CA1283273C - Process and apparatus for carrying out oxidation in the anthraquinone process for the preparation of hydrogen peroxide - Google Patents
Process and apparatus for carrying out oxidation in the anthraquinone process for the preparation of hydrogen peroxideInfo
- Publication number
- CA1283273C CA1283273C CA000508543A CA508543A CA1283273C CA 1283273 C CA1283273 C CA 1283273C CA 000508543 A CA000508543 A CA 000508543A CA 508543 A CA508543 A CA 508543A CA 1283273 C CA1283273 C CA 1283273C
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- Prior art keywords
- working solution
- gas
- reactor
- process according
- hydrogenated working
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00168—Controlling or regulating processes controlling the viscosity
Abstract
Abstract In a process for conducting oxidation in the cyclic process for the preparation of hyrogen peroxide according to the anthraquinone process, by gasifying the hydrogenated working solution with an oxidising gas in a co-current reactor at temperatures below 100°C and at over-pressures below 15 bar, and increasing the rate of reaction in the oxidation step, the hydrogenated working solution, after the hydrogenation stage, is intensively mixed with an oxidising gas to form a non-coalescing system and introduced into the lower part of a reactor essentially free of internal structures, so that there is substantially complete reaction of the oxygen with the hydroquinone present in the working solution. Apparatus suitable for carrying out the process comprises a mixer, a reactor free of internal structures and, as desired, a distributor.
Description
7~
The process for the preparation of hydrogen peroxide by reduction of an anthraquinone compouna, and oxidation of the resultant hydroquinone compound, is known; see, for example, Ullmann, Encyklopaedie der Technischen Chemie, Ath Edition, Volume 17, p. 697-705 (1975);
Winnacker-Kuechler, Chemische Technologie, Volume 1, Anoryanische Technologie I, p. 529-559.
In carrying out the oxidation step, it is essential that the non-instantaneous oxidation of the hydroquinone takes place as quickly as possible, in order that changes to the working solution, which lead to the formation of by-products, are kept low and, at best, completely avoided; see US-A-2902347.
Attempts have therefore been made to make the residence time of the working solution in the oxidation step as short as possible, loc. cit.
There is however the disadvantage that, owing to the necessary residence time, considerable expenditure on apparatus for several columns connected in sequence is necessary, especially for working solutions having high contents of tetrahydroanthrahydroquinone derivatives.
Further, the capacity of these columns ~counter-current columns are used) is limited to a very low flood level;
see DE-B-2003268.
The same applies for a cascade arrangement in multi-step continuous oxidation, in which, however, a certain bubble size for the oxidising gas as well as a low gas cross-sectional capacity may not be exceeded; see US-A-3073680.
In order to achieve better contact between the two reaction components, and thereby to achieve a reduction in the residence time, it has also been attempted to accelerate the oxidation by the use of included structures or packing material in the reactors, as is 7;~
described for the cascade arrangement for counter-current reaction in US-A-3752885.
Again, in the column described in DE-B-2003268, the working solution and oxidising gas are in counter-current in the complete column, but are passed together in a co-current stream in individual sections, included structures or packing materials are introduced to increase intermixing, as is also the case for the process described in Chem. Process Eng. 40, No. 1, 5 (1959).
Quite independently from the considerable pressure loss caused by included structures and packing material, the apparatus cannot be kept as small as is desirable, because the included structures and packing material require a certain proportion of the reaction space.
The art therefore has considerable interest in an e~fective but simplified procedure for the oxidation step in anthraquinone processes.
The object of the invention is therefore to conduct the oxidation of the hydrogenated working solution with the oxygen-containing gas in a shorter time and wlth less technical expenditure than for previously known processes, while protecting the working solution to the greatest possible degree.
It has now been found that this object can be attained by conducting the oxidation in the cyclic process for the preparation of hydrogen peroxide according to the anthraquinone process, by gasifying the hydrogenated working solution with an oxidising gas in a co-current reactor at temperatures below 100C and at over-pressures below 15 bar, if the hydrogenated working solution, following the hydrogenation step, is mixed intensively with an oxidising gas, with the formation of a non-coalescing system having a proportion of gas of at least 40% by volume, preferably 50 to 60~ by volume, and wherein the average diameter of the gas bubbles ~3;~'7;~
is no more than 2.5 mm, preferably less than 1.5 mm, whereby ~he non-coalescing system is passed directly ox via a distributor into the lower part of a tubular, preferably installation-free, reactor which is so dimensioned that as complete a reaction as possible of the oxygen with the hydroquinone in the hydrogenated working solution is facilitated, whereupon the thoroughly oxidised mlxture of hydrogenated working solution and oxidised gas is separated in known manner into gas and li~uid.
Non-coalescing systems are conventionally those in which the gas bubbles which are present maintain their size in the absence of any external action on the system.
In these systems, the liquids are distinguished by certain characteristics which depend on the interface, such as, for example, viscosity and specific surface tension. A simple test can be used to establish whether the liquid can form a non-coalescing system with the relevant gas.
It now appears that, in working solutions used for the anthraquinone process, in which hydrocarbons or mixtures thereof are introduced as quinone solvents, in order to give non-coalescing systems comprising oxygen or oxygen-nitrogen mixtures (the latter in any mixture ratio), it is clesirable that the total quotient of all interfacial.tensions of the relevant components has a value of at least 16 dyn/cm. Values of 17 to 25 dyn/cm are preferred. Widely used hydrocarbons are, for example, methylnaphthalene, dimethylnaphthalene, benzene, trimethylbenzene, tert-butylbenzene and aromatic benzenes having a boiling point of about 185 to 205C, with the exception of diphenyl and o dichlorobenzene. The recently-introduced tetra-substituted ureas can also be used as a components of the working solution.
3~
In order to prepare gas bubbles having an average diameter of no more than 2.5 mm, but preferably less than 1.5 mm, sieve plates or frits are used, whose apertures have a size corresponding to the desired bubble cross-section.
It has in ract been found particularly suitable to use known apparatus which comprises a tube whose initial tube nominal width narrows to a channel, and thereafter increases to the same or another nominal width.
Apparatus of this type causes low pressure loss.
In this apparatus, the hydrogenated working solution and the oxidising gas, either together or separate, but then in co-current flow, are introduced after the hydrogenation step. Before introduction into the channel, mixing of the working solution and gas has already begun. The intensive intermixing is achieved in streaming through the channel. A non-coalescing system, having a narrow spectrum of gas bubble diameters, is obtained. The size of the channel has an influence on this spectrum, depending on the stream volume throughout.
The bubble diameter depends on the energy input and this further depends on the pressure loss and on the volume through~ut. The appropriate pressure loss can be established for a given throughput by establishing the channel breadth.
In the case of a working solution comprising 2-ethyltetrahydroanthraquinone, ethylanthraquinone, aromatic benzenes having a boiling point of 185 to 205C
and triethylhexylphosphate and air, the bubble diameter is in general about 0.5 mm.
Suitable oxidising gases are any oxygen-nitrogen mixtures, and also pure oxygen. However, air is preferably used.
The non-coalescing system comprising hydrogenated working solution and oxidising gas which is obtained '7;~
accordln~ to the invention, is passed over a distributor into a tubular reactor. The mixing means for its preparation can be positioned on this reactor, directly on its floor or in the neighbourhood of the ~loor, in the side wall; it can also be positioned independently of the reactor, hoxizontally or vertically, and connected to the reactor by a conduit.
In any case, the non-coalescing system passes into the lower part of the reactor, if necessary through a distributor. This distributor, preferably in ring form, is so constructed that the mixture o~ hydrogenated working solution and oxidising gas is introduced uniformly across the cross-section of the reactor. The greater the cross-section of the reactor, the greater care must be taken with respect to uniform distribution.
Within the context of the invention, "distributor" does not of course refer to any inlet means such as, e.g., sieve bottoms, which cause the gas bubbles to coalesce.
The openings of the distributor must therefore be so dimensioned and positioned that the mixture is not separated but rather distributed uniformly, even at high throughput, across the cross-section of the reactor. The tube-like reactor itself, in its reaction volume, is free of any included structures, i.e. empty, except perhaps for the distributor.
The reactor has dimensions so that the degree of oxidation, based on the available hydroquinone, is at least 90%, but preferably at least 98~, be~ore the gas-containing working solution enters a liquid/gas separator. It appears that a reaction volume of 8 to 30 m height within the reactor meets this objective.
Particular care must be taken in order to achieve uniform distribution of the non-coalescing mixture, over the total cross-section of the reactor at cross-sections greater than 0.5 m, and more particularly when the mixing means is positioned outside the reactor.
The oxidation reaction takes place at pressures of 1 up to 15 bar, and preferably at 2 to 5 bar. The most suitable temperatures are 30 to 80C.
After conducting the oxidation, the working solution and the residual gas, which comprises mainly non-reactive nitrogen if nitrogen/oxygen mixtures, especially air, are used, is passed to a conventional liquid/gas separator, e.g. a centrifugal separator, and separated in known manner. This gas extractor can be positioned in the upper part of the reactor, in connection with the actual reaction volume, or it can be outside the reactor and connected therewith via a conduit.
The separated gas can be adsorbed on an active carbon unit. The oxidised working solution is passed for extraction.
The invention is illustrated in greater detail, in comparison with the state of the art, in the accompanying drawings. Figure 1 shows mixing means suitable for input according to the invention. Figure 2 shows various possibilities for combining mixer, distributor and reactor, according to the invention. Figure 3 shows an oxidation tower known from DE-A-2003268, and Figure 4 shows apparatus particularly suitable for conducting the process according to the invention.
In Figure 1, the hydrogenated working solution (WS) is introduced into the mixer 1 via the conduit 2, and the oxidising gas is introduced via the conduit 3. After streaming through the upper part of the mixer 1, the gas/liquid mixture enters into the channel S where very intensive intermixing takes place and the gas is separated into bubbles having a diameter of no more than 2.5 mm, and pxeferably substantially smaller. In consequence, there is the very high exchange area '7;~
necessary for the oxidation, and in a non-coalescing system. This non-coalesclng mixture is then passed into the empty reactor 6 as shown in Fig. 2, via a distributor 7 (embodiments a and b according to Fig. 2) or directly, by positioning the mixing means 1 on the floor of the reactor 6 tembodiment c according to Fig.
~) .
The technical advantages of the process according to the invention, with respect to the known procedure for the oxidation step in the anthraquinone process, lie in the very fine distribution of the oxidising gas in the working solution as well in the fact that the high exchange surface which is thus generated is retained during passage through the reactor and during the reaction, as a non-coalescing system.
This feasibility provides a new way of conducting the oxidation in the anthraquinone process. Owing to the great exGhange area, the rate of reaction is greatly increased, so that the degree of oxidation is at least as great as before, even if higher degrees, up to practically 100~, are not achieved, and over a shorter residence time for the oxidising mixture, than before.
The oxidation reactors can therefore be smaller, because the apparatus yield i5 increased and because bulky included structures such as packing materials are unnecessary. At the same time, the amounts of side-products and degradation products are reduced to a minimum, i.e. the working solution is protected.
Further, because the distribution of the non-coalescing mixture is controlled so that this is distributed uniformly over the entire cross-section of the reactor, re-mixing is effectively avoided. Owing to the completely installation-free reaction volume in the reactor, high cross-sectional capacity can be achieved.
For example, using air as the oxidising gas, 3~7;~
cross-sectional capacities for gas of 2000 to 3000 m3/m2h are achieved. The corresponding liquid capacity is from 40 to 60 m3/m2h.
Because the mixing means and also the mixture distributor are apparatus which do not cause great pressure loss, and because there is scarcely any pressure loss in the completely installation-free reaction volume, the apparatus arrangement of mixing means, distributor and reactor represents a total system having a very low pressure loss. The energy needs for such oxidation apparatus are clearly less than for previously known apparatus.
The following Example illustrates the invention in more detail, apparatus constructed for the purposes of the invention (corresponding to Fig. 4) being compared with a three-stage reactor cascade according to DE-B-2003268 (as in Fig. 3).
ta) Known procedure 260 m3/h of a working solution having an H2O2 equivalent of about 9.45 kg/m were passed through an o~idation tower according to Fig. 3 together with 10,000 m3 air/h. The tower had a diameter of 3.7 m and was divided into three sections which, together, had an effecti~e height of 15 m. At 2.5 bar at the head of the column and 4.0 bar at the column sump, and at an average temperature o~E 54C, 98.3% oxidation was achieved. The 2 content in the residual gas was below 5.9 vol %, and the current requirement for the air compressor was 0.36 kWh/kg ~22 From this, a working solution cross-sectional capacity of 24 m3/m2h and an air cross-sectional capacity of 930 m3/m2h are derived. The space-time yield was about 15 kg/m3h.
(b) Procedure according to the invention 345 m3/h of a working solution having an H2O2 g equivalent of about 11.4 kg/m3 were passed, together with about 16,300 m3 air/h through the mixer 1 and the distributor 7 in the oxidation tower 6 according to Fig.
The process for the preparation of hydrogen peroxide by reduction of an anthraquinone compouna, and oxidation of the resultant hydroquinone compound, is known; see, for example, Ullmann, Encyklopaedie der Technischen Chemie, Ath Edition, Volume 17, p. 697-705 (1975);
Winnacker-Kuechler, Chemische Technologie, Volume 1, Anoryanische Technologie I, p. 529-559.
In carrying out the oxidation step, it is essential that the non-instantaneous oxidation of the hydroquinone takes place as quickly as possible, in order that changes to the working solution, which lead to the formation of by-products, are kept low and, at best, completely avoided; see US-A-2902347.
Attempts have therefore been made to make the residence time of the working solution in the oxidation step as short as possible, loc. cit.
There is however the disadvantage that, owing to the necessary residence time, considerable expenditure on apparatus for several columns connected in sequence is necessary, especially for working solutions having high contents of tetrahydroanthrahydroquinone derivatives.
Further, the capacity of these columns ~counter-current columns are used) is limited to a very low flood level;
see DE-B-2003268.
The same applies for a cascade arrangement in multi-step continuous oxidation, in which, however, a certain bubble size for the oxidising gas as well as a low gas cross-sectional capacity may not be exceeded; see US-A-3073680.
In order to achieve better contact between the two reaction components, and thereby to achieve a reduction in the residence time, it has also been attempted to accelerate the oxidation by the use of included structures or packing material in the reactors, as is 7;~
described for the cascade arrangement for counter-current reaction in US-A-3752885.
Again, in the column described in DE-B-2003268, the working solution and oxidising gas are in counter-current in the complete column, but are passed together in a co-current stream in individual sections, included structures or packing materials are introduced to increase intermixing, as is also the case for the process described in Chem. Process Eng. 40, No. 1, 5 (1959).
Quite independently from the considerable pressure loss caused by included structures and packing material, the apparatus cannot be kept as small as is desirable, because the included structures and packing material require a certain proportion of the reaction space.
The art therefore has considerable interest in an e~fective but simplified procedure for the oxidation step in anthraquinone processes.
The object of the invention is therefore to conduct the oxidation of the hydrogenated working solution with the oxygen-containing gas in a shorter time and wlth less technical expenditure than for previously known processes, while protecting the working solution to the greatest possible degree.
It has now been found that this object can be attained by conducting the oxidation in the cyclic process for the preparation of hydrogen peroxide according to the anthraquinone process, by gasifying the hydrogenated working solution with an oxidising gas in a co-current reactor at temperatures below 100C and at over-pressures below 15 bar, if the hydrogenated working solution, following the hydrogenation step, is mixed intensively with an oxidising gas, with the formation of a non-coalescing system having a proportion of gas of at least 40% by volume, preferably 50 to 60~ by volume, and wherein the average diameter of the gas bubbles ~3;~'7;~
is no more than 2.5 mm, preferably less than 1.5 mm, whereby ~he non-coalescing system is passed directly ox via a distributor into the lower part of a tubular, preferably installation-free, reactor which is so dimensioned that as complete a reaction as possible of the oxygen with the hydroquinone in the hydrogenated working solution is facilitated, whereupon the thoroughly oxidised mlxture of hydrogenated working solution and oxidised gas is separated in known manner into gas and li~uid.
Non-coalescing systems are conventionally those in which the gas bubbles which are present maintain their size in the absence of any external action on the system.
In these systems, the liquids are distinguished by certain characteristics which depend on the interface, such as, for example, viscosity and specific surface tension. A simple test can be used to establish whether the liquid can form a non-coalescing system with the relevant gas.
It now appears that, in working solutions used for the anthraquinone process, in which hydrocarbons or mixtures thereof are introduced as quinone solvents, in order to give non-coalescing systems comprising oxygen or oxygen-nitrogen mixtures (the latter in any mixture ratio), it is clesirable that the total quotient of all interfacial.tensions of the relevant components has a value of at least 16 dyn/cm. Values of 17 to 25 dyn/cm are preferred. Widely used hydrocarbons are, for example, methylnaphthalene, dimethylnaphthalene, benzene, trimethylbenzene, tert-butylbenzene and aromatic benzenes having a boiling point of about 185 to 205C, with the exception of diphenyl and o dichlorobenzene. The recently-introduced tetra-substituted ureas can also be used as a components of the working solution.
3~
In order to prepare gas bubbles having an average diameter of no more than 2.5 mm, but preferably less than 1.5 mm, sieve plates or frits are used, whose apertures have a size corresponding to the desired bubble cross-section.
It has in ract been found particularly suitable to use known apparatus which comprises a tube whose initial tube nominal width narrows to a channel, and thereafter increases to the same or another nominal width.
Apparatus of this type causes low pressure loss.
In this apparatus, the hydrogenated working solution and the oxidising gas, either together or separate, but then in co-current flow, are introduced after the hydrogenation step. Before introduction into the channel, mixing of the working solution and gas has already begun. The intensive intermixing is achieved in streaming through the channel. A non-coalescing system, having a narrow spectrum of gas bubble diameters, is obtained. The size of the channel has an influence on this spectrum, depending on the stream volume throughout.
The bubble diameter depends on the energy input and this further depends on the pressure loss and on the volume through~ut. The appropriate pressure loss can be established for a given throughput by establishing the channel breadth.
In the case of a working solution comprising 2-ethyltetrahydroanthraquinone, ethylanthraquinone, aromatic benzenes having a boiling point of 185 to 205C
and triethylhexylphosphate and air, the bubble diameter is in general about 0.5 mm.
Suitable oxidising gases are any oxygen-nitrogen mixtures, and also pure oxygen. However, air is preferably used.
The non-coalescing system comprising hydrogenated working solution and oxidising gas which is obtained '7;~
accordln~ to the invention, is passed over a distributor into a tubular reactor. The mixing means for its preparation can be positioned on this reactor, directly on its floor or in the neighbourhood of the ~loor, in the side wall; it can also be positioned independently of the reactor, hoxizontally or vertically, and connected to the reactor by a conduit.
In any case, the non-coalescing system passes into the lower part of the reactor, if necessary through a distributor. This distributor, preferably in ring form, is so constructed that the mixture o~ hydrogenated working solution and oxidising gas is introduced uniformly across the cross-section of the reactor. The greater the cross-section of the reactor, the greater care must be taken with respect to uniform distribution.
Within the context of the invention, "distributor" does not of course refer to any inlet means such as, e.g., sieve bottoms, which cause the gas bubbles to coalesce.
The openings of the distributor must therefore be so dimensioned and positioned that the mixture is not separated but rather distributed uniformly, even at high throughput, across the cross-section of the reactor. The tube-like reactor itself, in its reaction volume, is free of any included structures, i.e. empty, except perhaps for the distributor.
The reactor has dimensions so that the degree of oxidation, based on the available hydroquinone, is at least 90%, but preferably at least 98~, be~ore the gas-containing working solution enters a liquid/gas separator. It appears that a reaction volume of 8 to 30 m height within the reactor meets this objective.
Particular care must be taken in order to achieve uniform distribution of the non-coalescing mixture, over the total cross-section of the reactor at cross-sections greater than 0.5 m, and more particularly when the mixing means is positioned outside the reactor.
The oxidation reaction takes place at pressures of 1 up to 15 bar, and preferably at 2 to 5 bar. The most suitable temperatures are 30 to 80C.
After conducting the oxidation, the working solution and the residual gas, which comprises mainly non-reactive nitrogen if nitrogen/oxygen mixtures, especially air, are used, is passed to a conventional liquid/gas separator, e.g. a centrifugal separator, and separated in known manner. This gas extractor can be positioned in the upper part of the reactor, in connection with the actual reaction volume, or it can be outside the reactor and connected therewith via a conduit.
The separated gas can be adsorbed on an active carbon unit. The oxidised working solution is passed for extraction.
The invention is illustrated in greater detail, in comparison with the state of the art, in the accompanying drawings. Figure 1 shows mixing means suitable for input according to the invention. Figure 2 shows various possibilities for combining mixer, distributor and reactor, according to the invention. Figure 3 shows an oxidation tower known from DE-A-2003268, and Figure 4 shows apparatus particularly suitable for conducting the process according to the invention.
In Figure 1, the hydrogenated working solution (WS) is introduced into the mixer 1 via the conduit 2, and the oxidising gas is introduced via the conduit 3. After streaming through the upper part of the mixer 1, the gas/liquid mixture enters into the channel S where very intensive intermixing takes place and the gas is separated into bubbles having a diameter of no more than 2.5 mm, and pxeferably substantially smaller. In consequence, there is the very high exchange area '7;~
necessary for the oxidation, and in a non-coalescing system. This non-coalesclng mixture is then passed into the empty reactor 6 as shown in Fig. 2, via a distributor 7 (embodiments a and b according to Fig. 2) or directly, by positioning the mixing means 1 on the floor of the reactor 6 tembodiment c according to Fig.
~) .
The technical advantages of the process according to the invention, with respect to the known procedure for the oxidation step in the anthraquinone process, lie in the very fine distribution of the oxidising gas in the working solution as well in the fact that the high exchange surface which is thus generated is retained during passage through the reactor and during the reaction, as a non-coalescing system.
This feasibility provides a new way of conducting the oxidation in the anthraquinone process. Owing to the great exGhange area, the rate of reaction is greatly increased, so that the degree of oxidation is at least as great as before, even if higher degrees, up to practically 100~, are not achieved, and over a shorter residence time for the oxidising mixture, than before.
The oxidation reactors can therefore be smaller, because the apparatus yield i5 increased and because bulky included structures such as packing materials are unnecessary. At the same time, the amounts of side-products and degradation products are reduced to a minimum, i.e. the working solution is protected.
Further, because the distribution of the non-coalescing mixture is controlled so that this is distributed uniformly over the entire cross-section of the reactor, re-mixing is effectively avoided. Owing to the completely installation-free reaction volume in the reactor, high cross-sectional capacity can be achieved.
For example, using air as the oxidising gas, 3~7;~
cross-sectional capacities for gas of 2000 to 3000 m3/m2h are achieved. The corresponding liquid capacity is from 40 to 60 m3/m2h.
Because the mixing means and also the mixture distributor are apparatus which do not cause great pressure loss, and because there is scarcely any pressure loss in the completely installation-free reaction volume, the apparatus arrangement of mixing means, distributor and reactor represents a total system having a very low pressure loss. The energy needs for such oxidation apparatus are clearly less than for previously known apparatus.
The following Example illustrates the invention in more detail, apparatus constructed for the purposes of the invention (corresponding to Fig. 4) being compared with a three-stage reactor cascade according to DE-B-2003268 (as in Fig. 3).
ta) Known procedure 260 m3/h of a working solution having an H2O2 equivalent of about 9.45 kg/m were passed through an o~idation tower according to Fig. 3 together with 10,000 m3 air/h. The tower had a diameter of 3.7 m and was divided into three sections which, together, had an effecti~e height of 15 m. At 2.5 bar at the head of the column and 4.0 bar at the column sump, and at an average temperature o~E 54C, 98.3% oxidation was achieved. The 2 content in the residual gas was below 5.9 vol %, and the current requirement for the air compressor was 0.36 kWh/kg ~22 From this, a working solution cross-sectional capacity of 24 m3/m2h and an air cross-sectional capacity of 930 m3/m2h are derived. The space-time yield was about 15 kg/m3h.
(b) Procedure according to the invention 345 m3/h of a working solution having an H2O2 g equivalent of about 11.4 kg/m3 were passed, together with about 16,300 m3 air/h through the mixer 1 and the distributor 7 in the oxidation tower 6 according to Fig.
4. This tower had a diameter of 3. a m and an effective height of 16 m. At 2.6 bar at the head of the column, 3.3 bar at the column sump and an average temperature of 53C, 99~ oxidation was achieved. The 2 content in the waste gas was 6 vol %.
The cross-sectional capacity for the working solution in this case was about 31 m3/m2h and, for air, 1440 m3/m2h. The space-yield was 22 kg/m3/m2h. The specific current requirement was determined as 0.26 kWh/kg H2O2 and thus 28% better than the energy need for the counter-current cascade. In this test, it was also possible to reduce the residence time to about 14 minutes.
The cross-sectional capacity for the working solution in this case was about 31 m3/m2h and, for air, 1440 m3/m2h. The space-yield was 22 kg/m3/m2h. The specific current requirement was determined as 0.26 kWh/kg H2O2 and thus 28% better than the energy need for the counter-current cascade. In this test, it was also possible to reduce the residence time to about 14 minutes.
Claims (7)
1. A process for conducting oxidation in the cyclic process for the preparation of hydrogen peroxide according to the anthraquinone process, by gasification of the hydrogenated working solution with an oxidising gas in a co-current reactor at temperatures below 100°C
and at over-pressures below 15 bar, and increasing the rate of reaction in the oxidation step, characterised in that the hydrogenated working solution, after the hydrogenation stage, is intensively mixed with an oxidising gas in such a manner that a non-coalescing system is obtained, having a gas content of at least 40 by volume, and wherein the average diameter of the gas bubbles is no more than 2.5 mm, whereupon the non-coalescing system is introduced via a distributor or directly into the lower part of a tubular reactor which has dimensions such that complete reaction of the oxygen with the hydroquinone in the hydrogenated working solution is facilitated and the reaction volume (apart from any distributor) is free of internal structures, whereupon the oxidised mixture of hydrogenated working solution and oxidising gas is separated into gas and liquid in known manner.
and at over-pressures below 15 bar, and increasing the rate of reaction in the oxidation step, characterised in that the hydrogenated working solution, after the hydrogenation stage, is intensively mixed with an oxidising gas in such a manner that a non-coalescing system is obtained, having a gas content of at least 40 by volume, and wherein the average diameter of the gas bubbles is no more than 2.5 mm, whereupon the non-coalescing system is introduced via a distributor or directly into the lower part of a tubular reactor which has dimensions such that complete reaction of the oxygen with the hydroquinone in the hydrogenated working solution is facilitated and the reaction volume (apart from any distributor) is free of internal structures, whereupon the oxidised mixture of hydrogenated working solution and oxidising gas is separated into gas and liquid in known manner.
2. A process according to claim 1, in which, for the intensive mixing, the hydrogenated working solution and the oxidising gas are introduced together into a tube whose initial tube nominal width narrows to a channel and then broadens again, to the same or a different nominal width.
3. A process according to claim 2, in which the hydrogenated working solution and the oxidising gas are introduced in co-current flow into the tube, and the bubble diameter, in dependence on the nominal width of the channel, the energy input and the volume stream, is so arranged that the diameter of the bubbles is no more than 2.5 mm.
4. A process according to claim 1, in which the non-coalescing system of working solution and oxidising gas is such that the total quotient of all specific surface tensions of the individual components in the system is at least 16 dyn/cm (16 mN/m).
5. A process according to claim 4, in which the non-coalescing system is such that the total quotient of all surface tensions is from 17 to 25 dyn/cm (17-25 mN/m).
6. A process according to claim 1, in which the average diameter of the gas bubbles is below 1.5 mm.
7. A process according to claim 1, in which the gas proportion of the non-coalescing system is 50 to 60% by volume.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ATA1361/85 | 1985-05-07 | ||
| AT136185 | 1985-05-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1283273C true CA1283273C (en) | 1991-04-23 |
Family
ID=3512223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000508543A Expired - Fee Related CA1283273C (en) | 1985-05-07 | 1986-05-06 | Process and apparatus for carrying out oxidation in the anthraquinone process for the preparation of hydrogen peroxide |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0221931B1 (en) |
| JP (1) | JPS62502821A (en) |
| AR (1) | AR240549A1 (en) |
| AT (1) | ATE47819T1 (en) |
| AU (1) | AU587257B2 (en) |
| CA (1) | CA1283273C (en) |
| DE (1) | DE3666797D1 (en) |
| IN (1) | IN168293B (en) |
| WO (1) | WO1986006710A1 (en) |
| ZA (1) | ZA863259B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE541158C2 (en) * | 2017-04-19 | 2019-04-16 | Eb Nuberg Ab | Oxidation column for hydrogen peroxide production |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI82920C (en) * | 1989-09-22 | 1995-04-04 | Kemira Oy | Process for producing hydrogen peroxide |
| FR2730987B1 (en) * | 1995-02-28 | 1997-05-23 | Chemoxal Sa | OXYGENATED WATER PRODUCTION FACILITY ON THE SITE OF A STATIONERY |
| DE19843573A1 (en) | 1998-09-23 | 2000-03-30 | Degussa | Bubble column and its use |
| DE10052323A1 (en) | 2000-10-21 | 2002-05-02 | Degussa | Continuous process for hydrogenation |
| EP1209122A1 (en) * | 2000-11-24 | 2002-05-29 | Degussa AG | Process for continuous oxidation |
| DE10207407A1 (en) * | 2002-02-21 | 2003-09-04 | Degussa | Process for the production of hydrogen peroxide |
| EP1919825B1 (en) * | 2005-08-31 | 2012-01-04 | Fmc Corporation | Auto-oxidation production of hydrogen peroxide via oxidation in a microreactor |
| JP2015020940A (en) * | 2013-07-22 | 2015-02-02 | 国立大学法人静岡大学 | Hydrogen peroxide synthesis method |
| CN105800563A (en) * | 2014-12-31 | 2016-07-27 | 湖南长岭石化科技开发有限公司 | Oxidative extraction method for hydrogen peroxide preparation through anthraquinone process and method for producing hydrogen peroxide |
| CN105800565A (en) * | 2014-12-31 | 2016-07-27 | 湖南长岭石化科技开发有限公司 | Hydrogenation method for hydrogen peroxide preparation through anthraquinone process and method for producing hydrogen peroxide |
| CN105800564A (en) * | 2014-12-31 | 2016-07-27 | 湖南长岭石化科技开发有限公司 | Oxidation method for hydrogen peroxide preparation through anthraquinone process and method for producing hydrogen peroxide |
| CN105800562A (en) * | 2014-12-31 | 2016-07-27 | 湖南长岭石化科技开发有限公司 | Extraction method for hydrogen peroxide preparation by anthraquinone process and preparation method of hydrogen peroxide |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE740674C (en) * | 1939-07-05 | 1943-10-26 | Ig Farbenindustrie Ag | Carrying out reactions between gases and liquids |
| GB740051A (en) * | 1953-04-01 | 1955-11-09 | Pintsch Bamag Ag | Method of continuously performing reactions between gases and liquid |
| DE1212970C2 (en) * | 1960-10-18 | 1966-09-29 | Bombrini Parodi Delfino Societ | Device for the catalytic oxidation of organic compounds in the liquid state with oxygen |
| DE2003268C3 (en) * | 1970-01-26 | 1974-01-31 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Device for carrying out the oxidation in the anthraquinone process for the production of hydrogen peroxide |
| SE377455B (en) * | 1973-05-11 | 1975-07-07 | Elektrokemiska Ab | |
| US4428923A (en) * | 1982-11-09 | 1984-01-31 | Degussa Aktiengesellschaft | Continuous process for the production of hydrogen peroxide according to the anthraquinone process |
-
1986
- 1986-04-29 IN IN382/DEL/86A patent/IN168293B/en unknown
- 1986-04-30 ZA ZA863259A patent/ZA863259B/en unknown
- 1986-05-06 CA CA000508543A patent/CA1283273C/en not_active Expired - Fee Related
- 1986-05-06 AU AU58681/86A patent/AU587257B2/en not_active Ceased
- 1986-05-06 DE DE8686902766T patent/DE3666797D1/en not_active Expired
- 1986-05-06 AT AT86902766T patent/ATE47819T1/en not_active IP Right Cessation
- 1986-05-06 AR AR30386686A patent/AR240549A1/en active
- 1986-05-06 WO PCT/AT1986/000039 patent/WO1986006710A1/en active IP Right Grant
- 1986-05-06 JP JP61502651A patent/JPS62502821A/en active Pending
- 1986-05-06 EP EP86902766A patent/EP0221931B1/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE541158C2 (en) * | 2017-04-19 | 2019-04-16 | Eb Nuberg Ab | Oxidation column for hydrogen peroxide production |
Also Published As
| Publication number | Publication date |
|---|---|
| IN168293B (en) | 1991-03-09 |
| JPS62502821A (en) | 1987-11-12 |
| ATE47819T1 (en) | 1989-11-15 |
| AU587257B2 (en) | 1989-08-10 |
| EP0221931B1 (en) | 1989-11-08 |
| AR240549A1 (en) | 1990-05-31 |
| WO1986006710A1 (en) | 1986-11-20 |
| AU5868186A (en) | 1986-12-04 |
| EP0221931A1 (en) | 1987-05-20 |
| ZA863259B (en) | 1986-12-30 |
| DE3666797D1 (en) | 1989-12-14 |
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