WO2013026720A1 - Procédé de fabrication de 1,2-dichloroéthane (dce) - Google Patents

Procédé de fabrication de 1,2-dichloroéthane (dce) Download PDF

Info

Publication number
WO2013026720A1
WO2013026720A1 PCT/EP2012/065720 EP2012065720W WO2013026720A1 WO 2013026720 A1 WO2013026720 A1 WO 2013026720A1 EP 2012065720 W EP2012065720 W EP 2012065720W WO 2013026720 A1 WO2013026720 A1 WO 2013026720A1
Authority
WO
WIPO (PCT)
Prior art keywords
fraction
dichloroethane
optionally
ethylene
stream
Prior art date
Application number
PCT/EP2012/065720
Other languages
English (en)
Inventor
Uwe Rodemerck
David Linke
Michel Strebelle
Original Assignee
Solvay Sa
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 Solvay Sa filed Critical Solvay Sa
Publication of WO2013026720A1 publication Critical patent/WO2013026720A1/fr

Links

Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the present invention relates to a process for the manufacture of a catalyst, to an oxydehydrogenation (ODH) process using such a catalyst, to a process for the manufacture of 1 ,2-dichloroethane (DCE), to a process for the manufacture of vinyl chloride (VC) and to a process for the manufacture of polyvinyl chloride (PVC).
  • ODH oxydehydrogenation
  • DCE 1 ,2-dichloroethane
  • VC vinyl chloride
  • PVC polyvinyl chloride
  • DCE is usually prepared by oxychlorination of ethylene using hydrogen chloride (HCl) and a source of oxygen or by direct chlorination of ethylene using chlorine.
  • HCl hydrogen chloride
  • the dehydrochlorination of DCE by pyro lysis thus results in the production of VC with release of HCl.
  • the oxychlorination and chlorination are generally carried out in parallel and the HCl produced in the pyro lysis is used in the oxychlorination.
  • ethylene which is more than 99.8 % pure is normally used for the manufacture of DCE.
  • This very high purity ethylene is obtained via the thermal cracking of various petroleum products, followed by numerous complex and expensive separation operations in order to isolate the ethylene from the other products of the cracking and to obtain a product of very high purity.
  • WO 2008/00693, WO 2008/000702 and WO 2008/000705 in the name of the Applicant aim at solving the above mentioned problems and use impure ethylene coming from the catalytic oxydehydrogenation (ODH) of ethane either used as such, or pre-treated by absorption/desorption steps.
  • ODH catalytic oxydehydrogenation
  • V Vanadium
  • Mo, W and V are the most effective ones. They namely offer a high selectivity to ethylene and a low selectivity to COx.
  • Such catalysts and their use in the ODH of ethane to ethylene are known for instance from US 4,250,346.
  • said catalysts are merely listed among others (namely examples 46 and 58 in a list of 58 examples) and they were obtained by merely drying a solution of catalytic precursors comprising Mo, V and W at atmospheric pressure.
  • the Applicant found out that surprisingly, such catalysts, when obtained by a process comprising a hydrothermal treatment step, are much more active in ODH reactions, especially in the ODH of ethane in ethylene and that they are especially useful if said ethylene is used to manufacture DCE by (oxy)chlorination i.e by chlorination and/or oxychlorination.
  • the present invention relates to a process for the manufacture of a catalyst for ODH reactions, said process comprising the hydrothermal treatment of a mixture of catalytic oxide precursors comprising Mo, V and W.
  • the present invention concerns a process for the manufacture of 1 ,2-dichloroethane (DCE)a catalyst for oxydehydrogenation (ODH) reactions, said process comprising :
  • ODH oxydehydrogenation
  • the present invention concerns a process for the
  • DCE 1 ,2-dichloroethane
  • said process comprising an ODH step of ethane to ethylene and a subsequent (oxy)chlorination step of the ethylene so obtained, wherein during the ODH step, a catalyst is used which has been obtained by the hydrothermal treatment of a mixture of catalytic oxide precursors comprising Mo, V and W.
  • catalytic oxide precursors are meant chemical compounds which after a thermal treatment and optionally, a calcination step, constitute a mixed oxide of Mo, V and W which is active in the catalysis of ODH reactions.
  • “hydrothermal treatment” is meant a treatment of the catalytic precursors in solution in water at a temperature above 100°C and under pressure.
  • the treatment temperature is from 100 to 300°C, more preferably from 120 to 250°C and even more preferably : from 150 to 200°C and the pressure is preferably the one corresponding to the liquid- vapor equilibrium conditions at the given temperature (which, considering the chemical medium, is a little less than the one given in wide available tables for pure water).
  • the catalytic oxide precursors used must be at least partially water soluble under the treatment conditions. They may either be organic compounds of Mo, V and W (like organic acids or salts thereof) or inorganic compounds of said elements (like oxides, hydroxides, sulphates, nitrates, chlorides...), as long as they are at least partially water soluble (i.e. as long as they can dissolve in a concentration allowing to get the required concentration in the final catalyst). Also, to the extent possible, the selected compounds of the various elements preferably are mutually soluble.
  • each catalytic oxide precursor is introduced in the mixture to be treated already as an aqueous solution thereof.
  • the molybdenum is preferably introduced into solution in the form of ammonium salts thereof such as ammonium paramo lybdate, and organic acid salts of molybdenum such as acetates, oxalates, mandelates and glycolates.
  • water soluble molybdenum compounds which may be used are partially water soluble molybdenum oxides, molybdic acid, and the chlorides of molybdenum.
  • the vanadium is preferably introduced into solution in the form of ammonium salts thereof such as ammonium meta- vanadate and ammonium decavanadate, and organic acid salts of vanadium such as acetates, oxalates and tartrates.
  • ammonium salts thereof such as ammonium meta- vanadate and ammonium decavanadate
  • organic acid salts of vanadium such as acetates, oxalates and tartrates.
  • Other water soluble vanadium compounds which may be used are partially water soluble vanadium oxides, and the sulfates of vanadium.
  • the tungsten is preferably introduced into solution in the form of ammonium salts such as ammonium paratungstate.
  • ammonium salts such as ammonium paratungstate.
  • Other water soluble tungsten compounds which may be used are the tungstic acids.
  • oxide precursors comprising Mo, V and W
  • at least one oxide precursor of at least one other element such as, for example Cr, Mn, Nb, Ta, Te, Ti, P, Sb, Bi, Zr, Ni, Ce, Al or Ca.
  • Oxide precursors of Te and/or Ti are preferred, especially when said catalyst is intended for the ODH of ethane in ethylene (see below).
  • P and/or Nb oxide precursors may also be added.
  • catalysts containing Mo, V and W, and additionally, at least one element selected from Te, Ti, P and Nb, but in a total amount of these element(s) of less than 0.1 expressed in atomic fraction of metals are believed to be novel an inventive i.e. to be active catalysts in ODH reactions namely of ethane to ethylene.
  • the present invention also relates to such catalysts independently of the way they are obtained.
  • catalysts obtained by the process described above and including a hydrothermal treatment are preferred.
  • Preferred catalyst compositions are those containing (expressed in atomic fraction of metals) 0.35 to 0.5 Mo, 0.1 to 0.3 W and 0.2 to 0.35 V. Even more preferred are those containing additionally Te and/or Ti (preferably both) but in a total atomic fraction of less than 0.1.
  • ICP-OES Inductively Coupled Plasma - Optical Emission Spectroscopy
  • XRF X-Ray Fluorescence
  • the mixture preferably comprises the following atomic fractions of metals : 0.3 to 0.6 Mo, 0.05 to 0.3 W, 0.1 to 0.4 V (preferably about 0.32 V) and optionally, less than 0.1 Te and/or Ti and/or P and/or Nb.
  • said mixture comprises an atomic fraction o f Te and Ti o f at least 0.01.
  • the process according to the first aspect of the invention preferably comprises, after the hydrothermal treatment step of the aqueous mixture, during which solids have crystallized/precipitated from a liquid aqueous medium, a step of separating these solids from said liquid aqueous medium. This may be done by any known technique like filtering, centrifuging...
  • These solids which have precipitated generally comprise at least one crystal phase diluted in an amorphous matrix.
  • This invention includes also processes where a solid is introduced in the crystallization stage or just after to obtain a supported catalyst. This allows an improved mechanical stability and a better efficiency of the active components from an accessibility point of view.
  • the solids are preferably calcined.
  • calcination is meant heating to a high temperature but below the melting or fusing point, causing loss of moisture, reduction or oxidation, and formation of desired crystal phases. Typically, calcination occurs at a temperature above 100°C, generally above 200°C and even, above 300°C.
  • a calcination at a lower temperature (typically : below 500°C, preferably below 450°C and even more preferably : below 400°C) gives better results than a calcination at a higher temperature (typically : above 800°C or even : above 600°C) although higher temperatures are generally recommended in literature as they enhance the formation of the above mentioned crystal phase(s) which are believed to be at the origin of the catalytic activity of the catalysts.
  • the duration of calcination is typically in the range of hours, namely : generally from 1 to 15h, preferably from 2 to lOh, even more preferably from 4 to 6h.
  • a thermal activation step (generally in an inert atmosphere or under vacuum, and at a temperature of at least 600°C may be applied if required and as known in the art.
  • the present invention concerns a process for the catalytic oxydehydrogenation (ODH) of ethane to ethylene using the catalyst obtained as described above.
  • catalytic oxydehydrogenation also known as catalytic oxidative dehydrogenation
  • ODH catalytic oxidative dehydrogenation
  • a stream of ethane is converted to a gas mixture containing ethylene, unconverted ethane, water and secondary constituents.
  • Said stream of ethane may or may not be chemically pure.
  • the stream of ethane used may contain up to 70 vol % of other gases such as methane, hydrogen, ethylene, oxygen, nitrogen, carbon oxides and even, chlorinated substances like DCE (see below).
  • the stream of ethane used advantageously contains at least 80 vol %, preferably at least 90 vol %, particularly preferably at least 95 vol % and more particularly preferably at least 98 vol % of ethane. If necessary, the ethane may be separated from the secondary compounds having a higher boiling point in any known device, for example by absorption, extraction, diffusion or distillation.
  • ODH may take place either at a temperature above 650°C up to 800°C, below the range of thermal cracking temperatures, or at a temperature less than or equal to 650°C.
  • the pressure at which ODH is carried out is advantageously at least 1, preferably at least 1.5 and particularly preferably at least 2 bar absolute. It is preferably at most 30 bar, advantageously at most 16, even more preferably at most 11 and particularly preferably at most 6 bar absolute. Rising pressure is generally advantageous in terms of productivity.
  • the oxygen used in the ODH may be "pure" (as commercially available : see below) oxygen or a gas containing oxygen with other inert gases, such as for example air.
  • oxygen is used.
  • the oxygen used advantageously contains more than 90 vol % and preferably more than 95 vol % of oxygen.
  • a source of oxygen containing from 95 to 99 vol % of oxygen is particularly preferred.
  • the amount of oxygen introduced is advantageously from 0.001 to 1 mol/mol, preferably from 0.005 to 0.5 mol/mol and particularly preferably from 0.05 to 0.3 mol/mol.
  • ODH may be carried out in any known device.
  • ODH is carried out in one reactor or a series of reactors of fixed bed type having one or more beds, between which a thermal conditioning step may be carried out, or in one reactor or a series of reactors of fluid bed type, preferably adiabatic or with temperature control using an auxiliary fluid inside the reactor (multitubular reactor or heat exchanger immersed in the catalytic bed) or outside the reactor.
  • the reactants may be previously mixed before introduction into the reaction zone.
  • One or more reactants may also be added differently, for example between the beds of a multi-bed reactor.
  • the reactor may be equipped with preheating means and with any means necessary to control the reaction temperature.
  • a cross exchanger advantageously enables the heat of the products formed to be recovered to reheat the incoming products.
  • the catalyst used for ODH may or may not be supported.
  • the support which may possibly be used includes silica, alumina, titanium oxide, silicon carbide, zirconia and mixtures thereof such as mixed oxides.
  • the catalyst used for ODH is advantageously resistant to DCE.
  • the presence of Te and/or Ti (especially both) in the catalyst is preferred.
  • the catalyst used may be placed on a bed or in tubes or outside of those tubes so that a temperature control may be obtained by a fluid surrounding these tubes or running through them.
  • ODH of the stream of ethane gives a gas mixture containing ethylene, unconverted ethane, water and secondary constituents.
  • the secondary constituents may be carbon monoxide, carbon dioxide, hydrogen, various oxygen-containing compounds such as, for example, acetic acid or aldehydes, nitrogen, methane, oxygen, and optionally organic compounds comprising at least 3 carbon atoms.
  • ODH takes place at a temperature above 650°C up to 800°C.
  • ODH takes place at a temperature less than or equal to 650°C.
  • ODH then takes place at a temperature less than or equal to 600°C, preferably less than or equal to 550°C, particularly preferably less than or equal to 500°C, more particularly preferably less than or equal to 450°C and most particularly preferably less than or equal to 400°C.
  • a temperature between 200 and 400°C is particularly advantageous.
  • the process according to the invention has the advantage of generating very small amounts of hydrogen responsible for many drawbacks, namely :
  • This second variant has the advantage that the ODH reaction generally does not generate troublesome amounts of heavy compounds having a number of carbon atoms greater than or equal to 3, such as for example propylene and olefins with a molecular weight higher than that of propylene.
  • heavy compounds having a number of carbon atoms greater than or equal to 3, such as for example propylene and olefins with a molecular weight higher than that of propylene.
  • Such compounds and also their chlorinated derivatives are strong inhibitors of the pyrolysis of DCE in VC and hence, could jeopardize the use of the ethylene for making DCE.
  • the second variant of the process according to the invention is hence preferred to the first.
  • the present invention concerns a process for the manufacture of 1 ,2-dichloroethane (DCE) comprising an ODH step of ethane to ethylene as described above, and a subsequent oxychlorination step of ethylene.
  • DCE diichloroethane
  • the invention relates to a process for the
  • said gas mixture is optionally washed and dried thus producing a dry gas mixture ;
  • the dry gas mixture is then conveyed to a chlorination reactor supplied with a flow of chlorine so that at least 10 % of the ethylene is converted to 1 ,2-dichloroethane ;
  • the 1 ,2-dichloroethane formed in the chlorination reactor is optionally isolated from the stream of products derived from the chlorination reactor ;
  • the stream of products derived from the chlorination reactor, from which the 1,2-dichloroethane has optionally been extracted is conveyed to an oxychlorination reactor in which the majority of the balance of ethylene is converted to 1,2-dichloroethane, after optionally having subjected the latter to an absorption/desorption step e'), during which the 1,2-dichloroethane formed in the chlorination reactor is optionally extracted if it has not previously been extracted ;
  • the 1 ,2-dichloroethane formed in the oxychlorination reactor is isolated from the stream of products derived from the oxychlorination reactor and is optionally added to the 1 ,2-dichloroethane formed in the chlorination reactor ;
  • the invention relates to a process for the manufacture of DCE starting from a stream of ethane according to which :
  • said gas mixture is optionally washed and dried thus producing a dry gas mixture ;
  • said dry gas mixture is subjected to an absorption Al which consists of separating said gas mixture into a fraction enriched with the compounds that are lighter than ethylene containing some of the ethylene (fraction A) and into a fraction Fl ;
  • fraction A is conveyed to a chlorination reactor in which most of the ethylene present in fraction A is converted to 1 ,2-dichloroethane and optionally the
  • absorption A2 is subjected to a desorption D which consists of separating fraction Fl into a fraction enriched with ethylene (fraction B) and into a fraction F3, optionally containing the 1 ,2-dichloroethane formed in the chlorination reactor then extracted if it has not been extracted previously, which is recycled to at least one of the absorption steps, optionally after an additional treatment intended to reduce the concentration of compounds that are heavier than ethane in fraction F3 ;
  • fraction B is conveyed to an oxychlorination reactor in which most of the ethylene present in fraction B is converted into 1,2-dichloroethane, the 1 ,2-dichloroethane obtained is separated from the stream of products derived from the oxychlorination reactor and is optionally added to the
  • the stream of products derived from the oxychlorination reactor, from which the 1 ,2-dichloroethane has been extracted, optionally containing an additional stream of ethane previously introduced in one of steps b) to g), is optionally recycled to step a) after having been optionally purged of gases and/or after an optional additional treatment in order to eliminate the chlorinated products contained therein.
  • the invention relates to a process for the manufacture of 1,2-dichloroethane starting from a stream of ethane according to which :
  • said gas mixture is optionally washed and dried thus producing a dry gas mixture ;
  • said dry gas mixture comprising the stream of products derived from the chlorination reactor R2 separated in step e) is subjected to an absorption A which consists of separating said gas mixture into a fraction enriched with the compounds that are lighter than ethylene containing some of the ethylene (fraction A) and into a fraction Fl ; d) fraction A is conveyed to a chlorination reactor Rl in which most of the ethylene present in fraction A is converted into 1 ,2-dichloroethane and the
  • fraction Fl is subjected to a desorption Dl which consists of separating fraction Fl into an ethylene fraction depleted of the compounds that are lighter than ethylene (fraction C) which is conveyed to a chlorination reactor R2, the stream of products derived from this reactor being added to the dry gas mixture subjected to step c) after having optionally extracted the
  • fraction F2 is subjected to a desorption D2 which consists of separating fraction F2 into a fraction enriched with ethylene (fraction B) and into a fraction F3, optionally containing the 1 ,2-dichloroethane formed in the chlorination reactor R2 then extracted, if it has not previously been extracted, which is recycled to the absorption A, optionally after an additional treatment intended to reduce the concentration, in fraction F3, of the compounds that are heavier than ethane ;
  • a desorption D2 which consists of separating fraction F2 into a fraction enriched with ethylene (fraction B) and into a fraction F3, optionally containing the 1 ,2-dichloroethane formed in the chlorination reactor R2 then extracted, if it has not previously been extracted, which is recycled to the absorption A, optionally after an additional treatment intended to reduce the concentration, in fraction F3, of the compounds that are heavier than ethane ;
  • fraction B is conveyed to an oxychlorination reactor in which most of the ethylene present in fraction B is converted into 1 ,2-dichloroethane, the
  • the stream of products derived from the oxychlorination reactor, from which the 1 ,2-dichloroethane has been extracted, optionally containing an additional stream of ethane previously introduced in one of steps b) to g), is optionally recycled to step a) after having been optionally purged of gases and/or after an optional additional treatment in order to eliminate the chlorinated products contained therein.
  • step a) thereof In the case a stream of ethane coming from a process according to any of the embodiments described above is recycled in step a) thereof (either in a continuous, loop process (which is generally the case in an industrial process) or in a batch one), it has been observed that the ODH step according to the invention is not detrimentally influenced by residual amounts of DCE and CO in said stream.
  • the DCE obtained by (oxy)chlorination of ethylene as described above may then be converted into VC.
  • the invention therefore also relates to a process for the manufacture of VC. Namely, in this process, the 1 ,2-dichloroethane obtained as described above is subjected to a pyro lysis thus producing VC.
  • the conditions under which the pyrolysis may be carried out are known to a person skilled in the art.
  • This pyrolysis is advantageously achieved by a reaction in the gas phase in a tube furnace.
  • the usual pyrolysis temperatures extend between 400 and 600°C with a preference for the range between 480°C and 540°C.
  • the residence time is advantageously between 1 and 60 seconds with a preference for the range of 5 to 25 seconds.
  • the conversion rate of the DCE is advantageously limited to 45 to 75 % in order to limit the formation of by-products and fouling of the furnace pipes.
  • the following steps make it possible, using any known device, to collect the purified VC and the hydrogen chloride to be upgraded preferably in the oxychlorination. Following
  • the unconverted DCE is advantageously reconveyed to the pyrolysis furnace.
  • the invention also relates to a process for the manufacture of
  • the process for the manufacture of PVC may be a bulk, solution or aqueous dispersion polymerization process, preferably it is an aqueous dispersion polymerization process.
  • aqueous dispersion polymerization is understood to mean radical polymerization in aqueous suspension and also radical polymerization in aqueous emulsion and polymerization in aqueous microsuspension.
  • radical polymerization in aqueous suspension is understood to mean any radical polymerization process performed in aqueous medium in the presence of dispersants and oil-soluble radical initiators.
  • radical polymerization in aqueous emulsion is understood to mean any radical polymerization process performed in aqueous medium in the presence of emulsifiers and water-soluble radical initiators.
  • polymerization in aqueous microsuspension also called polymerization in homogenized aqueous dispersion, is understood to mean any radical polymerization process in which oil-soluble initiators are used and an emulsion of monomer droplets is prepared by virtue of a powerful mechanical stirring and the presence of emulsifiers.
  • the process according to the invention making use of an ODH step has the advantage of combining an endothermic step (ethane converted into ethylene) with an exothermic water production step, of taking place at a moderate temperature and of avoiding having to provide the heat of reaction at a high temperature.
  • the process according to the invention also has the advantage of making it possible to recycle the stream of products derived from the oxychlorination, from which the DCE has been extracted, to the ODH step, thus ensuring an increased conversion of ethane into ethylene. Furthermore, given the moderate
  • the process according to the invention has the advantage of not generating compounds comprising at least 3 carbon atoms in troublesome amounts, these compounds generally being responsible for a certain inhibition during the pyrolysis of the DCE.
  • This inhibition is due to the formation of derivatives such as 1 ,2-dichloropropane and monochloropropenes.
  • Their aptitude for forming stable allyl radicals explains their powerful inhibitory effect on the pyrolysis of DCE which is carried out by the radical route.
  • the formation of these by- products containing 3 carbon atoms and heavier by-products furthermore constitutes an unnecessary consumption of reactants in the oxychlorination and in the chlorination, or generates costs for destroying them.
  • these heavy compounds contribute to the soiling of the columns and evaporators.
  • the process according to the invention is advantageously characterized, in addition, by the fact that the formation of heavy compounds by
  • the process according to the invention making use of an ODH step also has the advantage of allowing a limited conversion by passing to the ODH without having to resort to expensive separations such as those that require an ethylene distillation.
  • Another advantage of the process according to the invention is that it makes it possible to have, on the same industrial site, a completely integrated process ranging from the hydrocarbon source - namely ethane - up to the polymer obtained starting from the monomer manufactured.
  • the second variant of the process according to the invention according to which the ODH takes place at temperatures less than or equal to 650°C, has the advantage of generating very small amounts of hydrogen, responsible for numerous drawbacks.
  • the catalysts were prepared in small-scale autoclaves (50 ml, Parr) heated in a metal-block thermostat.
  • the starting solutions were dosed by a synthesis robot (Zinsser Sophas) to the autoclaves inlays (made of PTFE or glass).
  • the solutions of the different elements used for hydrothermal preparation route are listed in Table 1 below.
  • the autoclaves were closed, purged three times with Argon and put into the cold metal-block thermostat.
  • the catalysts were crushed and sieved after calcination ; for the catalytic tests a particle size fraction from 0.315 mm to 0.710 mm was used.
  • the catalyst were prepared and calcined according to US 4,250,346 mentioned before (conditions of Example 34).
  • the catalyst were prepared by preparing the solutions as described above for the hydrothermal synthesis and the mixtures obtained were dried using a standard laboratory spray drier with fixed nozzles.
  • the catalysts listed in Table 2 were tested at a temperature of 305°C and a pressure of 1 bara (bar absolute), under a gas flow of 8 Nml/min in each channel, with a gas feed of the following molar composition : 65 % ethane, 15 % oxygen and 0.5 % DCE or 2 % CO the case being, the balance being N2.
  • catalysts containing the 3 elements (Mo, W and V) and obtained by hydrothermal synthesis according to the invention generally perform the best, especially in the presence of DCE, and they are virtually inert towards CO. Their performances are even improved by the presence of both Te and Ti.
  • Figure 3 shows that the conversion of ethane (X) is negligible (less than 1 %) with catalysts obtained by the slurry route or spray dried, while catalysts according to the invention can reach conversions above 25 % (see namely the samples coded C01 to C03, C06, C10-D02, D05, D07, D10-E02).
  • a Mo/W ratio of about 2 to 10 seems to give the best results (see Figures 4 and 5 respectively obtained by reactions at a temperature of 290°C and 305°C).
  • the preferred catalysts identified in Figure 3 seem to also give high conversion (X(ethane)) under pressure and in the presence of DCE (see Figure 6 obtained at a reaction temperature of 305°C).

Abstract

L'invention concerne un procédé de fabrication de 1,2-dichloroéthane (DCE), ledit procédé comprenant : le traitement hydrothermique d'un mélange de précurseurs d'oxydes catalytiques comprenant Mo, V et W en vue de la fabrication d'un catalyseur pour les réactions d'oxydéshydrogénation (ODH); et une étape d'ODH de l'éthane en éthylène; et une étape d'(oxy)chloration de l'éthylène ainsi obtenu.
PCT/EP2012/065720 2011-08-25 2012-08-10 Procédé de fabrication de 1,2-dichloroéthane (dce) WO2013026720A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11178872.5 2011-08-25
EP11178872 2011-08-25

Publications (1)

Publication Number Publication Date
WO2013026720A1 true WO2013026720A1 (fr) 2013-02-28

Family

ID=46724387

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/065720 WO2013026720A1 (fr) 2011-08-25 2012-08-10 Procédé de fabrication de 1,2-dichloroéthane (dce)

Country Status (2)

Country Link
AR (1) AR087662A1 (fr)
WO (1) WO2013026720A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018015851A3 (fr) * 2016-07-19 2018-03-01 Nova Chemicals (International) S.A. Traitement hydrothermique à pression régulée de catalyseur de déshydrogénation oxydante
CN109843434A (zh) * 2016-10-18 2019-06-04 诺瓦化学品(国际)股份有限公司 使用水热处理和过氧化物处理生产氧化脱氢催化剂的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4250346A (en) 1980-04-14 1981-02-10 Union Carbide Corporation Low temperature oxydehydrogenation of ethane to ethylene
JP2000143244A (ja) * 1998-07-24 2000-05-23 Mitsubishi Chemicals Corp 複合金属酸化物の製造方法
US6171571B1 (en) * 1999-05-10 2001-01-09 Uop Llc Crystalline multinary metal oxide compositions, process for preparing and processes for using the composition
WO2008000702A1 (fr) 2006-06-26 2008-01-03 Solvay (Société Anonyme) PROCÉDÉ DE PRODUCTION de 1,2-DICHLOROÉTHANE
WO2008000693A1 (fr) 2006-06-26 2008-01-03 Solvay (Société Anonyme) Procédé de production de 1,2-dichloroéthane
WO2008000705A1 (fr) 2006-06-26 2008-01-03 Solvay (Société Anonyme) PROCÉDÉ DE PRODUCTION de 1,2-DICHLOROÉTHANE

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4250346A (en) 1980-04-14 1981-02-10 Union Carbide Corporation Low temperature oxydehydrogenation of ethane to ethylene
JP2000143244A (ja) * 1998-07-24 2000-05-23 Mitsubishi Chemicals Corp 複合金属酸化物の製造方法
US6171571B1 (en) * 1999-05-10 2001-01-09 Uop Llc Crystalline multinary metal oxide compositions, process for preparing and processes for using the composition
WO2008000702A1 (fr) 2006-06-26 2008-01-03 Solvay (Société Anonyme) PROCÉDÉ DE PRODUCTION de 1,2-DICHLOROÉTHANE
WO2008000693A1 (fr) 2006-06-26 2008-01-03 Solvay (Société Anonyme) Procédé de production de 1,2-dichloroéthane
WO2008000705A1 (fr) 2006-06-26 2008-01-03 Solvay (Société Anonyme) PROCÉDÉ DE PRODUCTION de 1,2-DICHLOROÉTHANE

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018015851A3 (fr) * 2016-07-19 2018-03-01 Nova Chemicals (International) S.A. Traitement hydrothermique à pression régulée de catalyseur de déshydrogénation oxydante
CN109475860A (zh) * 2016-07-19 2019-03-15 诺瓦化学品(国际)股份有限公司 Odh催化剂的受控压力水热处理
CN109475860B (zh) * 2016-07-19 2022-05-27 诺瓦化学品(国际)股份有限公司 Odh催化剂的受控压力水热处理
EP4212247A1 (fr) * 2016-07-19 2023-07-19 Nova Chemicals (International) S.A. Catalyseur d'odh, procédé odh au moyen de ce catalyseur
CN109843434A (zh) * 2016-10-18 2019-06-04 诺瓦化学品(国际)股份有限公司 使用水热处理和过氧化物处理生产氧化脱氢催化剂的方法
CN109843434B (zh) * 2016-10-18 2022-02-11 诺瓦化学品(国际)股份有限公司 使用水热处理和过氧化物处理生产氧化脱氢催化剂的方法

Also Published As

Publication number Publication date
AR087662A1 (es) 2014-04-09

Similar Documents

Publication Publication Date Title
JP4346822B2 (ja) プロピレンの低温度選択的酸化用のモリブデン−バナジウム系触媒、その製造方法及び使用方法
JP2008545743A (ja) エタンを選択的に酸化してエチレンを製造する方法
TW201041651A (en) Catalysts for the conversion of paraffins to olefins and use thereof
KR20040030707A (ko) 적어도 하나의 올레핀성 탄화수소의 부분 산화 생성물및/또는 부분 가암모니아산화 생성물의 제조방법
CN108025998A (zh) 烷烃氧化脱氢
JP2005536498A (ja) ｎ−ブタンからのブタジエンの製造方法
JP2011105771A (ja) 酢酸の製造
US6084135A (en) Production of formaldehyde using carbon oxides, hydrogen and H2 S
JP5476314B2 (ja) 低級アルカン炭化水素のアンモ酸化及び／又は酸化のための混合金属酸化物触媒を製造する方法
JP4159545B2 (ja) アルカンを脱水素するための等温処理法
WO2013026720A1 (fr) Procédé de fabrication de 1,2-dichloroéthane (dce)
EP2606963A1 (fr) Catalyseur, procédé de fabrication de catalyseurs et procédé pour déshydrogénation oxydatif catalytique
JP2008526718A (ja) 水蒸気の非存在下でのプロパンからアクリル酸の調製方法
US6028228A (en) Production of formaldehyde from CH4 and H2 S
CA2640631C (fr) Utilisation d'une reaction chimique pour separer l'ethylene de l'ethane dans des procedes a base d'ethane pour produire l'acide acetique
WO2005087368A1 (fr) Catalyseur et méthode de production de méthylnaphtaline
JP4809532B2 (ja) プロパンのアクリル酸への接触酸化用触媒、その製造法及び使用法
US6410793B1 (en) Production of formaldehyde from carbon oxides and H2S
JP4944798B2 (ja) プロパンのプロピレンへの部分的酸化を含むアクリル酸の製造方法
CN109071380A (zh) 混合甲烷/乙烷流的转化
RU2724109C1 (ru) Способ получения акриловой кислоты, способ селективного окисления монооксида углерода, катализатор селективного окисления монооксида углерода, способ его получения
US7417171B2 (en) Method for preparing an aromatic dialdehyde and manufacturing system for the same
TWI387580B (zh) 使用固定床反應器之氣相觸媒氧化方法
WO2020072163A1 (fr) Conversion d'éthane en oxyde d'éthylène à l'aide de réacteurs en série
WO2013092179A1 (fr) Catalyseur, procédé pour la fabrication de catalyseur et procédé de déshydrogénation par oxydation catalytique

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12750574

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12750574

Country of ref document: EP

Kind code of ref document: A1