EP2029508A1 - Procede d'hydrogenation de methylolalcanals - Google Patents

Procede d'hydrogenation de methylolalcanals

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Publication number
EP2029508A1
EP2029508A1 EP07726528A EP07726528A EP2029508A1 EP 2029508 A1 EP2029508 A1 EP 2029508A1 EP 07726528 A EP07726528 A EP 07726528A EP 07726528 A EP07726528 A EP 07726528A EP 2029508 A1 EP2029508 A1 EP 2029508A1
Authority
EP
European Patent Office
Prior art keywords
hydrogenation
hydrogen
catalyst
methylolalkanal
feed
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.)
Withdrawn
Application number
EP07726528A
Other languages
German (de)
English (en)
Inventor
Steffen Maas
Thorsten Johann
Michael Koch
Tilman Sirch
Stephan Schlitter
Stefan Rittinger
Michael Steiniger
Todd C. Spengeman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP2029508A1 publication Critical patent/EP2029508A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases

Definitions

  • the invention relates to a process for the preparation of polyhydric alcohols by catalytic hydrogenation of methylolalkanals in the liquid phase over a hydrogenation catalyst at a hyper-stoichiometric hydrogen / methylolalkanal ratio.
  • Methylolalkanale By aldol reaction of alkanals with excess formaldehyde in the presence of stoichiometric amounts of base Methylolalkanale be accessible. From WO 01/51438 it is known to use inorganic hydroxides such as sodium hydroxide or calcium hydroxide as base. WO 98/28253 and DE-A 1 957 591 describe amines as basic aldolization catalysts and WO 98/29374 describe basic ion exchangers. The Methylolalkanal is obtained by these methods as 20 to 80 wt .-% aqueous solution. The pH of this aqueous solution is only 3.5 to 6.0, since the basic aldolization catalyst also catalyzes the Cannizzaro reaction of formaldehyde to formic acid, which in turn at least partially neutralizes the base.
  • inorganic hydroxides such as sodium hydroxide or calcium hydroxide
  • polyhydric alcohols such as pentaerythritol, neopentyl glycol or trimethylolpropane from aqueous methylolalkanal solutions, these solutions must be hydrogenated.
  • This hydrogenation is generally carried out at temperatures above 80 ° C. There are remissions of the methylol group to free aldehyde, observed the Cannizzaro reaction of formaldehyde to formic acid and beyond ether, ester and acetal formation in the hydrogenation reactor. These side reactions lead to low hydrogenation selectivities and to low yields of polyhydric alcohol.
  • CO and CO2 have been used as catalyst poisons for copper and nickel catalysts for a long time, for example, from CW. Griffin, JACS (1927) 49, 2136-2145 and a number of processes have been developed to regenerate CO and CO2 deactivated catalysts.
  • DE-A 199 63 441 describes a process for regenerating a copper catalyst by "burning off.” Oxygen is passed over the active catalyst at elevated temperature, under which conditions organic deposits are oxidized to CO2 and the active copper to copper oxide.
  • the invention therefore an object of the invention to provide a process for the preparation of polyhydric alcohols by catalytic hydrogenation of Methylolalkanalen can be made available in the polyhydric alcohols with good conversions and yields and long service life of the catalyst.
  • R 1 and R 2 independently of one another, another methylol group or an alkyl group having 1 to 22 C atoms or an aryl or aralkyl group having 6 to 33 C Atoms, in the liquid phase with hydrogen over a hydrogenation catalyst, characterized in that hydrogen is used to Methylolalkanal in a molar ratio greater than 1.
  • the amount of exhaust gas in the hydrogenation is increased and the concentration of CO or CU2 in the hydrogenation reactor can be adjusted.
  • the deactivating effect of CO or CO2 can be substantially reduced.
  • the hydrogenation catalyst can be maintained at a high level of activity, that is, high conversions and yields are achieved with long catalyst life.
  • the hydrogen / methylolalkanal molar ratio is preferably adjusted to a value of 5 to 1, particularly preferably to a value of 2.5 to 1.1.
  • either a fixed quantity ratio of hydrogen and hydrogenation feed is set via the system controller or the amount of hydrogen controlled so that less than 4000 ppm CO, preferably less than 1000 ppm CO, are contained in the reaction offgas .
  • the CO determination can be carried out either continuously via an online measurement in the exhaust stream or discontinuously by means of gas chromatographic analysis in a conventional manner.
  • the amount of hydrogen not chemically consumed by hydrogenation leaves the reactor as waste gas and can be used, for example, in combustion for energy generation. It is also possible to separate the exhaust gas of the hydrogenation into its constituents and to recover the hydrogen as a feedstock.
  • a third form of utilization is the use of hydrogen in a process in which the secondary constituents resulting from the hydrogenation do not interfere.
  • a methylolalkanal of the general formula I containing aqueous solution in particular a 20 to 80 wt .-% methylolalkanal containing aqueous solution understood.
  • a hydrogenation feed is preferably prepared according to WO 98/28253 or DE-A 1 957 591 by reacting aldehydes with formaldehyde.
  • the reaction is carried out in such a way that the aldehyde is reacted with 1 to 8 times the amount of formaldehyde in the presence of a tertiary amine (aldolization), and the reaction mixture thus obtained is separated into two solutions, one solution comprising the mentioned methylolalkanal and the other Solution unreacted starting product has. This last solution is attributed to the reaction.
  • the separation follows by distillation or simply separating the aqueous from the organic phase.
  • the aqueous solution containing the methylolalkanal can be used as a hydrogenation feed in the process according to the invention.
  • the methylolalkanal of the general formula I is preferably dimethylolalkanal, pentaerythritol or hydroxypivalaldehyde.
  • the hydrogenation feed may be mixed with tertiary amine, inorganic base or inorganic or organic acid prior to the hydrogenation reactor inlet until the hydrogenation effluent withdrawn after reactor exit has a pH of 7.0 to 9.0 for the preparation of neopentyl glycol preferably has a pH of 8.0 to 9.0, for the preparation of trimethylolpropane has a pH of 6.0 to 8.0. It is also possible to separately feed and mix the hydrogenation feed and the tertiary amine, the inorganic base or the inorganic or organic acid into the reactor.
  • tertiary amines As suitable tertiary amines the amines listed in DE-A 25 07 461 are mentioned by way of example. As tertiary amines, tri-n-C 1 -C 4 -alkylamines are preferred and trimethylamine, triethylamine, tri-n-propylamine and tri-n-butylamine are particularly preferred. In general, up to 10% by weight (based on the hydrogenation feed) of the tertiary amine is added to the pH control in the process according to the invention. The amine can be used as a pure substance or as an aqueous solution.
  • Amines are particularly advantageous to use for pH adjustment, since they form with formic acid thermally decomposable salts, which can be split again after hydrogenation. Thus, a salt attack can be avoided and the tertiary amine can be recycled to the process. Particularly advantageous is the use of the same tertiary amine in the aldolization process to Methylolalkanal - the condensation of higher aldehyde and formaldehyde - and in the hydrogenation.
  • Mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid or organic acids such as citric acid, acetic acid or ethylhexanoic acid can be used according to the invention as inorganic or organic acids.
  • acetic acid is used.
  • 0 and 3% by weight (based on the hydrogenation feed) of a 10% aqueous solution of the pH control acid are added
  • the measurement of the pH takes place with the known techniques, preferably with a glass electrode and a pH meter.
  • Catalysts which can be used according to the invention are catalysts suitable for hydrogenations, which preferably contain at least one metal from subgroup 8 to 12 of the Periodic Table of Elements such as Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, preferably Fe, Co, Ni, Cu, Ru, Pd, Pt, particularly preferably Cu, preferably on a customary carrier material, particularly preferably on one of the oxides of titanium, zirconium, hafnium, silicon and / or aluminum exhibit.
  • the catalysts which can be used according to the invention can be prepared by processes known from the prior art for the preparation of such supported catalysts.
  • Such catalysts and their preparation are known from WO 99/44974.
  • copper-containing supported catalysts such as e.g. in WO 95/32171 and the catalysts disclosed in EP-A 44 444 and DE-A 1 957 591 are suitable for the hydrogenation according to the invention.
  • the hydrogenation can be carried out batchwise or continuously, for example in a reactor tube filled with a catalyst bed, in which the reaction solution is passed over the catalyst bed, for example in the trickle or bottoms mode, as described in DE-A 19 41 633 or DE-A 20 40 501 , It may be advantageous to recycle a partial stream of the reaction output, optionally with cooling, and to pass it again over the fixed catalyst bed.
  • This circulation procedure is preferably operated with a ratio of feed to feed of 10-20: 1.
  • the hydrogenation temperature is generally between 50 and 180 ° C, preferably 90 and 140 ° C.
  • the hydrogenation pressure used is generally from 10 to 250 bar, preferably from 20 to 120 bar.
  • the hydrogenation can be carried out with the addition of an inert solvent.
  • suitable solvents are water, cyclic ethers, such as THF or dioxane, as well as acyclic ethers, as well as lower alcohols, e.g. Methanol, ethanol or 2-ethylhexanol.
  • any hydrogenation methods can be used and hydrogenation catalysts can be used, as are customary for the hydrogenation of aldehydes and described in detail in the standard literature.
  • Starting materials were a 20% strength by weight sodium carbonate solution and an aqueous solution I which contained 2.67% by weight Al and 5% by weight Cu in the form of their nitrates.
  • solution I and soda solution were metered into a precipitation vessel at 80 ° C. in such a way that a pH of 5.6 was established.
  • the precipitation mixture was transferred to a larger stirred tank and adjusted at 80 ° C with sodium carbonate solution to a pH of 7.9. The suspension was then passed to a filter press.
  • the mixture was then filtered and washed with water nitrate-free.
  • the filter paste was suspended in water and dried in a spray tower with hot air at 130-150 ° C starting temperature. This is followed by a calcination at a temperature of 375 - 390 ° C. Subsequently, the powder with 3 wt .-% graphite was tabletted as an aid to tablets with 5 x 5 mm.
  • the resulting tablets were then placed in a heated rotary tube at a temperature of 600 ° C for 60 min. calcined.
  • the catalyst prepared in this way consisted of 55% CuO and 45% by weight Al 2 O 3, had a specific surface area (BET) of 95 m 2 / g, an Hg porosity of 0.44 ml / g with a shaking weight of 952 g / l on.
  • BET specific surface area
  • the starting solution was the mixture described above as Hydrierfeed. From 0 to 15% by weight (based on the hydrogenation feed) of a 15% strength by weight aqueous solution of trimethylamine were added to this mixture in order to adjust the pH of the hydrogenation effluent to greater than 8.
  • a pH meter from Knick Model 766 with a glass electrode N1041A from Schott was used.
  • Example 1 was repeated under the conditions indicated, but 1% CO was added to the hydrogen.
  • the hydrogenation feed was run in trickle mode at 37 bar H2 pressure over the reactor heated to 105 ° C.
  • the load was 0.32 kg HPA / (kg ⁇ cat * h).
  • From 0 to 17% by weight (based on the hydrogenation feed) of a 50% strength by weight aqueous solution of trimethylamine were added to this mixture in order to adjust the pH of the hydrogenation effluent to greater than 8 (hydrogen / hydroxypivalaldehyde - Mo). Ratio about 1, 5).
  • Part of the hydrogenation effluent was added to the feed again (circulation mode).
  • the ratio of circulation to feed was 16: 1. For several days, a mean conversion of 88.1% was achieved with a mean pH of 8.4.
  • Example 2 was repeated under the conditions indicated, but 10% CO2 was added to the hydrogen. Hydrogen / hydroxypivalaldehyde molar ratio ca. 1, 5. In order to keep the H2 partial pressure constant, the system pressure was increased to 41 bar. The mean conversion at this setting was 75.3% with a mean pH of 8.0
  • the catalyst according to Example 1 was used, but 3 ⁇ 3 mm tablets were produced.
  • the catalyst consisted of 55% CuO and 45% by weight Al 2 O 3, had a specific surface area (BET) of 95 m 2 / g, an Hg porosity of 0.38 ml / g with a shaking weight of 1042 g / l. hydrogenation
  • the hydrogenation feed was run in trickle mode at 40 bar H2 pressure over the reactor.
  • the temperature was 96 ° C in the upper half of the reactor and 106 ° C in the lower half.
  • the load was 0.37 kg HPA / (kg * cat * h). Together with the liquid feed about 1 10 mol% H2 (based on Methyolalkanale used), according to a hydrogen / Edukt molar ratio of 1, 1, dosed.
  • Part of the hydrogenation effluent was added to the feed again (circulation mode).
  • the ratio of circulation to feed was 16: 1. For several days, a mean conversion of 95.9% was achieved at a mean pH of 8.3.
  • Example 3 was repeated under the conditions indicated, but the amount of hydrogen was doubled to a hydrogen / reactant molar ratio of 2.2 and the temperature lowered to 93 ° C in the upper and 103 ° C in the lower half of the reactor. An average conversion of 95.6% at pH 8.4 was achieved.
  • the hydrogenation feed was prepared according to Example 6 of PCT / WO 98/28253.
  • the starting solution was the mixture described above as Hydrierfeed.
  • the hydrogenation feed was run in trickle mode at 90 bar H2 pressure and 1 10 ° C over the reactor.
  • the load was 0.2 kg DMB / (lkat * h).
  • 125 to 200 mol% of hydrogen (based on methylolalkanals) were metered in, corresponding to a hydrogen / methylolalkanal molar ratio of 1.25 to 2.0.
  • the system pressure was kept constant at 90 bar (flue gas mode). Part of the hydrogenation effluent was added to the feed again (circulation mode).
  • the circulation to feed ratio was 6.5: 1. Table 1 shows the conversion over a period of 21 12 h and the metered amount of hydrogen.

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

Abstract

Procédé d'hydrogénation catalytique de méthylolalcanals de la formule générale (I), dans laquelle R1 et R2 représentent indépendamment l'un de l'autre, un autre groupe méthylol ou un groupe alkyle ayant 1 à 22 atomes C ou un groupe aryle ou aralkyle ayant 6 à 33 atomes C, en phase liquide avec de l'hydrogène sur un catalyseur d'hydrogénation, caractérisé en ce que l'on utilise l'hydrogène en un rapport molaire supérieur à 1 par rapport au méthylolalcanal.
EP07726528A 2006-06-06 2007-02-27 Procede d'hydrogenation de methylolalcanals Withdrawn EP2029508A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/447,020 US7388116B2 (en) 2006-06-06 2006-06-06 Hydrogenation of methylolalkanals
PCT/EP2007/051829 WO2007141056A1 (fr) 2006-06-06 2007-02-27 Procédé d'hydrogénation de méthylolalcanals

Publications (1)

Publication Number Publication Date
EP2029508A1 true EP2029508A1 (fr) 2009-03-04

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP07726528A Withdrawn EP2029508A1 (fr) 2006-06-06 2007-02-27 Procede d'hydrogenation de methylolalcanals

Country Status (9)

Country Link
US (1) US7388116B2 (fr)
EP (1) EP2029508A1 (fr)
JP (1) JP5355390B2 (fr)
KR (1) KR101470038B1 (fr)
CN (1) CN101466657A (fr)
BR (1) BRPI0712337A2 (fr)
MX (1) MX2008015413A (fr)
MY (1) MY145433A (fr)
WO (1) WO2007141056A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008031338B4 (de) * 2008-07-02 2012-09-13 Oxea Gmbh Verfahren zur Herstellung von Neopentylglykol
US8710278B1 (en) 2013-01-31 2014-04-29 Eastman Chemical Company Process for producing polyols
US9056824B2 (en) 2013-01-31 2015-06-16 Eastman Chemical Company Preparation of hydroxy aldehydes
KR102245932B1 (ko) * 2017-10-23 2021-04-28 주식회사 엘지화학 트리메틸올프로판의 제조방법
CN109180428B (zh) * 2018-08-06 2020-06-05 吉林市道特化工科技有限责任公司 一种2，2-二甲基-1，3-丙二醇的生产工艺
CN113811523A (zh) * 2019-05-17 2021-12-17 Sika技术股份公司 用于制备2,2-二烷基-3-酰氧基丙醛的方法

Citations (3)

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Publication number Priority date Publication date Assignee Title
EP0484800A2 (fr) 1990-11-06 1992-05-13 Mitsubishi Gas Chemical Company, Inc. Procédé de préparation de néopentyl-glycol
JP2002012568A (ja) 2000-06-27 2002-01-15 Mitsubishi Gas Chem Co Inc ネオペンチルグリコールの精製法
WO2004092097A1 (fr) 2003-04-16 2004-10-28 Basf Aktiengesellschaft Procede d'hydrogenation de methylol-alcanals

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BE758910A (fr) * 1969-11-15 1971-05-13 Basf Ag Preparation de dimethyl-2, 2-propanediol-1, 3
DE2040501C3 (de) 1970-08-14 1984-01-05 Basf Ag, 6700 Ludwigshafen Verfahren zur Durchführung von exothermen Reaktionen zwischen einem Gas und einer Flüssigkeit
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DE3027890A1 (de) 1980-07-23 1982-03-04 Basf Ag, 6700 Ludwigshafen Hydrierkatalysatoren fuer die herstellung von propandiolen und verfahren zur herstellung von propandiolen mit solchen katalysatoren
JPH05117187A (ja) * 1991-04-26 1993-05-14 Aristech Chem Corp ネオペンチルグリコールの製造方法
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DE19542036A1 (de) * 1995-11-10 1997-05-15 Basf Ag Verfahren zur Herstellung von Polyalkoholen
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FI102474B (fi) * 1996-12-30 1998-12-15 Neste Oy Menetelmä moniarvoisten alkoholien valmistamiseksi
DE19963441A1 (de) 1999-12-28 2001-07-05 Basf Ag Verfahren zur Regenerierung von Hydrierkatalysatoren
DE10001257A1 (de) * 2000-01-14 2001-07-19 Bayer Ag Verfahren zur Herstellung von Trimethylolalkanen
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Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0484800A2 (fr) 1990-11-06 1992-05-13 Mitsubishi Gas Chemical Company, Inc. Procédé de préparation de néopentyl-glycol
JP2002012568A (ja) 2000-06-27 2002-01-15 Mitsubishi Gas Chem Co Inc ネオペンチルグリコールの精製法
WO2004092097A1 (fr) 2003-04-16 2004-10-28 Basf Aktiengesellschaft Procede d'hydrogenation de methylol-alcanals

Non-Patent Citations (1)

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Title
See also references of WO2007141056A1

Also Published As

Publication number Publication date
BRPI0712337A2 (pt) 2012-01-31
WO2007141056A1 (fr) 2007-12-13
JP5355390B2 (ja) 2013-11-27
CN101466657A (zh) 2009-06-24
JP2009539794A (ja) 2009-11-19
KR101470038B1 (ko) 2014-12-05
US20070282135A1 (en) 2007-12-06
US7388116B2 (en) 2008-06-17
MY145433A (en) 2012-02-15
MX2008015413A (es) 2008-12-12
KR20090094798A (ko) 2009-09-08

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