Title of Invention	" A PROCESS FOR THE PREPARATION OF HYDROGEN PEROXIDE"
Abstract	A cyclic anlhraquinone process for producing hydrogen peroxide using at least two differently substituted 2-alkylanthraqulnones and/or their tetrahydro derivatives. The working solution to be used contains (i) at least one reaction carrier from the series 2-(4-methyl-3-pentenyl) anthraquinone (IHEAQ), 2-(4-methylpentyl) anthraquinons (IHAQ) and their di and tetrahydro derivatives such as, In particular 2-(4-methylpenyl)-p-tetrahydroanthraquinone (THIHAQ), and (if) at least one reaction carrier from the series of the 2-(C1- to C5)-alkylanthraqulnones, especially 2-ethylanthraqulnone (EAQ), and their tetrahydro derivatives. The reaction carriers-according to (I) make up 5 to 95 molar %, especially 20 to 50 molar % of all reaction carriers. The method Is distinguished by greater H2O2 capacity, Improved hydrogenatton kinetics and lesser susceptibility to disturbances. A method for making THIHAQ is also disclosed.

Title of Invention

" A PROCESS FOR THE PREPARATION OF HYDROGEN PEROXIDE"

Abstract

A cyclic anlhraquinone process for producing hydrogen peroxide using at least two differently substituted 2-alkylanthraqulnones and/or their tetrahydro derivatives. The working solution to be used contains (i) at least one reaction carrier from the series 2-(4-methyl-3-pentenyl) anthraquinone (IHEAQ), 2-(4-methylpentyl) anthraquinons (IHAQ) and their di and tetrahydro derivatives such as, In particular 2-(4-methylpenyl)-p-tetrahydroanthraquinone (THIHAQ), and (if) at least one reaction carrier from the series of the 2-(C1- to C5)-alkylanthraqulnones, especially 2-ethylanthraqulnone (EAQ), and their tetrahydro derivatives. The reaction carriers-according to (I) make up 5 to 95 molar %, especially 20 to 50 molar % of all reaction carriers. The method Is distinguished by greater H2O2 capacity, Improved hydrogenatton kinetics and lesser susceptibility to disturbances. A method for making THIHAQ is also disclosed.

Full Text	1 Process for the preparation of hydrogen peroxide and reaction carrier for carrying out the process Description The invention relates to a process for the preparation of hydrogen peroxide by the anthraquinone cyclic process. The working solution to be used contains as reaction carrier at least two differently substituted 2-alkylanthraquinones and/or the corresponding 2-alkyltetrahydroanthraquinones. The invention relates also to a novel reaction carrier. In the so-called anthraquinone cyclic process for the preparation of hydrogen peroxide, 2-alkylanthraquinones and/or their 2-alkyl-ot- and/or -p-tetrahydroanthraquinones hydrogenated at the nucleus, acting as reaction carriers, are hydrogenated with hydrogen or a gas containing hydrogen, in an organic solvent system in the presence of a hydrogenation catalyst, the reaction carriers being converted at least partly into the hydroquinone form. The one or more reaction carriers in the hydrogenated or oxidated form and the solution containing the organic solvent system are generally described as the working solution. After the hydrogenation step, the working solution is freed of,the hydrogenation catalyst and treated in the oxidation step with an oxygen-containing gas, the quinone form of the reaction carriers being reformed with the formation of hydrogen peroxide. After the hydrogen peroxide that has formed has been separated from the oxidised working solution, usually by extraction with water and/or an aqueous solution containing hydrogen peroxide, the working solution is again fed to the hydrogenation step. In addition to the mentioned steps, the process may also include regeneration of the working solution, wherein anthraquinone derivatives formed during the cyclic process that are ineffective as reaction carriers, such as anthraquinone epoxides, are re-activated 2 and/or 2-alkyltetrahydroanthraquinones are dehydrogenated to the corresponding 2-alkylanthraquinone derivatives and also, as required, reaction carrier losses are made up by the addition of the corresponding 2-substitufced anthraquinones and/or their tetrahydro derivatives. A further step is directed towards the regeneration of the catalyst in order to maintain a high level of activity. An overview of the anthraquinone cyclic process will be found in Ullmann's Encyclopedia of Industrial Chemistry 5th ed. (1989), Vol. A13, 447-457. Great demands are made of the reaction carrier, in order to ensure that commercial installations operate at the highest possible capacity with the lowest possible susceptibility to failure and the lowest possible loss of reaction carriers. One of the demands is directed especially towards the highest possible solubility of the reaction carrier in the solvent system, both in the quinone form and in the hydroquinone form. The solubility of the hydroquinone form has a determining influence on the maximum H2O2 equivalent (= g of H2O2 per litre of working solution) obtainable during continuous operation. Further demands relate to the hydrogenation and oxidation kinetics; both reactions are to proceed as rapidly as possible. Since the hydrogenation and the oxidation are often affected in opposite ways by a change in the structure of a reaction carrier, even a good reaction carrier system consisting of two or more components is often only a compromise. Also of importance are the highest possible degree of chemical stability of the reaction carrier in the catalytic hydrogenation, a high degree of oxidative stability towards oxygen and hydrogen peroxide, and a high degree of stability towards acids or/and alkalis, such as are used in the regeneration. Finally, the reaction carrier is to be as water-insoluble as possible, toxicologically harmless and inexpensive to 3 According to GB Patent 1 252 822 there may be used, in the anthraquinone process for the preparation of hydrogen peroxide one or more 2-alkylanthraquinones having from 2 to 6 carbon atoms in the alkyl group, especially 2-ethyl-, 2-tert.-butyl- and 2-amyl-anthraquinone. The 2-alkyl-tetrahydroanthraquinones that form in the hydrogenation step are also effective. In the GB patent cited above, not a single 2-alkylanthra-quinone reaction carrier having 6 carbon atoms in the alkyl group is mentioned by way of example or even emphasised. In EP-A documents 0 286 610 and 0 778 085, 2-hexenylanthraquinone is mentioned as a reaction carrier in addition to other 2-alkylanthraquinones and mixtures thereof. That EP document does not indicate which of the possible hexenyl isomers is meant and whether or what advantages can be achieved therewith. It is known that as the chain length of the alkyl substituent in 2-alkylanthraquinones grows, the quinone solubility increases, but at the same time the rate of hydrogenation falls considerably, and that is of greater importance in practice. Accordingly, it was not obvious seriously to consider using a 2-C6-alkylanthraquinone as reaction carrier. It follows from JP-A 58 180452 and JP-A 59 051235 that 2-(4-methyl-3-pentenyl) -1, 4-dihydroanthraquinone and 2-(4-methyl-3-pentenyl)-anthraquinone and 2-(4-methylpentyl)-anthraquinone obtainable therefrom can be used as reaction carriers for the preparation of hydrogen peroxide. The preparation of the mentioned compounds, the starting material is obtained by Diels-Alder reaction from 1,4-naphthoquinone and myrcene, can be found in those documents. With regard to the use of those compounds in the anthraquinone cyclic process for the preparation of hydrogen peroxide, it is merely mentioned that the same 4 results as with known 2-alkylanthraquinones can be obtained. The demands made of a good reaction carrier are now and again only partly met when a single 2-alkylanthraquinone and/or the corresponding 2-alkyltetrahydroanthraquinone formed in situ is used, depending on the operating conditions. Experts have therefore made every effort to improve the reaction carrier by using at least two different 2-alkylanthraquinones and/or their tetrahydro derivatives. However, advantages regarding one or other of the demands made of a good reaction carrier system are often counteracted by disadvantages regarding other criteria. According to DE-AS 11 95 279 it is possible to increase the yield of hydrogen peroxide and/or minimise the formation of by-products in the hydrogenation if, instead of a single 2-alkylanthraquinone, such as 2-ethyl-, 2-isopropyl-, 2-sec.-butyl- or 2-tert.-butyl-anthraquinone, there is used a virtually eutectic mixture of at least two 2-alkylanthraquinones, such, as, preferably, 2-ethyl- and 2-sec.-butyl-anthraquinones, in a ratio by weight of 27 to 73, and the degree of hydrogenation is maintained below 40 %. A disadvantage of that process is the requirement that the degree of hydrogenation must be limited. A more serious disadvantage is the unsatisfactory hydrogenation kinetics of those eutectic mixtures. Similar mixtures of two C1- to C4-alkylanthraquinones, which may be present in the so-called "anthra" system as well as in the tetra system, are known from US Patent 2,966,397. US Patent 4,374,820 proposes using a mixture of 2-tert.-butylanthraquinone and 2-sec.-amylanthraquinone, including their tetrahydro compounds. Although that system has good oxidation kinetics, its hydrogenation kinetics is unsatisfactory. In DE Offenlegungsschriften 11 12 051 and 5 11 06 737, on the other hand, it is recommended to use as reaction carrier a mixture of isomeric 2- amylanthraquinones, especially a mixture of 2-sec.-amyl-and 2-tert.-amyl-anthraquinone and their tetrahydro derivatives. Although a high H2O2 equivalent can be achieved with such systems owing to their good quinone and hydroquinone solubility, the unsatisfactory hydrogenation kinetics is a disadvantage here too, the result of which is a poor space-time yield. The use of a reaction carrier system based on 2-ethyl-anthraquinone (EAQ) and 2-amylanthraquinone (AAQ) and their tetrahydro derivatives (THEAQ and THAAQ) is also known - see EP-A 0 4 53 94 9 and Chemical Economics Handbook-SRI International June 1992 CEH Product Review Hydrogen Peroxide. A reaction carrier system on that basis (EAQ/THEAQ and AAQ/THAAQ), as compared with a reaction carrier system based on 2-ethylanthraquinone and 2-ethyl-tetrahydroanthraquinone, leads to an increased H2O2 equivalent, which can also be maintained under operational cyclic conditions. A disadvantage of the reaction carrier system based on EAQ/THEAQ and AAQ/THAAQ is its susceptibility to failure in the hydrogenation step, which manifests itself in a reduced hydrogen absorption. When a suspension catalyst, such as Pd black, is used, that behaviour makes it necessary to ensure a relatively high circulation of hydrogenation catalyst and to increase it still further in the case of failures; however, the economic effectiveness of the process falls as a result. The object of the present invention is to provide a further process for the preparation of hydrogen peroxide using a working solution containing at least two differently substituted 2-alkylanthraquinones and/or their tetrahydro compounds, which process exhibits to a lesser extent the disadvantages of the processes using the prior-known 2-alkylanthraquinone combinations, especially those 6 based on ethyl- and amyl-anthraquinone and their tetrahydro derivatives. In addition, the reaction carrier system to be used, while having good hydrogenation kinetics, is to result in a higher H2O2 equivalent which can be reliably controlled during operation, and is to be less susceptible to failure. The object is achieved by a process for the preparation of hydrogen peroxide by the anthraquinone cyclic process, comprising a hydrogenation step, an oxidation step and a step for isolation of the hydrogen peroxide, using a working solution containing at least two differently substituted 2-alkylanthraquinones and/or their 2-alkyl-tetrahydroanthraquinones, which process is characterised in that the working solution used contains (i) at least one reaction carrier from the group 2-(4-methyl-3-/pentenyl)-anthraquinone (IHEAQ), 2-(4-methylpentyl)-anthraquinone (IHAQ) and their di- and tetra-hydroanthraquinone derivatives hydrogenated at the nucleus, and (ii) at least one reaction carrier from the group of the 2-(C1- to Cs)-alkyl-anthraquinones and their ,tetrahydroanthraquinone derivatives, the reaction carriers according to (i) being present in an amount of from 5 to 95 mol%, based on the sum of all the reaction carriers. The reaction carrier component according to (i) that is present according to the invention is one or more compounds from the group 2-(4-methyl-3-pentenyl)-anthraquinone, hereinafter also referred to as 2-isohexenylanthraquinone, abbreviated to IHEAQ, 2-(4-methylpentyl)-anthraquinone, hereinafter also referred to as isohexylanthraquinone, abbreviated to IHAQ, 2-(4-methyl-3-pentenyl)-1,4-dihydroanthraquinone (= 1,4-dihydro-IHEAQ), 1,2,3,4-tetrahydro-IHAQ (a-THIHAQ), 5,6,7,8-tetrahydro-IHAQ (P-THIHAQ), 5,6,7, 8-tetrahydro-IHEAQ (p-THIHEAQ) and intermediates from the hydrogenation of IHEAQ and IHAQ to THIHEAQ and THIHAQ, respectively, 7 under conditions of the anthraquinone process. In the cyclic process, P-THIHAQ is formed predominantly from IHAQ, together with a small amount of a-THIHAQ - the abbreviation THIHAQ represents the isomeric mixture formed in the process. Reaction carriers according to (i) that are especially preferred in the process according to the invention are IHEAQ and IHAQ and their p-tetrahydro derivatives, especially p-THIHAQ. As a result of the anthraquinone cyclic process, IHAQ and THIHAQ form in the working solution after prolonged operation when IHEAQ is used as the component according to (i). IHEAQ is obtainable by means of a Diels-Alder reaction from 1,4-naphthoquinone and myrcene, with subsequent base-catalysed oxidation of the resulting 1,4,4a,9a-tetrahydro-IHEAQ with air. IHAQ is obtainable by hydrogenation of IHEAQ, for example on Pt/C. a-THIHAQ is obtainable according to US 1,425,250 by hydrogenation of 1,4-dihydro-IHEAQ. The invention also provides 2-(4-methylpentyl)-5,6,7, 8-tetrahydroanthraquinone (THIHAQ), a previously unknown reaction carrier for the anthraquinone cyclic process. That compound can be obtained by hydrogenation of IHEAQ with Raney nickel or other hydrogenation catalysts, such as Pt, Pd, Rh in metal form or bonded to a support; it is also formed in the anthraquinone cyclic process from IHAQ and THIHEAQ. ß-THIHEAQ is also obtainable by Diels-Alder reaction of tetrahydronaphthoquinone and myrcene with subsequent base-catalysed oxidation. The 2-alkylanthraquinone(s) according to 8 contains especially 2-ethylanthraquinone (EAQ) and 2-ethyl-tetrahydroanthraquinone (a- and p-THEAQ, p-THEAQ generally being predominant by far). According to a preferred embodiment, the working solution contains as reaction carrier substantially a combination of EAQ and IHAQ or IHEAQ with the corresponding tetrahydro compounds THEAQ and THIHAQ and/or THIHEAQ. The invention is explained further with reference to that system. It is possible to stock up a working solution containing substantially EAQ and THEAQ as reaction carrier with 2-isohexenylanthraquinone (IHEAQ) or isohexylanthraquinone (IHAQ) and/or their tetrahydro derivatives, in order to increase the H2O2 capacity. The molar amount of the sum of the anthraquinone and tetrahydroanthraquinone derivatives having an isohexenyl and/or isohexyl group, that is to say the products according to (i), is usually from 5 to 95 %, based on the sum of all the active reaction carriers. During the stocking-up phase, the molar amount of products according to (i) may also be less than 5 %. It is advantageous to adjust the molar amount of anthraquinone derivatives according to (i) to values in the range of from 10 to 90 %, preferably from 20 to 80 mol% and especially from 20 to 50 %, and then maintain those values, since the advantageous effect of the combination according to the invention, namely an increase in the maximum H2O2 capacity with a simultaneous improvement in the hydrogenation kinetics as compared with the closest reaction carrier system, containing EAQ/THEAQ and AAQ/THAAQ, is most marked in that range. After the addition of 2-isohexenylanthraquinone (IHEAQ) to the working solution, the isohexenyl group is hydrogenated to the isohexyl group in the cyclic process. Although IHEAQ per se is not very stable to oxidation (see Example 3), surprisingly no appreciable degradation of the 9 isohexenyl group occurs during the oxidation step in the anthraquinone cyclic process. The content of IHEAQ falls slowly during the cyclic process, while the content of THAQ and THIHAQ rises. THIHEAQ, which is formed in small amounts at the beginning, falls to values below the detection limit again as the process proceeds. According to a preferred embodiment of the process, the ratio of IHAQ to THIHAQ and EAQ to THEAQ is kept substantially constant during the cyclic process. To that end, a portion of the working solution is withdrawn from the process and fed to a known dehydrogenating regeneration step, wherein the tetrahydro derivatives that are present are dehydrogenated and the anthraquinone system is re-formed; the proportion of the working solution so regenerated is fed to the cyclic process again. Advantageously, from 40 to 80 mol% of all the reaction carriers are in the tetrahydroanthraquinone form. It has been found that as the proportion of reaction carriers of type (i), that is to say especially IHAQ, IHEAQ and THIHAQ, increases, based on the sum of all the reaction carriers, the hydroquinone solubility and hence the maximum hydrogen peroxide production capacity (g of H2O2/litre of working solution) is increased; that capacity exceeds that of analogous systems containing the system AAQ/THAAQ instead of IHAQ/THIHAQ - see Examples 4.1 to 4.13. Furthermore, the capacity increases as the proportion of tetrahydroanthraquinones rises. Contrary to existing knowledge, according to which the hydrogenation kinetics becomes poorer as the number of carbon atoms in the alkyl group of a. reaction carrier increases, the hydrogenation kinetics of the reaction carrier according to (i) to be used in accordance with the invention having an isohexyl or -isohexenyl substituent is surprisingly substantially better than the hydrogenation kinetics of the isomeric 2-amylanthraquinones and 2-amyl- 10 tetrahydroanthraquinones (AAQ/THAAQ) - see Examples 5.1 to 5.6. The reason for the extraordinary advantage of the process according to the invention is that, with the reaction carrier combination according to the invention, as compared with the closest prior-known reaction carrier system (EAQ, AAQ and their tetrahydro derivatives), a higher H2O2 capacity is achieved while at the same time the hydrogenation kinetics is improved. The reaction carrier system according to the invention can be used in any process of the generic type for the preparation of hydrogen peroxide. In the hydrogenation step there may be used known catalysts, such as, especially, those based on noble metals, such as Pd, Pt, Ir, Rh, Ru or mixtures of such noble metals, and Raney catalysts of Ni, Co or Fe. The catalysts may be used as suspension catalysts - for example Pd black or noble metals bonded to a support - or in the form of fixed-bed catalysts. The support-suspension and fixed-bed catalysts are especially noble metals on an inorganic support, such as SiO2, TiO2, A12O3, zeolite, BaSO4, polysiloxane. Finally, the catalyst may also be arranged on the surface of a monolithic ceramics support or of a honeycomb component having a sufficiently large surface. Customary hydrogenation reactors are in the form of a loop-type reactor, fixed-bed reactor, mammoth-pump reactor as well as a reactor having integrated static mixers. The hydrogenation is generally carried out at a temperature in the range of from room temperature to 100°C, especially from 45 to 70°C. The hydrogenation pressure is usually in the range of approximately from 100 kPa to 1 MPa, especially from 200 kPa to 500 kPa. The hydrogenation is usually so conducted that the hydrogen introduced into the hydrogenation cycle is used up completely and the degree of hydrogenation is maintained in the range of from 30 to 80 %. 11 The working- solution containing the reaction carrier system according to the invention generally contains two or more solvents in order to keep the reaction carrier components in the quinone form and hydroquinone form in solution. Suitable solvents and solvent combinations are those which are known from prior-known anthraquinone cyclic processes. There are especially suitable solvent combinations that contain, in addition to a benzin aromatic compound (polyalkylated benzene), one or more solvents from the group of the secondary alcohols, such as diisobutylcarbinol, esters, such as methylcyclohexyl acetate, phosphoric acid esters, such as tris(2-ethylhexyl) phosphate, tri- and tetra-alkylated ureas, such as tetrabutylurea, cyclic ureas, pyrrolidones, carbamates and N-alkylated caprolactams, such as N-hexylcaprolactam. Essential advantages of the process according to the invention are: a capacity that is higher by at least 0.6 g of H2O2/litre of working solution as compared with the closest prior-known process; an improved hydrogenation kinetics; a lower susceptibility to failure during continuous operation; a smaller amount of circulating palladium where Pd black is used as the catalyst. The invention is explained in greater detail with reference to the Examples and Comparison Examples below. Example 1 Preparation of 2-(4-methyl-3-pentenyl)-anthraquinone ( 2-isohexenyl-anthraquinone, abbreviated to IHEAQ): 12 The preparation was carried out analogously to JP-A 59-51235 by means of a Diels-Alder reaction with subsequent aromatisation. 397 g (2.56 mol) of myrcene (88 %, Aldrich) were used initially and then 405 g (2.48 mol) of 1,4-naphthoquinone (97 %) were added thereto. The suspension was stirred for 2 hours at 100°C (the exothermic reaction was already almost complete after approximately 0.5 hour). The reaction mixture, a brown oil, was introduced into an ethanolic sodium hydroxide solution (3 litres of ethanol and 40 g of NaOH). The suspension was stirred at 50°C for 2 hours while air was passed in - undissolved material initially went into solution, finally a reddish-yellow precipitate began to form. After cooling, the solid was filtered off with suction and washed with 250 ml of ice-cooled ethanol. After drying, 616 g of yellow powder were obtained. HPLC analysis showed an IHEAQ content of 98.5 % by surface area. The 1H-NMR spectrum and the melting point (89-90°C, recrystallised once from n-heptane) corresponded to IHEAQ. Example 2 Preparation of 2-(4-methylpentyl)-p-tetrahydroanthraquinone (= p-THIHAQ). 500 g (= 1.7 mol) of IHEAQ (crude product), dissolved in 3.5 litres of n-butyl acetate, were placed at 50°C in a 5 litre hydrogenating vessel having a gassing stirrer. After flushing the apparatus with nitrogen, 100 g of Raney nickel (suspended in 500 ml of isopropanol) were introduced and the hydrogenation was then started. After the absorption of 35 litres of H2 (hydroquinone formation), the H2 absorption suddenly slowed. After 30 hours, when 88 litres of H2 had been absorbed, the reaction was stopped. According to HPLC, the reaction mixture, freed of 13 the catalyst and solvent, contained, in % by surface area: 33 % starting material (= IHEAQ) , 45 % 2-(4-methyl-3-pentenyl)-ß-tetrahydroanthraquinone (= ß-THIHEAQ), 11 % 2-{4-methylpentyl)-anthraquinone (= IHAQ) and 8 % of the desired THIHAQ. In order to remove alkali compounds entrained with the IHEAQ that was used, the reaction mixture, freed of the catalyst, was washed with 10 % hydrochloric acid, with aqueous sodium hydrogen carbonate solution and then with water, and was dried. 437 g of the residue that remained after removal of the solvent were hydrogenated again in n-butyl acetate (3 litres) (sic) isopropanol (0.5 litre) in the presence of 100 g of Raney nickel. After 27.5 hours, when the reaction mixture had absorbed 74 litres of H2, the reaction was terminated. After removal of the catalyst by filtration, the reaction mixture was thoroughly oxidised by gassing with air, and was then concentrated. The precipitate was filtered off with suction and washed with isopropanol and finally recrystallised. 304 g of ß-THIHAQ were obtained in the form of a light-yellow powder: According to HPLC, the purity was 99.7 % by surface area. The 1H-NMR spectrum corresponded to p-THIHAQ. Example 3 Determination of the oxidative stability of 2-(4-methyl-3-pentenyl)anthraquinone (IHEAQ) (= Example 3a) in comparison with 2-ethylanthraquinone (EAQ) (= Example 3b): 0.04 mol of the quinone IHEAQ or EAQ were dissolved in 100 ml of 1,2-dichlorobenzene. After the addition of 10 mg of azo-bis-isobutyronitrile as radical initiator, stirring was carried out at 150°C, with a covering layer of oxygen, using a gassing stirrer. After 24 hours, the quinone content was determined by chromatography. The residual quinone content was 41 % in the case of IHEAQ and 90 % in the case of EAQ. 14 In contrast to Example 3a, IHEAQ is surprisingly not oxidatively degraded any more than EAQ under the conditions of the anthraquinone cyclic process for the preparation of hydrogen peroxide, although IHEAQ is detectable for a long time in the cyclic process since it is hydrogenated only slowly to 2-(4-methylpentyl)-anthraquinone (IHAQ). Example 4 Determination of the hydroquinone solubility of various reaction carrier mixtures in various solvent systems. The reaction carriers used and the amounts thereof will be found in Tables 1 and 2. Method of determination: A suspension consisting of the corresponding working solution and a small amount of freshly precipitated palladium black was introduced into a magnetically stirred, thermostatically controlled double-walled vessel which was equipped with a device for electronic turbidity measurement. Using a gas burette, the mixture was slowly hydrogenated; in addition, in order to avoid over-hydrogenation as the limit of solubility was reached, seed crystals in the form of the hydroquinone were added. The maximum hydroquinone solubility was reached when permanent turbidity was recorded by the measuring device. The hydrogen absorbed at that point was converted into H2O2 equivalents, defined as g of H2O2 per litre of working solution at 20°C. Examples 4.1, 4.6, 4.8, 4.9 and 4.12 are systems which are not in accordance with the invention containing the reaction carriers EAQ/THEAQ plus AAQ/THAAQ. Examples according to the invention (4.2 to 4.5, 4.7, 4.10, 4.11 and 4.13) contain the reaction carriers EAQ/THEAQ plus IHAQ/THIHAQ or IHEAQ/THIHAQ, where: EAQ = 2-ethylanthraquinone; THEAQ = tetrahydro-EAQ; AAQ = 15 2-amylanthraqulnone, wherein amyl represents a mixture of 1,2-dimethylpropyl and 1,1-dimethylpropyl (= iso-sec- and tert.-amyl); IHAQ = 2-isohexylanthraquinone; THIHAQ = p-tetrahydro-IHAQ. In Example 4.7, LHEAQ was used instead of IHAQ. While the hydrogenation temperature in Examples 4.1 and 4.2 was 60°C, all the other Examples were carried out at 50°C. In Examples 4.1 to 4.5, a mixture of C9/C10-benzin aromatic compound (BA) and diisobutylcarbinol (DIBC) in a ratio by volume of 6:4 was used as solvent; in Examples 4.6 and 4.7, a mixture of substantially C9/C10-benzin aromatic compound and tetrabutylurea (TBU) in a ratio by volume of 2.5:1 was used. In Examples 4.8 to 4.11, the solvent system consisted of C9/C10-benzin aromatic compound and tris (2-ethylhexyl) phosphate (TOP) in a ratio by volume of 3:1, and in Examples 4.12 and 4.13 it consisted of substantially C9/C10-benzin aromatic compound and tetrabutylurea in a ratio by volume of 2.5:1. The working solutions of Examples 4.8 to 4.13 contained inert degradation products of the anthraquinones which had been used, owing to their prolonged use in a continuous laboratory installation. The working solutions of Examples 4.12 and 4.13 contained by virtue of their preparation - use of an operational working solution based on EAQ/THEAQ - a .substantially larger amount of inert substances than Examples 4.8 to A -1 1 WO 99/52819 16 )the IHAQ used still contained a few % IHEAQ ) pure IHEAQ was used instead of IHAQ Table 2: ) the IHAQ used still contained a few % IHEAQ *) pure IHEAQ was used instead of IHAQ It follows from the comparative Examples 4.1 with 4.2, 4.6 with 4.7, 4.8 with 4.10, 4.9 with 4.11 and 4.12 with 4.13 that the working solutions containing IHAQ/THIHAQ or IHEAQ/THIHAQ surprisingly lead to markedly higher H2O2 17 equivalents than do the analogous working solutions containing AAQ/THAAQ. It follows from Examples 4.3 to 4.5 that, as the molar ratio of the sum of the isohexyl-substituted anthraquinones to the sum of the ethyl-substituted anthraquinones increases, the H2O2 equivalent increases - the molar ratio increases from 40:60 through 50:50 to 60:40, the H2O2 equivalent from 11.9 through 12.4 to 13.0 g of H202/litre. Example 5 The hydrogenation kinetics of various working solutions were studied. The composition of the anthraquinones used and of the solvents and the rate constant k (mol / litre min) at an H2O2 equivalent of 10.0 and 12.0 g of H2O2/litre will be found in the Table. Hydrogenation kinetics standard test: 100 ml of the working solution and 30 mg of Pd black were dispersed by means of ultrasound and hydrogenated in a double-walled vessel, which was equipped with flow breakers and a gassing stirrer, at 2000 rpm, 50°C and an absolute pressure of 0.1 MPa hydrogen. The hydrogen absorption (Nml) over time was recorded. The rate constant k (mol / litre min) of the hydrogenation in dependence on the conversion was calculated from the differential H2 absorptions. The hydrogenatioii kinetics were compared with one another at 0.29 mol conversion, corresponding to an H2O2 equivalent of the working solution of 10.0 g of H2O2/litre, and at 0.35 mol conversion, corresponding to an H2O2 equivalent of 12.0 g of H2O2/litre. The higher k, the more rapidly the hydrogenation proceeds. 18 ) The working solutions of Examples 5.3 and 5.4 came from a laboratory test installation that had been operating for several months and accordingly additionally contained inert constituents from the reaction carrier. *) A Pd having a higher activity than in Examples 5.1 to 5.4 was used in the measurement. The comparative tests (5.1, 5.3 and 5.5 are not in accordance with the invention) show that reaction carrier systems according to the invention permit more rapid hydrogenation than do prior-known systems. The combination EAQ/THEAQ with IHAQ/THIHAQ hydrogenates more rapidly than 19 the combination EAQ/THEAQ with AAQ/THAAQ (compare Example 5.2 with 5.1) - that difference becomes especially clear at an H2O2 equivalent of 12 g/litre- Example 6 In a test arrangement for the cyclic process of the anthraquinone process for the preparation of hydrogen peroxide, consisting of the process steps hydrogenation, oxidation, extraction and drying, regeneration and purification, a working solution, consisting of 75 vol.% benzin aromatic compounds (mixture of C9/C10-alkyl aromatic compounds), 25 vol.% tris(2-ethylhexyl) (sic) phosphate, 0.11 mol/litre of 2-ethylanthraquinone, 0.29 mol/litre of 2-ethyl-tetrahydroanthraquinone, 0.13 mol/litre of 2-isohexylanthraquinone and 0.12 mol/litre of 2-isohexyl-tetrahydroanthraquinone, was studied with regard to the maximum H2O2 production capacity (g of H2O2 produced per litre of working solution) obtainable in continuous operation. The hydrogenation step (loop-type reactor) was conducted at a hydrogen pressure of 0.35 MPa and a temperature of 58°C. Pd black (from 0.5 to 1 g/litre) was used as the hydrogenation catalyst. The H2O2 equivalent in the hydrogenation was gradually raised to a value of 13.0 g/litre and was kept constant for several days, without hydroquinones being seen to crystallise out. When it was attempted to raise the capacity to 13.5 g/litre, hydroquinone crystallised out. Accordingly, the maximum H2O2 capacity of that working solution is between 13.0 and 13.5 g/litre. Example 7 (not in accordance with the invention) Analogously to Example 6, the maximum H2O2 capacity of a working solution consisting of 75 vol.% benzin aromatic compounds (mixture of C9/C10-alkyl aromatic compounds) , 25 vol.% tris(2-ethylhexyl) phosphate, 0.12 mol/litre of 20 2-ethylanthraquinone, 0.28 mol/litre of 2-ethyl-tetrahydroanthraquinone, 0.13 mol/litre of 2-amylanthraquinone and 0.12 mol/litre of 2-amyl-tetrahydroanthraquinone was determined. As compared with Example 6, a markedly greater amount of Pd black, namely from 2 to 3 g/litre, was required in this case in order to maintain the hydrogenation in the sense of complete conversion of the hydrogen used. The maximum H2O2 capacity of that working solution was below 12.4 g of H2O2/litre. Increasing the H2O2 equivalent above 12.4 led to the precipitation of hydroquinones. Example 8 Analogously to Example 6, the maximum H2O2 capacity of a working solution the solvent system of which was based substantially on a C9/C10-benzin aromatic compound and tetrabutylurea (ratio by volume BA:TBU about 3:1) at a hydrogenation temperature of 60°C was determined. The working solution contained as reaction carrier 0.20 mol/litre of 2-ethylanthraquinone, 0.35 mol/litre of 2-ethyltetrahydroanthraquinone, 0.09 mol/litre of 2-isohexylanthraquinone (IHAQ), which still contained a small amount of 2-isohexenylanthraquinone (IHEAQ), and 0.07 mol/litre of 2-isohexyl-tetrahydroanthraquinone (THIHAQ). The amount of catalyst was from 0.5 to 1.0 g/litre. The maximum H2O2 capacity was at least 14 g of H2O2/litre. An increase was not possible only because the test arrangement did not permit higher H2 gassing. 21 We claim: 1. A method of producing hydrogen peroxide according to a continuous anthraqulnone process, comprising: hydrogenating a working solution which comprises: (i) at least one reaction carrier selected from the group consisting of 2-(4-methyl-3-perrtenyl) anthraqulnone, dl-and tetrs-hydroanlhroquinone derivatives thereof, 2-(4-methytpentyl) anthraquinone, and di-and tetra-hydroanthroquinone derivatives thereof, and (ii) at least one reaction carrier selected from the group consisting of 2-alkylanthraquinones and tetrahydroanthraquinone derivatives thereof, wherein the alkyt substltuent of the 2-alkylanthraquinone Is an alkyl substltuent having from 1 to 5 carbon atoms; oxidating the hydrogenated working solution to produce hydrogen peroxide; and isolating the hydrogen peroxide, wherein the at least one reaction carrier according to (i) is present In an amount from 5 to 95 molar % relative to a total amount of reaction carriers. 2. Process as claimed in claim 1, wherein the working solution contains 2-ethylarrthraquinone (EAQ) and/or 2-ethyHetrahydroanthraqulnone (THEAQ) as the reaction carrier according to (II). 3. Process as claimed in claim 1 or 2, wherein the working solution contains IHAQ and/or IHEAO and/or their tetrahydroanthraquinone derivatives hydrogenated at the nucleus, especially p-THIHAQ, as the reaction carrier according to (0. 4. Process as claimed in any one of claims 1 to 3, wherein the working solution used contains reaction carrier according to (I) In an amount of from 10 to 90 mol%, preferably from 20 to 80 mol% and especially from 20 to 50 mol%, based on the sum of the reaction carriers. 22 5. Process as claimed in any one of claims 1 to 4, wherein the working solution used has been obtained by stocking up a working solution containing at least one reaction carrier according to (II), especially EAQ and THEAQ, with 2-(4- methylpentyl)-anthraquinone (IHAQ), their tetrahydro derivatives or mixtures of those reaction carriers, during the cyclic process. 6. Process as claimed In any of claims 1 to 5, wherein there is used during the cyclic process a working solution which contains from 95 to 5%, preferably from 60 to 20%, of the reaction carriers in the anthraquinone form and from 5 to 95%, preferably from 40 to 80%, of the reaction carriers In the tetrahydroanthraquinone form. 7. Process as claimed in any one of claims 1 to 6, wherein a suspension nobte metal catalyst, especially palladium black, or a suspension noble metal catalyst bonded to a support is used as the hydrogenation catalyst in the hydrogenation step. A cyclic anlhraquinone process for producing hydrogen peroxide using at least two differently substituted 2-alkylanthraqulnones and/or their tetrahydro derivatives. The working solution to be used contains (i) at least one reaction carrier from the series 2-(4-methyl-3-pentenyl) anthraquinone (IHEAQ), 2-(4-methylpentyl) anthraquinons (IHAQ) and their di and tetrahydro derivatives such as, In particular 2-(4-methylpenyl)-p-tetrahydroanthraquinone (THIHAQ), and (if) at least one reaction carrier from the series of the 2-(C1- to C5)-alkylanthraqulnones, especially 2-ethylanthraqulnone (EAQ), and their tetrahydro derivatives. The reaction carriers-according to (I) make up 5 to 95 molar %, especially 20 to 50 molar % of all reaction carriers. The method Is distinguished by greater H2O2 capacity, Improved hydrogenatton kinetics and lesser susceptibility to disturbances. A method for making THIHAQ is also disclosed.

Full Text

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Process for the preparation of hydrogen peroxide and reaction carrier for carrying out the process
Description

The invention relates to a process for the preparation of hydrogen peroxide by the anthraquinone cyclic process. The working solution to be used contains as reaction carrier at least two differently substituted 2-alkylanthraquinones and/or the corresponding 2-alkyltetrahydroanthraquinones. The invention relates also to a novel reaction carrier.

In the so-called anthraquinone cyclic process for the preparation of hydrogen peroxide, 2-alkylanthraquinones and/or their 2-alkyl-ot- and/or -p-tetrahydroanthraquinones hydrogenated at the nucleus, acting as reaction carriers, are hydrogenated with hydrogen or a gas containing hydrogen, in an organic solvent system in the presence of a hydrogenation catalyst, the reaction carriers being converted at least partly into the hydroquinone form. The one or more reaction carriers in the hydrogenated or oxidated form and the solution containing the organic solvent system are generally described as the working solution. After the hydrogenation step, the working solution is freed of,the hydrogenation catalyst and treated in the oxidation step with an oxygen-containing gas, the quinone form of the reaction carriers being reformed with the formation of hydrogen peroxide. After the hydrogen peroxide that has formed has been separated from the oxidised working solution, usually by extraction with water and/or an aqueous solution containing hydrogen peroxide, the working solution is again fed to the hydrogenation step. In addition to the mentioned steps, the process may also include regeneration of the working solution, wherein anthraquinone derivatives formed during the cyclic process that are ineffective as reaction carriers, such as anthraquinone epoxides, are re-activated

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and/or 2-alkyltetrahydroanthraquinones are dehydrogenated to the corresponding 2-alkylanthraquinone derivatives and also, as required, reaction carrier losses are made up by the addition of the corresponding 2-substitufced anthraquinones and/or their tetrahydro derivatives. A further step is directed towards the regeneration of the catalyst in order to maintain a high level of activity. An overview of the anthraquinone cyclic process will be found in Ullmann's Encyclopedia of Industrial Chemistry 5th ed. (1989), Vol. A13, 447-457.
Great demands are made of the reaction carrier, in order to ensure that commercial installations operate at the highest possible capacity with the lowest possible susceptibility to failure and the lowest possible loss of reaction carriers. One of the demands is directed especially towards the highest possible solubility of the reaction carrier in the solvent system, both in the quinone form and in the hydroquinone form. The solubility of the hydroquinone form has a determining influence on the maximum H2O2 equivalent (= g of H2O2 per litre of working solution) obtainable during continuous operation. Further demands relate to the hydrogenation and oxidation kinetics; both reactions are to proceed as rapidly as possible. Since the hydrogenation and the oxidation are often affected in opposite ways by a change in the structure of a reaction carrier, even a good reaction carrier system consisting of two or more components is often only a compromise. Also of importance are the highest possible degree of chemical stability of the reaction carrier in the catalytic hydrogenation, a high degree of oxidative stability towards oxygen and hydrogen peroxide, and a high degree of stability towards acids or/and alkalis, such as are used in the regeneration. Finally, the reaction carrier is to be as water-insoluble as possible, toxicologically harmless and inexpensive to

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According to GB Patent 1 252 822 there may be used, in the anthraquinone process for the preparation of hydrogen peroxide one or more 2-alkylanthraquinones having from 2 to 6 carbon atoms in the alkyl group, especially 2-ethyl-, 2-tert.-butyl- and 2-amyl-anthraquinone. The 2-alkyl-tetrahydroanthraquinones that form in the hydrogenation step are also effective.
In the GB patent cited above, not a single 2-alkylanthra-quinone reaction carrier having 6 carbon atoms in the alkyl group is mentioned by way of example or even emphasised. In EP-A documents 0 286 610 and 0 778 085, 2-hexenylanthraquinone is mentioned as a reaction carrier in addition to other 2-alkylanthraquinones and mixtures thereof. That EP document does not indicate which of the possible hexenyl isomers is meant and whether or what advantages can be achieved therewith. It is known that as the chain length of the alkyl substituent in 2-alkylanthraquinones grows, the quinone solubility increases, but at the same time the rate of hydrogenation falls considerably, and that is of greater importance in practice. Accordingly, it was not obvious seriously to consider using a 2-C6-alkylanthraquinone as reaction carrier.
It follows from JP-A 58 180452 and JP-A 59 051235 that 2-(4-methyl-3-pentenyl) -1, 4-dihydroanthraquinone and 2-(4-methyl-3-pentenyl)-anthraquinone and 2-(4-methylpentyl)-anthraquinone obtainable therefrom can be used as reaction carriers for the preparation of hydrogen peroxide. The preparation of the mentioned compounds, the starting material is obtained by Diels-Alder reaction from 1,4-naphthoquinone and myrcene, can be found in those documents. With regard to the use of those compounds in the anthraquinone cyclic process for the preparation of hydrogen peroxide, it is merely mentioned that the same

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results as with known 2-alkylanthraquinones can be obtained.
The demands made of a good reaction carrier are now and again only partly met when a single 2-alkylanthraquinone and/or the corresponding 2-alkyltetrahydroanthraquinone formed in situ is used, depending on the operating conditions. Experts have therefore made every effort to improve the reaction carrier by using at least two different 2-alkylanthraquinones and/or their tetrahydro derivatives. However, advantages regarding one or other of the demands made of a good reaction carrier system are often counteracted by disadvantages regarding other criteria.
According to DE-AS 11 95 279 it is possible to increase the yield of hydrogen peroxide and/or minimise the formation of by-products in the hydrogenation if, instead of a single 2-alkylanthraquinone, such as 2-ethyl-, 2-isopropyl-, 2-sec.-butyl- or 2-tert.-butyl-anthraquinone, there is used a virtually eutectic mixture of at least two 2-alkylanthraquinones, such, as, preferably, 2-ethyl- and 2-sec.-butyl-anthraquinones, in a ratio by weight of 27 to 73, and the degree of hydrogenation is maintained below 40 %. A disadvantage of that process is the requirement that the degree of hydrogenation must be limited. A more serious disadvantage is the unsatisfactory hydrogenation kinetics of those eutectic mixtures. Similar mixtures of two C1- to C4-alkylanthraquinones, which may be present in the so-called "anthra" system as well as in the tetra system, are known from US Patent 2,966,397.
US Patent 4,374,820 proposes using a mixture of 2-tert.-butylanthraquinone and 2-sec.-amylanthraquinone, including their tetrahydro compounds. Although that system has good oxidation kinetics, its hydrogenation kinetics is unsatisfactory. In DE Offenlegungsschriften 11 12 051 and

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11 06 737, on the other hand, it is recommended to use as reaction carrier a mixture of isomeric 2-
amylanthraquinones, especially a mixture of 2-sec.-amyl-and 2-tert.-amyl-anthraquinone and their tetrahydro derivatives. Although a high H2O2 equivalent can be achieved with such systems owing to their good quinone and hydroquinone solubility, the unsatisfactory hydrogenation kinetics is a disadvantage here too, the result of which is a poor space-time yield.
The use of a reaction carrier system based on 2-ethyl-anthraquinone (EAQ) and 2-amylanthraquinone (AAQ) and their tetrahydro derivatives (THEAQ and THAAQ) is also known - see EP-A 0 4 53 94 9 and Chemical Economics Handbook-SRI International June 1992 CEH Product Review Hydrogen Peroxide. A reaction carrier system on that basis (EAQ/THEAQ and AAQ/THAAQ), as compared with a reaction carrier system based on 2-ethylanthraquinone and 2-ethyl-tetrahydroanthraquinone, leads to an increased H2O2 equivalent, which can also be maintained under operational cyclic conditions. A disadvantage of the reaction carrier system based on EAQ/THEAQ and AAQ/THAAQ is its susceptibility to failure in the hydrogenation step, which manifests itself in a reduced hydrogen absorption. When a suspension catalyst, such as Pd black, is used, that behaviour makes it necessary to ensure a relatively high circulation of hydrogenation catalyst and to increase it still further in the case of failures; however, the economic effectiveness of the process falls as a result.
The object of the present invention is to provide a further process for the preparation of hydrogen peroxide using a working solution containing at least two differently substituted 2-alkylanthraquinones and/or their tetrahydro compounds, which process exhibits to a lesser extent the disadvantages of the processes using the prior-known 2-alkylanthraquinone combinations, especially those

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based on ethyl- and amyl-anthraquinone and their tetrahydro derivatives. In addition, the reaction carrier system to be used, while having good hydrogenation kinetics, is to result in a higher H2O2 equivalent which can be reliably controlled during operation, and is to be less susceptible to failure.
The object is achieved by a process for the preparation of hydrogen peroxide by the anthraquinone cyclic process, comprising a hydrogenation step, an oxidation step and a step for isolation of the hydrogen peroxide, using a working solution containing at least two differently substituted 2-alkylanthraquinones and/or their 2-alkyl-tetrahydroanthraquinones, which process is characterised in that the working solution used contains (i) at least one reaction carrier from the group 2-(4-methyl-3-/pentenyl)-anthraquinone (IHEAQ), 2-(4-methylpentyl)-anthraquinone (IHAQ) and their di- and tetra-hydroanthraquinone derivatives hydrogenated at the nucleus, and (ii) at least one reaction carrier from the group of the 2-(C1- to Cs)-alkyl-anthraquinones and their ,tetrahydroanthraquinone derivatives, the reaction carriers according to (i) being present in an amount of from 5 to 95 mol%, based on the sum of all the reaction carriers.
The reaction carrier component according to (i) that is present according to the invention is one or more compounds from the group 2-(4-methyl-3-pentenyl)-anthraquinone, hereinafter also referred to as 2-isohexenylanthraquinone, abbreviated to IHEAQ, 2-(4-methylpentyl)-anthraquinone, hereinafter also referred to as isohexylanthraquinone, abbreviated to IHAQ, 2-(4-methyl-3-pentenyl)-1,4-dihydroanthraquinone (= 1,4-dihydro-IHEAQ), 1,2,3,4-tetrahydro-IHAQ (a-THIHAQ), 5,6,7,8-tetrahydro-IHAQ (P-THIHAQ), 5,6,7, 8-tetrahydro-IHEAQ (p-THIHEAQ) and intermediates from the hydrogenation of IHEAQ and IHAQ to THIHEAQ and THIHAQ, respectively,

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under conditions of the anthraquinone process. In the cyclic process, P-THIHAQ is formed predominantly from IHAQ, together with a small amount of a-THIHAQ - the abbreviation THIHAQ represents the isomeric mixture formed in the process. Reaction carriers according to (i) that are especially preferred in the process according to the invention are IHEAQ and IHAQ and their p-tetrahydro derivatives, especially p-THIHAQ. As a result of the anthraquinone cyclic process, IHAQ and THIHAQ form in the working solution after prolonged operation when IHEAQ is used as the component according to (i).
IHEAQ is obtainable by means of a Diels-Alder reaction from 1,4-naphthoquinone and myrcene, with subsequent base-catalysed oxidation of the resulting 1,4,4a,9a-tetrahydro-IHEAQ with air. IHAQ is obtainable by hydrogenation of IHEAQ, for example on Pt/C. a-THIHAQ is obtainable according to US 1,425,250 by hydrogenation of 1,4-dihydro-IHEAQ.
The invention also provides 2-(4-methylpentyl)-5,6,7, 8-tetrahydroanthraquinone (THIHAQ), a previously unknown reaction carrier for the anthraquinone cyclic process. That compound can be obtained by hydrogenation of IHEAQ with Raney nickel or other hydrogenation catalysts, such as Pt, Pd, Rh in metal form or bonded to a support; it is also formed in the anthraquinone cyclic process from IHAQ and THIHEAQ. ß-THIHEAQ is also obtainable by Diels-Alder reaction of tetrahydronaphthoquinone and myrcene with subsequent base-catalysed oxidation.
The 2-alkylanthraquinone(s) according to

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contains especially 2-ethylanthraquinone (EAQ) and 2-ethyl-tetrahydroanthraquinone (a- and p-THEAQ, p-THEAQ generally being predominant by far).
According to a preferred embodiment, the working solution contains as reaction carrier substantially a combination of EAQ and IHAQ or IHEAQ with the corresponding tetrahydro compounds THEAQ and THIHAQ and/or THIHEAQ. The invention is explained further with reference to that system.
It is possible to stock up a working solution containing substantially EAQ and THEAQ as reaction carrier with 2-isohexenylanthraquinone (IHEAQ) or isohexylanthraquinone (IHAQ) and/or their tetrahydro derivatives, in order to increase the H2O2 capacity. The molar amount of the sum of the anthraquinone and tetrahydroanthraquinone derivatives having an isohexenyl and/or isohexyl group, that is to say the products according to (i), is usually from 5 to 95 %, based on the sum of all the active reaction carriers. During the stocking-up phase, the molar amount of products according to (i) may also be less than 5 %. It is advantageous to adjust the molar amount of anthraquinone derivatives according to (i) to values in the range of from 10 to 90 %, preferably from 20 to 80 mol% and especially from 20 to 50 %, and then maintain those values, since the advantageous effect of the combination according to the invention, namely an increase in the maximum H2O2 capacity with a simultaneous improvement in the hydrogenation kinetics as compared with the closest reaction carrier system, containing EAQ/THEAQ and AAQ/THAAQ, is most marked in that range.
After the addition of 2-isohexenylanthraquinone (IHEAQ) to the working solution, the isohexenyl group is hydrogenated to the isohexyl group in the cyclic process. Although IHEAQ per se is not very stable to oxidation (see Example 3), surprisingly no appreciable degradation of the

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isohexenyl group occurs during the oxidation step in the anthraquinone cyclic process. The content of IHEAQ falls slowly during the cyclic process, while the content of THAQ and THIHAQ rises. THIHEAQ, which is formed in small amounts at the beginning, falls to values below the detection limit again as the process proceeds.
According to a preferred embodiment of the process, the ratio of IHAQ to THIHAQ and EAQ to THEAQ is kept substantially constant during the cyclic process. To that end, a portion of the working solution is withdrawn from the process and fed to a known dehydrogenating regeneration step, wherein the tetrahydro derivatives that are present are dehydrogenated and the anthraquinone system is re-formed; the proportion of the working solution so regenerated is fed to the cyclic process again. Advantageously, from 40 to 80 mol% of all the reaction carriers are in the tetrahydroanthraquinone form.
It has been found that as the proportion of reaction carriers of type (i), that is to say especially IHAQ, IHEAQ and THIHAQ, increases, based on the sum of all the reaction carriers, the hydroquinone solubility and hence the maximum hydrogen peroxide production capacity (g of H2O2/litre of working solution) is increased; that capacity exceeds that of analogous systems containing the system AAQ/THAAQ instead of IHAQ/THIHAQ - see Examples 4.1 to 4.13. Furthermore, the capacity increases as the proportion of tetrahydroanthraquinones rises. Contrary to existing knowledge, according to which the hydrogenation kinetics becomes poorer as the number of carbon atoms in the alkyl group of a. reaction carrier increases, the hydrogenation kinetics of the reaction carrier according to (i) to be used in accordance with the invention having an isohexyl or -isohexenyl substituent is surprisingly substantially better than the hydrogenation kinetics of the isomeric 2-amylanthraquinones and 2-amyl-

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tetrahydroanthraquinones (AAQ/THAAQ) - see Examples 5.1 to 5.6. The reason for the extraordinary advantage of the process according to the invention is that, with the reaction carrier combination according to the invention, as compared with the closest prior-known reaction carrier system (EAQ, AAQ and their tetrahydro derivatives), a higher H2O2 capacity is achieved while at the same time the hydrogenation kinetics is improved.
The reaction carrier system according to the invention can be used in any process of the generic type for the preparation of hydrogen peroxide. In the hydrogenation step there may be used known catalysts, such as, especially, those based on noble metals, such as Pd, Pt, Ir, Rh, Ru or mixtures of such noble metals, and Raney catalysts of Ni, Co or Fe. The catalysts may be used as suspension catalysts - for example Pd black or noble metals bonded to a support - or in the form of fixed-bed catalysts. The support-suspension and fixed-bed catalysts are especially noble metals on an inorganic support, such as SiO2, TiO2, A12O3, zeolite, BaSO4, polysiloxane. Finally, the catalyst may also be arranged on the surface of a monolithic ceramics support or of a honeycomb component having a sufficiently large surface. Customary hydrogenation reactors are in the form of a loop-type reactor, fixed-bed reactor, mammoth-pump reactor as well as a reactor having integrated static mixers.
The hydrogenation is generally carried out at a temperature in the range of from room temperature to 100°C, especially from 45 to 70°C. The hydrogenation pressure is usually in the range of approximately from 100 kPa to 1 MPa, especially from 200 kPa to 500 kPa. The hydrogenation is usually so conducted that the hydrogen introduced into the hydrogenation cycle is used up completely and the degree of hydrogenation is maintained in the range of from 30 to 80 %.

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The working- solution containing the reaction carrier system according to the invention generally contains two or more solvents in order to keep the reaction carrier components in the quinone form and hydroquinone form in solution. Suitable solvents and solvent combinations are those which are known from prior-known anthraquinone cyclic processes. There are especially suitable solvent combinations that contain, in addition to a benzin aromatic compound (polyalkylated benzene), one or more solvents from the group of the secondary alcohols, such as diisobutylcarbinol, esters, such as methylcyclohexyl acetate, phosphoric acid esters, such as tris(2-ethylhexyl) phosphate, tri- and tetra-alkylated ureas, such as tetrabutylurea, cyclic ureas, pyrrolidones, carbamates and N-alkylated caprolactams, such as N-hexylcaprolactam.
Essential advantages of the process according to the invention are: a capacity that is higher by at least 0.6 g of H2O2/litre of working solution as compared with the closest prior-known process; an improved hydrogenation kinetics; a lower susceptibility to failure during continuous operation; a smaller amount of circulating palladium where Pd black is used as the catalyst.
The invention is explained in greater detail with reference to the Examples and Comparison Examples below.
Example 1
Preparation of 2-(4-methyl-3-pentenyl)-anthraquinone ( 2-isohexenyl-anthraquinone, abbreviated to IHEAQ):

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The preparation was carried out analogously to JP-A 59-51235 by means of a Diels-Alder reaction with subsequent aromatisation.
397 g (2.56 mol) of myrcene (88 %, Aldrich) were used initially and then 405 g (2.48 mol) of 1,4-naphthoquinone (97 %) were added thereto. The suspension was stirred for 2 hours at 100°C (the exothermic reaction was already almost complete after approximately 0.5 hour). The reaction mixture, a brown oil, was introduced into an ethanolic sodium hydroxide solution (3 litres of ethanol and 40 g of NaOH). The suspension was stirred at 50°C for 2 hours while air was passed in - undissolved material initially went into solution, finally a reddish-yellow precipitate began to form. After cooling, the solid was filtered off with suction and washed with 250 ml of ice-cooled ethanol. After drying, 616 g of yellow powder were obtained. HPLC analysis showed an IHEAQ content of 98.5 % by surface area. The 1H-NMR spectrum and the melting point (89-90°C, recrystallised once from n-heptane) corresponded to IHEAQ.
Example 2
Preparation of 2-(4-methylpentyl)-p-tetrahydroanthraquinone (= p-THIHAQ).
500 g (= 1.7 mol) of IHEAQ (crude product), dissolved in 3.5 litres of n-butyl acetate, were placed at 50°C in a 5 litre hydrogenating vessel having a gassing stirrer. After flushing the apparatus with nitrogen, 100 g of Raney nickel (suspended in 500 ml of isopropanol) were introduced and the hydrogenation was then started. After the absorption of 35 litres of H2 (hydroquinone formation), the H2 absorption suddenly slowed. After 30 hours, when 88 litres of H2 had been absorbed, the reaction was stopped. According to HPLC, the reaction mixture, freed of

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the catalyst and solvent, contained, in % by surface area: 33 % starting material (= IHEAQ) , 45 % 2-(4-methyl-3-pentenyl)-ß-tetrahydroanthraquinone (= ß-THIHEAQ), 11 % 2-{4-methylpentyl)-anthraquinone (= IHAQ) and 8 % of the desired THIHAQ. In order to remove alkali compounds entrained with the IHEAQ that was used, the reaction mixture, freed of the catalyst, was washed with 10 % hydrochloric acid, with aqueous sodium hydrogen carbonate solution and then with water, and was dried. 437 g of the residue that remained after removal of the solvent were hydrogenated again in n-butyl acetate (3 litres) (sic) isopropanol (0.5 litre) in the presence of 100 g of Raney nickel. After 27.5 hours, when the reaction mixture had absorbed 74 litres of H2, the reaction was terminated. After removal of the catalyst by filtration, the reaction mixture was thoroughly oxidised by gassing with air, and was then concentrated. The precipitate was filtered off with suction and washed with isopropanol and finally recrystallised. 304 g of ß-THIHAQ were obtained in the form of a light-yellow powder: According to HPLC, the purity was 99.7 % by surface area. The 1H-NMR spectrum corresponded to p-THIHAQ.
Example 3
Determination of the oxidative stability of 2-(4-methyl-3-pentenyl)anthraquinone (IHEAQ) (= Example 3a) in comparison with 2-ethylanthraquinone (EAQ) (= Example 3b): 0.04 mol of the quinone IHEAQ or EAQ were dissolved in 100 ml of 1,2-dichlorobenzene. After the addition of 10 mg of azo-bis-isobutyronitrile as radical initiator, stirring was carried out at 150°C, with a covering layer of oxygen, using a gassing stirrer. After 24 hours, the quinone content was determined by chromatography. The residual quinone content was 41 % in the case of IHEAQ and 90 % in the case of EAQ.

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In contrast to Example 3a, IHEAQ is surprisingly not oxidatively degraded any more than EAQ under the conditions of the anthraquinone cyclic process for the preparation of hydrogen peroxide, although IHEAQ is detectable for a long time in the cyclic process since it is hydrogenated only slowly to 2-(4-methylpentyl)-anthraquinone (IHAQ).
Example 4
Determination of the hydroquinone solubility of various reaction carrier mixtures in various solvent systems. The reaction carriers used and the amounts thereof will be found in Tables 1 and 2.
Method of determination: A suspension consisting of the corresponding working solution and a small amount of freshly precipitated palladium black was introduced into a magnetically stirred, thermostatically controlled double-walled vessel which was equipped with a device for electronic turbidity measurement. Using a gas burette, the mixture was slowly hydrogenated; in addition, in order to avoid over-hydrogenation as the limit of solubility was reached, seed crystals in the form of the hydroquinone were added. The maximum hydroquinone solubility was reached when permanent turbidity was recorded by the measuring device. The hydrogen absorbed at that point was converted into H2O2 equivalents, defined as g of H2O2 per litre of working solution at 20°C.
Examples 4.1, 4.6, 4.8, 4.9 and 4.12 are systems which are not in accordance with the invention containing the reaction carriers EAQ/THEAQ plus AAQ/THAAQ. Examples according to the invention (4.2 to 4.5, 4.7, 4.10, 4.11 and 4.13) contain the reaction carriers EAQ/THEAQ plus IHAQ/THIHAQ or IHEAQ/THIHAQ, where: EAQ = 2-ethylanthraquinone; THEAQ = tetrahydro-EAQ; AAQ =

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2-amylanthraqulnone, wherein amyl represents a mixture of 1,2-dimethylpropyl and 1,1-dimethylpropyl (= iso-sec- and tert.-amyl); IHAQ = 2-isohexylanthraquinone; THIHAQ = p-tetrahydro-IHAQ. In Example 4.7, LHEAQ was used instead of IHAQ.
While the hydrogenation temperature in Examples 4.1 and 4.2 was 60°C, all the other Examples were carried out at 50°C.
In Examples 4.1 to 4.5, a mixture of C9/C10-benzin aromatic compound (BA) and diisobutylcarbinol (DIBC) in a ratio by volume of 6:4 was used as solvent; in Examples 4.6 and 4.7, a mixture of substantially C9/C10-benzin aromatic compound and tetrabutylurea (TBU) in a ratio by volume of 2.5:1 was used.
In Examples 4.8 to 4.11, the solvent system consisted of C9/C10-benzin aromatic compound and tris (2-ethylhexyl) phosphate (TOP) in a ratio by volume of 3:1, and in Examples 4.12 and 4.13 it consisted of substantially C9/C10-benzin aromatic compound and tetrabutylurea in a ratio by volume of 2.5:1. The working solutions of Examples 4.8 to 4.13 contained inert degradation products of the anthraquinones which had been used, owing to their prolonged use in a continuous laboratory installation. The working solutions of Examples 4.12 and 4.13 contained by virtue of their preparation - use of an operational working solution based on EAQ/THEAQ - a .substantially larger amount of inert substances than Examples 4.8 to
A -1 1

WO 99/52819
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*)the IHAQ used still contained a few % IHEAQ **) pure IHEAQ was used instead of IHAQ
Table 2:

*) the IHAQ used still contained a few % IHEAQ **) pure IHEAQ was used instead of IHAQ
It follows from the comparative Examples 4.1 with 4.2, 4.6 with 4.7, 4.8 with 4.10, 4.9 with 4.11 and 4.12 with 4.13 that the working solutions containing IHAQ/THIHAQ or IHEAQ/THIHAQ surprisingly lead to markedly higher H2O2

17
equivalents than do the analogous working solutions containing AAQ/THAAQ. It follows from Examples 4.3 to 4.5 that, as the molar ratio of the sum of the isohexyl-substituted anthraquinones to the sum of the ethyl-substituted anthraquinones increases, the H2O2 equivalent increases - the molar ratio increases from 40:60 through 50:50 to 60:40, the H2O2 equivalent from 11.9 through 12.4 to 13.0 g of H202/litre.
Example 5
The hydrogenation kinetics of various working solutions were studied. The composition of the anthraquinones used and of the solvents and the rate constant k (mol / litre min) at an H2O2 equivalent of 10.0 and 12.0 g of H2O2/litre will be found in the Table.
Hydrogenation kinetics standard test: 100 ml of the working solution and 30 mg of Pd black were dispersed by means of ultrasound and hydrogenated in a double-walled vessel, which was equipped with flow breakers and a gassing stirrer, at 2000 rpm, 50°C and an absolute pressure of 0.1 MPa hydrogen. The hydrogen absorption (Nml) over time was recorded. The rate constant k (mol / litre * min) of the hydrogenation in dependence on the conversion was calculated from the differential H2 absorptions. The hydrogenatioii kinetics were compared with one another at 0.29 mol conversion, corresponding to an H2O2 equivalent of the working solution of 10.0 g of H2O2/litre, and at 0.35 mol conversion, corresponding to an H2O2 equivalent of 12.0 g of H2O2/litre. The higher k, the more rapidly the hydrogenation proceeds.

18

*) The working solutions of Examples 5.3 and 5.4 came from a laboratory test installation that had been operating for several months and accordingly additionally contained inert constituents from the reaction carrier.
**) A Pd having a higher activity than in Examples 5.1 to 5.4 was used in the measurement.
The comparative tests (5.1, 5.3 and 5.5 are not in accordance with the invention) show that reaction carrier systems according to the invention permit more rapid hydrogenation than do prior-known systems. The combination EAQ/THEAQ with IHAQ/THIHAQ hydrogenates more rapidly than

19
the combination EAQ/THEAQ with AAQ/THAAQ (compare
Example 5.2 with 5.1) - that difference becomes especially
clear at an H2O2 equivalent of 12 g/litre-
Example 6
In a test arrangement for the cyclic process of the anthraquinone process for the preparation of hydrogen peroxide, consisting of the process steps hydrogenation, oxidation, extraction and drying, regeneration and purification, a working solution, consisting of 75 vol.% benzin aromatic compounds (mixture of C9/C10-alkyl aromatic compounds), 25 vol.% tris(2-ethylhexyl) (sic) phosphate, 0.11 mol/litre of 2-ethylanthraquinone, 0.29 mol/litre of 2-ethyl-tetrahydroanthraquinone, 0.13 mol/litre of 2-isohexylanthraquinone and 0.12 mol/litre of 2-isohexyl-tetrahydroanthraquinone, was studied with regard to the maximum H2O2 production capacity (g of H2O2 produced per litre of working solution) obtainable in continuous operation. The hydrogenation step (loop-type reactor) was conducted at a hydrogen pressure of 0.35 MPa and a temperature of 58°C. Pd black (from 0.5 to 1 g/litre) was used as the hydrogenation catalyst. The H2O2 equivalent in the hydrogenation was gradually raised to a value of 13.0 g/litre and was kept constant for several days, without hydroquinones being seen to crystallise out. When it was attempted to raise the capacity to 13.5 g/litre, hydroquinone crystallised out. Accordingly, the maximum H2O2 capacity of that working solution is between 13.0 and 13.5 g/litre.
Example 7 (not in accordance with the invention)
Analogously to Example 6, the maximum H2O2 capacity of a working solution consisting of 75 vol.% benzin aromatic compounds (mixture of C9/C10-alkyl aromatic compounds) , 25 vol.% tris(2-ethylhexyl) phosphate, 0.12 mol/litre of

20
2-ethylanthraquinone, 0.28 mol/litre of 2-ethyl-tetrahydroanthraquinone, 0.13 mol/litre of 2-amylanthraquinone and 0.12 mol/litre of 2-amyl-tetrahydroanthraquinone was determined. As compared with Example 6, a markedly greater amount of Pd black, namely from 2 to 3 g/litre, was required in this case in order to maintain the hydrogenation in the sense of complete conversion of the hydrogen used. The maximum H2O2 capacity of that working solution was below 12.4 g of H2O2/litre. Increasing the H2O2 equivalent above 12.4 led to the precipitation of hydroquinones.
Example 8
Analogously to Example 6, the maximum H2O2 capacity of a working solution the solvent system of which was based substantially on a C9/C10-benzin aromatic compound and tetrabutylurea (ratio by volume BA:TBU about 3:1) at a hydrogenation temperature of 60°C was determined. The working solution contained as reaction carrier 0.20 mol/litre of 2-ethylanthraquinone, 0.35 mol/litre of 2-ethyltetrahydroanthraquinone, 0.09 mol/litre of 2-isohexylanthraquinone (IHAQ), which still contained a small amount of 2-isohexenylanthraquinone (IHEAQ), and 0.07 mol/litre of 2-isohexyl-tetrahydroanthraquinone (THIHAQ). The amount of catalyst was from 0.5 to 1.0 g/litre. The maximum H2O2 capacity was at least 14 g of H2O2/litre. An increase was not possible only because the test arrangement did not permit higher H2 gassing.

21
We claim:
1. A method of producing hydrogen peroxide according to a continuous
anthraqulnone process, comprising:
hydrogenating a working solution which comprises:
(i) at least one reaction carrier selected from the group consisting of 2-(4-methyl-3-perrtenyl) anthraqulnone, dl-and tetrs-hydroanlhroquinone derivatives thereof, 2-(4-methytpentyl) anthraquinone, and di-and tetra-hydroanthroquinone derivatives thereof, and
(ii) at least one reaction carrier selected from the group consisting of 2-alkylanthraquinones and tetrahydroanthraquinone derivatives thereof, wherein the alkyt substltuent of the 2-alkylanthraquinone Is an alkyl substltuent having from 1 to 5 carbon atoms;
oxidating the hydrogenated working solution to produce hydrogen
peroxide; and
isolating the hydrogen peroxide,
wherein the at least one reaction carrier according to (i) is present In
an amount from 5 to 95 molar % relative to a total amount of reaction
carriers.
2. Process as claimed in claim 1, wherein the working solution contains
2-ethylarrthraquinone (EAQ) and/or 2-ethyHetrahydroanthraqulnone
(THEAQ) as the reaction carrier according to (II).
3. Process as claimed in claim 1 or 2, wherein the working solution
contains IHAQ and/or IHEAO and/or their tetrahydroanthraquinone
derivatives hydrogenated at the nucleus, especially p-THIHAQ, as the
reaction carrier according to (0.
4. Process as claimed in any one of claims 1 to 3, wherein the working
solution used contains reaction carrier according to (I) In an amount of
from 10 to 90 mol%, preferably from 20 to 80 mol% and especially
from 20 to 50 mol%, based on the sum of the reaction carriers.

22
5. Process as claimed in any one of claims 1 to 4, wherein the working solution
used has been obtained by stocking up a working solution containing at least
one reaction carrier according to (II), especially EAQ and THEAQ, with 2-(4-
methylpentyl)-anthraquinone (IHAQ), their tetrahydro derivatives or mixtures
of those reaction carriers, during the cyclic process.
6. Process as claimed In any of claims 1 to 5, wherein there is used during the
cyclic process a working solution which contains from 95 to 5%, preferably
from 60 to 20%, of the reaction carriers in the anthraquinone form and from 5
to 95%, preferably from 40 to 80%, of the reaction carriers In the
tetrahydroanthraquinone form.
7. Process as claimed in any one of claims 1 to 6, wherein a suspension nobte
metal catalyst, especially palladium black, or a suspension noble metal
catalyst bonded to a support is used as the hydrogenation catalyst in the
hydrogenation step.

A cyclic anlhraquinone process for producing hydrogen peroxide using at least two differently substituted 2-alkylanthraqulnones and/or their tetrahydro derivatives. The working solution to be used contains (i) at least one reaction carrier from the series 2-(4-methyl-3-pentenyl) anthraquinone (IHEAQ), 2-(4-methylpentyl) anthraquinons (IHAQ) and their di and tetrahydro derivatives such as, In particular 2-(4-methylpenyl)-p-tetrahydroanthraquinone (THIHAQ), and (if) at least one reaction carrier from the series of the 2-(C1- to C5)-alkylanthraqulnones, especially 2-ethylanthraqulnone (EAQ), and their tetrahydro derivatives. The reaction carriers-according to (I) make up 5 to 95 molar %, especially 20 to 50 molar % of all reaction carriers. The method Is distinguished by greater H2O2 capacity, Improved hydrogenatton kinetics and lesser susceptibility to disturbances. A method for making THIHAQ is also disclosed.

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Patent Number

207475

Indian Patent Application Number

IN/PCT/2000/00288/KOL

PG Journal Number

24/2007

Publication Date

15-Jun-2007

Grant Date

14-Jun-2007

Date of Filing

01-Sep-2000

Name of Patentee

DEGUSSA AG,

Applicant Address

BENNIGSENPLATZ 1,D-40474, DUSSELDORF,

Inventors:

#	Inventor's Name	Inventor's Address
1	STAAB, Dr. EUGEN	SPESSARTSTRASSE 30, DE-63768 HOSBACH
2	ANGERT, Dr. HUBERT	SCHONBORNSTRASS 80b DE-63456 HANAU
3	GLENNEBERG, DR. JURGEN	Bieberer Strasse 37, DE-63065 Offenbach,
4	GOOR, Dr. GUSTAAF	GLEIWITZER STRASSE 1, DE-63457 HANAU

PCT International Classification Number

C01B 15/023, C07C 50/16

PCT International Application Number

PCT/EP99/01972

PCT International Filing date

1999-03-20

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	198 16 297.9	1998-04-11	Germany