US20030004380A1 - Method for producing 1,2-dichloroethane - Google Patents

Method for producing 1,2-dichloroethane Download PDF

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Publication number
US20030004380A1
US20030004380A1 US10/181,185 US18118502A US2003004380A1 US 20030004380 A1 US20030004380 A1 US 20030004380A1 US 18118502 A US18118502 A US 18118502A US 2003004380 A1 US2003004380 A1 US 2003004380A1
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Prior art keywords
dichloroethane
process according
carbon dioxide
line
reaction mixture
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Abandoned
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US10/181,185
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English (en)
Inventor
Helmut Grumann
Manfred Stoger
Jurgen Eichler
Dieter Jaculi
Winfried Lork
Arend Greve
Jan Wilkens
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Vinnolit Technologie GmbH and Co KG
Vintron GmbH
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Individual
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Priority claimed from DE2000159229 external-priority patent/DE10059229A1/de
Priority claimed from DE2001107092 external-priority patent/DE10107092A1/de
Application filed by Individual filed Critical Individual
Assigned to VINTRON GMBH, VINNOLIT TECHNOLOGIES GMBH & CO. KG reassignment VINTRON GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: EICHLER, JURGEN, GRUMANN, HELMUT, JACULI, DIETER, STOGER, MANFRED, WILKENS, JAN, GREVE, AREND, LORK, WINFRIED
Priority to US10/280,704 priority Critical patent/US7309804B2/en
Publication of US20030004380A1 publication Critical patent/US20030004380A1/en
Abandoned legal-status Critical Current

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    • 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
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
    • C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
    • C07C17/156—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of unsaturated hydrocarbons

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  • the invention relates to a process for the preparation of 1,2-dichloroethane that is very pure with respect to chloral or/and chloral hydrate and carbon dioxide, which process comprises oxychlorination of ethylene, using hydrogen chloride and an oxygen-containing gas such as air or oxygen, and alkali treatment of the dichloroethane, and also to 1,2-dichloroethane prepared in accordance with that process.
  • a known process for the preparation of 1,2-dichloroethane is the oxychlorination of ethylene using hydrogen chloride and oxygen, wherein chloral or/and chloral hydrate are formed as undesirable by-products.
  • the product of the process often comprises relatively large amounts of dissolved carbon dioxide formed as a by-product of the reaction of ethylene with oxygen.
  • German Patent Specification 1 468 480 describes an oxychlorination process wherein the undesirable by-products chloral and/or chloral hydrate are converted into sodium formate and chloroform by means of alkali treatment and can therefore be readily separated out from the product of the process, 1,2-dichloroethane.
  • the problem of the present invention accordingly was to provide, for the preparation of 1,2-dichloroethane, an oxychlorination process that avoids the disadvantages of the known processes.
  • the problem of the present invention was especially to reduce, or to avoid altogether, the consumption of alkali solution, and the salt charge, during conversion of the undesirable by-products chloral and chloral hydrate and, at the same time, to prepare 1,2-dichloroethane that has only a low content of the said by-products, if any at all.
  • the problem is solved by a process for the preparation of 1,2-dichloroethane, which process comprises oxychlorination of ethylene, using hydrogen chloride and an oxygen-containing gas such as oxygen or air, and alkali treatment of the dichloroethane-containing reaction mixture and which is characterised in that carbon dioxide is especially removed from the 1,2-dichloroethane-containing organic phase before alkali treatment of the 1,2-dichloroethane is carried out.
  • pure or very pure EDC has, per kg of EDC, a 2-chloroethanol content of ⁇ 100 mg, especially ⁇ 50 mg, preferably ⁇ 20 mg, more preferably ⁇ 10 mg, even more preferably ⁇ 5 mg, and very preferably ⁇ 2 mg.
  • very pure EDC has, per kg of EDC, a chloral content of ⁇ 20 mg, preferably ⁇ 10 mg, and very preferably ⁇ 5 mg.
  • very pure EDC has, per kg of EDC, an iron chloride content of ⁇ 20 mg, preferably ⁇ 10 mg, more preferably ⁇ 5 mg, and very preferably ⁇ 1 mg.
  • the process of the invention preferably comprises the following process steps:
  • a catalyst is preferably used for the oxychlorination step, with CuCl 2 or FeCl 3 catalysts having been found to be especially suitable for the purpose.
  • the reaction mixture Before removal of the carbon dioxide, the reaction mixture is preferably blown into a washing-liquid-containing sump region, in the form of a bubble column, of a washing or quenching zone.
  • the reaction mixture coming from the reaction zone which reaction mixture may under certain circumstances include solids, with catalyst fragments under certain circumstances also being present in addition to the gaseous and/or liquid products of oxychlorination of the ethylene, is passed through a washing zone; the washing zone may comprise, for example, a column and a lower sump region arranged in the form of a bubble column.
  • the reaction mixture preferably enters the lower portion of the bubble column, where it comes into intimate contact with the washing liquid present therein and, at the same time, is quantitatively freed of catalyst fragments. That process step can also be designated quenching.
  • the consumed washing liquid from the sump region of the washing zone is directed away, for example being neutralised and sent to waste water treatment.
  • the gaseous portion of the reaction mixture, which has been cooled and washed in the washing zone, is passed, by way of a gas line, into a condensing zone, in which there preferably prevail an elevated pressure and a low temperature.
  • the EDC-containing reaction mixture is substantially condensed therein, preferably under pressure, and is separated from the volatile by-products.
  • the carbon dioxide is present in dissolved form in the condensate.
  • the carbon dioxide, present especially in the 1,2-dichloroethane-containing organic phase may be separated out using any suitable procedure or apparatus. Separating the carbon dioxide out from the 1,2-dichloroethane-containing phase is preferably carried out by a method involving at least relieving the phase of pressure, for example in a vessel (desorption vessel). In that process, before the pressure is relieved, the phase has, for example, a pressure in the region of about 4 bar abs., whereas after the pressure is relieved it has, for example, a pressure in the region of about 1.1 bar abs.
  • a vessel of that kind preferably has an outlet for drawing off the carbon dioxide (gaseous) and an outlet for the 1,2-dichloroethane-containing phase (liquid).
  • a further process step is alkali treatment of the dichloroethane, which is already very pure with respect to CO 2 , for the purpose of removing chloral and/or chloral hydrate.
  • the carbon dioxide is separated out from the 1,2-dichloroethane phase in a column, by introduction of an inert gas.
  • an inert gas Any inert gas that is suitable in this process step may be used as the inert gas.
  • the inert gas is preferably nitrogen. 1,2-Dichloroethane and inert gas are advantageously directed past one another in counterflow, as a result of which the mass transfer can be improved. A process course having concurrent flow is, however, also possible.
  • the 1,2-dichloroethane or the 1,2-dichloroethane-containing phases is/are heated, by the introduction of heat, it being possible to use the customary procedures and apparatus known to the person skilled in the art. Special preference is given to carrying using a heat exchanger.
  • the 1,2-dichloroethane-containing organic phase preferably has a carbon dioxide content of less than 0.3% (w/w), preferably less than 0.2% (w/w) and especially less than 0.06% (w/w).
  • the process according to the invention makes possible, by simple technical means and in economical manner, effective removal of the catalyst fragments and/or the carbon dioxide from the 1,2-dichloroethane-containing phase.
  • the process according to the invention is first in resulting, in advantageous manner, in significant carbon dioxide separation, allowing a reduced use of base together with effective breakdown of chloral and/or chloral hydrate and accordingly resulting in a reduced salt charge.
  • the 1,2-dichloroethane-containing product from oxychlorination is quenched before the carbon dioxide is separated out.
  • quenching for example in the form of cooling and condensing, means that unreacted starting materials, for example hydrogen chloride, are completely or at least substantially removed by means of suitable liquids, solutions, gases or gas mixtures.
  • Quenching according to the invention has the advantage that, in the oxychlorination step, all, or the major portion, of unreacted starting materials are removed from the phase which is subjected to the further process steps.
  • the product from the oxychlorination process preferably contains, after quenching, less than 0.010% (w/w) hydrogen chloride, especially less than 0.005% (w/w) and most preferably less than 0.001% (w/w).
  • hydrogen chloride especially less than 0.005% (w/w) and most preferably less than 0.001% (w/w).
  • the alkali treatment of the 1,2-dichloroethane-containing phase to be carried out after separating out the carbon dioxide may be accomplished using any suitable procedure and by means of customary apparatus. This process step is preferably carried out using an aqueous alkali solution.
  • the aqueous alkali solution preferably has a pH of more than 8.5, especially more than 9.5.
  • the organic and aqueous waste products of the process are removed from the process circuit and are disposed of or recycled as necessary.
  • the aqueous alkali solution obtained from the final process step is preferably recycled, especially together with further aqueous phases to which other process steps give rise.
  • recycling is understood to mean that products of the process, intermediates or auxiliaries are returned to and used again in a process step.
  • the aqueous alkali solution alone or together with the further aqueous phases, is recycled to the quench.
  • the product of the process, 1,2-dichloroethane, obtained using the process according to the invention is substantially free of chloral and chloral hydrate. It preferably has a chloral or/and chloral hydrate content of less than 0.02% (w/w), preferably less than 0.005% (w/w) and especially less than 0.002% (w/w).
  • a further aspect of the invention relates to 1,2-dichloroethane that is very pure with respect to chloral and/or chloral hydrate and obtainable using a process as described above.
  • 1,2-Dichloroethane according to the invention may advantageously be used in applications where chloral or chloral hydrate would have an adverse effect.
  • FIG. 1 showing a flow diagram of a process of the invention according to a first preferred embodiment
  • FIG. 2 showing a flow diagram of a further preferred embodiment of the process according to the invention.
  • FIG. 3 showing a flow diagram of a further preferred embodiment of the process.
  • FIG. 1 shows a flow diagram of a process according to the invention, wherein EDC denotes the 1,2-dichloroethane being produced and 5 denotes an oxychlorination step.
  • the oxychlorination is carried out in known manner under customary conditions known to the person skilled in the art.
  • the process gas of the oxychlorination step 5 is transferred to a quenching step 7 by way of a line 6 .
  • the reaction mixture obtained therefrom is transferred into a decanter 1 by way of a line 8 provided with a heat exchanger 21 , whereas the waste water is directed away from the quenching step 7 by way of a waste water line 20 .
  • Recycle gases are recycled from the decanter 1 , by way of a line 9 , to the oxychlorination step 5 .
  • the aqueous phase is separated off in the decanter 1 and it is recycled to the quenching step 7 by way of a line 10 by means of a pump 16 .
  • the 1,2-dichloroethane(EDC)-containing organic phase from the decanter 1 is relieved of pressure in a vessel 2 by way of a control valve 19 , the carbon dioxide given off being removed by way of a carbon dioxide take-off line 11 .
  • an inert gas in this instance nitrogen, can, in addition, be fed in by way of an inert gas supply line 13 .
  • the 1,2-dichloroethane-containing phase is treated by introduction of lye by way of an inlet line 12 .
  • the aqueous alkaline phase is separated from the organic 1,2-dichloroethane-containing phase and recycled to the quenching step 7 by way of a line 14 by means of a pump 17 .
  • 1,2-dichlorothane that is very pure with respect to chloral or/and chloral hydrate is obtained from the end product take-off line 15 .
  • FIG. 2 shows a flow diagram, corresponding to FIG. 1, in accordance with a further preferred embodiment of the invention.
  • the difference from the process shown in FIG. 1 lies in the fact that carbon dioxide removal is carried out by means of a column 2 A in conjunction with a heat exchanger 18 , with inert gas, in this instance nitrogen, being introduced in counterflow; the heat exchanger 18 is situated upstream of the control valve 19 . Otherwise, the course of the process corresponds to that shown in FIG. 1, for which reason corresponding parts and process steps are given reference symbols corresponding to FIG. 1.
  • FIG. 3 shows an oxychlorination step 5 , a washing or quenching zone 7 , a vessel 2 , a condensing step 105 , a desorption zone 104 , a separating zone 107 and a distillation zone 108 as central zones.
  • the process gases hydrogen chloride, oxygen, ethylene and recycle gas, that is to say gas obtained by recycling are pre-heated and fed into the oxychlorination step 5 .
  • the oxychlorination step 5 comprises a fluidised-bed reactor having a steam generator for dissipating the reaction heat; the reacted reaction gas flows out of the fluidised-bed reactor at a temperature of 210° C., through the reaction gas line 6 and into the lower region of the quenching or washing zone 7 .
  • the washing zone 7 comprises a column (dia.: 2.2 m) having 8 valve trays and having a sump region 7 a arranged very especially in the form of a bubble column.
  • the reaction gas enters the lower region of the bubble column, where it comes into contact with the washing liquid and, at the same time, is quantitatively freed of catalyst fragments.
  • the reaction gas is cooled to a temperature of from 95° C. to 100° C. by the washing solution.
  • the washing liquid at the base of the bubble column runs off, through the run-off line 121 , into the vessel 2 for the purpose of neutralisation by means of sodium hydroxide solution introduced by way of line 114 and is finally passed, by way of line 126 , to the waste water plant for further treatment.
  • the washed and cooled reaction gases are passed from the washing zone 7 , through the gas line 122 and into the condensing zone 105 .
  • Non-condensed recycle gas is passed, through the line 131 , to the recirculating compressor 106 and is returned, by way of the line 120 , to the oxychlorination step 5 .
  • a portion of the recycle gas is taken away by way of the waste gas line 133 .
  • the condensate line 124 the EDC/water mixture, which is in liquid form under a pressure of about 4 bar and which contains dissolved carbon dioxide, at a temperature of 37° C. is relieved of pressure in the desorption zone 104 , down to a pressure of about 1.6 bar, where it separates into carbon dioxide, which leaves at the top, and EDC/water mixture, which runs off at the base. It is also optionally possible for separation of water and the remaining reaction mixture to be carried out beforehand.
  • Nm 3 /h of nitrogen are fed into the condensing zone 105 , by way of the line 129 , for thorough mixing of the condensate, and 3 Nm 3 /h of nitrogen are fed into the pressure-relieving zone 104 , at the base, by way of line 132 , for stabilising the carbon dioxide flow, the addition of nitrogen also bringing about more effective or improved removal of the carbon dioxide.
  • the aqueous phase obtained in that manner in the separating zone 107 can therefore be introduced into the quenching or washing zone 102 as washing liquid.
  • the separating zone 107 After an average dwell time, in the separating zone 107 , in the region of preferably from 0.5 to 3 hours, especially of about 1 hour, the upper, aqueous alkaline phase (having a pH adjusted to more than 9.5) is returned, by way of the line 123 , to the washing/quenching zone 102 and the lower, 1,2-dichloroethane phase is passed, by way of line 128 , into the distillation zone.
  • the distillation zone 108 comprises a perforated-plate column (dia.: 2 m) having an evaporator 109 , condenser 110 and separator 111 .
  • the process is distinguished by the fact that, in accordance with the invention, without a circulating procedure for the suspension, which may possibly contain solids, and irrespective of production changes and of the pH in the course of the washing and/or dwell zone, after separating out carbon dioxide in the desorption zone, the 1,2-dichloroethane/water mixture obtained from the condensing zone at a temperature of preferably from 25 to 45° as a result of its being relieved of pressure needs only to be subjected to alkali treatment with sodium hydroxide solution at an adjustable pH of preferably >8.5, especially >9.5, more especially in the range from 10.5 to 13, and for a dwell time of, for example, from 0.5 to 3 hours in the separating zone in order to obtain effective reduction of the chloral and 2-chloroethanol contents in the 1,2-dichloroethane and, therefore, to ensure the desired EDC quality for a lasting period.
  • the iron chloride content in the product is below the limit of detection at all times.
  • a certain portion of the separated aqueous phase and/or organic phase can be returned to the line leading into the separating zone in order to achieve additional thorough mixing.
  • the course of the process in this instance is as shown in FIG. 1.
  • the oxychlorination is carried out under customary process conditions, which will be known to the person skilled in the art and are therefore not explicitly mentioned here.
  • the process gases from the oxychlorination step 5 essentially 1,2-dichloroethane, water and the undesirable by-products carbon dioxide, chloral and/or chloral hydrate and possibly further by-products, are quenched in a following process step (the quenching step 7 ) using an aqueous solution.
  • the quenching step 7 traces of hydrogen chloride that have not been reacted during oxychlorination and, possibly, catalyst residues are washed out from the product mixture obtained from oxychlorination.
  • the 1,2-dichloroethane-containing phase, together with water, is then distilled off from the quenching step and condensed.
  • the quench is distilled at a pressure of from 2 to 4 bar and at a temperature of from 90 to 110° C. in a suitable distillation apparatus, is condensed and is then transferred to a separating vessel, preferably a decanter 1 .
  • the aqueous phase is separated from the organic 1,2-dichloroethane-containing phase.
  • the gaseous constituents therefrom can be recycled to the oxychlorination step 5 .
  • the aqueous phase is recycled to the quenching step 7 and the organic phase is relieved of pressure in a vessel 2 , the carbon dioxide being substantially evolved from the 1,2-dichloroethane and drawn off through an outlet from the vessel.
  • the carbon dioxide content in the 1,2-dichloroethane phase obtained is from 0.2% to 0.3% (w/w) carbon dioxide, based on the 1,2-dichloroethane-containing phase.
  • the 1,2-dichloroethane-containing, organic phase is transferred to an apparatus 3 located downstream and alkali treatment is carried out.
  • a lye preferably an NaOH solution having a concentration of ⁇ 10% (w/w) is introduced into the apparatus 3 , as a result of which the chloral and/or chloral hydrate is broken down.
  • the mixture is passed into a further decanter 4 , in which the 1,2-dichloroethane and the alkaline aqueous phase are separated from one another.
  • the alkaline aqueous phase is recycled to the quenching step 7 , and 1,2-dichloroethane that is very pure with respect to chloral/chloral hydrate, having a chloral or/and chloral hydrate content of less than 0.002% to 0.005% (w/w) based on the 1,2-dichloroethane-containing phase, is obtained.
  • the course of the process is as shown in FIG. 2.
  • the process steps and the course of the process therein also correspond to those of FIG. 1, with the difference that, for separating out the carbon dioxide from the 1,2-dichloroethane-containing phase, that phase is passed from the first separating vessel, a decanter 1 , into a column 2 A in which the carbon dioxide is separated off by means of the introduction of nitrogen by way of an inert gas supply inlet 13 .
  • the 1,2-dichloroethane-containing phase has a carbon dioxide content of from 0.05% to 0.1% (w/w).

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US10/181,185 2000-11-29 2001-11-29 Method for producing 1,2-dichloroethane Abandoned US20030004380A1 (en)

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DE10059229.5 2000-11-29
DE2000159229 DE10059229A1 (de) 2000-11-29 2000-11-29 Verfahren zur Herstellung von mit Bezug auch Chloral sehr reinem 1,2-Dichlorethan (EDC), das durch Oxichlorierung hergestellt worden ist
DE10107092.6 2001-02-13
DE2001107092 DE10107092A1 (de) 2001-02-13 2001-02-13 Verfahren zur Reinigung von 1,2 Dichlorethan

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US8282810B2 (en) 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
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US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
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JP2015147738A (ja) * 2014-02-05 2015-08-20 東ソー株式会社 １，２−ジクロロエタンの製造方法
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems

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US20030055301A1 (en) 2003-03-20
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RU2002119011A (ru) 2004-01-10
NO20023549L (no) 2002-07-25
CN1396893A (zh) 2003-02-12
DE50102118D1 (de) 2004-06-03
US7309804B2 (en) 2007-12-18
NO20023549D0 (no) 2002-07-25
HUP0204129A3 (en) 2004-08-30
CA2392461A1 (en) 2002-06-06
RU2280637C2 (ru) 2006-07-27
TR200401073T4 (tr) 2004-08-23
AU2002218319A1 (en) 2002-06-11
EP1228023A1 (de) 2002-08-07
CN1173905C (zh) 2004-11-03
WO2002044116A1 (de) 2002-06-06

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