WO2014067600A1 - Verfahren zur herstellung von neopentylglykol - Google Patents
Verfahren zur herstellung von neopentylglykol Download PDFInfo
- Publication number
- WO2014067600A1 WO2014067600A1 PCT/EP2013/002922 EP2013002922W WO2014067600A1 WO 2014067600 A1 WO2014067600 A1 WO 2014067600A1 EP 2013002922 W EP2013002922 W EP 2013002922W WO 2014067600 A1 WO2014067600 A1 WO 2014067600A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogenation
- barium
- manganese
- catalyst
- amount
- Prior art date
Links
Classifications
-
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/75—Reactions with formaldehyde
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
- B01J2523/17—Copper
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
- B01J2523/25—Barium
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
- B01J2523/67—Chromium
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/70—Constitutive chemical elements of heterogeneous catalysts of Group VII (VIIB) of the Periodic Table
- B01J2523/72—Manganese
Definitions
- the present invention relates to a process for the preparation of neopentyl glycol by hydrogenation of hydroxypivalaldehyde in the liquid phase on barium and manganese-doped copper chromite catalysts.
- Polyhydric alcohols or polyols have a considerable economic importance as condensation components for the construction of polyesters or polyurethanes, synthetic resin paints, lubricants and plasticizers.
- those polyhydric alcohols of interest which are obtained by a mixed aldol addition of formaldehyde with iso- or n-butyraldehyde.
- an aldehydic intermediate first forms which subsequently has to be reduced to the polyhydric alcohol.
- a technically significant polyhydric alcohol obtainable by this process is neopentyl glycol [NPG, 2,2-dimethylpropanediol- (1,3)] from the mixed aldolization of formaldehyde and isobutyraldehyde.
- the aldol addition is carried out in the presence of basic catalysts, for example alkali metal hydroxides or aliphatic amines, and initially yields the isolable intermediate hydroxypivalaldehyde (HPA).
- HPA hydroxypivalaldehyde
- This intermediate can then be converted into neopentyl glycol with excess formaldehyde according to the Cannizzaro reaction to give one equivalent of a formate salt.
- Copper chromite catalysts are also frequently used for the hydrogenation of
- Copper chromite catalysts often contain other metals as activators, for example barium, cadmium, magnesium, manganese and / or a rare earth metal.
- barium, cadmium, magnesium, manganese and / or a rare earth metal According to US Pat. No. 4,855,515, particularly manganese-doped copper chromite catalysts are distinguished in the hydrogenation of the aldolization product from the reaction of formaldehyde with isobutyraldehyde.
- WO98 / 29374 A1 discloses the use of a barium-doped copper chromite catalyst for the hydrogenation of hydroxypivalaldehyde in a methanolic solution.
- a mixture of hydroxypivalaldehyde and excess isobutyraldehyde is hydrogenated to neopentyl glycol and isobutanol in the presence of a copper chromite catalyst which is doped with barium.
- the known from the prior art copper chromite catalysts operate at relatively high hydrogenation temperatures.
- copper chromite catalysts have good hydrogenation activity towards hydroxypivalaldehyde to neopentyl glycol, but they are also sufficiently active to cleave under-hydrogenation by-products formed in the aldolization of isobutyraldehyde with formaldehyde, and to neutralize neo-bound release pentylglycol.
- Such by-products are, for example, neopentylglycol isobutyrate or the Tishchenko ester formed by disproportionation of hydroxypivalaldehyde Neopentylglykolmonohydroxy- pivalinklaer.
- the specific hydrogenating cleavage of high-boiling by-products from neopentyl glycol production using copper chromite catalysts is described in DE 10 2008 033163 A1.
- Neopentyl glycol is of great commercial importance as a manufactured product and therefore there is a need to always improve the known processes for neopentyl glycol production, be it through improved product yield, better plant utilization or lower energy input.
- neopentyl glycol can be prepared by hydrogenation of hydoxypivalaldehyde in high selectivity and high space-time yield when the hydrogenation is in the liquid phase in the presence of a copper chromite catalyst doped with both manganese and barium.
- the present invention therefore relates to a process for the preparation of neopentyl glycol by addition of isobutyraldehyde and formaldehyde in the presence of a tertiary alkylamine as a catalyst for hydroxypivalaldehyde with subsequent hydrogenation at a temperature of 80 to 220 ° C and at a pressure of 2 to 18 MPa in the liquid phase, characterized in that the hydrogenation in the presence of a
- Copper chromite catalysts containing both barium and manganese as activators can be achieved at significantly lower temperatures already complete hydrogenation of Hydroxypivalinaldehyds and thereby very high space-time yields can be achieved.
- a hydrogenation temperature 80 to 220 ° C, preferably from 80 to 180 ° C and in particular from 1 10 to 140 ° C
- the selective hydrogenation of hydroxypivalaldehyde succeeds to neopentyl glycol at high space-time yields.
- Hydrogenation also occurs increasingly a decomposition of the used as Aldoli- s istskatalysator tertiary alkylamine, which leads to difficult to separate secondary products and is therefore undesirable.
- the high boilers are oxygenated compounds such as esters or cyclic acetals in which equivalents of neopentyl glycol are chemically bound. In high boomers, the proportion of mono- and di-iso
- the aldol addition of isobutyraldehyde and an aqueous formaldehyde solution takes place in the presence of tertiary alkylamines as aldol addition catalyst, which may contain the same or different alkyl groups and thus can be constructed symmetrically or asymmetrically, as well as in the presence of tertiary alkylamines having several trialkylamine functions.
- Dimethyl-tert-butylamine or ⁇ , ⁇ '-tetramethylethylenediamine worked.
- Particularly suitable catalysts have proven to be trimethylamine, triethylamine, tri-n-propylamine and tri-n-butylamine.
- the aldehydes can be reacted in a molar ratio, but it is also possible to use one of the two reactants in excess.
- Formaldehyde is used as the aqueous solution, and the formaldehyde content is usually from 20 to 50% by weight. It has been found that the doped used in the process according to the invention
- Kupchromite catalyst has a surprisingly high resistance to formaldehyde. Therefore, in the aldol addition stage, molar ratios of formaldehyde to iso-butyraldehyde can be adjusted from 1: 1 to formaldehyde, generally up to 1.2: 1, preferably to 1.1: 1. By reducing the isobutyraldehyde use, isobutanol formation in the hydrogenation stage is suppressed and the neopentyl glycol yield, based on isobutyraldehyde use, is increased.
- the reaction between isobutyraldehyde and formaldehyde is carried out at temperatures between 20 and 100 ° C, expediently carried out at 80 to 95 ° C. In general, the reaction is carried out at atmospheric pressure, but it is also possible to use elevated pressure.
- the tertiary alkylamine used as aldol addition catalyst is contained in the reaction mixture in an amount of 1 to 20, preferably 2 to 12, mol%, based on isobutyraldehyde.
- the reaction mixture is optionally still iso-butanol added as a diluent.
- the iso-butanol addition is not mandatory, but if iso-butanol is added, its content in the reaction mixture is in the range of 10 to 20 wt .-%, based on the total reaction mixture. Further solvents and diluents are not required.
- the practical implementation of the addition reaction takes place in a stirred tank, in a stirred tank cascade or in a reaction tube, which may be charged for better mixing of the reactants with packing or other internals.
- the reaction is exothermic, it can be accelerated by heating.
- the crude mixture obtained after the aldol addition is optionally after distillative removal of volatile components such as water, methanol, isobutanol and residual amounts of formaldehyde, isobutyraldehyde and optionally the aldolization or without prior separation into its components or separation of individual components in the presence of barium and manganese copper chromite Catalytically hydrogenated catalyst.
- volatile components such as water, methanol, isobutanol and residual amounts of formaldehyde, isobutyraldehyde and optionally the aldolization or without prior separation into its components or separation of individual components in the presence of barium and manganese copper chromite Catalytically hydrogenated catalyst.
- the hydrogenation is carried out in the presence of an aliphatic alcohol which is miscible with the Aldolmaschinesroh GmbH.
- Suitable aliphatic alcohols have been found to be linear or branched alcohols having from 1 to 5 carbon atoms, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, neopentyl glycol or mixtures thereof.
- Iso-butanol is particularly useful since residual amounts of isobutyraldehyde are hydrogenated to iso-butanol.
- iso-butanol is already used in the aldol addition stage as a diluent and not previously separated by distillation, there is already a solvent in the hydrogenation stage. Small amounts of methanol which are introduced via the aqueous formaldehyde solution are also present.
- the proportion of aliphatic alcohol as organic solvent or diluent is in this embodiment of the invention 15 to 27 wt .-%, preferably 15 to 23 wt .-%, based on the organic content in the feed mixture.
- the liquid phase used for the hydrogenation in addition to the aliphatic alcohol also contains water in an amount of 15 to 25 wt .-%, preferably 18 to 25 wt .-%, based on the total amount.
- the entire mixture used for the hydrogenation is homogeneous and thus contains 15 to 25 wt .-% water and the balance to 100 wt .-% an organic content, which in turn contains 15 to 27 wt .-% of an aliphatic alcohol.
- the proportion of water promotes an advantageous heat distribution and an advantageous removal of the heat of reaction in the hydrogenation step and reduces the risk of the occurrence of local temperature peaks.
- the crude mixture containing hydroxypivalaldehyde is hydrogenated without further purification and work-up steps.
- the hydrogenation of the crude hydroxypivalaldehyde is carried out at a temperature of 80 to 220 ° C, preferably from 80 to 180 ° C and in particular from 1 10 to 140 ° C, in the liquid phase in the presence of barium and manganese-doped copper chromite catalysts.
- the reaction pressure is 2 to 18 MPa, preferably 4 to 15 MPa.
- a reaction temperature of 110 to 140 ° C. and a reaction pressure of 4 to 15 have proven particularly suitable MPa. At lower reaction pressures, satisfactory hydrogenation of the hydroxypivalaldehyde is no longer observed.
- Copper chromite catalysts containing barium and manganese as activators can be prepared according to H. Adkin, Org. React. 8, 1954, 1-27 describe as an equimolar combination of copper oxide and copper chromite, although they do not necessarily contain copper chromite.
- the catalysts can be either without carriers as so-called full catalysts or with carriers, for example with kieselguhr, silica gel or aluminum oxide as powder or in the form of tablets, stars,
- Strands, rings or other particles of relatively large surface can be used.
- insoluble compounds of copper, chromium, manganese and barium are mixed, for example, in angelessnesster form and formed into suitable moldings such as strands or tablets. After shaping, it is dried and calcined up to 500 ° C., during which the solid is compacted and the metals present are optionally converted into the oxides.
- the barium and manganese doped copper chromite catalysts contain from 0.5 to 8 wt.%, Preferably from 3 to 5 wt.% Manganese and from 0.5 to 8 wt.%, Preferably from 1 to 4 wt. Barium, based on the sum of the content of copper, chromium, barium and manganese.
- further activators such as cadmium, magnesium, strontium and / or a rare earth metal may optionally be present.
- the hydrogenation is carried out continuously or discontinuously in the liquid phase, for example on fixed catalysts by the trickle or sumping method and after the suspension hydrogenation.
- a catalyst loading V / Vh expressed in flow rate per catalyst volume and time, of 0.2 to 4.0 h- 1 , preferably 0.8 to 2.0 h- 1 , has proven expedient.
- discontinuous process control based on the liquid feedstock, 1 to 20, preferably 2 to 15 wt .-% of
- the hydrogenation is carried out continuously in the liquid phase in a tubular reactor on fixed catalysts. Under a tube reactor is also a bunch of several closely parallel connected To understand pipes.
- the tubular reactors used may also contain fillers or internals, for example Raschig rings, saddles, pallets, filter plates or column trays, and optionally stirring devices or devices for removing the heat of reaction.
- the hydrogenation of hydroxypivalaldehyde takes place in a tubular reactor on a fixed bed without internals and without stirring devices.
- the hydrogenation is preferably carried out with pure hydrogen. However, it is also possible to use mixtures which contain free hydrogen and, in addition, inert constituents under the hydrogenation conditions.
- the recovery of pure neopentyl glycol from the hydrogenated reaction mixture is carried out by conventional distillation methods. Solvent or diluent separated off can be recycled back to the aldol addition stage and / or hydrogenation stage.
- hydroxypivalaldehyde is converted at high conversion with high selectivity and high space-time yield in neopentyl glycol.
- the low proportion of high boilers after hydrogenation and the formation of high boilers in the hydrogenation can be sustainably prevented.
- the cleavage of the tertiary alkylamine in volatile, nitrogen-containing compounds which lead to undesirable impurities and are difficult to separate in the subsequent work-up by distillation and interfere with the further processing of neopentyl glycol, suppressed.
- Example 1 Preparation of a barium-doped copper chromite catalyst
- the catalyst had the following composition: 42.1% copper, 48.4% chromium, 9.5% barium.
- the dried solid was calcined at 350 ° C for four hours, the heating rate was 2 ° C / min. After calcination and cooling of the solid, this was stirred with 200 ml of 10% acetic acid. Thereafter, the solid was acid-washed with water and dried again at 110 ° C and annealed at 350 ° C at a heating rate of 2 ° C / min.
- the solid obtained could be used in this form as a catalyst. Based on the metals, the catalyst had the following composition: 50.0% copper, 45.8% chromium, 4.2% manganese.
- Example 3 Preparation of a manganese- and barium-doped copper chromite catalyst
- the dried solid was calcined at 350 ° C for four hours, the heating rate was 2 ° C / min. After calcination and cooling of the solid, this was stirred with 20 liters of 10% acetic acid. Thereafter, the solid was washed free of acid with water and dried again at 1 10 ° C and annealed at 350 ° C at a heating rate of 2 ° C / min.
- the solid obtained could be used in this form as a catalyst. Based on the metals, the catalyst had the following composition: 47.5% copper, 46.5% chromium, 4.0% manganese, 2.0% barium.
- Example 4 Comparison of the Catalytic Activity of the Catalysts of Examples 1-3
- Tishchenko ester neopentyl glycol monohydroxypivalic acid ester
- the hydrogenation was carried out in an autoclave at 130 ° C and at a
- Example 5 Influence of the Tertiary Amine on the Hydrogenation Activity 10% by mass of the catalyst from Example 3 were used to hydrogenate a crude hydroxypivalaldehyde of the following composition:
- Example 6 Use of the catalyst from Example 3 as a fixed bed catalyst
- the catalyst from Example 3 was mixed with 3% graphite and tabletted.
- the resulting 3x3 mm tablets were placed in a 2.2 liter tubular reactor.
- the catalyst was depressurized at 240 ° C for five hours in a gas stream containing 15 mol% of hydrogen and 85 mol% of nitrogen.
- 200 standard liters / h of this gas mixture were passed over the catalyst.
- 1 standard liter means 1 liter of gas volume at a temperature of 20 ° C and at a pressure of 0.1 MPa.
- Crude hydroxypivalaldehyde corresponding to the composition of Example 4 and hydrogen were fed continuously at the bottom of the tubular reactor.
- Catalyst loads is also a nearly complete conversion achieved, however, decreases the selectivity to neopentyl glycol. At these, not quite optimal experimental settings is also expected to amplified cleavage reactions of the aldolization used as tertiary amines.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020157010991A KR102110117B1 (ko) | 2012-10-29 | 2013-09-28 | 네오펜틸 글리콜의 제조 방법 |
EP13770841.8A EP2912000B1 (de) | 2012-10-29 | 2013-09-28 | Verfahren zur herstellung von neopentylglykol |
CN201380048126.XA CN104640829B (zh) | 2012-10-29 | 2013-09-28 | 新戊二醇的生产方法 |
JP2015538313A JP6263191B2 (ja) | 2012-10-29 | 2013-09-28 | ネオペンチルグリコールの製造方法 |
US14/427,181 US9353032B2 (en) | 2012-10-29 | 2013-09-28 | Method for the production of neopentyl glycol |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102012021280.1 | 2012-10-29 | ||
DE102012021280.1A DE102012021280A1 (de) | 2012-10-29 | 2012-10-29 | Verfahren zur Herstellung von Neopentylglykol |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014067600A1 true WO2014067600A1 (de) | 2014-05-08 |
Family
ID=49274597
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2013/002922 WO2014067600A1 (de) | 2012-10-29 | 2013-09-28 | Verfahren zur herstellung von neopentylglykol |
Country Status (8)
Country | Link |
---|---|
US (1) | US9353032B2 (de) |
EP (1) | EP2912000B1 (de) |
JP (1) | JP6263191B2 (de) |
KR (1) | KR102110117B1 (de) |
CN (1) | CN104640829B (de) |
DE (1) | DE102012021280A1 (de) |
TW (1) | TW201416343A (de) |
WO (1) | WO2014067600A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9133083B2 (en) | 2012-10-29 | 2015-09-15 | Oxea Gmbh | Continuous method for the production of neopentyl glycol |
JP2016535089A (ja) * | 2014-09-25 | 2016-11-10 | エルジー・ケム・リミテッド | 高効率のネオペンチルグリコールの製造方法及びその製造装置 |
CN107108413A (zh) * | 2015-09-07 | 2017-08-29 | Lg化学株式会社 | 制备二醇的装置及其制备方法 |
EP3747855A1 (de) | 2019-06-04 | 2020-12-09 | OXEA GmbH | Verfahren zur kontinuierlichen herstellung von diolen aus aldehyden mittels raney-cobalt katalyse |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102052084B1 (ko) * | 2015-09-21 | 2019-12-04 | 주식회사 엘지화학 | 네오펜틸 글리콜의 제조방법 |
WO2019083700A1 (en) | 2017-10-25 | 2019-05-02 | Dow Technology Investments Llc | PROCESS FOR REDUCING THE FORMATION OF HEAVY MINERALS IN A SOLUTION COMPRISING ALDEHYDE COMPOUNDS FORMED DURING A HYDROFORMYLATION PROCESS |
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 |
CN112028758A (zh) * | 2020-05-25 | 2020-12-04 | 广安摩珈生物科技有限公司 | 羟基醛的制备方法以及使用电渗析技术拆分光学异构体的方法 |
CN112280097A (zh) * | 2020-10-20 | 2021-01-29 | 安徽世华化工有限公司 | 一种混合型增塑剂及其制备方法 |
CN113956132B (zh) * | 2021-11-19 | 2024-03-19 | 吉林化工学院 | 一种三甲基戊二醇的制备方法 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1518784A1 (de) | 1964-10-21 | 1969-08-21 | Eastman Kodak Co | Verfahren zur gleichzeitigen Herstellung von Neopentylglykol und Isobutanol |
EP0006460A1 (de) | 1978-06-24 | 1980-01-09 | Chemische Werke Hüls Ag | Verfahren zur Gewinnung von reinem Neopentylglykol |
EP0278106A1 (de) | 1986-12-30 | 1988-08-17 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung von 2,2-Dimethylpropandiol-(1,3) |
EP0301853A1 (de) * | 1987-07-29 | 1989-02-01 | DAVY McKEE (LONDON) LIMITED | Katalysator |
US4855515A (en) | 1987-08-12 | 1989-08-08 | Eastman Kodak Company | Process for the production of neopentyl glycol |
EP0484800A2 (de) | 1990-11-06 | 1992-05-13 | Mitsubishi Gas Chemical Company, Inc. | Verfahren zur Herstellung von Neopentylglykol |
EP0522368A1 (de) | 1991-06-28 | 1993-01-13 | Aristech Chemical Corporation | Herstellung von Neopentylglykol (IV) |
WO1998029374A1 (en) | 1996-12-30 | 1998-07-09 | Neste Chemicals Oy | Process for the preparation of polyvalent alcohols |
DE102008033163A1 (de) | 2008-07-15 | 2010-01-21 | Oxea Deutschland Gmbh | Verfahren zur Gewinnung von Neopentylglykol durch Spaltung von im Herstellverfahren anfallenden Hochsiedern |
GB2482887A (en) * | 2010-08-18 | 2012-02-22 | Johnson Matthey Plc | Catalyst and process for hydrogenation of aldehydes |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2702582C3 (de) * | 1977-01-22 | 1980-12-04 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Trimethylolalkanen |
DE10024542A1 (de) * | 2000-05-18 | 2001-11-22 | Basf Ag | Verfahren zur Herstellung von gesättigten C3-C20-Alkoholen |
CN102249854B (zh) * | 2011-07-06 | 2014-02-19 | 上海焦化有限公司 | 一种制备新戊二醇的二步法加氢工艺 |
CN102311313B (zh) * | 2011-07-06 | 2014-09-10 | 上海焦化有限公司 | 一种采用铜锌铝催化剂催化加氢制备新戊二醇的方法 |
DE102012021276A1 (de) | 2012-10-29 | 2014-04-30 | Oxea Gmbh | Kontinuierliches Verfahren zur Herstellung von Neopentylglykol |
-
2012
- 2012-10-29 DE DE102012021280.1A patent/DE102012021280A1/de not_active Ceased
-
2013
- 2013-09-28 CN CN201380048126.XA patent/CN104640829B/zh active Active
- 2013-09-28 KR KR1020157010991A patent/KR102110117B1/ko active IP Right Grant
- 2013-09-28 WO PCT/EP2013/002922 patent/WO2014067600A1/de active Application Filing
- 2013-09-28 EP EP13770841.8A patent/EP2912000B1/de active Active
- 2013-09-28 US US14/427,181 patent/US9353032B2/en active Active
- 2013-09-28 JP JP2015538313A patent/JP6263191B2/ja active Active
- 2013-10-28 TW TW102138825A patent/TW201416343A/zh unknown
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1518784A1 (de) | 1964-10-21 | 1969-08-21 | Eastman Kodak Co | Verfahren zur gleichzeitigen Herstellung von Neopentylglykol und Isobutanol |
EP0006460A1 (de) | 1978-06-24 | 1980-01-09 | Chemische Werke Hüls Ag | Verfahren zur Gewinnung von reinem Neopentylglykol |
EP0278106A1 (de) | 1986-12-30 | 1988-08-17 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung von 2,2-Dimethylpropandiol-(1,3) |
EP0301853A1 (de) * | 1987-07-29 | 1989-02-01 | DAVY McKEE (LONDON) LIMITED | Katalysator |
US4855515A (en) | 1987-08-12 | 1989-08-08 | Eastman Kodak Company | Process for the production of neopentyl glycol |
EP0484800A2 (de) | 1990-11-06 | 1992-05-13 | Mitsubishi Gas Chemical Company, Inc. | Verfahren zur Herstellung von Neopentylglykol |
EP0522368A1 (de) | 1991-06-28 | 1993-01-13 | Aristech Chemical Corporation | Herstellung von Neopentylglykol (IV) |
WO1998029374A1 (en) | 1996-12-30 | 1998-07-09 | Neste Chemicals Oy | Process for the preparation of polyvalent alcohols |
DE102008033163A1 (de) | 2008-07-15 | 2010-01-21 | Oxea Deutschland Gmbh | Verfahren zur Gewinnung von Neopentylglykol durch Spaltung von im Herstellverfahren anfallenden Hochsiedern |
GB2482887A (en) * | 2010-08-18 | 2012-02-22 | Johnson Matthey Plc | Catalyst and process for hydrogenation of aldehydes |
Non-Patent Citations (1)
Title |
---|
H. ADKIN, ORG. REACT., vol. 8, 1954, pages 1 - 27 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9133083B2 (en) | 2012-10-29 | 2015-09-15 | Oxea Gmbh | Continuous method for the production of neopentyl glycol |
JP2016535089A (ja) * | 2014-09-25 | 2016-11-10 | エルジー・ケム・リミテッド | 高効率のネオペンチルグリコールの製造方法及びその製造装置 |
US9914682B2 (en) | 2014-09-25 | 2018-03-13 | Lg Chem, Ltd. | Highly efficient neopentyl glycol preparation method and device therefor |
CN107108413A (zh) * | 2015-09-07 | 2017-08-29 | Lg化学株式会社 | 制备二醇的装置及其制备方法 |
CN107108413B (zh) * | 2015-09-07 | 2021-03-05 | Lg化学株式会社 | 制备二醇的装置及其制备方法 |
EP3747855A1 (de) | 2019-06-04 | 2020-12-09 | OXEA GmbH | Verfahren zur kontinuierlichen herstellung von diolen aus aldehyden mittels raney-cobalt katalyse |
WO2020245101A1 (de) | 2019-06-04 | 2020-12-10 | Oxea Gmbh | Verfahren zur kontinuierlichen herstellung von diolen aus aldehyden mittels raney-cobalt katalyse |
Also Published As
Publication number | Publication date |
---|---|
JP6263191B2 (ja) | 2018-01-17 |
JP2016500693A (ja) | 2016-01-14 |
CN104640829B (zh) | 2017-03-08 |
CN104640829A (zh) | 2015-05-20 |
US9353032B2 (en) | 2016-05-31 |
EP2912000A1 (de) | 2015-09-02 |
DE102012021280A1 (de) | 2014-04-30 |
KR102110117B1 (ko) | 2020-05-15 |
US20150239809A1 (en) | 2015-08-27 |
TW201416343A (zh) | 2014-05-01 |
KR20150076177A (ko) | 2015-07-06 |
EP2912000B1 (de) | 2017-03-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2912000B1 (de) | Verfahren zur herstellung von neopentylglykol | |
EP2318342B1 (de) | Verfahren zur herstellung von neopentylglykol | |
EP2912001B1 (de) | Kontinuierliches verfahren zur herstellung von neopentylglykol | |
EP2307340B1 (de) | Verfahren zur gewinnung von neopentylglykol durch spaltung von im herstellverfahren anfallenden hochsiedern | |
EP2501667B1 (de) | Verfahren zur herstellung eines geträgerten hydrierkatalysators mit erhöhter hydrieraktivität | |
DE3027890A1 (de) | Hydrierkatalysatoren fuer die herstellung von propandiolen und verfahren zur herstellung von propandiolen mit solchen katalysatoren | |
DE102005032726A1 (de) | Katalysator und Verfahren zur Hydrierung von Carbonylverbindungen | |
EP1993983B1 (de) | Verfahren zur hydrierung von methylolalkanalen | |
DE102013021512A1 (de) | Verfahren zur Herstellung von 3-Hydroxyalkanalen | |
DE102013021509B4 (de) | Verfahren zur Herstellung von 3-Hydroxyalkanalen | |
DE102011122356A1 (de) | Verfahren zur Gewinnung von mit Trimethylolpropan angereicherten Produktströmen aus den Nebenströmen der Trimethylolpropanherstellung | |
EP1440049A1 (de) | Verfahren zur zersetzung von ammoniumformiaten in polyolhaltigen reaktionsgemischen | |
DE102013021508A1 (de) | Verfahren zur Herstellung von Neopentylglykol | |
DE102015000809A1 (de) | Verfahren zur Herstellung von 3-Hydroxyalkanalen | |
WO2007099049A2 (de) | Verfahren zur hydrierung von methylolalkanalen zu mehrwertigen alkoholen mit geringem acetalgehalt | |
DE102015000810A1 (de) | Verfahren zur Herstellung von 3-Hydroxyalkanalen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13770841 Country of ref document: EP Kind code of ref document: A1 |
|
DPE2 | Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 14427181 Country of ref document: US |
|
REEP | Request for entry into the european phase |
Ref document number: 2013770841 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013770841 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20157010991 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2015538313 Country of ref document: JP Kind code of ref document: A |