OXICHLORINATION CATALYSTS WITH MOLYBDENUM TERNARY CHALCOGENIDES

D'oxycfllorat3 £on catalyst-based

CHALCOGEIJRES

, ternary, molybdenum catalysts the oxychlorination chalcogenide ternary molybdenum. The 1.2 to-

díchloroéthane

(D. 12) is a product produced industrially by several million tonnes per year, which by pyrolysis gives vinyl chloride monomer (VCMs) and hydrochloric acid (HCl). The VCM is

polymérìsé

poly (vinyl chloride) (or PVC) plastics commonly used. HCl obtained confectioneries pyrolysis of the VCM is separated and is then contacted with ethylene and oxygen in the presence of a catalyst to give d 12, respectfully the oxychlorination reaction. This

rêaction

is very general and can be

effectuêe

with most of the hydrocarbons. The oxychlorination was described in many patents, in particular in FR 2,063,365, FRs 2,260,551, FRs 2,242,143, FRs 2,213,259 2,125,748 and FR.The catalyst is

constitute

of a copper salt

dêposé

on alumina powder.It has now finds a new

procédê

oxychlorination catalyst wherein the chalcogenide is a ternary molybdenum containing

cuìvre

.The present invention is therefore an oxychlorination process a hydrocarbon to form a chlorinated hydrocarbon wherein the hydrocarbon, an oxygen-containing gas and hydrochloric acid gas pass over a load comprising a chalcogenide ternary molybdenum containing copper and formula:The Cu-Mo ch8 wherein X is any number between 0 and 4, and CH is sulfur, selenium or tellurium the.- the -, "28 these chalcogenides can be compounds

pseudomoléculaires

based on the pattern of Mo" ch which constitutes a network host to the rigid structure, developing channels

séoants

in three dimensions the O accommodate the cations of Cu.These phase pseudo-molecular may also be presented as more interpenetrating networks: an array of metal atoms (octahedron mo6) inscribed in a network pseudo cubic anionic chalcogen ("cubic" ch8), finally a network of tunnels which develop between mo6 ch8 patterns.These tunnels are occupied by cations Cu that stabilize the structure. These chalcogenides crystallize in the hexagonal system-a rhombohedral.These chalcogenides are used usually in the form of powders or granules.The hydrocarbon can be a mixture of several hydrocarbons, chosen from aliphatic hydrocarbons in c1 C20, the cycloaliphatic up in c12 and aromatics having up to four benzene rings condensed as well as chlorinated substitution derivatives thereof. They can be selected for example from among methane, ethane, propane, ethylene and propylene. The invention is particularly useful for the ethylene. The oxygen-containing gas is simply air but it can also be used, oxygen depleted or enriched.The purpose of the oxychlorination is essentially to use hydrochloric acid as the source of chlorine. Therefore adjusted the amount of oxygen and hydrocarbon to obtain approximately stoichiometrically the chlorinated hydrocarbon by consuming the maximum HCl and hydrocarbon.In the case of ethylene the reaction is:

Æ

HCI c2 h4 cl2 02 + 2 + (D. 12) 2 + h2 0 c2h4 although operate fixed-bed or fluidized bed, the fluidized bed is preferred.When the operation is carried out with a catalyst disposed in a fluidized bed, the temperature at which occurs the oxychlorination reaction will usually be between 150 and 450 °c. Preferably, this temperature is between 200 and 300 °c.The pressure at which the oxychlorination reaction is performed is not critical per se. Typically, the process is conducted at pressures between 1 and 10 atm and preferably with pressures between 1 and 8 atms.The fluidization rate catalyst compositions is not

pascritique

in itself and is primarily dependent upon the particle size of the catalyst and dimensions of the apparatus. Generally, it is carried out with velocities between 5 and i00 centimeters/s and preferably between and cm/sec. i0.Finally, the ratio of reactants used is the same as that used in previous processes

gênéralement

.Typically, it is carried out with a slight excess of ethylene relative the amount of HCl in oeuvre° however, the catalyst compositions of the invention can also work in the vicinity of the stoichiometry, or even in excess of HCl.All these conditions

opêratoires

are known in the prior arts.The advantage of the invention is that the catalyst is much more mechanically resistant that the oxychlorination catalysts prior, however performance in the conversion of the hydrocarbon hydrochloric acid and selectivity in dichloroethane are not good.The applicant has discovered ' that if supplemented chalcogenides of known catalytic oxychlorination, performance is achieved than similar known catalysts. These known catalysts are the conventional catalysts made of copper (including copper salt) deposited on a porous medium which can fireplace alumina,

c'est

say it is carried out with a mixture of chalcogenide and conventional catalysts, the catalysts are for example described in patents FR's 2,125,748, FRs 2,063,365, FRs 2,141,452, the EP 57796, the EP 623201 i - 3aep 119933 255156 and EP.These known catalysts are advantageously powders essentially alumina-based particle size between 200 and surface and between 90 and 450 m2/g and between 30 and 90

préfêrence

and between 250 and 400 m2/gm. These powders are impregnated with copper or a copper salt be capable

pouvantç

:, :, theS 2ii i0% up to, and preferably 3 to i0% by weight of copper to finished catalyst.The applicant has also discovered that can be added to these chalcogenides of oxychlorination catalysts which are in turn consist of a mixture of a catalyst and a solid catalytically and chemically inert.

C'est

to say it is carried out with a mixture of a chalcogenide, a conventional catalyst oxychlorination and an inert substance. Oxychlorination catalysts consist of a mixture of catalyst and an inert substance are described in the French Patent 2,242 143.By way of example as a substance catalytically and chemically inert include micro-spheres of glass or fused silica, alpha alumina and, of

préfêrence

, siliceous sand found in their natural state and having a particle size distribution of the particle size is adapted to the needs of the fixed bed or fluid bed.Advantageously the inert particles is between 20 and 200 the amount of inert material may vary within wide limits. Advantageously the amount of inert may represent 1 to 20 times by weight the amount of catalyst,

c'est

to say the set chalcogenide and conventional catalyst oxychlorination.The applicant has also found that can be combined to support these chalcogenides

cätalyseur

unimpregnated,

c'est

i.e. alumina powders not containing copper. This are for example powders and particle size between 200 and 450 m2/surface between 90 and G that was previously mentioned but not impregnated with copper.May also be added in addition to the catalyst support impregnated with a solid non-catalytically and chemically inert. This substance was defined

précêdemment

:micro-spheres of glass or fused silica, alpha alumina...The oxychlorination process of the invention may therefore be implemented with loads the subsequent catalyst:- chalcogenides, - a mixture of chalcogenides and conventional catalysts for oxychlorination and

êventuellement

a substance catalytically and chemically inert, - a mixture of chalcogenides and non-impregnated catalyst support and optionally a material catalytically and chemically inert.These fillers may be used catalytic fixed-bed or fluidized bed. Previous chalcogenides,

c'està

e. chalcogenides xCux mo6 HSC, are known (J.. To Solid State Routing Network Mal. 515, 519 (1971) by against the catalytic charge comprising a mixture of chalcogenides and conventional oxychlorination catalyst and optionally a material catalytically and chemically inert are new.So are the mixtures of chalcogenides and non-impregnated catalyst support and optionally a material catalytically and chemically inert.The present invention thus also relates these loads catalytic.These can be prepared according to a chalcogenides process described in J to solid state routing network mal. 515 - 519 (1971).The different components in the form of member or sulfide, are intimately mixed in a mortar in Agatha then, the powder is pelletized, introduced into a silica tube, sealed under dynamic vacuum (10 - 2

numHg

, argon gas). The chalcogenide is obtained after heating to about 750 °c. To have a pure product it is often useful to perform several cycles: grinding - COB - annealing. All of these operations are made in a controlled atmosphere, in a glove box under argon.This method can only be used to prepare that small amounts. The applicant has found a method is industrially usable and also being capable of preparing an entire family of chalcogenides.The invention is therefore a process for the preparation of formula MX mo6 s8 chalcogenides where X is any number between 0 and 4 and m denotes a metal, characterized in that it involves hydrogen-reducing a mixture 6 J., F.., ..of mos2 and metal m or their precursors. The metal m may be for example an alkali, an alkaline earth metal, an element of column 3 b of the periodic table of elements, a lanthanide, actinide, lead, tin, magnesium, zinc, manganese, cadmium, copper, nickel, iron or cobalt.It does not exit the the scope of the invention using mos2 and a precursor of the metal m, the metal m and a mos2 precursor, a mixture of mos2, mos2 precursor and a metal M or any combination. The hydrogen reduction can be accomplished by simply contacting hydrogen with the mixture mos2, meters.It can be accomplished to any hydrogen pressure, the temperature is between 450 and ii00 °C, the precursors of mos2 and m are those which, in these hydrogenation conditions, give mos2 and M. the mos2 precursor can be for example:(Nh4) 2mo3si3 2 mos4 (nh4) or the precursor of the metal m may be a salt such as a chloride, a sulfide, a nitrate, a sulfate, or acetate. The proportions of mos2 and m the mixture prior to the hydrogenation are adjusted based on the chalcogenide sought and particular reactivities of m, or precursor thereof. There can also be

míxtes

precursors, for example Cu (nh4) mos4.As the chalcogenides that intended to fabricate, they can be used alone or with other precursor metal or mos2•need not isolate mos2 or m before preparing the chalcogenide,

c'est

to say that manufactured in situ the reagents mos2 and m, then the reaction is continued to the chalcogenide.The chalcogenides mxmo6 s8 have the same structure as the chalcogenides

CUxMO

6 ch8 that has the above,

c'est'à

e. adjuvated mo6 s8 regains a pattern that creates a host lattice of rigid structure. These chalcogenides crystallize in the hexagonal system

rhomboédriqueo

) I-I-s at £3 8 the invention also relates to a process for the preparation of chalcogenides mxmo6 s8 formula wherein X is any number between 0 and 4 and m denotes a metal, characterized in that it involves insertion of the metal M in existing mo6 s8 presence ' of a gas stream.The metal can be used as such or as a salt thereof.Is simply mixed metal and mo6 s8 preferably each being in divided state and heating while scans the reaction mixture with a gas. It is advantageous to use nitrogen. The

tempërature

may be between 150 and 400 °c.The present invention also relates to a chalcogenide mxmo6 s8 formula wherein X is any number between 0 and 4 and m denotes a metal characterized in that it is a supported poreux° these chalcogenides are those which have now been found include a preparation process. The porous support can be alumina, silica, of the silico aluminas, graphite, coal, TiO2, the zro2, and generally all that is used as a catalyst carrier, it may be mentioned more particularly the alumina powders with particle size between 200 and surface m and between 90 and 450 m2/gm, and preferably between 30 and 90 m and between 250 and 400 m2/gm.The chalcogenides supported with m being the copper are useful as catalysts for oxychlorination of hydrocarbons.Can be prepared by impregnating the support carrier

chalcogénüres

precursors mos2 and of metal M, followed by reduction with hydrogen. The precursors of mos2 and m are those which have been mentioned hereinbefore. The precursor also can be prepared in situ in the pores of the support, for example (nh4) 2 mos4 can be

préparë

by reaction between the

paramolybdate

(nh4) 6 mo7 024 - 4:20 in solution in nh4oh with h2 sec. example 2 mo3 si3 (nh4) can be prepared by reacting (nh4) 6 mo7 024 - 4:00 2, 0 with an ammonium polysulfide.The latter being itself prepared by reacting h2 s with a solution of nh4 0:00 and sulfur (mal. Cradle. 112 w 778 - 780 - 1979).Also can be prepared from these chalcogenides supported by starting from a product already deposited on a porous support but not as chalcogenides.It is possible for example to use a catalyst such as an already existing

hydrodésulZuration

Ni-

Mo.S

or Mo-s-deposited on alumina. It is sufficient then to reduction with

hydï

'

ogène

.The examples which follow have been carried out by CNRS in the laboratory of molecular inorganic solid chemistry and the University reindeer (French), and laboratories company

ATOCHEM

.Such as I - synthesis cu2 .5 mo6 s8 in sealed tube is mixed:2.5 cu + 4 mos2 + 2 MB is pellet powders. Introduced in a silica tube sealed under dynamic vacuum (10 - 2 mm Hg pressure). Annealing at 800 °c for 70 hours. The powder obtained has a X-ray diffraction diagram. The product crystallizes in the hexagonal system rhombohedral.Mesh parameter in the hexagonal system: a=9.6 has c=10.2 has (it may remain of the mos2 as impurity).Example 2 - 6 s8

CuzMo

synthesis by reduction with

LwHYDROGENE

0.4107 grams (nh4) 2 mos4 + 0.0901 grams cuci2, 2:00 2, 0 is mixed, are ground powders in a mortar in Agatha is then put in a nacelle of

silíce

. Reduction in a horizontal oven Angstroms 700 °c during 89 hours, at a flow rate 1.5 ml/sec. h2# identifying by Rx: hexagonal mesh parameter: a=9.60 has c=10.22 has (if there remains the mos2, the reaction is not completed, continuing the reduction).Mos2 identified by X-ray diffraction diagram:With ASTM n° 6 - 0097. d e no. 9 - 312 ç1í

íi

." example 3 - synthesis

CuxMo

6 s8/ai2 03 (chalcogenide deposited on a porous support) 1 - impregnation precursors dissolved 0.4107 grams (nh4) 2 mos4 in 6.5 ml of concentrated ammonia solution and adds 12 grams a12 030 allowed 24 hours in a drawer filled p2 05 and vacuum.In a horizontal oven, h2 during 8 min, the time of mounting the furnace temperature ambient to 400 °c, flow rate=0.5 ml/sec. h2# produced.Is dissolved in 8 ml of 0.0901 cucl2 2:00 2, 0 grams nh4ohcc and added the product A. allowed 75 hours in a desiccator filled p2 05 and vacuum. Focusing on the reduction of total in 1.5 ml/s during h2# 89 hours, in a horizontal oven. Taken a few pellets. The meals is a silica tube sealed under dynamic vacuum during 24 hours and annealing to 900 °c.2 - way

heptamolybdate

2 different methods:I) an air pathway is dissolved 1.5 grams (nh4) 4:00 2 6 mo7 024. 0 1.36 grams of Cu and (no3) 3:00 2 2. 0 in 5 ml of concentrated ammonia solution. L0 g of ai2 03 is added and allowed to ambient air during 1 hr 30.

Ã

is oven air to 120 °c during 2 hours. Calcination in air at 350 °c during 2 hours to. Calcination in air at 500 °c during 2 hours on Angstroms fraction i0 granules (mass < 1 gm). Sulfurization h2 s to 400 °c by 30 min during. 1.5 ml/h2 reduction # s during 49 hours. Identifying by the EXAFS: K-Mo a mixture

CUxMO

6 s8 mos2 and the value of X is not known although X 2.2) channel (22) is dissolved 1.5 grams (nh4) 4:00 2 6 mo7 024. 0 1.36 grams of Cu and (no3) 3:00 2 2. 0 in 5 ml of nh4

OHCC

. I0 g of added ai203 pelletized and allowed to ambient air during 1 hr nitrogen sweep to 120 °c during 3 hours. Hydrogen during 16 hours at 200 °c during 2 hours at 240 °c and then 67 hours at 245 °c. 500 °c during 24 hours to nitrogen.the O 0 O 8 on a fraction=i0 granules (=500 mg).Sulfurization h2 s to 400 °c by 30 min during. Reduction in 1.5 ml/s during h2# 49 or 89 hours. Identifying by the EXAFS: K-Mo a mixture

CUxMO

6 s8 and mos2.The EXAFS measurements at K-Mo result from comparisons between the products which are described above and crystallized powders, and reference cu4mo6 s8 mos2 (syntheses in sealed tube).We have carried out the measurements on the reference compounds because it does not exist in the EXAFS at cu4 mo6 s8 fir on K-Mo. There are references for IDL mos2.Example 4 testing is performed in the oxychlorination device according. The reactor is a vertical glass tube filled with catalyst. It is supplied with gas from below for its fluidization. Thermocouples placed in a glass envelope in the middle of the reactor follow the evolution of the temperature in both the time and direction of height in the catalyst bed. The output of the reactor, the gas passes over a column slaughter, by washing with distilled water, retrieves all the HCl which has not reacted. The latter can be found in a separatory funnel. The rest of the gas then flows successively through a water cooler, a refrigerant to brine (t=- 5 °c) where condense solvents recovered in another separatory funnel, then pick bulbs for dosages of remaining gas are scanned before D reach a volumetric meter whose measurement gives the flow rate output. The temperature reading, at that level, can be used to estimate the correction required for return to the conditions STP (standard temperature and pressure). Atmospheric pressure is read on a mercury manometer.There are thus three different types of samples which lead to the results after analysis:- an aqueous HCl - condensed solvents, among which d 12 - exit gas: coextruded, co2,

DI2

, and the unreacted reagents: c2 h4, airflow.Compared with) a conventional catalyst comprising alumina surface 357 m2/gm, 53 m in average diameter, pore volume 33 cm3/100g impregnated copper chloride and an inert substance that is silica having an average diameter of 50 m and between 20 and 300 meters; with b) a catalyst formed of a chalcogenide cu2 .5 mo6 SSs, alumina and an inert substance (silica). Alumina and silica have the same characteristics as in A except the absence of copper.The results are shown in Table I.Table 1 operating conditions:- supply: the NL/hr air-c2 h4 4.4 16.2 the NL/hr HCl/hr - 8.6 20nl reactor diameter 20 mm amount of Cu (grams) (°C) T-conversion rate c2h4 selectivity in d 12 cu25 mo6 s8 4.25 grams

A12ó3

6.00 grams sio2 22.60 0.68 78, 5 99, 2 g of alumina with copper 9.70 grams sio2 23.60 g of catalyst conventional the catalyst loading 0.58 72, 3 99, 1 of the present invention proves a higher conversion and selectivity (selectivity expresses the fraction of c2 h4 converted which has been transformed into d 12).A ° 9' 9, 12 5, .8 Example 5 - scanning outputs used reactor inlet airflow: 12.2 20nl!hr c2 h4: 4.4 the NL/hr HCI: 8.6 the NL/H for 1.2 g of copper for 59 g of catalyst loading tested in total (Cu-included), except testing 2.Definitions named xG conversion rate c2 h4 HS conversion rate of HCl AD conversion rate of 02 list tests! Ai2 03 sio2 cu2.smo6s8:A12 03 cu2.smo6s8:I-5a1203 cuci2/ai203: 30.0 grams (4% had) 16 ai2 03:55, 8 grams cuci22h20: 3.2 gm 12.0 grams 39, 6 grams 7.4 7.4 grams 29.0 g at 51, 6 grams cu2 .smo6 grams S8: 63, 9 grams in the same way to alumina with or without impregnated with copper (a12 03) used in the above tests is identical to that of the example 4. the same applies for the MPET

siliceo

table 2!. time named xG HS AD

rendetest

duration (°C) of comstically -%%% (e) co + co2 1 4:25 249 4.5 88, 3 64, 9 78, 6 0.7 2 0:15 264 4.8 3.1 2.1 17.1 1.7 4 4:00 216, 5 centeredly day 32, 2 42, 8 26.1 0.8 6 4:00 249 5.6 54, 4 46, 5 64, 2 8.5 16 4:00 241 5.8 26.6 16.9 11.3 0.4 °9 ci + c2 1.7 0.3 3.1 5.0 13.5 efficiency and selectivity di2 97, 3 36, 0 87, 9 75, 2 47, 8 c2 denote the Cl and chlorinated products other than D c2 12.Example 6 synthesis

CUxMO

6 s8 by insertion into mo6 s8 under nitrogen. The synthesis is described in mo6 s8

Rev.

Chem. Minutes. 21, 509 (1984) o-we inserted copper in " mo6 s8 under nitrogen to a temperature at or above 200 °c. The copper starting may be metallic, or in the form of copper chloride.The reagents are in stoichiometric proportions of Mo: cu=6: X-.Example 7 synthesis

CUxMO

6 s8/ai2 03 from catalyst existing kind: moo3, the NiO/ai2 03 (MB: 9% - nor + of Mo: 12%) ai2 03 large area.Sulfurization method on 500 mg, 15% by h2/h2 e, to 400 °c, during 4 hours.Which is then followed by reduction under h2 to 800 °c, during 66 hours (rate h2 different or equal of 1 ml/sec.). The product is identified by its X-ray diffraction diagram after annealing in vacuum sealed tube 900 °c during 24 hours to.The achievements of L " disclosure, at which an exclusive right of property or privilege is claimed, are defined as follows:the L. Oxychlorination process a hydrocarbon to form a chlorinated hydrocarbon wherein the hydrocarbon, an oxygen-containing gas and the gaseous hydrochloric

acìde

pass over a load comprising a chalcogenide ternary molybdenum containing copper and formula

CuxMo

" HM where X is any number between 0 and 4 and CH is sulfur, selenium or tellurium the.2. method according to claim I-, characterized in that added to an oxychlorination catalyst chalcogenide.3. method according to claim I-, characterized in that a catalyst is added

oxychloratìon

of chalcogenide and a substance catalytically and chemically inert.4. method according to claim 2, characterized in that the oxychlorination catalyst is alumina impregnated with a copper salt.5. method according to claim 3, characterized in that the oxychlorination catalyst is alumina impregnated with a copper salt and the inert substance is silica.6. method according to claim I-, characterized in chalcogenide is added a catalyst carrier.7. the I

Procêdé

claim, characterized in that added to chalcogenide a catalyst carrier and a