DE2126190A1 - Process for the production of sulphides and oxysulphides of lanthanoids and yttrium as well as solid solutions of these sulphides and oxysulphides - Google Patents

Description

Process for the production of sulphides and oxysulphides of lanthanides and yttrium and of solid solutions of these sulphides and oxysulphides

The invention relates to a method for obtaining the sulfides and oxysulfides of at least one lanthanoid and of yttrium and of solid solutions of these sulfides or Oxysulfides.

The sulfides are simple sulfides or mixed sulfides. The former are defined connections genes that contain sulfur and a single metallic element. Mixed sulfides are defined compounds to understand which of sulfur and at least two different ones metallic elements. Oxysulfides are defined compounds, which are made up of sulfur, Compound oxygen and one or more metallic elements. Solid solutions are made up of homogeneous phases formed, which sulfur and optionally oxygen as well as several metallic elements with different proportions contain.

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The sulfur-containing phases defined above have at least one lanthanoid Ln, i. H. an element with an ordinal number between 57 and 71 »or yttrium with of atomic number 39 · You are ordinarily made by reactions accustomed, which are carried out at temperatures above 1000 ° C.

The known manufacturing processes are disadvantageous in four ways. For example, the reaction temperatures are very high and the duration of the reactions is considerable, because the existing phases are solid, crystallized, refractory and therefore not very reactive. Responsive Atmospheres are impermissible and should be avoided. They are associated with the risk of contamination of the products. It is therefore necessary to work in a vacuum or in an atmosphere of pure argon. It is not possible to complete it To carry out sulphurisation at low temperature and to gain certain metastable phases, which exist only at low temperature. The phases obtained are always well crystallized, which is related to the Research into their structure and the exploitation of certain physical ones Properties is advantageous, but is disadvantageous when such phases are used as the starting material for new chemical reactions, to be used as catalysts or for those purposes in which certain of their physical properties are to be used, which require a very fine grain.

The object of the invention is accordingly to provide a method to convey the extraction of sulfur compounds of the lanthanides, which is easier and easier to carry out and is therefore more economical. Furthermore, new such products are to be created.

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-: "It has been found that amorphous carbonates are primarily Line for the production of simple and mixed sulphides and oxysulphides of lanthanides as well as solid solutions such phases should be selected by sulfurization at low temperature. It is essential that that an amorphous and therefore very reactive phase is used because the sulfurization crystallizes Oxycarbonates are at least as difficult as those that are crystallized Oxides, which lead to sulfides only at temperatures above 1200 ° C.

The inventive method of the initially specified kind is characterized in that at a temperature of at most 1000 ^Q C, an amorphous Oxykarbonat at least one lanthanide or yttrium with gaseous hydrogen sulfide * dry, optionally admixed with hydrogen, or is treated with gaseous, moist hydrogen sulfide.

For the extraction of the simple sulphides or oxysulphides or of solid solutions - these simple sulfides or oxysulfides an amorphous oxycarbonate is used according to the invention, which only contains lanthanoids or yttrium. For the production of mixed sulfides or oxysulfides at least of a lanthanide, including yttrium, with aluminum, Gallium, manganese or vanadium or of solid solutions of these mixed sulphides or oxysulphides is used according to the invention amorphous carbonate is used, which contains the respective elements in the proportions desired in the finished product. For the production of mixed sulfides of a lanthanide or According to the invention, yttrium and calcium, strontium, barium, lead, cadmium, manganese or zinc are the corresponding

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amorphous mixed oxycarbonate with an Ln / M atom number ratio of 2 treated with pure and dry hydrogen sulfide at a temperature below 800 ° G (Ln - xanthanoid or yttrium). For the production of solid solutions of the sulphides of europium and of calcium, strontium, barium, According to the invention, lead, cadmium, zinc or manganese is the corresponding amorphous misoxy carbonate with an Eu / M atom number ratio of (1-x) / x with pure and dry hydrogen sulfide at a temperature between 600 and 700 C. treated (M = calcium, strontium, barium, lead, cadmium, zinc or manganese; χ »lying between 0 and 1).

According to the invention, the following new ones can also be used Manufacture fabrics in the manner specified in claims to 13:

1. Simple ot-lanthanum sulfide of the formula

2. Mixed sulfides of the formula Ln ^ M ^, ^ ₇ S.,., Where M = Mn and Ln = La, Pr or Nd or * M = Ga and Ln = Dy or M = Y and Ln = La, d. H,

3. Solid solutions of simple sulfides of the formula

Ln ^l _o Ln ' ¹ S \ ,. where χ is between 0 and 2 and Ln ¹ and Ln ¹ '= La, Pr or ITdj

4. Solid, solutions of simple sulfides of the formula Ln ¹ O ^ _x Ln ¹¹ S ₇ , in ti or # form, where χ is between 0 and 2 and Ln ¹ and Ln ' ¹ = La, Pr, Ifd, Sm, Gd or Dyi

5 «Solid solutions of simple oxysulphides of the

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Formula ^ ¹ ? «^ '^ ⁰ ? ^' Where χ is between O and 2 and Ln ¹ and Ln ¹ '= La, Pr, Nd, Sm, Gd, Dy, Ho, Er, Tb or Lu;

6. Solid solutions of mixed sulfides of the formula ^ 'ix ^' Ve ^(Mt 1-x ' ^M " _X '> 3.33 ^S W where χ and x 'are each between 0 and 1 and Ln ¹ and Ln ¹ ' = La , Pr, ITd or Sm, also M ¹ and M ¹ '= Al, Ga, Mn or Y;

7 · mixed sulfide of the formula SrDy ₂ S ₄ or BaSm ₂ S ₄ or PbNd ₂ S ₄ or PbGd ₃ S ₄ or PbSm ₂ S ₄ ;

8. Solid solutions of sulfides of the formula (PbiEu ,,) S and (Cd Eu ^ _V ) S, where χ is between 0 and 1;

The sulphuring of the amorphous oxycarbonates can be carried out with very different temperatures, reaction times and compositions of the gas phase are carried out, so that different Products. Depending on the chosen conditions, one obtains:

I. Simple lanthanide sulfides;

■ II. Lanthanide oxysulfides;

III. Mixed sulfides;

IV. Solid solutions of sulfides and oxysulfides.

I, Simple Lanthanide Sulphides

The amorphous oxy-carbonates LapOpCO - ,,, Pr ₀ O ₀ OO ^ and Nd ₀ O ₀ GO, lead by treatment with pure and dry

c-c-J

Scüwefelwaniiersboff at up to 550 to 650 0 increasing

ι a \ i -I- I. : ■ - i

Temperature at which they are kept for 2 hours the corresponding polysulfides LapS ^, PrpS ^

Those treated with pure and dry hydrogen sulphide at a temperature which rises up to 100 ° C and amorphous carbonates held on the same for 5 h lead with respect to the lanthanoids La, Pr, Nd, Sm, Gd, Dy to the # -And and a half sulfides of lOrmel

Those with a dry hydrogen sulfide / hydrogen gas mixture with a hydrogen sulfide / hydrogen volume ratio of 1 at up to 600 to 700 ° C increasing temperature treated amorphous carbonates lead to the same lanthanoids La, Pr, Nd, Sm, Gd, Dy to the QC one-and-a-half sulfides of the formula

The amorphous europium oxycarbonate E ^ C ^ CO ^ leads by treatment with pure and dry hydrogen sulphide at a temperature increasing to 350 to 450 ° C, on which the oxycarbonate is held for 2 hours, to phase Eu ^ S ^. However, this sulphuration will lead if the temperature is increased to over 550 ° C, to phase EuS, and a mixture of these two phases is obtained when working at a temperature between 450 and 550 ° C.

II. Lanthanide oxysulfides

The amorphous oxycarbonates LnpOpCO- lead by treatment with. a hydrogen sulfide / water gas mixture with a water content of about 6% by volume over a period of .iuif / a 10 h and at temperatures which grow with the atomic number of the respective Laiith-anoid and a-wipe 500

ι t'i 9 j : ί -'ihi η

for lanthanum and 800 C for ytterbium and lutetium are, with regard to all lanthanides with the exception of europium and cerium, to the oxysulfides Ln ₂ OpS with a mixed structure.

III. Mixed sulfides

For the production of those sulfides which contain a lanthanoid Ln and another trivalent metal M, such as Al, Ga, Mn or V, where the Ln / M atomic ratio is 1, amorphous I ¹ I-carbonates with an Ln / M -Ratio = treated with pure and dry hydrogen sulfide for 15 hours at temperatures between 700 and 900 ° C. The mixed sulfides obtained crystallize in the hexagonal system. Their structures are dealt with in the following publications:

DAHUTA de St GINIEZ, P. LARUELLE, J. KLAHAUT Comptes rendus Ac. Sc. 267, 1968, p. 1029; M. PATRIE, M. GUITTARD - Comptes rendus Acad. Sc. 268, 1969-, P * 1136.

These compounds, to which the formula Ln ^ -M-, x * ⁰ ^ (M = Al (III), Ga (III)) is ascribed, can be easily prepared using the process according to the invention.

To produce the mixed sulfides of formula _2, which contain a lanthanoid Ln (from lanthanum to dysprosium inclusive) and a divalent metal, in particular calcium, strontium, barium, lead, cadmium, manganese or zinc, amorphous mixed oxycarbonates with an Ln / M ratio equal to 2 with pure and dry hydrogen sulfide for 5 to 8 h at temperatures below 800 ° G

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act.

The compounds obtained have a cubic structure of the Th ₅ P ^ type.

IV. Solid solutions of sulfides and oxysulfides

Solid solutions of the type Ln ' _o "Ln" Sy, (with Ln ¹ and Ln ¹ ', La, Pr or Kd) or of the type Ln ¹ 2 ^ _x IaI ¹ ' _χ ^ ζ ^ ^η Ok- or JfclOrm with Ln ¹ and Ln ¹¹ = La, Pr, Nd, Sm, Gd or Dy).

The solid solution of the formula (M Eu _x .) S _$ where M represents a divalent Ga, Sr, Ba, Pb, Cd, Zn or Mn cation and χ is between 0 and 1. Those of these solid solutions in which M represents lead or cadmium are new substances.

The solid solutions of the oxysulfides can also be obtained by sulfurizing the mixed oxycarbonates with a hydrogen sulfide / water mixture, ie phases of the type Ln ^l ₂ _ _x Ln " _x O ₂ S (with Ln ¹ and Ln" - La, Pr, Nd, Sm, Gd, Dy i Ho, Er, Lu or Tb).

Finally, sulfurization using pure and dry hydrogen sulfide from oxycarbonates,

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which contain several lanthanoids and several trivalent metals, for example Al and Ga, solid solutions of mixed sulfides of the general formula (Ln ¹ ,, Ln ¹ ') ₍ - (M ¹ ,,, M "ι)," S _x , ^ obtained (with Ln ¹ and Ln ¹¹ = La, Pr, Nd, Sm and M ¹ as well as M "» Al, Ga, Mn, V).

As with all reactions between a gaseous and a solid phase, the rate of sulfurization depends of the oxycarbonates depend on the device used to carry them out. Various facilities can be used will. For example, a device can be used in which the starting material is passed through the sulfurizing gas mixture is coated. As a rule, only small amounts of substance can be treated in such a facility will. In another facility, the raw material is completely permeated by the sulfurization gas mixture, where 'fixed or fluidized bed is used.

In "the preparation of the amorphous carbonate, a simple or mixed complex can be prepared first which contains various lanthanoids with different proportions selected according to those are what you want in the end product. The most suitable complexes are the citrates, but others can also be used. Then a pyrolysis in air or COo atmosphere carried out with the complex obtained in this way, under such temperature and time conditions, that an X-ray amorphous oxycarbonate is obtained.

When obtaining an amorphous mixed oxycarbonate, which is a lanthanoid Ln and a metal M, for example aluminum, gallium, manganese or vanadium, or a metal

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M ¹ , for example calcium, strontium, barium, lead, cadmium, manganese or zinc, a mixed citrate is first produced which contains the metals Ln and M or M ¹ in the desired ratio, for example an Ln / M ratio of 1 or has an Ln / M ¹ ratio of 2. This is done in a known manner, for example as described in French Patent No. 1 ^ MA- 155. The mixed citrates are then pyrolyzed, so that an amorphous mixed oxycarbonate is obtained. This is then treated according to the method according to the invention.

In the manner according to the invention produce certain known sulfurized substances as well as also win new products.

The following examples serve to illustrate the invention.

example 1

This example relates to lanthanum polysulphide (La2S The citrate LaCgH ₁ -On, 3 H ^ O is first produced. For this purpose, commercial lanthanum oxide ^ (99 »9%) is dissolved in 1 N nitric acid in the heat. The nitrate obtained is subjected to several recrystallizations. It is then dissolved in water and an ammonium citrate solution neutralized by ammonia is added in such an amount that one mole of citrate is present for each lanthanum atom so that LaC ₆ H ₅ O ₇ , 3 H ₂ O is obtained.

1 0 9 8 S 1/1 6 1 0

Then the hydrated citrate is pyrolyzed in air by raising the temperature is gradually increased to 15O ° C / h down to 65O ⁰ C. The amorphous oxycarbonate is obtained from pyrolysis

This is then subjected to sulfurization. Thereby a stream becomes pure and. dry hydrogen sulfide H ₂ S passed over the oxycarbonate, which is applied as a thin layer on a flat boat, the temperature being slowly increased at 150 ° 0 / h up to 550 ° C.

After cooling the tube containing the boat in air while maintaining the flow of hydrogen sulfide, a yellow-brown powder of cubic polysulfide La ₂ S. with a sieve mesh parameter of 8.20 Å is obtained is.

Example 2

This example relates to Praseodymsulfid Pr ₂ S .. The citrate PRCV _H-1 -O _7, 3 H ₂ O is produced as described in Example _i. 1 The citrate is then dissolved in a solution of neutral ammonium citrate. This solution is evaporated so that a solid which is amorphous with respect to X-rays is obtained, which is more or less hydrated depending on the conditions observed during drying and corresponds to _{the formula (NH ^), (PrGgH 1} -Or ₇ ) XH _{2 O.} This lanthanide / ammonium mixed citrate. is in the Hegel to be preferred to the simple citrates, since its pyrolysis leads to the oxycarbonates more regularly *

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The pyrolysis of the specified citrate is carried out by increasing the temperature at 150 ° C./h up to 560 ° C. and leads to the amorphous oxycarbonate Pr ₂ O ₂ CO; ,, which is then _{subjected to sulfurization with pure and dry H 2} S, and although under the conditions given in Example 1, but the temperature is increased to 640.degree.

After the tube containing the boat has cooled down in air while maintaining the hydrogen sulfide atmosphere a brown powder of polysulphide Pr0S4 with a sieve mesh parameter of 8.08 Å is obtained Analysis is given in the table listed in Example 3

Example 5

This example concerns neodymium polysulfide Nd ₂ S ^. The procedure described in Example 1 is used to produce Nd ₂ O ₂ CO. After sulfurization of the same with pure and dry hydrogen sulfide at temperatures of up to 650 ° C., a brown polysulfide powder ₂ with a sieve mesh parameter of 8.04 A, the analysis of which is given in the table below, is kept in the boat.

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Example I. La Example II Pr Example III Nd Elementary
analysis S. 68.50 S. 68.80 S. 69.35 Weight%
(found) 31.20 68.42 31.15 68.78 30.50 69.23 Weight %
(theore
table) 31.58 31.27 30.77

Example 4

This example concerns the europium sulfides EuS and ^ S ^. The procedure is as in Example 2 with respect to Pr ^ OpCO-, described to the amorphous oxycarbonate to deliver.

The amorphous oxycarbonate Eu ^ OpCO, after treatment with pure and dry hydrogen sulphide at increasing temperature, staying for two hours at a temperature of 420 ⁰ C and cooling in a hydrogen sulphide atmosphere leads to a black-reddish sulphide powder Eu, S ^ with a sieve mesh parameter of 8.537 A (cubic structure of the type Th ^ P ^,), the analysis of which is given in the table below.

The same amorphous Oxykarbonat Eu ^ O ^ CO-, leading to treatment by pure and dry hydrogen sulfide at ⁰ to 700 C at a temperature increasing blackening

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zen sulfide powder EuS with a sieve mesh parameter of
5.969 A (cubic structure of the NaCl type), its analysis
is given in the table below.

Eu ₃ S ₄ S. Eu EuS S. Eu Elementary
analysis 21.50 78.37 17.30 81.80 Weight %
(found) 21.92 78.08 17.42 82.58. Weight %
(theoretically)

Example 5

This example concerns the OC phase of La ₂ S ^. The amorphous oxycarbonate La ₂ O ₂ CO is sulfurized with a temperature rising to 600 ° C for 3 h, with a
dry HpS / Hp gas mixture (Hp / HpS volume ratio = 1). One obtains the previously unknown OC phase La ₂ S- ,, which is isotypically the OC- ^ aseo · ^ η ₂ ^ χ, which are known for praseodymium, neodymium, samarium, gadolinium and dysprosium.

The latter can easily be achieved by sulfurizing the corresponding amorphous oxycarbonates using an HpS / Hp gas mixture obtained, whereby the temperature during the sulfurization up to 600 ° C (Pr; Nd) or 700 ° C (Sm) or » 750 ° C (Gd; Dy) is increased.

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Example 6

This example "relates to gallium / dysprosium mixed sulfide DygGa ^ ^ S ^. A hydrated mixed citrate DyGa (CgH ₁ -Or ₇ ^ ⁿ ^ O is prepared by adding an ammoniacal solution of equidistant quantities of the citrates Dy (CgHnOn) and Ga (C ^ HCON) is evaporated. the Mischzitrat is subjected to pyrolysis by raising the temperature gradually to 150 ° 0 / h is increased up to 400 ⁰ C. This shows an amorphous Oxykarbonat.

This is sulfurized with pure and dry hydrogen sulphide, wherein the temperature is up to 1000 ⁰ C increased. The new product obtained in this way is the sought-after mixed sulfide, which crystallizes in a hexagonal lattice that is isotypic to the known thiogallates and has the following parameters:

ο ο, a = 9.68 Ai c- 6.08 Aj c / a «0.628.

Example 7

This example concerns the thiomanganites of the lanthanum, Praseodymium and neodymium, also lanthanum thiovanadite. By sulfurization of the mixed oxycarbonates, which by Pyrolysis of the mixed citrates are obtained under the conditions analogous to the conditions given in Example 6, one wins the new compounds, the parameters of which are given in the following table.

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Example 8

link O
a (A) c (A) c / a La ₆ Mn ₅₁₃₃ S ₁₄ 10.248 6.05 0.590 ^Pr 6 ^Mn 3.33 ^S 14 10.00
9.91 6.04
6.04 0.604
0.609 ^La 6 ^V 3.33 ^S 14 10.196 6.02 0.591

This example concerns solid solutions of sulfides and oxysulfides of lanthanum and praseodymium.The production of a mixed citrate of two lanthanides, for example (NH ^), (La _Q gPr ₀ ^ CgH ₁ -O ₇ ) χ HpO, can be carried out starting from simple citrates, and although analogous to the manner indicated in Example 2.

The pyrolysis of the mixed citrate at temperatures up to

at 500 ° C leads to the amorphous oxycarbonate La ,, 0 ^ ¹ O 8 ^ 2 ^ V

This oxycarbonate leads under after sulfurization
the conditions given in Example 1, but with a temperature increase up to 600 ° C, and after cooling to a brown powder, which is the solid solution of the polysulfides of lanthanum and praseodymium, namely La ^ ρ ^Pr 0.8 ^S 4 ·

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The same oxycarbonate is subjected to sulphidation with pure and dry hydrogen sulphide, the temperature gradually increasing at 150 C / h. is increased up to about 1000 ° C. After cooling, a beige powder is obtained which is the solid solution of the f-one-and-a-half sulfides of lanthanum and praseodymium, namely La ,, 0 ^ ¹ O 8 ^ V

The same oxycarbonate is also obtained after sulfurization under the conditions given in Example 5 and after cooling a brown powder, which is the solid solution of the Ot-one-and-a-half sulfides of lanthanum and praseodymium represents, namely La ,, o ^ o 8 ^ 3 *

The same Oxykarbonat is subjected to a sulfurization with moist hydrogen sulfide (6 vol% of water vapor), the temperature being with I5O ⁰ C / up to about 500 ° C increases h and 7 k maintained at this 500 ° G long. After cooling, a yellow powder * is obtained which is the solid solution of the oxysulfides of lanthanum and praseodymium, namely La ^, p ^ ^r O 8 ^ 2 ^ ·

Example 9

This example relates to the solid solution of mixed sulfides of the formula (La _QQ Pr _{0 2} ) g CA- ¹ Q 5 ^Ga o 5) 3 33 ^S 14 ^{# I) by} evaporation of an ammoniacal solution of the simple citrates of lanthanum, praseodymium, aluminum and gallium which are used in suitable aliquots, one obtains a hydrated Mischzitrat corresponding to the formula laq g ^ Q ^A1 O, ^Ga 5 O 5 ⁽⁰ ° 6 5 7 ^Η> 2

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This mixed citrate, which is pyrolyzed at temperatures up to 400 ° C., leads to an amorphous mixed oxycarbonate. This is sulfurized with pure and dry HpS, the temperature being increased at 150 ° C / h up to 700 ° C. After cooling in a hydrogen sulfide atmosphere, a hexagonal solid solution of mixed sulfides results, which the
"Crystallographic" formula (La _Q gPiQ ₂ ) g (A1 _Q c & a ₀ , -) -x 33 S ^.

Example 10

This example relates to the production of mixed sulfides of the formula MLn ₂ S ^, where M is Ca, Sr, Ba or Pb, and Ln is a lanthanoid, namely La, Pr, Nd, Sm,
Gd or Dy. First, a citrate of the formula M ₅ . (CgH ₁ -Or;) η H ^ O produced by adding the chloride MCl _{2 to} a diammonium citrate solution, neutralized by ammonia. Warming it to around 40 ° C gives an ample
Precipitation. The citrate obtained is filtered, washed
and dried. It corresponds to one of the formulas Ca ^ (CgH ^ On) 4 H ₂ Oj Sr ₅ (C ₆ H ₅ O ₇ ) ₂ , 6 H ₂ Oj Ba ^ C ^ O ^, 7 H ₂ Oj Pb ₅ (C ₆ H ₅
O _{7) 2} 5 H ₂ O.

In addition, the lanthanum oxide citrate Ln (CgHc-Or ₇ ), η
HpO prepared in the manner indicated in Example 1 for the Lan thanzitrrat La (CgHj-Or ₇ ), 3 H ₂ O. Then the citrate of the divalent metal is dissolved with the lanthanoid citrate in an ammoniacal solution, in such amounts that an Ln / M ratio of 2 results.
This solution is evaporated to give the solid mixed citrate
obtain. The latter is slow with I50 ⁰ C / h except for one
Temperature of 600 ° C (Ca) or 6J0 ° C (Sr) or 650 ° C (Ba

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and Pb) heated.

This pyrolysis leads to a mixed oxycarbonate which is amorphous to X-rays and is then treated with hydrogen sulfide for 5 to 8 hours at temperatures between 700 and 800 ° C, so that the mixed sulfide MLn ₂ S ₄ is obtained, as the chemical analysis shows. This mixed sulfide has a cubic lattice of the ThJP ₄ type, the sieve mesh parameters of which, depending on the alkaline earth metal and lanthanoid used, are given in angstroms in the table below.

Approx Ln: La Pr Nd Sm 8th Gd I. > y Sr 8th M: Ba 8.685 8,580 8.530 8.475 , 425 8th, 370 Pb 8,790 8,680 8,650 8,595 8th , 550 8th, 495 8,920 8.820 8,790 8.720 - 8.718 8.615 8,600 8.520 , 485 8th, 440

Of these mixed sulfides, the compounds SrDy ₂ S ₄ , BaSm ₂ S ₄ , PbNd ₂ S ₄ , PbSm ₅ S ₄ and PbGd ₃ S ₄ have not yet become known.

Example 11

This example concerns solid solutions of sulfides of lead and europium of the formula (Pb Eu *) S, where χ is between 0 and 1.

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There are mixed oxycarbonates of lead and europium prepared in the manner indicated in Example 10, which have different (1-x) / x ratios. They are treated with pure and dry hydrogen sulfide for 8 h

treated at about 600 C for a long time.

So far unknown cubic solid solutions (Pb _x Eu ^ _x ) S of the NaCl type are obtained, the parameters of which are a in Angstrom in the following table as a function of the value χ
is specified.

X 1 0.66 0.50 0.33 0 a 5.920 5,950 5,958 5.961 5,970

Example 12

This example concerns the solid solution of the sulphide of cadmium and europium (Cd ^ c ^ a _n c) S.

The cadmium citrate can be converted into diammonium citrate, neutralized by ammonia, with cadmium sulfate
Solution and at about 400 ° C.

The mixed oxycarbonates are obtained from the mixed citrates in the manner indicated in Example 11 and are sulfurized in order to obtain the cubic solid solution (Cd _Q cEuq c) S with a parameter a >> 5.905 A.

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There are many uses for the invention sulfur-containing products, for example they are used in the construction of refractory containers, such as crucibles, as catalysts and as luminescent materials the latter, for example, on television screens Find use.

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Claims (12)

- 22 claims. 2 7 2 6 7 9 (XvTl ^ 1. Process for the production of sulphides or oxosulphides at least one lanthanide, including yttrium, or solid solutions of these sulfides or oxysulfides, characterized in that an amorphous oxycarbonate of these elements at a temperature of at most 1000 ° C with gaseous, dry hydrogen sulfide, optionally mixed with hydrogen, or with gaseous, moist hydrogen sulfide is treated. 2. The method according to claim 1 for obtaining the simple sulfides or oxysulfides or solid solutions of these simple sulfides or oxysulfides, characterized in that that an amorphous oxycarbonate is used which only contains lanthanoids or yttrium. 3. The method according to claim 1 for obtaining the mixed sulfides or oxysulfides of at least one lanthanide, including Yttrium, with aluminum, gallium, manganese or vanadium or from solid solutions of these mixed sulfides or · Oxysulfide, characterized in that an amorphous oxycarbonate is used, which is the respective Contains elements with the proportions desired in the finished product 4. The method according to claim 1 for the production of miseh sulfides of a lanthanide or yttrium and of calcium, strontium, barium, lead, cadmium, manganese or zinc, characterized in that that at a temperature below 800 ° C the corresponding amorphous mixed oxycarbonate with an Ln / M atom number ratio treated by 2 with pure and dry hydrogen sulfide; becomes (Ln = lanthanoid or yttrium). ) ij a 8 51/1 ß 1 ο 5. The method according to claim 1 for obtaining solid solutions the sulphides of europium and of calcium, strontium, barium, lead, cadmium, zinc or manganese, characterized in that that at a temperature between 600 and 700 ° C the corresponding amorphous mixed oxycarbonate with an Eu / M atom number ratio of (1-x) / x is treated with pure and dry hydrogen sulfide (M = calcium, strontium, Barium, lead, cadmium, zinc or manganese; χ = between 0 and 1 lying). 6. The method according to claim 2 for the production of QC-lanthanum sulfide of the formula La-S ^, characterized in that the amorphous oxycarbonate La ₂ OoCO- is treated with gaseous, dry, hydrogen sulfide at a temperature increasing to 600 ° C . 7. The method according to claim 3 for obtaining mixed sulfides of the formula Ln ^ -M _x "S ^, where M = Mn and Ln = La, Pr or Nd or M = Ga and Ln = Dy or M = V and Ln = La, characterized in that the corresponding amorphous mixed oxycarbonate is treated with pure and dry hydrogen sulfide at a temperature rising to 1000 ° C. 8. The method according to claim 2 for obtaining solid solutions of simple sulfides of the formula Ln ¹ 2 ^ _x Ln ¹ ' _x ^, where χ is between 0 and 2 and Ln ¹ and Ln ¹ ' = La, Pr or Nd, characterized in, that the corresponding amorphous carbonate is treated with pure and dry hydrogen sulfide at a temperature rising to 600 ° C. 9 · The method according to claim 2 for obtaining solid solutions of simple sulfides of the formula Ln ¹ O ^ _x Ln ¹¹ S ^ in Ot or i form, where χ is between O and 2 and Ln ¹ and 10 9 8 5 1/16 10 . - 24 - Ln ¹ 'β La, Pr, ITd, Sm, Gd or Dy, characterized in that the corresponding amorphous oxycarbonate is mixed with gaseous and dry hydrogen sulphide at Ms increasing to 600 ° C , or with pure, dry hydrogen sulphide at is treated up to 1000 ° C increasing temperature. 10. The method according to claim 2 for obtaining solid solutions of simple oxysulfides of the formula Ln ' n- ^ fi ¹¹ ''X ⁰ P ^ * where χ is between 0 and 2 and Ln ¹ and Ln ¹ ' - La, Pr, Nd, Sm, Gd, Dy, Ho, Er, Yb or Lu, characterized in that the corresponding amorphous oxycarbonate is treated with gaseous hydrogen sulfide mixed with water vapor at a temperature increasing to about 500 ° ö. 11. The method according to claim 3 for obtaining solid solutions of mixed sulfides of the formula (Ln ¹ ^ _x Ln * * _χ ) - ₆ (^ 'ΐ-χ «H ^M _j3i ^ S ^, where χ and x' each between 0 and 1 and Ln 'and Ln ¹ ' = La, Pr, lid or Sm, also M ¹ and M ¹ '= Al, Ga, Mh or V, characterized in that the corresponding amorphous mixed oxycarbonate with pure and dry hydrogen sulfide at up to 700 ° C rising temperature is treated * 12. The method according to claim 4 for the production of mixed sulfides of the formula MLn ^ S ^, where Ln = Ud, Gd or Sm and M = Pb or Ln ■ "Sm and M = Ba or Ln = Dy and M" -Sr, thereby "characterized in that at a temperature between 700 and 800 ° C the corresponding amorphous mixed oxycarbonate treated with pure and dry hydrogen sulfide. 13 · Method according to claim 5 for obtaining the solid solutions of sulfides of the formula M Eu ,, S, where M lead or 1 09 8 5 1/16 1 0 Means cadmium and χ is between 0 and 1, thereby characterized in that at a temperature of about 600 ° C the corresponding amorphous mixed oxycarbonate with pure and dry hydrogen sulfide is treated. 09851/1 6 1'O