TW201311625A - Process for the manufacture of propanediol - Google Patents

Abstract

Process for manufacturing propanediol comprising 1, 3-propanediol, wherein chloropropanediol comprising 2-chloro-1, 3-propanediol is reacted with hydrogen in the presence of a catalyst and/or at a temperature higher than 25 DEG C.

Description

Method for producing propylene glycol

This application claims the benefit of the European Patent Application No. 1 117 773, filed on Aug. 17, 2011, the disclosure of which is incorporated herein in

In the event that any disclosure of patents, patent applications, and publications incorporated herein by reference is inconsistent with the description of the present application to the extent that it may make the term unclear, this description should be preferred.

The present invention relates to a process for the manufacture of propylene glycol, in particular for the manufacture of propylene glycol comprising 1,3-propanediol, and more particularly for the manufacture of 1,3-propanediol.

Propylene glycol is an important intermediate in the chemical industry. Propylene glycol (1,2-propanediol) is used as a starting material in a variety of applications, including unsaturated polyester resins, cosmetic and personal care products, functional fluids, and Antifreezes, liquid detergents, and dog foods. Trimethylene glycol (1,3-propanediol) is mainly used as a structural unit in the manufacture of polymers such as polytrimethylene terephthalate, and it can be formulated into a variety of industrial products, including composites. Materials, adhesives, laminates, coatings, moldings, aliphatic polyesters, copolyesters. It is also a solvent and is used as an antifreeze and wood paint.

Propylene glycol is industrially produced from propylene by hydration of propylene oxide or by hydrogenation of glycerol. The propylene glycol can be synthesized chemically, which can be obtained by hydration of acrolein; or hydroformylation of ethylene oxide to obtain 3-hydroxypropanal, hydrogenating the 3-hydroxypropionaldehyde to obtain 1,3-propanediol; Or using some microorganisms to biologically treat glucose and glycerol.

Eiji Ochiai et al. (Biochemische Zeitschrift, 282, 293-295, 1935) discloses the preparation of 1,2-propanediol by alcohol in methanol and in potassium hydroxide in methanol. This is achieved by catalytic hydrogenation of 1-chloro-2,3-propanediol in the presence of a solution.

EP 1 020 421 A1 discloses the preparation of 1,2-propanediol, which can be carried out in an alcoholic solvent and in the presence of from 0.9 to one mole relative to 1-chloro-2,3-propanediol. 1-Chloro-2,3-propanediol is achieved by catalytic hydrogenation.

Louis Henry (Bul. de l'Acad. Roy. De Belgique), 3, 33, 110-114, 1896) discloses the preparation of 1,3-propanediol, which can be This is accomplished by treating the 2-chloro-1,3-propanediol with a mono-halogen amalgam in an acidic water-alcohol mixture.

These manufacturing methods have several drawbacks. For some processes, the original source (propylene or ethylene) is derived from a non-renewable feedstock, namely petroleum, gas or coal, which are limited. Chemical processes initiated from renewable feedstocks require harsh temperature and pressure reaction conditions. Biological methods exhibit low performance and/or are very complex. Some methods are not suitable for industrial manufacturing because they use toxic and/or hazardous chemicals, or because They produce stoichiometric amounts of by-products that must be separated and disposed of.

Accordingly, it would be desirable to provide improved methods for preparing propylene glycol.

These and other problems are solved by the present invention as described below.

The present invention relates to a process for the manufacture of propylene glycol comprising 1,3-propanediol, wherein the chloropropanediol comprising 2-chloro-1,3-propanediol is reacted in the presence of a catalyst and/or at a temperature above 25 °C Hydrogen reaction.

One of the advantages of the process according to the invention is that it uses chloropropanediol comprising 2-chloro-1,3-propanediol and hydrogen as starting material to produce propylene glycol. Without wishing to be bound by any theory, it is believed that such combinations allow for less stringent reaction conditions which result in better process performance in terms of yield and selectivity to the target product. Surprisingly, the use of a mixture of 2-chloro-1,3-propanediol and 1-chloro-2,3-propanediol allowed to obtain a better monochloropropanediol than when starting from pure 1-chloro-2,3-propanediol. Total conversion rate. Unexpectedly, 2-chloro-1,3-propanediol is more readily hydrodechlorinated than 1-chloro-2,3-propanediol, with similar or even better selectivity for the corresponding propylene glycol.

Another advantage of the process according to the invention is that the process produces hydrogen chloride, a by-product that is easily separated and recycled.

A further advantage of the process according to the invention is that it allows a mixture of propylene glycol and propylene glycol to be obtained in a very simple manner. Such mixtures may be of interest as starting materials in, for example, additional polycondensation reactions.

A further advantage of the method according to the invention is that it utilizes hydrogen, Non-toxic reagents that are commercially available in large quantities at reasonable prices.

In a first embodiment, the invention relates to a process for the manufacture of propylene glycol comprising 1,3-propanediol, wherein the chloropropanediol comprising 2-chloro-1,3-propanediol and hydrogen are at a temperature above 25 °C reaction.

In a second preferred embodiment, the invention relates to a process for the manufacture of propylene glycol comprising 1,3-propanediol, wherein the chloropropanediol comprising 2-chloro-1,3-propanediol is reacted with in the presence of a catalyst Hydrogen reaction.

In the process according to the invention, propylene glycol is intended to mean any of 1,2-propanediol (or propylene glycol), 1,3-propanediol (or propylene glycol) and mixtures thereof. In the process according to the invention, the chloropropanediol is intended to mean 2-chloro-1,3-propanediol (or beta-monochlorohydrin of glycerol), 1-chloro-2,3-propanediol (or alpha-mono of glycerol) Any of chlorohydrin) and mixtures thereof.

In the process according to the invention, the content of 2-chloro-1,3-propanediol in the chloropropanediol is generally higher than or equal to 0.01 wt%, often higher than or equal to 0.1 wt%, often higher than or equal to 1 wt%, in many cases higher than or equal to 10 wt%, often higher than or equal to 25 wt%, often more than or equal to 40 wt%, in particular higher than or equal to 50 wt%, specifically Above or equal to 65 wt%, more specifically higher than or equal to 75 wt%, more specifically higher than or equal to 90 wt%, still more specifically higher than or equal to 95 wt%, and very specifically Said higher than or equal to 99 wt%. This content of 2-chloro-1,3-propanediol in the chloropropanediol is generally less than or equal to 99.99 wt%. Monochloropropanediol mainly composed of 2-chloro-1,3-propanediol is also suitable. Monochloropropanediol consisting of 2-chloro-1,3-propanediol is also suitable.

In the process according to the invention, the chloropropanediol is obtained from at least one process selected from the group consisting of allyl alcohol hypochlorination, glycidol hydrochlorination, epichlorohydrin hydrolysis, dioxins The alkane-dioxolane acetal mixture is subjected to chlorination of glycerol followed by hydrolysis, and dehydroxylation of glycerol with chlorine. Glycerol is preferably natural glycerol, a glycerol prepared during the conversion of a renewable raw material. Glycerol prepared during the conversion of a renewable raw material is intended to mean glycerol obtained from a process selected from the group consisting of: hydrolysis of oil and/or fat from animal and/or plant and/or algae sources. , saponification, transesterification, amine hydrolysis, and hydrogenation; fermentation, hydrogenation, and hydrogenolysis of mono- and polysaccharides derived from biomass or naturally occurring therein, and derivatized alcohols; and any combination thereof. In the process of biodiesel production, ie in the transesterification of oils and/or fats of animals and/or plants, and preferably in the transesterification of vegetable-derived oils and/or fats, the glycerol system is particularly suitable. Glycerol obtained in the manufacture of biodiesel is more particularly suitable.

Allyl alcohol hypochlorination is usually carried out by reacting allyl alcohol with chlorine and water, or with hypochlorous acid. Glycidyl hydrochlorination is usually carried out by reacting glycidol with gaseous hydrogen chloride and/or aqueous hydrogen chloride. Dehydroxylation of glycerol with chlorine is usually carried out by reacting glycerol with gaseous hydrogen chloride and/or aqueous hydrogen chloride. This final reaction can be carried out in the presence or absence of a catalyst. 2-Chloro-1,3-propanediol is preferably obtained by the processes mentioned above.

The chloropropanediol is preferably a chloropropanediol obtained by dehydroxylation of a renewable raw material such as chlorine from natural glycerin.

Propylene glycol is preferably propylene glycol obtained from renewable raw materials, such as chloropropanediol prepared by dehydroxylation of natural glycerol with chlorine. In the process according to the invention, hydrogen can be obtained from any source. Hydrogen is preferably a molecular hydrogen.

In the process according to the invention, hydrogen is preferably obtained from at least one process selected from the group consisting of: steam reforming of hydrocarbons; partial oxidation of hydrocarbons; autothermal reforming of hydrocarbons Water gas shift; coal gasification; pyrolysis of organic waste products (tar, lignite pitch, petroleum distillation residue, plastic, rubber, cellulose, paper, textiles, wood products, straw, mixed municipal waste, ...) and organic Waste products are co-pyrolysis with coal (including bituminous coal, lignite, ...); thermal and non-thermal plasma cracking of water or a mixture of steam and fuel; biomass gasification; biomass pyrolysis and subsequent gasification; nitrogen compounds Thermal or catalytic decomposition of classes (such as ammonia, hydrazine); biochemical hydrogen fermentation; steam reforming of alcohols (such as monohydric alcohols such as methanol or ethanol, and polyols such as propylene glycol and glycerol); Alkaline cracking of fatty acids (especially oleic acid and ricinoleic acid), electrolysis of an aqueous solution of hydrogen halide; electrolysis of an aqueous solution of a metal halide such as, for example, sodium chloride or potassium chloride; Hydrolysis of metal or metal hydrides; from, for example, alkaline electrolysis, proton-exchange membrane electrolysis, solid oxide electrolysis, high pressure electrolysis, water pyrolysis of high temperature electrolysis; photoelectrochemical water cracking; photocatalytic water splitting; photobiochemistry Water cracking; and water pyrolysis. When the selected process is an electrolysis of an aqueous solution of hydrogen halide, the hydrogen halide is often selected from the group consisting of hydrogen chloride, hydrogen fluoride, and any mixture thereof, and is often hydrogen chloride. When the selected process is sodium chloride or chlorination In the electrolysis of the aqueous solution of potassium, the electrolysis may be any one of mercury electrolysis, membrane electrolysis, or membrane electrolysis. Membrane electrolysis is preferred.

In the process according to the invention, hydrogen can be used in admixture with another compound. The other compound is typically selected from the group consisting of nitrogen, helium, argon, carbon dioxide, steam, hydrochloric acid, saturated hydrocarbons, and any mixtures thereof.

In the process according to the invention, the resulting mixture comprising hydrogen generally comprises at least 10 vol% hydrogen, usually at least 50 vol%, preferably at least 75 vol%, more preferably at least 90 vol%, More preferably, it is at least 95 vol%, more preferably at least 99 vol%, and most preferably at least 99.9 vol%. This mixture contains up to 99.99 vol% hydrogen overall. A mixture consisting essentially of hydrogen is also suitable. A mixture of hydrogen is also suitable.

The method according to the invention can be carried out according to any mode of operation. The mode of operation can be continuous or discontinuous. The continuous mode of operation is intended to indicate an mode of operation in which chloropropanediol and hydrogen are continuously added to the process and propylene glycol is continuously withdrawn from the process. Any other mode of operation is considered to be discontinuous. A continuous mode is preferred.

In a second embodiment of the process according to the invention, the reaction is carried out in the presence of a catalyst. The reaction is preferably carried out in the presence of at least one catalyst. The catalyst preferably comprises a hydrogenation catalyst. More preferably, the catalyst is a hydrogenation catalyst. The hydrogenation catalyst is intended to represent a catalyst capable of activating molecular hydrogen. The catalyst may also be capable of activating other compounds that are not molecular hydrogen, such as, for example, chloropropanediol.

In a second embodiment of the process according to the invention, the catalyst comprises at least one metal and/or compound selected in general from the group consisting of: pure and applied chemistry (Pure and Applied Chemistry) 60(3), 431-436 (1988) p. 433, elements of groups 2, 6, 7, 8, 9, 10, 11, 12, 13 and 14 of the IUPAC Periodic Table of the Elements disclosed in FIG. The metal compounds may be, for example, carbides, nitrides, sulfides, oxides, hydroxides, oxide hydrates, halides, and/or organic ligand-based metal compounds. The at least one metal and/or compound of an element is often selected from the group consisting of lanthanides, actinides, elements of groups 6, 7, 8, 9, 10, and 11 of the IUPAC Periodic Table of the Elements. , often selected from the group consisting of Co, Ni, Cu, Mo, Ru, Rh, Pd, Ir, Re, Pt, and Au, and in particular selected from the group consisting of Pd and Pt. .

In a second embodiment of the method according to the invention, the catalyst is preferably at least one metal comprising an element selected from the group consisting of: 8, 9, 10, 11 of the IUPAC Periodic Table of Elements And the elements of the 12 family. The at least one metal of an element is preferably selected from the group consisting of elements of Groups 7, 8, 9, 10 and 11 of the IUPAC Periodic Table of the Elements, more preferably selected from the group consisting of Group of: Re, Co, Ni, Ru, Rh, Pd, Ir, Pt, and Au, and even more preferably selected from the group consisting of Ni, Pd, and Pt.

In a second embodiment of the method according to the invention, the catalyst is preferably at least one metal comprising an element selected from the group consisting of: 6, 7, 8, 9 of the IUPAC Periodic Table of Elements Elements of the 10, 11 and 11 families. Preferably, the element is selected from the group consisting of chromium, molybdenum, ruthenium, iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, gold, rhodium, iridium, platinum, and combinations thereof. More preferably, the element is selected from the group consisting of ruthenium, cobalt, nickel, ruthenium, rhodium, palladium, gold, rhodium, platinum, and combinations thereof. More preferably, the element is selected from the group consisting of ruthenium, cobalt, nickel, and combinations thereof. The best of this element is nickel.钌 as an element is also suitable. In a second embodiment of the process according to the invention, at least one metal and/or compound of the element contained in the catalyst, hereinafter referred to as a hydrogen transfer substance, may be applied (supported) or not (supported) At least one carrier. Non-hydrogen transfer support substance class instance black-based metal, such as for example platinum black and palladium black; and a metal skeleton, a metal such as Raney ^®. The carrier is typically selected from the group consisting of inorganic materials, organic materials, and any combination thereof. Suitable inorganic materials are preferably selected from the group consisting of inorganic oxides, inorganic hydroxides, inorganic halides, inorganic carbides, inorganic nitrides, inorganic sulfates, inorganic Hydrogen sulphates, inorganic phosphates, inorganic hydrogen phosphates, inorganic carbonates, inorganic hydrogencarbonates, and mixtures thereof. Examples of inorganic oxides are diatomite, vermiculite, aluminum oxides (aluminas), alkali metal and alkaline earth metal silicates, aluminum citrate (aragonite-vanadium), clay-like Oxidation of montmorillonite and kaolin, zeolite (such as ZSM-5), spinel, magnesium niobate, zirconia (sulfated or unsulfated), titanium oxide, magnesium oxide, tungsten oxide, zinc oxide, asbestos, and mixed A substance such as zirconium- vermiculite or zirconium-tungsten oxide. An example of an inorganic halide is fluorinated vanadium. Examples of inorganic carbonates are dolomite and calcium carbonate. An example of a lanthanide-based inorganic carbide. Examples of inorganic phosphates are aluminum phosphate and boron phosphate. An example of a barium sulfate-based inorganic sulfate. Suitable organic materials are preferably selected from the group consisting of activated carbon, naturally occurring organic materials or organically synthesized compounds having a high molecular weight, such as silk, polyamido, polystyrene, fibers. Or a polyurethane. Inorganic oxides, activated carbons, and mixtures thereof are preferred carriers. The inorganic carrier material is more preferred. Inorganic oxides are also better carriers. Vermiculite, vanadium, zirconium, tungsten oxide, and any combination thereof, such as, for example, mixed oxides, are even better carriers. The best inorganic oxides of vermiculite, vermiculite-vanadium, vanadium, zirconium- vermiculite, and zirconium-tungsten oxide. Activated carbon is also suitable.

In a second embodiment of the process according to the invention, when a catalyst is used, the catalyst is generally in a form selected from the group consisting of: cyclics, beads, spheres Objects, saddles, spherulites, flakes, extrudates, granules, crushed materials, flakes, honeycombs, filaments, cylinders, polygons And any mixture thereof, or in powder form.

In a second embodiment of the process according to the invention, when the catalyst is supported, the content of the hydrogen-transporting substance is generally greater than or equal to 0.01 weight percent (% wt) relative to the total weight of the supported catalyst, often Greater than or equal to 0.05% wt, often greater than or equal to 0.1% wt, generally greater than or equal to 0.5% wt, in many cases greater than or equal to 1% wt, and more specifically greater than or equal to 5% wt. Hydrogen-transporting substance This content is usually less than or equal to 50 weight percent (% wt), often less than or equal to 30% wt, often less than or equal to 20% wt, overall less than or equal to 15% wt, and in many cases Below is less than or equal to 10% wt.

Although the hydrogen-transporting substance may be uniformly distributed in the carrier material, a preferred catalyst is a catalyst in which the hydrogen-transporting substance is deposited in the outer layer of the catalyst or deposited on the surface thereof. The preparation and shaping of the catalyst which can be used in the process according to the invention can be carried out in a known manner.

In a second embodiment of the process according to the invention, the specific surface area of the catalyst measured according to the nitrogen BET method is generally higher than or equal to 0.1 m ² /g, often higher than or equal to 1 m ² /g, often higher than Or equal to 10 m ² /g, overall higher than or equal to 50 m ² /g, and in particular higher than or equal to 100 m ² /g. This BET surface area is typically less than or equal to 2000 m ² /g, often less than or equal to 1000 m ² /g, often less than or equal to 500 m ² /g, and generally less than or equal to 250 m ² /g, and In particular, it is lower than or equal to 150 m ² /g.

In a second embodiment of the method according to the invention, the dispersion of the hydrogen transfer material, ie the ratio between the number of atoms or molecules on the surface of the hydrogen transfer material and the total number of atoms or molecules of the hydrogen transfer substance, expressed as a percentage of atoms or molecules And as measured by suitable techniques (eg, chemisorption, X-ray diffraction, electron microscopy), typically greater than or equal to 5%, generally greater than or equal to 10%, often greater than or equal to 25%, often Above or equal to 50%, and in particular above or equal to 75%. This dispersion is usually less than or equal to 100%, often less than or equal to 95%, often less than or equal to 90%, overall less than or equal to 85%, and in particular below or equal to 80%.

In a second embodiment of the method according to the invention, the catalyst is preferably selected from the group consisting of palladium supported on vanadium, niobium supported on vanadium, supported on vermiculite铑, gold and palladium supported on zirconia-chondrite, platinum supported on zirconia-tungsten oxide, ruthenium-ruthenium supported on vermiculite, and any mixture thereof. More preferably, the catalyst is rhodium supported on the vanadium.

In a second embodiment of the process according to the invention, when the catalyst is unsupported, it is preferably selected from the group consisting of oxide catalysts and black catalysts. The oxide catalyst is, for example, palladium oxide, platinum oxide, ruthenium oxide or ruthenium oxide/platinum oxide according to Nishimura. The black catalyst type is, for example, palladium black, platinum black or ruthenium black. They can be prepared by reducing a corresponding metal salt or metal salt with a mixture of, for example, hydrazine, formaldehyde, hydrogen or a more electropositive metal.

In a second embodiment of the method according to the invention, it is also possible to use a skeleton catalyst, particularly in terms Satoshi (Urushibara) type or Raney ^® type skeletal metal catalysts, such as by John Wiley & Sons, edited by Shigeo Nishimura for an organic Handbook Of Heterogeneous Catalytic Hydrogenation For Organic Synthesis Shigeo Nishimura Edited by John Wiley & Sons, 2001, p. 19, Section 1.1.4. and page 26, Section 1.2.4. Handbook of Heterogeneous Catalysis Edited by G. Ertl, H. Knözinger, J. Weitkamp, 1997, by G. Antu, H. Kunozig, J. Wetkahn Volume 1, Section 2.1.2., as defined on pages 64-72. The skeletal metal catalyst is Raney ^® type preferred, more preferably is selected from the group consisting of: Raney ^® iron, Raney ^® cobalt, Raney ^® Nickel, Raney ^® copper, Raney ^® ruthenium, palladium, Raney ^®, Raney ^® platinum, Raney ^® Mo - Ni, Raney ^® chromium - nickel and any mixtures thereof, and still more preferably is selected from the group consisting of: Raney ^® Nickel, cobalt, and Raney ^® any mixture thereof. The preferred catalyst is a skeletal Raney ^® nickel.

In carrying out the second embodiment of the process according to the invention it is also possible to use mixtures of two or more of said catalysts.

In the process according to the invention, the reaction can be carried out in the presence of a hydrogen chloride acceptor such as, for example, a basic compound. The hydrogen chloride acceptor can be used in stoichiometric, sur-stoichiometric or substoichiometric amounts. The hydrogen chloride acceptor is typically employed in substoichiometric amounts, for example, at a level of less than or equal to 90 moles relative to the stoichiometric amount, often less than or equal to 50 mole percent, often less than or equal to 10 mole percent, and In many cases less than or equal to 1 mol%.

The basic compound may be an organic or inorganic basic compound. The organic basic compound is, for example, an amine, a phosphine, and a hydroxide of ammonium, phosphonium or arsenic. The expression "inorganic compound" is understood to mean a compound which does not comprise a carbon-hydrogen bond. The inorganic basic compound may be selected from the group consisting of oxides, hydroxides, carbonates, hydrogencarbonates, phosphates, hydrogen phosphates, and borates of alkali metals and alkaline earth metals, and mixtures thereof.

In the process according to the invention, the reaction is often in no significant amount The hydrogen chloride receptor is carried out in the presence of a reagent. A substantial amount is intended to mean that the amount of hydrogen chloride acceptor used is less than or equal to 0.01% stoichiometric amount. The stoichiometric amount corresponds to one equivalent of hydrogen chloride acceptor per mole of monochloropropanediol.

In the process according to the invention, the reaction can be carried out in a gas phase or in at least one liquid phase, preferably in at least one liquid phase. In this latter case and in a second embodiment of the process according to the invention, the catalyst may be soluble in the reaction mixture or substantially insoluble in the reaction. Preferably, the catalyst is substantially insoluble in the reaction mixture.

In the process according to the invention, when the reaction is carried out in at least one liquid phase, the at least one liquid phase preferably comprises less than 90% of a hydrogen chloride acceptor relative to the monochloropropanediol, preferably alkaline. The percentage of the compound is expressed as the equivalent of the hydrogen chloride acceptor per liter of monochloropropanediol, preferably an alkaline reagent. For a monobasic reagent such as, for example, sodium hydroxide, this will correspond to less than 0.9 mol of NaOH per mole of monochloropropanediol. For a binary alkaline agent such as, for example, calcium hydroxide or sodium carbonate, this would correspond to less than 0.45 mol of Ca(OH) ₂ or Na ₂ CO ₃ per mole of monochloropropanediol. Preferably, the hydrogen chloride acceptor, preferably the alkaline agent, is present in an amount of less than or equal to 50%, more preferably less than or equal to 10%, and most preferably less than 1%, and most preferably It is less than 0.01%. Preferably, the hydrogen chloride acceptor, preferably the alkaline agent, is selected from the group consisting of oxides, hydroxides, carbonates, and hydrogencarbonates of alkali metals and alkaline earth metals. , phosphates, hydrogen phosphates and borates, and mixtures thereof, and more preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, and any mixtures thereof. An advantage of having at least one liquid phase of less than 90% of a hydrogen acceptor, preferably a basic compound, is that it allows for a better selectivity of the corresponding propylene glycol. A further advantage of carrying out the reaction under such conditions is that it produces a low amount of chloride-containing salts that must be disposed of or that does not form such salts. Conversely, the generated hydrogen chloride by-products are easily separated and recycled.

In the process according to the invention, when the reaction is carried out in at least one liquid phase, it can be carried out in the absence or presence of a solvent. The solvent may be selected from the group consisting of inert inorganic solvents, inert organic solvents, and combinations thereof. Examples of inert inorganic solvents are water, supercritical carbon dioxide, and inorganic ionic liquids. Examples of inert organic solvents are alcohols, ethers, saturated hydrocarbons, esters, perfluorinated hydrocarbons, nitriles, guanamines, and any mixtures thereof. Examples of alcohols are methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2,3-propanetriol. Examples of ethers are diethylene glycol, dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, and diethylene glycol diethylene glycol. ether. An example of a saturated hydrocarbon is cyclohexane. An example of an ester is ethyl acetate. Examples of perfluorinated hydrocarbons are perfluorinated alkane such as perfluorinated hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, dimethylcyclohexane or tri methylcyclohexane, perfluorinated ethers, Galden ^® HT, such as from Solvay Solexis (Solvay Solexis), perfluoromethyl tetrahydrofuran, or perfluorinated amines, such as from 3M Fluorinert ^TM FC. An example of a nitrile is acetonitrile. An example of a guanamine is dimethylformamide.

In the process according to the invention, the reaction is preferably in a solvent Exist in the presence. The solvent is preferably selected from the group consisting of water, an alcohol or a mixture thereof. Preferably, the alcohol is from the group consisting of alcohols having from 1 to 20 carbon atoms, more preferably from the group consisting of methanol, ethanol, Isopropanol, hexanol, dodecanol, 1,2-propanediol, 1,3-propanediol, glycerin, and any mixture thereof. More preferably, the solvent is water. One of the advantages of using water is that it is a less harmful solvent. A further advantage of using water is that it is a cheap solvent. Yet another advantage is that it allows for a better conversion of the chloropropanediol and a better selectivity for the corresponding propylene glycols, more specifically 1,3-propanediol. Glycerin is also a preferred solvent.

In the process according to the invention, when the reaction is carried out in the presence of a solvent, the ratio between the solvent and the monochloropropanediol is usually expressed in weight percent, usually higher than or equal to 10%, preferably higher than or equal to 50%, and more preferably higher than or equal to 90%.

In the process according to the invention, the reaction can also be carried out with less solvent, i.e. the ratio between the solvent and the monochloropropanediol, expressed as less than 1% by weight.

In the process according to the invention, the reaction can suitably be carried out in a gas phase.

In addition to hydrogen and the monochloropropanediol, the gas phase may further comprise a diluent. The diluent can be a compound as described above as a solvent, or a compound used in combination with hydrogen as described herein above. The diluent is preferably selected from the group consisting of water, an alcohol, and any mixture thereof. More preferably, the alcohol is selected from the group consisting of Group: alcohols containing from 1 to 20 carbon atoms, and most preferably selected from the group consisting of methanol, ethanol, isopropanol, hexanol, dodecanol, 1,2- Propylene glycol, 1,3-propanediol, glycerin, and any mixture thereof. Water is a preferred diluent. Glycerol is another preferred diluent. The diluent is preferably in the form of a gas.

In addition to hydrogen, the monochloropropanediol, and the diluent to be used, the gas phase may further comprise a hydrogen chloride acceptor. The hydrogen chloride receptor can be as described herein above.

The process according to the invention can be carried out in a plurality of reaction apparatuses which are made of or coated with a material suitable for hydrogenation under pressure, the presence of a corrosion-resistant compound such as hydrogen chloride, a material suitable for the reaction conditions. And other materials. Suitable materials may be selected from the group consisting of: glass; enamel; enamel steel; graphite; impregnated graphite, such as, for example, graphite impregnated with a perfluorinated polymer such as polytetrafluoroethylene or impregnated with a Graphite of phenolic resin; polyolefins such as, for example, polyethylene or polypropylene; fluorinated polymers such as perfluorinated polymers such as, for example, polytetrafluoroethylene, poly(perfluoropropyl vinyl ether) a copolymer of tetrafluoroethylene and hexafluoropropylene, and as a partially fluorinated polymer such as, for example, poly(vinylidene fluoride); a sulfur-containing polymer such as, for example, a polyfluorene or a polysulfide; Metals such as, for example, tantalum, titanium, copper, gold, silver, nickel, and molybdenum; and metal alloys such as, for example, alloys containing nickel, such as Hastelloy B, Hastelloy C, alloys containing molybdenum, such as Inconel 600, Inconel 625 or Inconel 825.

The materials may be in the form of a block, or in the form of a coating, or by means of How to apply the coating method. Enamel steel systems are particularly suitable.

In a second embodiment according to the invention, the inner wall of the device carrying out the method may function as a catalyst as described above, for example when the inner wall is comprised of a hydrogen transfer material such as, for example, iron, nickel, as described above. And/or chrome) when the material is made or coated. In a preferred aspect, the inner wall of the apparatus in which the method is carried out does not function as a catalyst as described above.

In a first embodiment of the process according to the invention, the reaction is carried out at a temperature which is preferably higher than or equal to 35 ° C, more preferably higher than or equal to 50 ° C, and even more preferably It is higher than or equal to 75 ° C, more preferably higher than 100 ° C, most preferably higher than or equal to 110 ° C, and most preferably higher than 140 ° C. This temperature is typically less than or equal to 400 ° C, generally less than or equal to 300 ° C, in many cases less than or equal to 200 ° C, often less than or equal to 170 ° C, and often less than or equal to 150 ° C.

In a second embodiment of the process according to the invention, when the reaction is carried out in the presence of a catalyst, the reaction is carried out at a temperature which is generally higher than or equal to 25 ° C, generally higher than or equal to 50 °C, in many cases greater than or equal to 75 ° C, often greater than or equal to 100 ° C, more preferably above 110 ° C, and most preferably above 140 ° C. This temperature is usually lower than or equal to 400 ° C, generally lower than or equal to 300 ° C, in many cases lower than or equal to 200 ° C, more preferably lower than or equal to 170 ° C, and often lower than or equal to 150 ° C .

In the process according to the invention, the reaction is carried out under a partial pressure of hydrogen, which is usually higher than or equal to 1 bar absolute, and is generally higher than or equal to 10 bar absolute, in many cases higher than or Equal to 50 bar For pressure, and often higher than or equal to 100 bar absolute. This hydrogen partial pressure is typically less than or equal to 400 bar absolute, and is generally less than or equal to 300 bar absolute, in many cases less than or equal to 200 bar absolute, and often less than or equal to 150 bar absolute. This pressure is suitably higher than or equal to 50 bar absolute and less than or equal to 80 bar absolute.

In the process according to the invention, the reaction is carried out at a total pressure which is generally higher than or equal to 1 bar absolute, generally higher than or equal to 10 bar absolute, in many cases higher than or equal to 50 bar absolute pressure, and often higher than or equal to 100 bar absolute pressure. This total pressure is typically less than or equal to 400 bar absolute, generally less than or equal to 300 bar absolute, in many cases less than or equal to 200 bar absolute, and often less than or equal to 150 bar absolute. This pressure is suitably higher than or equal to 50 bar absolute and less than or equal to 80 bar absolute.

In the process according to the invention carried out in a continuous mode, especially in the presence of at least one liquid phase, the residence time, ie the ratio of the volume of the liquid phase to the flow rate (vol%) of the reactants, depends on the reaction rate, The partial pressure of hydrogen, the degree of thoroughness of mixing the reaction mixture, and the activity and concentration of the hydrogenation catalyst when a catalyst is used. This residence time is usually higher than or equal to 5 minutes, often higher than or equal to 15 minutes, often higher than or equal to 30 minutes, and in particular higher than or equal to 60 minutes. This residence time is usually less than or equal to 25 hours, often less than or equal to 20 hours, often less than or equal to 10, and in particular less than or equal to 5 hours.

In the method according to the invention, which is carried out in a continuous mode, in particular When a gas and a liquid phase are present, the residence time of the liquid phase, ie the ratio of the volume of the reactor volume to the flow rate (vol%) of the liquid phase, is generally higher than or equal to 5 minutes, often higher than or equal to 15 Minutes, often higher than or equal to 30 minutes, and in particular higher than or equal to 60 minutes. The residence time is typically less than or equal to 25 hours, often less than or equal to 10 hours, and often less than or equal to 5 hours.

In the process according to the invention carried out in a continuous mode, in particular in the presence of a gas and a liquid phase, the residence time of the gas phase, ie the volume of the reactor volume and the flow rate (vol%) of the gas phase The ratio is usually higher than or equal to 1 second, often higher than or equal to 5 seconds, often higher than or equal to 10 seconds, and in particular higher than or equal to 30 seconds. The residence time is typically less than or equal to 10 minutes, often less than or equal to 5 minutes, and often less than or equal to 2 minutes.

In the process according to the invention carried out in a continuous mode, in particular when the reaction is carried out in a gas phase, the residence time of the gas phase, ie the ratio of the volume of the reactor volume to the flow rate (vol%) of the gas phase, Usually higher than or equal to 1 second, often higher than or equal to 5 seconds, often higher than or equal to 10 seconds, and in particular higher than or equal to 30 seconds. This residence time is typically less than or equal to 10 minutes, often less than or equal to 5 minutes, and often less than or equal to 2 minutes.

In the process according to the invention carried out in a discontinuous mode, the reaction time required for the process according to the invention depends on the reaction rate, the partial pressure of hydrogen, the degree of thorough mixing of the reaction mixture, and the hydrogenation when a catalyst is used. Catalyst activity and concentration. The required reaction time is usually high It is at or equal to 5 minutes, often higher than or equal to 15 minutes, often higher than or equal to 30 minutes, in particular higher than or equal to 60 minutes, and more specifically higher than or equal to 160 minutes. This residence time is usually less than or equal to 25 hours, often less than or equal to 20 hours, often less than or equal to 10, and in particular less than or equal to 5 hours.

In the process according to the invention carried out in a discontinuous mode, especially in the presence of a gas and a liquid phase, the reaction time of the liquid phase is usually higher than or equal to 5 minutes, often higher than or equal to 15 minutes, often high It is at or equal to 30 minutes, in particular higher than or equal to 60 minutes, and more specifically higher than or equal to 180 minutes. This reaction time is usually less than or equal to 25 hours, often less than or equal to 10 hours, and often less than or equal to 5 hours.

In the process according to the invention carried out in a discontinuous mode, especially in the presence of a gas and a liquid phase, the reaction time of the gas phase is usually higher than or equal to 1 second, often higher than or equal to 5 seconds, often high It is equal to or greater than 10 seconds, and in particular higher than or equal to 30 seconds. This reaction time is usually less than or equal to 10 minutes, often less than or equal to 5 minutes, and often less than or equal to 2 minutes.

In the process according to the invention, especially when the reaction is carried out continuously in a gas phase, the ratio between the flow rates of hydrogen and chloropropanediol is generally higher than or equal to 0.1 mol/mol, often higher than or equal to 0.5 mol/mol. , often higher than or equal to 1 mol/mol, and in particular higher than 1 mol/mol. This ratio is usually lower than or equal to 100 mol/mol, often lower than or equal to 50 mol/mol, often lower than or equal to 20 mol/mol, and especially low Or equal to 10 mol/mol.

The process according to the invention can be carried out in any type of reactor. Particularly when the reaction is carried out in the presence of a catalyst, the reactor may be selected from the group consisting of a slurry reactor, a fixed bed reactor, a trickle bed reactor, a fluidized bed reactor, and combinations thereof. Slurry reactors or trickle bed reactors are particularly suitable when the reaction is carried out in at least one liquid phase. A trickle bed reactor is more particularly suitable. A trickle reactor of cocurrent feed of hydrogen and chloropropanediol is very particularly suitable. Fixed bed reactors, fluidized bed reactors, moving bed reactors are particularly suitable when the reaction is carried out in the gas phase. When the reaction is carried out in the gas phase, a reactor comprising a catalyst of a filler having a honeycomb structure is completely suitable.

In the simplest embodiment, the process according to the invention can be carried out discontinuously in such a way that a pressure cooker having a stirring or mixing unit and which can be thermostated is charged with the chloropropanediol to be hydrogenated, possibly Hydrogenation catalyst and a possible solvent. Thereafter, a force is applied to the hydrogen until the desired pressure is reached, and the mixture is heated to the selected reaction temperature while being thoroughly mixed. The course of the reaction can be easily monitored by measuring the amount of hydrogen consumed, which is compensated by the addition of hydrogen. When hydrogen is no longer consumed, the hydrogenation is complete and the amount of hydrogen consumed corresponds approximately to the amount of hydrogen theoretically required.

The mixture present after hydrogenation can be treated, for example, as follows: when the hydrogenation is complete, the reaction vessel is cooled, the pressure is lowered, and the possible catalyst is filtered off and washed with the possible solvent used, and then under reduced pressure or at atmospheric pressure. Remove solvent. The remaining crude product can be reused under reduced pressure The purification is carried out in the same manner by distillation under atmospheric pressure. When a high boiling solvent is used, it is also possible to first distill off propylene glycol. When no solvent is used, the mixture can be directly subjected to distillation under reduced pressure or at atmospheric pressure. Flash distillation may be performed to remove the formed hydrogen chloride before subjecting the residue to distillation. The recovered possible catalyst can be used in the discontinuous process as such or after reactivation by a physico-chemical treatment.

In another embodiment, the process according to the invention can be carried out continuously in such a way that a vertically cylindrical reactor, which can be thermostated, is charged with a catalyst provided in a suitable shape for obtaining in the reactor. A fixed bed of catalyst. The top portion of the reactor is provided with an inlet for the hydrogenated propylene glycol and hydrogen to be hydrogenated or dissolved in a solvent, the bottom portion of which is provided with an outlet for recovering the reaction mixture, and a regular pressurizing device is installed. A vessel is used to recover the reaction mixture and separate the liquid phase from the gas phase. Thereafter, a force is continuously applied to the hydrogen in the reactor until the desired pressure is reached, and then the reactor is heated to a selected reaction temperature in which the mixture is continuously or dissolved in a solvent. Monochloropropanediol exerts a force and the reaction mixture is continuously collected in a recovery vessel. The extent of the reaction can be easily monitored by analyzing the composition of the liquid separated in the collection vessel. The liquid mixture present in the vessel can be recovered, for example, by distillation under reduced pressure or at atmospheric pressure.

The content of organic compounds in samples taken at different stages of the process is typically evaluated using gas chromatography.

The invention further relates to a process for the manufacture of a polymer selected from the group consisting of polyethers, polyurethanes, polyesters and Any mixture comprising obtaining 1,3-propanediol by reacting a chloropropanediol comprising 2-chloro-1,3-propanediol with hydrogen in the presence of a catalyst and/or at a temperature above 25 °C Propylene glycol, and the propylene glycol is reused as a raw material.

In the method for producing a polymer according to the present invention, the propylene glycol containing 1,3-propanediol is preferably obtained by reacting a chloropropanediol containing 2-chloro-1,3-propanediol in the presence of a catalyst. Hydrogen is obtained by reaction.

The process for producing a polyether comprises obtaining 1,3,3 by reacting a chloropropanediol comprising 2-chloro-1,3-propanediol with hydrogen in the presence of a catalyst and/or at a temperature above 25 °C. Propylene glycol of propylene glycol, and the propylene glycol is further subjected to a reaction with at least one compound selected from the group consisting of halogenated organic compounds, organic epoxides, alcohols or any mixture thereof.

The method for producing a polyurethane comprises obtaining a 1,3-containing reaction by reacting a chloropropanediol comprising 2-chloro-1,3-propanediol with hydrogen in the presence of a catalyst and/or at a temperature above 25 °C. Propylene glycol of propylene glycol, and the propylene glycol is further subjected to a reaction with a polyisocyanate, preferably a diisocyanate.

In the method for producing a polymer according to the present invention, the polymer is preferably a polyester.

Accordingly, the present invention also relates to a process for the manufacture of a polyester comprising the step of reacting chlorine comprising 2-chloro-1,3-propanediol in the presence of a catalyst and/or at a temperature above 25 °C. Propylene glycol is reacted with hydrogen to obtain propylene glycol containing 1,3-propanediol, and the propylene glycol is further subjected to a kind The reaction of a carboxylic acid and/or a carboxylic acid ester.

Accordingly, the present invention also relates to a process for the manufacture of a polyester which comprises obtaining an inclusion by reacting a chloropropanediol comprising 2-chloro-1,3-propanediol with hydrogen in the presence of a catalyst, preferably in the presence of a catalyst. Propylene glycol of 1,3-propanediol, and the propylene glycol is further subjected to a reaction with a carboxylic acid and/or a carboxylic acid ester.

The features mentioned above with regard to the process for the manufacture of propylene glycol comprising 1,3-propanediol are suitable for obtaining propylene glycol comprising 1,3-propanediol for the production of polymers, preferably polyesters.

In the method for producing a polyester according to the present invention, the carboxylic acid is preferably a polycarboxylic acid, more preferably a dicarboxylic acid. The polycarboxylic acid is preferably selected from the group consisting of aliphatic saturated or unsaturated, aromatic, alkyl aromatic saturated or unsaturated, heteroaromatic, alkyl hetero Aromatic saturated or unsaturated, or any mixture thereof.

More preferably, the aliphatic dicarboxylic acid containing from 2 to 16 carbon atoms is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and cerium. Acid, sebacic acid and any mixture thereof.

Preferred unsaturated dicarboxylic acids are selected from the group consisting of fumaric acid, maleic acid, and any mixture thereof.

Preferred aromatic compounds are selected from the group consisting of o-phthalic acid, m-phthalic acid, p-phthalic acid (terephthalic acid), naphthalene dicarboxylic acid, and any mixtures thereof. A preferred aromatic carboxylic acid is more preferably terephthalic acid.

Preferred alkyl aromatic compounds are selected from the group consisting of 4-methyl phthalic acid, 4-methyl phthalic acid, and any mixtures thereof.

Preferred unsaturated aromatic dicarboxylic acids are selected from the group consisting of a plurality of vinyl phthalic acids and any mixtures thereof.

Preferred heteroaromatic acids are selected from the group consisting of furan dicarboxylic acids and any mixtures thereof, and preferably 2,5-furandicarboxylic acid.

In the process for producing a polyester according to the present invention, the carboxylic acid ester is preferably an ester of the above carboxylic acid, preferably a methyl or ethyl ester. Preferred esters are selected from the group consisting of esters of terephthalic acid, esters of furandicarboxylic acid, and any mixtures thereof. More preferably, the ester is a terephthalate, and most preferably dimethyl terephthalate.

Polyesters are manufactured, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Horst. Horst Köpnick, Manfred. Manfred Schmidt, Wilhelm. Wilhelm Brügging, John. Jörn Rüter and Walter. Walter Kaminsky, published online: June 15, 2000, DOI: 10.1002/14356007.a21_227, pp. 623-649.

The polymer obtained by the method of the present invention, the preferred polyester, typically exhibit a ¹⁴ C / ¹² C, the ¹⁴ C / ¹² C greater than or equal to 10 ^-12 0.33, often higher than or equal to 0.5 10 ^-12 , often higher than or equal to 0.75 10 ^-12 , in many cases higher than or equal to 1.0 10 ^-12 , and in particular higher than or equal to 1.1 10 ^-12 .

In another embodiment, the present invention relates to a polyester which exhibits a ¹⁴ C / ¹² C, the ¹⁴ C / ¹² C greater than or equal to 10 ^-12 0.33, often higher than or equal to 0.5 10 ^-12 , often higher than or equal to 0.75 10 ^-12 , in many cases higher than or equal to 1.0 10 ^-12 , and in particular higher than or equal to 1.1 10 ^-12 .

The polyester is preferably obtained by reacting a chloropropanediol comprising 2-chloro-1,3-propanediol with hydrogen in the presence of a catalyst and/or at a temperature above 25 ° C. The propylene glycol of 1,3-propanediol is reacted, and the propylene glycol is further subjected to a reaction with a carboxylic acid and/or a carboxylic acid ester as described above.

More preferably, the polyester is obtained by reacting a chloropropanediol comprising 2-chloro-1,3-propanediol with hydrogen in the presence of a catalyst and/or at a temperature above 25 °C. The propylene glycol of 3-propanediol is reacted, and the propylene glycol is further subjected to a reaction with a carboxylic acid and/or a carboxylic acid ester as described above.

The invention further relates to a process for the manufacture of polyester fibres comprising the step of reacting a chloropropanediol comprising 2-chloro-1,3-propanediol in the presence of a catalyst and/or at a temperature above 25 °C Reacting with hydrogen to obtain propylene glycol containing 1,3-propanediol, and subjecting the propylene glycol to a reaction with a carboxylic acid and/or a carboxylic acid ester to obtain a polyester, and converting the polyester into a fiber .

The polyester obtained according to the method of the present invention typically exhibit a ¹⁴ C / ¹² C, the ¹⁴ C / ¹² C greater than or equal to 10 ^-12 0.33, often higher than or equal to 0.5 10 ^-12, often higher than or equal to 0.75 10 ^-12 is higher than or equal to 1.0 10 ^-12 in many cases, and in particular higher than or equal to 1.1 10 ^-12 .

The method for measuring the ¹⁴ C content is precisely described in the standard ASTM D 6866 (notably D 6866-06 and D 6866-08) and in the standard ASTM 7026 (notably D 7026-04). Preferably, the method used is described in standard ASTM D6866-08.

The above-mentioned methods for producing propylene glycol comprising 1,3-propanediol and the features mentioned in the process for producing polyester are suitable for obtaining propylene glycol comprising 1,3-propanediol and polyester for producing polyester fibers. .

Polyester fibers are manufactured, for example, in the Ullmann Industrial Chemistry Encyclopedia, Helmut. Helmut Sattler and Michael. Michael Schweizer, published online: October 15, 2011, DOI: 10.1002/14356007.o10_o01, described on pages 1 to 34.

These polyester fibers have many applications and can be used, for example, in tires, ropes, ropes, sewing threads, seat belts, hoses, belt fabrics, coated fabrics, carpets, garments, household decoration. , soft bag garnish, medicine, lining, filter structure, fiber filler, high-loft, roofing material, geotextile, and substrate.

The following examples are intended to illustrate the invention and not to limit it.

In a 100 ml Hastelloy (C-22) pressure cooker Hydrogenation of chloropropanediol equipped with the following Hastelloy (C-22) material: a reactor sealed to a head equipped with a gas injection stirrer; for temperature probes One tube; and another tube for liquid sampling.

--monochloroethanol (α-MCG, 1-chloro-2,3-propanediol) dissolved in a solvent and β-monochloroethanol (β-MCG, 2-chloro-1,3-diol) A mixture of propylene glycol) (about 52 g of solution) was filled with a catalyst in an autoclave. The autoclave is then pressurized with nitrogen (to about 30 bar absolute) and depressurized for about 5-7 pressurization-reduced cycles, and thereafter, the autoclave is pressurized with hydrogen (to about 50 bar absolute) And decompression (about 7-9 pressurization-decompression cycles). The reactor was then pressurized at room temperature with hydrogen at the desired pressure (about 65 bar absolute, except that Example 1 was about 50 bar) and then heated to the desired temperature. When the desired temperature is reached, the reaction mixture is mechanically stirred at a desired rate of rotation per minute (about 1960 rpm) at a constant hydrogen pressure (about 65 bar absolute, except that Example 1 is about 50 bar). This is counted as the time zero of the test. During the hydrogenation process, liquid samples were periodically withdrawn and filtered on a polypropylene screening program prior to gas chromatography analysis.

The separation conversion ratio of monochloropropanediol at any time was calculated as follows: conversion = 100 × [(the number of moles of monochloropropanediol introduced - the number of moles of monochloropropanediol recovered at the selected time) / ( The number of moles of monochloropropanediol introduced)).

The total conversion of monochloropropanediol at any time is calculated as follows: conversion = 100 x [(total moles of monochloropropanediol introduced - total moles of monochloropropanediol recovered over the selected time) / (total number of moles of monochloropropanediol introduced)].

The selectivity of propylene glycol (12PDO for 1,2-propanediol and 13PDO for 1,3-propanediol) at any time is calculated as follows: selectivity = 100 x [(mole of propylene glycol recovered at the selected time) / (the number of moles of the corresponding monochloropropanediol introduced - the molar number of the corresponding monochloropropanediol recovered at the selected time)]. 3-Chloro-1,2-propanediol is the corresponding monochloropropanediol for 12PDO, and 2-chloro-1,3-propanediol is the corresponding monochloropropanediol for 13PDO.

The yield of propylene glycol at any time is calculated by multiplying the selectivity of propylene glycol for the selected time by the corresponding conversion of monochloropropanediol for the selected time and dividing by 100.

The mixture of α- and β-MCG used is presented in Table 1 below:

The catalyst used is presented in Table 2 below:

(a) The catalyst is based on Heeres HJ et al., German Applied Chemistry ( Angew . Chem . Int . Ed .), 2011, 50 , 7083, and is used as it is from Johnson Matthey (Ref: 56551/12) and Aldrich (Ref: 227196-100G; batch: #STBC0599V) prepared from ruthenium (RhCl ₃ .xH ₂ O) and SiO ₂

(b) Catalyst according to EP application 11188055.5, used as it is from Adrici (ZrOCl2->Ref: 31670; batch: #SZBA0330V; PdCl2->Ref: 520659; batch: #MKBJ2974V; AuCl4->Ref :334049; batch: #MKBH2249V) and Yong-Yi's zirconium, palladium and gold precursors and vermiculite

(c) a catalyst system according to Davis BH (Davis BH) et al., Catalysis Today (. Catal today), 2002, 71, 411, as is used in correspondence Adelaide from Aldrich (Ref: 239267; Batch: MKBF8722V) Prepared with cobalt precursors Co(NO ₃ ) ₂ and SiO _{2 of} Fuji silysia (ref: CARIACT G-6; batch: #GH120201)

(d) and (e) Catalysts are used according to Li L. (Li L.) et al., Applied Catalysis B: Environment ( Appl . Catal . B. Environ .), 2012, 115-116 , 7, using the corresponding Palladium precursors (PdCl2) and HZSM- from Adrici (Ref: 205885; batch: STBC 3593V) and Southern Chemical (Sud Chemie) (Ref: TZP724-TKP-12.040a; batch: TC 9E 10 M43) 5 to prepare. In the preparation process, catalyst calcination was carried out with air under the conditions described in the paper.

ZrO2 is based on Barton DG et al., J. Catal., 1999, 181 , 57, using ZrOCl2 from Aldrich (Ref: 31670; batch: SZBA3280V) as it is. .8H2O) to prepare

(f) Catalysts are based on Chen C.-L. (Chen C.-L.) et al., Green Chemistry ( Green chem .), 2010, 12 , 1466, correspondingly from Johnson Matthey (Ref: 240- 010-7; batch: 181100), Adrici (Ref 463922; batch: MKBJ4740V) and Adrici (Ref: 31670; batch: SZBA3280V) of platinum (H2PtCl6), tungsten ((NH4)6H2W12O40.xH2O And zirconium (ZrOCl2.8H2O) precursors are prepared,

(g) The catalyst system is used as it is according to JP2009275029, correspondingly from Adrici (Ref: 455962; batch: #MKBJ4530V), Adrici (ref: 316954; batch: #MKBH1293V), and Fujitsu (ref: CARIACT) G-6; batch: #GH120201) prepared by hydrazine (H2IrCl6.xH2O) and hydrazine (NH4ReO4) precursor and SiO2.

Examples 1 to 4 (not according to the invention)

A mixture of monochloropropanediol (I) was used. Water is used as a solvent. Monochloropropanediol was used in an amount of 100 g per 900 g of solvent. The catalyst was used in an amount of 3.1% by weight in a solution of monochloropropanediol. The reaction temperature was 120 °C. The duration of the reaction was 3 h. The results are reported in Table 3 below:

Examples 5 to 8 (according to the invention)

The conditions were the same as in Examples 1 to 4 except that the mixture (VII) of monochloropropanediol was used, and the reaction duration of Example 5 was 4.8 h. The results are reported in Table 4 below:

Examples 9 to 15 (according to the invention)

The conditions were the same as in Examples 1 to 4 except that the mixture (III) of monochloropropanediol was used. The results are reported in Table 5 below:

Examples 16 to 17 (according to the invention)

The conditions were the same as in Examples 1 to 4 except that a mixture (V) of monochloropropanediol was used, and Example 17 used a catalyst of 2.8% g/g. The results are reported in Table 6 below:

Examples 18 to 24 (according to the invention)

The conditions were the same as in Examples 1 to 4 except that the mixture (VII) of monochloropropanediol was used, the reaction temperature was set at 160 ° C, and the reaction duration of Example 21 was 4 h. The results are reported in Table 7 below:

Examples 25 to 31 (according to the invention)

The conditions were the same as in Examples 18 to 24 except that several mixtures of monochloropropanediol were used and several solvents were used. The results are reported in Table 8 below:

Examples 32 to 35 (according to the invention)

The conditions were the same as in Examples 18 to 24, except that several mixtures of monochloropropanediol were used, different amounts of water were used as the solvent, the reaction duration was 1 h, and for the special example 33, 25 g of the monochloropropanediol solution was used. The results are reported in Table 9 below:

Examples 36 to 39 (according to the invention)

The conditions were the same as in Examples 18 to 24 except that several reaction temperatures were used, several reaction times and several catalyst concentrations were used. The results are reported in Table 10 below:

Examples 40 to 41 (according to the invention)

The conditions were the same as in Examples 18 to 24 except that several catalyst concentrations and reaction durations were used. The results are reported in Table 11 below:

Examples 42 to 43 (not according to the invention)

The experimental part was the same as Examples 1 to 41 except that for Example 43, a mixture of monochloropropanediol in water containing hydrazine was used along with the catalyst to fill the autoclave. The results are reported in Table 12 below.

Example 44 (not according to the invention)

Example 44 was carried out according to Eiji Ochiai et al., Biochemische Zeitschrift, 282, 293-295, 1935. The reaction was carried out in the same autoclave as in Examples 1 to 41 as follows.

7.14 g of glycerol dissolved in 22.49 g of methanol (MeOH) Reactor for filling a pressure cooker with a mixture of α-monochloroethanol (α-MCG, 1-chloro-2,3-propanediol) and glycerol β-monochloroethanol (β-MCG, 2-chloro-1,3-propanediol) . To the solution were added 3.41 g of 5% Pd/C and 20.40 g of 20% KOH in MeOH. The autoclave is then pressurized with nitrogen (to about 30 bar absolute) and depressurized for about 5-7 pressurization-reduced cycles, and thereafter, the autoclave is pressurized with hydrogen (to about 50 bar absolute) And decompression (about 7-9 pressurization-decompression cycles). The autoclave was then pressurized with hydrogen at about 1 bar absolute pressure at room temperature, and then the reaction mixture was mechanically stirred at a constant hydrogen pressure (about 1 bar absolute) at a rate of about 1960 rotations per minute. This is counted as the time zero of the test. After 2.2 h, the liquid sample was filtered on a polypropylene screening program prior to gas chromatography analysis.

The results are reported in Table 13 below:

Example 45 (not according to the invention)

Example 45 was carried out in accordance with EP1020421. The reaction was carried out in the same autoclave as in Examples 1 to 41 by using 5 g of α-monochloroethanol (α-MCG, 1-chloro-2,3-propanediol) dissolved in 19.6 g of isopropanol and glycerol. A mixture of β-monochloroethanol (β-MCG, 2-chloro-1,3-propanediol) was charged to the reactor of the autoclave. To the solution, 3.58 g of a 48% aqueous NaOH solution was added dropwise over 30 minutes in an ice bath. The mixture was stirred at room temperature for 30 minutes, and then 0.249 g of 10% Pd/C was added thereto. The pressure cooker is then pressurized with nitrogen (to about 30 bar absolute) and depressurized for about 5-7 A pressurization-reduction cycle, and thereafter, the autoclave was pressurized with hydrogen (to about 50 bar absolute) and depressurized (about 7-9 pressurization-reduced cycles). The autoclave was then pressurized with hydrogen at about 5 bar absolute pressure at room temperature and then the reaction mixture was mechanically stirred at a constant hydrogen pressure (about 5 bar absolute) at a rate of about 1960 rotations per minute. This is counted as the time zero of the test. After 2 h, the liquid sample was filtered on a polypropylene screening program prior to gas chromatography analysis.

The results are reported in Table 14 below.

Example 46 (according to the invention)

The hydrogenation of monochloropropanediol is carried out in a vapor phase in a continuous facility at atmospheric pressure, the facility being equipped with a glass evaporator above a vertical fixed bed tubular flow reactor, the reactor being connected The reaction product was recovered on a water-filled gas glass trap. The reaction proceeds as follows.

2.7 g of Catalyst 1 (volume: about 8 ml, height in the reactor: about 1.5 cm) was loaded into a tubular glass flow reactor. Nitrogen (about 13 l/h) was passed through the facility for about 30 minutes. The reactor was then heated under nitrogen flow (about 13 l/h) to obtain a catalyst temperature of about 200 ° C, and the glass trap was cooled at about 4 °C. When the desired temperature is reached, hydrogen (about 25 l/h) is passed through the facility for about 30 minutes and then maintained at about 8 l/h. The evaporator was heated at about 168 °C. Then, a mixture (VII) of liquid monochloropropanediol was introduced into the evaporator at about 6 ml/h. During the hydrogenation, water was periodically withdrawn from the glass trap, replaced with fresh water, and then analyzed by gas chromatography. The total conversion of monochloropropanediol was 32 mol%, and the selectivity of 1,2-PDO and 1,3-PDO was correspondingly 16 mol% and 41 mol%.

Example 47 (according to the invention)

The conditions were the same as in Example 46 except that the catalyst temperature was 250 °C. The conversion ratios of α-MCG and β-MCG were correspondingly 67 mol% and 84 mol%, and the selectivity of 1,2-PDO and 1,3-PDO was correspondingly 14 mol% and 12 mol%.

Claims (82)

A process for the manufacture of propylene glycol comprising 1,3-propanediol, wherein the chloropropanediol comprising 2-chloro-1,3-propanediol is reacted with hydrogen in the presence of a catalyst and/or at a temperature above 25 °C. The method of claim 1, wherein the chloropropanediol comprising 2-chloro-1,3-propanediol is reacted with hydrogen in the presence of a catalyst. The method of claim 1 or 2, wherein the content of 2-chloro-1,3-propanediol in the chloropropanediol is higher than or equal to 0.01 wt%. The method of claim 3, wherein the content of 2-chloro-1,3-propanediol in the chloropropanediol is higher than or equal to 1 wt%. The method of claim 4, wherein the content of 2-chloro-1,3-propanediol in the chloropropanediol is higher than or equal to 10 wt%. The method of claim 5, wherein the content of 2-chloro-1,3-propanediol in the chloropropanediol is higher than or equal to 25 wt%. The method of claim 6, wherein the content of 2-chloro-1,3-propanediol in the chloropropanediol is higher than or equal to 40 wt%. The method of claim 7, wherein the content of 2-chloro-1,3-propanediol in the chloropropanediol is higher than or equal to 50% by weight. The method of claim 8, wherein the content of 2-chloro-1,3-propanediol in the chloropropanediol is higher than or equal to 65 wt%. The method of claim 9, wherein the content of 2-chloro-1,3-propanediol in the chloropropanediol is higher than or equal to 75 wt%. For example, the method of claim 10, wherein the chloropropane The content of 2-chloro-1,3-propanediol in the alcohol is higher than or equal to 90% by weight. The method of claim 11, wherein the content of 2-chloro-1,3-propanediol in the chloropropanediol is higher than or equal to 95 wt%. The method of claim 12, wherein the content of 2-chloro-1,3-propanediol in the chloropropanediol is higher than or equal to 99 wt%. The method of claim 13, wherein the chloropropanediol consists essentially of 2-chloro-1,3-propanediol. The method of claim 14, wherein the chloropropanediol consists of 2-chloro-1,3-propanediol. The method of claim 1 or 2, wherein the chloropropanediol is obtained from at least one selected from the group consisting of allyl alcohol hypochlorite, glycidol hydrochlorination, epichlorohydrin Hydrolysis, dioxan-dioxolan acetal mixture followed by glycerol chlorination followed by hydrolysis, and glycerol chlorination dehydroxylation. The method of claim 16, wherein the glycerol has been prepared during the conversion of the renewable raw material. The method of claim 1 or 2, wherein the hydrogen is obtained from at least one selected from the group consisting of: steam reforming of hydrocarbons; partial oxidation of hydrocarbons; water gas shift; coal gasification Thermal or catalytic decomposition of nitrogen compounds; alcohols and polyols, especially steam reforming of methanol, ethanol, propylene glycol and glycerol; electrolysis of aqueous solutions of hydrogen halide; and electrolysis of aqueous solutions of sodium chloride or potassium chloride; Water cracking, including alkaline electrolysis, proton exchange membrane electrolysis, solid oxide electrolysis, high pressure electrolysis, high temperature electrolysis, photoelectrochemical water cracking, photocatalytic water splitting Solution, water biolysis, and water pyrolysis. The method of claim 1 or 2, wherein the hydrogen is mixed with a compound selected from the group consisting of nitrogen, helium, argon, carbon dioxide, steam, hydrogen chloride, saturated hydrocarbons, and the like Any mixture, and the resulting mixture contains at least 10 vol% hydrogen. The method is carried out in a continuous mode as in the method of claim 1 or 2. The method of claim 1 or 2, wherein the catalyst comprises a hydrogenation catalyst. The method of claim 21, wherein the hydrogenation catalyst comprises at least one metal selected from the group consisting of elements of Groups 6, 7, 8, 9, 10 and 11 of the IUPAC Periodic Table of Elements and/or Or a compound. The method of claim 22, wherein the element is selected from the group consisting of chromium, molybdenum, niobium, iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, osmium, iridium, platinum, gold. And its combination. The method of claim 23, wherein the element is selected from the group consisting of ruthenium, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, gold, and combinations thereof. The method of claim 24, wherein the element is selected from the group consisting of ruthenium, cobalt, nickel, and combinations thereof. For example, the method of claim 25, wherein the element is 钌. The method of claim 25, wherein the element is nickel. The method of claim 22, wherein at least one metal and/or compound of the selected element is applied to at least one carrier selected from the group consisting of inorganic oxides, inorganic hydroxides , inorganic halides, inorganic carbides, inorganic nitrides, inorganic sulfates, inorganic hydrogen sulfates, inorganic phosphates, inorganic hydrogen phosphates, inorganic carbonates, inorganic hydrogencarbonates, active Carbon, naturally occurring organic materials or organically synthesized compounds with high molecular weight and any mixtures thereof. The method of claim 28, wherein the at least one carrier is selected from the group consisting of inorganic oxides, activated carbons, and any mixtures thereof. The method of claim 29, wherein the inorganic oxide is selected from the group consisting of: vanadium, vermiculite, zirconium, tungsten oxide, and any combination thereof. The method of claim 30, wherein the inorganic oxide is selected from the group consisting of vermiculite, vermiculite-vanadium, vanadium, zirconium- vermiculite, and zirconium-tungsten oxide. The method of claim 21, wherein the catalyst is in the form of a group selected from the group consisting of a cyclic species, a bead, a sphere, a saddle, a pellet. Classes, tablets, extrudates, granules, crushed materials, flakes, honeycombs, filaments, cylinders, polygons, and any mixtures thereof. The method of claim 21, wherein the catalyst is in the form of a powder. The method of claim 21, wherein the catalyst is selected from the group consisting of palladium supported on vanadium, niobium supported on vanadium, niobium supported on vermiculite, supported on zircon - gold and palladium on vermiculite, platinum supported on zirconia-tungsten oxide, ruthenium-ruthenium supported on vermiculite, and any mixture thereof. The method of claim 34, wherein the catalyst is supported on ruthenium on alumina. The method of claim 21, wherein the catalyst is a framework metal catalyst. The method of application of the group 36 of patentable scope, wherein the skeletal metal catalyst is selected from the group consisting of Raney ^® Catalyst: Raney ^® iron, Raney ^® cobalt, Raney ^® Nickel, Raney ^® copper, Raney ^® ruthenium, Raney ^® Palladium, Raney ^® Platinum, Raney ^® Molybdenum - Nickel, Raney ^® Chromium - Nickel and any mixture thereof. The group of 37 to apply the scope of patents, Raney ^® wherein the catalyst is selected from the group consisting of: Raney ^® Nickel, cobalt, and Raney ^® any mixtures thereof. The patentable scope of application of the method of 38, wherein the catalyst is Raney ^® Nickel Raney ^® system. The method of claim 1 or 2, wherein the reaction is carried out in at least one liquid phase. For example, the method of claim 40, wherein the reaction is It is carried out in the presence of at least one solvent. The method of claim 41, wherein the solvent is selected from the group consisting of water, alcohol, and any mixture thereof. The method of claim 42, wherein the alcohol is selected from the group consisting of alcohols of 1 to 20 carbon atoms. The method of claim 43, wherein the alcohol is selected from the group consisting of methanol, ethanol, isopropanol, hexanol, dodecanol, 1,2-propanediol, 1,3-propanediol , glycerin and any mixture thereof. The method of claim 42, wherein the solvent is water. The method of claim 41, wherein the ratio between the solvent and the monochloropropanediol is 10% or more by weight percent. The method of claim 46, wherein the ratio between the solvent and the monochloropropanediol is greater than or equal to 50% by weight. The method of claim 47, wherein the ratio between the solvent and the monochloropropanediol is greater than or equal to 90% by weight. The method of claim 40, wherein the at least one liquid phase comprises less than 90% of the basic compound relative to the monochloropropanediol, the percentage being expressed as the equivalent of the alkaline reagent per equivalent of monochloropropanediol. Such as the method of claim 49, wherein the alkalization The content of the compound is less than or equal to 50%. The method of claim 50, wherein the basic compound is less than or equal to 10%. The method of claim 51, wherein the basic compound is less than or equal to 1%. The method of claim 52, wherein the basic compound is less than or equal to 0.01%. The method of claim 49, wherein the basic compound is selected from the group consisting of oxides, hydroxides, carbonates, hydrogencarbonates, phosphoric acid of alkali metals and alkaline earth metals Salts, hydrogen phosphates, and borates, and mixtures thereof. The method of claim 54, wherein the alkaline agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, and any mixture thereof. The method of claim 1 or 2, wherein the reaction is carried out in the gas phase. The method of claim 56, wherein the gas phase comprises a diluent selected from the group consisting of water, alcohol, and any mixture thereof. The method of claim 57, wherein the alcohol is selected from the group consisting of alcohols of 1 to 20 carbon atoms. The method of claim 58, wherein the alcohol is selected from the group consisting of methanol, ethanol, isopropanol, hexanol, dodecanol, 1,2-propanediol, 1,3-propanediol , glycerin and any mixture thereof Things. The method of claim 59, wherein the diluent is water. The method of claim 56, wherein the gas phase comprises a hydrogen chloride acceptor. The method of claim 1 or 2, wherein the reaction is carried out at a temperature higher than or equal to 25 ° C and lower than or equal to 400 ° C. The method of claim 62, wherein the reaction is carried out at a temperature higher than or equal to 100 ° C and lower than or equal to 300 ° C. The method of claim 63, wherein the reaction is carried out at a temperature higher than or equal to 120 ° C and lower than or equal to 200 ° C. The method of claim 64, wherein the reaction is carried out at a temperature higher than or equal to 140 ° C and lower than or equal to 180 ° C. The method of claim 1 or 2, wherein the reaction is carried out at a partial pressure of hydrogen of greater than or equal to 1 bar absolute and less than or equal to 400 bar absolute. The method of claim 66, wherein the reaction is carried out at a partial pressure of hydrogen of greater than or equal to 10 bar absolute and less than or equal to 200 bar absolute. The method of claim 67, wherein the reaction is carried out at a partial pressure of hydrogen of greater than or equal to 50 bar absolute and less than or equal to 100 bar absolute. For example, the method of claim 40, wherein the reaction is It is carried out in a trickle bed reactor. The method of claim 40, wherein the reaction is carried out in a slurry reactor. A method for producing a polymer selected from the group consisting of polyesters, polyethers, polyurethanes, and any mixtures thereof, the method comprising: utilizing, as claimed in claim 1 or 2 The method of the present invention obtains propylene glycol containing 1,3-propanediol, and the propylene glycol is reused as a raw material. The method of claim 71, wherein the polymer-based polyester, and the propylene glycol comprising the 1,3-propanediol, are subjected to a reaction with a carboxylic acid and/or a carboxylic acid ester. The method of claim 72, wherein the carboxylic acid is an aromatic dicarboxylic acid. The method of claim 72, wherein the carboxylic acid ester is an aromatic dicarboxylic acid ester. The method of claim 73, wherein the substituted aromatic carboxylic acid is terephthalic acid. The method of claim 74, wherein the substituted aromatic carboxylic acid ester is a terephthalic acid ester. The method of claim 76, wherein the substituted aromatic carboxylic acid ester is dimethyl terephthalate. The method of claim 71, wherein the polymer exhibits ¹⁴ C/ ¹² C greater than or equal to 0.33 10 ^-12 . The method of claim 78, wherein the polymer A polyester. A polyester exhibiting ¹⁴ C/ ¹² C higher than or equal to 0.33 10 ^-12 . The polyester of claim 80, which is obtained by the method of any one of claims 72 to 79. A method for producing a polyester fiber, the method comprising: obtaining a polyester by a method as in claim 72 of the patent application, and converting the polyester into a fiber.