DE1667712A1 - Process for the production of hydrogen peroxide - Google Patents

Description

DR-WILRATH,
DR. WEpER. June i

W.ESBADEN 1667712

<35B

«OCiete 'ΐ ^ Γ-ΓΜ * ??!,
6, line Oogn-cq-J y
Te- France

Process for the production of VT iBaeretoffsuperoxyd

Priority -? 7. June »966 according to

P 'tent immeldung in Pr iikrelch' ^T o. PV 67

^? #i dor 'ier <itollirag from ^: 03nQTato £ taupOFoxjä iat it is known "one or more Caonero baw" homologous Chjnonvarblndungen

daunganittel in a? ir / or geeignetoia Löaungaeniach a "uaet55ön" The rbeitagänge, el ie to Geviinnun of lead 'aaerstoffperoxyd, consist in 4 ×? rrn 3 nacheina Direction quinones "u liydraehisonen reduced unl latter d · ηπ ίΐ- Λ f'eroxydiert and Sühlie91ioh d: # '/ ^ - esersto ff per nit one!, Norg. ^ Niaeisen i-litt * l extr.ihiert h ^ iov in η die g K ¹ ^ r''edaktioneatuft im Kr « ie surHekfiihtft · '- * ti «i dli« · i $ * tittel der ChlnonT «r-ljiHdun .-.>. <iin or ^ nldciiss ⁵ Π - door ^ with <7> 89« rnloht miaohirsr find »
for VHiteretoff peroxide au «v;

109830 / U87

The quinones are generally reduced to hydroahinones in the presence of a ε-talyeatora based on niokel or palladium. Under these conditions, however, this reaction cannot be carried out as the only one, but other slower reactions can also be carried out Among these side reactions, the fastest is the fixation of hydrogen in the nuclei of the anthraquinone with delivery of the following hydrogenation products tetrahydroethylanthraquinone and octahydronnthraquinone. These derivatives still have the quinone function and beeowUnre das first «behave in practice as a producer of hydrogen peroxide. Other reactions, on the other hand, impair the quinone function and the reduction attacks one or both CO groups. These degradation products ent They tend to lose ohinones and usually try to limit their growth in the work environment by either introducing their formation rate by improving the selectivity of the catalyst or other measures, or by converting them into productive quinones in a station connected to the circuit performs. Ta allganeiain trfolgt JE = but the accumulation of these Abbaiipro & uJEt "very od * y less rneoh" Si "transmits check result ά" τ inrnnglMufig 'n Kompensi®rmiig by Eusäts * on tntapreohende Ohinonrerlust * "on the other hand is dl · Sntwloklung the property · »The job release will be a träohtiit.

109830 / U87

As from the explanations above about the accompanying reactions the reduction to hydroohinones emerges, one of these reactions occurs, which eioh occurs at a relatively high rate Great draws in the formation of the tetrahydro derivative. The ion centering this derivative disadvantageously increases that of quinones, while their sum in the absence of bu degradation products leading reactions remains constant * In practice the concentration of Tetrahydroderlvates increases to a maximum Value of that of the working conditions of the entire circle! On process depends *

At the highest productivity, i.e. quinone reduction »of 90 # or more, the production capacity is siemlloh quickly due to the solubility of the tetrahydro derivative in the solvent. Namely, the solvent generally consists of aas a mixture of two ingredients, one of which is a good solvent for the quinone form and the other of which is a good solvent good solvent for the hydroquinone form is * a real one The ratio of the two components enables the highest productivity to be achieved, i.e. a practical saturation Im Quinone state as in the hyroehinone state, at the working temperature of the cycle. So you are dish the productivity in terms of productivity Solubility of the quinones and especially of the tetrahydro derivative which is generally less soluble than the original quinone.

109830 / 1A87

Sin means to increase production output consists in increasing the concentration of the auagangsohinon, wae thanks to the mutually related properties of the Ohlnon hydroquinone compounds the solubility in the hydrogenated state is ererbeesert “If you at the same time consider the proportion of the better Solvent for the ohinone form in the binary solvent increases "if you ererbeseert the solubility of the tetrahydro" ethyl anthraquinone in the non-reduced state. However, one has found that this agent has only a limited gain in solubility of the non-reduced form of tetrahydroethyl anthraquinone leads in proportion to those whom one gets Invention achieved.

Sit Belgian patent specification 672 419 tob 17. NcYtfltfcer 19 * 5 for a process for the production of ron Waastrstoffptroacytf tfta * Laporte Chemicals states that the presence of clay degradation products is advantageous under certain conditions, because it is based on the solubility of the hydroehinone forms, i.e. the production output for hydrogen peroxide to increase the working solution, and allows the hydrogenation temperature to be reduced, the overall performance being the same as in the absence of degradation products achieved. According to the known method, an amount of τοη 20 to 120 g / l solids other than. Ohinone and hydroohinoir bonds, which occur during the continuous cycles of the arbtital solution formed from 2-ethylanthraohinone and 2-ethyltetrahydroanthraohinone have been identified as eligible · Bas ror known Procedure shows that one unites around this syllabus

109830 / U87 - 5 -

Production of 6.5 g / l * 9 β ο * · ^{Γ 11} βΑ hydrogen peroxide should be expected} if one corresponds to the same production output in the absence of red degradation products at a lower hydrogenated »» temperature.

Naoh foregoing "is eheint ea _y that the production output duroh the solubility of Tetrahydroderiyates in non-reduced state limited, the less is generally soluble than the Ausgangsohinon · The Ubliohen trbeitstemperaturen a cycle are such daf the * - E 'a ^' retur The extraction stage is lowest, which determines the LO conductivity of the quinones. According to the invention, a process has now been developed which allows the solubility of the non-reduced tetrabydroderiratee to be increased noticeably.

The method according to the invention is characterized in that the working solution a high concentration clay more than 120 g / l in solid products other than the ohinone and hydroquinone compounds which have been formed from the quinones and tetrahydroohinones during the cycles of the working solution

At the beginning, the "handle" of the ohinone used in the selected solvent means the highest level of performance. It has been found that this solubility is based on the amount of solid degradation products and accordingly the production output is defined as the amount Wasseretoffoxyd _f Ait at> the SSyklus may arise st & r Sijüieä.t to Arbsits *

109830 / U8?

166V712

solution also increases. The method according to the invention

allows higher production rates to be achieved than the known processes · With a concentration of 250 g / l A production of about 15 g / l of degradation products can be observed tfaeaere t off peroxy d achieve »what a very important step forward means.

The alternative method is applicable to any chlorine system and any solvent. Ba is particularly well suited for the cyclic process for Waeses t off peroxy dehydration, in which the hydrogenation is subjected to a working solution of 2-thylanthraohinone and 2-ethyltetrahydroanthraohinone dissolved in a binary solvent, which is an aromatic hydrocarbon, preferably with nine carbon atoms, and an oyaloalkanol ether such as methyloyolohexylaoetate. The hydrogenation ratio is high. It corresponds to at least $ 80> of the theoretical maximum, and in a rortellian way can reach 90 ^ or more; the temperature is βwischen 50 and 100 ⁰ C ₁ ⁰ O 70 wherein ά for carrying · β traversed is particularly favorable. The main part of the quinones used in the hydrogenation consists of 2-ethyl-tetrahydroanthraehinone.

The development of the properties with an increase in the total solute practically represents a limit for the invention on which the conditions applied in the procedure depend. at of this urease one must maintain the composition of the solution, by taking periodic cleaning of the solutions " the duroh addition of τοη solution compensates without degradation substances

109830/1487
"earth.

DIt naohetthendtn In "pi" l "explain the invention. In these examples, solutions are used which are composed of 2-ethyl-9 # 10-anthraquinone, a tetrahydroderiTate 2-ethyl-5>6.7> 8-tetra · Hydro-9-10-anthraquinone and its breakdown products, dissolved in a binary solution mean, consist · Al “last” a mixture of methyl-oyclohexyl-acetate and an aromatic Og-hydrocarbon is used the concentration of degradation products was chosen arbitrarily, with the various solutions investigated being obtained from a stock solution. Then, each solution was saturated at a temperature of 17 ⁰ C to Tetrahydroäthylanthraohin-on and sohlitölich the concentration of ethyl at tkraohinon to $ 10> en "Tettehydroäthylanthraohinons eingeetellt" There, "Lösungemittel enthült in all cases 57? Olum- # methyl cyelohexylaeetat and 4 $ YoIubhC aromatic hydrocarbons, so that the "solvent as a parameter could not work in the results obtained."

example 1

ο On «in« «Palladium catalyst become one at 70 ⁰ O 400 oa

"Solution of the following type hydrogenated, dl" al "additive solution without

° Inert was prepared and contained

^ 66, β g / l tetrahydroethyl anthraquinone

** 6.7 g / l Ethylftnthraohinon

73.5 l / l gt «aat öelöete ·

166/712

in the solvent, which consisted of 57 full aliquot of methyloyolohexylaoetat and 43 volum of fluids of aromatic Cg-hydrocarbon and in the following examples all solvents 57/43 counted. Ee hydrogen was absorbed corresponding to 9 »55 g of solution. The analysis actually showed 9.56 g of solution. The temperature at which insolubility in the hydrogenated solution occurred is 58 to 60 ^° C *

Example 2

A solution is hydrogenated under the same conditions as in Example 1

28.4 g / l degradation substances 79 2 g / l tetrahyiroethylanthraohinone 7.9 g / l ethyl anthraquinone

115.5 β / l total dissolved in the solvent 57/43.

Hydrogen is in accordance with the formation of 11.3 g ron ^ ₂ ⁰ solution absorbed. Analysis shows 11.19 g of H ₂ O ₂ /! Solution. The temperature occurs in the UnlBsliohkelt in the hydrogenated solution is 56 to 58 ⁰ O.

Example J S

Under the above conditions, 400 cm ^{5 of} a solution are hydrogenated-i

63.1 g / l degradation substances
33.8 g / l Tttrahydroäthylanthraehinon 10983Q / U87 ^ ^ _{AthrlaBthraahlB0It}

155 »3 g / l gteanttt in the solvent 57/43 aelöetes

Hydrogen is absorbed corresponding to the formation of 11.95 g of H ₂ C ₂ / solution. The analysis gives 12.10 g of H ₂ O _; / l solution,

The temperature occurs during ünlösliohkeit in the hydrogenated solution is 56 to 58 ⁰ G.

Example 4-

A solution is always found under the same conditions containing

119.7 g / l degradation materials 92.2 g / l tetrahydroethyl anthraquinone 9.2 g / l ethyl anthraquinone

221.1 g / l of total desire.

Hydrogen is absorbed corresponding to the formation of 13.16 g of H ₂ O ₂ A solution. The analysis gives 13.04 g of H ₂ O ₂ A solution. The temperature "at which insolubility in the hydrogenated solution occurs is from 52 to 54 ^° C.

3 game 5

Containing in a solution

154.1 g / l degradation substances 92.4 g / l tetrahydroanthraohinone 9.2 g / l xthylanthraohinone

255.7 i / l total YellowB.t ·· <M®HAL WSPBCTCD

- 10 109830 / U87

Ib6 / 712

- ίο -

one absorbs hydrogen corresponding to 13.20 g H 0 OVl solution · The .msljae results in 13.20 g H ₀ OVj. Löpung.

Si · Tenptratur, wherein the Unlöaliohkeit in the hydrogenated solution occurs, is 43 ⁰ C 45 We

This example, in which the reduction is the same as is Example 3 shows ά · η sole influence of the degradation products to the temperature of UnlöeliobJteit.

Example 6 Containing in a solution

190.9 g / l breakdown substances
97.7 g / l Tetrahydroäthylanthraohinon H, 2 g / l Ethylanthraohinon

302.8 g / l oil tea

absorbs aan hydrogen corresponding to 13.95 g H ₂ O ₂ /! Solution The .malyet yields 13.80 g of Hg

Example 7 Containing in a solution

228.0 g / l breakdown substances
104 »7 g / l letrahjrdroäthylanthraohinon 11.3 g / l Äfcjlanthraohonon

30 / U 87

166/712

one absorbs hydrogen corresponding to 14.95 g ^H 2 ° 2 ^/ ' ¹

Bit analysis gives H # g H ₂ O ₂ A solution. Di · temperature, at

the ünlösliohkeit in the hydrogenated solution occurs, is at 33 to 35 ⁰ C.

Tig. 1 and 2 explain the overall results of the examples 1 to 7.

Tig, 1 shows the development of the solubility of the Tetrahydroäthylanthraohltnone as a function of the concentration of the working solution in degradation substances. This Kontentration of degraded substances "expressed in g / l beseiohnet stit C, is plotted on the Abxisse" while the solubility of the Tetrahydroäthyl anthraquinones at 17 ⁰ C, ausgdrtiokt in g / l, is plotted on the ordinate and with beseiohnet S H. SAQ «

The curve of the Tig · 1 awigt particularly interpreting lent the partially favorable influence of degraded substances of the solubility tone Tetrahydroäthylanthraohinon and the production capacity in g hydrogen peroxide per liter Arbeitslttsung "ausgedrüokt This performance in g / l, is plotted on the sweiten ordinate and ait FH ₃ O ₃ rewarded. Consideration of this curve shows that a concentration of 120 g / l of degradation substances permits a higher production output than 13 g / l * expressed in terms of H ₂ O ₂ , while a concentration of 200 g permits int production of hydrogen peroxide of 14 g / l and bti · 1η · Ρ 250 g of building material

109830 / U87. - 12 -

Concentration a production of approximately 1f g / l hydrogen peroxide to achieve"

2 shows the development of the temperature at which insolubility occurs in the solutions after the hydrogenation under the conditions described above, ie with increasing concentrations of degraded substances and of hydroquinone at the same time. The concentration of degraded substances, auegedrückt in g / l and duroh denotes the Buohataben C, i "t plotted on the Vbszisse, while the" T it is plotted ⁰ C designated Unlöslichkeitstemperatur, expressed in degrees centigrade "on the ordinate. This curve proves the particularly favorable influence of: bbauatoffta at consentrations above 120 g / l.

Example 8 A solution of 95 g / l tetrahydroethyl anthraquinone

15 g / l ethyl anthraohinone 110 g / l ohinone and 150 g / l degradation substances

dissolved in a mixture of 57 and 43 Yolum- # Methylcyclohexylaoetat i> Cg aromatic hydrocarbons Sohon the type described is utilized in a Herstellungseyklus of hydrogen peroxide, 75 1 of this solution are successively the hydrogenation on a P - = lladiunikatalyaator at a temperature of 70 ⁰ O with the oxidation by air at 70 ⁰ O, after which it is extracted ^{with water at 25 0 O.} The cycle also includes a reverse conversion station for building materials in quinone between extraction and hydrogenation.

1 09830 / U87

- 13 ~

The hydrogenation is carried out on the basis of suitable catalysts regulated to tin «production level equal to 14.0 and then 14» 4 g HgOg / L organic solution to maintain what 98.0 baw. 101.5 g / l hydroohinone deprived. In the course of operation «« • In ·· such a cycle, «u recognize» that the tetra- ■ content was found hydroäthylanthraohinon increases progressively and then see something 100 and 105 «/ 1 stabilized, the construction of Ohinonen duroh «in« increase in building materials to about 15 g / l sum expression, which is compensated by adding quinones *

Even though you found yourself outside the solubility limits in the foregoing, which resulted from the enclosed curves "• r there was no unldsliohieei * in the cycle in the course of several operations due to the working temperatures" was heated breakdown products of 150 to 170 g / l according to the preceding Belepielen "the femperatur, occurred at the lasing in the hydrogenated Unlöeliohkeit, was 52 to 54 ⁰ O.

The curve of the pig. 2 for the UnlUslichkeitatemperaturen, the lower Auenutsungsgrense represents the hydrogenated 18sung for the considered Waeserstoffsuperaqiiivalent · The equivalent H obtained ₂ O ₂ iet a puncture solubility, 3etrahydroäthylanthra ~ ohinone · In Examples 1 bie 7 is started from the Löelichkeit at 17 ⁰ C “As can be seen from example 8 for a cycle in which“ the minimum temperature is higher, namely 25 ⁰ O, one can have a higher production output. However, the temperature at which insolubility occurs in the hydrogenated solution is then higher. The above examples provide among the

109830 / 1A87. '

-1A-

IbBVV12

specified conditions solutions of the specified type in terms of nature and quantitative ratio of the sea parts, the invention is but neither limited to this type of solution nor to the cathode of the above-described rough guide results see for every other syatheme of chanons and solvents, in which the content of building products increases leaves a possibility to increase the maximum production.

- 15 -

109830 / U87

Claims (5)

Ί6677Ί2 - 15 claims 1. Process for the cyclic production of τοη hydrogen peroxide, in which a working solution τοη quinone and Ietrahydroohinon, dissolved in a binary solvent of aromatic hydrocarbon and a Cyoloalkanoleater »Oxydoreduktionsverktionen undergoes and the hydrogen peroxide formed in each oxidation stage is separated, with the hydration ^ nlsal 80 in the theoretical maximum mood and the quinones subjected to the hydrogenation consist mainly of tetrahydrofuran, characterized in that the working solution has a higher concentration than 120 g / l of solid degradation products, which are made up of quinone and anthraquinone during the circulation of the Have formed work solution 2. Process according to Claim 1, characterized in that the quinones are made from 2-ethylanthraquinone and 2-tetrahydroethylanthraquinone exist· 3. The method according to claim 1, characterized in that the concentration of solid degradation products between 120 and 250 g / l the working solution is 4 «Process according to claim 1, characterized in that the hydrogenation temperature is between 50 and HO ⁰ , or rather close to 70 ⁰ C. - 16 1 0 9 8 3 0 / U 8 7 5. The method according to claim 1, characterized in that the hydraulic ratio between 80 and 100 $, preferably close to 90 ° of the theoretical maximum. 6, "A method according to Ampruoh 1, characterized in that the Tetrahydroohinonanteil between 80 and 100 ^, is located on rorsugsweiee quinones at approximately 90 i> of the total weights« « 7 · The method according to claim 1, characterized in »that the IiuevermittelgemAsch Methyl-Oyclohexylaoetat and one Contains aromatic hydrocarbon with nine carbon atoms in the molecule. 109830 / U87