US3434802A - Apparatus for the staged nitration of aromatic hydrocarbons - Google Patents

Apparatus for the staged nitration of aromatic hydrocarbons Download PDF

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Publication number
US3434802A
US3434802A US502194A US3434802DA US3434802A US 3434802 A US3434802 A US 3434802A US 502194 A US502194 A US 502194A US 3434802D A US3434802D A US 3434802DA US 3434802 A US3434802 A US 3434802A
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stage
nitrating
apparatuses
product
separator
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Expired - Lifetime
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US502194A
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English (en)
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Karl Engelbert Ludwig Toischer
Horst Sigurd Max Bergmann
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Josef Meissner GmbH and Co KG
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Josef Meissner GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B43/00—Formation or introduction of functional groups containing nitrogen
    • C07B43/02—Formation or introduction of functional groups containing nitrogen of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups

Definitions

  • a two stage system for the selective production of either a monoor dinitro-product including a first stage for converting raw material into a mono nitro product and a second stage having a convertible nitrating-extraction unit, and valved conduit means for connecting the second stage in cascade with the first stage and connecting the convertible unit as a nitrating unit to produce a dinitro product at the output of the second stage or for connecting both stages in parallel and connecting the convertible unit as an extraction unit for causing both stages to produce a mononitro-product.
  • the present invention relates to nitrating system, and particularly to a two-stage system for nitrating aromatic hydrocarbons.
  • Systems for producing a dinitro-product are usually multistage systems which are so constructed that the nonnitrated starting material is nitrated in a first stage to form a mononitro-product which is then nitrated in a second stage to form a dinitro-product.
  • Both nitro-products are commercially salable as such and can then be processed further elsewhere, so that it is desirable to be able to produce both nitro-products in a single system.
  • One way in which this was previously sought to be done was, if only the mononitro-product was to be made in a two-stage system, to disconnect the second nitrating stage and to produce the mononitro-product in the first nitrating stage only. It is true that this made it possible to produce different nitrated products in a multiple-stage system, depending on the particular manufacturing process selected, but the drawback of this was that whenever a mononitro-product was to be produced, a substantial part of the system as a whole remained unused.
  • this is achieved by providing a system which is primarily composed of a first stage for producing a mononitro-product and a second stage for producing a dinitro-product.
  • the system also includes converter means which are connectable in the second stage for enabling it to produce a mononitro-product.
  • selectively openable and closeable fluid conveyor lines are connected to the two stages and between the second stage and the supplementary means for permitting the fluid flow pattern through the system to be switched between a first configuration in which the second stage is fed by the output of the first stage, and the supplementary means are disconnected, for producing a dinitro-product at the output from the second Patented Mar. 25, 1969 'ice stage, and a second configuration in which the two stages are connected in parallel, and the supplementary means are operatively connected in the second stage, for producing a mononitro-product in both stages.
  • a plurality of temporary storage tanks are provided for storing the substances removed from the various apparatuses of the two stages when it is desired to change over from one process to another.
  • FIGURE 1 is a flow diagram of a two-stage nitrating system according to the present invention.
  • FIGURE 2 shows the arrangement of the discharge receptacles when a different starting material is to be nitrated in the system.
  • FIGURE 1 there is shown a system according to the present invention which can be used either for producing a dinitro-product or a mononitro-product.
  • the system is composed of a group of supply tanks 30-34 for supplying fluids for use in the process, a first reaction stage, or mono-stage, I having an extraction apparatus 10, nitrating apparatuses 11-12, and separators 14 and 15, and a second reaction stage II, which may be either a monostage or a di-stage, having a convertible nitrating-extraction apparatus 20, nitrating apparatuses 21-22, and separators 24 and 25.
  • the system is also equipped with suitable dosing devices 13 and 130, and selectively openable and closeable conduits 100, 101, 110, 111, 121, 140, 141, -152, 200, 201, 210, 211, 220-224, 241 and 250-253 are provided for conveying fluids to and from the various apparatuses and separators.
  • the system is also equipped with a plurality of storage tanks 40-44 connected to store the contents of the various apparatuses 10-12 and 20-22 when the system is to be changed over from a pure mononitration to a dinitration, or vice versa, or when a different material is to be nitrated, or when the apparatuses have to be cleaned or repaired.
  • the mono-stage I contains three apparatususes 10, 11 and 12, while the distage II likewise contains three ap aratuses 20, 21 and 22, the convertible apparatus 20 acting as a nitrating apparatus for this process.
  • the mono-stage I includes two separators 14 and 15 and the di-stage II two separators 24 and 25.
  • the separator 24, which constitutes the converter means for the system is connected so as to be switched into and out of the system and is provided for the case when the stage II is to be used for the production of a mononitro-product.
  • Both stages I and II have associated with them tanks 30, 31, 32, 33 and 34 as well as dosing devices 13, 130, whose flow control elements, shown schematically, control the flow of the individual media.
  • the tanks 30, 32 and 33, as well a the dosing devices 13 and 130 come into play for the production of the dinitrotoluene as well as for the production only for the mononitrotoluene, toluene being supplied by tank 30 and acid by tanks 32 and 33.
  • the flow control elements, as well as their conduits, will be described below in conjunction with the operation of the system.
  • the tanks 31, 32 and 34 are provided if the system is to be switched over for the nitrating of benzene, benzene being supplied by tank 31 and acid by tank 32 and 34.
  • the apparatuses 20, 21 and 22 as well as the lines which lead from the di-stage to the mono-stage are heated when the system is to be used for manufacturing a dinitroproduct. If the starting medium is chlorobenzene, the apparatuses 10, 11 and 12 are also equipped so a to be heated.
  • the heating means themselves are provided with suitable means which make it possible for them to be turned on and off.
  • the discharge receptacles or tanks 40, 41, 42, 43, 44 shown in FIGURE 2 are generally provided even when the system is to be used for nitrating a single starting material either into a dinitro-product or into a mononitroproduct, in which case the dinitro-product will be transferred, the spent acid of the di-stage, however, then being discharged into the receptacle 40.
  • All of the tanks 30-34 and 40-44, the apparatuses 12 and 20-22, the dosing devices 13 and 130, and the separators 14, 15, 24 and 25 are constituted by wellknown, commercially available devices and hence will not be described in detail in the present specification.
  • the units are interconnected as represented by the heavy and light solid lines in FIGURES 1 and 2.
  • the toluene is passed from tank 30 via the dosing device 13 and the line 100 to the first apparatus 10 of the mononitrating stage I.
  • the second component supplied to the apparatus 10 is constituted by spent or residuary acid which was separated in the separator from the finished mononitro product, this acid reaching the apparatus 10 via a line 151.
  • the spent acid is extracted from the toluene and is delivered, together with the already nitrated toluene, via line 101 to the second separator 14 of this first nitrating stage I.
  • the spent acid which has been separated out is eliminated via a line 140, while the nitrated toluene is applied to the main nitrating apparatus 11 via a further line 141.
  • This main nitrating apparatus 11 additionally has delivered to it, via a line 111, concentrated nitric acid from tank 33 and, via a further line 251, spent acid which was separated out in the separator 25 of the second nitrating stage.
  • the reaction mixture is delivered via a line 120 to the last nitrating apparatus 12 and from there, via a line 121, to the separator 15.
  • the finished mononitrotoluene is conveyed from this separator 15 via a line 150 to the nitrating stage II and, more particularly, to the first nitrating apparatus 21 thereof, which apparatus also receives, via lines 210 and 211, fresh sulfuric acid and concentrated nitric acid from tank 32 and 33, respectively. From there the mixture i delivered successively via lines 220 and 221, respectively, to the other nitrating apparatuses 22 and 20. The apparatus 22 receives still more fresh acid, via the lines 223 and 224. The mixture passes from the last nitrating apparatus 20, via the line 201, to the separator 25 where the dinitrotoluene and the spent acid are separated from each other. The dinitrotoluene passes via a line 252 to a scrubber 300, the spent acid being delivered, via line 251, to the main nitrating apparatus 11 of the nitrating stage I.
  • discharge receptacles are provided for storing these media until the system is once more to produce dinitrotoluene.
  • the variou discharge receptacles are shown in FIGURE 2 to be connected to receive the various media.
  • each nitrating apparatus does not have to have its own discharge receptacle. Instead, only as many receptacles as necessary have to be provided and utilized to obtain products of the desired quality. Consequently, the contents of the apparatuses 11 and 12 can be collected in a common receptacle 42, while a separate receptacle 41 is provided to receive the contents of the extraction apparatus 10.
  • stage II can be separated from stage II by closing suitable ones of the illustrated valves and production in stage I can be continued even while stage II is being drained.
  • the line 150 is closed and the apparatuses .10, .11 and 12 as well as 20, 21 and 22 are filled, as will be described in detail below, the units now being connected as shown by the dot-dash lines and the light solid lines.
  • benzene is supplied from the tank 31, the benzene flowing, firstly, via the dosing device 13 and the line into the apparatus .10 of stage I, and, secondly, via the dosing device 130 and line 200 into the convertible apparatus 20 of stage II, which now functions as an extraction apparatus.
  • Spent acid is supplied to both of the last-named apparatuses, the apparatus 10 being supplied from the separator 15 via the line 151 and the apparatus 20 being supplied from the separator 24 via the line 241.
  • the spent acid is extracted by means of the freshly supplied benzene after which it is separated from the benzene in the separators 14 and 25, respectively, and passed on the the lines .140 and 250, respectively.
  • nitrated benzene separated in separators 14 and 25 is conveyed to apparatuses 11 and 21, respectively, via lines 141 and 253, respectively.
  • fresh acid is supplied to the apparatuses 11 and 21, sulfuric acid being supplied from tank 32 via the lines and 210, respectively, and diluted nitric acid being supplied from the tank 34 via lines .111 and 211, respectively.
  • the lines 223 and 224 are closed off.
  • the mixtures produced in apparatuses 11 and 21 are transferred to apparatuses 12 and 22, respectively, via lines and 220, respectively, where they go through the final process reaction.
  • the outputs from the latter apparatuses flow through lines 121 and 222, respectively, to separators 15 and 24, respectively, where the spent acid is separated from the finished mononitrobenzene.
  • the finished mononitrobenzene is conveyed to scrubber 300 from separators 15 and 24 via line 152 and the spent acid is returned to apparatuses 10 and 20 via lines .151 and 241, respectively.
  • the apparatuses 10, 11 and 12 and 20, 21 and 22 are again drained. This time the contents of apparatuses 10 and 20 flow into the receptacle 43 while the contents of the apparatuses .11, 12, 21 and 22 flow into the receptacle 44.
  • the contents of the receptacles 40, 41 and 42 is once again quickly pumped into the system, via conduits (not shown) connected inputs for the various apparatuses so that the system is rapidly prepared to begin a new production cycle and the necessity of an extended warm-up period is eliminated. If necessary, the system can be flushed after each draining.
  • the second nitrating stage is equipped with additional parts, which can be switched in and out and which are normally intended solely for the first nitarting stage, the so-called mono-stage.
  • the material to be nitrated and the nitrating acid can be made to flow, selectively, into either of two conduit systems, whose inlets can be selectively opened or closed.
  • One of these systems leads solely to the mono-stage, except for certain bypass lines, and from there to the dinitrating stage.
  • the other system leads both to the mono-stage and the di-stage, and the discharge from the mono-stage to the inlet of the di-stage can be disconnected and connected to lead to the washing device, or scrulbber.
  • the present invention is applicable to installations which are designed for nitrating but a single aromatic hydrocarbon, for example, toluene, which is to be converted either to mononitrotoluene or dinitrotoluene, or to systems in which one or several hydrocarbons is to be nitrated into a monoand/ or dinitro-product.
  • a single aromatic hydrocarbon for example, toluene, which is to be converted either to mononitrotoluene or dinitrotoluene, or to systems in which one or several hydrocarbons is to be nitrated into a monoand/ or dinitro-product.
  • each two-stage system would have one container for each of the stages, there being an additional receptacle for discharging the extraction vessel of the mono-stage.
  • additional discharge receptacles will be provided for these materials, the number of receptacles depending on the number of starting materials to be treated.
  • the provision of these receptacles is particularly significant and useful if not only the starting material is to be changed, but each of the various starting materials is to be subjected to a mononitration as well as to a dinitration.
  • a two-stage system for nitrating different aromatic hydrocarbons comprising, in combination:
  • a first processing stage for producing a mononitro product including an extraction apparatus, a plurality of nitrating apparatuses connected in cascade, and a first separator having an input connected to the output of said extraction apparatus, a first output connected to supply nitrated material to said nitrating apparatuses, and a second output for eliminating spent acid separated in said separator;
  • a second processing stage including a plurality of nitrating apparatuses connected in cascade, a convertible nitrating-extraction apparatus, and a second separator having an input, a first output connected for delivering separated spent acid to said convertible apparatus, and a second output for delivering nitrated material out of said system;
  • conduit means connected between said dosing means and said apparatuses of said stages for supplying selected reagents to the first nitrating apparatus in cascade in each said stage;
  • valves of said piping means being selectively operable between:
  • said first stage further comprises a second separator having an input connected to receive the output from said nitrating apparatuses, a first output connected to convey spent acid separated in said second separator to said extraction apparatus, and a second output connected to convey the mononitro product separated in said second separator, and wherein said second valved means are connected to said second output of said second separator for selectively conveying the mononitro product to said second stage when the valves are in said first condition and conveying such product to subsequent treating apparatus when the valves are in said second condition.
  • said second stage further comprises a third separator having an input connected to receive the output from said convertible apparatus, a first output connected for the outflow of spent acid separated in said first separator, and a second output connected for the outflow of the nitro product separated in said third separator, and wherein said second and third valved means are connected to said third separator outputs for selectively conveying the spent acid from said first output thereof to said first stage only when the valves are in said first condition and for selectively operatively connecting said second output of said third separator to an input of said two nitrating apparatuses of said second stage only when the valves are in said second condition and to subsequent treating apparatus only when the valves are in said first condition.
  • An arrangement as defined in claim 1 further comprising a plurality of storage receptacles selectively connectable to said first and second stages, with each of said receptacles being connectable for receiving at least one of the fluids present in said stages.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
US502194A 1964-10-23 1965-10-22 Apparatus for the staged nitration of aromatic hydrocarbons Expired - Lifetime US3434802A (en)

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DEM0062855 1964-10-23

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US (1) US3434802A (de)
CH (1) CH459165A (de)
DE (1) DE1468362A1 (de)
ES (1) ES318787A1 (de)
GB (1) GB1123204A (de)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4420645A (en) * 1982-07-19 1983-12-13 Monsanto Company Process for the nitration of halobenzenes
US4918250A (en) * 1989-04-21 1990-04-17 Olin Corporation Process for the production of dinitrotoluene using an inorganic salt as a phase separation agent
US4935557A (en) * 1984-08-07 1990-06-19 Air Products And Chemicals, Inc. Conitration of mixed aromatic hydrocarbons
US5001272A (en) * 1988-06-22 1991-03-19 Olin Corporation Process for the production of dinitrotoluene
US5001286A (en) * 1987-02-18 1991-03-19 Bayer Aktiengesellschaft Process for separating sulphuric acid and nitric acid from dinitrotoluene mixtures obtained during the nitration of toluene
US5354924A (en) * 1988-06-22 1994-10-11 Olin Corporation Process for the production of dinitrotoluene
US5488187A (en) * 1988-06-22 1996-01-30 Olin Corporation Process for the production of dinitrobenzene and mononitrobenzene
US5663462A (en) * 1995-06-14 1997-09-02 Bayer Aktiengesellschaft Process for the production of dinitrotoluene and isomeric mixtures of dinitrotoluene
US20080242900A1 (en) * 2004-02-05 2008-10-02 Basf Aktiengesellschaft Method for Producing Dinitrotoluene
WO2008148608A1 (en) * 2007-06-06 2008-12-11 Huntsman International Llc Process for preparing mixtures of diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4361712A (en) * 1980-05-19 1982-11-30 Air Products And Chemicals, Inc. Cyanide reduction in nitroaromatic process

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2357531A (en) * 1939-08-05 1944-09-05 Universal Oil Prod Co Catalytic conversion of hydrocarbons
US2951746A (en) * 1957-02-25 1960-09-06 Hercules Powder Co Ltd Apparatus for stage-wise nitration of toluene
US3266872A (en) * 1962-04-13 1966-08-16 Sumitomo Chemical Co Reaction and separation apparatus

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2357531A (en) * 1939-08-05 1944-09-05 Universal Oil Prod Co Catalytic conversion of hydrocarbons
US2951746A (en) * 1957-02-25 1960-09-06 Hercules Powder Co Ltd Apparatus for stage-wise nitration of toluene
US3266872A (en) * 1962-04-13 1966-08-16 Sumitomo Chemical Co Reaction and separation apparatus

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4420645A (en) * 1982-07-19 1983-12-13 Monsanto Company Process for the nitration of halobenzenes
US4935557A (en) * 1984-08-07 1990-06-19 Air Products And Chemicals, Inc. Conitration of mixed aromatic hydrocarbons
US5001286A (en) * 1987-02-18 1991-03-19 Bayer Aktiengesellschaft Process for separating sulphuric acid and nitric acid from dinitrotoluene mixtures obtained during the nitration of toluene
US5488187A (en) * 1988-06-22 1996-01-30 Olin Corporation Process for the production of dinitrobenzene and mononitrobenzene
US5001272A (en) * 1988-06-22 1991-03-19 Olin Corporation Process for the production of dinitrotoluene
US5354924A (en) * 1988-06-22 1994-10-11 Olin Corporation Process for the production of dinitrotoluene
US4918250A (en) * 1989-04-21 1990-04-17 Olin Corporation Process for the production of dinitrotoluene using an inorganic salt as a phase separation agent
US5663462A (en) * 1995-06-14 1997-09-02 Bayer Aktiengesellschaft Process for the production of dinitrotoluene and isomeric mixtures of dinitrotoluene
US20080242900A1 (en) * 2004-02-05 2008-10-02 Basf Aktiengesellschaft Method for Producing Dinitrotoluene
US7851661B2 (en) 2004-02-05 2010-12-14 Basf Aktiengesellschaft Method for producing dinitrotoluene
WO2008148608A1 (en) * 2007-06-06 2008-12-11 Huntsman International Llc Process for preparing mixtures of diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates
EP2014641A3 (de) * 2007-06-06 2009-03-18 Huntsman International Llc Verfahren zur Herstellung von Mischungen aus Diphenylmethandiisocyanaten und Polyphenylpolymethylenpolyisocyanaten
US20100185011A1 (en) * 2007-06-06 2010-07-22 Huntsman International Llc Process for preparing mixtures of diphenyl-methane diisocyanates and polyphenyl-polymethylene polyisocyanates
JP2015107979A (ja) * 2007-06-06 2015-06-11 ハンツマン・インターナショナル・エルエルシー ジフェニルメタンジイソシアネート及びポリフェニルポリメチレンポリイソシアネートの混合物の製造法

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DE1468362A1 (de) 1968-11-28
ES318787A1 (es) 1966-04-16
GB1123204A (en) 1968-08-14
CH459165A (de) 1968-07-15

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