[go: up one dir, main page]

WO2008037693A1 - Procédé de production de citral en continu - Google Patents

Procédé de production de citral en continu Download PDF

Info

Publication number
WO2008037693A1
WO2008037693A1 PCT/EP2007/060115 EP2007060115W WO2008037693A1 WO 2008037693 A1 WO2008037693 A1 WO 2008037693A1 EP 2007060115 W EP2007060115 W EP 2007060115W WO 2008037693 A1 WO2008037693 A1 WO 2008037693A1
Authority
WO
WIPO (PCT)
Prior art keywords
methyl
citral
column
butenal
catalyst
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.)
Ceased
Application number
PCT/EP2007/060115
Other languages
German (de)
English (en)
Inventor
Günter WEGNER
Gerd Kaibel
Jörg Therre
Werner Aquila
Hartwig Fuchs
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 WO2008037693A1 publication Critical patent/WO2008037693A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
    • 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
    • C07C29/44—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond
    • 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
    • C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/28—Preparation of ethers by reactions not forming ether-oxygen bonds from acetals, e.g. by dealcoholysis
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
    • 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
    • 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
    • C07C45/70—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 with functional groups containing oxygen only in singly bound form
    • C07C45/71—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 with functional groups containing oxygen only in singly bound form being hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
    • C12C11/00—Fermentation processes for beer
    • C12C11/02—Pitching yeast

Definitions

  • the present invention relates to a process for the preparation of citral (3,7-dimethyl-octa-2,6-dienal) in which the product citral can be obtained in an environmentally friendly manner in high yields starting from cheap products.
  • various synthetic routes for the production of citral are known.
  • Citral is a valuable intermediate for the production of various odors and fragrances, such as geraniol.
  • citral has also gained importance as a source material for the production of vitamins, in particular of vitamin A.
  • Citral can also be obtained from lemongrass in a complex process, which, however, is not economical in view of the high demand for citral.
  • Another conventional large-scale process which is based on ß-pinene as starting material, can not be carried out economically on a large scale due to the environmentally harmful by-products.
  • the intermediates or the unreacted starting materials formed in the various reaction stages should preferably be recirculated back into the production process in order to reduce the amount of by-products which pollute the environment.
  • the end product citral is obtained in high yield as cost-effective reactants in a process which is also easy to control industrially.
  • the overall process is preferably carried out continuously in the individual stages, in particular as a fully continuous overall process.
  • Another embodiment of the invention relates to a process for the preparation of citral, wherein the process is carried out fully continuously and the by-products from process steps b) and d) are introduced again into the process.
  • An embodiment of the invention relates to a process in which the process is carried out fully continuously and the by-products from process steps a), b), d) and e) are introduced again into the process in each case.
  • a further embodiment of the invention relates to a process for the preparation of citral, wherein in the isomerization of 3-methyl-3-butenal sodium acetate is used as a catalyst and that the entire process is carried out fully continuously and the by-products from the process steps a), b), c), d) and e) are each reinjected into the procedure.
  • the subject matter is also a process for the preparation of citral, wherein the oxidative dehydrogenation of 3-methyl-3-buten-1-ol (isoprenol) with an oxygen-containing gas on a supported silver catalyst (process step b) is carried out such that 3-methyl-3-buten-1-ol is evaporated, then this vapor is added to the oxygen-containing gas, the thus obtained, oxygen-containing alcohol vapor initially at a temperature above the dew point of 3-methyl-3-butene-1 but below the starting temperature of the reaction by an at least 0.5 cm thick layer of supported silver catalyst is passed and then the oxygen-containing vapor of 3-methyl-3-buten-1-ol in a desired capacity corresponding number of arranged parallel and flow around with a fluid heat transfer reaction tubes having an inner diameter of 1 to 2 cm and a length of 35 to 60 cm and filled with the supported silver catalyst t, is reacted at temperatures of 300 ° to 600 0 C to a mixture of isomeric aldehydes.
  • a further embodiment of the invention relates to a process for the preparation of citral, wherein in the isomerization of 3-methyl-3-buten-1-ol (isoprenol) to 3-methyl-2-buten-1-ol (prenol) (process step d ) in the presence of hydrogen as a noble metal-containing fixed bed catalyst, a catalyst containing palladium and selenium or tellurium or a mixture of selenium and tellurium on a silica support is used.
  • One embodiment of the invention relates to a process for the preparation of citral, which comprises the starting materials 3-methyl-2-buten-1-ol (prenol ) and 3-methyl-2-butenal (Prenal) are only partially reacted in the reaction column and the resulting unsaturated acetal is concentrated in at least two successive evaporator stages and the recovered starting materials are recycled back to the reaction column.
  • prenol 3-methyl-2-buten-1-ol
  • Prenal 3-methyl-2-butenal
  • a further embodiment of the invention relates to a process for the preparation of citral, which comprises the intermediates 3-methyl-2-butene in the thermal cleavage of the 3-methyl-2-butenealdiprenyl acetal and the subsequent rearrangements (process step f)).
  • the invention also relates to a process for the preparation of citral, in which the citral obtained by thermal cleavage of the 3-methyl-2-butenal-diprenyl acetal and the subsequent rearrangements is separated off from the crude mixture by rectification, where: a) the crude mixture is introduced laterally into an intake column with a reinforcing part located above the feed point and a driven part located below the feed point,
  • Isomerization of isoprenol to 3-methyl-2-buten-1-ol can be carried out in the presence of hydrogen and a catalyst (process step d), wherein a fixed bed catalyst can be used as the catalyst, in particular the palladium and selenium or tellurium or containing a mixture of selenium and tellurium on a silica support.
  • a catalyst in particular the palladium and selenium or tellurium or containing a mixture of selenium and tellurium on a silica support.
  • DE-C-19 01 709 describes a process for the preparation of buten-2-ol-4 compounds in which buten-1-ol-4 compounds are reacted in the presence of palladium or palladium compounds and hydrogen.
  • the double bond of the compounds is significantly hydrogenated and a saturated product is formed.
  • low-boiling compounds such as hydrocarbons and aldehydes are formed as by-products, for example by hydrogenolysis and isomerization.
  • the hydrogenation of the double bond is undesirable because some butenols only low boiling point differences between unreacted starting material and hydrogenation exist.
  • the boiling point of 3-methyl-3-buten-1-ol for example, at 1020 mbar 131, 5 0 C, the boiling point of the corresponding hydrogenation product 3-methyl-1-butanol 130.9 0 C. This makes a distillative separation of Hydrogenation product and starting product difficult.
  • EP-A 841 090 discloses the provision of a process for the continuous preparation of 2-buten-1-ol compounds by isomerization of 3-buten-1-ol compounds, the proportion of resulting hydrogenation products and low-boiling components being very low.
  • a fixed-bed catalyst containing palladium and selenium or tellurium or a mixture of selenium and tellurium on a silica support is used, and a BET surface area of 80 to 380 m 2 / g and a pore volume of 0.6 to 0.95 cm 3 / g in the pore diameter range of 3 nm to 300 microns, wherein 80 to 95% of the pore volume in the pore diameter range of 10 to 100 nm.
  • the catalyst contains 0.1 to 2.0 wt .-% palladium and 0.01 to 0.2 wt .-% selenium, tellurium or a mixture of selenium and tellurium, based on the total weight of the catalyst.
  • the BET surface area is, for example, 100 to 150 m 2 / g, in particular 110 to 130 m 2 / g.
  • the BET surface area is determined by N 2 adsorption in accordance with DIN 66131.
  • the pore volume in the pore diameter range from 3 nm to 300 ⁇ m is preferably 0.8 to 0.9 cm 3 / g, in particular 0.8 to 0.85 cm 3 / g.
  • the catalyst contains 0.2 to 0.8 wt .-%, in particular from 0.4 to 0.6% by weight of palladium.
  • the catalyst contains 0.02 to 0.08, in particular 0.04 to 0.06 wt .-% selenium, tellurium or a mixture of selenium and tellurium, preferably selenium.
  • further metals can be present on the catalyst to a small extent.
  • FR-A-2 231 650 (Givaudan, 1974) describes the preparation of aldehydes and ketones from the corresponding alcohols by air oxidation at 250 to 600 ° C. in the presence of a gold catalyst.
  • the advantage of the gold catalyst is the higher selectivity compared to copper and silver catalysts, thus reducing by-product formation. Disadvantages of this process are the high catalyst costs, since a solid gold contact is used.
  • a disadvantage of this very advantageous combination of processes is that in the continuous implementation of the process despite frequent burning off of soot and other incrustations on the catalyst after a few weeks, both the conversion and the selectivity drops sharply, so that the catalyst must be replaced.
  • opening such a reactor showed that the reaction tubes are clogged for the most part.
  • the plugs in the individual tubes are so hard that the affected tubes must be drilled with a drill, which is technically very complicated and can lead to damage to the pipes.
  • the slow clogging of the individual tubes can be prevented permanently by pre-switching an ordered packing of metal mesh as a pre-filter nor by overlaying the catalyst layer with inert particles, such as glass or porcelain balls, as a filter.
  • Another disadvantage of this method is that the construction of tube bundle reactors with very short reaction tubes for such tube bundle reactors in which high capacity, d. H. to work with a very large number of reaction tubes, prepares more technical difficulties.
  • the object of this reaction step is a process for the continuous preparation of the unsaturated aliphatic aldehyde isoprenal
  • the oxygen-containing alcohol vapor in a number corresponding to the desired capacity of parallel arranged and surrounded by a fluid heat carrier and filled with one of said support catalyst reaction tubes having an inner diameter D of about 0.5 to 3 cm, preferably 1 to 2 cm , and a length of at least 5 cm, preferably 35 to 60 cm, at temperatures of 300 to 600 0 C to the corresponding aldehyde react.
  • the unsaturated acetal 3-methyl-2-butenal-diprenylacetal is prepared starting from prenol and prenal using a catalyst.
  • prenal is reacted together with prenol in the presence of catalytic amounts of acid and with removal of the water formed during the reaction.
  • the components are reacted only partially in a reaction column, the acetal obtained is concentrated in at least two successive evaporator stages and the recovered components are returned to the reaction column.
  • the method described represents an advance for the production of acetals, but unfortunately has some disadvantages. Since, according to the known state of the art, high conversions of over 90% are desired, the production plant is difficult to control. Small fluctuations in the amount of inflows or in the purities of the starting materials cause the desired conversion in the reaction column can not be met. This fact is particularly noticeable when using feedstocks with impurities.
  • impurities are e.g. Derivative products of the aldehyde and the alcohol, e.g. Formates of the alcohol, ethers formed from the alcohol or condensation products of alcohol and aldehyde linked via C-C bonds.
  • Difficult is also the addition of the right amount of acid.
  • the amount of acid Even a slight underdosing of the amount of acid to break down the Um- record in the reaction column. But if more than the right amount of acid is added, this leads to a large increase in the amount of high-boiling secondary components and ethers.
  • the control of the amount of acid is made more difficult by the fact that the acid accumulates in the reaction column and as a result an overdose or an underdosing is usually not noticed until after a considerable time delay.
  • the apparatus for producing the unsaturated acetals preferably consists of a distillation column which is used as a reaction column.
  • the rising at the top of the column vapors are condensed in the condenser and passed into a phase separation vessel in which the water separates as the lower phase.
  • the upper phase consists essentially of organic compounds (aldehyde, alcohol and low boiling side compounds such as the formates of the alcohol used). Most of the organic phase is recycled as reflux to the top of the column, a smaller portion discharged to remove the minor components.
  • the amount of reflux is per 1000 kg freshly added aldehyde 200 kg to 50,000 kg, in particular 1000 kg to 20,000 kg. This small amount of reflux and thus the low energy requirement represent a particular advantage of the process step.
  • the amount of discharge is - depending on the purity of the starting materials used - per 1000 kg freshly added aldehyde between 1 kg and 400 kg, in particular between 5 kg and 200 kg.
  • the bottom of the column passes into the evaporator, which is the first stage of the two-stage concentration of the acetal.
  • the vapors recovered in the evaporator consist of 10 wt .-% to 80 wt .-% alcohol, up to 10 wt .-% of the acetal and 10 wt .-% to 40 wt .-% of the aldehyde.
  • the conversion of aldehyde in the reaction column is therefore below 90%. It is possible to dispense with the condensation of the vapors and to return the vapors in gaseous form to the column.
  • the vapors are condensed in the condenser.
  • the amount of vapors generated in the vaporizer stage that is, the amount of reactants recycled in the first vaporizer stage is between twice and thirty times, more preferably between three and twenty times, the amount of freshly added aldehyde.
  • Too small an amount of the reactants recycled in the first evaporator stage will result in a loss of selectivity. Too high an amount in the first evaporator Although the stage of recycled reactants is favorable for the selectivity of acetal synthesis, it consumes unnecessarily large amounts of energy.
  • a great advantage of the process according to the invention is its easy controllability and stable operation, since the amount of reactants to be recycled in the first evaporator stage can easily be determined by observing the temperatures in the column and the evaporators.
  • a reactor in which the condensate obtained in the condenser and the starting materials alcohol and aldehyde are added.
  • the reactor is used to adjust the thermodynamic equilibrium between alcohol and aldehyde on the one hand and water and acetal on the other.
  • backmixed reactors such as stirred tanks
  • non-backmixed tubular reactor reactors such as packed columns
  • the residence time of the reaction mixture in the reactor is between 0.1 sec and 10 hours. Since the thermodynamic equilibrium often sets very fast, may be sufficient for a very short residence time.
  • the usual mixing means such. static mixers or stirred tanks are used.
  • the acid can be added to the reactor or the evaporator.
  • the acid is added to the reaction column and added there again advantageously in the lower part of the column or in the evaporator, if it is a volatile and in particular nitric acid. It is also possible to add the acid in different places, e.g. at two or more points in the column or partly in the column and partly in the reactor.
  • the liquid emerging from the reactor should preferably be added in the upper part of the column. It is also possible to add the liquid, optionally mixed with the reflux, directly as reflux to the top of the column.
  • the addition point of fresh aldehyde and fresh alcohol is not critical.
  • the two starting materials can also be added separately at different points of the column and / or the reactor.
  • the starting materials are preferably combined with the effluent from the condenser.
  • the added amount of freshly added alcohol is controlled so that the ratio of alcohol to aldehyde is between 1 and 3, in particular between 1, 5 and 2.5.
  • a particular advantage of the method step according to the invention is that even the contaminated starting materials described above can be used without problems.
  • the liquid leaving the evaporator usually contains the acetal in a concentration of between 10% by weight and 70% by weight. The remainder consists essentially of the aldehyde and the alcohol.
  • This liquid is placed in a downstream evaporator where the acetal is recovered in a concentration between 30 wt .-% and 99.9 wt .-% as a liquid, in particular from 50 wt .-% to 95 wt .-%.
  • the vapors rising from the evaporator are preferably returned to the bottom of the column and thus used to heat the column.
  • reaction conditions for the preparation of the unsaturated acetal reference is also made to EP-A 1 186 589 (BASF, 2002).
  • the intermediate 2,4,4-trimethyl-3-formyl-1,5-hexadiene can be obtained by thermal cleavage in the presence of a catalyst and subsequent Claisen rearrangement of the resulting butadiene ether (process step f). , which can then be converted to citral by a Cope rearrangement.
  • both the prenol formed and the intermediately formed intermediates of the formulas IV and V and the citral already during the reaction can be removed by distillation from the reaction mixture continuously and thus achieve improved yields.
  • the process step succeeds in carrying out the thermal cleavage of the acetal of the formula II in the lower part or in the bottom of a distillation column which functions as a cleavage column and has from 5 to 100 theoretical plates. It has proved to be very useful when introducing the acetal of formula II and optionally the acid catalyst in the lower part of the distillation column, in the bottom of the distillation column or in the evaporator of the distillation column.
  • One possibility for carrying out the process step according to the invention is characterized in that one carries out the thermal cleavage of the acetal of the formula II in the lower part or in the bottom of a distillation column with 5 to 100 theoretical plates, wherein the acetal of the formula II by suitable selection of the distillation conditions in holding lower part or in the bottom of the column, the citral of the formula I formed, the intermediately formed intermediates of formulas IV and V and the split prenol of the formula III collectively together at the top of the column as overhead and then the mixture by distillation, for. In a further distillation column.
  • the inventive method if one carries out the thermal cleavage of the acetal of formula II in the lower part or in the bottom of a distillation column with 5 to 100 theoretical plates, wherein the acetal of the formula II by suitable selection of the distillation conditions in the lower part or holds in the bottom of the column, the citral of formula I formed and the intermediately formed intermediates of formulas IV and V together liquid or vapor withdraws on a arranged in the middle or lower part of the column side draw and the cleaved prenol of the formula III at the top of Separate column with the overhead stream.
  • the mixture of citral withdrawn at the side draw or from the top stream of a column without side draw and the intermediately formed intermediates of the formulas IV and V is then suitably passed through a heated residence time tube in which the intermediates of formulas IV and V at temperatures of 100 be transferred to 200 0 C to citral.
  • the acetal required as the starting compound can, as described above, be prepared by reacting 3-methyl-2-buten-1-ol (prenol) with 3-methyl-2-butenal (Prenal). Depending on the conditions of preparation of the acetal, this may contain between 0.1 and 30% by weight of unreacted prenal and between 0.1 and 60% by weight of unreacted prenol. It is advantageous for the process if the concentration of the acetal of the formula II used in the starting material is above 30% by weight, preferably above 70% by weight.
  • the cleavage of the acetal of the formula II to prenol, citral and the citral precursors of the formulas IV and V takes place in a distillation column, the so-called split column, which is equipped with an evaporator and a condenser.
  • Suitable internals for the column are trays, fillers and in particular structured packings of sheet metal or metal mesh.
  • the number of theoretical plates of the column should be between 5 and 100. In a preferred embodiment, there is a side draw from which the citral and citral precursors are in vapor or liquid
  • the side draw is located in the middle or lower part of the column, wherein the side draw is expediently between 2 and 20 theoretical plates above the addition point of the acetal. Above the
  • the recovered from the top stream in the condenser Prenol and optionally 3-methyl-2-butenal can be removed at the sampling point and again for the preparation of the
  • Acetals of formula II are recycled in the process.
  • the in the process accumulating relatively small amounts of sump drain can be removed at the sampling point.
  • the acetal is added in the lower part of the cleavage column, but preferably in the bottom of the cleavage column or in the evaporator.
  • the bottom of the cleavage column can be enlarged by a container to have a larger reaction volume available.
  • the inflow to the acetal of the formula II is expediently such that the residence time relative to the inflow of acetal is between one minute and 6 hours, preferably between 5 minutes and 2 hours.
  • This relatively short residence time and the resulting smaller cost-effective equipment represent an advantage of the process step.
  • This process section can in principle be carried out batchwise, semicontinuously or continuously. For the semi-continuous process, a certain amount of acetal is initially charged at the beginning of the reaction and then optionally further acetal is added. With particular advantage, the process is carried out continuously.
  • a high-boiling inert compound can be introduced to start the apparatus in the bottom of the column to ensure a minimum level of the sump and the evaporator.
  • Suitable are all inert under the reaction conditions liquid substances which have a higher boiling point than citral and in particular as the acetal of formula II, such as the hydrocarbons tetradecane, pentadecane, hexadecane, octadecane, eicosane, or ethers such as diethylene glycol dibutyl ether, white oils, paraffin oils or mixtures of said compounds.
  • the reaction can be carried out without catalyst, ie only by heating. With particular advantage, however, it is carried out in the presence of an acidic catalyst.
  • Non-volatile protic acids such as sulfuric acid, p-toluenesulfonic acid and, above all, phosphoric acid are particularly suitable as acidic catalysts.
  • the catalyst is advantageously added to the lower part of the cleavage column, preferably into the bottom of the cleavage column or into the evaporator.
  • Example 1 Preparation of 3-methyl-3-buten-1-ol (MBE) in a 3000 ml autoclave
  • the formaldehyde solution and isobutene from a steel bottle are placed in an autoclave and the autoclave is closed.
  • the autoclave is heated to 260 0 C, whereby an autogenous pressure of about 100 bar is formed.
  • the autoclave is pressed with nitrogen to about 250 bar.
  • the mixture is stirred at about 260 0 C and about 250 bar for one hour. After one hour, allow to cool to room temperature and relax. Released isobutene is collected (about 1800 g) and can be used for other approaches.
  • the liquid reaction is balanced and analyzed. The result is a discharge of:
  • distillation is carried out in a 2 liter double-jacket four-necked flask with thermostat, column (with 1 m Sulzer EX packing), reflux divider, vacuum pump, distillation templates, thermometer and cold trap with dry ice.
  • Raw material :
  • the removal of water is carried out under normal pressure (1013 mbar) at a pot temperature up to 135 ° C and a transition temperature to 101 0 C.
  • the reflux ratio in this case carries loading about 5: 1.
  • the MBE purifying distillation is then carried out at a pressure of about 100 mbar at a bottom temperature of about 155 ° C and a transition temperature to about 73 ° C.
  • the reflux ratio is approximately 5: 1.
  • the weight of sump discharge after the distillation end is 40 g.
  • the fractions 1 and optionally 2 can be used for further distillations.
  • a short tube reactor (length: 100 mm, diameter 12 mm) with a sand bath heater is used.
  • Raw material 1000 g (11, 6 mol)
  • MBE approx. 12 g of 6% silver-shell catalyst (corresponding to a bulk height of 100 mm)
  • the reactor is heated to a temperature of 130 0 C.
  • the coolers are operated with a brine with a temperature of 3 ° C.
  • the sand bath is heated to a temperature of about 360 0 C, in this case, a nitrogen stream of 50 liters / hour manufacturer is provided.
  • the MBE inlet is started at approx. 110 g / h via the pump and at the same time 51 l / h of air are fed in (the nitrogen is switched off here).
  • the reaction has started as soon as the hot spot measurement is well above 360 0C.
  • the system is rendered inert with nitrogen and turned off.
  • Temperature quartz sand outside approx. 360 ° C
  • Temperature reactor at the hotspot approx. 450 ° C
  • IMBA 3-methyl-3-butenal
  • the reaction is carried out in a 2 liter four-necked flask equipped with stirrer, thermometer, oil bath and condenser.
  • the upper phase effluent from the reaction obtained in Example 2 is heated to about 150 0 C together with sodium acetate as the catalyst for about 2 hours. Subsequent analytical examination gives the following products:
  • distillation column In a 2 liter double-jacket four-necked flask with thermostat, distillation column (with 1 m Sulzer EX-packing), reflux divider, vacuum pump, distillation templates, thermometer and cold trap, the cleaning takes place.
  • the purifying distillation takes place at a vacuum of about 250 mbar.
  • the low boilers and the water are distilled off first to a top temperature of about 87 0 C.
  • the reflux ratio here is approximately 10: 1.
  • the MBA pure distillation takes place at a bottom temperature of up to about 165 0 C, a vacuum of 250 mbar and a top temperature to about 94 0 C.
  • the reflux ratio is about 5: 1.
  • the weight of bottoms discharge (MBE) after distillation is 340 g.
  • the recovered MBE can be used again in the reaction.
  • a tube reactor For the isomerization of MBE to prenol on a Pd / Se catalyst, a tube reactor is used.
  • the output is: 1000 g; Analysis: 470.0 g (47%) MBE
  • the thus recovered MBE is used together with the low-boiling components (especially isoamyl alcohol) preferably in the synthesis of MBA.
  • the Prenol pure distillation is then carried out at a bottom temperature of up to 165 0 C, a vacuum of 500 mbar and a top temperature to 122 0 C.
  • the greedier- ratio is in this case 5: 1.
  • the bottoms discharge is 9 g.
  • the starting materials are charged and heated at a vacuum of 80 mbar up to a bottom temperature of 110 0 C, wherein the resulting water is removed from the system.
  • the trial period is about 8 hours for the acetalization. The result is the following:
  • the turnover of MBA is: 64.1%
  • the selectivity to the acetal is: 95.7%.
  • the starting materials are submitted and heated under a vacuum of 50 mbar up to a sump temperature of 160 0 C. Overhead, the resulting prenol and the low boilers are distilled off.
  • the reflux ratio should be about 5: 1.
  • the test duration is about 6 hours for the acetal cleavage. The result is the following:
  • the citral thus obtained can be subjected to further purification or used directly as starting material for further syntheses.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Mycology (AREA)
  • Food Science & Technology (AREA)
  • Microbiology (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production de 3,7-diméthyl-octa-2,6-diénal (citral) comprenant les opérations suivantes et permettant de fabriquer le produit à l'échelle industrielle. Selon l'invention, a) du 3-méthyl-3-butène-1-ol (isoprénol) est d'abord obtenu à partir d'isobutène et de formaldéhyde, b) du 3-méthyl-2-buténal (prénal) et du 3-méthyl-3-buténal (I-soprénal) sont obtenus à partir du 3-méthyl-3-butène-1-ol (isoprénol) par déshydrogénation oxydative au moyen d'un gaz contenant de l'oxygène sur catalyseur supporté d'argent, c) un autre 3-méthyl-2-buténal (prénal) est obtenu à partir d'un mélange contenant du 3-méthyl-3-buténal par isomérisation, d) le 3-méthyl-2-butène-1-ol (prénol) est obtenu à partir du 3-méthyl-3-butène-1-ol (isoprénol) par isomérisation, e) l'acétal insaturé 3-méthyl-2-buténal-diprenylacétal est obtenu à partir du 3-méthyl-2-butèn-1-ol (prénol) et du 3-méthyl-2-buténal (prénal) au moyen d'un catalyseur acide, et f) le citral est obtenu à partir du 3-méthyl-2-buténal-diprénylacétal par fission et transposition subséquente.
PCT/EP2007/060115 2006-09-26 2007-09-24 Procédé de production de citral en continu Ceased WO2008037693A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP06121289.0 2006-09-26
EP06121289 2006-09-26

Publications (1)

Publication Number Publication Date
WO2008037693A1 true WO2008037693A1 (fr) 2008-04-03

Family

ID=39027617

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/060115 Ceased WO2008037693A1 (fr) 2006-09-26 2007-09-24 Procédé de production de citral en continu

Country Status (1)

Country Link
WO (1) WO2008037693A1 (fr)

Cited By (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009115492A1 (fr) * 2008-03-19 2009-09-24 Basf Se Utilisation d'un catalyseur supporté contenant des métaux précieux pour la déshydrogénation oxydative
CN101381290B (zh) * 2008-10-30 2011-03-16 浙江大学 异戊二烯基-3-甲基丁-2-烯基醚的连续气相反应法
US8263813B2 (en) 2008-02-28 2012-09-11 Basf Se Method for isomerizing olefinically unsaturated alcohols
EP2597081A1 (fr) 2011-11-25 2013-05-29 Basf Se Procédé de préparation de 2-alcenals 3-substitués, en particulier le prenal
CN103819309A (zh) * 2014-01-29 2014-05-28 中国石油集团东北炼化工程有限公司吉林设计院 异戊烯醇生产中脱水塔系统塔顶尾气回收利用装置
CN103861633A (zh) * 2014-02-24 2014-06-18 万华化学集团股份有限公司 一种非均相催化剂及其制备方法及利用该催化剂制备3-甲基-2-丁烯-1-醇的方法
WO2017150337A1 (fr) 2016-03-01 2017-09-08 株式会社クラレ Procédé de production de composé dialdéhyde
WO2017157897A1 (fr) 2016-03-15 2017-09-21 Basf Se Procédé de fabrication de prénol et de prénal à partir d'isoprénol
WO2018002040A1 (fr) 2016-06-29 2018-01-04 Basf Se Procédé de préparation d'aldéhydes alpha,bêta-insaturés par oxydation d'alcools en présence d'une phase liquide
CN107935833A (zh) * 2017-12-07 2018-04-20 万华化学集团股份有限公司 一种3‑甲基‑2‑丁烯‑1‑醛的制备方法
WO2018172110A1 (fr) 2017-03-20 2018-09-27 Basf Se Procédé de préparation d'aldéhydes alpha,bêta-insaturés par oxydation d'alcools en présence d'une phase liquide
WO2019121012A1 (fr) 2017-12-21 2019-06-27 Basf Se Procédé de préparation d'aldéhydes alpha,bêta-insaturés par oxydation d'alcools en présence d'une phase liquide
WO2019121011A1 (fr) 2017-12-21 2019-06-27 Basf Se Procédé de préparation de 3-méthyl-2-butèn-1-al
CN110225902A (zh) * 2017-01-31 2019-09-10 株式会社可乐丽 γ，δ-不饱和醇的制造方法
CN110407680A (zh) * 2019-08-20 2019-11-05 万华化学集团股份有限公司 一种制备异戊烯醛的方法
WO2020049111A1 (fr) 2018-09-05 2020-03-12 Basf Se Procédé de production d'isoprénol
WO2020048855A1 (fr) 2018-09-07 2020-03-12 Basf Se Procédé de préparation d'aldéhydes alpha,bêta-insaturés par oxydation d'alcools en présence d'une phase liquide
WO2020048852A1 (fr) 2018-09-07 2020-03-12 Basf Se Procédé de préparation d'aldéhydes alpha, bêta insaturés par oxydation d'alcools en présence d'une phase liquide
CN111018682A (zh) * 2019-12-17 2020-04-17 南通天泽化工有限公司 一种柠檬醛的制备方法
WO2020099390A1 (fr) 2018-11-13 2020-05-22 Basf Se Lit de catalyseur comprenant des corps de catalyseur d'argent et processus de déshydrogénation oxydative d'alcools à insaturation oléfinique
CN111807936A (zh) * 2020-07-22 2020-10-23 万华化学集团股份有限公司 一种异戊二烯基异戊烯基醚的制备方法
CN112574018A (zh) * 2020-11-30 2021-03-30 万华化学集团股份有限公司 一种低色号柠檬醛及其制备方法
US10974225B1 (en) 2020-01-17 2021-04-13 Zhejiang Nhu Company Ltd. Metal oxide coated ceramic corrugated plate catalyst, preparation and application in preparation of key intermediates of citral
CN113861005A (zh) * 2021-11-15 2021-12-31 江苏宏邦化工科技有限公司 一种通过管式反应器连续化合成柠檬醛的方法
CN114163315A (zh) * 2021-11-18 2022-03-11 万华化学集团股份有限公司 一种3-甲基-2-丁烯-1-醛的制备方法
CN114163303A (zh) * 2021-11-16 2022-03-11 万华化学集团股份有限公司 一种3-甲基-3-丁烯-1-醇的连续制备方法
CN114195619A (zh) * 2021-11-26 2022-03-18 万华化学(四川)有限公司 一种2-甲基-3-丁烯-2-醇的制备方法
CN114315537A (zh) * 2021-12-31 2022-04-12 万华化学集团股份有限公司 一种3-甲基-2-丁烯-1-醛二异戊烯基缩醛的制备方法
CN114349613A (zh) * 2022-01-11 2022-04-15 万华化学集团股份有限公司 一种3-甲基-2-丁烯醛的制备方法
CN114380677A (zh) * 2020-10-16 2022-04-22 万华化学集团股份有限公司 一种3-甲基-2-丁烯醛的制备方法
CN114534631A (zh) * 2022-01-27 2022-05-27 绍兴明业化纤有限公司 一种异戊烯醇生产用进料装置
WO2023109746A1 (fr) * 2021-12-17 2023-06-22 Basf Se Procédé de préparation d'isoprénol et de matériau zéolitique nitruré
WO2023222895A1 (fr) 2022-05-20 2023-11-23 Basf Se Purification d'un flux d'alcool éthyléniquement insaturé, préparation d'un aldéhyde éthyléniquement insaturé, en particulier prenal, et composés dérivés de celui-ci
WO2023241952A1 (fr) 2022-06-14 2023-12-21 Basf Se Réacteur d'échange de chaleur à tubes et calandre pour la mise en œuvre d'une réaction d'oxydation partielle en phase gazeuse catalytique et procédé pour la mise en œuvre d'une oxydation partielle en phase gazeuse catalytique
WO2024002503A1 (fr) 2022-06-30 2024-01-04 Symrise Ag Procédé de production d'odorisants et de parfums sur un évaporateur à couche mince
WO2024068852A1 (fr) 2022-09-28 2024-04-04 Basf Se Procédé amélioré de préparation de 3,7-diméthyl-octa-2,6-diénal
WO2024089254A1 (fr) 2022-10-28 2024-05-02 Basf Se Procédé de fabrication d'un produit chimique d'intérêt dérivé d'une 4-oléfine, en particulier du citral, à partir d'éthanol d'origine renouvelable
WO2024133082A1 (fr) 2022-12-20 2024-06-27 Basf Se Fabrication d'un produit chimique d'intérêt dérivé d'éthylène en combinaison avec la production d'énergie thermique
WO2024235790A1 (fr) 2023-05-12 2024-11-21 Basf Se Réaction de guerbet mixte d'éthanol et de méthanol pour produire de l'isobutanol
WO2024246272A1 (fr) 2023-06-02 2024-12-05 Basf Se Procédés de préparation de citral et produits interdépendants
WO2024260908A1 (fr) 2023-06-19 2024-12-26 Basf Se Attributs environnementaux pour arôme chimique
WO2025078316A1 (fr) 2023-10-13 2025-04-17 Basf Se Procédé de préparation de prénal et d'isovaléraldéhyde
WO2025108976A2 (fr) 2023-11-20 2025-05-30 Basf Se Procédé d'isomérisation d'un alcool à insaturation éthylénique
WO2025108852A1 (fr) 2023-11-20 2025-05-30 Basf Se Procédé de préparation d'esters insaturés
WO2025114332A1 (fr) 2023-11-27 2025-06-05 Basf Se Procédé d'isomérisation d'un alcool éthyléniquement insaturé dans une cascade de réacteurs
WO2025176792A1 (fr) 2024-02-21 2025-08-28 Basf Se Procédés de préparation d'isoprénol et de produits dérivés de celui-ci

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2715209A1 (de) * 1977-04-05 1978-10-19 Basf Ag Verfahren zur herstellung von 3-alkyl-buten-l-alen
EP0244632A2 (fr) * 1986-04-11 1987-11-11 BASF Aktiengesellschaft Réacteur à faisceau de tubes, son application pour des réactions organiques exothermiques et procédé pour la préparation des cétones et des aldhéhydes
US4933500A (en) * 1988-05-16 1990-06-12 Rhone-Poulenc Sante Process for the preparation of citral
EP0992477A1 (fr) * 1998-10-07 2000-04-12 Basf Aktiengesellschaft Procédé de préparation de citral
DE10064751A1 (de) * 2000-12-22 2002-06-27 Bayer Ag Verfahren zur Herstellung von Alk-3-en-1-olen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2715209A1 (de) * 1977-04-05 1978-10-19 Basf Ag Verfahren zur herstellung von 3-alkyl-buten-l-alen
EP0244632A2 (fr) * 1986-04-11 1987-11-11 BASF Aktiengesellschaft Réacteur à faisceau de tubes, son application pour des réactions organiques exothermiques et procédé pour la préparation des cétones et des aldhéhydes
US4933500A (en) * 1988-05-16 1990-06-12 Rhone-Poulenc Sante Process for the preparation of citral
EP0992477A1 (fr) * 1998-10-07 2000-04-12 Basf Aktiengesellschaft Procédé de préparation de citral
DE10064751A1 (de) * 2000-12-22 2002-06-27 Bayer Ag Verfahren zur Herstellung von Alk-3-en-1-olen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KOGAN ET AL: "Liquid phase isomerization of isoprenol into prenol in hydrogen environment", APPLIED CATALYSIS A: GENERAL, ELSEVIER SCIENCE, AMSTERDAM, NL, vol. 297, no. 2, 6 January 2006 (2006-01-06), pages 231 - 236, XP005193063, ISSN: 0926-860X *

Cited By (65)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8263813B2 (en) 2008-02-28 2012-09-11 Basf Se Method for isomerizing olefinically unsaturated alcohols
US8410315B2 (en) 2008-02-28 2013-04-02 Basf Se Method for producing olefinically unsaturated carbonyl compounds by oxidative dehydrogenation of alcohols
WO2009115492A1 (fr) * 2008-03-19 2009-09-24 Basf Se Utilisation d'un catalyseur supporté contenant des métaux précieux pour la déshydrogénation oxydative
US8779212B2 (en) 2008-03-19 2014-07-15 Basf Se Use of a supported catalyst containing precious metal for oxidative dehydrogenation
CN101381290B (zh) * 2008-10-30 2011-03-16 浙江大学 异戊二烯基-3-甲基丁-2-烯基醚的连续气相反应法
EP2597081A1 (fr) 2011-11-25 2013-05-29 Basf Se Procédé de préparation de 2-alcenals 3-substitués, en particulier le prenal
WO2013076226A1 (fr) 2011-11-25 2013-05-30 Basf Se Procédé pour la préparation de 2-alcénals 3-substitués, en particulier de prénal
US9000227B2 (en) 2011-11-25 2015-04-07 Basf Se Process for preparing 3-substituted 2-alkenals, in particular prenal
CN103819309A (zh) * 2014-01-29 2014-05-28 中国石油集团东北炼化工程有限公司吉林设计院 异戊烯醇生产中脱水塔系统塔顶尾气回收利用装置
CN103861633A (zh) * 2014-02-24 2014-06-18 万华化学集团股份有限公司 一种非均相催化剂及其制备方法及利用该催化剂制备3-甲基-2-丁烯-1-醇的方法
WO2017150337A1 (fr) 2016-03-01 2017-09-08 株式会社クラレ Procédé de production de composé dialdéhyde
WO2017157897A1 (fr) 2016-03-15 2017-09-21 Basf Se Procédé de fabrication de prénol et de prénal à partir d'isoprénol
JP2019510018A (ja) * 2016-03-15 2019-04-11 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ プレノール及びプレナールをイソプレノールから生成する方法
US10414707B2 (en) 2016-03-15 2019-09-17 Basf Se Process for producing prenol and prenal from isoprenol
WO2018002040A1 (fr) 2016-06-29 2018-01-04 Basf Se Procédé de préparation d'aldéhydes alpha,bêta-insaturés par oxydation d'alcools en présence d'une phase liquide
US10532970B2 (en) 2016-06-29 2020-01-14 Basf Se Process for the preparation of alpha, beta unsaturated aldehydes by oxidation of alcohols in the presence of a liquid phase
CN110225902B (zh) * 2017-01-31 2022-07-15 株式会社可乐丽 γ,δ-不饱和醇的制造方法
CN110225902A (zh) * 2017-01-31 2019-09-10 株式会社可乐丽 γ，δ-不饱和醇的制造方法
WO2018172110A1 (fr) 2017-03-20 2018-09-27 Basf Se Procédé de préparation d'aldéhydes alpha,bêta-insaturés par oxydation d'alcools en présence d'une phase liquide
US10875821B2 (en) 2017-03-20 2020-12-29 Basf Se Process for the preparation of alpha, beta unsaturated aldehydes by oxidation of alcohols in the presence of a liquid phase
CN107935833A (zh) * 2017-12-07 2018-04-20 万华化学集团股份有限公司 一种3‑甲基‑2‑丁烯‑1‑醛的制备方法
US11111197B2 (en) 2017-12-21 2021-09-07 Basf Se Process for the preparation of alpha, beta unsaturated aldehydes by oxidation of alcohols in the presence of a liquid phase
WO2019121012A1 (fr) 2017-12-21 2019-06-27 Basf Se Procédé de préparation d'aldéhydes alpha,bêta-insaturés par oxydation d'alcools en présence d'une phase liquide
WO2019121011A1 (fr) 2017-12-21 2019-06-27 Basf Se Procédé de préparation de 3-méthyl-2-butèn-1-al
US11046632B2 (en) 2017-12-21 2021-06-29 Basf Se Process for the preparation of 3-methyl-2-buten-1-al
WO2020049111A1 (fr) 2018-09-05 2020-03-12 Basf Se Procédé de production d'isoprénol
WO2020048852A1 (fr) 2018-09-07 2020-03-12 Basf Se Procédé de préparation d'aldéhydes alpha, bêta insaturés par oxydation d'alcools en présence d'une phase liquide
WO2020048855A1 (fr) 2018-09-07 2020-03-12 Basf Se Procédé de préparation d'aldéhydes alpha,bêta-insaturés par oxydation d'alcools en présence d'une phase liquide
WO2020099390A1 (fr) 2018-11-13 2020-05-22 Basf Se Lit de catalyseur comprenant des corps de catalyseur d'argent et processus de déshydrogénation oxydative d'alcools à insaturation oléfinique
CN110407680A (zh) * 2019-08-20 2019-11-05 万华化学集团股份有限公司 一种制备异戊烯醛的方法
CN110407680B (zh) * 2019-08-20 2022-08-02 万华化学集团股份有限公司 一种制备异戊烯醛的方法
CN111018682A (zh) * 2019-12-17 2020-04-17 南通天泽化工有限公司 一种柠檬醛的制备方法
US10974225B1 (en) 2020-01-17 2021-04-13 Zhejiang Nhu Company Ltd. Metal oxide coated ceramic corrugated plate catalyst, preparation and application in preparation of key intermediates of citral
CN111807936B (zh) * 2020-07-22 2022-11-08 万华化学集团股份有限公司 一种异戊二烯基异戊烯基醚的制备方法
CN111807936A (zh) * 2020-07-22 2020-10-23 万华化学集团股份有限公司 一种异戊二烯基异戊烯基醚的制备方法
CN114380677B (zh) * 2020-10-16 2023-12-19 万华化学集团股份有限公司 一种3-甲基-2-丁烯醛的制备方法
CN114380677A (zh) * 2020-10-16 2022-04-22 万华化学集团股份有限公司 一种3-甲基-2-丁烯醛的制备方法
CN112574018A (zh) * 2020-11-30 2021-03-30 万华化学集团股份有限公司 一种低色号柠檬醛及其制备方法
CN112574018B (zh) * 2020-11-30 2022-07-12 万华化学集团股份有限公司 一种低色号柠檬醛及其制备方法
CN113861005A (zh) * 2021-11-15 2021-12-31 江苏宏邦化工科技有限公司 一种通过管式反应器连续化合成柠檬醛的方法
CN114163303A (zh) * 2021-11-16 2022-03-11 万华化学集团股份有限公司 一种3-甲基-3-丁烯-1-醇的连续制备方法
CN114163315A (zh) * 2021-11-18 2022-03-11 万华化学集团股份有限公司 一种3-甲基-2-丁烯-1-醛的制备方法
CN114163315B (zh) * 2021-11-18 2023-05-30 万华化学集团股份有限公司 一种3-甲基-2-丁烯-1-醛的制备方法
CN114195619A (zh) * 2021-11-26 2022-03-18 万华化学(四川)有限公司 一种2-甲基-3-丁烯-2-醇的制备方法
CN114195619B (zh) * 2021-11-26 2023-05-30 万华化学(四川)有限公司 一种2-甲基-3-丁烯-2-醇的制备方法
WO2023109746A1 (fr) * 2021-12-17 2023-06-22 Basf Se Procédé de préparation d'isoprénol et de matériau zéolitique nitruré
CN114315537A (zh) * 2021-12-31 2022-04-12 万华化学集团股份有限公司 一种3-甲基-2-丁烯-1-醛二异戊烯基缩醛的制备方法
CN114315537B (zh) * 2021-12-31 2023-05-30 万华化学集团股份有限公司 一种3-甲基-2-丁烯-1-醛二异戊烯基缩醛的制备方法
CN114349613B (zh) * 2022-01-11 2023-05-26 万华化学集团股份有限公司 一种3-甲基-2-丁烯醛的制备方法
CN114349613A (zh) * 2022-01-11 2022-04-15 万华化学集团股份有限公司 一种3-甲基-2-丁烯醛的制备方法
CN114534631A (zh) * 2022-01-27 2022-05-27 绍兴明业化纤有限公司 一种异戊烯醇生产用进料装置
WO2023222895A1 (fr) 2022-05-20 2023-11-23 Basf Se Purification d'un flux d'alcool éthyléniquement insaturé, préparation d'un aldéhyde éthyléniquement insaturé, en particulier prenal, et composés dérivés de celui-ci
WO2023241952A1 (fr) 2022-06-14 2023-12-21 Basf Se Réacteur d'échange de chaleur à tubes et calandre pour la mise en œuvre d'une réaction d'oxydation partielle en phase gazeuse catalytique et procédé pour la mise en œuvre d'une oxydation partielle en phase gazeuse catalytique
WO2024002503A1 (fr) 2022-06-30 2024-01-04 Symrise Ag Procédé de production d'odorisants et de parfums sur un évaporateur à couche mince
WO2024068852A1 (fr) 2022-09-28 2024-04-04 Basf Se Procédé amélioré de préparation de 3,7-diméthyl-octa-2,6-diénal
WO2024089254A1 (fr) 2022-10-28 2024-05-02 Basf Se Procédé de fabrication d'un produit chimique d'intérêt dérivé d'une 4-oléfine, en particulier du citral, à partir d'éthanol d'origine renouvelable
WO2024133082A1 (fr) 2022-12-20 2024-06-27 Basf Se Fabrication d'un produit chimique d'intérêt dérivé d'éthylène en combinaison avec la production d'énergie thermique
WO2024235790A1 (fr) 2023-05-12 2024-11-21 Basf Se Réaction de guerbet mixte d'éthanol et de méthanol pour produire de l'isobutanol
WO2024246272A1 (fr) 2023-06-02 2024-12-05 Basf Se Procédés de préparation de citral et produits interdépendants
WO2024260908A1 (fr) 2023-06-19 2024-12-26 Basf Se Attributs environnementaux pour arôme chimique
WO2025078316A1 (fr) 2023-10-13 2025-04-17 Basf Se Procédé de préparation de prénal et d'isovaléraldéhyde
WO2025108976A2 (fr) 2023-11-20 2025-05-30 Basf Se Procédé d'isomérisation d'un alcool à insaturation éthylénique
WO2025108852A1 (fr) 2023-11-20 2025-05-30 Basf Se Procédé de préparation d'esters insaturés
WO2025114332A1 (fr) 2023-11-27 2025-06-05 Basf Se Procédé d'isomérisation d'un alcool éthyléniquement insaturé dans une cascade de réacteurs
WO2025176792A1 (fr) 2024-02-21 2025-08-28 Basf Se Procédés de préparation d'isoprénol et de produits dérivés de celui-ci

Similar Documents

Publication Publication Date Title
WO2008037693A1 (fr) Procédé de production de citral en continu
EP2986589B1 (fr) Procédé destiné à la fabrication de méthylméthacrylate
DE69824148T2 (de) Verfahren, Katalysator und Vorrichtung zur Herstellung von Acetaldehyd aus Essigsäure
EP3625199B1 (fr) Procédé d'hydroformylation servant dans la production industrielle d'alcools et/ou d'aldéhydes
WO2015158584A1 (fr) Production de 4-hydroxy-4-méthyl-tétrahydropyranes à partir de produits de départ contenant de la 2-alkyl-4,4-dimethyl-1,3-dioxane
WO2015158585A1 (fr) Production de 4-hydroxy-4-méthyl-tétrahydropyranes à substitution en position 2 à partir de matières de départ contenant du 2-alkyl-4,4-diméthyl-1,3-dioxane
DE3037536C2 (de) Verfahren zur Herstellung von Carbonylverbindungen
EP1456158B1 (fr) Procede d'isomerisation d'alcools allyliques
DE2715209B2 (de) Verfahren zur Herstellung von 3-Alkyl-buten-l-alen
DE102009027978A1 (de) Verfahren zur Herstellung von Decancarbonsäuren
DE10044352A1 (de) Kontinuierliches Verfahren zur Herstellung von Acetalen
DE69716059T2 (de) Kontinuiertes verfahren zur umwandlung von 2,5-dihydrofuran in 2,3-dihydrofuran
EP1294667A1 (fr) Procede de production d'aldehydes
US7465839B2 (en) Method for the hydrogenation of ketones
DE10359026A1 (de) Verfahren zur Herstellung von Tetrahydrogeranylaceton
EP0008013B1 (fr) Procédé pour la préparation de composés carbonylés
WO2000055108A1 (fr) PROCEDE DE PRODUCTION DE CETONES CYCLIQUES α, β-INSATUREES
EP2467355B1 (fr) Procédé de production d'acide pentène-4-oïque
DE69004199T2 (de) Herstellung von Cymenol durch direkte Dehydrogenierung.
EP1711452A2 (fr) Composition a activite catalytique et son utilisation dans des procedes de deshydrogenation
DE68904748T2 (de) Verfahren zur herstellung von p-isobutylstyrol.
WO2024068852A1 (fr) Procédé amélioré de préparation de 3,7-diméthyl-octa-2,6-diénal
WO2024246272A1 (fr) Procédés de préparation de citral et produits interdépendants
DE1917244C (de) Verfahren zur katalytischen Spaltung von Isobutyraldehyd
DE10238140A1 (de) Kontinuierliches Verfahren zur Herstellung von Carbonylverbindungen

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: 07820521

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07820521

Country of ref document: EP

Kind code of ref document: A1