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CN110746792B - Preparation method of rare earth sulfide compound - Google Patents

Preparation method of rare earth sulfide compound Download PDF

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CN110746792B
CN110746792B CN201911101646.8A CN201911101646A CN110746792B CN 110746792 B CN110746792 B CN 110746792B CN 201911101646 A CN201911101646 A CN 201911101646A CN 110746792 B CN110746792 B CN 110746792B
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rare earth
suspension
product
sodium
compound
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CN110746792A (en
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李成宇
庞然
张洪杰
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Zhongke Zebang (Qingdao) new material Co.,Ltd.
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Jilin Huisheng Technology Co ltd
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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
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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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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
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    • C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
    • C—CHEMISTRY; METALLURGY
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    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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Abstract

The invention relates to a preparation method of a rare earth sulfide compound, which comprises the following steps: (1) uniformly mixing soluble fluoride, a surfactant, soluble alkaline sodium salt, a rare earth compound and sulfur in water to prepare a suspension A; (2) spray drying the suspension A to obtain a product B; (3) roasting the product B in the presence of activated carbon and protective gas to obtain a rare earth sulfide compound primary product; (4) and washing the primary product of the rare earth sulfide compound with water and drying to obtain a final product. The invention also relates to the rare earth sulphide complexes prepared by this process and to their use as colorants.

Description

Preparation method of rare earth sulfide compound
Technical Field
The invention relates to rare earth sulfide, in particular to a preparation method of a fluorine-containing rare earth sulfide compound, the rare earth sulfide compound prepared by the method and application of the rare earth sulfide compound as a coloring agent.
Background
The rare earth sulfide as a coloring agent can replace the coloring agents which can not meet the requirement of environmental protection, such as organic pigments, pigments and the like which are used in large quantity at present, due to the characteristics of excellent coloring performance, no toxicity, no harm and the like. Rare earth sulfide is listed in the Ministry of industry and communications and the Ministry of environmental protection of the Ministry of science and technology in the book of poisonous and harmful raw material product substitutes which is jointly issued in 2016 and encourages the development of the nation.
The rare earth sulfide is generally synthesized by heating and reacting rare earth compounds serving as raw materials and hydrogen sulfide or carbon disulfide serving as a sulfur source in closed equipment, for example, rare earth sulfides disclosed in CN1201441A, CN1271332A and CN1426376A are prepared by adopting the method. The synthesis of rare earth sulfide can also be carried out by taking rare earth compound as raw material, sulfur as vulcanizing agent, alkali metal salt as catalyst and active carbon as adjuvant, and reacting at high temperature to prepare rare earth sulfide, such as cerium sulfide disclosed in CN102107902B and CN 102120602A.
Currently, rare earth sulfide materials prepared by either gas-solid reaction or solid-solid reaction need to be ground and crushed to control the particle size before being used as a colorant. On one hand, the integrity of the crystal grains of the rare earth sulfide can be seriously damaged in the grinding and crushing process, so that the surface defects of the grains are increased, and the vividness of the material is reduced. On the other hand, the particle size of the material obtained by grinding is uneven, the particle appearance is irregular, and the coloring performance of the material is seriously influenced. Although the coloring performance of the ground rare earth sulfide can be improved after the rare earth sulfide is washed by fluoride ions, the fluoride washing process can cause the problem of treatment of fluoride-containing wastewater, and the production cost is increased.
Therefore, there is a need to develop a novel rare earth sulfide and a preparation method thereof, wherein the novel rare earth sulfide prepared by the method has regular morphology and uniform particle size without grinding and has higher brilliance and tinting strength without fluorine washing.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a rare earth sulfide compound which has bright color, uniform particle size distribution, regular appearance and no toxicity and a preparation method thereof. By changing the types of rare earth elements in the rare earth sulfide compound and adjusting the component ratio of the raw materials, the rare earth sulfide compound can present different colors and can be used as a colorant.
The invention provides a preparation method of the rare earth sulfide compound, which comprises the following steps: :
(1) uniformly mixing soluble fluoride, a surfactant, soluble alkaline sodium salt, a rare earth compound and sulfur in water to prepare a suspension A;
(2) spray drying the suspension A to obtain a product B;
(3) roasting the product B in the presence of activated carbon and protective gas to obtain a rare earth sulfide compound primary product;
(4) and washing the primary product of the rare earth sulfide compound with water and drying to obtain a final product.
The above steps are described in detail below.
Step (1)
There is no particular limitation on the manner in which the respective components are mixed uniformly in water, as long as the solubles are dissolved and the respective components are mixed uniformly. In addition, the dissolving and blending process can be accelerated by using a stirrer, a homogenizer, or the like. In the embodiment, the suspension a may be prepared by first dissolving the soluble fluoride, the surfactant and the soluble alkali sodium salt in water and then adding the rare earth compound and sulfur, but the present invention is not limited thereto.
The soluble fluoride may be one or more selected from ammonium fluoride, sodium fluoride, potassium fluoride, preferably ammonium fluoride and sodium fluoride.
The surfactant may be one or more selected from polyvinylpyrrolidone (PVP), stearic acid, polyethylene glycol (PEG, also known as polyethylene oxide (PEO)), polyvinyl alcohol (PVA), citric acid, sodium dodecylbenzenesulfonate and OP-10; preferably one or more selected from PVP, PEG and sodium dodecyl benzene sulfonate.
The soluble alkaline sodium salt may be one or more selected from sodium carbonate, sodium bicarbonate, sodium sulfide, sodium hydroxide, preferably one or more selected from sodium carbonate, sodium bicarbonate and sodium hydroxide.
The molar ratio of fluorine ions to sodium ions in the suspension a may be 0.1:1 to 15:1, preferably 2:3 to 10: 1.
The molar ratio of the fluorine element in the fluoride to the rare earth element in the rare earth compound may be 1:3.9 to 1:2000, preferably 1:10 to 1: 200.
The mass ratio of insoluble solids (including sulfur and rare earth compounds) to water in the suspension A is 1:3 to 1:100, preferably 1:5 to 1: 20.
The surfactant may be used in an amount of 0.5% to 5%, preferably 0.1% to 2%, by weight of the total solids in suspension a.
The rare earth compound can be rare earth carbonate (or called rare earth carbonate) and/or rare earth oxide (or called rare earth oxide), and the rare earth carbonate is one or more selected from cerium carbonate, lanthanum carbonate, praseodymium carbonate, neodymium carbonate and samarium carbonate; the rare earth oxide is one or more selected from cerium dioxide, lanthanum oxide, praseodymium oxide, neodymium oxide and samarium oxide. The particle size of the rare earth compound (carbonate/oxide) may be 300 to 2000 mesh, preferably 500 to 1000 mesh.
The particle size of the sulfur may be 300 to 1000 mesh, preferably 500 to 1000 mesh.
The molar ratio of sulfur element in the sulfur to rare earth element in the rare earth compound may be 1.5:1 to 10:1, preferably 2:1 to 5: 1.
Step (2)
The apparatus for performing the spray drying is not particularly limited, and for example, a spray dryer including a centrifugal type, a pressure type, or an air flow type can be used.
The temperature of the spray drying may be set to 80 ℃ to 280 ℃, preferably 120 ℃ to 200 ℃.
Step (3)
The activated carbon is one or more of activated carbon granules, activated carbon powder, carbon blocks or carbon rods, and the like, and preferably the activated carbon granules and the activated carbon powder.
The mass ratio of the activated carbon to the product B is 1:2 to 1:100, preferably 1:5 to 1: 20.
The protective gas can be one or more selected from nitrogen, argon, helium, hydrogen sulfide, carbon disulfide, hydrogen and a nitrogen-hydrogen mixed gas, and is preferably one or more selected from nitrogen, argon and helium.
The firing temperature may be 500 to 1000 ℃, preferably 700 to 900 ℃.
The calcination time may be 30 to 300min, preferably 60 to 150 min.
The heating apparatus for firing is not particularly limited as long as it can provide the desired firing conditions. For example, the heating device may be a box-type electric furnace, a tube furnace, a tunnel kiln, or the like into which gas can be introduced.
In the heating apparatus, the product B and the activated carbon may be placed either together or separately, preferably separately. For example, product B may be placed in an open container with activated carbon placed at the periphery of the container, or product B may be placed on one side with activated carbon placed on the other side, or product B may be placed in the center with activated carbon placed at the periphery of product B, but is not limited thereto. Preferably, product B is placed in an open container, and activated carbon is placed around the perimeter of the container. The open container is not particularly limited, and may be, for example, a crucible. The crucible can be a corundum crucible, a ceramic crucible, a metal crucible, a graphite crucible, a zirconia crucible, a quartz crucible and the like, and is preferably a corundum crucible, a zirconia crucible, a graphite crucible and a metal crucible. There is no particular requirement on the shape of the crucible.
Step (4)
The addition amount of the washing water is such that the mass ratio of the rare earth sulfide compound primary product to water is more than or equal to 1: 1; for example, 1:5, 1:10, 1:20, etc. may be used.
In order to increase the washing effect, any suitable method may be employed without particular limitation, and for example, stirring, shaking, etc. may be employed. The washing time is not particularly limited as long as most of the soluble salts in the primary product of the rare earth sulfide complex can be dissolved out, and may be, for example, 10min or more, for example, 30min or more, 120min or more, or 300min or more.
The drying may be by any suitable method known in the art, such as spray drying, oven drying, air drying, etc., as long as the product meets the product specification requirements. The product specification requirements can be determined according to the requirements for moisture content in the applied field, the storage mode and the like.
Another aspect of the present invention provides a rare earth sulfide complex prepared by the above method. In particular, it has the following general formula: :
RE(2-x/3)NaxS(3-y/2)Fy，
wherein RE is selected from one or more of La, Ce, Pr, Nd and Sm, x and y are molar coefficients of Na ions and F ions, x is more than or equal to 0.0001 and less than or equal to 0.5, preferably more than or equal to 0.003 and less than or equal to 0.30, y is more than or equal to 0.0001 and less than or equal to 0.6, and preferably more than or equal to 0.012 and less than or equal to 0.5.
In a further aspect the present invention provides the use of a rare earth sulphide complex according to the invention as a colourant. Colorants may also be referred to as pigments.
In yet another aspect, the invention provides an article comprising the rare earth sulfide composite of the invention. The article is not particularly limited as long as it contains the rare earth sulfide composite of the present invention. For example, the article may be, but is not limited to, a paint, a cosmetic (e.g., eyebrow pencil, eye shadow, eyeliner, lipstick, color cosmetic, nail polish, foundation, pack, blush, etc.), a door, a window, furniture, an automobile, a bicycle, a cup, a can, a label, a package, a billboard, a balloon, a tire, a pharmaceutical, a box, paper, a plastic product, etc.
The invention has the beneficial effects that: the method comprises the steps of fully contacting solid and liquid raw materials through liquid phase mixing treatment of partial raw materials, and then carrying out spray drying granulation to reduce reaction temperature and control granularity and morphology; and fluorine is introduced into the reaction raw materials to enhance the vividness of the product. The obtained product has a narrow particle size distribution range and a regular appearance without grinding and crushing, and has high vividness and tinctorial strength without fluorine washing. The production process of the rare earth sulfide compound has the advantages of simple operation, low cost and easy realization of industrial production.
The present invention has been described in detail hereinabove, but the above embodiments are merely illustrative in nature and are not intended to limit the present invention. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or the summary or the following examples.
Unless expressly stated otherwise, a numerical range throughout this specification includes any sub-range therein and any numerical value incremented by the smallest sub-unit within a given value. Unless expressly stated otherwise, numerical values throughout this specification represent approximate measures or limitations to the extent that such deviations from the given values, as well as embodiments having approximately the stated values and having the exact values stated, are included. Other than in the operating examples provided at the end of the detailed description, all numbers expressing quantities or conditions of parameters (e.g., quantities or conditions) used in the specification (including the appended claims) are to be understood as being modified in all instances by the term "about" whether or not "about" actually appears before the number. "about" means that the numerical value so stated is allowed to be somewhat imprecise (with some approach to exactness in that value; about or reasonably close to that value; approximately). As used herein, "about" refers to at least variations that can be produced by ordinary methods of measuring and using such parameters, provided that the imprecision provided by "about" is not otherwise understood in the art with this ordinary meaning. For example, "about" can include less than or equal to 10%, less than or equal to 5%, less than or equal to 4%, less than or equal to 3%, less than or equal to 2%, less than or equal to 1%, or less than or equal to 0.5% variation, and in some aspects, less than or equal to 0.1% variation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the embodiments or the prior art will be briefly described with reference to the following drawings.
FIG. 1 is an X-ray powder diffraction pattern of a cerium sulfide composite obtained in example 3 according to the present invention.
FIG. 2 is a scanning electron micrograph of a cerium sulfide composite obtained according to example 3 of the present invention.
FIG. 3 is an X-ray powder diffraction pattern of a praseodymium sulfide compound obtained in example 6 according to the present invention.
FIG. 4 is a scanning electron micrograph of a praseodymium sulfide complex obtained in example 6 of the present invention.
FIG. 5 is a scanning electron micrograph of the cerium sulfide composite obtained in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the technical solutions of the present invention will be provided below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The chemical formulas, molecular weights, purities and sources of the reagents used in the examples and comparative examples are as follows:
Figure BDA0002270039550000051
the X-ray powder diffraction spectrum was measured by an X-ray powder diffractometer model Bruker D8, and the Scanning Electron Microscope (SEM) photograph was measured by a Hitachi S-4800 field emission scanning electron microscope.
Example 1
The cerium sulfide compound is prepared by the following method:
(1) 0.02mol of sodium fluoride, 0.010mol of sodium carbonate and 1.0g of PVP are dissolved in 500ml of deionized water and stirred for 30min to obtain a solution A1.
(2) 0.095mol of 1000 mesh cerium carbonate and 0.4mol of 500 mesh sulfur were added to the solution A1, and the mixture was stirred for 60 minutes to obtain a suspension B1.
(3) Setting the temperature of a spray head of a spray drying system to be 120 ℃, and obtaining the suspension B through the spray drying system to obtain C1.
(4) Placing the crucible C in a corundum crucible A, then placing the crucible in a large crucible B, placing 400g of activated carbon particles around the crucible A, covering, placing in a box-type electric furnace, introducing nitrogen to drive off the air in the furnace cavity, heating to 700 ℃, and carrying out roasting reaction for 150min to obtain a cerium oxysulfide compound primary product;
(5) and placing the obtained primary product in a beaker, adding 500ml of deionized water, stirring for 60min, filtering, and drying for 12h to obtain the cerium sulfide colorant.
The chemical formula of the cerium sulfide compound is Ce1.9Na0.3S2.9F0.2。
Example 2
The cerium sulfide compound is prepared by the following method:
(1) 0.03mol of ammonium fluoride, 0.0015mol of sodium carbonate and 0.8g of PEG are dissolved in 300ml of deionized water and stirred for 120min to obtain a solution A2.
(2) 0.199mol of 500 mesh ceria and 0.40mol of 1000 mesh sulfur were added to the solution A2, and the mixture was stirred for 180 minutes to obtain a suspension B2.
(3) Setting the temperature of a spray head of a spray drying system at 200 ℃, and obtaining the suspension C2 after the suspension passes through the spray drying system.
(4) Placing C2 in a corundum crucible A, then placing the crucible in a large crucible B, placing 600g of activated carbon particles around the crucible A, covering, placing in a box-type electric furnace, introducing argon to drive away the air in the furnace cavity, heating to 900 ℃, and roasting for 60min to obtain a cerium oxysulfide compound initial product;
(5) and placing the obtained primary product in a beaker, adding 300ml of deionized water, stirring for 300min, filtering, and drying for 12h to obtain the cerium sulfide compound.
The chemical formula of the cerium sulfide compound is Ce1.99Na0.03S2.85F0.3。
Example 3
The cerium sulfide compound is prepared by the following method:
(1) 0.01mol of ammonium fluoride, 0.003mol of sodium carbonate and 1.6g of PVP are dissolved in 400ml of deionized water and stirred for 90min to obtain a solution A3.
(2) 0.099mol of 800 mesh cerium carbonate and 1.0mol of 800 mesh sulfur were added to the solution A3, and the mixture was stirred for 90 minutes to obtain a suspension B3.
(3) Setting the temperature of a spray head of a spray drying system to be 150 ℃, and obtaining the suspension B through the spray drying system to obtain C3.
(4) Placing C3 in corundum crucible A, placing crucible in large crucible B, placing 500g of activated carbon powder around crucible A, covering, placing in a tubular electric furnace, introducing helium to drive off air in the furnace cavity, heating to 800 ℃, and roasting for 120min to obtain a cerium sulfide compound primary product;
(5) and placing the obtained primary product in a beaker, adding 500ml of deionized water, stirring for 90min, filtering, and drying for 12h to obtain the cerium sulfide colorant.
The chemical formula of the cerium sulfide compound is Ce1.98Na0.06S2.95F0.1. The X-ray powder diffraction pattern of the cerium sulfide composite is shown in figure 1, wherein the upper figure is the X-ray powder diffraction pattern of the obtained product, and the lower figure is gamma-Ce2S3The standard spectrum, the particle size and the morphology of the X-ray diffraction are shown in figure 2.
Example 4
The cerium sulfide compound is prepared by the following method:
(1) 0.0012mol of ammonium fluoride, 0.0003mol of sodium bicarbonate and 0.6g of sodium dodecyl benzene sulfonate are dissolved in 800ml of deionized water and stirred for 60min to obtain a solution A4.
(2) 0.1999mol of 800 mesh ceria and 0.80mol of 800 mesh sulfur were added to the solution A4, and the mixture was stirred for 60 minutes to obtain a suspension B4.
(3) Setting the temperature of a spray head of a spray drying system to be 150 ℃, and obtaining the suspension B through the spray drying system to obtain C4.
4) Placing C4 in a metal crucible A, then placing the crucible in a large metal crucible B, placing 500g of activated carbon powder around the crucible A, covering, placing in a tunnel kiln, introducing helium to drive away the air in the furnace cavity, heating to 750 ℃, and carrying out roasting reaction for 120min to obtain a cerium sulfide compound primary product;
(5) and placing the obtained primary product in a beaker, adding 800ml of deionized water, stirring for 60min, filtering, and drying for 12h to obtain the cerium sulfide compound.
The chemical formula of the cerium sulfide compound is Ce1.999Na0.003S2.994F0.012。
Example 5
The cerium sulfide compound is prepared by the following method:
(1) 0.05mol of ammonium fluoride, 0.015mol of sodium hydroxide and 1.0g of PVP are dissolved in 500ml of deionized water and stirred for 30min to obtain a solution A5.
(2) 0.095mol of 1000 mesh cerium carbonate and 0.5mol of 800 mesh sulfur were added to the solution A5, and the mixture was stirred for 60 minutes to obtain a suspension B5.
(3) Setting the temperature of a spray head of a spray drying system to be 150 ℃, and obtaining the suspension B through the spray drying system to obtain C5.
(4) Placing C5 in a graphite crucible A, then placing the crucible in a large graphite crucible B, placing 1200g of activated carbon particles around the crucible A, covering, placing in a box-type electric furnace, introducing nitrogen to drive away the air in the furnace cavity, heating to 750 ℃, and carrying out roasting reaction for 120min to obtain a cerium sulfide compound primary product;
(5) and placing the obtained primary product in a beaker, adding 300ml of deionized water, stirring for 60min, filtering, and drying for 12h to obtain the cerium sulfide compound.
The chemical formula of the cerium sulfide compound is Ce1.95Na0.15S2.9F0.5。
Example 6
The praseodymium sulfide compound is prepared by the following method:
(1) 0.01mol of ammonium fluoride, 0.003mol of sodium carbonate and 0.7g of PVP are dissolved in 400ml of deionized water and stirred for 90min to obtain a solution A6.
(2) 0.033mol of 800 mesh praseodymium oxide and 0.8mol of 800 mesh sulfur were added to the solution A6, and stirred for 90min to obtain a suspension B6.
(3) Setting the temperature of a spray head of a spray drying system to be 150 ℃, and obtaining the suspension B through the spray drying system to obtain C6.
(4) Placing C6 in a corundum crucible A, then placing the crucible in a large corundum crucible B, placing 300g of activated carbon particles around the crucible A, covering, placing in a box-type electric furnace, introducing nitrogen to drive away air in a furnace cavity, heating to 800 ℃, and carrying out roasting reaction for 120min to obtain a praseodymium sulfide compound primary product;
(5) and placing the obtained initial product in a beaker, adding 600ml of deionized water, stirring for 90min, filtering, and drying for 12h to obtain the praseodymium sulfide compound.
The chemical formula of the praseodymium sulfide compound is Pr1.98Na0.06S2.95F0.1The X-ray powder diffraction pattern is shown in figure 3, wherein the upper figure is the X-ray powder diffraction pattern of the obtained compound, and the lower figure is gamma-Pr2S3The standard X-ray diffraction pattern, particle size and morphology of (A) are shown in FIG. 4.
Example 7
The samarium sulfide compound is prepared by the following method:
(1) 0.01mol of ammonium fluoride, 0.003mol of sodium carbonate and 0.7g of PVP are dissolved in 400ml of deionized water and stirred for 90min to obtain a solution A7.
(2) 0.099mol of 800-mesh samarium oxide and 0.8mol of 800-mesh sulfur were added to the solution A, and the mixture was stirred for 90 minutes to obtain a suspension B7.
(3) Setting the temperature of a spray head of a spray drying system to be 150 ℃, and obtaining the suspension B through the spray drying system to obtain C7.
(4) Placing C7 in a corundum crucible A, then placing the crucible in a large corundum crucible B, placing 300g of activated carbon particles around the crucible A, covering, placing in a box-type electric furnace, introducing nitrogen to drive away air in a furnace cavity, heating to 800 ℃, and carrying out roasting reaction for 120min to obtain a samarium sulfide compound primary product;
(5) and placing the obtained primary product in a beaker, adding 600ml of deionized water, stirring for 90min, filtering, and drying for 12h to obtain the samarium sulfide compound.
The chemical formula of the samarium sulfide compound is Sm1.98Na0.06S2.95F0.1。
Example 8
The lanthanum sulfide compound is prepared by the following method:
(1) 0.01mol of ammonium fluoride, 0.003mol of sodium carbonate and 0.7g of PVP are dissolved in 400ml of deionized water and stirred for 90min to obtain a solution A8.
(2) 0.099mol of 800 mesh lanthanum oxide and 0.8mol of 800 mesh sulfur were added to the solution A8, and the mixture was stirred for 90min to obtain a suspension B8.
(3) Setting the temperature of a spray head of a spray drying system to be 150 ℃, and obtaining the suspension B through the spray drying system to obtain C8.
(4) Placing C8 in a corundum crucible A, then placing the crucible in a large crucible B, placing 300g of activated carbon granules around the crucible A, covering, placing in a box-type electric furnace, introducing nitrogen to drive away the air in the furnace cavity, heating to 750 ℃, and roasting for reaction for 120min to obtain a lanthanum sulfide compound primary product;
(5) and placing the obtained primary product in a beaker, adding 600ml of deionized water, stirring for 90min, filtering, and drying for 12h to obtain the lanthanum sulfide compound.
The chemical formula of the lanthanum sulfide compound is La1.98Na0.06S2.95F0.1。
Example 9
The neodymium sulfide compound is prepared by the following method:
(1) 0.01mol of ammonium fluoride, 0.003mol of sodium carbonate and 0.7g of PVP are dissolved in 500ml of deionized water and stirred for 90min to obtain a solution A9.
(2) 0.099mol of 800 mesh neodymium oxide and 0.8mol of 800 mesh sulfur were added to the solution A9, and the mixture was stirred for 90 minutes to obtain a suspension B9.
(3) Setting the temperature of a spray head of a spray drying system to be 150 ℃, and obtaining the suspension B through the spray drying system to obtain C9.
(4) Placing C9 in a corundum crucible A, then placing the crucible in a large crucible B, placing 300g of activated carbon granules around the crucible A, covering, placing in a box-type electric furnace, introducing nitrogen to drive away air in a furnace cavity, heating to 850 ℃, roasting and reacting for 120min to obtain a neodymium sulfide compound primary product;
(5) and placing the obtained primary product in a beaker, adding 600ml of deionized water, stirring for 90min, filtering, and drying for 12h to obtain the neodymium sulfide compound.
The chemical formula of the neodymium sulfide compound is Nd1.98Na0.06S2.95F0.1。
Comparative example 1
The cerium sulfide compound is prepared by the following method:
weighing 0.01mol of ammonium fluoride, 0.099mol of 800-mesh cerium carbonate, 0.003mol of 800-mesh sodium carbonate and 0.8mol of 800-mesh sulfur, uniformly mixing in a three-dimensional mixer, loading the mixed raw materials into a corundum crucible A, then placing the corundum crucible A into a large corundum crucible B, placing 300g of activated carbon particles around the crucible A in the crucible B, covering, placing the crucible A into a box-type electric furnace, introducing nitrogen to drive the air in the furnace cavity away, heating to 1000 ℃, and carrying out roasting reaction for 120min to obtain a cerium sulfide colorant primary product. And (3) placing the initial product in a ball mill, crushing in a nitrogen atmosphere, and sieving with a 800-mesh sieve. And (3) placing the crushed product in a beaker, adding 300ml of deionized water, adding 9g of ammonium fluoride while stirring, controlling the temperature at 40 ℃, stirring for 120min, filtering, and drying to obtain the final product.
The chemical formula of the cerium sulfide compound is Ce1.98Na0.06S2.95F0.1The particle size and morphology of the product are shown in FIG. 5.
Comparative example 2
The cerium sulfide compound is prepared by the following method:
weighing 0.099mol of 800-mesh cerium carbonate, 0.003mol of 800-mesh sodium carbonate and 0.8mol of 800-mesh sulfur, uniformly mixing in a three-dimensional mixer, loading the mixed raw materials into a corundum crucible A, then placing the corundum crucible B into a large corundum crucible B, placing 300g of activated carbon particles around the crucible A in the crucible B, covering, placing the crucible B into a box-type electric furnace, introducing nitrogen to drive off the air in the furnace cavity, heating to 1000 ℃, and carrying out roasting reaction for 120min to obtain a cerium sulfide colorant primary product. And (3) placing the initial product in a ball mill, crushing in a nitrogen atmosphere, and sieving with a 800-mesh sieve. And (3) placing the crushed product in a beaker, adding 300ml of deionized water, adding 9g of ammonium fluoride while stirring, controlling the temperature at 40 ℃, stirring for 120min, filtering, and drying to obtain the final product.
The chemical formula of the cerium sulfide compound is Ce1.98Na0.06S3。
Examples of the experiments
The rare earth sulfide complexes obtained in the above examples 1 to 9 and comparative examples 1 and 2 were measured as an index of the pigment.
The index testing method comprises the following steps:
the chromatic value of the product is measured by a Kenimeda CM-5 spectrocolorimeter;
the particle size D50 of the product was determined by a laser particle size analyzer model winner 2000D.
The particle size distribution range of the product is obtained from the S4800 scanning electron microscope photograph.
The tinting strength of the product was measured according to GB-T5211.19-1988.
TABLE 1 index for cerium sulfide complexes
Figure BDA0002270039550000101
TABLE 2 indexes of praseodymium sulfide, samarium sulfide, lanthanum sulfide, and neodymium sulfide compounds
Index (I) Example 6 Example 7 Example 8 Example 9
chroma/L, a, b 88，-39，67 80，20，88 78，2，74 75，-39，35
Particle size range/. mu.m 1 to 5 1 to 5 1 to 5 1 to 5
D50/μm 3.2 3.4 3.5 3.7
As can be seen from the comparison of the indexes of the rare earth sulfide compounds of examples 1 to 5 and comparative examples 1 and 2 as the coloring agents, the rare earth compound of the present invention introduces the element F into the raw materials, and performs liquid phase treatment on part of the raw materials, so that the prepared rare earth sulfide has better uniformity of particle size distribution and regularity of morphology than comparative examples 1 and 2, and the chromatic value and the coloring power of the coloring agent without fluorine washing treatment are higher than those of comparative examples 1 and 2.

Claims (16)

1. A method of preparing a rare earth sulfide complex, comprising the steps of:
(1) uniformly mixing soluble fluoride, a surfactant, a soluble alkaline sodium salt, a rare earth compound and sulfur in water to prepare a suspension A, wherein the molar ratio of fluorine ions to sodium ions in the suspension A is 0.1: 1-15: 1, the molar ratio of fluorine elements in the fluoride to rare earth elements in the rare earth compound is 1: 3.9-1: 2000, the molar ratio of sulfur elements in the sulfur to rare earth elements in the rare earth compound is 1.5: 1-10: 1, and the dosage of the surfactant is 0.5 per thousand-5% of the total solid weight in the suspension A;
(2) spray drying the suspension A to obtain a product B;
(3) roasting the product B in the presence of activated carbon and protective gas to obtain a rare earth sulfide compound primary product;
(4) and washing the primary product of the rare earth sulfide compound with water and drying to obtain a final product.
2. The method of claim 1, wherein step (1) is performed by: firstly, soluble fluoride, a surfactant and soluble alkaline sodium salt are dissolved in water, and then a rare earth compound and sulfur are added to prepare a suspension A.
3. The method of claim 1 or 2, wherein,
the soluble fluoride is one or more selected from ammonium fluoride, sodium fluoride and potassium fluoride;
the surfactant is one or more selected from polyvinylpyrrolidone, stearic acid, polyethylene glycol, polyvinyl alcohol, citric acid, sodium dodecyl benzene sulfonate and OP-10;
the soluble alkaline sodium salt is one or more selected from sodium carbonate, sodium bicarbonate, sodium sulfide and sodium hydroxide;
the rare earth compound is rare earth carbonate and/or rare earth oxide, and the rare earth carbonate is one or more selected from cerium carbonate, lanthanum carbonate, praseodymium carbonate, neodymium carbonate and samarium carbonate; the rare earth oxide is one or more selected from cerium dioxide, lanthanum oxide, praseodymium oxide, neodymium oxide and samarium oxide; and/or
The molar ratio of fluorine ions to sodium ions in the suspension A is 2:3 to 10: 1; the molar ratio of fluorine elements in the fluoride to rare earth elements in the rare earth compound is 1:10 to 1: 200; the dosage of the surfactant is 0.1 to 2 percent of the total solid weight in the suspension A; and/or
The particle size of the rare earth compound is 300-2000 meshes;
the granularity of the sulfur is 300 meshes to 1000 meshes and/or the molar ratio of sulfur element in the sulfur to rare earth element in the rare earth compound is 2:1 to 5: 1.
4. The method of claim 3, wherein,
the soluble fluoride is ammonium fluoride and sodium fluoride; and/or
The surfactant is one or more selected from PVP, PEG and sodium dodecyl benzene sulfonate; and/or
The soluble alkaline sodium salt is one or more selected from sodium carbonate, sodium bicarbonate and sodium hydroxide; and/or
The particle size of the rare earth compound is 500-1000 meshes; and/or
The granularity of the sulfur is 500-1000 meshes.
5. The method according to claim 2, wherein the mass ratio of the insoluble solid to water in the suspension A is 1:3 to 1: 100.
6. The method according to claim 5, wherein the mass ratio of the insoluble solid to water in the suspension A is 1:5 to 1: 20.
7. The method according to claim 1 or 2, wherein, in the step (2), the temperature of the spray drying is set to 80 ℃ to 280 ℃.
8. The method of claim 7, wherein the temperature of the spray drying is set to 120 ℃ to 200 ℃.
9. The method according to claim 1 or 2, wherein, in the step (3),
the active carbon is one or more selected from active carbon granules, active carbon powder, carbon blocks and carbon rods; and/or
The mass ratio of the activated carbon to the product B is 1:2 to 1: 100; and/or
The protective gas is one or more selected from nitrogen, argon, helium, hydrogen sulfide, carbon disulfide, hydrogen and nitrogen-hydrogen mixed gas; and/or
The roasting temperature is 500 to 1000 ℃; and/or
The roasting time is 30-300 min; and/or
In the heating apparatus for calcination, the product B is placed separately from the activated carbon.
10. The method of claim 9, wherein,
the active carbon is active carbon particles and active carbon powder; and/or
The mass ratio of the activated carbon to the product B is 1: 5-1: 20; and/or
The protective gas is one or more selected from nitrogen, argon and helium; and/or
The roasting temperature is 700 to 900 ℃; and/or
The roasting time is 60 to 150 min.
11. The method according to claim 1 or 2, wherein, in the step (4), the washing water is added in an amount such that the mass ratio of the rare earth sulfide complex primary product to water is 1:1 or more.
12. A rare earth sulphide complex produced using the method of any one of claims 1 to 11.
13. The rare earth sulfide complex of claim 12, having the general formula:
RE(2-x/3)NaxS(3-y/2)Fy，
wherein RE is selected from one or more of La, Ce, Pr, Nd and Sm, x and y are molar coefficients of Na ions and F ions, x is more than or equal to 0.0001 and less than or equal to 0.5, and y is more than or equal to 0.0001 and less than or equal to 0.6.
14. The rare earth sulfide complex of claim 13, wherein 0.003 ≦ x ≦ 0.30, and 0.012 ≦ y ≦ 0.5.
15. Use of the rare earth sulfide complex of any one of claims 12-14 as a colorant.
16. An article comprising the rare earth sulfide composite prepared by the method of any one of claims 1-11, or the rare earth sulfide composite of any one of claims 12-14.
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FR2719576B1 (en) * 1994-05-06 1996-07-12 Rhone Poulenc Chimie Composition based on a rare earth sulfide comprising at least one alkaline element, its preparation process and its use as a colored pigment.
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