WO2010054462A1 - Method for reducing the formation of by-product dinitrobenzene in the production of mononitrobenzene - Google Patents
Method for reducing the formation of by-product dinitrobenzene in the production of mononitrobenzene Download PDFInfo
- Publication number
- WO2010054462A1 WO2010054462A1 PCT/CA2008/001996 CA2008001996W WO2010054462A1 WO 2010054462 A1 WO2010054462 A1 WO 2010054462A1 CA 2008001996 W CA2008001996 W CA 2008001996W WO 2010054462 A1 WO2010054462 A1 WO 2010054462A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reactor
- nitric acid
- inlet end
- mononitrobenzene
- sulfuric acid
- Prior art date
Links
Classifications
-
- 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
-
- 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
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
Definitions
- the invention pertains to methods and apparatuses for manufacturing mononitrobenzene so as to minimize the formation of by- product dinitrobenzene.
- Mononitrobenzene is made industrially by mixing benzene and nitric acid in the presence of sulfuric acid as a reaction catalyst.
- the majority of mononitrobenzene is produced in adiabatic units using either a series of continuous stirred tank reactors (CSTR) or a plug flow reactor.
- CSTR continuous stirred tank reactors
- plug flow reactor the heat of reaction is used to reconcentrate the spent sulfuric acid catalyst. Both the nitric acid and benzene reactants and the sulfuric acid are introduced at the reactor entrance.
- Dinitrobenzene formation consumes mononitrobenzene and nitric acid and thereby reduces the yield of product mononitrobenzene. Further, most industrial mononitrobenzene is hydrogenated to make aniline, and dinitrobenzene in mononitrobenzene is suspected of poisoning the catalyst of industrial aniline reactors.
- the invention provides a method for making mononitrobenzene in which only a low concentration of dinitrobenzene by-product is produced.
- the method thus improves the reaction yield of mononitrobenzene while also avoiding the need for a distillation step as in the prior art process, with its attendant energy input and yield loss.
- an adiabatic method of making mononitrobenzene in which benzene, nitric acid and sulfuric acid are introduced into a plug flow reactor train and a product stream comprising produced mononitrobenzene is removed at the outlet end thereof. Substantially all of the benzene and some or all of the sulfuric acid are introduced at the inlet end of the reactor train. A first portion of the nitric acid is introduced into the inlet end of the reactor train by a first nitric acid feed and a second portion of the nitric acid is introduced into the reactor train at one or more feeds that are spaced between the inlet end and the outlet end.
- All of the sulfuric acid is introduced at the inlet end, or, alternatively, a portion of the sulfuric acid may be mixed with the second portion of the nitric acid prior to introducing the second portion of the nitric acid into the reactor, or alternatively a portion of the sulfuric acid may be fed into the reactor train downstream of the inlet end.
- the invention further provides an apparatus for conducting an adiabatic reaction for making mononitrobenzene.
- the reactor train of the apparatus has an inlet end for receiving substantially all of the benzene and some or all of the sulfuric acid catalyst used in the reaction, and an outlet end for removing a product stream comprising produced mononitrobenzene.
- the apparatus includes a first nitric acid feed for introducing a first portion of the nitric acid into the inlet end, and one or more additional nitric acid feeds for introducing a second portion of the nitric acid, spaced between the inlet end and the outlet end.
- the apparatus may include means for mixing a portion of the sulfuric acid with the second portion of the nitric acid.
- the reactor train comprises a plug flow reactor, or, alternatively, it comprises a reactor train in which a portion thereof has plug flow conditions present.
- Figure 1 is a schematic drawing of a plug flow reactor apparatus according to the invention.
- the plug flow reactor 10 is an elongated tube having an inlet end 12 and an outlet end 14.
- a benzene conduit 16 feeds into the inlet end 12.
- a sulfuric acid conduit 26 for feeding reconcentrated sulfuric acid into the reactor (as further described below) also feeds into the inlet end 12.
- a nitric acid conduit 18 feeds nitric acid into the plug flow reactor 10 at three positions along its length, namely through the conduit 20 into the sulfuric acid conduit 26, forming mixed acid in the inlet conduit 27, which feeds into the inlet end 12 of the reactor; secondly, through the conduit 22 to feed nitric acid into the reactor at a position about one-sixth of the length from the inlet end 12 to the outlet end 14 of the reactor; and thirdly, through the conduit 24 to feed nitric acid into the reactor at a position about one-third of the length from the inlet end 12 to the outlet end 14 of the reactor.
- An outlet conduit 28 leads from the outlet end 14 of the reactor for transferring the product stream to a separator 30 for separating the produced mononitrobenzene from a sulfuric acid and water solution.
- the mononitrobenzene conduit 32 provides for the exit of produced mononitrobenzene from the separator 30.
- a conduit 34 provides for the transfer of the separated sulfuric acid and water to a sulfuric acid concentrator 36.
- a water conduit 38 provides for the removal of water from the concentrator and the conduit 26 provides for the recirculation of the concentrated sulfuric acid to the inlet end of the reactor.
- the recirculation loop includes a sulfuric acid makeup source (not shown).
- the nitric acid feed is split into three flows into the reactor, through conduits 20, 22 and 24, in a selected flow ratio.
- the flows may be equal or unequal.
- Benzene and sulfuric acid are fed into the reactor.
- the flow of nitric acid (100% basis) introduced into the reactor 10 at each of the three locations is preferably between 0.01 and 8% by weight of the sulfuric acid flow rate.
- the reactor average temperature is in the range of 60 to 130° C.
- the reaction product stream is fed into the separator 30, which produces a mononitrobenzene stream through the conduit 32.
- the separated sulphuric acid and water is fed into the sulfuric acid concentrator, which separates out the water and produces reconcentrated sulfuric acid for use in the nitration process.
- a conduit (not shown) is provided between the sulfuric acid conduit 26 and the nitric acid conduit 22. This permits a portion of the sulfuric acid to be mixed with the portion of nitric acid being fed into the reactor 10 through conduit 22.
- a conduit (not shown) is provided between the sulphuric acid conduit 26 and a sulphuric acid feed located at a position between the inlet end and the outlet end of the reactor. This permits a portion of the sulphuric acid to be introduced directly into the reactor downstream of the inlet end of the reactor, while another portion is introduced at the inlet end.
- an industrial adiabatic plug flow reactor producing nitrobenzene was operated at steady state under the following conditions: sulfuric acid strength at the entrance to the reactor was 70 wt % ; all benzene and nitric acid feed were introduced at the reactor entrance; the reactor entrance temperature was 100° C ; the nitric acid concentration in the mixed acid at the entrance to the reactor was 1.6 wt % ; benzene was introduced in molar excess. Under these conditions the produced mononitrobenzene contained 241 ppm of dinitrobenzene.
- Example 1 The industrial reactor of Example 1 was modified by splitting the nitric acid feed. The split was as follows: 80% of the nitric acid was introduced at the entrance of the reactor, and the remainder of the nitric acid was introduced at a location approximately one third up the length of the reactor. The other reaction conditions were the same as in Example 1. Analysis showed that the produced mononitrobenzene contained 205 ppm of dinitrobenzene.
- Example 4 The reaction of Example 2 was repeated while changing only the ratio of the nitric acid split.
- the nitric acid split was 60% at the entrance to the reactor with the remainder introduced one-third up the length of the reactor. Analysis showed that the produced mononitrobenzene contained 177 ppm of dinitrobenzene.
- a stirred laboratory-scale adiabatic reactor was filled with an organic phase consisting of pure benzene and an aqueous phase consisting of 70 wt% sulfuric acid and 30 wt% water.
- the added benzene was sufficient to be in excess of that required by the reaction.
- the mixture was well mixed and the temperature increased to 100° C.
- Sufficient nitric acid to produce a nitric acid concentration of 2.9 wt% in the aqueous phase was then quickly introduced in the reactor (within 3 to 4 seconds).
- the reactor temperature increased to approximately 117° C , producing an average reaction temperature of 109° C , in approximately 1 minute.
- Analysis of the produced organic phase showed 94 wt% mononitrobenzene, 6 wt% benzene, and 205 ppm of dinitrobenzene.
- Example 4 The stirred reactor of Example 4 was filled with an organic phase consisting of pure benzene and an aqueous phase consisting of 70 wt% sulfuric acid and 30 wt% water. The added benzene was sufficient to be in excess of that required by the reaction. The mixture was well mixed and the temperature increased to 100° C. Sufficient nitric acid to produce a nitric acid concentration of 2.9 wt% in the aqueous phase was then slowly introduced into the reactor (approximately 30 seconds), simulating an infinite number of nitric acid addition splits. The reactor temperature increased to approximately 117° C, producing an average reaction temperature of 109° C. Analysis of the produced organic phase showed 94 wt% mononitrobenzene, 6 wt% benzene, and 51 ppm of dinitrobenzene.
- the stirred reactor of Example 4 was filled with an organic phase consisting of pure benzene and an aqueous phase consisting of 70 wt% sulfuric acid and 30 wt% water.
- the added benzene was sufficient to be in excess of that required by the reaction.
- the mixture was well mixed and the temperature increased to 108° C.
- Sufficient nitric acid to produce a nitric acid concentration of 2.9 wt% in the aqueous phase was then quickly introduced in the reactor (within 3 to 4 seconds).
- the reactor temperature increased to approximately 125° C, producing an average reaction temperature of 116° C, in approximately 1 minute.
- Analysis of the produced organic phase showed 94 wt% mononitrobenzene, 6 wt% benzene, and 306 ppm of dinitrobenzene.
- Example 4 The stirred reactor of Example 4 was filled with an organic phase consisting of pure benzene and an aqueous phase consisting of 70 wt% sulfuric acid and 30 wt% water. The added benzene was sufficient to be in excess of that required by the reaction. The mixture was well mixed and the temperature increased to 108° C. Sufficient nitric acid to produce a nitric acid concentration of 2.9 wt% in the aqueous phase was then slowing introduced into the reactor (approximately 30 seconds), simulating an infinite number of nitric acid addition splits. The reactor temperature increased to approximately 125° C, producing an average reaction temperature of 116° C. Analysis of the produced organic phase showed 94 wt% mononitrobenzene, 6 wt% benzene, and 185 ppm of dinitrobenzene. Table 1 : Summary of Data for Examples 4 to 7
- Examples 2 and 3 show that splitting the nitric acid feed along the length of the reactor decreases the dinitrobenzene formation relative to introducing all of the nitric acid at the reactor entrance, as in control Example 1.
- the results of Examples 4 to 7 show that adding nitric acid gradually to a nitration mixture produces less dinitrobenzene than adding it quickly in a single dose. The gradual addition simulates the addition of nitric acid at different points along the reaction train.
- the data of Examples 4 to 7 also show that lower nitration temperatures favour lower dinitrobenzene production for the same nitric acid feed split.
- Examples 4 to 7 were carried out in a batch mode in an insulated, continuously stirred reactor. From chemical reactor theory, the reaction with time in a batch stirred reactor is approximately equivalent to a reaction with distance in an ideal continuously mixed plug flow reactor. Therefore the results from these batch stirred reactor experiments more closely represent the performance of an ideal plug flow nitration reactor than a CSTR reactor.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
HUE08878055A HUE029695T2 (en) | 2008-11-14 | 2008-11-14 | Method for reducing the formation of by-product dinitrobenzene in the production of mononitrobenzene |
PL08878055.6T PL2352718T3 (en) | 2008-11-14 | 2008-11-14 | Method for reducing the formation of by-product dinitrobenzene in the production of mononitrobenzene |
JP2011534976A JP5602143B2 (en) | 2008-11-14 | 2008-11-14 | A method for reducing the formation of by-product dinitrobenzene in the production of mononitrobenzene |
KR1020117013406A KR101585704B1 (en) | 2008-11-14 | 2008-11-14 | Method for reducing the formation of by-product dinitrobenzene in the production of mononitrobenzene |
PT08878055T PT2352718E (en) | 2008-11-14 | 2008-11-14 | Method for reducing the formation of by-product dinitrobenzene in the production of mononitrobenzene |
US13/129,023 US8604256B2 (en) | 2008-11-14 | 2008-11-14 | Method for reducing the formation of by-product dinitrobenzene in the production of mononitrobenzene |
EP08878055.6A EP2352718B1 (en) | 2008-11-14 | 2008-11-14 | Method for reducing the formation of by-product dinitrobenzene in the production of mononitrobenzene |
CN200880131957.2A CN102216253B (en) | 2008-11-14 | 2008-11-14 | Method for reducing the formation of by-product dinitrobenzene in the production of mononitrobenzene |
PCT/CA2008/001996 WO2010054462A1 (en) | 2008-11-14 | 2008-11-14 | Method for reducing the formation of by-product dinitrobenzene in the production of mononitrobenzene |
SA109300674A SA109300674B1 (en) | 2008-11-14 | 2009-11-11 | Method for Reducing the Formation of By-Product Dinitrobenzene in the Production of Mononitrobenzene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CA2008/001996 WO2010054462A1 (en) | 2008-11-14 | 2008-11-14 | Method for reducing the formation of by-product dinitrobenzene in the production of mononitrobenzene |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010054462A1 true WO2010054462A1 (en) | 2010-05-20 |
Family
ID=42169554
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CA2008/001996 WO2010054462A1 (en) | 2008-11-14 | 2008-11-14 | Method for reducing the formation of by-product dinitrobenzene in the production of mononitrobenzene |
Country Status (10)
Country | Link |
---|---|
US (1) | US8604256B2 (en) |
EP (1) | EP2352718B1 (en) |
JP (1) | JP5602143B2 (en) |
KR (1) | KR101585704B1 (en) |
CN (1) | CN102216253B (en) |
HU (1) | HUE029695T2 (en) |
PL (1) | PL2352718T3 (en) |
PT (1) | PT2352718E (en) |
SA (1) | SA109300674B1 (en) |
WO (1) | WO2010054462A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3160932B1 (en) | 2014-06-24 | 2018-03-14 | Covestro Deutschland AG | Process for producing nitrobenzene |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104507903B (en) * | 2012-07-27 | 2017-03-08 | 科思创德国股份有限公司 | The method that Nitrobenzol is prepared by adiabatic nitration |
CN112469501A (en) | 2018-07-24 | 2021-03-09 | 诺拉姆国际公司 | Nitration reactor and process |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0436443A2 (en) * | 1990-01-04 | 1991-07-10 | Nrm International Technologies C.V. | Nitration process |
US20030055300A1 (en) * | 2001-09-10 | 2003-03-20 | Andreas Chrisochoou | Tubular reactor for adiabatic nitration |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4021498A (en) * | 1975-12-09 | 1977-05-03 | American Cyanamid Company | Adiabatic process for nitration of nitratable aromatic compounds |
US4091042A (en) * | 1977-08-19 | 1978-05-23 | American Cyanamid Company | Continuous adiabatic process for the mononitration of benzene |
BR9107188A (en) * | 1990-12-24 | 1994-09-27 | Hoechst Ag | Process for continuous nitration of nitratable aromatic compounds. |
DE4410417A1 (en) * | 1994-02-14 | 1995-08-17 | Bayer Ag | Process for the adiabatic production of mononitrotoluenes |
DE4437047A1 (en) * | 1994-10-17 | 1996-04-18 | Bayer Ag | Process for the dinitration of aromatic compounds |
JP2001002626A (en) * | 1999-04-19 | 2001-01-09 | Sankyo Co Ltd | Production of nitric ester |
UA93890C2 (en) * | 2005-11-08 | 2011-03-25 | Ами Агролинц Меламин Интернациональ Гмбх | Process for producing of sulphurous nitrogen fertilizer in tubular reactor |
DE102006033722A1 (en) | 2006-07-21 | 2008-01-24 | Bayer Materialscience Ag | Process for the preparation of dinitrotoluene |
DE102008048713A1 (en) * | 2008-09-24 | 2010-03-25 | Bayer Materialscience Ag | Process for the continuous production of nitrobenzene |
PL2352717T3 (en) * | 2008-11-10 | 2018-02-28 | Noram International Limited | Adiabatic process for making mononitrobenzene |
-
2008
- 2008-11-14 KR KR1020117013406A patent/KR101585704B1/en active IP Right Grant
- 2008-11-14 PL PL08878055.6T patent/PL2352718T3/en unknown
- 2008-11-14 EP EP08878055.6A patent/EP2352718B1/en active Active
- 2008-11-14 US US13/129,023 patent/US8604256B2/en active Active
- 2008-11-14 WO PCT/CA2008/001996 patent/WO2010054462A1/en active Application Filing
- 2008-11-14 PT PT08878055T patent/PT2352718E/en unknown
- 2008-11-14 JP JP2011534976A patent/JP5602143B2/en not_active Expired - Fee Related
- 2008-11-14 HU HUE08878055A patent/HUE029695T2/en unknown
- 2008-11-14 CN CN200880131957.2A patent/CN102216253B/en not_active Expired - Fee Related
-
2009
- 2009-11-11 SA SA109300674A patent/SA109300674B1/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0436443A2 (en) * | 1990-01-04 | 1991-07-10 | Nrm International Technologies C.V. | Nitration process |
US20030055300A1 (en) * | 2001-09-10 | 2003-03-20 | Andreas Chrisochoou | Tubular reactor for adiabatic nitration |
Non-Patent Citations (3)
Title |
---|
QUADROS ET AL.: "Continuous adiabatic industrial benzene nitration with mixed acid at a pilot plant scale", CHEMICAL ENGINEERING JOURNAL, vol. 108, 2005, pages 1 - 11, XP004850881 * |
QUADROS ET AL.: "Different Modeling Approaches for a Heterogeneous Liquid- Liquid Reaction Process", INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, vol. 44, no. 25, 2005, pages 9414 - 9421, XP008139576 * |
See also references of EP2352718A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3160932B1 (en) | 2014-06-24 | 2018-03-14 | Covestro Deutschland AG | Process for producing nitrobenzene |
Also Published As
Publication number | Publication date |
---|---|
EP2352718B1 (en) | 2016-04-13 |
JP2012507570A (en) | 2012-03-29 |
SA109300674B1 (en) | 2013-11-04 |
PL2352718T3 (en) | 2016-10-31 |
KR20110086153A (en) | 2011-07-27 |
CN102216253A (en) | 2011-10-12 |
JP5602143B2 (en) | 2014-10-08 |
US20110218368A1 (en) | 2011-09-08 |
CN102216253B (en) | 2015-01-14 |
EP2352718A1 (en) | 2011-08-10 |
HUE029695T2 (en) | 2017-03-28 |
KR101585704B1 (en) | 2016-01-14 |
PT2352718E (en) | 2016-06-06 |
EP2352718A4 (en) | 2012-08-29 |
US8604256B2 (en) | 2013-12-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR0185424B1 (en) | Process for the production of hydrogen peroxide from hydrogen and oxygen | |
EP2490997B1 (en) | Process for nitroalkane recovery by aqueous phase recycle to nitration reactor | |
JP5497052B2 (en) | Adiabatic process for producing mononitrobenzene | |
US20140256980A1 (en) | Process for manufacturing hmb and salts thereof | |
TW200819414A (en) | A process for the production of dinitrotoluene | |
CN108250176A (en) | A kind of quick continuous flow synthesis technology of fluorinated ethylene carbonate | |
CN1918109A (en) | Method for producing dinitrotoluene | |
US8604256B2 (en) | Method for reducing the formation of by-product dinitrobenzene in the production of mononitrobenzene | |
CN109320423A (en) | A kind of method of micro passage reaction synthesizing nitryl compound | |
CN114957193A (en) | Method for green synthesis of vinylene carbonate | |
EP2516379B1 (en) | Hydrocarbon feed flexible high pressure nitration plant design | |
CN102432410A (en) | Production method of nitro compounds by tubular continuous nitrification reaction | |
CN106316857A (en) | Method for adjusting p/o ratio of chlorobenzene nitration product in micro-channel reactor | |
CN109400480B (en) | Method and equipment for preparing methyl nitrite | |
US9718791B2 (en) | Facile method for preparation of sodium 5-nitrotetrazolate using a flow system | |
CN111875503A (en) | Preparation method of 2, 6-dichloro-4-trifluoromethylaniline | |
US5948944A (en) | Two-stage dinitrotoluene production process | |
EP4029602A1 (en) | Device for continuously preparing 2,6-dihydroxybenzaldehyde and application thereof | |
CN115057780B (en) | Preparation method and device of 3, 5-dinitro-4-chlorotrifluoromethane | |
CN112191217B (en) | Continuous flow tubular reaction system and process for synthesizing adipic acid | |
JP2022548164A (en) | Addition reaction method between acetylene and ketone compound | |
CN106748753A (en) | The method of ethanol ethyl acetate coproduction arylamine |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200880131957.2 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 08878055 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011534976 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2008878055 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13129023 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20117013406 Country of ref document: KR Kind code of ref document: A |