EP3649100A1 - Hydrogénation de composés aromatiques - Google Patents

Hydrogénation de composés aromatiques

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Publication number
EP3649100A1
EP3649100A1 EP18740917.2A EP18740917A EP3649100A1 EP 3649100 A1 EP3649100 A1 EP 3649100A1 EP 18740917 A EP18740917 A EP 18740917A EP 3649100 A1 EP3649100 A1 EP 3649100A1
Authority
EP
European Patent Office
Prior art keywords
reactor
catalyst
hydrogenation
aromatic
operated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP18740917.2A
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German (de)
English (en)
Inventor
Frank Poplow
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
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Publication of EP3649100A1 publication Critical patent/EP3649100A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1812—Tubular reactors
    • B01J19/1837—Loop-type reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1812—Tubular reactors
    • B01J19/1843—Concentric tube
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/32—Packing elements in the form of grids or built-up elements for forming a unit or module inside the apparatus for mass or heat transfer
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/78—Benzoic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80—Phthalic acid esters
    • C07C69/82—Terephthalic acid esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00162—Controlling or regulating processes controlling the pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/185—Details relating to the spatial orientation of the reactor vertical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/75—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids

Definitions

  • the present invention relates to a process for the hydrogenation of aromatic compounds on a solid catalyst, in particular to a process for the preparation of alicyclic carboxylic acid esters by hydrogenating the corresponding aromatic carboxylic esters on a solid catalyst.
  • Methods for the hydrogenation of aromatic compounds are of central importance in the chemical industry. They serve, for example, the preparation of alicyclic carboxylic acids or alicyclic carboxylic acid esters by hydrogenation of aromatic carboxylic acids or aromatic carboxylic acid esters.
  • Alicyclic carboxylic esters such as the esters of cyclohexane-1, 2-dicarboxylic acid, are used as a component of lubricants, adhesives, paints or varnishes, or as auxiliaries in metalworking. Furthermore, they are used as plasticizers for polyolefins or PVC use. Methods for the hydrogenation of aromatic carboxylic acid esters to the corresponding alicyclic carboxylic acid esters are known to those skilled in the art.
  • DE 102 32 868 A1 or DE 102 25 565 A1 describes the hydrogenation of aromatic polycarboxylic acid esters in two reactors connected in series, the first reactor being operated in loop mode (partial recycling of the reactor effluent) and the second reactor in straight pass.
  • the hydrogenation is carried out in the liquid / gas mixed phase or liquid phase.
  • the improved process should make it possible to make better use of the catalyst.
  • An improved catalyst utilization is evident, for example, in the fact that, with the same hydrogenation temperature, a higher hydrogenation conversion is achieved or, for a certain hydrogenation conversion, a lower hydrogenation temperature is necessary.
  • a certain hydrogenation conversion can be achieved with a lower hydrogenation temperature
  • the lifetime of the catalyst is increased, for example, so that longer service intervals should be possible.
  • a lower hydrogenation temperature should contribute to less by-product formation.
  • the object is achieved by a process for the hydrogenation of aromatic compounds on a solid catalyst in the presence of a hydrogen-containing gas, comprising a first reactor which is operated in loop fashion, a second reactor operated in a straight pass,
  • the first reactor is designed as a trickle bed reactor and is operated in trickle bed mode
  • the hydrogenation of the aromatic compounds is carried out continuously or batchwise. It is preferred that the hydrogenation is carried out continuously.
  • Aromatic compounds are hydrogenated in the process according to the invention to their alicyclic compounds.
  • Aromatic compounds which can be used in the process according to the invention are, for example, phenols, aromatic carboxylic acids or aromatic carboxylic esters.
  • Aromatic carboxylic acids or aromatic carboxylic esters are preferred.
  • Aromatic carboxylic acid esters are particularly preferred.
  • Aromatic carboxylic acids may have one or more carboxylic acid groups.
  • aromatic carboxylic acids have one, two or three carboxylic acid groups. The carboxylic acid groups are connected via their carbonyl carbon with an aromatic ring.
  • Aromatic carboxylic acids have one or more aromatic rings. For example, in the case of multiple aromatic rings, the aromatic rings may be fused and / or bridged. If the aromatic carboxylic acid has several aromatic rings and several carboxylic acid groups, the carboxylic acid groups may be on one aromatic ring or on different aromatic rings.
  • Aromatic carboxylic acids having a carboxylic acid group are referred to as aromatic monocarboxylic acids.
  • Aromatic monocarboxylic acids are, for example, benzoic acid or 1-naphthoic acid, with benzoic acid being preferred.
  • Aromatic carboxylic acids having two carboxylic acid groups are referred to as aromatic dicarboxylic acids.
  • Aromatic dicarboxylic acids are, for example, phthalic acid, isophthalic acid, terephthalic acid, 1, 2-naphthalenedicarboxylic acid, 1, 3-naphthalenedicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 1, 7-naphthalenedicarboxylic acid or 1, 8-naphthalenedicarboxylic acid, where phthalic acid, isophthalic acid or terephthalic acid are preferred.
  • Aromatic carboxylic acids having more than two carboxylic acid groups are referred to as aromatic polycarboxylic acids.
  • Aromatic polycarboxylic acids are, for example, hemimellitic acid, trimellitic acid, trimesic acid or benzene-1,2,3,4-tetracarboxylic acid, with trimellitic acid being preferred.
  • Aromatic carboxylic acid esters are obtained, for example, by esterification of aromatic carboxylic acids with alcohols or by transesterification of aromatic carboxylic acid esters. If an aromatic carboxylic acid has more than one carboxylic acid group, it is generally preferable to esterify as much as possible each carboxylic acid group.
  • the carboxylic acid groups can be independently esterified with the same or with different alcohols. In general, it is preferred that the carboxylic acid groups be esterified with the same alcohol or with a mixture of isomers of an alcohol.
  • An alcohol is a single chemical compound or a mixture of isomers.
  • An alcohol may have one or more hydroxy groups.
  • An alcohol that has a hydroxy group is called a monool.
  • An alcohol having two hydroxy groups is called a diol.
  • An alcohol containing more than two hydroxy groups is called a polyol.
  • An alcohol preferably has 1 to 18, more preferably 3 to 13, particularly preferably 8 to 13 and most preferably 9 carbon atoms.
  • an alcohol is linear or branched.
  • An alcohol is, for example, an alkyl, cycloalkyl or alkoxyalkyl alcohol. It is preferred that an alcohol is an alkyl alcohol. It is further preferred that an alcohol is an alkylmonool.
  • alkylmonool having 8 to 13 carbon atoms is, for example, n-octanol, isooctanoyl, 2-ethylhexanol, n-nonanol, 2-propylhexanol, isononanol, n-decanol, isodecanol, 2-propylheptanol, n Undecanol, iso-undecanol, n-dodecanol, iso-dodecanol, n-tridecanol or iso-tridecanol.
  • Alkyl monools with 9 carbon atoms are preferred. Iso-nonanol is particularly preferred.
  • Iso-octanol, iso-nonanol, iso-decanol, iso-undecanol, iso-dodecanol or iso-tridecanol is not a single compound but a mixture of different isomers.
  • the exact composition of such an isomer mixture depends on the preparation conditions and / or the starting compounds used. Depending on The production conditions and / or the starting compounds used are disclosed in WO 2015/082676 exemplary compositions of possible isomer mixtures.
  • Aromatic carboxylic esters having an ester group are referred to as aromatic monocarboxylic acid esters.
  • Aromatic monocarboxylic acid esters are, for example, phthalic acid monomethyl ester, phthalic monoglycol ester, monomethyl terephthalate, monoglycol terephthalate, monomethyl isophthalate or monoglycoside of isophthalic acid.
  • Aromatic monocarboxylic esters are, for example, esters of benzoic acid. Benzoic acid can be esterified with monools, diols or polyols.
  • esters of benzoic acid with monools are iso-octyl benzoate, 2-ethylhexyl benzoate, isononyl benzoate, isodecyl benzoate or 2-propyl heptylbenoate.
  • esters of benzoic acid with diols are glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol dibenzoate or propylene glycol dibenzoate.
  • aromatic monocarboxylic acid esters iso-nonylbenzoate, iso-decylbenzoate or 2-propylheptylbenzoate are preferred. Iso-nonyl benzoate or iso-decyl benzoate are particularly preferred.
  • Aromatic carboxylic acid esters having two ester groups are referred to as aromatic dicarboxylic acid esters.
  • Aromatic dicarboxylic acid esters are, for example, phthalic acid diesters, isophthalic diesters, terephthalic diesters, 1,2-naphthalenedicarboxylic acid diesters, 1,3-naphthalenedicarboxylic acid diesters, 1,4-naphthalenedicarboxylic acid diesters, 1,5-naphthalenedicarboxylic acid diesters, 1,7-naphthalenedicarboxylic acid diesters or 1,8-naphthalenedicarboxylic acid diesters.
  • phthalic diesters or terephthalic diesters are preferred. Phthalic diesters are particularly preferred.
  • Phthalic acid diesters are, for example, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, di-iso-butyl phthalate, di-tert-butyl phthalate, phthalic acid diglycol ester, n-octyl phthalate, phthalic acid. iso-octyl ester, di-2-ethylhexyl phthalate, di-naphthalenyl phthalate, di-iso-nonyl thiol.
  • Phthalic diisonyl ester, phthalic diisodecyl or phthalic di-2-propylheptyl ester are preferred.
  • Di-iso-nonyl phthalate or di-2-propylheptyl phthalate are further preferred.
  • Di-iso-nonyl phthalate is particularly preferred.
  • Terephthalic acid diesters are, for example, terephthalic acid dimethyl ester, terephthalic acid di-n-propyl ester, terephthalic acid di-isopropyl ester, terephthalic acid di-n-butyl ester, di-iso-terephthaloyl terephthalate, tert-butyl terephthalate, terephthalic acid diglycol ester, n-octyl terephthalate , Terephthalic acid iso-octyl ester, terephthalic di-2-ethylhexyl ester, di-n-nonyl terephthalate, di-iso-nonyl terephthalate, di-n-decyl terephthalate, di-isodecyl terephthalate, di-2-propyl heptyl terephthalate, terephthalic di-n-terephthalate -und
  • diiso-nonyl phthalate diiso-nonyl phthalate, phthalic diisodecyl, di-2-propylheptyl phthalate or di-2-ethylhexyl terephthalate are preferred. Phthalic di-iso-nonyl ester or terephthalic di-2-ethylhexyl ester are more preferred. Di-iso-nonyl phthalate is particularly preferred.
  • Aromatic carboxylic acid esters having more than two ester groups are also referred to as aromatic polycarboxylic acid esters.
  • Aromatic polycarboxylic acid esters are obtained, for example, by esterification of hemimellitic acid, trimellitic acid, trimesic acid or benzene-1, 2,3,4-tetracarboxylic acid with an alcohol or a mixture of alcohols.
  • the main products obtained by the process according to the invention by hydrogenation of the aromatic compounds depend, for example, on the hydrogenation conditions, such as temperature and / or pressure and / or the catalyst used.
  • the main products of hydrogenation are also referred to as hydrogenation products in the context of the present invention.
  • the alicyclic compounds are obtained as hydrogenation products. If the aromatic compounds are aromatic carboxylic acids, the alicyclic carboxylic acids are obtained as hydrogenation products. When the aromatic compounds are aromatic carboxylic acid esters, the alicyclic carboxylic esters are obtained as the hydrogenation products.
  • di- (isononyl) -1,2-cyclohexanedicarboxylate as the hydrogenation product from di-2-propyl heptyl phthalate di (2-propylheptyl) -1,2-cyclohexanedicarboxylate as hydrogenation product can be prepared by the process according to the invention from phthalic diiso-nonyl ester , from phthalic-di-iso-decylphthalate di-2 (isodecyl) -1, 2-cyclohexandicarboxalt or from terephthalic di-2-ethylhexyl di- (2-ethylhexyl) -1, 4-cyclohexanedicarboxylate obtained as the hydrogenation.
  • the aromatic compounds are hydrogenated on a solid catalyst in the presence of a hydrogen-containing gas. It is preferable that the aromatic compounds are hydrogenated continuously on a solid catalyst in the presence of a hydrogen-containing gas.
  • the catalyst is arranged in a fixed bed as a random bed or as a packing in the first and second reactor. It is further preferred that the catalyst in the fixed bed is arranged as a random bed in the first and second reactor.
  • a reactor may contain one or more catalyst beds connected in series. For multiple series catalyst beds, the length of the catalyst beds may vary. It is preferred that the catalyst volume is divided in a ratio of 85:15 to 60:40 between the first and second reactor.
  • the catalyst preferably contains metals and / or metal oxides of VI. to VIII.
  • the Periodic Table of the Elements in particular platinum, rhodium, palladium, cobalt, nickel and / or ruthenium as the catalytically active component, with ruthenium being particularly preferred.
  • Such a catalyst may also metals and / or metal oxides of the V. or IX.
  • Subgroup of the Periodic Table of the Elements in particular rhenium and / or copper.
  • the metals and / or metal oxides may be deposited on a support material. If the metals and / or metal oxides are deposited on a support material, a support material having an average pore diameter which is in the range from 2 to 50 nm is generally used in the preparation of such a catalyst (the determination of the average pore diameter is carried out by HG). Porosimetry, in particular according to DIN 66133).
  • the support material can comprise activated carbon, silicon carbide, aluminum oxide, silicon oxide, aluminosilicate, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide or a mixture of two or more of the stated components.
  • the support material may also contain alkali metals, alkali metal oxides, alkaline earth metals, alkaline earth metal oxides and / or sulfur.
  • Catalysts which are preferred for the hydrogenation of aromatic compounds, in particular aromatic carboxylic acids or aromatic carboxylic acid esters, are described, for example, in EP-B1 1042273B1, DE-A 10232868, DE-A 10225565 or EP-A2 1676828.
  • a preferred catalyst has, for example, a Ru content of 0.45 to 0.55 percent by weight based on the weight of the support material, a specific surface area of 220 to 290 m 2 / g (BET, ISO 9277) and a pore volume of 0.48 to 0 , 62 ml / g (Hg porosimetry, DIN 66133), the support material comprises alumina.
  • Another, preferred catalyst has for example a Ru content of 0.3 to 0.45 weight percent based on the weight of the support material, a specific surface area of 310 to 360 m 2 / g (BET, ISO 9277) and a pore volume of 0, 7 to 0.9 ml / g (Hg porosimetry, DIN 66133), the support material comprises silicon oxide.
  • a hydrogen-containing gas is any hydrogen-containing gas mixture that does not contain harmful amounts of catalyst poisons such as carbon monoxide and / or sulfur compounds.
  • a hydrogen-containing gas may contain an inert medium.
  • An inert medium does not react with the starting materials, products and the catalyst under the reaction conditions.
  • An inert medium may be nitrogen, methane, helium, argon, or a mixture of these.
  • It is preferred that as hydrogen-containing gas as pure as possible hydrogen is used.
  • pure hydrogen as possible has a purity of at least 90 percent, preferably at least 95 percent and more preferably at least 98 percent.
  • the use of hydrogen which is as pure as possible has the advantage that the accumulation of the inert medium in the reaction space is reduced. A purging of the inert medium in the reaction space would lead to a reduction of the hydrogen partial pressure, which would have a negative effect on the space-time yield of the hydrogenation reaction.
  • aromatic compounds preferably aromatic carboxylic acid esters
  • a hydrogen-containing gas having a hydrogen content of at least 95 percent and preferably at least 98 percent.
  • the amount of hydrogen used in the process according to the invention is at least equal to the stoichiometric amount needed to hydrogenate the aromatic compounds. However, it is preferred to use an excess of up to 30 percent above the stoichiometrically required amount for hydrogenation. It is further preferred that an excess of up to 20 percent, and more preferably an excess of up to 10 percent, be used above the stoichiometrically required amount.
  • the process according to the invention for the hydrogenation of the aromatic compounds comprises a first reactor which is operated in a loop mode and a second reactor which is operated in a straight run.
  • the second reactor is connected to the first reactor in such a way that at least part of the discharge of the first reactor is fed to the second reactor.
  • the first and the second reactor is a tubular reactor, in particular a vertical tubular reactor. It is also preferred that the first and the second reactor have no heating or cooling devices.
  • first reactor which is operated in loop mode
  • second reactor which is operated in a straight pass
  • a plurality of reactors which are operated in a straight pass and are connected in series or in parallel.
  • Each of the reactors may contain one or more catalyst beds with the catalyst beds connected in series.
  • the catalyst beds can vary in length.
  • the first loop-type reactor is designed as a trickle bed reactor and is operated in trickle bed mode. Although not preferred, it is generally possible to operate the first reactor as a loop reactor in the upflow mode.
  • the first reactor is supplied with circulating current and fresh feed.
  • the circulating current can be mixed with the fresh feed, for example, and the mixture fed to the first reactor.
  • Circulating flow and fresh feed can also be fed separately to the first reactor.
  • the fresh feed contains aromatic compounds which are to be hydrogenated in the context of the process according to the invention.
  • the liquid loading of the catalyst with fresh feed is preferably from 50 to 1000 kg of fresh air / (hour * m 3Polkatai y satorvoiumen).
  • the total catalyst volume is the catalyst volume distributed over the reactors used. It is further preferred that the liquid loading of the catalyst with fresh feed 100 to 500 kg Fr (m * 3Polkataiysat OWO iumen hour) is ischzuiauf /.
  • the feed preferably has a temperature of 70 to 150 ° C and more preferably a temperature of 80 to 120 ° C, when it is fed to the first reactor. For example, the feed has a temperature of 85, 90, 95, 100, 105, 110 or 15 ° C.
  • the circulating stream and the fresh feed are fed separately to the first reactor, they have, independently of one another, preferably a temperature of from 70 to 150 ° C. and more preferably a temperature of from 80 to 120 ° C.
  • the circulating current and the fresh feed can independently of one another have a temperature of 85, 90, 95, 100, 105, 110 or 15 ° C.
  • the discharge of the first reactor is separated into a circulation stream and a hydrogenation stream.
  • the circulating stream is returned to the first reactor, the hydrogenation stream is fed to the second hydrogenation in the second reactor.
  • the separation of the discharge from the first reactor into a circulating stream and into a hydrogenation stream can be carried out by methods known in the art for stream splitting, for example by means of a pump template with overflow, or a flow divider. It is preferred that the circulating stream is cooled before being returned to the first reactor.
  • the discharge is taken from the first reactor in the lower part, for example at the bottom.
  • the circulation ratio between the circulation stream and the hydrogenation stream is preferably 1: 1 to 20: 1. It is further preferred that the circulation ratio is 2: 1 to 15: 1. It is particularly preferred that the circulation ratio is 4: 1 to 10: 1. For example, the circulation ratio is 5: 1, 6: 1, 7: 1, 8: 1 or 9: 1.
  • the hydrogenation conversion of the aromatic compounds is preferably 80 to 98 percent based on the total hydrogenation conversion in the first and second reactor, more preferably 85 to 95 percent. If, for example, aromatic carboxylic acids or aromatic carboxylic esters are used as aromatic compounds, the hydrogenation conversion is preferably 80 to 98 percent, based on the total hydrogenation conversion in the first and second reactor and more preferably 85 to 95 percent. For example, the hydrogenation conversion in the first reactor is 86, 88, 90, 92 or 94 percent. Since the discharge of the first reactor usually has a higher temperature than the fresh feed when it is fed to the first reactor, the discharge of the first reactor can be cooled before it is separated into a circulating stream and a hydrogenation stream.
  • the circulation can be cooled after separation of the discharge from the first reactor.
  • the cooling of the discharge and / or the circulating current can take place in one or more heat exchangers. It may be advantageous to heat-couple the cooling of the discharge and / or the circulating current with the heating of the fresh feed.
  • the circulation ratio between the circulating stream and the fresh feed is preferably 1: 1 to 20: 1 in the first reactor. It is further preferred that the circulation ratio is 2: 1 to 15: 1. It is particularly preferred that the circulation ratio is 4: 1 to 10: 1. For example, the circulation ratio may be 5: 1, 6: 1, 7: 1, 8: 1 or 9: 1.
  • Circulating flow and fresh feed are fed to the first reactor in such a way that the most uniform distribution of the liquids across the reactor cross-section is ensured.
  • This has the advantage of a uniform catalyst utilization as possible.
  • the supply of circulating current and fresh feed can take place via one or more, distributed over the reactor cross-section, feeders.
  • the feeds are located in the upper part of the reactor, above the catalyst.
  • one or more distribution devices, such as distributor plates, can be arranged in the reactor above the catalyst and below the feeders.
  • the liquid loading of the catalyst (empty tube velocity) in the first reactor is preferably 30 to 180 m / h, more preferably 50 to 150 m / h and particularly preferably 60 to 120 m / h.
  • the empty tube velocity in the first reactor is 70, 80, 85, 90, 95, 100, 105, 110 or 15 m / h.
  • a sufficiently high liquid load ensures complete wetting of the entire catalyst bed. This avoids that liquid strands form and a portion of the catalyst remains unused.
  • the higher the liquid load the more intensive the mass transfer becomes. As a result, for example, the space-time yield can be positively influenced.
  • the hydrogenation of the aromatic compounds may be carried out in the absence or in the presence of an inert solvent.
  • Suitable inert solvents are all liquids which, under the reaction conditions, do not react with the educts, products and the catalyst, which form homogeneous solutions with the educts and products and can easily be separated off from the products.
  • the inert solvent may also be a mixture of different liquids.
  • An inert solvent may be, for example, the hydrogenation product of the particular hydrogenation proceeding, an isomer mixture of long-chain hydrocarbons, or an isomer mixture of alcohols having 9 to 13 carbon atoms.
  • the use of an inert solvent has the advantage, for example, that the temperature development of the hydrogenation can be better controlled.
  • the inert solvent with the circulating stream and / or the fresh feed can be fed to the first reactor.
  • the inert solvent can be mixed with the circulating stream and / or the fresh feed before the resulting mixture is fed to the first reactor.
  • the first reactor has a plurality of catalyst beds connected in series, the inert solvent can also be supplied to the first reactor between the catalyst beds. This can be done regardless of whether inert solvent with the circulating stream and / or the fresh feed is fed to the first reactor. If the inert solvent is fed between the catalyst beds to the first reactor, this can be mixed with hydrogen-containing gas.
  • the hydrogen-containing gas is fed to the first reactor.
  • the hydrogen-containing gas is fed separately or mixed with the circulating stream and / or fresh feed to the first reactor. It is preferred that the hydrogen-containing gas is fed to the first reactor separately from the circulating stream and / or fresh feed. If the hydrogen-containing gas is supplied separately to the first reactor, it can take place via one or more feeders distributed over the reactor cross-section.
  • the hydrogen-containing gas is supplied to the first reactor in the same or countercurrent, wherein it is preferred that the hydrogen-containing gas is supplied to the first reactor in cocurrent. If the hydrogen-containing gas is supplied to the first reactor in cocurrent, one or more feeds for the hydrogen-containing gas are usually in the upper part of the reactor, above the catalyst.
  • the first reactor has a plurality of catalyst beds connected in series, part of the hydrogen-containing gas can also be fed between the catalyst beds to the first reactor.
  • the hydrogen-containing gas can be fed to the first reactor directly or mixed with an inert solvent.
  • the hydrogenation of the aromatic compounds in the first reactor may be carried out adiabatically, polytropically or practically isothermally, that is with a temperature rise of typically less than 10 to 15 ° C.
  • the hydrogenation of the aromatic compounds in the first reactor largely adiabatically.
  • the hydrogenation of the aromatic compounds is carried out so that the discharge at the exit from the first reactor preferably has a temperature of 90 to 180 ° C or less. It is further preferred that the discharge at the exit from the first reactor has a temperature of 90 to 160 ° C or less.
  • the temperature of the discharge at the exit from the first reactor is, for example, from the temperature of the fresh feed, from the temperature of the circulating stream fed to the first reactor, from the hydrogenation conversion in the first reactor, from the ratio of fresh feed to circulation flow and / or from the ratio between hydrogenation flow Circulating current dependent.
  • the pressure in the first reactor is preferably 50 to 500 bar, more preferably 100 to 400 bar and particularly preferably 200 to 280 bar.
  • the pressure in the first reactor may be 210, 220, 230, 240, 250, 260 or 270 bar.
  • the pressure in the first reactor is preferably 50 to 500 bar, more preferably 100 to 400 bar, particularly preferably 150 to 300 bar and particularly preferably 200 to 280 bar.
  • the pressure in the first reactor may be 210, 220, 230, 240, 250, 260 or 270 bar.
  • the second reactor is operated in a straight run.
  • the catalyst in the second reactor is partially flooded. It is preferred that the non-flooded part of the catalyst in the second reactor is operated in trickle mode.
  • a flooding of the catalyst can be generated by damming of the inlet of the second reactor and standing position. Methods for the stagnation and maintenance of liquids in reactors or in containers are known in the art.
  • the degree of flooding of the catalyst can be controlled for example by a differential pressure measurement in combination with a control of the discharge volume flow from the second reactor.
  • a partial flooding of the catalyst part of the catalyst volume is surrounded by a continuous liquid phase.
  • the catalyst in the second reactor is flooded such that 10 to 98 percent of the catalyst volume is surrounded by a continuous liquid phase. It is further preferred that 15 to 95 percent of the catalyst volume is surrounded by a continuous liquid phase. It is particularly preferred that 50 to 95 percent of the catalyst volume is surrounded by a continuous liquid phase.
  • 55, 60, 65, 70, 75, 80, 85 or 90 percent of the catalyst volume may be surrounded by a continuous liquid phase.
  • the hydrogenation stream forms the inlet of the second reactor.
  • the hydrogenation stream is fed to the second reactor in the upper part of the reactor, above the catalyst. It is preferred that the hydrogenation stream is fed to the second reactor in such a way that the most uniform possible distribution of the hydrogenation stream over the reactor cross-section is ensured. This has the advantage of a uniform catalyst utilization as possible.
  • the feed of the hydrogenation stream can take place via one or more distributors distributed over the reactor cross-section.
  • the feeds are located in the upper part of the reactor, above the catalyst.
  • the hydrogenation stream preferably has a temperature of 80 to 180 ° C and more preferably a temperature of 90 to 160 ° C, when it is fed to the second reactor.
  • the hydrogenation stream may have a temperature of 95, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150 or 155 ° C when fed to the second reactor.
  • it can be heated or cooled, for example by means of a heat exchanger.
  • the second reactor in the form of a vertical tubular reactor comprises a free space in the upper part and a first and a second compartment in the lower part.
  • the first compartment is configured as an upwardly open cylinder and forms an annular space.
  • the second compartment forms an annular gap space surrounding the annulus.
  • the first compartment is arranged substantially concentrically in the second reactor.
  • the outer wall of the first compartment and the inner wall of the second reactor form the annular gap space.
  • the annular space and the annular space surrounding the annular space are open to the upper part of the reactor.
  • the annular space and the annular space surrounding the annular space are not fluidly connected to each other in the plane of their cross-sections.
  • the lower part of the second reactor preferably extends over the lower 30 to 80 percent of the internal volume of the reactor.
  • the upper part of the second reactor preferably extends over the upper 70 to 20 percent of the internal volume of the reactor.
  • the discharge of the first reactor is fed to the second reactor in the upper part of the second reactor in the region of free space.
  • the discharge of the first reactor is preferably fed to the second reactor in such a way that the most uniform possible distribution of the discharge of the first reactor over the reactor cross section of the second reactor is ensured.
  • the feed of the discharge from the first reactor can take place via one or more feeders distributed over the reactor cross-section.
  • the feeders are located in the upper part of the reactor in the area of free space. Also in the upper part and below the feeders can be arranged one or more distribution devices, such as distribution plates.
  • the catalyst is arranged either in the annular space or in the annular gap space. It is preferred that the catalyst is arranged in the annulus.
  • the annulus or annulus may contain one or more catalyst beds. If the annular space or annular gap space contains a plurality of catalyst beds, these are usually connected in series. The length of the individual catalyst beds can vary.
  • the compartment containing the catalyst is run in a straight pass with the catalyst partially flooded.
  • the part of the catalyst which is not flooded is preferably operated in trickle mode.
  • the compartment, which does not contain the catalyst is fluidly connected to the first reactor.
  • the part of the feed of the second reactor, which is supplied to this compartment, is at least partially recycled to the first reactor and thus constitutes the circuit.
  • the second reactor in the form of a vertical tubular reactor formed as a substantially concentrically arranged, upwardly open cylinder first compartment for receiving the catalyst and an annular space formed between the outer wall of the first compartment and the inner wall of the reactor second Compartment for receiving a liquid phase volume comprises. It is further preferred that the second compartment is liquid-conductively connected to the first reactor.
  • the second compartment is connected to the first compartment in a fluid-continuous manner via an overflow.
  • the discharge from the first reactor is supplied to the second reactor in such a way that the entire feed of the second reactor is first fed to the second compartment.
  • This can be achieved for example by a suitable arrangement of the feeders and / or distribution devices.
  • Such an arrangement has the advantage that in the second compartment always a volume of liquid is kept. Only when a certain liquid level is reached does liquid phase pass from the second compartment into the first compartment and pass through the catalyst arranged therein. It is preferred to design the overflow in such a way that the most uniform possible distribution of the liquid passing over the catalyst is made possible.
  • the second reactor is described, for example, in DE 100 36 172 A1, to the contents of which reference is made in full to the second hydrogenation reactor described therein.
  • the second compartment is connected in a fluid-conducting manner to the first reactor, with which at least part of the feed into the second compartment is recycled as a circulating stream into the first reactor.
  • the discharge from the first reactor, which is fed to the second reactor is separated within the second reactor into a circulating stream and into a hydrogenating stream.
  • the part of the discharge of the first reactor, which is supplied to the compartment containing the catalyst within the second reactor, thereby represents the hydrogenation flow.
  • the part of the discharge of the first reactor, which is taken within the second reactor the compartment containing no catalyst and recycled to the first reactor represents the circulating current.
  • the liquid loading of the catalyst (empty tube velocity) in the second reactor is preferably 5 to 100 m / h, more preferably 10 to 80 m / h and particularly preferably 15 to 70 m / h.
  • the liquid loading of the catalyst in the second reactor is, for example, 20, 25, 30, 35, 40, 45, 50, 55, 60 or 65 m / h.
  • the hydrogenation of the aromatic compounds in the second reactor may be carried out adiabatically, polytropically or practically isothermally, that is with a temperature rise of typically less than 10 to 15 ° C. In general, it is preferred to carry out the hydrogenation of the aromatic compounds adiabatically in the second reactor.
  • the hydrogenation of the aromatic compounds is carried out so that the discharge at the outlet from the second reactor has a temperature of 220 ° C or less. It is preferable that the discharge at the exit from the second reactor has a temperature of 180 ° C or less.
  • the discharge at the outlet from the second reactor for example, have a temperature of 100 to 220 ° C.
  • the discharge at the outlet from the second reactor may have a temperature of 100 to 180 ° C.
  • the discharge is taken from the second reactor in the lower part, for example at the bottom. If the second reactor has a first and a second compartment, the discharge is taken from the compartment containing the catalyst. The discharge is preferably removed in the lower part of the corresponding compartment, for example on the ground.
  • the pressure in the second reactor is preferably 50 to 500 bar. It is further preferred that the pressure in the second reactor is 100 to 400 bar, more preferably 200 to 280 bar.
  • the pressure in the second reactor is preferably 50 to 500 bar, more preferably 100 to 400 bar and particularly preferably 210 to 280 bar.
  • the pressure in the second reactor may be 220, 230, 240, 250, 260 or 270 bar.
  • the first and the second reactor have a common pressure maintenance and therefore present comparable pressures in both reactors.
  • the pressures in the first and second reactor differ by a maximum of 10 bar, preferably by a maximum of 2 bar.
  • the hydrogenation conversion in the second reactor is preferably 2 to 20 percent, based on the total hydrogenation conversion in the first and second reactor, more preferably 5 to 15 percent. If, for example, aromatic carboxylic acids or aromatic carboxylic esters are used as aromatic compounds, the hydrogenation conversion in the second reactor is preferably 2 to 20 percent, based on the total hydrogenation conversion in the first and second reactor, more preferably 5 to 15 percent.
  • the hydrogenation conversion of the aromatic compounds is preferably at least 95 percent, more preferably at least 98 percent and most preferably at least 99.9 percent, based on the total hydrogenation in the first and second reactor.
  • the hydrogenation conversion is preferably 95 to 100 percent, more preferably 98 to 100 percent, and particularly preferably 99.9 to 100 percent.
  • the hydrogenation conversion of the aromatic compounds in the discharge of the second reactor is, for example, 99.99 percent or more.
  • aromatic carboxylic acids or aromatic carboxylic acid esters such as di-iso-nonyl phthalate or di-2-ethylhexyl terephthalic acid
  • the residual aromatic content is preferably not more than 100 ppm, more preferably not more than 50 ppm
  • the discharge from the second reactor can be worked up by methods known to those skilled in the art in order to isolate the hydrogenation products.
  • the effluent from the second reactor may be subjected to distillation and / or stripping to isolate the hydrogenation products. Distillation may be carried out as simple distillation or rectification.
  • Distillation may be carried out in one or more columns connected in series or in parallel.
  • columns for the distillation are, for example, tray columns, such as valve tray column.
  • Columns with packages are preferred.
  • packs are random packs or ordered packs. Ordered packages are preferred.
  • the number of separation stages can be adjusted by those skilled in the art due to his expertise and by a few routine experiments on the desired separation effect.
  • a stripping medium is, for example, gases such as water vapor, nitrogen and / or hydrogen.
  • a stripping may be in one or more, in
  • Series or parallel connected columns are executed.
  • tray columns such as valve tray columns.
  • Columns with packages are preferred.
  • packs are random packs or ordered packs. Ordered packages are preferred.
  • the hydrogenation products are alicyclic carboxylic acid esters, such as di- (isononyl) -1,2-cyclohexanedicarboxylate, di- (2-propylheptyl) -1,2-cyclohexanedicarboxylate, di-2 (isodecyl) -1,2-cyclohexanedicarboxalt or
  • di- (2-ethylhexyl) -1,4-cyclohexanedicarboxylate may be used as a plasticizer or as a component of plasticizer compositions for plastics such as PVC.
  • Another use of these compounds is, for example, the production of plastisols, in particular PVC plastisols.
  • the compounds mentioned are used together with other plasticizers, advantageously plasticizers which lower the gelling temperature.
  • An advantage of the method according to the invention is, for example, better catalyst utilization.
  • a better catalyst utilization can be shown, for example, in the fact that a higher hydrogenation conversion is achieved at the same hydrogenation temperature, or a lower hydrogenation temperature is required for a certain hydrogenation conversion.
  • a lower hydrogenation temperature has less by-product formation advantage.
  • a lower hydrogenation temperature generally results in a longer catalyst life, allowing for longer service intervals.
  • phthalic diisonyl ester was hydrogenated to di- (isononyl) -1,2-cyclohexanedicarboxylate.
  • the hydrogenation takes place in two reactors connected in series.
  • the catalyst is arranged in a fixed bed in both reactors. 72% of the total catalyst volume is in the first reactor, 28% of the total catalyst volume is in the second reactor.
  • the catalyst used has a ruthenium content of 0.5 percent by weight based on the total weight of the carrier material, a specific surface area of 220 to 290 m 2 / g (BET, IS09277) and a pore volume of 0.48 to 0.62 ml / g (Hg porosimetry, DIN 66133), the support material comprises alumina.
  • the first reactor is operated in loop mode, the second reactor is operated in a straight run.
  • the hydrogen pressure was 215 bar in both reactors.
  • the hydrogenation plant was operated with a di-iso-nonyl phthalate fresh feed of 292 kg / (hour * m 3 total catalyst volume).
  • the circulation ratio in the first reactor between the circulating stream and the fresh feed was 12: 1.
  • the hydrogenation is operated such that in the discharge from the second reactor, the residual aromatic content based on di- (isononyl) -1, 2-cyclohexandicarboxylat less than 100 ppm.
  • the first reactor was operated in trickle bed mode.
  • the catalyst was 70% flooded.
  • the following feed temperatures were set:
  • Second reactor 98 ° C.
  • the hydrogen losses during this procedure were 0.5 kg / t of di- (isononyl) -1,2-cyclohexanedicarboxylate.
  • a lower feed temperature increases the remaining service life of the catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé d'hydrogénation de composés aromatiques sur un catalyseur solide en présence d'un gaz contenant de l'hydrogène consistant en ce qu'un premier réacteur est actionné en mode de conduite de bride, en ce qu'un deuxième réacteur est actionné en déroulement droit, au moins une partie de la distribution du premier réacteur étant conduite au deuxième réacteur, caractérisé en ce que le premier réacteur est configuré sous la forme d'un réacteur à lit fluidifié et est actionné en mode de conduite de lit fluidifié et le deuxième réacteur est actionné de telle sorte que le catalyseur qu'il contient est partiellement immergé.
EP18740917.2A 2017-07-05 2018-07-17 Hydrogénation de composés aromatiques Withdrawn EP3649100A1 (fr)

Applications Claiming Priority (2)

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EP17179827.5A EP3424901B1 (fr) 2017-07-05 2017-07-05 Hydrogénation de composés aromatiques
PCT/IB2018/055292 WO2019008561A1 (fr) 2017-07-05 2018-07-17 Hydrogénation de composés aromatiques

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PL3424901T3 (pl) 2017-07-05 2021-01-11 Basf Se Uwodornianie związków aromatycznych
EP4148038B1 (fr) * 2021-09-14 2024-01-10 Evonik Oxeno GmbH & Co. KG Procédé d'hydrogénation du noyau des dialkyltéréphtalates à faible formation de sous-produits

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CN100406428C (zh) 1997-12-19 2008-07-30 巴斯福股份公司 用含大孔的催化剂对苯多羧酸或其衍生物加氢的方法
DE10036172A1 (de) 1999-07-27 2001-03-08 Basf Ag Verfahren zur Hydrierung organischer Verbindungen und Reaktor hierfür
DE10225565A1 (de) * 2002-06-10 2003-12-18 Oxeno Olefinchemie Gmbh Katalysator und Verfahren zur Hydrierung von aromatischen Verbindungen
DE10232868A1 (de) 2002-07-19 2004-02-05 Oxeno Olefinchemie Gmbh Feinporiger Katalysator und Verfahren zur Hydrierung von aromatischen Verbindungen
DE102004063673A1 (de) * 2004-12-31 2006-07-13 Oxeno Olefinchemie Gmbh Verfahren zur kontinuierlichen katalytischen Hydrierung von hydrierbaren Verbindungen an festen, im Festbett angeordneten Katalysatoren mit einem wasserstoffhaltigen Gas
DE102004063637A1 (de) 2004-12-31 2006-07-13 Oxeno Olefinchemie Gmbh Verfahren zur Herstellung von alicyclischen Carbonsäuren oder deren Derivaten
TR201808387T4 (tr) 2013-12-06 2018-07-23 Basf Se Tetra hidrofuran türevleri ve 1,2- siklo heksan dikarboksilik asit esteri içeren yumuşatıcı bileşimi.
WO2017060352A1 (fr) 2015-10-08 2017-04-13 Basf Se Procédé pour le traitement d'eaux usées contenant une matrice organique résultant de la synthèse de zéolite
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CN110914232B (zh) 2023-03-14
US11203566B2 (en) 2021-12-21
EP3424901A1 (fr) 2019-01-09
CN110914232A (zh) 2020-03-24
TW201906810A (zh) 2019-02-16
RU2018126735A (ru) 2020-01-20
EP3424901B1 (fr) 2020-06-10
WO2019008561A1 (fr) 2019-01-10
ES2814342T3 (es) 2021-03-26
PL3424901T3 (pl) 2021-01-11
US20210032189A1 (en) 2021-02-04

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