn / γ-Al2O3 catalysts may be activated thiourea in reducing under the reaction conditions, so that the dog 3+ in an acidic solution of thiourea can be
easily oxidized formamidine disul de, while! ^ 3 + is reduced to 2 dogs + further, thiourea kaolin! ^ 3 + complexed dog (III) SO4Tu + complex, serving to strengthen
reduction. Experimentally known, Zn / γ-Al2O3 initial amount of activated catalyst was added thiourea 5% by weight.

[0007] Further, Applicants investigated thiourea addition on bleaching effect, when thiourea is added in an amount of 0.2% ~ 0. 3% by dry weight of kaolin can achieve
better economic and technical effects.

[0008] The phyllosilicate mineral kaolinite aqueous belongs, wherein the cation is bonded only to oxygen ions, and a hydroxyl group, as well as water molecules are not
polyhedral structure, constituting + cells [(0,0! 1 ,! 120)} polyhedral radical connected to each other. After completion of the reduction reaction, addition of a salt
containing the cation valency, wherein the high aspect Mn + ions to ll the position of Fe3 + ion-exchanged form, on the other hand with the surface of the clay particles,
the hydroxyl groups on dangling bonds and other structure boundary bond, forming Μη + (0, OH, H2O) group is attached, so as to shield the surface of kaolin, iron
kinetically blocking clay recombination, preferably the colorless metal of high valence aluminum salt such as aluminum sulfate, aluminum chloride.

[0009] In the complexation reaction, the complexing agent solution! ^ 2 + ions, a complexing agent to form an organic metal complex with the role of iron, with greater
solubility and migration, so that the washing iron from the clay during a surface, removing a greater extent. The complexing agent is humic acid, oxalic acid, citric acid,
oxalic acid, or a combination of two, EDTA and citric acid and EDTA, triethanolamine, preferably.

[0010] The present invention employs a hydrocyclone, blenders commonly used equipment, centrifuges and dryers and other clay minerals bleaching, drying temperature
is 110 ° C.

[0011] Compared with the prior art process, because the bleaching reaction is carried out at room temperature and weak acid slurry, the technical and economic
feasibility, the process does not produce a strongly acidic or basic waste water; kaolin by signi cantly reducing the iron content to improve the whiteness of kaolin, solve
the problem of reducing yellowing of the product. The resulting powder product Kaolin whiteness of greater than 85% of natural, calcined whiteness above 90%, has high
luminance, and dispersion stability, can be widely used for high-grade ne ceramics, paint and paper industries.

BRIEF DESCRIPTION

[0012] DETAILED DESCRIPTION The Figures process ow diagram of the present invention

[0013] Hereinafter, the embodiments of the present invention will be described in detail in conjunction with the accompanying drawings and examples:

[0014] Example 1

[0015] North Sea kaolin weathered granite belonging to incompletely weathered residual deposits, iron-containing minerals such as iron ore and iron oxide, mica, and
other impurities affect kaolin widely used in the North Sea. The present embodiment selects the North Sea kaolin raw materials, which is about 77% natural whiteness,
whiteness about 82% calcined, the calcination temperature is 1200 ° C (hereinafter the same). First 600kg water was added with stirring slurried kaolin, kaolin clay was
added 0.2% by weight of the dispersant sodium hexametaphosphate and sodium hydroxide pH adjusting agent, PH value of the slurry is about 7. 0-8. 5, stirred for 30
minutes , to prepare a slurry of 23-28%, and then puri ed by settling, sedimentation to a concentration of about 20% volume of the slurry, then the slurry with sulfuric acid
to adjust the pH of 3.0, was added 0.6% by weight of kaolin, sodium dithionite and after 0.2% by weight of kaolin auxiliary reducing agent thiourea, and thiourea was
added 5% by weight of Zn / y -Al2O3 catalyst, slowly stirring for 30 minutes, followed by addition of 0.5% by weight of aluminum sulfate, kaolin, stirred for 20 minutes was
added kaolin 0.3% by weight of citric acid or oxalic acid or other complexing agents, and continue stirring slowly, vigorous stirring to avoid excessive bubbles. After 30
minutes, the lter press was washed with water, dehydrated, and then dried at 110 ° C, to obtain a whiteness of 86% natural kaolin concentrate product, calcined detected
90.7% of whiteness (brightness kaolin Blu-ray re ectance measurement as a standard).

[0016] Example 2

[0017] In the bleaching reaction, the amount of secondary reducing agent thiourea to 0.5% by weight of kaolin, of the same other conditions as in Example 1, to obtain a
whiteness of natural kaolin 86.2% concentrate product, calcined detected whiteness of 91.3%.

[0018] Example 3

Under [0019] In the bleaching reaction, the other conditions the same as in Example 1 in the case of the embodiment, the auxiliary reducing agent is not added thiourea
case, the resulting concentrate product kaolin, natural whiteness of 80%, a whiteness of 83.4% was calcined . Description bleaching effect is not obvious.

[0020] Example 4

[0021] In the bleaching reaction, the other conditions the same as the case of Example 1, screening agents without the addition of aluminum sulfate, the resulting
concentrate product kaolin, natural whiteness of 84%, 88.6% brightness calcined. Example 1 than in the bleaching effect decline.

[0022] The following is a list of various embodiments chemical Parameters Example:

[0023]

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Cited By (5)

Publication number Priority date Publication date Assignee Title

Family To Family Citations

CN102205230B * 2011-05-14 2013-01-02 山西大学 Method for processing atlapulgite for decolorizing grease

CN102583412A * 2012-01-17 2012-07-18 合肥工业大学 Method for carrying out deironing and whitening on kaolin

CN104528750B * 2014-12-12 2016-12-07 景德镇陶瓷学院 One sol - gel method of coating kaolin whitening method

CN104528749B * 2015-01-20 2016-06-15 江西省源通陶瓷科技有限公司 A process method of whitening feldspar concentrates

CN105329908A * 2015-11-20 2016-02-17 中国高岭土有限公司 Kaolin bleaching method

* Cited by examiner, † Cited by third party, ‡ Family to family citation

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Priority Applications (1)

Application Priority date Filing date Title

CN 201010004271 2010-01-16 2010-01-16 Process for enhanced reduction and bleaching of kaolin by using thiocarbamide

Applications Claiming Priority (1)

Application Filing date Title

CN 201010004271 2010-01-16 Process for enhanced reduction and bleaching of kaolin by using thiocarbamide

Legal Events

Date Code Title Description

2010-07-14 C06 Publication

2010-09-15 C10 Request of examination as to substance

2011-11-09 C14 Granted

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