Method and plant for producing nitric acid
11390523 · 2022-07-19
Assignee
Inventors
Cpc classification
C01B21/26
CHEMISTRY; METALLURGY
International classification
Abstract
A process and a plant for producing nitric acid involves oxidizing ammonia in the presence of catalysts to provide nitrogen monoxide-containing process gas in an oxidation reactor. The formed nitrogen monoxide may be supplied with oxygen-containing gas, and nitrogen monoxide is oxidized to provide nitrogen dioxide that is reacted with water in an absorption apparatus to give nitric acid, nitrous acid, and/or solutions of nitrates and/or nitrites. Oxidation of the nitrogen monoxide may be effected in an additional reactor positioned between the oxidation reactor and the absorption apparatus and traversed by the process gas. The oxidation of the nitrogen monoxide may be effected in an additional reactor parallel and connected to the absorption apparatus and traversed by the process gas. The disclosed processes and plants feature a high energy efficiency combined with a simple construction, and existing plants are easily upgradeable.
Claims
1. A process for producing nitric acid comprising: oxidizing ammonia with oxygen in a presence of catalysts to provide a process gas containing nitrogen monoxide in an oxidation reactor; supplying oxygen-containing gas to the nitrogen monoxide; oxidizing the nitrogen monoxide in a second reactor to provide nitrogen dioxide that is reacted with water in an absorption apparatus to provide nitric acid, nitrous acid, and/or solutions of nitrates and/or nitrites, wherein the second reactor is a container charged with a catalyst for oxidizing the nitrogen monoxide to provide the nitrogen dioxide, wherein the second reactor is at least one of: positioned between the oxidation reactor and the absorption apparatus with respect to a flow direction of the process gas such that the process gas traverses the second reactor, or positioned in parallel with the absorption apparatus and connected to the absorption apparatus such that the process gas traverses the second reactor; and causing the process gas to enter the second reactor at a temperature of 160° C.-350° C.
2. The process of claim 1 wherein the second reactor is positioned downstream of the oxidation reactor and upstream of a residual gas heater with respect to the flow direction of the process gas.
3. The process of claim 1 wherein the second reactor is a container whose total gas content is large enough for the oxidation of the nitrogen monoxide to provide the nitrogen dioxide as a gas-phase reaction to proceed completely.
4. The process of claim 1 wherein the second reactor is a radial bed reactor comprising a concentric catalyst bed that is traversed by the process gas.
Description
BRIEF DESCRIPTION OF THE FIGURES
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DETAILED DESCRIPTION
(7) Although certain example methods and apparatus have been described herein, the scope of coverage of this patent is not limited thereto. On the contrary, this patent covers all methods, apparatus, and articles of manufacture fairly falling within the scope of the appended claims either literally or under the doctrine of equivalents. Moreover, those having ordinary skill in the art will understand that reciting “a” element or “an” element in the appended claims does not restrict those claims to articles, apparatuses, systems, methods, or the like having only one of that element, even where other elements in the same claim or different claims are preceded by “at least one” or similar language. Similarly, it should be understood that the steps of any method claims need not necessarily be performed in the order in which they are recited, unless so required by the context of the claims. In addition, all references to one skilled in the art shall be understood to refer to one having ordinary skill in the art.
(8) The present disclosure generally relates to processes for producing nitric acid by oxidation of ammonia with oxygen in the presence of catalysts to afford nitrogen monoxide-containing process gas in an oxidation reactor. In the course of some example processes, the nitrogen monoxide is oxidized to afford nitrogen dioxide that is reacted with water in an absorption apparatus to afford nitric acid, nitrous acid, and/or solutions of nitrates and/or nitrites. The present disclosure also generally relates to plants for producing nitric acid.
(9) It has now been found that, surprisingly, the process for production of nitric acid can proceed with enhanced energy efficiency when at least one additional reactor is provided in which NO oxidation (reaction II) proceeds in a localized manner and as completely as possible.
(10) The process according to the invention provides that the oxidation of the NO to afford NO.sub.2 is effected in at least one additional reactor arranged between the oxidation reactor and an absorption apparatus and traversed by the NO-containing process gas and/or that the oxidation of the NO to afford NO.sub.2 is effected in at least one additional reactor arranged in parallel with the absorption apparatus and connected to the absorption apparatus such that said reactor is traversed by NO-containing process gas; wherein the additional reactor is a container of any desired shape charged with a catalyst for the oxidation reaction of nitrogen monoxide to afford nitrogen dioxide.
(11) In current nitric acid production processes (prior art) the reaction heat of reaction (I) from the combustion reaction is generated at a high caloric level and largely recovered and reused again in the gas cooling section of the process/of the plant.
(12) The reaction heat from the absorption reaction (III) is generated at a very low caloric level and virtually entirely emitted into the cooling water.
(13) Since the reaction rate is unusually proportional to 1/T.sup.3 and proceeds in a non-localized manner over the entire pipeline system, the reaction heat of the gas phase reaction (II) is likewise preferably evolved at a low caloric level. The design of the gas cooling section/of the energy recovery section of modern nitric acid plants does nevertheless allow utilization of about 50% of the total reaction heat of reaction (II) for steam generation or for recovery in the residual gas turbine. However, the remainder of the reaction heat is evolved in condensers/in the absorption apparatus and is emitted into the cooling water.
(14) The additional reactor employed according to the invention in which the NO oxidation proceeds in a localized manner is integrated into the process such that the reaction proceeds at a high thermal level and the generated reaction heat can thus be efficiently recovered. More usable heat is therefore generated in the process.
(15) In the additional reactor employed according to the invention typically at least 30 vol % of the NO present in the process gas is to be converted into NO.sub.2, preferably at least 50 vol % and very particularly preferably at least 80 vol %.
(16) It is preferable when the additional reactor in which the NO oxidation proceeds in a localized manner is arranged in the process/in the plant such that the entry temperature of the NO-containing process gas into the reactor in which the NO oxidation proceeds in a localized manner is 160-350° C., preferably 200-340° C., particularly preferably 220-320° C.
(17) One possible preferred variant of the process provides that the additional reactor in which the NO oxidation proceeds in a localized manner is arranged downstream of the oxidation reactor for NH.sub.3 combustion and upstream of a residual gas heater. The residual gas heater is to be understood as meaning a heat exchanger of any desired geometry in which the NOx-containing process gas is cooled and residual gas, which is supplied to a residual gas turbine for energy recovery, is heated.
(18) An alternative preferred variant of the process provides that the additional reactor in which the NO oxidation proceeds in a localized manner is arranged downstream of the oxidation reactor for NH.sub.3 combustion between an additional compression stage for compressing the process gas to the desired absorption pressure and a heat exchanger.
(19) Another alternative preferred variant of the process provides that the additional reactor in which the NO oxidation proceeds in a localized manner is arranged downstream of the oxidation reactor for NH.sub.3 combustion and upstream of an economizer. The economizer is to be understood as meaning a heat exchanger of any desired geometry in which the NOx-containing process gas is cooled and either water (usually for but not limited to the purpose of steam generation) is heated or else steam is generated directly.
(20) Another alternative preferred variant of the process provides that the additional reactor in which the NO oxidation proceeds in a localized manner is arranged downstream of the oxidation reactor for NH.sub.3 combustion and upstream of a heat exchanger which transfers the heat into a system providing a thermodynamic process for conversion of heat into mechanical energy. The application of such systems in nitric acid plants is described for example in DE 39 03 570 A1.
(21) Another alternative preferred variant of the process provides that an additional reactor in which the NO oxidation proceeds in a localized manner is arranged in parallel with an apparatus in which the absorption of NO.sub.2 in water proceeds and comprises integration points and feed points to this apparatus. The reactor in which the NO oxidation proceeds in a localized manner is thus fed via an intermediate takeoff. Further apparatuses, for example heat exchangers, may optionally be arranged between the reactor according to the invention and the absorption apparatus for purposes of thermal recovery.
(22) An alternative further preferred variant of the process provides that the additional reactor in which the NO oxidation proceeds in a localized manner is arranged downstream of the oxidation reactor for NH.sub.3 combustion between two apparatuses in which the absorption of NO.sub.2 in water proceeds. Further apparatuses, for example heat exchangers, may optionally be arranged between the reactor according to the invention and the apparatuses for purposes of thermal recovery.
(23) The additional reactor employed according to the invention in which the NO oxidation proceeds in a localized manner is a container of any shape whose total gas content is large enough to allow the reaction (II) to proceed largely completely as before as an uncatalyzed gas phase reaction. In the reactor employed according to the invention the reaction (II) proceeds in the presence of a catalyst, thus resulting in an acceleration compared to the uncatalyzed gas phase reaction.
(24) The reactor employed according to the invention in which the NO oxidation proceeds in a localized manner may be realized by simple modification of existing plants. This is of particular advantage in the upgrading of existing plants since only insubstantial apparatus alterations, if any, are required. Often the pipelines for the NO-containing process gas are charged with a catalyst for the oxidation of NO to afford NO.sub.2. This may be effected by coating the internal walls of these pipelines and/or by introducing dumped beds of shaped bodies containing the catalytically active component and/or consisting of the catalytically active component. In the process according to the invention the catalyst shaped body may be installed into the pipeline or into a reactor as a dumped bed or as an ordered packing, for example of honeycomb bodies.
(25) The reactor employed according to the invention may likewise be in the form of a pipeline and connected to the absorption apparatus in parallel. Here too, the pipeline generally contains a heterogeneous oxidation catalyst as described hereinabove for the alternative process variants.
(26) However, the additional reactors in which the NO oxidation proceeds in a localized manner may also be in the form of vessels/containers installed in pipelines for NO-containing gases and increasing the volume of these pipelines so that the oxidation reaction of NO to afford NO.sub.2 proceeds primarily or entirely in these vessels. The interior of these vessels is preferably provided with heterogeneous oxidation catalyst as described above for the process variants with reactors in the form of pipelines.
(27) It is particularly preferable to employ noble metal-containing or non-noble metal-containing heterogeneous oxidation catalysts. These NO oxidation catalysts are known per se and are employed for example as a standard component in the automotive industry. Catalysts suitable for the process according to the invention include in principle all catalysts containing as the active component at least one noble metal, metal or metal oxide which catalyzes the oxidation reaction of NO to afford NO.sub.2.
(28) The noble metals may be silver, gold or platinum-group metals. In the context of this description a platinum-group metal is to be understood as meaning an element of periods 5 and 6 of groups 8 to 10 of the periodic table, i.e. an element from the group of Ru, Rh, Pd, Os, Ir and Pt.
(29) The non-noble metals may be for example iron, manganese, cobalt or nickel or their metal oxides or metal-doped aluminosilicates such as for example zeolites.
(30) It is particularly preferable to employ oxidation catalysts that are also used predominantly in diesel engines to reduce harmful emissions. These are generally supported catalysts. Shaped bodies provided with noble metal-containing coatings are preferred. Production thereof may comprise depositing finely divided noble metal particles, in particular particles of the noble metals platinum and/or palladium, on oxidic coatings/support materials, for example aluminum oxide.
(31) To impart a shape to such an active component it may be incorporated/embedded into any desired, preferably ceramic, matrix or else applied to any desired, preferably ceramic, support.
(32) Ceramic support material based on oxides, carbides or nitrides of the elements selected from the group Si, Al, Mg, Zr and B is preferred and ceramic materials such as cordierite, mullite, magnesium oxide or very particularly silicon carbide which features high chemical and mechanical resistance and exceptional thermal conductivity are especially preferred.
(33) Particularly preferred heterogeneous oxidation catalysts are honeycomb bodies coated with catalytically active materials (so-called monoliths). These coated honeycomb bodies may be integrated directly into the pipeline to form, together with the pipeline, the reactor employed according to the invention in which the NO oxidation proceeds in a localized manner.
(34) Such catalysts may be produced by standard methods of catalyst production.
(35) Likewise particularly suitable and preferred in the context of the invention is the use of unsupported catalysts, i.e. of shaped bodies consisting essentially of catalytically active material. Thus the catalyst shaped bodies should consist of catalytically active material to an extent of more than 70%, preferably to an extent of more than 80%, particularly preferably to an extent of more than 85%, based on the total weight of the shaped body.
(36) The catalyst shaped body may be in the form of a shaped body of any desired size and geometry, preferably geometries which have a large ratio of surface area to volume and which generate the smallest possible pressure drop upon traversal. All geometries known in catalysis are typical, for example cylinders, hollow cylinders, multi-hole cylinders, rings, crushed granulate, trilobes or honeycomb structures. Honeycomb-shaped monoliths made of unsupported catalyst are particularly preferred. Also preferred are so-called miniliths, i.e. very small honeycomb-shaped bodies, which are generally used as a dumped bed material. The shaped bodies may be produced by shaping processes known in ceramic processing, for example dry pressing, granulation or extrusion.
(37) The arrangement of the catalyst shaped bodies in the reactor employed according to the invention may be in the form of an irregular dumped bed or an ordered packing for example.
(38) Particularly if an irregular dumped bed of unsupported catalysts is to be used, a preferred configuration of the reactor according to the invention is a radial reactor. Here, the catalyst/the catalysts is/are introduced into a concentric catalyst bed which is traversed by the process gas either from the inside outward or from the outside inward.
(39) A process simulation shows that the proportion of reusable heat resulting from reaction (II) may be increased from 50-55% to about 70-75% simply by providing a reactor A (cf.
(40) In addition to the above-referenced energy recovery from the quantitative performance of reaction (II) at a higher caloric level, the inventive use of the reactors in which the NO oxidation proceeds in a localized manner also brings further advantages: the first and second coolers and condensers may be operated more efficiently, thus relieving the absorption apparatus and optionally allowing said apparatus to be made smaller; in a two-pressure plant the volume flow from the first cooler and condenser to the NO compressor may be reduced due to a low temperature increase in the pipeline to the NO compressor; the volume flows in the plant are lower due to the volume reduction associated with reaction (II); this results in lower pressure drops in the pipelines; design certainty for heat exchangers is altogether increased, in particular for the heat exchanger/residual gas heater and thus the offgas aftertreatment due to the defined position of the NO/NO.sub.2 equilibrium; specifications for necessary pipeline volumes (for sufficient oxidation (II)) no longer apply; this results in new potential for optimizing apparatus setup and in lower pipeline weights and altogether reduced space requirements for the plant; cooling water consumption can be reduced; enhanced safety in respect of the risk of an ammonia breakthrough in the NH.sub.3 oxidation reactor can be achieved since the catalysts employed according to the invention often also exhibit an activity for the oxidation of ammonia to afford nitrogen. The present invention further provides a plant for producing nitric acid comprising at least the following elements: A) at least one oxidation reactor for ammonia oxidation fitted with at least one feed conduit for an ammonia- and oxygen-containing reactant gas mixture and with at least one discharge conduit for a nitrogen monoxide (NO)-containing process gas, B) a catalyst for the oxidation of ammonia with oxygen in the interior of the oxidation reactor, C) at least one absorption apparatus for absorption of nitrogen dioxide (NO.sub.2) and formation of nitric acid (HNO.sub.3), nitrous acid (HNO.sub.2) or solutions of nitrates and/or nitrites, and D) at least one additional reactor for oxidation of NO to afford NO.sub.2 arranged between the oxidation reactor and the absorption apparatus or downstream of the absorption apparatus and traversed by the NO-containing process gas and/or at least one additional reactor for oxidation of NO to afford NO.sub.2 arranged in parallel with the absorption apparatus and connected to the absorption apparatus such that said reactor is traversed by NO-containing process gas; wherein in the additional reactor the oxidation reaction of nitrogen monoxide to afford nitrogen dioxide is effected over a catalyst.
(41) In a preferred development of the invention the plant further comprises at least one residual gas heater having a heat exchanger function which is operatively interconnected with the absorption apparatus and which is traversed by a residual gas stream exiting the absorption apparatus, wherein the additional reactor is arranged between the oxidation reactor and a residual gas heater.
(42) In a preferred development of the invention the plant further comprises at least one residual gas heater having a heat exchanger function which is operatively interconnected with the absorption apparatus, and which is traversed by a residual gas stream exiting the absorption apparatus, and the plant further comprises an additional compression stage for compressing the process gas to the desired absorption pressure, wherein the additional reactor is arranged between the compression stage and a residual gas heater.
(43) In a preferred development of the invention the plant further comprises at least one residual gas heater having a heat exchanger function which is operatively interconnected with the absorption apparatus, and which is traversed by a residual gas stream exiting the absorption apparatus, and the plant further comprises at least one economizer traversed by the process gas stream, wherein the additional reactor is arranged between a residual gas heater and the economizer.
(44) In a preferred development of the invention the plant comprises at least two additional reactors for oxidation of NO to afford NO.sub.2, of which at least one is arranged between the oxidation reactor and a residual gas heater and of which at least one is arranged between an additional compression stage for compressing the process gas to the desired absorption pressure and a further residual gas heater.
(45) In a preferred development of the invention the plant comprises at least two additional reactors for oxidation of NO to afford NO.sub.2, of which at least one is arranged between the oxidation reactor and a residual gas heater and of which at least one is arranged between a residual gas heater and at least one economizer traversed by the process gas stream.
(46) In a preferred development of the invention the plant comprises at least two additional reactors for oxidation of NO to afford NO.sub.2, of which at least one first reactor is arranged between the oxidation reactor and an absorption apparatus in the flow direction of the process gas and of which at least one further reactor is arranged either in parallel with an absorption apparatus in the flow direction or downstream of an absorption apparatus in the flow direction or between two absorption apparatuses in which the absorption of NO.sub.2 in water proceeds.
(47) In a preferred development of the invention the plant comprises at least one additional reactor arranged in parallel with the absorption apparatus and connected to the upper third and the middle or the lower third of the absorption apparatus.
(48)
(49) There is generally no limitation on the number and sequence of the heat exchangers used for cooling the process gas above the dew point (residual gas heater, economizer, heat exchanger with other cooling media). The number and sequence is determined by manufacturing, construction or infrastructural technical factors and design requirements. Further residual gas heaters, economizers or heat exchangers with other cooling media may occupy each of positions 10a, 10b, 10c, 10d.
(50) The residual gas exits the absorption apparatus 8 in the top region thereof and is heated in the residual gas heater 2 to then arrive into a residual gas reactor 11 in which residual NO.sub.x and optionally N.sub.2O are removed generally by catalytic means. The residual gas finally traverses a residual gas turbine 18 for energy recovery during decompression of the residual gas into the atmosphere.
(51) There is generally no limitation on the number and sequence of the heat exchangers used for heating the residual gas (residual gas heater, heat exchanger with other heating media). The number and sequence are determined by manufacturing, construction or infrastructural technical factors and design requirements. Further residual gas heaters or heat exchangers with other heating media may occupy each of positions 12a, 12b.
(52) The plant further comprises a functional unit 9 for workup of the product acid produced in the absorption apparatus 8 using the secondary air stream. This secondary air stream is a substream diverted upstream of the reactor 1 from the combustion air produced by the air compressor 15. After exiting the functional unit 10 this secondary air stream may be supplied to the process gas stream via conduit 9b, for example downstream of the cooler and condenser 4. This increases the oxygen content of the process gas.
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(58) Similar alternative variants of this invention both in the monopressure and in the two-pressure process are the arrangement of the additional reactor (E) in parallel with only one absorption apparatus 8 by means of an intermediate takeoff or else the arrangement of the additional reactor E between cooler/condenser 6 and absorption apparatus 8.
LIST OF REFERENCE NUMERALS
(59) 1 NH.sub.3 oxidation reactor
(60) 2 residual gas heater
(61) 3 economizer
(62) 4 steam generator
(63) 6a cooler/condenser
(64) 6b cooler/condenser
(65) 7 compression stage/compressor
(66) 8 absorption apparatus
(67) 8a absorption apparatus
(68) 8b absorption apparatus
(69) 9 functional unit
(70) 9b conduit
(71) 10 residual gas reactor
(72) 10a further residual gas heater, economizer or heat exchanger
(73) 10b further residual gas heater, economizer or heat exchanger
(74) 10c further residual gas heater, economizer or heat exchanger
(75) 10d further residual gas heater, economizer or heat exchanger
(76) 11 residual gas reactor
(77) 12a further residual gas heater or heat exchanger
(78) 12b further residual gas heater or heat exchanger
(79) 15 air compressor/compressor
(80) 18 residual gas turbine
(81) 20 shaft
(82) 21 compression
(83) 22 decompression/downstream heat exchanger
(84) 25 downstream heat exchanger
(85) A additional reactor
(86) B additional reactor
(87) C additional reactor
(88) D additional reactor
(89) E additional reactor