WO2024126176A1 - Procédé de préparation en continu de (méth)acrylate de tert-butyle - Google Patents

Procédé de préparation en continu de (méth)acrylate de tert-butyle Download PDF

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Publication number
WO2024126176A1
WO2024126176A1 PCT/EP2023/084417 EP2023084417W WO2024126176A1 WO 2024126176 A1 WO2024126176 A1 WO 2024126176A1 EP 2023084417 W EP2023084417 W EP 2023084417W WO 2024126176 A1 WO2024126176 A1 WO 2024126176A1
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meth
reactor
isobutene
acrylic acid
tert
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PCT/EP2023/084417
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German (de)
English (en)
Inventor
Armin Schraut
Ortmund Lang
Jonathan Thomas Lefebvre
Manfred Julius
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Basf Se
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Publication of WO2024126176A1 publication Critical patent/WO2024126176A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds

Definitions

  • the invention relates to a process for the continuous production of tert-butyl (meth)acrylate by reacting (meth)acrylic acid in the liquid phase in a reactor with gaseous isobutene, which is passed through the liquid phase, in the presence of an acid catalyst, at a temperature in the range from 30 to 90 °C and an absolute pressure in the range from 0.1 to 20 bar.
  • the tert-butyl esters of acrylic acid and methacrylic acid [in short: (meth)acrylic acid] have a wide range of applications.
  • (Meth)acrylic acid tert-butyl esters for example, are important starting materials for the production of polymers that are used as components of paints, adhesives and varnish resins, among other things.
  • tert-butyl (meth)acrylate for short, can be produced by an addition reaction of acrylic acid (AS) or methacrylic acid to isobutene (IB) under the influence of an acid (e.g. sulfuric acid) as a catalyst.
  • AS acrylic acid
  • IB isobutene
  • This process is described in WO 2016/156410 A1 (BASF SE) and WO 2002/10110 A2 (BASF AG) and WO 2002/10109 A1 (BASF AG), among others.
  • the TBA process is described in more detail below; the same applies to the TBMA process.
  • the reaction is an equilibrium reaction.
  • the reaction is carried out continuously in a vertical reactor divided into sections and cooled between them, with chemical equilibrium probably being largely achieved at the top outlet.
  • the reaction mixture emerging at the top therefore contains acrylic acid, TBA, dissolved IB and the catalyst (e.g. sulfuric acid).
  • This reaction mixture is then evaporated under vacuum (e.g. approx. 60 mbar), with IB as well as TBA and AS preferably being evaporated.
  • the TBA and AS arising in this gas phase are condensed and sent for distillative processing.
  • the uncondensed IB is returned to the reactor via vacuum machines.
  • the problem is that polymers of IB and/or TBA can form and deposit, which can affect the operation of the Vacuum machines can be affected.
  • the liquid high boiler portion remaining after evaporation is also returned to the reactor.
  • the object of the present invention was to provide an improved process for the production of TB(M)A in high yield and purity, which eliminates the above-mentioned disadvantages and can thus be scaled up better.
  • a process was found for the continuous production of tert-butyl (meth)acrylate by reacting (meth)acrylic acid in the liquid phase in a reactor with gaseous isobutene, which is passed through the liquid phase, in the presence of an acid catalyst, at a temperature in the range from 30 to 90 °C and an absolute pressure in the range from 0.1 to 20 bar, which is characterized in that the two reactants are used in a molar ratio of isobutene: (meth)acrylic acid in the range from 5 to 60, the gas stream leaving the reactor, containing unreacted reactants and tert-butyl (meth)acrylate, is partially condensed, whereby tert-butyl (meth)acrylate and unreacted (meth)acrylic acid are obtained as a liquid mixture, which is separated by subsequent distillation and whereby the tert-butyl (meth)acrylate is obtained, and the uncondensed isobutene is returned to the reactor. becomes.
  • TSA tert-butyl acrylate
  • TBMA product tert-butyl methacrylate
  • the addition of acrylic acid (or methacrylic acid) to isobutene is also carried out in a reactor, but with a much larger amount [based on the (meth)acrylic acid used] of gaseous isobutene passed through, which thus functions both as a reactant (educt) and as a stripping gas.
  • the reactor discharge is therefore carried out here by a gas stream which contains isobutene, TB(M)A and acrylic acid or methacrylic acid. Contains methacrylic acid, but not the catalyst (e.g. particularly sulfuric acid). A re-cleavage of the TBA or TBMA in the reactor discharge is thus prevented.
  • the stripping gas is then subjected to partial condensation, whereby TB(M)A and acrylic acid or methacrylic acid are obtained in liquid form and are fed for further separation, e.g. analogous to the processes described in WO 2016/156410 A1 (BASF SE), WO 2002/10110 A2 (BASF AG) or WO 2002/10109 A1 (BASF AG).
  • the uncondensed isobutene is returned to the reactor, preferably predominantly, particularly completely, e.g. 75 to 99% by weight; it can also be referred to as cycle gas and/or stripping gas.
  • the process according to the invention is carried out in a reactor which is in particular a cylindrical reactor.
  • a reactor which is a stirred tank, a bubble column reactor or a loop reactor is further preferably used.
  • the isobutene is fed into the reactor in gaseous form.
  • the isobutene can also be used in the form of a hydrocarbon gas mixture containing isobutene.
  • the gas mixture can be a C4 gas mixture containing isobutene, isobutane, butane, 1-butene and 2-butene.
  • the two reactants are used in the reactor in a molar ratio of isobutene:(meth)acrylic acid in the range from 5 to 60, preferably in the range from 8 to 50, more preferably in the range from 10 to 45.
  • a characteristic feature of the process according to the invention is therefore, among other things, a large molar excess of isobutene used.
  • the reaction of the reactants preferably takes place in the absence of a solvent.
  • Acidic catalysts used are those which are at least partially soluble in the reaction mixture.
  • Preferred catalysts are strong inorganic or organic acids, such as mineral acids, particularly mineral acids containing sulfur or phosphorus, for example sulfuric acid, phosphoric acid and polyphosphoric acid, preferably sulfuric acid or alkyl and aryl sulfonic acids, such as p-toluene, benzene, dodecylbenzene and methanesulfonic acid.
  • Sulfuric acid is particularly preferred, which is also catalytically active under the reaction conditions in the form of the sulfuric acid mono-tert-butyl ester formed.
  • the amount of catalyst is preferably 0.1 to 10 wt.%, preferably 0.5 to 3 wt.%, based in each case on the weight of both reactants [(meth)acrylic acid and isobutene].
  • the reaction is preferably carried out in the presence of an inhibitor which inhibits the polymerization of the (meth)acrylic acid and the tert-butyl ester.
  • an inhibitor which inhibits the polymerization of the (meth)acrylic acid and the tert-butyl ester.
  • Particularly suitable inhibitors are hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, p-nitrosophenol, phenothiazine, 4-hydroxy-2,2,6,6-tetramethyl-1-oxyl-piperidine and methylene blue.
  • the inhibitors are preferably used in amounts in the range from 200 to 2000 ppm, based on the weight of both reactants [(meth)acrylic acid and isobutene].
  • the reactor can advantageously be equipped with internals to improve the mixing of the reaction mixture.
  • Suitable internals are known to the person skilled in the art; for example, they can be static mixing elements such as gratings, distributor plates or sieve trays.
  • the reactant (meth)acrylic acid is very preferably fed into the reactor in liquid form.
  • the feed can be made directly, e.g. via a dip tube, but it is preferred to provide means which enable uniform distribution and mixing of the reactants.
  • Such means are known to the person skilled in the art, for example distributor plates, perforated plates and tubes, nozzles, etc.
  • the gaseous isobutene is preferably fed in via an annular tube with several outlet openings.
  • the (meth)acrylic acid is preferably fed in via a nozzle which causes the mixing of a gas and a liquid and the mixing of the reactor contents. It is preferably arranged in the bottom or at the top of the reactor.
  • Suitable nozzles are known to the person skilled in the art (jet nozzle, mixing nozzle, two-fluid nozzle, etc.) and are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. B4, 5th Ed., 1992, page 280 ff.
  • the gas stream leaving the reactor, containing unreacted reactants and tert-butyl (meth)acrylate, is partially condensed, whereby tert-butyl (meth)acrylate and unreacted (meth)acrylic acid are obtained as a liquid mixture.
  • the uncondensed isobutene is preferably returned predominantly, particularly completely, to the reactor in gaseous form, preferably via the nozzle mentioned.
  • the catalyst is preferably fed as a mixture with the (meth)acrylic acid, whereby fresh catalyst or recovered catalyst or a mixture thereof can be used.
  • the temperature of the reactor is preferably controlled by one or more internal heat exchangers or by one or more external heat exchangers or by means of one or more external liquid circuits.
  • the reaction is carried out at a temperature in the range of 30 to 90 °C and an absolute pressure in the range of 0.1 to 20 bar, preferably at a temperature in the range of 35 to 85 °C and an absolute pressure in the range of 0.2 to 15 bar, more preferably at a temperature in the range of 40 to 80 °C and an absolute pressure in the range of 0.5 to 13 bar.
  • the liquid mixture obtained by the partial condensation of the gas stream leaving the reactor contains a high proportion, e.g. > 30% by weight (based on the mixture), of the desired tert-butyl ester. In addition, it contains unreacted (meth)acrylic acid, inhibitor and other minor by-products.
  • the mixture contains only very small amounts of isobutene oligomerization product, particularly ⁇ 2% by weight (based on the mixture).
  • Figure 1 shows schematically a preferred embodiment of the method according to the invention in an overall overview.
  • Figure 2 shows a schematic embodiment of the TB(M)A process according to the state of the art.
  • the condensation of the vapors (4) can be carried out in the usual way, for example in condensers (B, C) of conventional design.
  • condensers (B, C) of conventional design.
  • two condensers connected in series are used, in particular plate or tube bundle condensers, the second condenser (C) being operated at a lower cooling temperature.
  • the temperature difference is about 30 to 50 °C, the cooling temperature of the first condenser (B) being in the range of about 10 to 35 °C. In this way, rapid distillation and condensation is made possible and the formation of polymers is suppressed.
  • the uncondensed vapors (5) are preferably predominantly fed to the reactor (A) (7), preferably to an extent of 80 to 99.9% by weight, and the remainder of the uncondensed vapors (6) are discharged.
  • the uncondensed vapors (5) preferably contain > 75% by weight of isobutene, ⁇ 23% by weight of inert compounds and ⁇ 2% by weight of the remainder.
  • the inhibitor used is preferably a mixture of phenothiazine (PTZ) and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (4-HT), which is expediently introduced, for example, as a solution in the target ester, e.g. in an amount of 0.02 to 0.15 kg 4-HT and 0.5 to 1.5 kg PTZ in 100 l target ester, preferably in the top region of the condenser, here in the top region of a vertically arranged second condenser (C).
  • PTZ phenothiazine
  • 4-HT 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl
  • the inhibitor solution is preferably applied in such an amount that the inhibitor concentration in the combined condensates (8) is approximately in the range of 100 ppm to 500 ppm.
  • the inhibitor is introduced in the usual way, preferably the inhibitor solution is sprayed in.
  • it has proven advantageous to reduce polymer formation by introducing and in particular spraying at least five times the amount by weight of the distillate, based on the amount by weight of vapor, into the condenser, here into the first condenser (B), preferably in the top region of a vertically arranged condenser (B).
  • the condensate (8) is separated in a distillation unit (D), e.g. a conventional distillation unit comprising an evaporator, column and condenser, into a top product (10) and a bottom product (11).
  • the distillation temperature (bottom temperature) is generally in the Range from 40 to 90 °C.
  • the pressure is selected depending on the product, i.e. TBA or TBMA: preferably the pressure is the same for both target esters.
  • the top product (10) contains the low-boiling components such as tertiary butyl acetate, tertiary butanol and diisobutene. It can also contain up to 40% by weight, based on the top product, of target ester.
  • the bottom product essentially comprises target ester and (meth)acrylic acid.
  • the condensation of the low-boiling components takes place in the usual way.
  • the condensation preferably takes place in two condensers connected in series, for example tube bundle condensers.
  • the cooling temperature of the second condenser is preferably about 30 to 50 °C lower, the first condenser is operated at a cooling temperature of preferably about 10 to 35 °C.
  • the condensates are combined and partly used as column reflux.
  • the rest of the condensate (10) is discharged.
  • the uncondensed vapors (9) are preferably predominantly, particularly completely, passed back to the reactor (A).
  • the uncondensed vapors (9) preferably contain > 85 wt.% isobutene, ⁇ 2 wt.% inert compounds and ⁇ 13 wt.% remainder.
  • a solution of an inhibitor in the target ester is preferably applied to the first condenser.
  • the inhibitor used is preferably a mixture of PTZ and 4-HT, which is expediently introduced as a solution in the target ester, e.g. in an amount of 0.02 to 0.15 kg 4-HT and 0.5 to 1.5 kg PTZ in 100 l target ester, preferably in the head region of a vertically arranged second condenser.
  • the inhibitor solution is applied in such an amount that the inhibitor concentration in the combined condensates is approximately in the range from 100 ppm to 500 ppm.
  • the target ester is obtained in a purity of preferably at least 99.5% by weight from the bottom product (11) of the low boiler distillation (D) in a distillation unit, preferably of conventional design (evaporator, column and condenser).
  • the resulting bottom product (13) generally contains at least 70% by weight of (meth)acrylic acid and is preferably predominantly, particularly completely, returned to the reactor (A).
  • the distillation temperature is generally in the range from 50 to 100 °C.
  • the pressure is selected according to the target ester to be distilled.
  • the purification distillation is preferably carried out using a conventional tray column, for example a column with 30 to 50 dual-flow trays, and feed in the middle column region.
  • the pure target ester is separated off at the top.
  • the condensation of the target ester is preferably carried out in two condensers arranged in series, in particular in tube bundle condensers.
  • the temperature of the coolant in the second condenser is preferably about 30 to 50°C lower than that of the first condenser, in which the coolant preferably has a temperature in the range of about 10 to 35°C.
  • the combined condensates are used partly as column reflux and partly to stabilize the column top and the condenser, here the first condenser, i.e. to avoid polymerization in the column top and in the condenser, here the first condenser.
  • the other part of the target ester is obtained as a valuable product (12).
  • a solution of an inhibitor is introduced into the target ester.
  • a solution of, for example, 0.5 to 2% by weight of hydroquinone monoethyl ether (MEHQ) is used, the amount of inhibitor introduced preferably being selected such that the inhibitor content of the combined condensates is 10 to 20 ppm.
  • MEHQ hydroquinone monoethyl ether
  • a portion (preferably about 5 to 10 times the weight of the target ester discharged, based on the weight of vapor) of the combined, stabilized condensates is introduced into the vapor pipe.
  • the condensates are preferably introduced by injecting them into the vapor pipe above the column in the opposite direction to the gas flow and/or in the region of the condenser inlet in the same direction as the gas flow. Polymerization in the column is suppressed on the one hand by the return flow of the condensate, which contains, for example, 10 to 20 ppm of inhibitor.
  • a solution of another inhibitor in target ester is also preferably applied to a tray in the upper column region.
  • a solution of PTZ and 4-HT in the target ester is used, e.g.
  • a solution of MEHQ in the target ester e.g. 15 to 30 g MEHQ in 100 l target ester, is preferably introduced into the column hood or into the vapor pipe above the column and/or into the upper condenser hood.
  • the resulting target ester (12) is of high purity and generally has the following composition: tertiary-butyl (meth)acrylate 99.5 to 99.9 wt.% tertiary-butyl acetate 0.001 to 0.01 wt.% tertiary-butyl propionate 0.02 to 0.03 wt.% tertiary-butanol 0.001 to 0.01 wt.% (meth)acrylic acid 0.005 to 0.02 wt.% inhibitor (MEHQ) 0.001 to 0.002 wt.% remainder 0.072 to 0.428 wt.%
  • the liquid reaction mixture (14) from the reactor (A) is separated as a discharged partial stream in a distillation (F).
  • the distillation which is preferably continuous, can take place at the same pressure as the reactor pressure.
  • the temperature depends on the desired product in each case (i.e. TBA or TBMA); it is generally selected so that the target ester is split back and only a small proportion of the target ester, e.g. less than 5% by weight of the target ester (based on the amount of bottoms), remains in the bottoms.
  • the resulting gaseous isobutene is preferably predominantly, particularly completely, returned to the reactor (15).
  • the resulting bottoms (16) essentially comprise the acid catalyst, the remaining (i.e. unreacted) (meth)acrylic acid and high-boiling constituents [i.e. by-products with a boiling point higher than TB(M)A at the same pressure], in particular polymeric (meth)acrylic compounds.
  • the distillation can be carried out in conventional devices. However, preference is given to using devices which allow rapid distillation, for example film evaporators, thin-film evaporators or spiral tube evaporators. Suitable film evaporators are known to the person skilled in the art, see for example Ullmanns Encyclopedia of Industrial Chemistry, 5th Ed., Vol. B3, 2-21 to 2-24 and 3-1 to 3-25, 1988.
  • the condensation of the vapors can be carried out in the usual way, for example in condensers of conventional design.
  • two condensers connected in series are used, in particular plate or tube bundle condensers, the second condenser preferably being operated at a lower cooling temperature.
  • the temperature difference is about 30 to 50 °C
  • the cooling temperature of the first condenser preferably being in the range of about 10 to 35 °C.
  • an inhibitor dissolved in the target ester is introduced into the condenser, here the second condenser.
  • the inhibitor used is preferably a mixture of PTZ and 4-HT, which is conveniently introduced as a solution, e.g. in an amount of 0.02 to 0.15 kg 4-HT and 0.5 to 1.5 kg PTZ in 100 l target ester, preferably in the top area of the condenser, here in the top area of a vertically arranged second condenser.
  • the inhibitor solution is applied in such an amount that the inhibitor concentration in the combined condensates is approximately in the range of 100 ppm to 500 ppm.
  • the inhibitor is introduced in the usual way, preferably the inhibitor solution is sprayed in.
  • it has proven advantageous to reduce polymer formation by introducing and in particular spraying at least five times the amount by weight of the distillate (crude ester), based on the amount by weight of vapor, into the condenser, here into the first condenser, preferably in the top region of a vertically arranged condenser.
  • condensation can be dispensed with and the vapors formed are fed directly back into the reactor (A) (15).
  • the pressure in the residue distillation (F) is then equal to the pressure in the reactor.
  • thermodynamic simulations The Aspen Plus® (Aspen) software is used for this, which can be found on the website https://www.aspentech.com. Aspen is a comprehensive simulation software that is used to model, simulate and optimize chemical processes and plants in industry. Aspen has extensive model databases for modeling the basic operations as well as material databases for the material properties of many different substances. The properties of mixtures are calculated by Aspen using different thermodynamic models from the material data of the pure substances.
  • thermodynamic simulation of the entire system according to Fig. 2 is carried out by Aspen and provides the following results: Isobutene with a mass flow of 479 kg/h is fed to a reactor A through a line 1, the catalyst sulfuric acid through a line 2 with a mass flow of 2 kg/h and acrylic acid through a line 3 with a mass flow of 605 kg/h.
  • a vaporous recycle stream from the condensation stage C is fed to reactor A via line 7 with a mass flow of 343 kg/h
  • a vaporous recycle stream from the low-boiling distillation D is fed via line 9 with a mass flow of 21 kg/h
  • a liquid recycle stream from the pure distillation E is fed via line 13 with a mass flow of 320 kg/h
  • a liquid recycle stream from the residue distillation F is fed via line 18 with a mass flow of 2256 kg/h.
  • the reaction in reactor A is carried out at a temperature of 16-32 °C, an absolute pressure of 1200 mbar and a residence time of 4 hours.
  • the vapor phase has the following composition:
  • Acrylic acid ⁇ 0.01 wt.%
  • Triisobutene ⁇ 0.01 wt.%
  • a liquid phase is passed through a line 19 with a mass flow of 4016 kg/h to the residue distillation F.
  • the liquid phase has the following composition:
  • Acrylic acid 26.70 wt.%
  • Diacrylic acid 2.00 wt.%
  • tert.-butyl acrylate 48.09 wt.%
  • Triisobutene 4.53 wt.%
  • a liquid phase is passed through a line 8 with a mass flow of 1378 kg/h to the low-boiling distillation D.
  • the liquid phase has the following composition:
  • Acrylic acid 19.74 wt.%
  • Triisobutene 5.10 wt.%
  • a vaporous phase is passed through a line 7 with a mass flow of 343 kg/h to reactor A.
  • the vapor phase has the following composition:
  • Acrylic acid 0.07 wt.%
  • Triisobutene 0.05 wt.%
  • a liquid phase is passed from the column bottom through a line 11 with a mass flow of 1351 kg/h to the pure distillation E.
  • the liquid phase has the following composition:
  • Acrylic acid 20.11 wt.%
  • the low boilers are discharged from the process after the condenser as a liquid phase through a line 10 with a mass flow of 19 kg/h.
  • the liquid phase has the following composition:
  • Acrylic acid ⁇ 0.01 wt.%
  • Triisobutene ⁇ 0.01 wt.%
  • a vaporous phase is passed after the condenser through a line 9 with a mass flow of 21 kg/h to reactor A.
  • the vapor phase has the following composition:
  • Acrylic acid ⁇ 0.01 wt.%
  • Triisobutene ⁇ 0.01 wt.%
  • a liquid phase is discharged from the process through a line 12 with a mass flow of 1000 kg/h as the pure product tert-butyl acrylate.
  • the liquid phase has the following composition:
  • Acrylic acid ⁇ 0.01 wt.%
  • Diacrylic acid ⁇ 0.01 wt.%
  • tert.-butyl acrylate 99.84 wt.%
  • Diisobutene 0.02 wt.%
  • Triisobutene ⁇ 0.01 wt.%
  • a liquid phase from the column bottom is returned to reactor A through a line 13 with a mass flow of 320 kg/h.
  • the liquid phase has the following composition:
  • Acrylic acid 76.71 wt.%
  • Triisobutene 17.01 wt.%
  • a liquid phase is returned to reactor A through a line 18 with a mass flow of 2256 kg/h and the high boilers are discharged from the process through a line 17 with a mass flow of 63 kg/h.
  • the liquid phase has the following composition:
  • Acrylic acid 41.95 wt.%
  • Triisobutene 4.70 wt.%
  • thermodynamic simulation of the entire system according to Fig. 1 is carried out by Aspen and provides the following results:
  • Isobutene with a mass flow of 455 kg/h is fed to a reactor A through a line 1, the catalyst sulfuric acid through a line 2 with a mass flow of 7 kg/h and acrylic acid through a line 3 with a mass flow of 598 kg/h.
  • a vaporous recycle stream from the condensation stage C is fed via line 7 with a mass flow of 31521 kg/h
  • a vaporous recycle stream from the low boiler distillation D is fed via line 9 with a mass flow of 561 kg/h
  • a liquid recycle stream from the pure distillation E is fed via lines 13 with a mass flow of 481 kg/h
  • a vaporous recycle stream from the residue distillation F is fed via lines 15 with a mass flow of 5 kg/h to reactor A
  • a liquid recycle stream from the residue distillation F is fed via line 18 with a mass flow of 11 kg/h to reactor A.
  • the reaction in reactor A is carried out at a temperature of 50 °C, an absolute pressure of 1000 mbar and a residence time of 2 hours.
  • a vaporous phase is passed through a line 4 with a mass flow of 33580 kg/h to condenser B.
  • the vapor phase has the following composition:
  • Acrylic acid 1.37 wt.%
  • Triisobutene ⁇ 0.01 wt.%
  • a liquid phase is passed through a line 14 with a mass flow of 60 kg/h to the residue distillation F.
  • the liquid phase has the following composition: Isobutene: 3.93 wt.%
  • Acrylic acid 30.18 wt.%
  • Triisobutene 0.10 wt.%
  • a liquid phase is passed through a line 8 with a mass flow of 2054 kg/h to the low boiler distillation D.
  • the liquid phase has the following composition:
  • Acrylic acid 22.11 wt.%
  • Triisobutene 0.03 wt.%
  • a vaporous phase is passed through a line 7 with a mass flow of 31521 kg/h to reactor A and the low boilers are discharged from the process through a line 6 with a mass flow of 5 kg/h.
  • the vapor phase has the following composition:
  • Acrylic acid 0.02 wt.%
  • Triisobutene ⁇ 0.01 wt.%
  • the liquid phase has the following composition:
  • Acrylic acid 29.66 wt.%
  • Diacrylic acid 1.00 wt.%
  • tert.-butyl acrylate 68.10 wt.%
  • Triisobutene 0.04 wt.%
  • the low boilers are discharged from the process after the condenser as a liquid phase through a line 10 with a mass flow of 12 kg/h.
  • the liquid phase has the following composition:
  • Acrylic acid ⁇ 0.01 wt.%
  • Triisobutene ⁇ 0.01 wt.%
  • a vaporous phase is passed after the condenser through a line 9 with a mass flow of 561 kg/h to reactor A.
  • the vapor phase has the following composition:
  • Acrylic acid ⁇ 0.01 wt.%
  • Triisobutene ⁇ 0.01 wt.%
  • a liquid phase is discharged from the process through a line 12 with a mass flow of 1000 kg/h as the pure product tert-butyl acrylate.
  • the liquid phase has the following composition:
  • Acrylic acid ⁇ 0.01 wt.%
  • Triisobutene ⁇ 0.01 wt.%
  • the liquid phase has the following composition:
  • Acrylic acid 91.23 wt.%
  • Triisobutene 0.12 wt.%
  • a liquid phase is returned to reactor A through a line 18 with a mass flow of 11 kg/h and the high boilers are discharged from the process through a line 17 with a mass flow of 44 kg/h.
  • the liquid phase has the following composition:
  • Acrylic acid 43.00 wt.%
  • a vaporous phase is returned to reactor A through a line 15 with a mass flow of 5 kg/h.
  • the vapor phase has the following composition:
  • Acrylic acid 3.08 wt.%
  • Diacrylic acid ⁇ 0.01 wt.%
  • tert.-butyl acrylate ⁇ 0.01 wt.%
  • Triisobutene ⁇ 0.01 wt.%
  • the specific low boiler discharge is 0.012 kg of low boilers per kg of tert-butyl acrylate and the specific high boiler discharge is 0.044 kg per kg of tert-butyl acrylate.
  • the specific low boiler discharge is 0.019 kg low boiler per kg tert-butyl acrylate and the specific high boiler discharge is 0.063 kg per kg tert-butyl acrylate.
  • the low boiler discharge is 37% lower and the high boiler discharge is 30% lower than in the comparative example.
  • the process according to the invention is significantly more economical than the conventional process.
  • the concentration of the polymerizable component tert-butyl acrylate in the circulating gas (line 5) is 3.72% by weight in the comparative example and only 0.18% by weight in the example according to the invention. This significantly reduces the risk of polymerization in the circulating gas blower, which is warm at operating temperature.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation en continu de (méth)acrylate de tert-butyle par conversion d'acide (méth)acrylique en phase liquide dans un réacteur avec de l'isobutène gazeux, qui traverse la phase liquide, en présence d'un catalyseur acide, à une température dans la plage de 30 à 90°C et une pression absolue dans la plage de 0,1 à 20 bars, les deux réactifs sont utilisés dans un rapport molaire isobutène : acide (méth)acrylique dans la plage allant de 5 à 60, le flux de gaz comprenant des réactifs non convertis et du (méth)acrylate de tert-butyle qui quitte le réacteur est partiellement condensé pour obtenir du (méth)acrylate de tert-butyle et de l'acide (méth)acrylique non converti en tant que mélange liquide qui est ensuite séparé par distillation ultérieure, et le (méth)acrylate de tert-butyle étant récupéré, et l'isobutène non condensé étant renvoyé au réacteur.
PCT/EP2023/084417 2022-12-15 2023-12-06 Procédé de préparation en continu de (méth)acrylate de tert-butyle WO2024126176A1 (fr)

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EP22213714.3 2022-12-15

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002010110A2 (fr) 2000-07-28 2002-02-07 Basf Aktiengesellschaft Procede pour la production d'esters de tert-alkyle c4-c8 de l'acide (meth)acrylique
WO2002010109A1 (fr) 2000-07-28 2002-02-07 Basf Aktiengesellschaft Procede de production de tert-butylesters d'acides carboxyliques c1-c4 aliphatiques
WO2016156410A1 (fr) 2015-03-31 2016-10-06 Basf Se Production de tert-butylesters d'acides carboxyliques aliphatiques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002010110A2 (fr) 2000-07-28 2002-02-07 Basf Aktiengesellschaft Procede pour la production d'esters de tert-alkyle c4-c8 de l'acide (meth)acrylique
WO2002010109A1 (fr) 2000-07-28 2002-02-07 Basf Aktiengesellschaft Procede de production de tert-butylesters d'acides carboxyliques c1-c4 aliphatiques
WO2016156410A1 (fr) 2015-03-31 2016-10-06 Basf Se Production de tert-butylesters d'acides carboxyliques aliphatiques

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Ullmanns Encyclopedia of Industrial Chemistry", vol. B3, 1988, pages: 3 - 25
ULLMANN'S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY, vol. B4, 1992, pages 280

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