CN113415818B - Preparation method of rare earth sulfide pigment - Google Patents

Preparation method of rare earth sulfide pigment Download PDF

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CN113415818B
CN113415818B CN202110704065.4A CN202110704065A CN113415818B CN 113415818 B CN113415818 B CN 113415818B CN 202110704065 A CN202110704065 A CN 202110704065A CN 113415818 B CN113415818 B CN 113415818B
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rare earth
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CN113415818A (en
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邱忠贤
廉世勋
杨辛
严晋
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Hunan Normal University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/10—Preparation or treatment, e.g. separation or purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/288—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

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Abstract

The invention discloses a preparation method of rare earth sulfide pigment, which comprises the following preparation steps: zinc sulfide is used as sulfur source and mixed with rare earth oxideAnd carrying out high-temperature solid-phase reaction in a reducing atmosphere to obtain rare earth sulfide powder. Simple preparation process without using H2S、CS2Or elemental sulfur powder and other toxic inflammable and explosive vulcanizing agents, and is one green preparation process of RE sulfide pigment.

Description

Preparation method of rare earth sulfide pigment
Technical Field
The invention belongs to the field of chemical pigment preparation, and particularly relates to a preparation method of a rare earth sulfide pigment.
Background
In a colorful world, pigments of different chroma are required. Compared with toxic pigments containing cadmium, mercury, lead and other elements, the nontoxic light rare earth sulfide represented by cerium sulfide and lanthanum sulfide has the advantages of bright color, no toxicity, strong covering power and the like, can replace organic pigments and inorganic pigments containing toxic heavy metals which are widely used at present, and has wide application markets in the fields of plastics, paints, coatings, ceramics and the like.
Light rare earth sulfide Ln2S3(Ln ═ La, Ce, Pr, Nd, Sm) is called rare earth sulfide, also called sesquisulfide, and has three crystal forms of alpha, beta and gamma. The alpha phase is a low-temperature phase, is stable at 900 ℃ or below and has Gd2S3The crystal structure belongs to the orthorhombic system. The beta phase belongs to a tetragonal system, the stable temperature range is 900-1300 ℃, a trace impurity oxygen atom is required to stabilize the crystal lattice, and the structural general formula can be written as Ln10S14+xO1-x. The gamma phase is a high-temperature phase, is formed by transforming the beta phase at the temperature higher than 1200 ℃, belongs to a cubic crystal system and has Th3P4The crystal structure of the crystal type has 28 cation vacancies (shown by V) in each unit cell, and the structural general formula can be written as 4 (Ln)3-xVxS4) (x is more than or equal to 0 and less than or equal to 1/3). The nontoxic rare earth sulfide pigment is high temperature phase Ln with gamma crystal form2S3. Due to the crystal structure characteristics, the rare earth sulfide pigment has the difficulties of difficult deoxidation, high energy consumption, limited productivity and the like in preparation, and the expansion production, popularization and application of the nontoxic rare earth sulfide pigment are severely restricted.
At present, the preparation methods of rare earth sulfides mainly comprise three types: (I) QiThe solid method. E.g. patent EP95400860.3 et al with H2S or CS2The rare earth metal is a vulcanizing agent, and rare earth metal simple substance, oxide or oxysalt is vulcanized at high temperature. The patent CN98120016.8 adopts a two-stage method, sulfur is placed in a low-temperature region, H is introduced2Reaction with S to give H2S, with surplus H2As carrier gas for CeO in high-temperature region2And (4) carrying out vulcanization treatment. The method uses or generates sulfur-containing toxic gas, so that the synthesis process is not environment-friendly, and needs to be improved. (II) solid fixation method. Sublimed sulfur powder and rare earth metal oxide or oxysalt are mixed for high-temperature reaction. The patent CN201010621447.2 takes Ce compound as raw material, sulphur as vulcanizing agent and active carbon as auxiliary agent to prepare gamma-Ce by high-temperature reaction2S3. Patent CN201710513423.7 discloses a rare earth sulfide colorant and a preparation method thereof, according to the description of the embodiment and related articles (J.Rare Earth, 2021, DOI:10.1016/j.jre.2021.03.012), elemental sulfur powder is mainly used as a sulfur source and reacts with light rare earth metal oxygen-containing compounds at high temperature to prepare rare earth metal sesquisulfide colorant RE with different colors2-2xS3-3x·2y[REPO4](RE ═ Ce, La, Sm). The method uses a large amount of sulfur powder, and sulfur steam has leakage danger at high temperature and has high requirements on reaction equipment. And (III) a liquid phase method. Patent CN200810031536.4 and patent CN201610751094.5 propose respectively that soluble cerium salt and sulfide are used as raw materials, precipitation reaction is carried out in an aqueous solution system to obtain a precursor containing rare earth and sulfur, and gamma-Ce is prepared through high-temperature solid-phase reaction2S3. The method does not use toxic vulcanizing agents such as hydrogen sulfide, carbon disulfide or sulfur vapor and the like, but needs a matched wastewater treatment device, and is not beneficial to expanding production.
Disclosure of Invention
The technical problem to be solved by the present invention is to overcome the disadvantages and drawbacks mentioned in the background art and to provide a method for eliminating H2S、CS2Or elemental sulfur powder and other toxic inflammable and explosive vulcanizing agents.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of rare earth sulfide pigment comprises the following steps:
zinc sulfide is used as a sulfur source and is subjected to high-temperature solid-phase reaction with rare earth oxide in a reducing atmosphere to obtain rare earth sulfide powder.
In the application, zinc sulfide is used as a sulfur source and has double decomposition reaction with rare earth oxide, the reaction is completed in one-time calcination, the steps are simple, and H is not used2S、CS2Or toxic, flammable and explosive vulcanizing agents such as sulfur powder and the like, and is environment-friendly.
With CeO2Preparation of Ce2S3For example, the reaction principle of the present application is as follows: (1)
Figure BDA0003131484740000021
(2)Ce2O3+3ZnS→Ce2S3+3ZnO；(3)
Figure BDA0003131484740000022
the overall reaction equation is (4):
Figure BDA0003131484740000023
Figure BDA0003131484740000024
the reaction needs to be carried out in a reducing atmosphere, and the reducing atmosphere has two functions: firstly, promote CeO2Reduction to Ce2O3(ii) a Secondly, the reaction (3) is carried out to promote the total reaction (4) to be carried out rightwards, thereby generating Ce2S3. If the rare earth metal ion valence in the adopted rare earth compound raw material is +3 valence, the reaction (1) is not involved. O in the product2Carrying out oxidation-reduction reaction with reducing gas to generate oxide gas which escapes from the reaction system; the zinc simple substance in the product is gas at high temperature, and is collected in a tail gas treatment device after escaping from the high temperature region.
Preferably, the source of rare earth oxide comprises one or more of a rare earth oxide, hydroxide, carbonate, hydroxycarbonate, oxalate or sulphate.
Preferably, the raw material ratio of the rare earth oxide to the zinc sulfide is that the mass ratio of rare earth metal to sulfur is 1: 1.5-1: 2.5.
Preferably, the reducing atmosphere consists of H2/N2Mixed gas, H2Mixed gas of/Ar and CO/CO2One or more of a mixed gas, an alkali metal borohydride or hydride, an alkaline earth metal borohydride or hydride is provided.
Preferably, the high-temperature solid-phase reaction temperature is 900-1500 ℃, and the reaction time is 2-10 h.
In the high temperature solid phase reaction of the present application, the rare earth oxide and zinc sulfide form zinc oxide, which is formed by the reaction (3)
Figure BDA0003131484740000025
Figure BDA0003131484740000026
The method has the advantages that the method generates side reaction in reducing atmosphere to generate simple substance zinc and oxygen, the simple substance zinc is gasified at the high temperature of 900 ℃ or above, and finally escapes from a solid phase reaction system in a gaseous form, so that the rare earth sulfide solid can be directly obtained, the product does not need screening and impurity removal, and the process is simple.
Preferably, the high-temperature solid-phase reaction takes alkali metal and/or alkaline earth metal compounds as additives, and the alkali metal and alkaline earth metal compounds comprise one or more of oxides, oxysalts and halides.
The rare earth sulfide has complex crystal structure and three crystal forms of alpha, beta and gamma, wherein the high-temperature phase is gamma-Ln2S3The pigment has bright color and strong tinting strength, and is a substitute of the most potential heavy metal pigment. gamma-Ln2S3Has Th3P4Crystal configuration, writable Ln3- xVxS4(0. ltoreq. x. ltoreq. 1/3) where V is a cation vacancy. Alkali metal and alkaline earth metal compounds as metal additives participate in the reaction, and alkali metal and alkaline earth metal ions enter cation vacancies to promote high-temperature phase gamma-Ln2S3Formation of (c) and stabilization of the crystal lattice.
Under the reducing atmosphere at the temperature higher than 900 ℃, alkali metal and alkaline earth metal ions react with zinc sulfide in the form of metal oxide to generate an intermediate phase, and zinc oxide is generated from the intermediate phase and is decomposed into zinc and oxygen. Alkali metal and alkaline earth metal compounds participate in the reaction, promote the reaction of zinc sulfide to generate rare earth sulfide to be carried out rightwards, and have a catalytic effect. Meanwhile, the product can also be used as a fluxing agent, so that the reaction temperature is reduced, the reaction time is shortened, and a synergistic effect is generated with the main reaction of the invention.
Taking calcium oxide as an example, the chemical reaction equation is CaO + ZnS ═ CaZnOS (intermediate phase) ═ CaS + ZnO, since calcium oxide also reacts with zinc sulfide to generate calcium sulfide, the alkaline earth metal calcium ions therein can enter the cation vacancies of rare earth sulfide again, i.e. alkali metal compounds participate in the reaction, consuming zinc sulfide to generate metal sulfide, and promoting the overall reaction of zinc sulfide to proceed to the right.
Preferably, the addition amount of the alkali metal and/or alkaline earth metal compound is 0.06:1 to 0.5:1 in terms of the amount ratio of the sum of the amounts of the alkali metal and alkaline earth metal substances to the amount of the rare earth metal substance.
Preferably, the molecular formula of the rare earth sulfide is Ln2S3Ln is at least one of La, Ce, Pr, Nd or Sm.
Compared with the prior art, the invention has the beneficial effects that:
(1) this application does not use H2S、CS2Or toxic, flammable and explosive vulcanizing agents such as elemental S and the like, has simple one-step synthesis process flow and low equipment requirement, and is a green preparation method suitable for rare earth sulfide pigment.
(2) Alkali metal and/or alkaline earth metal compound as additive to promote high-temperature phase gamma-Ln2S3The formation of (2) and the stabilization of crystal lattices promote the reaction of zinc sulfide to generate rare earth sulfide to proceed rightwards, and the catalyst has a catalytic effect. Meanwhile, the product can also be used as a fluxing agent, so that the reaction temperature is reduced, the reaction time is shortened, and a synergistic effect is generated with the main reaction of the invention.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is La of example 12S3A product XRD diffraction pattern;
FIG. 2 is Ce of example 42S3And (4) a product XRD diffraction pattern.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
0.01mol of lanthanum carbonate, 0.035mol of zinc sulfide, 0.0006mol of sodium sulfate and 0.008mol of calcium chloride are evenly mixed, H2/N2Reacting for 6h at 1100 ℃ under the atmosphere to obtain yellow La2S3And (3) powder.
FIG. 1 is La of example 12S3And (4) a product XRD diffraction pattern.
Example 2:
0.005mol of lanthanum oxide, 0.02mol of zinc sulfide and 0.001mol of sodium carbonate are uniformly mixed, H2/N2Reacting for 6h at 1200 ℃ under the atmosphere to obtain yellow La2S3And (3) powder.
Example 3:
0 is added.005mol of cerium oxalate, 0.02mol of zinc sulfide and 0.001mol of borax are uniformly mixed, H2Reacting for 8 hours at 1150 ℃ under Ar atmosphere to obtain red Ce2S3And (3) powder.
Example 4:
0.01mol of cerium sulfate, 0.016mol of zinc sulfide, 0.00075mol of sodium thiosulfate and 0.001mol of calcium carbonate are uniformly mixed, and CO/CO2Reacting for 5 hours at 1250 ℃ in atmosphere to obtain red Ce2S3And (3) powder.
FIG. 2 is Ce of example 42S3And (4) a product XRD diffraction pattern.
Example 5:
0.01mol of cerium oxide, 0.018mol of zinc sulfide, 0.001mol of sodium borohydride and 0.001mol of calcium carbonate are uniformly mixed, H2Reacting for 4 hours at 1300 ℃ under Ar atmosphere to obtain red Ce2S3And (3) powder.
Example 6:
uniformly mixing 0.005mol of praseodymium nitrate, 0.011mol of zinc sulfide and 0.0025mol of calcium hydride, and reacting at 1100 ℃ for 4 hours in argon atmosphere to obtain green Pr2S3And (3) powder.
Example 7:
uniformly mixing 0.005mol of neodymium oxide, 0.024mol of zinc sulfide, 0.000325mol of sodium carbonate and 0.0015mol of calcium carbonate, and mixing with CO/CO2Reacting for 4 hours at 1300 ℃ in the atmosphere to obtain green Nd2S3And (3) powder.
Example 8:
0.005mol of samarium oxide, 0.025mol of zinc sulfide and 0.004mol of calcium bromide are uniformly mixed, H2Reacting for 6 hours at 950 ℃ under Ar atmosphere to obtain yellow Sm2S3And (3) powder.

Claims (4)

1. The preparation method of the rare earth sulfide pigment is characterized by comprising the following preparation steps:
zinc sulfide is used as a sulfur source to perform high-temperature solid-phase reaction with rare earth oxide in a reducing atmosphere to obtain rare earth sulfide powder, wherein the molecular formula of the rare earth sulfide is Ln2S3Ln comprises at least one of La, Ce, Pr, Nd or Sm, rare earth oxideThe raw material ratio of the rare earth metal to the zinc sulfide is 1: 1.5-1: 2.5 calculated by the mass ratio of the rare earth metal to the sulfur; the high-temperature solid phase reaction takes alkali metal and/or alkaline earth metal compounds as additives, the alkali metal and/or alkaline earth metal compounds comprise one or more of oxide, oxysalt and halide, the reaction temperature is 900-1500 ℃, and the reaction time is 2-12 h.
2. The method of claim 1, wherein the reducing atmosphere is formed from H2/N2Mixed gas, H2Mixed gas of/Ar and CO/CO2One or more of a mixed gas, an alkali metal borohydride or hydride, an alkaline earth metal borohydride or hydride is provided.
3. The method according to claim 1, wherein the alkali metal and/or alkaline earth metal compound is added in such an amount that the ratio of the sum of the amounts of the alkali metal and alkaline earth metal substances to the amount of the rare earth metal substance is 0.06:1 to 0.5: 1.
4. The method of claim 1, wherein the source of rare earth oxide comprises one or more of a rare earth oxide, a rare earth hydroxide, a rare earth carbonate, a rare earth oxalate, or a rare earth sulfate.
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CN1086493A (en) * 1993-09-16 1994-05-11 冶金工业部包头稀土研究院 A kind of preparation method of cerium trisulfide
CN101104746A (en) * 2007-08-07 2008-01-16 中国科学院长春应用化学研究所 Red rare-earth lanthanum cerium sulfide dye and preparation method thereof
CN101255285A (en) * 2008-03-28 2008-09-03 内蒙古科技大学 Method for preparing rare earth sulfide pigment
CN103949634B (en) * 2014-04-16 2017-01-04 包头市宏博科技有限责任公司 A kind of preparation method of rare-earth sulfide

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