DE1792505C - - Google Patents

Description

^T 4

SfSxvdSfnSS ^ f ^Eb f ^{nS0 iSt it is possible to acidify} - ^{Γη the} hydrochloric iodine solution presented can be

landlord chafEen ΟΛηΣ w '? ^{to be carried out} . From a pipette 50 ml of the to be examined,

Γη te i nth? ^ ZrJu ,? ^{Jed0Ch Ci} " ^{e level} " ^ h! the diluted solution, using a glass

wM m vie? St six Stufef "I"' ^Vorzu 8 ^swe ^ stab is stirred and titrated after the addition of starch is under Γ H Die *. D "= number of 5 solutions as an indicator with n / 10 sodium thiosulphate solution.

? _a tsoroduttiön £ -Hm T "? ΐ" * ^ desired The reaction should be terminated if the

Sns aunts beerest w Ή ^d ? ? ^TÖÜ * ^ " ^Reak ' ^{iodine titer} ' expressed as consumption in ml n / 10 J ₂ -Lo-

iSS ffiSSr ^{by KÜh} ' ^{Ung SUn} ^ ^{ml Lau} ^ ^{after the Odti inen value results}

ShreSe ffioSSr ^{g SUn} ^ ^{ml Lau} ^ ^{after the Ox} y ^{dati0n ei g}

The ReittnSSl- "" ^{der by} ° · ^{5 to 3} · preferably 1 to 3 units larger

SI ft T '^ ^ ^{same size 10 is} ^ ^ half of the value before oxidation. at

ΊΤί ^Unter l ^{chiedlih di} Ub Odid

knnnf t T ^ ^ ^{same size 10 is} ^ ^ half of the value before oxidation. at

be rehabilitated GlS ΪοΊΤί ^sub l ^{chiedlich dimen} "exceeding the specified Oxydationsgrades

° "dS Siw ⁸ ? ^ Volurnma require that the following reactions occur preferentially:

the sulfur barium laum in all tubes

Before the time dS Siw ⁸ ? ^ Volurnma require that the

The sulphurous barium dwells in all vessels

is equal to. With different DJ dimensions "the ⁸ ^ ³ + ^Ba ( ^0H ^ + ² έ ° 2 + BaS ₈ O ₃ + ^BaS0 3 + ^H 2 °

For the first stages, reaction spaces are small. 15 ^BaS Aj + Ba (OH) ₂ + O ₂ + 2 BaSO ₃ + H ₂ O

'^ JSTT ^Ve _f T " ^d " ^{n and} shorten the residence time, that is, poorly soluble sulfur-barium

* ZLo _n ^{the following stages} the residence time in oxygen compounds, which the precipitated barium

S ^ r, w 3 · ^{those Verrm} g ^erte Reaktionsgeschwindig- contaminate hydroxide.

kct is increased with correspondingly larger prostitutes- These reactions occur when there is no poly-

^SW 'lZ ^ J "ÄeaktI ° ^ns f ^ume - 20 sulphide is present in the ^{sulphurous barium liquor. Um}

. With other suitable apparatus for carrying out the formation of these compounds as little as possible

fi \ ™, n ΊΓ ^β > ^ l ^V " ^are oxidation holdings and an optimum with regard to the oxidation

can, depending on the amount of heat to be dissipated, achieve this at .speed, it is recommended that

'-N'rttni * Γρ u ^hlun g must ^bear the molar ratio of total sulfur to mono

uno in those by adding baffles and / or _a5 suiridschwefel in the barium sulfide starting solution

Form for an intensive mixture of sulfur is 1.2 to 2, preferably 1.6 to 1.8.

ba, iumlauge is provided with air. The latter can have proven to be the most favorable oxidation temperatures

^ ^l "i \ -nln ^gen A ^d . ^Ur ? ^A V ^sb » ^Id . ^un 8 of ^the column proved to be 45 to 80 ^° C., preferably 50 to 55 ^° C. The

Stirred column. However, be. Use of oxy-oxidation temperature depends to a certain extent

Dauons columns need higher air pressure. 30 of the molar ratio of total sulfur to mono-

The uxydation column can through soils in mehsulfidschulfel in the starting liquor. At a MoI

rcrc reaction chambers be subdivided. The incorporation of a ratio of 1.2 to 1.5 should reduce the oxidation temperature

But soil is not absolutely necessary; be the temperature from 65 to 8O ⁰ C, preferably 68 to 75 ⁰ C,

The column is then more intertwined as a volumetric number and with a molar ratio of 1.6 to 1.9 = 45 to

To understand reaction and consumption spaces. _{35 6οχ preferably 48 to 53} ^ _

Air and barium sulfide solution are preferred

guided in countercurrent, so that the already largely B e i: ä ρ i e 1

oxidized solution with the air richest in oxygen. A polysulfide-containing barium sulfide liquor with

comes into contact and which as a result of the oxidation , ^ _nn .

most oxygen-depleted air reacts to 40 ¹ ^. '· "**

Oxidation of the freshly entering barium sulfide solution WJ ₀ At (OH) ₂

serves. . 2.2% S (mainly as polysulphide)

It goes without saying that instead of air, an 80.3% H _:! 0,

other oxygen-containing gas or pure oxygen d. H. with a ratio of total sulfur to

can be used for oxidation. 45 sulphide sulfur of 1.7 and an iodine titer of

A particular difficulty in the oxidation is 23.2 ml n / 10 iodine solution / cm ³ alkali after the addition

Then it said that during the blowing in, the 4.5 g of Separan NP 20® (polyacrylamide polymer

In the air, so strong foaming occurred that one from Dow Chemical) per m ^{3 of} barium sulfide solution

efficient work was not possible. It was now continuously in the A b b. 1 shown oxy-

found that the 50 dation apparatus fed by the addition of flocculants.

Foaming can be prevented. Already one in the reactors of the oxidation battery is about

a small amount of about 4 to 5 g / m ^{3 of} lye prevents 30 m 3 of air / m ^{3 of} lye blown in, ie 7.5 m ^{3 of} air / m ³

the foam formation is practically complete. Of course, lye in every container. During the oxidation will

Depending on the composition of the alkali, the temperature can also be increased by cooling the reaction vessels

slightly larger amount of flocculant required, kept ^{at about 5J 0 C.} The ones from the last reaction

scin .. More than 10 g / m ^3, however, are likely to emerge only in seldom ionic vessels.

Exceptions may be necessary. As particularly suitable:

net. have flocculants based on polyacrylic acid 030 / _BaS

ba-.is. and their derivatives have been proven. o'oo / Ra (OHi

It is recommended to use the Oxv- ^6o , ' _c “', ° _c /. ^a . , _. ,, .. ..

dation to cancel before half of the ^ originally IfJ / ^ (vo-.egend present as polysulphides)

barium sulfide present in the lye to barium 78 * 6 ° / ° HO *

is hydroxide umgesetzi. A suitable measure for the '

right time of the termination of the reaction is the *) ^Diescr next BaS ₁ O, all of ^who comprises' schwerlös-

^S chwefel-SauerstofT connections, including - Jodtiter He is as FOLET determined · fie ^{union Bariurn}

ιη, ν, ι A » _r ,., u-," α ι ·· '·. BaSO ₃ , BaSO, etc. and also BaCO ₁ .

IU ml of the solution to be determined are on

500 ml filled up. The slurry had an iodine titer of 12.6 ml n / 10 iodine

ml n / 10 iodine solution with 5 ml 10% hydrochloric acid solution per ml slurry. For the separation of BaS, O, and

other sparingly soluble barium compounds such as BaCO ₃ and BaSO ₃ , it is decanted in a clarifying tip and then cooled to 15 ° C; the Ba (OH) ₂ · 8 H _a O crystallizes out. This is filtered off and has the following composition:

80.4% Ba (OH) ₁₁ 8 H ₂ O 0.4% BaS 2.0% BaS ₈ O,

17.2% H ₁ O

This crude baryta hydrate can be brought to the desired degree of purity by recrystallization will.

152.3 kg of raw baryta hydrate and 848 kg of mother liquor of the following composition were obtained per ton of starting liquor:

9.5% BaS 2.7% Ba (OH) ₂

4.2% S (mainly as barium polysulphides) 83.6% H, 0 5

66% of the mother liquor is fed back in the circuit to dissolve fresh sulphurous barium; the remaining portions of the mother liquor are discharged from the barium hydroxide process and used for the production of other barium compounds. This results in an increase in the yield of barium hydroxide from 37.4 to 76.8%, based on the amount used Barium. However, since the remaining 34% mother liquor is also worked up on barium compounds can, assuming a quantitative work-up of the remaining 34% mother liquor, an approximately i »6%« Yield, based on barium, can be achieved.

1 sheet of drawings

Claims (4)

1 2 form is oxidized with air until a sample of Patenfinsnriirhr- the reaction mass does not require an increase in alkalinity. Recognize more The barium hydroxide is extracted from the reaction mass with hot water. 1. Process for the production of barium hydroxide 5 In the German patent specification 519 891, the hydroxide is produced by oxidation of a barium polysulfide a temperature 8O ⁰ C, characterized in that described above 50 ° C. In the associated one, the barium sulfide solution, continuously in the additional patent 526 796, it is stated that the reaction space is initiated, the oxidation is carried out in several oxidation stages, even at temperatures below 50 ° C, through successive stages, which can lead to a cloudy reaction solution formed in the barium sulfide solution sulphide or dissolved sulfur is continuously released. and after removing the turbid matter it cools down and all these processes have in common that they dis- separating the crystallized barium hydroxide. i = operated continuously. You have so far too 2. The method according to claim 1, characterized in that no entry has been made in technology,
draws, c ¹ ; Q the oxidation in an oxy- A process for the production of dation column was now carried out, the temperature of which is barium hydroxide adjusted by oxidation of a barium polydurch external and / or internal cooling sulphide-containing barium sulphide liquor with an oxygen and in the for intensive mixing of the Ao-containing gas at temperatures between 45 and 80 ⁰ C air with the sulfuric acid baffles and / found, which is characterized in that rna.i or frits are installed. the barium sulfide solution continuously in the react 3. The method according to claim 1, characterized by initiating the marking space, the oxidation in several underdraws, that the oxidation is carried out in a stirred column that is connected to one another and is carried out will. as rising cloudy reaction solution continuously drains and after 4. The method according to claims 1 to 3, da- removal of the cloudy substances cools and the auskristaldurch characterized in that the oxidation in the Iized separates barium hydroxide. Final stage is canceled before half of the It was found that the oxidation Although the sulfur present in the barium sulphide liquor proceeds relatively quickly at the beginning, the reaction barium is converted, preferably when the iodine rate increases with the progress of the reaction titer of the oxidized liquor, expressed in ml n / 10, decreases sharply. The resulting Difficult-J, -solution per ml of barium sulphide solution, around 0.5 to keiten for continuous operation are invented Units, preferably 1 to 3, is greater than the corrected according to the fact that the oxidation in Half of the corresponding value before the oxy- several successive stages of expiration. 35 leads. In this working world, the main part takes place 5. The method according to claims 1 to 4, that the reaction in the first vessels or reaction through characterized in that the barium sulfide solution clears up and is used in subsequent stages a flocculant is added. End led. 6. The method according to claims 1 to 5, a suitable apparatus for carrying out the characterized in that the molar ratio of 40 process is in the accompanying A b b. 1 shown. Total sulfur to Munusuifidschwefei in which it consists of a battery of 4 consecutive barium sulfide starting solutions 1.2 to 2.0, preferred reaction vessels A, B, C, D, which is 1.6 to 1.8 . Cooling jacket 12 and an effective stirring device S. 7. The method according to claims 1 to 6, are provided DA, the air compressor 3, the flow-through by in that the oxidation at a 45 meter 1 for the feed liquor and the DurchfluD molar ratio of total sulfur to monosulfide diameters la, Ib , Ic and Id for regulating the amount of air sulfur in the barium sulphide solution from 1.2 to 1.5. at temperatures from 65 to 8O ⁰ C, preferably The apparatus is operated as follows: Diezuoxy- at 68 to 75 ° C, and with a molar ratio of the barium sulfide solution enters the reaction vessel A via the flow-1.6 to 1.9 at temperatures of 45 to 60 ° C, knife 1 from above at 7 in the reaction vessel A. preferably at 48 to 53 ⁰ C. is carried out. At the same time, air is from the compressor 3 via the 8. Device for carrying out the method, flow meter la at 6 via a dip tube under, characterized in that the successively pressed the stirrer into the barium sulfide solution, switched reaction vessels each with an air through vigorous stirring, for example by means of a stirring device, a stirring device and a 55 basket stirrer, lye and air are extraordinarily provided with a cooling jacket. intensely mixed. The lye flows through outlet 8 to the second, similarly constructed oxidation vessel B, into which air is blown in the same way. This process is repeated completely analogously in the 3rd and 60 4. Oxidation vessels C and D. For cooling, the oxidation vessels are provided with a cooling jacket 12, into which the cooling water enters at 10 and exits at U The extraction of barium hydroxide by hydro- runs. The exhaust air leaves the reaction vessels during 9th lysis of a barium sulfide solution while at the same time the completely oxidized lye leaves the 4th oxidation introduction of air is known. «5 vessel D at 8 and is transferred to the downstream crystalline In the German patent specification 415 897, for example, a sationsanlage is pumped. Process for the production of barium hydroxide. It is emphasized that the process according to the invention »'.'! Rubbed, in the case of the raw sulfur barium in hydrate also in more than four series-connected