EP1725511A1 - Procedes et systemes de traitement de flux de produits, et melanges associes - Google Patents

Procedes et systemes de traitement de flux de produits, et melanges associes

Info

Publication number
EP1725511A1
EP1725511A1 EP04704095A EP04704095A EP1725511A1 EP 1725511 A1 EP1725511 A1 EP 1725511A1 EP 04704095 A EP04704095 A EP 04704095A EP 04704095 A EP04704095 A EP 04704095A EP 1725511 A1 EP1725511 A1 EP 1725511A1
Authority
EP
European Patent Office
Prior art keywords
mol
product
stream
halogen exchange
halogen
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Withdrawn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
EP04704095A
Other languages
German (de)
English (en)
Other versions
EP1725511A4 (fr
Inventor
Vimal Sharma
William R. Lowery
Shaun E. Mckay
Benny D. Evers
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.)
Great Lakes Chemical Corp
Original Assignee
Great Lakes Chemical Corp
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 Great Lakes Chemical Corp filed Critical Great Lakes Chemical Corp
Publication of EP1725511A1 publication Critical patent/EP1725511A1/fr
Publication of EP1725511A4 publication Critical patent/EP1725511A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation

Definitions

  • the present invention relates generally to product stream processing methods, mixtures and systems. More particularly, the present invention relates to halogenated compound product stream processing methods, mixtures and systems.
  • Halogenated compounds such as fluorocarbons, hydrofluorocarbons, chlorofluorocarbons, and hydro chlorofluorocarbons have been found to be particularly useful chemicals. Exemplary uses for these chemicals include use as solvents, extinguishants, and refrigerants. It can be difficult to produce halogenated compounds free of production reactants and by-products. Many halogenated compounds can be produced through halogen exchange reactions.
  • One exemplary halogen exchange reaction is the production of CH 2 F 2 (difluoromethane, R-32) by combining CH 2 CI 2 (dichloromethane, R-30) and HF to produce CH F 2 .
  • this reaction is performed with an excess of HF and substantial amounts of HF remain with the product CH 2 F 2 .
  • CH 2 F 2 and HF form an azeotrope.
  • the azeotropic concentration of HF and CH 2 F 2 remains relatively constant at varying temperatures and pressures.
  • the azeotrope of CH 2 F 2 and HF has a typical concentration of 1.2% (mol/mol) HF with the remainder being CH 2 F 2 .
  • Another exemplary azeotrope that results from a halogen exchange reaction is the azeotrope of HF and CF 3 CFCICF 3 (2-chloroheptafluoropropane, CFC-217ba). It has been documented that this azeotrope exists between 38.4 to 47.9 % (mol/mol) CF 3 CFCICF3 with the remainder HF.
  • the present invention provides improved halogenated compound product stream processing methods, systems, and mixtures.
  • product stream processing methods include providing a reaction product stream that includes a halogen exchange reaction product, a halogen donating reactant, and a first amount of a halogen exchange by-product.
  • the halogen exchange reaction product and the halogen donating reactant of the reaction product stream can form an azeotropic composition having azeotropic amounts of the halogen exchange reaction product and the halogen donating reactant.
  • Methods can include removing a majority of the halogen exchange by-product from the reaction product stream to produce an intermediate product stream.
  • the intermediate product stream includes the halogen exchange reaction product, the halogen donating reactant, and a second amount of the halogen exchange by-product.
  • the second amount of the halogen exchange by-product is less than the first amount of the halogen donating reactant.
  • Methods can also include removing a majority of the halogen exchange reaction product from the intermediate product stream.
  • the halogen exchange reaction product removed contains less than the azeotropic amount of the halogen donating reactant.
  • An aspect of the present invention includes methods that provide a first product stream having C a X b ZdH (2 a +2 -b-d) and HZ, and a first amount of HY.
  • the C a XbZ d H(2a +2 -b- ) and HZ may form an azeotropic composition having an azeotropic amount of HZ.
  • the CaXbZ d H ( 2a + 2-b-d) can be produced from a halogen exchange reaction of C a XbY c H ⁇ 2 a+2 -b-c) and HZ.
  • a majority of the HY from the first product stream is removed to produce a second product stream that includes C a XbZdH (2a+ 2. b .d), HZ, and a second amount of HY which is less than the first amount of HY.
  • a majority of the C a X b Z H (2 a +2 - b -d ) containing less than the azeotropic amount of HZ can then be removed from the second product stream.
  • Embodiments of the present invention can provide mixtures that can be utilized during the product stream processing.
  • An exemplary mixture can comprise and/or consist essentially of CH 2 F 2 , HF, and from about 10% (mol/mol) to about 15% (mol/mol) HCI.
  • Embodiments of the present invention can also include systems for processing product streams.
  • One such system includes a first reaction product stream having a halogen exchange reaction product, a halogen donating reactant, and a halogen exchange by-product.
  • the halogen exchange reaction product and halogen donating agent can form an azeotropic composition having an azeotropic amount of the halogen donating agent.
  • the system also includes a halogen exchange by-product removal section.
  • the halogen exchange by-product removal section is configured to remove a majority of the halogen exchange by-product and produce a second product stream comprising the halogen exchange reaction product, the halogen donating reactant, and the halogen exchange by-product.
  • An amount of the halogen exchange by-product in the second product stream can be less than an amount of the halogen exchange by-product in the first reaction product stream.
  • Systems can also include a halogen exchange reaction product removal section configured to produce a halogen exchange reaction product having less than the azeotropic amount of the halogen donating reactant.
  • the present invention provides methods, systems and mixtures for processing product streams. Aspects of the present invention provide these methods, systems, and compositions for producing fluorocarbon, chlorofluorocarbons, and hydrofluorocarbons. In particular aspects, the present invention provides methods for processing product streams containing halogen exchange reaction products.
  • a production system 10 is shown.
  • Production system 10 includes a reaction product stream 12, a halogen exchange by-product removal section 14, halogen exchange by-product stream 16, and intermediate product stream 18.
  • System 10 also includes a halogen exchange reaction product removal section 20, a halogen exchange reaction product stream 22 and an excess reactant stream 24.
  • Reaction product stream 12 can comprise the reaction products of a halogen exchange reaction.
  • An exemplary halogen exchange reaction can occur between reactants 28, 30, and 32 where reactant 28 can be a halogenated compound reactant, reactant 30 can be a halogen donating reactant, and reactant 32 can include other reactants and or diluents useful when performing halogen exchange reactants.
  • System 10 is exemplary of a production system that may be used in accordance with the present invention. Other configurations are possible. An aspect of the present invention provides for the use of system 10 with the product stream processing methods in accordance with the present invention.
  • Exemplary halogenated compound reactants include those compounds having the general formula C a XbY c H( 2a+2 -b-c) where, within this general formulaic framework: X can include one or more of F, Cl, Br or I; Y can include one or more of Cl, Br, or I; and 1 ⁇ a> 4, 0 ⁇ b ⁇ 9, and 1 ⁇ c ⁇ 10.
  • Exemplary halogenated compound reactants include CH 2 CI 2 and/or CF 3 CCI 2 CF 3 (CFC-216, 2,2-dichloro-hexafluoropropane). Halogen exchange reactions can be performed by reacting the halogenated compound reactant with the halogen donating reactant.
  • Exemplary halogen donating reactants include those compounds having the general formula HZ where, within this general formulaic framework, Z can include one or more of F, Cl, or Br.
  • An exemplary halogen donating reactant includes HF.
  • Halogenated compound reactants and halogen donating reactants may be reacted in the presence of other compounds as well.
  • Other reactants and/or diluents that can be utilized when performing a halogen exchange reaction include organic diluents such as CH 2 F 2 or CF 3 CHFCF 3 (HFC-227ea, heptafluoropropane) and/or inorganic diluents such as Cl 2 or O 2 .
  • An exemplary halogen exchange reaction is the reaction of a halogenated compound reactant such as CH 2 CI 2 with a halogen donating reactant such as HF.
  • This reaction can take place in the presence of a catalyst.
  • this reaction can take place in the presence of an additional gas that may be utilized in some embodiments to cool the exothermic reaction when necessary. Additionally this reaction can take place in gas, liquid, and liquid/gas phases.
  • An exemplary reaction includes reacting a halogenated compound reactant in the gas phase with a halogen donating reactant in the gas phase in the presence of a catalyst.
  • Another exemplary reaction includes reacting both the halogenated compound reactant and the halogen donating reactant in the liquid phase in the presence of a catalyst.
  • reaction product stream 12 can comprise and/or consist essentially of a halogen exchange reaction product such as C a XbZdH (2a+2 . .d), a halogen donating reactant such as HZ and a halogen exchange by-product such as HY.
  • C a X b ZdH (2a+2 -b- ) can be produced from the halogen exchange reaction of C a XbY c H (2a+2 -b-c) and HZ.
  • Reaction product stream 12 includes an azeotropic composition having azeotropic amounts of the halogen exchange reaction product and the halogen donating reactant.
  • An exemplary reaction product stream 12 can include C a XbZdH( 2a+2 -b-d) and HZ that can form an azeotropic composition having an azeotropic amount of HZ.
  • Reaction product stream 12 can include an amount of the halogen exchange by-product that is greater than or equal to the mole equivalent of an amount of the halogen exchange reaction product.
  • reaction product stream 12 can include a molar amount of halogen exchange byproduct HCI that is greater than a molar amount of halogen exchange reaction product
  • azeotrope can refer to a constant blowing add mixture of one or more halogen exchange reaction product(s) with one or more halogen donating reactant(s).
  • One characteristic of an azeotrope is that it behaves as a single substance in that the vapor phase, when produced by partial evaporation or distillation of the liquid phase, has the same composition as the liquid phase (i.e., distills without compositional change).
  • the term azeotrope-like for purposes of this disclosure, refers generally to any such mixture of one or more halogen exchange reaction product(s) and the halogen donating reactant(s) that exhibits essentially a constant composition on boiling.
  • reaction product stream 12 can include an azeotropic composition comprising CH 2 F 2 and HF.
  • the reaction of halogenated compound reactant CH 2 CI 2 and halogen donating reactant HF can yield reaction product stream 12 comprising and/or consisting essentially of halogen exchange reaction product CH 2 F 2 , the halogen donating reactant HF, and halogen exchange by-product HCI.
  • the azeotropic composition of CH 2 F 2 and HF typically includes greater than 1.2% (mol/mol) HF.
  • the azeotropic composition can consist essentially of CH 2 F 2 and HF.
  • the present invention is not limited to the azeotropic composition of CH 2 F 2 and HF.
  • the azeotropic composition can include from about 1 % (mol/mol) to about 99% (mol/mol) halogen exchange reaction product and from about 1 % (mol/mol) to about 99% (mol/mol) halogen donating agent.
  • Other compositions not encompassed by the general formulaic framework utilized herein can be suitable for purification in accordance with the methods and systems herein disclosed.
  • the halogen exchange by-product removal section 14 can be used to remove a majority of the halogen exchange by-product from reaction product stream 12. Halogen exchange by-product removal section 14 can produce another product stream, the intermediate product stream 18.
  • Halogen exchange by-product removal section 14 can include a distillation apparatus configured to distill reaction product stream 12 and produce halogen exchange by-product 16 as a top product and intermediate product stream 18 as a bottom product.
  • reaction product stream 12 comprises the azeotropic composition of CH 2 F 2 and HF
  • halogen exchange by-product removal section 14 can be configured to distill reaction product stream 12 at a temperature less than about 285.4 °K or at least 283.2 °K.
  • Halogen exchange by-product stream 16 can include a majority of the halogen exchange by-product present in reaction product stream 12.
  • Intermediate product stream 18 can include the halogen exchange reaction product, the halogen donating reactant and an amount of the halogen exchange by-product.
  • the amount of the halogen exchange by-product of intermediate product stream 18 can be less than the amount of the halogen donating reactant.
  • An exemplary composition of intermediate product stream 18 includes CH 2 F 2 , HF and from about 10% (mol/mol) to about 15% (mol/mol) HCI.
  • the second amount of the halogen exchange by-product can be at least about 10% (mol/mol) of the intermediate product stream 18.
  • intermediate product stream 18 can comprise a mixture that includes CH 2 F 2 , HF and from about 10% (mol/mol) to about 15% (mol/mol) HCI.
  • Intermediate product stream 18 can be transferred to halogen exchange reaction product removal section 20.
  • An exemplary halogen exchange reaction product removal section 20 is a distillation apparatus.
  • Removal section 20 can be operated from about 299.8 °K to about 302.6 °K. Removal section 20 may also be operated at a pressure of approximately 6.2 x 10 5 Pa.
  • Halogen exchange product removal section 20 can be configured to remove a majority of the halogen exchange reaction product from intermediate product stream 18 as halogen exchange reaction product stream 22.
  • Halogen exchange reaction product stream 22 can be removed as a top stream from halogen exchange reaction product removal section 20 while excess reactant stream 24 can be recovered and/or recycled into the system.
  • Halogen exchange reaction product stream 22 includes the halogen exchange reaction product having less than the azeotropic amount of the halogen donating reactant.
  • halogen exchange reaction product stream 22 comprises and/or consists essentially of CH 2 F 2 and less than 1.2% (mol/mol) HF.
  • An aspect of the present invention also provides a halogen exchange reaction product stream 22 that includes CH 2 F 2 and from about 0.1% to less than 1.2% (mol/mol) HF.
  • Halogen exchange reaction product stream 22 can also comprise and/or consist essentially of CH 2 F 2 , HCI, and less than 1.2% (mol/mol) HF as well as from about 0.1 % to less than about 1.2% (mol/mol) HF.
  • Excess reactant stream 24 can include halogen donating reactant, halogen exchange by-product and/or intermediate halogen exchange reactants.
  • an exemplary intermediate can be CH 2 FCI.
  • Excess reactant stream 24 can be recovered and/or recycled to, for example, reactor 26. Aspects of the present invention are further described with reference to the following non-limiting example. Starting materials as indicated below by run number are charged into a previously evacuated stainless steel 316 distillation column having a top diameter of 300 millimeters and bottom diameter 500 millimeters. The column is packed to a height of about 10 meters with 316 stainless steel Intalox® IT structured packing.
  • the distillation apparatus being held at a temperature indicated by run number below and a pressure indicated by run number below.
  • Intermediate product as indicated below in Table 1 was removed from the bottom of the first distillation apparatus.
  • This intermediate product was then transferred to a second distillation apparatus having the temperature and pressures indicated by run number in Table 1 below.
  • the second distillation apparatus is a stainless steel 316 distillation column having a top diameter of 300 millimeters and bottom diameter 500 millimeters. The column is packed to a height of about 10 meters with 316 stainless steel Intalox® IT structured packing. (Available from Koch-Glitsch, North Wichita Kansas, 67220).
  • the column is held at the temperature and pressures indicated in Table 1 below by run number. As indicated in Table 1 , the azeotropic content of HF and the halogen exchange product CH 2 F 2 is approximately ten-fold less in runs 3 and 4 than in the initial runs 1 and 2.

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

Abstract

L'invention concerne des procédés et des systèmes de traitement de flux de produits, ainsi que des mélanges associés. Un flux de produits de réaction peut avoir une première quantité de sous-produits d'échange d'halogène et une composition azéotrope d'un produit de réaction d'échange d'halogène et d'un réactif donneur d'halogène. Une grande partie du sous-produit d'échange d'halogène du flux de produits de réaction peut être évacué afin de produire un mélange. Ce mélange peut comporter le produit de réaction d'échange d'halogène, le réactif donneur d'halogène, et une seconde quantité du sous-produit d'échange inférieure à la première quantité de réactif donneur d'halogène. Une grande partie du produit de réaction d'échange d'halogène contenant moins que la quantité azéotrope du réactif donneur d'halogène peut être évacuée du mélange. CH2F2, HF et HCl sont respectivement représentatifs d'un produit de réaction d'échange d'halogène, d'un réactif donneur d'halogène et d'un sous-produit d'échange d'halogène.
EP04704095A 2004-01-21 2004-01-21 Procedes et systemes de traitement de flux de produits, et melanges associes Withdrawn EP1725511A4 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2004/001686 WO2005080303A1 (fr) 2004-01-21 2004-01-21 Procedes et systemes de traitement de flux de produits, et melanges associes

Publications (2)

Publication Number Publication Date
EP1725511A1 true EP1725511A1 (fr) 2006-11-29
EP1725511A4 EP1725511A4 (fr) 2007-11-14

Family

ID=34887927

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04704095A Withdrawn EP1725511A4 (fr) 2004-01-21 2004-01-21 Procedes et systemes de traitement de flux de produits, et melanges associes

Country Status (3)

Country Link
EP (1) EP1725511A4 (fr)
CN (1) CN1946659A (fr)
WO (1) WO2005080303A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0876314B1 (fr) * 1995-08-01 2003-02-26 E.I. Du Pont De Nemours And Company Procedes de fabrication d'halocarbures et de composes selectionnes, et azeotropes formes avec hf

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06263658A (ja) * 1993-03-11 1994-09-20 Showa Denko Kk ジフルオロメタンの製法
US6605193B2 (en) * 2001-04-25 2003-08-12 Atofina Chemicals, Inc. Recovery of HFC-32

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0876314B1 (fr) * 1995-08-01 2003-02-26 E.I. Du Pont De Nemours And Company Procedes de fabrication d'halocarbures et de composes selectionnes, et azeotropes formes avec hf

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 199442 Derwent Publications Ltd., London, GB; AN 1994-338218 XP002453604 & JP 06 263658 A (SHOWA DENKO KK) 20 September 1994 (1994-09-20) *
See also references of WO2005080303A1 *

Also Published As

Publication number Publication date
CN1946659A (zh) 2007-04-11
EP1725511A4 (fr) 2007-11-14
WO2005080303A1 (fr) 2005-09-01

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