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    • 专利摘要:
    The present invention relates to an oligomerization process using a reaction device comprising a vortexable means. In particular the process relates to the oligomerization of ethylene to linear alpha-olefins such as 1-butene, 1-hexene, 1-octene or a mixture of linear alpha-olefins.
    公开号:FR3068621A1
    申请号:FR1756518
    申请日:2017-07-10
    公开日:2019-01-11
    发明作者:Frederic Augier；Alexandre VONNER
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    TECHNICAL AREA
    The present invention relates to an oligomerization process using a reaction device, in particular the method relates to the oligomerization of ethylene into linear alphaolefins such as 1-butene, 1-hexene, 1-octene or a mixture of linear alphaolefins.
    PRIOR ART
    The invention relates to the field of oligomerization processes using gas / liquid reactors also called bubble point reactors because they operate under conditions allowing the coexistence of two liquid and gas phases. Due to the exothermic nature of oligomerization reactions, bubble point reactors also include a recirculation loop consisting in withdrawing a liquid fraction, cooling it and reintroducing it into the reaction vessel. Said recirculation loop makes it possible to obtain good homogeneity of the concentrations and to control the temperature throughout the reaction volume, due to the good heat transfer capacity linked to the recirculation loop.
    A drawback encountered in the oligomerization processes during the implementation of this type of reactors is the management of the gas phase also called gaseous sky. Indeed, said gaseous sky comprises gaseous compounds which are sparingly soluble in the liquid phase, as well as ethylene which has not reacted in the process. However, the gaseous sky is purged in order to eliminate said gaseous compounds. When the quantity of ethylene present in the gas overhead is significant, the purging of the gas overhead results in a significant loss of unreacted ethylene, which affects the yield of the process and therefore the cost of the oligomerization process.
    In order to improve the efficiency of the oligomerization process, in particular in terms of cost, it is therefore essential to limit the loss of unreacted ethylene contained in the gas overhead in order to improve its conversion in said process.
    The methods of the prior art, using a recirculation loop, as illustrated in FIG. 1, do not make it possible to limit the loss of ethylene and the purging of the gas overhead causes an ethylene outlet from the reactor which is harmful to the process yield.
    Application WO 2013/116922 discloses a process in which the overhead gas is directly introduced into the recirculation loop by means of a low pressure system. This technology makes it possible to limit the accumulation of ethylene in the gaseous atmosphere but is accompanied by a loss of the homogeneity of the concentration of ethylene dissolved in the liquid phase within the reaction vessel.
    Application WO 2009/060343 discloses the use of devices of the Venturi or gas / liquid nozzle type in order to generate two-phase jets with the gas / liquid interphase making it possible to dissolve the ethylene contained in the gaseous sky. These types of devices consume energy, in particular in the form of pressure drop in the recirculation loop and also have the disadvantage of causing eddies in the gas / liquid interphase, which is unfavorable for level control. in the reactor.
    The methods of the prior art, using a recirculation loop, as illustrated in FIG. 1, do not make it possible to limit the loss of ethylene and the purging of the gas overhead causes an ethylene outlet from the reactor which is harmful to the process yield.
    SUMMARY OF THE INVENTION
    An object of the present invention is to provide an oligomerization process implemented at a pressure between 0.1 and 10 MPa, at a temperature between 30 and 200 ° C comprising the following steps:
    a) A step of introducing the oligomerization catalytic system comprising a metal catalyst and an activating agent, into a reaction vessel comprising a liquid phase and a gas phase,
    b) A step of bringing said catalytic system into contact with ethylene by the introduction of said ethylene into the lower part of the reaction vessel,
    c) A step of withdrawing a fraction of liquid at a flow rate of between 500 and 10,000 t / h in the lower part of the reaction vessel,
    d) A step of cooling the liquid fraction drawn off in step c) by passing said liquid fraction through a heat exchanger,
    e) A step of introducing the liquid fraction cooled in step d) into the upper part of the liquid phase of the reaction vessel, said introduction is carried out with an angle a between the pipe and the surface of the vessel reaction between 0 and 35 °, said introduction allows the formation of a stable vortex at the interface between the liquid phase and the gas phase, in which steps c) to e) constitute a recirculation loop.
    An advantage of the present invention is to increase the exchange surface between the liquid phase and the gaseous sky by the formation at the interface of the two phases of a stable vortex, and thus making it possible to increase the amount of ethylene dissolved in the liquid phase. The ethylene thus dissolved is brought back into contact with the catalytic system. This step advantageously makes it possible to dissolve the unreacted ethylene contained in the gaseous atmosphere towards the liquid phase and therefore to optimize its conversion in the oligomerization process.
    Another advantage of the present invention is to improve the productivity of the device used in the process.
    DEFINITIONS & ABBREVIATIONS
    Throughout the description, the terms or abbreviations below have the following meaning.
    The term “oligomerization” means any reaction of addition of a first olefin to a second olefin, identical or different from the first. The olefin thus obtained has the crude formula C n H 2n where n is equal to or greater than 4.
    By alpha-olefin is meant an olefin on which the double bond is located in the terminal position of the alkyl chain.
    The term “catalytic system” means the mixture of at least one metal catalyst and at least one activating agent, optionally in the presence of at least one additive and optionally in the presence of at least one solvent.
    By liquid phase is meant the mixture of all the compounds which are in a liquid physical state under the temperature and pressure conditions of the reaction vessel.
    The term “gaseous phase” or “gaseous sky” is understood to mean the mixture of all the compounds which are in the gas physical state under the temperature and pressure conditions of the reaction vessel: in the form of bubbles present in the liquid, and also in the upper part of the reactor (reactor sky).
    The lateral lower part of the reaction vessel is understood to mean a part of the reactor envelope situated in the lower part and on the side.
    By incondensable gas is meant a species in physical form gas which dissolves only partially in the liquid at the temperature and pressure conditions of the reaction vessel, and which can, under certain conditions, accumulate in the sky of the reactor ( example here: ethane).
    By t / h is meant the value of a flow rate expressed in tonnes per hour.
    The term “stable vortex” is understood to mean an interface hollowed out due to the rotation of the liquid phase, of parabolic shape, the dimensions of which are stable over time and which do not cause eddies at the interface of the liquid and gaseous phases.
    The term “reactor or device” denotes all of the means enabling the oligomerization process according to the invention to be implemented, such as in particular the reaction vessel and the recirculation loop.
    DETAILED DESCRIPTION OF THE INVENTION
    It is specified that, throughout this description, the expression "comprised between ... and ..." must be understood as including the limits cited.
    In the sense of the present invention, the various embodiments presented can be used alone or in combination with each other, without limitation of combination.
    The present invention relates to an oligomerization process implemented at a pressure between 0.1 and 10 MPa, at a temperature between 30 and 200 ° C, and comprising the following steps:
    a) A step of introducing the oligomerization catalytic system comprising a metal catalyst and an activating agent, into a reaction vessel comprising a liquid phase and a gas phase,
    b) A step of bringing said catalytic system into contact with ethylene by the introduction of said ethylene into the lower part of the reaction vessel,
    c) A step of withdrawing a fraction of liquid at a flow rate of between 500 and 10,000 t / h in the lower part of the reaction vessel,
    d) A step of cooling the liquid fraction drawn off in step c) by passing said liquid fraction through a heat exchanger,
    e) A step of introducing the liquid fraction cooled in step d) into the upper part of the liquid phase of the reaction vessel, said introduction is carried out with an angle a between the pipe and the surface of the vessel reaction between 0 and 35 °, said introduction allows the formation of a stable vortex at the interface between the liquid phase and the gas phase, in which steps c) to e) constitute a recirculation loop.
    Oligomerization process
    The oligomerization process according to the invention makes it possible to obtain linear olefins by bringing ethylene into contact, with a catalytic system and optionally in the presence of a solvent.
    All the catalytic systems known to those skilled in the art and capable of being used in the oligomerization process according to the invention are part of the field of the invention. Said catalytic systems as well as their implementations are notably described in applications FR2984311, FR2552079, FR3019064, FR3023183, FR3042989 or also in application FR3045414. Preferably, the catalytic systems comprise at least one metallic catalyst preferably based on nickel, titanium, or chromium, at least one activating agent, optionally in the presence of at least one additive and optionally in the presence of at least one solvent.
    Preferably, the nickel-based catalyst comprises a nickel catalyst of degree of oxidation (+ II). Preferably, the nickel-based catalyst is chosen from nickel (II) carboxylates such as for example nickel 2-ethylhexanoate, nickel (II) phenates, nickel (II) naphthenates, acetate of nickel (ll), nickel trifluoroacetate (ll), nickel triflate (ll), nickel acetylacetonate (ll), nickel hexafluoroacetonylacetonate (ll), TT-allylnickel chloride (ll), TT-allylnickel (ll) bromide, methallylnickel (ll) chloride dimer, n 3 -allylnickel hexafluorophosphate (ll), η 3 methallylnickel (ll) hexafluorophosphate and nickel 1,5-cyclooctadienyl (II), in their hydrated form or not, taken alone or in mixture.
    Preferably, the titanium-based catalyst comprises an alkoxy or aryloxy compound of titanium. Preferably, the titanium-based catalyst is chosen from phenoxy of titanium, 2-methylphenoxy of titanium, 2,6-dimethylphenoxy of titanium, 2,4,6-trimethylphenoxy of titanium, 4-methylphenoxy of titanium , titanium 2-phenylphenoxy, titanium 2,6-diphenylphenoxy, titanium 2,4,6-triphenylphenoxy, titanium 4-phenylphenoxy, titanium 2-tert-butyl-6phenylphenoxy, 2,4 -ditertbutyl-6-phenylphenoxy titanium, 2,6 diisopropylphenoxy titanium, 2,6-ditert-butylphenoxy titanium, 4-methyl-2,6-ditertbutylphenoxy titanium, 2,6-dichloro-4-tert -butylphenoxy of titanium, 2,6-dibromo-4-tertbutylphenoxy of titanium, biphenoxy of titanium, binaphthoxy of titanium, 1,8-naphthalenedioxy of titanium, tetraethoxy of titanium, tetraisopropoxy of titanium, tetra-n -butoxy of titanium, tetra-2-ethyl-hexyloxy of titanium.
    Preferably, the chromium compound can be a chromium (II) or chromium (III) salt, but also a salt of different oxidation degree which can comprise one or more identical or different anions such as for example halides, carboxylates, acetylacetonates, alkoxy or aryloxy anions. Preferably, the chromium-based catalyst is chosen from CrCI 3 , CrCI 3 (tetrahydrofuran) 3 , Cr (acetylacetonate) 3 , Cr (naphthenate) 3 , Cr (2-ethylhexanoate) 3 , Cr (acetate) 3 .
    Preferably, an activating agent is at least one aluminum compound independently chosen from methyl aluminum dichloride (MeAICI 2 ), dichloroethyl aluminum (EtAICI 2 ), ethyl aluminum sesquichloride (Et 3 AI 2 CI 3 ), chlorodiethyl aluminum ( And 2 AICI), chlorodiisobutylaluminium (/ -Bu 2 AICI), triethylaluminium (AIEt 3 ), tripropylaluminium (AI (/ i-Pr) 3 ), triisobutylaluminium (Al (/ - Bu) 3 ), diethyl- ethoxyaluminium (Et 2 AIOEt), methylaluminoxane (MAO), ethylaluminoxane and modified methylaluminoxanes (MMAO).
    Preferably, an additive is at least one ether type compound independently selected from diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether 2-methoxy-2methylpropane, 2-methoxy-2-methylbutane, dimethoxy-2,2 propane, di (2-ethylhexyloxy) 2,2 propane, 2,5-dihydrofuran, tetrahydrofuran, 2-methoxytetrahydrofurane, 2 methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,3-dihydropyrane, tetrahydropyran, 1 , 3-dioxolane, 1,3-dioxane, 1,4-dioxane, dimethoxyethane, di (2methoxyethyl) ether and benzofuran, glyme, diglyme, taken alone or as a mixture.
    Preferably, an additive is at least one amine-type compound independently selected from trimethylamine, triethylamine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2fluoropyridine, 3-fluoropyridine, 3-trifluromethylpyridine, 2-phenylpyridine, 3phenylpyridine, 2-benzylpyridine, 3,5-dimethylpyridine, 2,6-diterbutylpyridine and 2,6diphenylpyridine, quinoline, 1,10-phenanthroline, N-methylpyrrole, N-butylpyrrole Nmethylimidazole, N-butylimidazole, 2,2'-bipyridine, N, N'-dimethyl-ethane-1,2-diimine, N , N'-di-t-butyl-ethane-1,2-diimine, N, N'-di-t-butyl-butane-2,3-diimine, N, N'-diphenylethane-1,2- diimine, N, N'-bis- (2,6-dimethyl-phenyl) -ethane-1,2-diimine, N, N'-bis (diisopropyl-2,6-phenyl) -ethane-1,2 -diimine, N, N'-diphenyl-butane-2,3-diimine, N, N'-bis (dimethyl-2,6-phenyl) -butane-2,3-diimine, N, N'-bis- (2,6-diisopropyl-phenyl) -butane-2,3diimine.
    Preferably, an additive is at least one phosphine type compound independently selected from tributylphosphine, triisopropylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, tris (otolyl) phosphine, bis (diphenylphosphino) ethane, trioctyl oxide , triphenylphosphine oxide, triphenylphosphite.
    Preferably, an additive is at least at least one aryloxy compound of an element M chosen from the group formed by magnesium, calcium, strontium and barium, preferably magnesium, of general formula [M (RO) 2 - n Xn] y in which RO is an aryloxy radical of a ROH derivative containing from 6 to 80 carbon atoms, X is a halogen or a hydrocarbyl radical containing from 1 to 30 carbon atoms, n is an integer which can take the values of 0 or 1, and y is an integer between 1 and 10, preferably y equal to 1 or 2 or 3 or 4. Among the preferred aryloxy radicals, non-limiting examples that may be mentioned: 4-phenylphenoxy, 2-phenylphenoxy, 2,6-diphenylphenoxy, 2,4,6-triphenylphenoxy, 2,3,5,6-tetraphenylphenoxy, 2-tert-butyl-6-phenylphenoxy, 2 , 4-ditertbutyl-6-phenylphenoxy, 2,6-diisopropylphenoxy, 2,6-dimethylphenoxy, 2,6ditert-butylphenoxy, 4-methyl-2,6-ditert-butylphen oxy, 2,6-dichloro-4-tert-butylphenoxy and 2,6-dibromo-4-tert-butylphenoxy. The two aryloxy radicals can be carried by the same molecule, such as for example the biphenoxy radical, binaphthoxy or 1,8 naphthalene-dioxy, substituted or not by alkyl, aryl, or halide radicals. Preferably, the aryloxy radical RO is 2,6-diphenylphenoxy, 2-tert-butyl-6-phenylphenoxy or 2,4-ditert-butyl-6-phenylphenoxy.
    Preferably, an additive is at least one compound corresponding to the general formula (I) or one of the tautomers of said compound.
    O AR 1 ®
    (i) in which
    - A and A ’, identical or different, are independently an oxygen or a single bond between the phosphorus atom and a carbon atom,
    the groups R 1a and R 1b are independently chosen from the methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, cyclohexyl, adamantyl groups, substituted or unsubstituted, containing or not containing heteroelements; phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylephenyl, 2-methylphenyl, 4-methoxyphenyl, 2methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl groups 4-methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-di (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl.
    the group R 2 is independently chosen from the methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, cyclohexyl, adamantyl groups, substituted or unsubstituted, containing heteroelements or not ; phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylephenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4methoxyphenyl, 2-isopropoxyphenyl, 4- methoxy-3,5-dimethylphenyl, 3,5-ditertbutyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-bis (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl
    Preferably, the linear olefins obtained comprise from 4 to 20 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 4 to 10 carbon atoms, and preferably from 4 to 8 carbon atoms. Preferably, the olefins are linear alpha-olefins, chosen from but-1-ene, hex-1-ene or oct-1-ene.
    In one embodiment, a solvent or a mixture of solvents can be used in the oligomerization process. Said solvent is independently chosen from the group formed by aliphatic and cycloaliphatic hydrocarbons such as hexane, cyclohexane, heptane, butane or isobutane.
    The oligomerization process is carried out at a pressure between 0.1 and 10 MPa and preferably between 0.3 and 8 MPa, at a temperature between 30 and 200 ° C and preferably between 35 and 150 ° C, and the throughput of the liquid recirculation loop is between 500 and 10,000 t / h, and preferably between 800 and 7,000 t / h.
    Preferably, the concentration of catalyst in the catalytic system is between 0.1 and 50 ppm by mass of atomic metal relative to the reaction mass, preferably between 0.5 and 20 ppm, and preferably between 0.8 and 10 ppm.
    According to another embodiment, the oligomerization process is carried out continuously. The catalytic system, constituted as described above, is injected at the same time as ethylene into a reactor stirred by conventional mechanical means known to those skilled in the art or by external recirculation, and maintained at the desired temperature. The components of the catalytic system can also be injected separately into the reaction medium. The ethylene is introduced through an inlet valve controlled by the pressure, which keeps the latter constant in the reactor. The reaction mixture is withdrawn by means of a valve controlled by the liquid level so as to keep it constant. The catalyst is continuously destroyed by any usual means known to those skilled in the art, then the products resulting from the reaction and the solvent are separated, for example by distillation. Untransformed ethylene can be recycled to the reactor. The catalyst residues included in a heavy fraction can be incinerated.
    According to one embodiment, the oligomerization process is carried out batchwise. The catalytic system, constituted as described above, is introduced into a reactor fitted with the usual stirring, heating and cooling devices, then pressurized with ethylene at the desired pressure, and the temperature is adjusted to the desired value. The oligomerization device is maintained at a constant pressure by the introduction of ethylene until the total volume of liquid produced represents, for example, from 2 to 50 times the volume of the catalytic solution previously introduced. The catalyst is then destroyed by any usual means known to a person skilled in the art, then the product is withdrawn and the reaction products are separated from the solvent.
    Step a) introduction of the catalytic system
    The process according to the invention comprises a step a) of introducing the catalytic system comprising a metal catalyst and an activating agent, and optionally a solvent or a mixture of solvents, into a reaction vessel comprising a liquid phase and a gas phase.
    Preferably, the introduction of the catalytic system is carried out in the lower part of the reaction vessel and preferably in the bottom of the reaction vessel.
    Preferably, the pressure of introduction into the reaction vessel is between 0.1 and 10 MPa, preferably between 0.3 and 8 MPa.
    Preferably the temperature of introduction into the reaction vessel is between 30 and 200 ° C, preferably between 35 and 150 ° C.
    Step b) of contacting with ethylene
    The process according to the invention comprises a step b) of bringing the catalytic system introduced in step a) into contact with ethylene. Said ethylene is introduced at the lower part of the reaction chamber, preferably on the lower lateral part of the reaction chamber.
    Preferably, the ethylene is distributed by dispersion when it is introduced into the lower liquid phase of the reaction vessel by a means capable of producing said dispersion uniformly over the entire section of the reactor. Preferably, the dispersing means is chosen from a distribution network with a homogeneous distribution of the ethylene injection points over the entire section of the reactor.
    Preferably, the ethylene gas is introduced at a flow rate of between 1 and 250 t / h, preferably between 3 and 200 t / h, preferably between 5 and 150 t / h and preferably between 10 and 100 t / h .
    According to a particular embodiment of the invention, a flow of gaseous hydrogen can also be introduced into the reaction vessel, with a flow rate representing 0.2 to 1% by mass of the flow of incoming ethylene. Preferably, the flow of hydrogen gas is introduced through the pipe used for the introduction of ethylene gas.
    Step c) withdrawal of a fraction of the liquid phase
    The method according to the invention comprises a step c) of drawing off a fraction of the liquid phase in the lower part of the reaction vessel.
    The withdrawal used in step c) is carried out in the lower part of the reaction vessel, preferably below the level of the ethylene injection, and preferably in the bottom of the vessel. The racking is carried out by any means capable of carrying out the racking and preferably by a pump.
    Preferably, the withdrawal rate is between 500 and 10,000 t / h, and preferably between 800 and 7000 t / h.
    According to a preferred embodiment, the liquid fraction withdrawn from the liquid phase is divided into two streams. The first so-called main flow is sent to step d) of cooling. The second flow corresponds to the effluent obtained at the end of the oligomerization process and can be sent to a separation section located downstream of the device used in the process according to the invention. Advantageously, the flow rate of said effluent is regulated to maintain a constant liquid level in the reactor. Preferably, the flow rate of said effluent is 5 to 200 times lower than the liquid flow rate sent to the cooling step. Preferably, the flow rate of said effluent is 5 to 150 times lower, preferably 10 to 120 times lower and more preferably 20 to 100 times lower.
    Step d) cooling the liquid fraction
    The method according to the invention comprises a step d) of cooling the liquid fraction drawn off in step c).
    Preferably, the cooling step is implemented by circulating the main liquid stream withdrawn in step c) through one or more heat exchangers located inside or outside the reaction vessel and preferably outside.
    The heat exchanger makes it possible to decrease the temperature of the liquid fraction from 2 to 10 ° C, preferably from 3 to 9 ° C, preferably from 4 to 8 ° C. Advantageously the cooling of the liquid fraction makes it possible to maintain the temperature of the medium. reaction in the desired temperature ranges.
    Preferably, step d) of cooling the liquid fraction comprises any means known to those skilled in the art and necessary for its implementation such as a pump for drawing off the liquid fraction, a means capable of regulating the flow rate of the liquid fraction drawn off, or else a line for purging at least part of the liquid fraction.
    Advantageously, the implementation of the liquid cooling step, by means of the recirculation loop also makes it possible to agitate the reaction medium, and thus to homogenize the concentrations of the reactive species throughout the volume. liquid from the reaction vessel.
    Step e) of introduction of the cooled liquid fraction
    The method according to the invention comprises a step e) of introducing the liquid fraction cooled in step d) into the upper lateral part of the reaction vessel below the level of the liquid phase, with an angle a of introduction between the pipe and the surface of the reaction vessel between 0 and 35 °, said introduction allowing the formation of a stable vortex at the interface between the liquid phase and the gas phase.
    The introduction of the cooled liquid fraction from step d) is carried out in the upper lateral part of the liquid phase of the reaction vessel.
    According to the invention, the introduction of the cooled liquid fraction into the liquid phase within the reaction vessel is carried out by at least one pipe having an angle a between the injection pipe and the tangent to the surface of the reaction chamber near the injection point between 0 and 35 °, preferably between 0 and 25 °, preferably between 0 and 10 °, and preferably between 0 and 5 °.
    Advantageously, the introduction of the fraction according to the invention allows the formation of a stable vortex at the interface between the liquid phase and the gas phase. The formation of said vortex makes it possible to curve the gas-liquid interface in order to increase the exchange surface between the liquid phase and the gas overhead and thus to favor the dissolution of the unreacted ethylene contained in the gas overhead within of the liquid phase. The ethylene thus dissolved is brought back into contact with the catalytic system. This step makes it possible to recycle the unreacted ethylene contained in the gaseous overhead towards the liquid phase and therefore to optimize its conversion in the oligomerization process according to the invention, and thus to improve the productivity of the reactor.
    According to the invention, the formation of the vortex makes it possible to obtain a parabolic interface between the liquid phase and the gaseous sky. Said vortex is stable, that is to say that it does not cause eddies at the interface.
    Preferably, the speed of introduction of the cooled liquid fraction into the reactor is between 1 and 15 meters per second (m / s), preferably between 1 and 10 m / s, and preferably between 2 and 6 m / s.
    The diameter of the pipe for introducing the cooled liquid fraction is chosen according to the desired speed of introduction in accordance with the knowledge of a person skilled in the art.
    Preferably, the height of formation of the vortex (denoted hv) is regulated so that the low point of the vortex is situated at a level close to that of the point of introduction of the cooled liquid fraction (denoted hi). Preferably, hv is included in the interval [hi-0.2D, hi + 0.2D], where D is the internal diameter of the reaction vessel.
    Preferably, the introduction of the cooled liquid fraction is carried out in the upper part of the liquid phase, preferably in the upper third of the height of the liquid phase, preferably in the upper quarter, preferably in the upper fifth and preferably in the upper tenth of the liquid phase.
    According to a particular embodiment, the introduction of the cooled liquid fraction is carried out at several injection points, having angles a between the injection pipe and the surface of the reaction vessel near the injection point, identical or different, as defined above.
    Preferably the surface of exchange of the liquid with the gaseous sky is increased by the vortex between 1.1 and 10 times, and preferably between 1.5 and 5 times compared to the free surface of the liquid volume introduced without formation of vortex.
    Reactive oligomerization device
    Many reactors using a gas-liquid mixture consist of a reaction chamber comprising a liquid phase and a gas phase, a loop for recirculating a liquid fraction towards a heat exchanger allowing the cooling of the liquid fraction before its reinjection. in the main enclosure. Commonly, the large flow circulating in the recirculation loop allows good homogenization of the concentrations to be obtained and the temperature in the liquid fraction within the reaction vessel to be controlled.
    The reaction device implemented by the method according to the invention belongs to the field of gas / liquid reactors commonly called bubble point reactors. In particular, the reaction device according to the invention comprises the following elements:
    • A reaction vessel i), of elongated shape along the vertical axis comprising a liquid phase comprising and preferably consisting of the reaction products, dissolved ethylene, the catalytic system and a possible solvent, and d '' a gas phase located above said liquid phase comprising unreacted ethylene, as well as the noncondensable gases (especially methane) and, • a means for introducing ethylene ii), located in the lower lateral part of said reaction enclosure using a means of distributing ethylene within said liquid phase of the reaction enclosure, • a means of introducing the catalytic system iii), comprising a metal catalyst, at least one activator and at minus an additive, said means being located in the lower part of the reaction vessel, • a recirculation loop iv) comprising a means of withdrawal at the base (of preferably at the bottom) of the reaction vessel for drawing off a liquid fraction towards a heat exchanger allowing the cooling of said liquid, and a means for introducing said cooled liquid, said introduction allowing the formation of a stable vortex in the part upper part of the liquid phase at the interface between said liquid phase and the gaseous sky.
    i) A reaction vessel
    According to the invention, any reaction vessel known to a person skilled in the art and capable of implementing the method according to the invention is conceivable. Preferably, the reaction chamber is cylindrical in shape and has a height to width ratio (noted H / D) of between 1 and 8, preferably between 1 and 4.
    Preferably, the reaction vessel comprises a means for purging incondensable gases.
    Preferably, the reaction chamber also includes a pressure sensor, making it possible to maintain the pressure within the reaction chamber constant. Preferably said pressure is kept constant by the introduction of additional ethylene into the reaction vessel.
    Preferably, the reaction chamber also includes a liquid level sensor, said level is kept constant by modulating the flow rate of the effluent withdrawn in step c). Preferably, the level sensor is located at the interphase between the liquid phase and the gaseous sky.
    ii) a means of introducing ethylene
    According to the invention, the reaction enclosure i) comprises a means for introducing gaseous ethylene located in the lower part of said enclosure, more particularly in the lower lateral part.
    Preferably the means of introduction ii) of ethylene is chosen from a pipe, a network of pipes, a multitubular distributor, a perforated plate or any other means known to those skilled in the art.
    In a particular embodiment, the means for introducing ethylene is located in the recirculation loop iv).
    Preferably, a gas distributor, which is a device enabling the gas phase to be dispersed uniformly over the entire liquid section, is positioned at the end of the introduction means ii) within the reaction vessel i). Said device comprises a network of perforated conduits, the diameter of the orifices of which is between 1 and 12 mm, preferably between 3 and 10 mm, to form bubbles of ethylene in the liquid of millimeter size.
    Preferably, the speed of the ethylene at the outlet of the orifices is between 1 and 30 m / s. Its surface velocity (volume velocity of gas divided by the section of the reaction vessel) is between 0.5 and 10 cm / s and preferably between 1 and 8 cm / s.
    iii) a means of introducing the catalytic system
    According to the invention, the reaction chamber i) comprises a means of introduction iii) of the catalytic system.
    Preferably, the introduction means iii) is located on the lower part of the reaction enclosure, and preferably at the bottom of said enclosure.
    According to an alternative embodiment, the introduction of the catalytic system is carried out in the recirculation loop.
    The means of introduction iii) of the catalytic system is chosen from any means known to those skilled in the art and preferably is a pipe.
    In the embodiment where the catalytic system is used in the presence of a solvent or a mixture of solvents, said solvent is introduced by an introduction means located in the lower part of the reaction vessel, preferably at the bottom of the reaction vessel or even in the recirculation loop.
    iv) a recirculation loop
    According to the invention, the homogeneity of the liquid phase, as well as the regulation of the temperature within the reaction vessel are carried out by the use of a recirculation loop comprising a means on the lower part of the vessel reaction, preferably at the bottom, for drawing off a liquid fraction towards one or more heat exchanger (s) allowing the cooling of said liquid, and a means for introducing said cooled liquid into the gaseous sky at the head of the reaction chamber.
    The recirculation loop can advantageously be implemented by any means necessary and known to those skilled in the art, such as a pump for drawing off the liquid fraction, a means capable of regulating the flow rate of the drawn off liquid fraction, or another condition for purging at least part of the liquid fraction.
    Preferably the means for withdrawing the liquid fraction from the reaction vessel is a pipe.
    The heat exchanger (s) capable of cooling the liquid fraction is (are) chosen from any means known to those skilled in the art.
    The recirculation loop allows good homogenization of the concentrations and control of the temperature in the liquid fraction within the reaction vessel.
    According to the invention, the introduction of the cooled liquid fraction into the reaction chamber is carried out tangentially on the surface of said chamber at the top of the liquid phase and advantageously allows the formation of a stable vortex at the interface between said liquid phase and the gaseous sky.
    The introduction of the cooled liquid fraction is carried out by any means known to the skilled person and preferably by a pipe.
    According to the invention, the introduction of the cooled liquid fraction is carried out in the upper part of the liquid phase, preferably in the upper third of the height of the liquid phase, preferably in the upper quarter, preferably in the fifth higher and preferably in the upper tenth of the liquid phase.
    According to the invention, the introduction of the cooled liquid fraction into the liquid phase within the reaction vessel is carried out by one or more injection points, said introduction is carried out with an angle a between the line of injection (9) and the tangent to the surface of the reaction vessel near the injection point between 0 and 35 °, preferably between 0 and 25 °, preferably between 0 and 10 °, and preferably between 0 and 5 °.
    Preferably, the introduction of the cooled liquid fraction into the liquid phase within the reaction vessel is carried out by several injection points, preferably between 2 and 30, preferably between 3 and 20, and preferably between 5 and 15.
    When several injection points are used for the introduction of the liquid fraction, said injection points are positioned at the same longitudinal level, that is to say at the same height and are distributed around the enclosure reaction.
    DESCRIPTION OF THE FIGURES
    Figure 1 illustrates a reaction device according to the prior art. This device consists of a reaction chamber (1) comprising a liquid phase A and a gas phase B also called gaseous sky, of a means for introducing ethylene gas (2) into a gas distributor (3) in the liquid phase A. The gaseous sky B comprises a purging means (4). In the bottom of the reaction chamber (1) there is a pipe for withdrawing a liquid fraction (5), towards a heat exchanger (6), the liquid fraction thus cooled is sent via a line (7) to the liquid phase A via an introduction means (9) below the liquid / gas interface (10). Line (8) in the bottom of the reaction vessel allows the introduction of the catalytic system.
    FIG. 2 illustrates a device allowing the implementation of the method according to the invention. Said device differs from the device of FIG. 1 in that the introduction of the cooled liquid fraction is carried out in the upper part of the liquid phase at an angle a with the surface of the reaction vessel between 0 and 30 ° and allows the formation of a stable vortex at the interface (10) between the liquid phase A and the gaseous sky B.
    Figure 3 is a horizontal section of the device illustrated in Figure 2, at the line (9) for introducing the cooled liquid fraction. FIG. 3 illustrates the angle a between the pipe (9) and the surface of the reaction vessel (1), as well as the movement of the liquid fraction once introduced into the liquid phase A.
    Figures 2 and 3 schematically illustrate a particular embodiment of the object of the present invention.
    EXAMPLES
    The examples below illustrate the invention without limiting its scope.
    The oligomerization process in the following examples is carried out at a pressure of 2.6 MPa, at a temperature of 45 ° C. The catalytic system introduced into the reaction vessel comprises Ni (2-ethylhexanoate) 2 as a nickel catalyst at a concentration of 3 ppm by weight of nickel, tricyclohexylphosphine at a molar ratio of 10 of tricyclohexylphosphine to the nickel catalyst, and 15 molar equivalents of ethyl aluminum dichloride relative to the nickel catalyst in the presence of n-heptane as solvent.
    The oligomerization process in the examples below is carried out in a device whose internal diameter of the reaction vessel is 2.6 m. The height of the liquid phase is 5.1 m, and the total volume of the reaction vessel is 37 m 3 . The height of the gaseous sky is 2 m. The volume of the recirculation loop is 3 m 3 .
    The reaction kinetics can be expressed as the product of an apparent constant K and the concentration of ethylene dissolved in the liquid noted [C 2 ]. The constant K is 1.26.10 3 s 1 .
    Example 1: comparison corresponding to Figure 1
    The ethylene oligomerization process is carried out in a bubble point device, in which the introduction of the cooled liquid fraction coming from the recirculation loop is carried out in the liquid phase of the reaction vessel, under the level of the gas-liquid interface.
    The flow rate of the recirculation loop is 625 t / h.
    In this implementation, the exchange surface between the gas and liquid phases is limited to the free surface of the liquid and corresponds to 5.3 m 2 .
    The overall residence time in the reactor is 164.5 min.
    The volume productivity of this reactor is 152 kg of oligomer produced per hour and per m 3 of reactor.
    Example 2: according to the invention corresponding to Figures 2 and 3
    The oligomerization process according to the invention is implemented in a device of dimensions identical to that used in Example 1, in which and in accordance with the invention the cooled liquid fraction coming from the recirculation loop is introduced at an angle of 5 ° to the tangent of the surface of the reaction vessel. The flow rate of the recirculation loop is 1037 t / h. The diameter of the pipe for introducing the cooled liquid fraction is chosen so that the speed of the fraction is 4 m / s at the pipe outlet. The level of vortex formation is regulated so that the bottom of the vortex is at the same level as the injection site. Under these conditions, the vortex generated in the reaction vessel is stable and has a height of approximately 0.9 m. Advantageously, the formation of a stable vortex makes it possible to increase the surface of the gas-liquid interface by about 130%.
    The overall residence time in the reactor is 94 min.
    The volume productivity of the oligomerization process according to the invention is 250 kg 5 of oligomer produced per hour and per m 3 of reactor, which is 1.6 times that of the previous case. It therefore clearly appears that the oligomerization process according to the invention advantageously increases the gas / liquid exchange surface by the use of a stable vortex and thus improves the productivity of the process.
    权利要求:
    Claims (14)
    [1" id="c-fr-0001]
    1. The oligomerization process carried out at a pressure between 0.1 and 10 MPa, at a temperature between 30 and 200 ° C comprised the following steps:
    a) A step of introducing the oligomerization catalytic system comprising a metal catalyst and an activating agent, into a reaction vessel comprising a liquid phase and a gas phase,
    b) A step of bringing said catalytic system into contact with ethylene by the introduction of said ethylene into the lower part of the reaction vessel,
    c) A step of withdrawing a fraction of liquid at a flow rate of between 500 and 10,000 t / h in the lower part of the reaction vessel,
    d) A step of cooling the liquid fraction drawn off in step c) by passing said liquid fraction through a heat exchanger,
    e) A step of introducing the liquid fraction cooled in step d) into the upper part of the liquid phase of the reaction vessel, said introduction is carried out with an angle a between the pipe and the surface of the vessel reaction between 0 and 35 °, said introduction allowing the formation of a stable vortex at the interface between the liquid phase and the gas phase, in which steps c) to e) constitute a recirculation loop.
    [2" id="c-fr-0002]
    2. Method according to claim 1, implemented in a device comprising a reaction enclosure comprising a liquid phase and a gaseous phase, a loop for recirculating a liquid fraction towards a heat exchanger and a means capable of tangentially introducing the liquid fraction cooled within the liquid phase of said reaction enclosure.
    [3" id="c-fr-0003]
    3. Method according to one of the preceding claims wherein the catalytic systems introduced in step a) comprise at least one metallic catalyst preferably based on nickel, chromium or titanium, at least one activating agent, in the optional presence at least one additive and optionally in the presence of at least one solvent.
    [4" id="c-fr-0004]
    4. Method according to one of the preceding claims wherein the ethylene is introduced in step b) at a flow rate between 1 and 250 t / h.
    [5" id="c-fr-0005]
    5. Method according to one of the preceding claims in which a flow of gaseous hydrogen is introduced in step b) into the reaction vessel, with a flow rate representing 0.2 to 1% by mass of the flow of ethylene entering .
    [6" id="c-fr-0006]
    6. Method according to one of the preceding claims in which step d) makes it possible to reduce the temperature of the liquid fraction from 2 to 10 ° C.
    [7" id="c-fr-0007]
    7. Method according to one of the preceding claims wherein the speed of introduction of the cooled liquid fraction within the reaction chamber is between 1 and 15 meters per second (m / s), preferably between 1 and 10 m / s and preferably between 2 and 6 m / s.
    [8" id="c-fr-0008]
    8. Method according to one of the preceding claims wherein the height of formation of the vortex (denoted hv) is regulated so that the low point of the vortex is located at a level close to that of the point of introduction of the fraction cooled liquid (noted hi).
    [9" id="c-fr-0009]
    9. The method of claim 8 wherein the height of vortex formation (hv) is in the range [hi-0.2D, hi + 0.2D], where D is the internal diameter of the reaction vessel.
    [10" id="c-fr-0010]
    10. Method according to one of the preceding claims wherein the introduction of the cooled liquid fraction is carried out in the upper third of the height of the liquid phase.
    [11" id="c-fr-0011]
    11. Method according to one of the preceding claims, in which the introduction of the cooled liquid fraction is carried out at several injection points.
    [12" id="c-fr-0012]
    12. Gas / liquid oligomerization reaction device comprising:
    • A reaction vessel i), of elongated shape along the vertical axis comprising a liquid phase comprising and preferably consisting of the reaction products, dissolved ethylene, the catalytic system and a possible solvent, and d '' a gas phase located above said liquid phase comprising unreacted ethylene, as well as the noncondensable gases (methane in particular) and, • a means for introducing ethylene ii), located in the lower lateral part of said reaction vessel using a means of distributing ethylene within said liquid phase of the reaction vessel, • a means of introducing the catalytic system iii), comprising a catalyst
    5 metallic, of at least one activator and at least one additive, said means is located in the lower part of the reaction enclosure, • a recirculation loop iv) comprising a means of withdrawal at the base (preferably at the bottom) from the reaction vessel for drawing off a liquid fraction towards a heat exchanger allowing the cooling of said liquid,
    10 and a means for introducing said cooled liquid, said introduction is carried out in the upper part of the liquid phase and allows the formation of a vortex in the upper part of the liquid phase at the interface between said liquid phase and the gaseous sky.
    [13" id="c-fr-0013]
    13. Device according to claim 12 wherein the introduction of the liquid fraction
    15 cooled is carried out in the upper third of the height of the liquid phase.
    [14" id="c-fr-0014]
    14. Device according to claims 12 and 13 wherein the introduction of the cooled liquid fraction in the liquid phase within the reaction vessel is implemented by several injection points.
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    同族专利:
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    CA2767615C|2012-02-08|2019-01-15|Nova Chemicals Corporation|Multi reactor ethylene oligomerization process with recycle|
    FR3019064B1|2014-03-25|2020-02-28|IFP Energies Nouvelles|NOVEL CATALYTIC COMPOSITION AND PROCESS FOR THE OLIGOMERIZATION OF ETHYLENE TO HEXENE-1|
    FR3023183A1|2014-07-04|2016-01-08|IFP Energies Nouvelles|CATALYTIC COMPOSITION AND METHOD FOR SELECTIVE DIMERIZATION OF ETHYLENE TO BUTENE-1|
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    FR3105018B1|2019-12-18|2021-12-10|Ifp Energies Now|OLIGOMERIZATION GAS / LIQUID REACTOR INCLUDING TRANSVERSAL INTERNALS|
    FR3105019A1|2019-12-18|2021-06-25|IFP Energies Nouvelles|GAS / LIQUID REACTOR FOR OLIGOMERIZATION WITH SUCCESSIVE ZONES OF VARIABLE DIAMETER|
    FR3112342A1|2020-07-09|2022-01-14|IFP Energies Nouvelles|OLIGOMERIZATION PROCESS USING A GAS/LIQUID EXCHANGER|
    FR3112775A1|2020-07-24|2022-01-28|IFP Energies Nouvelles|Process of oligomerization implementing a recycling of the gaseous sky|
    法律状态:
    2019-01-11| PLSC| Search report ready|Effective date: 20190111 |
    2019-07-25| PLFP| Fee payment|Year of fee payment: 3 |
    2020-07-28| PLFP| Fee payment|Year of fee payment: 4 |
    2021-07-26| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1756518A|FR3068621B1|2017-07-10|2017-07-10|OLIGOMERIZATION PROCESS USING VORTEX|
    FR1756518|2017-07-10|FR1756518A| FR3068621B1|2017-07-10|2017-07-10|OLIGOMERIZATION PROCESS USING VORTEX|
    CN201880046371.XA| CN110891926A|2017-07-10|2018-06-20|Oligomerization process using vortexes|
    PCT/EP2018/066477| WO2019011609A1|2017-07-10|2018-06-20|Oligomerisation method using a vortex|
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