Catalyst and method of obtaining branched unsaturated aldehydes

FIELD: chemistry.

SUBSTANCE: claimed invention relates to continuous method of obtaining branched unsaturated aldehydes, which can be used for obtaining branched alcohols or acids. method includes preparation of raw material, containing from 5 to 90 wt % of Cn aldehyde, in which n equals from 3 to 8, with raw material additionally containing from 10 to 95 wt % of solvent, interaction of raw material with resin, with resin containing acidic functional groups and not containing a metal from group VIII; reaction of mixture with resin with obtaining effluent flow, containing from 5 to 99.99 wt % of branched unsaturated C2n aldehyde and characterised by reaction selectivity constituting not less than 92%, with formation of branched unsaturated C2n aldehyde; removal of at least part of branched unsaturated C2n aldehyde from effluent flow; and optionally recirculation of part of effluent flow for re-use in raw material. Invention also relates to system for claimed method realisation.

EFFECT: elaboration of continuous method of obtaining branched unsaturated aldehydes.

12 cl, 1 tbl, 6 ex

 

The present invention relates to the use of catalysts for production of unsaturated aldehydes. In particular, the present invention relates to the use of acidic polymeric heterogeneous catalyst to obtain a branched unsaturated aldehydes, which, if desired, you can then hydrate and get branched alcohols, or optionally be oxidized and to obtain branched acid.

Branched unsaturated C2naldehydes can be synthesized from Cnaldehydes using catalysts. In many cases the conversion of aldehydes is carried out using homogeneous catalysis using a basic catalyst. As described in WO 93/20034, this includes continuous method, which is introduced into the reaction of the aldehyde, the catalyst and water and then share with obtaining unsaturated branched C2naldehyde, water, Cnaldehyde and impurities. However, since the catalyst is a homogeneous portion of the catalyst removed from any by-products, such as water that must be removed from the system. For example, if n-butanol used as aldehyde-raw material for the preparation of 2-ethylhexenal, in the system, such as described in WO 93/20034, the waste stream contains water, heavy by-products and sodium butyrate, a by-product of the alkaline catalyst.In this thread sodium butyrate consumes the catalyst, increases costs and is an undesirable impurity in the water; installations for water treatment must be able to process the organic waste, which increases costs. In addition, the flow of water to be removed can be very large, resulting in the need for costly water treatment.

In other cases, the conversion of aldehydes to alcohols is carried out using heterogeneous catalysis with the use of basic or acid catalyst and a metal compound. For example, in the publication of US patent No. 2011/0021845 disclosed alcohols derived from aldehydes in the presence of acidic or basic solid compound and metal compound.

In US patent No. 3037052 discloses the use of polymeric strongly acidic cationogenic macroporous and gel-type resins in the hydrogen form as catalysts. The method used in examples, includes carried out in batchwise reaction of butanal with the formation of 2-ethylhexanal. In patent No. 3037052 stated that macroporous resins are better catalysts than gel-like catalysts. As the benefits are that macroporous resins lead to improved selectivity and degree of conversion and yield in comparison with gel-type strongly acidic cationogenic polymeric catalysts. However, in patent No. 3037052 selectivity to desired �the product was only 85%. Components 15% loss due to the formation of unwanted products, are significant economic losses.

According to the invention found that a much better selectivity can be ensured when using some macroporous resins and gel when carrying out the reaction under suitable conditions. Therefore, the present invention relates to more efficient heterogeneous catalyst, which allows you to make the necessary reaction in the formation of fewer waste. For example, compared to WO 93/20034 in addition to the above higher selectively this catalyst allows to carry out the method, which eliminates the sodium butyrate removed from water, eliminating the need for water treatment.

The first object of the present invention is a continuous method of producing a branched unsaturated aldehydes comprising preparing a raw material containing from 5 to 99.9 wt.% Cnaldehyde, in which n is from 3 to 8; the interaction of materials with the resin; the reaction mixture with the resin with obtaining exit stream containing from 5 to 99.99 wt.% branched unsaturated C2naldehyde, and is characterized by a component of not less than 92% selectivity of the reaction with the formation of branched unsaturated C2naldehyde; removing at least cha�ti branched unsaturated C 2naldehyde from the effluent; and the optional recirculation of the effluent for reuse in raw materials. The resin contains an acid functional group and does not contain any metal of group VIII of the Periodic system of elements.

A second object of the present invention is a system for producing branched unsaturated aldehydes comprising a reactor, in which the incoming raw material containing from 5 to 99.9 wt.% Cnaldehyde, in which n is from 3 to 8; the output stream that exits the reactor; the separation zone, which receives the effluent from the reactor, and the allocation of at least part of the branched unsaturated C2naldehyde from the exit stream of the reactor in the form of a crude product; and an optional return channel through which at least a portion of at least one of the outgoing flows separation step is recycled to the reactor for re-treatment in the reactor. The reactor contains a resin containing an acid functional group and not containing a metal of group VIII of the Periodic system of elements. The effluent contains from 5 to 99.99 wt.% branched unsaturated aldehyde component and is characterized by not less than 92% selectivity of the reaction with the formation of branched unsaturated alder�Yes.

In this object of the present invention formed containing the aldehyde mixture by any suitable technique separated from other components of the crude reaction mixture in which are formed containing the aldehyde mixture. Suitable separation techniques used in the separation zone include, for example, solvent extraction, crystallization, distillation, evaporation, use of a film evaporator, evaporator, falling film of liquid, phase separation and filtering.

As noted above, in the method proposed in the present invention, the desired aldehydes can be separated from the reaction mixture used in the method proposed in the present invention. For example, in a continuous way the liquid reaction mixture (containing the formed aldehyde, etc.), i.e. the reaction liquid is removed from the reaction zone, can be directed to phase separation, for example, a distillation column, where desired the resulting aldehyde can be isolated from the reaction liquid by distillation in one or more stages under normal, reduced or elevated pressure and, if necessary, further purified. Then a portion of the liquid reaction mixture, which is not removed from the product stream from the separation step, containing the formed aldehydes, download, al�of Devida, the solvent, water, reaction byproducts, impurities contained in raw materials, etc., can be fully or partially recycled to the reactor. It may be desirable subsequent separation of the components of the remaining liquid reaction mixture by any means of separation described above, in the same distillation column or in later stages of separation, for example, from recycled liquid reaction mixture can be identified and removed from the water system and any other components contained in the stream to be deleted from the system to prevent the accumulation of undesirable substances in concentrations in the reactor or in the separation step. Usually, if as a means of separation using distillation, it is preferable to highlight the desired branched aldehydes from the reaction mixture under reduced pressure and at low temperature to minimize the formation of unwanted by-products in the separation step. However, the temperature and pressure used in the separation by distillation, are not critical to the present invention and may identify any person skilled in the art.

The present invention relates to a method for producing branched unsaturated aldehydes using resins and preferably cycloterpenic heterogeneous catalysts, without the formation of sodium salts. The method is continuous. Which is the raw material Cnthe aldehyde may be any aldehyde, which when reacted over an acid catalyst gives with more long chain branched aldehyde. Suitable aldehyde reactants include, but are not limited to, propanal, n-butanal, n-pentanal, 2-methylbutanal, 3-methylbutanal, hexanal, heptanal, octanal with longer chain aldehydes, and mixtures thereof. The preferred aldehydes are propanal, n-butanal, n-pentanal, 2-methylbutanal, 3-methylbutanal, hexanal, heptanal and octanal and mixtures thereof. The preferred aldehydes include butanol, n-pentanol, 2-methylbutanal and 3-methylbutanal and mixtures thereof. Typical branched unsaturated aldehydes, which can be obtained, include 2-ethylhexenal derived from n-butanal and 2-propylheptanol derived from n-pentanal.

When used in the present invention the terms hexanal, heptanal and octanal include all their isomers.

Preferably, if the raw material contains from 5 to 99.9 wt.% aldehyde. More preferably, if the raw material contains 40 to 80 wt.% aldehyde.

Preferably, if used resin is a resin pellets, which are macroporous gel-like or a combination thereof.The term "gel" or "gel-like" resin means a resin, which is synthesized from having a very low porosity (from 0 to 0.1 cm3/g), small average pore volume (from 0 to 17 Å) and low surface area BET (from 0 to 10 m2/g) copolymer (measured according to the method BETH (brunauer, Emett and teller)).

The macroporous resin is a resin that is synthesized from a copolymer having a higher porosity and larger surface area BET than the copolymers used for the synthesis of gel-type resins.

Preferably, the pellets of the resin are crosslinked pellets vinylaromatic polymer. On the surface of these granules are formed by strongly acidic functional groups with giving cation-exchange capacity, a component of from 0.1 to 4.0 mEq./L.

The terms "funktsionalizirovannyi surface" and "functionalized surface" means functionalized polymeric materials containing a limited number of functional groups located on the polymer surface or close to it and not necessarily limited by the surface layer of the aromatic nuclei. Depth functionalization of catalyst pellets with functionalized surface is severely limited, however, by limiting functionalization component to 4.0 mEq./l or less and by functionalization of the granules in such a way that stimulated �unctionality from the surface down, so functionalities only the first layer of the aromatic nuclei. Such functionalization known to those skilled in the art.

As monomers, polymerizable upon receipt sewn granules vinylaromatic polymer, preferred are vinylaromatic monomers and polivinilatsetatnye monomers. Vinylaromatic monomers contain exactly one vinyl group in the molecule. Polivinilatsetatnye monomers containing more than one vinyl group in the molecule. Preferred vinylaromatic monomers are styrene, vinyltoluene, vinylnaphthalene, their substituted versions, and mixtures thereof. Preferred vinylaromatic monomers are styrene and α-methylsterol. May contain small amounts mineralogicheskih monomers, preferably less than 20 wt.% in terms of the weight of the monomers, but because they do not contain functionalities aromatic nucleus, they tend to reduce the overall catalytic activity of functionalized on the surface of the catalyst granules. More preferably, if the number mineralogicheskih monomer is 5% or less, more preferably 1% or less in terms of the total mass of the monomer. Preferred polymers are derived from mixtures of monomers containing from 75 to 98 wt.% vinieron�political monomers.

Pellets of the polymers that are produced by polymerization of the monomer or mixture of monomers are crosslinked. These crosslinking represent a methylene bridges or other cross-linking, which are formed during the functionalization or other reactions carried out after polymerization, and their number is preferably increased by introducing into the mixture of monomers, crosslinking monomers, i.e. containing more than one polymerizable vinyl group. Preferred are polivinilatsetatnye monomers, such as divinylbenzene, trivinylbenzene, Divinington, etc., but as cross-linking monomer may also contain one or more polivinilatsetatnyh monomers, such as, for example, etilenglikolevykh, trimethylolpropane, etc. Preferred polivinilatsetatnym monomer is divinylbenzene. Crosslinking monomers can be entered at a level of from 1 to 100 wt.% in terms of the total mass of the monomer. In the case of crosslinked pellets polyvinylimidazole polymer, which in a large part or entirely formed from crosslinking monomers, the preferred monomers are polivinilatsetatnye monomers described above. Preferred polymers are derived from mixtures of monomers containing from 2 to 25 wt.% polivinilatsetatnyh m�rooms.

Strongly acidic functional groups applicable for functionalization of granules vinylaromatic polymer to obtain functionalized granules of the catalyst, preferably represent a sulfonic acid group and salts thereof. Methodology limitations functionalization of the polymer surface are known to those skilled in the art. Most of them are based on the fact that functionalitiy reagent, such as, for example, sulfuric acid or chlorosulfonic acid, penetrates into the polymer beads from the surface at a constant speed, as the penetration in functionalliteracy aromatic nuclei of the sheath is formed of a relatively constant thickness, in which the aromatic nucleus is mostly or fully functionalized. By proper selection of conditions, including functionalitiy reagent and the use and type of solvents, in which there is swelling, the rate at which functionalitiy the reagent penetrates into pellets and functionalitywith their support is quite small, so they can monitor the depth of penetration. Functionalization stop, when it occurred to the required depth, which is sufficient to ensure the capacity of cationic measurement, a component of from 0.1 to 4.0 mEq./l, by stopping the reaction with water or by other methods�IR, obvious to those skilled in the art. Sulfonated polymer preferably has a ratio S/aromatic ring (the ratio of the number of moles of sulfonic acid groups to the number of moles of aromatic rings) comprising from 1/1000 to 2/1 and more preferably has a ratio S/aromatic ring comprising from 0.5/1 to 2/1.

The formation of cross-linked granules vinylaromatic polymer using suspension polymerization is well known to experts in the art. The formation of such granules containing macropores, also well known and disclosed several methods for their preparation.

Resins which are thermally stable and have improved performance characteristics, including high selectivity, no decomposition or weak decomposition in the case of use at high temperature and resulting in negligible corrosion does not lead to corrosion of the reactor, are preferred. Thermally stable resin is preferably chlorinated and tested in the temperature range from 40 to 200°C.

The resin may include an aromatic group containing more than one fragment SO3H and the polymer main chain. The resin can be polysulfonamide, monosulfonamyl and neocolonialism. Polysulfonamide resin has a relation�education the number of moles of sulfonic acid groups to the number of moles of aromatic rings, ratio of more than 1/1. Monosulfonamyl resin has a ratio of the number of moles of sulfonic acid groups to the number of moles of the aromatic rings constituting 1/1. Nedosolennaya resin has a ratio of the number of moles of sulfonic acid groups to the number of moles of the aromatic rings constituting less than 1/1. The expression "sulfonic acid group" includes protonated and salt forms of the fragment SO3H.

The resin may be an inter-penetrating resin. Resin does not contain any metal of group VIII, including iron (Fe), ruthenium (Ru), osmium (Os) and Jassi (Hs), cobalt (Co), rhodium (Rh), iridium (Ir), materi (Mt), Nickel (Ni), palladium (Pd), platinum (Pt) and darmstadtium (Ds). When used in the present invention, the term "metal" includes alkali elements (group #1 of the Periodic system of elements) or alkali-earth elements (group #2 of the Periodic system of elements). Preferably, if the resin contains no metal. If the present invention is told that the resin does not contain metal or the metal is missing, this means that the amount of metal in the resin is equal to zero or less than 0.01 wt.% in recalculation on weight of resin.

In one embodiment of the resin is a gel-like resin having a particle size of from 100 to 2000 μm, and the distribution of particles p� size, which is the Gaussian or singlemode. If the distribution of particle size is Gaussian, about 90% of the particles has a diameter, with an accuracy of +/-100 microns average particle diameter. Single-mode distribution of particle size is such that when the particles have a mostly uniform in size. When a single-mode distribution of 90% of the particles has a diameter, with an accuracy of +/-20 microns average particle diameter. Resins that can be used in the method include organic acid group polymers (for example, Nafion® NR50, produced by E. I. du Font de Nemours and Company, Wilmington, Delaware, and resin AMBERLYST™ and DOWEX™, produced by the DOW Chemical Company, Midland, Michigan).

Expressed in wt.% the solvent content in the raw material in terms of the mass of the raw material is 0% or more; preferably 10% or more; more preferably 20% or greater; even more preferably 30% or more. Expressed in wt.% the solvent content in the raw material in terms of the mass of the raw material is 95% or less; preferably, 80% or less; more preferably 60% or less; even more preferably 40% or less.

Preferably, if the solvent in the raw material is water and it is directionspanel in the reactor. More preferably, if the solvent in the raw material is one or more hydrocarbons; more� preferably one or more aliphatic hydrocarbons; even more preferably one or more alkanes; even more preferably one or more alkane containing from 4 to 12 carbon atoms; even more preferably one or more alkanes containing from 6 to 10 carbon atoms.

Preferably, if the raw materials are continuously charged into the reactor at a temperature of 40°C or higher; more preferably is 80°C or higher; more preferably equal to 100°C or higher. Preferably, if the raw materials are continuously charged into the reactor at a temperature of 200°C or lower; more preferably equal to 160°C or lower; even more preferably equal to 130°C or below.

Preferably, if the temperature in the reactor to 80°C or higher; more preferably 100°C or higher. Preferably, if the temperature in the reactor to 200°C or lower; more preferably 170°C or lower; more preferably 130°C. or below.

Aldehyde feedstock is reacted in a continuous reactor. Preferably, if the continuous reactor is a column reactor with a layer of media or vessel-type reactor with continuous stirring.

For column reactors with a layer of the carrier preferably, if the reactor is a column with a ratio of height to width that is greater than 1. The column contains a layer of resin. In this way we can� to use one or more, comprising a layer of media. To ensure the necessary product mixture can pass several times through the same or different columns. Typical columns include a tubular reactor, a loop reactor, a capillary microreactor, gas-liquid two-phase reactor with a layer of a media reactor with supercritical carbon dioxide, a reactor and a bubble column reactor.

If using a column reactor with a layer of media, materials containing aldehyde, is passed through the resin layer. The layer may be washed with solvent, then adding the aldehyde. Solvents that can be used include chloroform, dichloro methane, tetrahydrofuran, dioxane, furan, diglis, acetone, ethyl acetate, hexane, cyclohexane, pentane, heptane, isooctane, n-octane, benzene, toluene, and other hydrocarbons, oxygendemand solvents, ethers, esters and mixtures thereof. Preferred solvents are hydrocarbons.

If using a column reactor with a layer media, the hourly space velocity of fluid (COSI) is preferably from 0.1 to 20 (h-1), more preferably from 0.5 to 10 (h-1) and most preferably from 2 to 10 CASE (h-1). Preferably, if the pressure is from 0.1 to MPa and more preferably from 0.3 to 3 MPa. When the reactor in continuous �Otok to build up pressure in the reactor is possible to use an inert gas, but this is not critical to the present invention.

The continuous reactor with stirring (RNDP) represents the reaction vessel, which comprises mixing means, such as, but not limited to, mechanical mixing device; a continuous input stream of raw materials and continuous output flow of raw materials. In embodiments using RDP, RDP preferably operates at a temperature of 40-200°C and a pressure equal to from 0.1 to 10 MPa.

If used RNDP, raw materials for the aldehyde is passed through the continuous reactor with stirring (RNDP) containing the resin-catalyst. The resin-catalyst may be washed with solvent, then adding the aldehyde. Solvents that can be used include chloroform, dichloro methane, methanol, ethanol, propanol, tetrahydrofuran, dioxane, furan, diglis, acetone, ethyl acetate, pentane, hexane, cyclohexane, heptane, isooctane, n-octane, benzene, toluene, cresol, hydrocarbons, oxygendemand solvents, ethers, esters and mixtures thereof. Preferred solvents are hydrocarbons.

In the reactor the continuous action interacts with the aldehyde resin with the formation of the output stream. Preferably, if the output stream contains from 5 to 99.99 wt.% branched and unsaturated�of elegida. More preferably, if the output stream contains from 30 to 99.99 wt.% branched unsaturated aldehyde, and most preferably, if the output stream contains 35-70 wt.% branched unsaturated aldehyde.

In one preferred embodiment of the 2-ethylhexenal prepared from a raw material which contains butanol.

When used in the present invention the degree of transformation is equal to 100*(1-(WAOUT/WAIN)), where WAIN means mass per unit time reagent aldehyde in raw materials in the steady state and WAOUT means mass per unit time unreacted reagent aldehyde in the effluent in a stationary state. Typical degree of conversion in industrial processes ranging from 10% to 100%. Typically desirable higher degree of conversion, but this is not critical to the present invention.

Selectivity in the present invention is defined as 100*WEPA/WOTHER where WEPA means the mass of the product is a branched unsaturated aldehyde per unit time in the effluent in the steady state and where WOTHER means the mass of all reaction products formed by reacting reagent aldehyde per unit time in the effluent in a stationary state, including the desired product is a branched unsaturated aldehyde. WOTHER not include the mass not entered into �eakly reagent aldehyde and solvent, introduced in raw materials. Preferably, if the selectivity is at least 92%; more preferably 95%.

Preferably, if the effluent does not contain the sodium salt of organic acid, such as sodium butyrate.

The exit stream preferably enters the zone of separation, such as distillation column, which separates branched unsaturated C2nthe aldehyde in the form of a crude product and at least a portion of at least one of remaining in the separation zone effluent streams is recycled through the return channel into the reactor for processing in the reactor. Recircularize stream, which may contain some amount of the formed branched unsaturated C2naldehyde, unreacted raw materials - Cnaldehyde, water, various impurities and inert substances, such as dissolved inert gases, and/or a certain amount of solvent can be combined with fresh raw material and pass through the reactor. Water may also be produced by the reaction of Cnaldehyde and resin and it can be separated from other threads using typical means and removed from the system. Preferably, if a certain amount of solvent and unreacted Cnaldehyde is passed through the return channel to combine with the flow, which is loaded into the reactor

The following examples are intended to illustrate the present invention. In the examples the following abbreviations.

wt.% means mass %;

Å means Angstrom;

°C indicates degrees centigrade scale;

cm means centimeter;

EGS means 2-ethylhexenal;

g means grams;

PMF means of high molecular weight products compared to the EGS;

kg means kilogram;

CHOSE mean hourly space velocity of the liquid;

m stands for meters;

mEq. means milliequivalent;

mEq./l means volume exchange capacity in milliequivalents per 1 liter of the catalyst;

mEq./kg mean mass exchange capacity in milliequivalents per 1 kg of catalyst per equivalent weight in the dry state;

min means minutes;

ml means milliliters;

IPA means megapascal; and

cm3rpm means the gas flow rate in cubic centimeters per minute of gas at standard conditions;

GL means pellets sulfonated polystyrene gel-type resins;

Mr. means pellets polystyrene sulfonated macroporous resin;

GC-MS means of gas chromatography in combination with mass spectroscopy.

RESEARCH METHODS

For the separation of volatile components of the mixture used gas chromatography (GC method). In NR�CI gained a small amount of the test sample. A syringe needle was inserted into the hot port to inject the sample gas chromatograph and the injected sample. The injector temperature was set to exceed the boiling point of the components, so that components of the mixture evaporated into the gas phase inside the injector. A carrier gas such as helium, is passed through the injector and replaced the gaseous components in the GC column. In GC column separates the components. In column (molecules are distributed between the carrier gas (mobile phase) and high-boiling liquid (stationary phase).

EXAMPLES

In all the examples tested, whether in effluent streams any sodium salt; in all examples, the sodium salt was detected.

The characteristics of the USED RESIN-CATALYST:

Designation resinMR1MR2MR3MR4MR5GL1GL2GL3
Units
Volumetric exchange capacity (VC)EQ./l1,71,90,71,953,60,71,151,35
The surface area BET (SA)m2/g5350803528NRNRNR

Example 1: a Comparison of macroporous resin and gel-like resin.

30 ml of sulfonated Polystyrene catalyst (MR1, MR2, GL1 and GL2) granted by the company The Dow Chemical Company, Midland, MI, was placed in a flow-through column reactor with an inner diameter equal to 1.58, see the quality of the raw materials used butanal purity of 97.7% and it was passed through the reactor at 4 CASE (h-1at a pressure of inert gas equal to 2 MPa and a flow rate equal to 250 cm3/min temperature Used was equal to 80°C. the Degree of conversion and selectivity were determined by the GC method.

Table 1
Comparison of gel and macroporous resins. The degree of conversion and selectivity.
Designation resinTypeThe degree of transformation of butanes, wt.%2-Ethylhexenal (EGS), selectivity, wt.%The RATIO of EGS/PMF
MR1Macroporous30853,2
MR2Macroporous29863,0
GL1Gel2993the 6.6
GL2Gel31946,5

The present invention provides superior selectivity and acceptable high degree of conversion.

Example 2: a Macroporous resin with a low volume exchange capacity. 30 ml of sulfonated Polystyrene catalyst MR3), provided by the company The Dow Chemical Company, Midland, MI, was placed in a flow-through column reactor with an inner diameter equal to 1.58, see the quality of the raw materials used butanal purity of 97.7% and it was passed through the reactor at 4 CASE (h-1at a pressure of inert gas, equal to 0.7 MPa, and the flow velocity of 50 cm3/min temperature Used was equal to 80°C. the Degree of conversion and selectivity were determined by the GC method.

Designation resinThe type of catalystThe degree of transformation of butanes, wt.%2-Ethylhexenal (EGS), selectivity, wt.%The RATIO of EGS/PMF
MR4Macroporous36854,1

The present invention provides superior selectivity and acceptable high degree of conversion.

Example 3: Method using gel-type resins and raw materials with low concentrations of butanes.

30 ml of sulfonated Polystyrene catalyst (GL3) granted by the company The Dow Chemical Company, Midland, MI, was placed in a flow-through column reactor with an inner diameter equal to 1.58 cm Solution butanes readyand�and by dilution in isooctane in a weight ratio of 20/80 and it was used as a raw material. Then the solution was passed through the reactor at 4 CASE (h-1at a pressure of inert gas equal to 1 MPa, and the flow velocity of 100 cm3/min temperature Used was equal to 130°C. the Degree of conversion and selectivity were determined by the GC method. GL3 is a catalyst from the gel sulfonated polystyrene resin.

Designation resinThe type of catalystThe degree of transformation of butanes, wt.%2-Ethylhexenal (EGS), selectivity, wt.%The RATIO of EGS/PMF
GL3Gel959833

According to the technique of GC-MS in the product of this reaction is sodium butyrate was not found.

The present invention provides superior selectivity and acceptable high degree of conversion.

Comparative example 4: the results of the method using the reactor with stirring using (MR4) (COMPARATIVE EXAMPLE USING the PERIODIC METHOD)

The catalyst As used in the reactor with stirring. 1 g Sample of the dried catalyst (MR4) and 5 ml (55 wt./wt.% Bhutan�La in isooctane) were placed in a small reactor with stirring. The reactor was closed, with nitrogen creating pressure equal to 0.3 MPa and kept at 120°C for 4 h at 180 Rev/min., the reaction Product was filtered and the liquid was injected in a gas chromatograph (GC).

Designation resinThe type of catalystThe degree of transformation of butanes, wt.%2-Ethylhexenal (EGS), selectivity, wt.%The RATIO of EGS/PMF
MR4Macroporous9685a 5.4

In this comparative example, the selectivity was low.

Example 5: Method using Pentanes as raw materials to obtain 2-propylheptanol or "propylpyrrolidine" ("PBA")

30 ml of sulfonated Polystyrene catalyst (MR4) granted by the company The Dow Chemical Company, Midland, MI, was placed in a flow-through column reactor with an inner diameter equal to 1.58, see the Solution of raw materials - pentanal prepared by dissolving pentanal (98%) in isooctane with the provision of the weight ratio of 80/20 Pentanes to the solvent. Then the solution was passed through the reactor at 2 CASE (h-1at a pressure of inert gas equal to 1 MPa, and the speed n�current strip, equal to 50 cm3/min temperature Used was equal to 120°C. the Degree of conversion and selectivity were determined by the GC method. MR4 is a catalyst of macroporous sulfonated polystyrene resin.

Designation resinThe type of catalystThe degree of transformation of Pentanes, wt.%BBA, selectivity, wt.%The RATIO of PBA/PMF
MR4Macroporous609310

According to the technique of GC-MS in the product of this reaction the sodium salt of pentane acid is not detected.

Example 6: RNDP

For this method, you can use 3 made in the laboratory RNDP reactor connected in series. The volume of each reactor was equal to 80 ml was loaded with 60 ml of catalyst in 20 ml each of the three reactors. Used catalyst MR4. The raw material was 55 wt./wt.% butanal in isooctane. The flow rate used in the way that was 2 ml/min (2 CASE) for trejectory configuration. The pressure used in the method was 0.5 MPa and the temperature was equal to 120°C. the Contents of each reactor� continuously stirred at 120 rpm. The reaction was performed for 12 h. After the first 4 h, the product was discarded and typical samples were collected after 12 h when operating in a steady state. Collected samples and the degree of conversion and selectivity were determined by the GC method. Expected results:

Designation resinThe type of catalystThe degree of transformation of butanes, wt.%2-Ethylhexenal (EGS), selectivity, wt.%The RATIO of EGS/PMF
MR4Macroporous609728

The present invention provides superior selectivity and acceptable high degree of conversion.

1. A continuous method of producing a branched unsaturated aldehydes, including:
preparation of raw materials containing from 5 to 90 wt.% Cnaldehyde, in which n is from 3 to 8;
wherein the raw material further comprises from 10 to 95 wt.% solvent;
the interaction of materials with the resin, the resin contains an acid functional group and does not contain any metal of group VIII;
the reaction mixture with the resin with obtaining exit stream containing from 5 to 99.99 wt.% branched�wow unsaturated C 2naldehyde component and is characterized not less than 92% selectivity of the reaction with the formation of branched unsaturated C2naldehyde;
removing at least part of the branched unsaturated C2naldehyde from the effluent; and
optional recirculation of part of the effluent for reuse in raw materials.

2. A method according to claim 1, wherein the resin constitutes at least one of the following: macroporous resin and gel-like resin.

3. A method according to claim 1, wherein the resin is a gel-like resin having a particle size equal to from 100 to 2000 μm and a distribution of particle size, which is the Gaussian, or single-mode, or both, and in which the gel-like resin selected from the group including polysulphone resin, monosulfonamyl resin and nedosushennye resin.

4. A method according to claim 1, wherein the interaction includes continuous feeding of raw material into the reactor at a temperature of from 40 to 200°C and a pressure equal to from 0.1 to 10 MPa.

5. A method according to claim 1, wherein the resin is an acidic polymeric heterogeneous catalyst.

6. System for producing branched unsaturated aldehydes, including:
the reactor, in which the input load raw material containing from 5 to 90 wt.% Cnaldehyde, in which n is equal� from 3 to 8, the reactor contains a resin containing an acidic functional group in the absence of any metal of group VIII;
wherein the raw material further comprises from 10 to 95 wt.% solvent;
the output stream that exits the reactor, the effluent contains from 10 to 99.99 wt.% branched unsaturated C2naldehyde component and is characterized by not less than 92% selectivity of the reaction with the formation of branched unsaturated C2naldehyde;
the separation zone, which receives the effluent from the reactor and the effluent from the reactor allocate at least a portion of the branched unsaturated C2naldehyde in the form of a crude product; and
optional return channel through which at least a portion of at least one of the outgoing flows separation step is recycled to the reactor for re-treatment in the reactor.

7. A system according to claim 6, wherein the resin constitutes at least one of the following: macroporous and gel-like resin.

8. A system according to claim 6 in which the resin is a gel-like resin having a particle size equal to from 100 to 2000 μm and a distribution of particle size, which is the Gaussian, or single-mode, or both, in which gel-like resin selected from the group including polysulphonate�s resin, monosulfonamyl resin and nedosushennye resin.

9. A system according to claim 6, in which the reactor is a column reactor with a layer of recording medium, which continuously loads the raw material and which operates at a temperature of from 40 to 200°C and a pressure equal to from 0.1 to 10 MPa.

10. A system according to claim 6, in which the reactor is a continuous reactor with stirring, in which the resin remains in the reactor; in which continuously loads the raw materials and in which the reactor operates at a temperature of 40-200°C and a pressure equal to from 0.1 to 10 MPa.

11. A method according to claim 1, wherein the interaction of materials with the resin is carried out at a temperature of 100°C or higher.

12. A system according to claim 6, in which the interaction of materials with the resin is carried out at a temperature of 100°C or higher.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a novel acyclic aldehyde having 16 carbon atoms, containing at least three branches and selected from a group consisting of: 3-ethyl-7,11-dimethyldodecanal, 2,3,7,11-tetramethyl-dodecanal, 7,11,-dimethyl-3-vinyldodeca-6,10-dienal and 4,8,12-dimethyltrideca-4,7,11-trienal, to a composition of substances suitable for use as starting material for producing surfactants and containing at least one of the disclosed acyclic aldehydes, to a composition of detergent alcohols, suitable for producing a composition of surfactants and containing at least one acyclic alcohol converted from the disclosed acyclic aldehyde, and to a surfactant composition suitable for use in a detergent or cleaning composition and containing one or more surfactant derivatives of isomers of the acyclic detergent alcohol converted from the disclosed acyclic aldehyde. The invention also relates to versions of a cleaning composition and to versions of a method of producing an alcohol mixture for a composition of detergent alcohols.

EFFECT: improved properties of compounds.

19 cl, 10 tbl, 24 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel compounds of general formula (I)

, in which X denotes a CHO, CH2OH or CH2OC(O)R group, where R denotes a straight of branched C1-C5 alkyl chain; as well as to a synthesis method, particularly synthesis of 6,8-dimethylnon-7-enal (1) through hydroformylation of 5,7-dimethylocta-1,6-diene. The invention also relates to fragrant compositions containing formula (I) compounds. Owing to their fragrant properties, these compounds are of great interest in perfumery, particularly cosmetic products and household chemicals.

EFFECT: obtaining novel fragrant compositions.

12 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention refers to cis/trans-citral and (iso)piperitenole processes to be then used in perfumery, household chemicals, vitamin synthesis. The process involves isomerisation of cis-trans verbenol in supercritical lower alcoholic vehicles (C1-C3) at temperature 420°C and lower. As a rule, supercritical lower alcoholic vehicles include supercritical methyl or ethyl alcohol, or supercritical 1-propanol. Commonly thermal isomerisation is ensured at temperature 280-420°C and pressure 100-120 atm.

EFFECT: high yield end products with controlled selectivity and high reaction time.

6 cl, 1 tbl, 2 dwg, 3 ex

The invention relates to an improved process for the preparation of citral, which is a mixture of CIS-and TRANS-isomers of 3,7-dimethylocta-2,6-dienes, which is widely used for the production of high-value components of perfumes and high-quality cosmetic and perfumery products, in particular lineolata, geranylacetone, linalool, geraniol, citronellol, Ivanov and so on, used in the synthesis of vitamins a and E

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing a compound of formula , where Z is optionally substituted phenyl and Q is phenyl or 1-naphthalenyl, each optionally substituted. The method involves distillation of water from a mixture containing a compound of formula , a compound of formula , a base containing at least one compound selected from a group comprising alkali-earth metal hydroxides of formula 4 M(OH)2, where M is Ca, Sr or Ba, alkali metal carbonates of formula 4a (M1)2CO3 , where M1 is Li, Na or K, 1,5-diazabicyclo[4,3.0]non-5-ene and 1,8-diazabicyclo[5.4.0]undec-7-ene, and an aprotic solvent capable of forming a low-boiling azeotrope with water. The invention also relates to a method of producing a compound of formula 2, a method of producing a compound of formula from a compound of formula 1 and a compound of formula 2.

EFFECT: method enables to obtain a product with high output.

20 cl, 15 tbl, 8 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing phenylacetone by interaction of phenylacetic acid with acetic acid in gaseous phase in their mole ratio = 1:(2-5) on catalyst comprising a mixture of calcium oxide and magnesium oxide at temperature 350oC, not below. Loading on catalyst is 2.2-2.8 kg of the parent mixture/(kg cat h). Method provides elevating yield up to 79.9-82.6%.

EFFECT: improved preparing method, increased yield.

5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of polymerisation in circulation reactor. Claimed is method of polymerisation in circulation reactor of at least one olefin monomer in liquid diluents in order to obtain suspension, including solid particles of olefin polymer and said diluents, with ratio of factual volume concentration of solid substances in suspension and maximally possible geometrical volume concentration of solid substances in suspension, measured as volume density of non-compacted precipitated layer of particles RVCSP, constitutes V×0.065 or more, and ratio of integral path of middle-size particle precipitation in any point of reactor in any direction, perpendicular to flow direction to internal diameter of reactor loop is supported lower than [0.084×(V-6.62)+(0.69-RVCSP)×1.666], where V represents rate of suspension circulation, expressed in m/s, integral path of precipitation is determined as the total distance, expressed in diameter parts, passed by particle in any direction, perpendicular to flow direction, after pump, located upstream flow. Circulation reactor includes vertical and horizontal sections, as well as one pump. RVCSP represents ratio between factual volume concentration of solid particles in suspension and maximally possible geometric volume concentration of solid particles in suspension.

EFFECT: in claimed method of polymerisation lower packing of suspension particles in the process of passage through reactor is provided.

21 cl, 4 dwg, 14 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: reactor contains input branch pipe, evaporator of liquid initial reaction mixture, device, creating vortex gas flow, porous distribution membrane, monolithic multi-channel unit, additional porous membrane and output branch pipe. Multi-channel unit is made of material with high heat conductivity, is disc-shaped and has channels, directed perpendicular to disc plane, length of which is considerably smaller than disc diameter.

EFFECT: uniform distribution of input flow by channels, reduction of gradient of temperatures along flow direction, reduction of hydrodynamic resistance in case of immobile layer of catalyst and possibility of fast replacement of catalyst.

13 cl, 3 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to production of super pure silicon to be used in semiconductor production, for example, in fabrication of solar cells or microchips. Monosilane is used for decomposition and mixed with carrier gas composed of hydrogen or hydrogen mix with inert gas. The latter is heated in plasma generator before mixing to temperature higher than silicon fusion point. Thereafter mix of monosilane and carrier gas is fed into reactor. Gas carrier is separately heated to feed monosilane in preheated carrier gas to produce super pure silicon in liquid phase to be continuously discharged.

EFFECT: continuous operation of reactor.

7 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: inventions can be used in chemical industry. Method of plastic wastes depolymerisation includes heating initial solid material and obtaining liquid bath of low-melting metals or metal alloys in reservoir or reactor (311) with induction heater (23). Initial solid material is supplied in dosed way by supplying device (11) into liquid bath of low-melting metals or metal alloys (3) with temperature from 50°C to 550°C.

EFFECT: inventions make it possible to carry out depolymerisation of plastic wastes without their additional processing, without development of overheating and deposits.

13 cl, 2 dwg, 1 ex

FIELD: machine building.

SUBSTANCE: method involves passing of one or more fluid media from a tray set above to a chamber, the chamber includes one or more side walls fitted by a hole and the above set tray is fitted by a drain, the method also implies creation of a channel leading out of the chamber and connecting the respective drain with the respective hole to increase time and area of contact inside the channel and the chamber.

EFFECT: efficient mixing of different phases.

10 cl, 7 dwg

FIELD: chemistry.

SUBSTANCE: claimed invention relates to method of obtaining methanol, which includes the following stages: a) conversion of hydrocarbon raw material at the stage of conversion process to obtain fresh synthesis-gas, which contains carbon oxides and hydrogen; b) reaction between components of fresh synthesis-gas in the circuit of methanol synthesis to obtain raw methanol; c) processing raw methanol to obtain methanol with required purity degree, characterised by the fact that it additionally includes the following stages: d) trapping at least one flow with high content of CO2 in the process of raw methanol processing and e) recirculation of said at least one flow with high content of CO2 in form of input flow for conversion process. Invention also relates to installation for claimed method realisation and to method of reconstructing installation for obtaining methanol.

EFFECT: claimed inventions make it possible to correct stoichiometric factor of synthesis gas.

15 cl, 3 dwg, 6 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: method includes the supply of diluents and the first monomer into the first polymerisation reactor, formation of the first polyolefin in the first suspension, continuous discharge of the transported suspension from the first polymerisation reactor into the second polymerisation reactor. After that, the polymerisation of the second monomer is performed in the second polymerisation reactor with the formation of the second polyolefin. By means of the first discharge device of a continuous action, located on the second polymerisation reactor, pressure regulation in the second polymerisation reactor is realised and the rate of the suspension flow, discharged from the first polymerisation reactor, is supported higher than 4 ft/sec (1.2 m/s).

EFFECT: prevention of the reactor clogging and support of the suspension in a stable state in transportation makes it possible to increase efficiency, reduce the time of the system standstill and increase the total amount of production.

20 cl, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method for gas-phase polymerisation of olefins. The method for gas-phase polymerisation of one or more α-olefins in the presence of a polymerisation catalyst includes at least a polymerisation step, where polymer particles move downwards in dense form under the force of gravity such that a dense polymer layer forms, feeding anti-clogging material to said polymerisation step through at least N feed lines situated at different levels of said dense polymer layer, where N is an integer which satisfies the condition N≥(1+0.08·H), and H is the height (expressed in metres) of the polymer layer.

EFFECT: continuous release of the polymer from the reactor, preventing aggregation of the polymer in the gas-phase reactor, achieving a high level of incorporation of the antistatic agent.

10 cl, 1 dwg, 5 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method for continuous production of aqueous betaine solution of formula , wherein n is equal to 1, 2 or 3, R1 and R2 denote a straight or branched alkyl group containing 1-3 carbon atoms, R denotes a straight or branched hydrocarbon chain containing 3-30 carbon atoms, or an -A-NH-CO-R3 group, where R3 denotes a straight or branched hydrocarbon chain containing 3-30 carbon atoms, and A denotes a straight or branched divalent hydrocarbon group containing 1-6 carbon atoms, optionally substituted with a hydroxyl group, preferably selected from CH2-CH2-CH2- and -CH2CHOH-CH2-. The disclosed method includes reaction of an amine of formula NRR1R2, where values of R, R1 and R2 are given above, with an ω-halocarboxylic acid of formula X-(CH2)n-COOH, where X denotes a halogen atom, n has a value given above, in the presence of water and a base, e.g., an alkali metal hydroxide or more specifically KOH or NaOH. The method is characterised by that it is carried out in an apparatus which consists of at least two series reactors (R1) and (R2), wherein the reactor (R2) is a tube reactor.

EFFECT: method enables to obtain aqueous betaine solutions of high concentration and permanent quality with shorter holding time.

14 cl, 5 dwg, 11 ex

FIELD: chemistry.

SUBSTANCE: method includes formation in a reactor, which contains a laser, optically connected with a focusing objective, and a system of a reagent supply by means of the plasma source, of the plasma formation, influencing it with the laser radiation, supply of reagents into the said plasma formation and the output of obtained reaction products. A set of lasers with different wavelengths with resonators or with resonators and additional resonators is used, with placement of the plasma formation in the said resonators of the lasers.

EFFECT: reduction of the energy consumption with high production quality.

2 cl, 2 dwg

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