EP1720822A1 - Procede pour produire des esters nitriques liquides - Google Patents

Procede pour produire des esters nitriques liquides

Info

Publication number
EP1720822A1
EP1720822A1 EP05715339A EP05715339A EP1720822A1 EP 1720822 A1 EP1720822 A1 EP 1720822A1 EP 05715339 A EP05715339 A EP 05715339A EP 05715339 A EP05715339 A EP 05715339A EP 1720822 A1 EP1720822 A1 EP 1720822A1
Authority
EP
European Patent Office
Prior art keywords
microreactor
alcohol
glycerol
microns
channel diameter
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05715339A
Other languages
German (de)
English (en)
Inventor
Jürgen Antes
Dusan Boskovic
Jürgen HAASE
Stefan LÖBBECKE
Cornelius Ruloff
Tobias TÜRCKE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dynamit Nobel AG
Dynamit Nobel GmbH Explosivstoff und Systemtechnik
Original Assignee
Dynamit Nobel AG
Dynamit Nobel GmbH Explosivstoff und Systemtechnik
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dynamit Nobel AG, Dynamit Nobel GmbH Explosivstoff und Systemtechnik filed Critical Dynamit Nobel AG
Publication of EP1720822A1 publication Critical patent/EP1720822A1/fr
Withdrawn legal-status Critical Current

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
    • C07C201/02—Preparation of esters of nitric acid
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00822—Metal
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00824—Ceramic
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00824—Ceramic
    • B01J2219/00826—Quartz
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00831—Glass
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00858—Aspects relating to the size of the reactor
    • B01J2219/0086—Dimensions of the flow channels
    • 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
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00889—Mixing

Definitions

  • the invention relates to a method for producing liquid nitrate esters.
  • Liquid nitrate esters e.g. Glycerol trinitrate (nitroglycerin) are obtained by reacting nitrating acid (mixture of nitric acid, sulfuric acid and sulfur trioxide) with an alcohol, e.g. Glycerin, obtained (cf. Winnacker, Küchler, "Chemische Technologie", Volume 7, 1986, pages 359 to 402). The production and handling of nitroglycerin is associated with dangers.
  • nitrating acid mixture of nitric acid, sulfuric acid and sulfur trioxide
  • an alcohol e.g. Glycerin
  • the object of the invention is therefore to overcome the disadvantages of the prior art and in particular to provide a process for the preparation of liquid nitrate esters, such as nitroglycerin, which is safer than the previously known processes.
  • Nitrate esters with the features of the main claim.
  • Microreactors or micromixers are highly miniaturized tubular reactors with channel dimensions in the sub-millimeter range or volumes in the sub-milliliter range and are known as such. Descriptions can be found e.g. B. in:
  • the wastewater flows can be significantly reduced by up to 75%.
  • the method according to the invention offers the possibility of producing both small and large product quantities in a scalable and economical manner, since hardly any nitrate ester quantities are produced when starting up and shutting down the system get lost.
  • the production quantities can be flexibly adapted to the needs.
  • Microreactors in which fluid flows are mixed with one another are fundamentally suitable for the method according to the invention. Examples include microreactors that work according to the split and recombine principle or microreactors that work according to the multilamination principle, or microreactors that contact fluid flows in a simple manner in a T-piece-like configuration.
  • the fluid flows are split up and brought together again after passing through different distances.
  • the repeated repetition of this flow guidance for example in parallel microchannels arranged several times, leads to an effective mixing of the liquid flows.
  • the internal channel diameter of the micro-channel structures of such microreactors is approximately 50 to 3000 ⁇ m in diameter.
  • the length of the parallel microchannel structures can vary between 1 and 50 mm, preferably between 15 and 20 mm.
  • the individual fluid flows are first divided into parallel lamella flows before they are alternately combined with the second multilaminated fluid flow and thus mixed.
  • the internal channel diameter of the micro-channel structures of such microreactors is approximately 50 to 3000 ⁇ m in diameter.
  • the length of the parallel microchannel structures can vary between 1 and 50 mm, preferably between 15 and 20 mm.
  • the internal channel diameter of the microreactor can vary between 50 and 3000 ⁇ m. Channel inside diameters of 100 to 1000 ⁇ m are preferably used, very particularly preferably 200 to 300 ⁇ m.
  • the reaction in the microreactor is preferably carried out with a laminar flow of the liquids, the Reynolds number being particularly preferably less than 1000.
  • microreactors which ideally contain microstructured passive mixed structures.
  • simple T or Y mixers with comparable internal channel dimensions can also be used.
  • Microreactors with glass or silicon are preferably used as the material.
  • reactors with materials made of metal, ceramic or enamel can also be used.
  • microreactor systems It can also be provided according to the invention to connect several identical or different microreactors in series (microreactor systems).
  • the reaction mixture flows through a thermostatted residence zone, for example a capillary made of Teflon, after it has left the microreactor.
  • the microreactor and the dwell section form a microreactor system.
  • the length of the residence zone can be varied relatively freely within wide limits, for example it can be 20 to 100 cm, preferably 40 to 80 cm, particularly preferably 50 cm.
  • the inner diameter of this capillary can be 500 to 3000 ⁇ m, preferably 800 ⁇ m.
  • the chosen channel diameter of the microreactor '/ microreactor systems a very large surface-to-volume ratio is set. A preferred isothermal mode of operation is thereby realized.
  • Monohydric or polyhydric alcohols are preferably used as alcohols. Glycerol is very particularly preferably used as the alcohol.
  • a mixture of concentrated sulfuric acid and concentrated nitric acid in a weight ratio of 0.8: 1 to 1.2: 1 is preferably used as the nitrating acid.
  • the concentrated sulfuric acid can contain oleum.
  • the concentrated sulfuric acid preferably contains up to 10% by weight of oleum, particularly preferably 2 to 6% by weight. The reaction can also be carried out without oleum.
  • nitrate esters produced by the process according to the invention can be mono-, di- or polynitrate esters. Trinitroglycerin or glycol dinitrate esters are particularly preferred.
  • the molar ratio of HNO 3 to glycerol is preferably 3: 1 to 10: 1.
  • the process according to the invention for the production of nitrate esters is preferably carried out in a temperature range from 20 to 50 ° C., a temperature range from 30 to 45 ° C. being particularly preferred.
  • Example 1 Representation of nitroglycerin in a microreactor
  • the reaction was carried out in a microreactor (or micromixer) made of silicon material according to the split and recombine principle.
  • a microreactor or micromixer
  • liquid flows are split up and brought together again after passing through different distances.
  • the repeated repetition of this flow guidance in parallel microchannels leads to an effective mixing of the liquid flows.
  • the micro-channel structures of the microreactor are approximately 200 to 300 ⁇ m in diameter.
  • the length of the parallel microchannel structures varies between 15 and 20 mm.
  • the starting materials glycerol and mixed acid concentrated nitric acid and 4% by weight oleum-containing concentrated sulfuric acid in a weight ratio of 1: 1 were pumped into the microreactor via syringe pumps.
  • the microreactor was thermostatted to 50 ° C. in a water bath.
  • the reaction mixture After exiting the microreactor, the reaction mixture flowed through a 50 cm long, thermostatted Teflon capillary as a dwell section with an inner diameter of 800 ⁇ m.
  • the microreactor and Teflon capillary together form the microreaction system.
  • the volume flows of the starting materials and the residence time in the microreaction system are given in Table 1.
  • the crude nitroglycerin product composition obtained was analyzed by means of known high pressure liquid chromatography (HPLC). The results are also shown in Table 1.
  • V volume flow
  • VWZ dwell time
  • T R reaction temperature
  • GMN glycerol mononitrate
  • GDN 1,2- 1,3-glycerol dinitrate
  • GTN glycerol trinitrate
  • Example 2 Representation of nitroglycerin in a system of two microreactors
  • Example 2 The esterification of glycerol was carried out analogously to Example 1 with the following deviations: Two examples of the microreactor described in Example 1 were connected in series. The reaction mixture that emerges from the first microreactor was divided between the two inlets of the second microreactor. The reaction temperature in this example was 40 ° C. The volume flows of the starting materials, the residence time and the result of the HPLC analysis are summarized in Table 2. Table 2
  • V volume flow
  • VWZ dwell time
  • T R reaction temperature
  • GMN glycerol mononitrate
  • GDN 1,2 and 1,3-glycerol dinitrate
  • GTN glycerol trinitrate
  • Example 3 Representation of nitroglycerin in a simple T-microreactor The esterification of glycerin was carried out in a microreaction system consisting of a glass T-piece with an internal channel diameter of 800 ⁇ m and a subsequent 50 cm long Teflon capillary. The volume flows of the starting materials, the residence time and the result of the HPLC analysis are summarized in Table 3. Table 3
  • V volume flow
  • VWZ dwell time
  • T R reaction temperature
  • GMN glycerol mononitrate
  • GDN 1,2- 1,3-Glycerindinitrat
  • GTN glycerol trinitrate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention concerne un procédé pour produire des esters nitriques liquides, par ex. de la nitroglycérine, selon lequel un alcool est estérifié au moyen d'un mélange sulfonitrique, cette réaction étant réalisée dans un ou plusieurs microréacteurs.
EP05715339A 2004-02-16 2005-02-15 Procede pour produire des esters nitriques liquides Withdrawn EP1720822A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004007706A DE102004007706A1 (de) 2004-02-16 2004-02-16 Verfahren zur Herstellung von flüssigen Nitratestern
PCT/EP2005/001505 WO2005077883A1 (fr) 2004-02-16 2005-02-15 Procede pour produire des esters nitriques liquides

Publications (1)

Publication Number Publication Date
EP1720822A1 true EP1720822A1 (fr) 2006-11-15

Family

ID=34801931

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05715339A Withdrawn EP1720822A1 (fr) 2004-02-16 2005-02-15 Procede pour produire des esters nitriques liquides

Country Status (12)

Country Link
US (1) US20070287852A1 (fr)
EP (1) EP1720822A1 (fr)
JP (1) JP2007522253A (fr)
CN (1) CN1922127A (fr)
AR (1) AR047675A1 (fr)
AU (1) AU2005212822A1 (fr)
CA (1) CA2556395A1 (fr)
DE (1) DE102004007706A1 (fr)
IL (1) IL177290A0 (fr)
NO (1) NO20064116L (fr)
RU (1) RU2006133095A (fr)
WO (1) WO2005077883A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT501927B1 (de) * 2005-05-23 2007-06-15 Dsm Fine Chem Austria Gmbh Verbessertes verfahren zur durchführung von ritterreaktionen, elektrophilen additionen an alkenen oder friedel-crafts-alkylierungen
EP2048129A1 (fr) * 2007-10-12 2009-04-15 Lonza Ag Procédé pour la préparation de nitrates organiques
PL2222628T3 (pl) * 2007-12-20 2012-12-31 Dsm Fine Chemicals Austria Nfg Gmbh & Co Kg Tworzenie estrów azotanowych w mikroreaktorach i milireaktorach z zastosowaniem ciągłej ekstrakcji produktu w układzie przepływu burzliwego
JP2011178678A (ja) * 2010-02-26 2011-09-15 Dic Corp アルキル置換ベンゼンジオールの製造方法
US8658818B2 (en) * 2010-11-23 2014-02-25 Alliant Techsystems Inc. Methods of producing nitrate esters
JP5744696B2 (ja) * 2011-10-13 2015-07-08 バイオ燃料技研工業株式会社 液体燃料の製造方法、その製造方法により製造された液体燃料およびその液体燃料を含んでなるａ重油代替燃料組成物
CN102557954B (zh) * 2011-12-30 2013-12-04 北京理工大学 硝酸甲酯的制备方法
CN102816033B (zh) * 2012-09-11 2015-02-25 北京理工大学 甲醇硝酸酯全仿真炸药模拟物
CN106045860A (zh) * 2016-06-27 2016-10-26 山东益丰生化环保股份有限公司 一种新型高效十六烷值改进剂及其制备方法
US10703707B2 (en) 2018-11-07 2020-07-07 Industrial Technology Research Institute Method for preparing nitrate ester
US10562873B1 (en) * 2018-12-07 2020-02-18 Northrop Grumman Innovation Systems, Inc. Methods of producing glycidyl nitrate
CN111559964B (zh) * 2020-05-19 2021-04-20 启东市新晨企业管理咨询有限公司 一种硝酸甘油的绿色制备方法
CN111568859B (zh) * 2020-05-19 2022-07-19 启东市新晨企业管理咨询有限公司 一种硝酸甘油的外用制剂

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BE515328A (fr) * 1951-11-06 1900-01-01
US3053842A (en) * 1957-02-08 1962-09-11 Firm Josef Meissner Mixing method
DE3602067A1 (de) * 1986-01-24 1987-07-30 Mack Chem Pharm 2,6-dioxabicyclo(3.3.0)octan-derivate, ihre herstellung und verwendung als arzneimittel
US4908466A (en) * 1987-09-29 1990-03-13 Union Carbide Chemicals And Plastics Company Inc. Process and reaction vessel for production of alkyl nitrite
US5089652A (en) * 1990-01-17 1992-02-18 Atlas Powder Company Nitrate ester preparation
US5807847A (en) * 1996-06-04 1998-09-15 Queen's University At Kingston Nitrate esters
CA2370145C (fr) * 1999-10-14 2003-05-06 Dyno Nobel Asa Procede de preparation d'un agent plastifiant de grande energie
ITMI20022410A1 (it) * 2002-11-14 2004-05-15 Dinamite Dipharma S P A Procedimento per la nitrazione di alcandioli.
DE102004007708A1 (de) * 2004-02-16 2005-08-25 Dynamit Nobel Gmbh Explosivstoff- Und Systemtechnik Verfahren zur Aufarbeitung von flüssigen Stoffen

Non-Patent Citations (1)

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Also Published As

Publication number Publication date
RU2006133095A (ru) 2008-04-10
IL177290A0 (en) 2006-12-10
AU2005212822A1 (en) 2005-08-25
CN1922127A (zh) 2007-02-28
AR047675A1 (es) 2006-02-01
NO20064116L (no) 2006-11-02
US20070287852A1 (en) 2007-12-13
DE102004007706A1 (de) 2005-08-25
CA2556395A1 (fr) 2005-08-25
WO2005077883A8 (fr) 2006-10-26
WO2005077883A1 (fr) 2005-08-25
JP2007522253A (ja) 2007-08-09

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