CN1426384A - Method for producing ketal and/or acetal - Google Patents
Method for producing ketal and/or acetal Download PDFInfo
- Publication number
- CN1426384A CN1426384A CN01808717A CN01808717A CN1426384A CN 1426384 A CN1426384 A CN 1426384A CN 01808717 A CN01808717 A CN 01808717A CN 01808717 A CN01808717 A CN 01808717A CN 1426384 A CN1426384 A CN 1426384A
- Authority
- CN
- China
- Prior art keywords
- ketal
- acetal
- palladium
- production
- reaction
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/08—1,3-Dioxanes; Hydrogenated 1,3-dioxanes condensed with carbocyclic rings or ring systems
-
- 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
- C07C41/54—Preparation of compounds having groups by reactions producing groups by addition of compounds to unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
- C07D321/02—Seven-membered rings
- C07D321/10—Seven-membered rings condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The object of the present invention is to produce ketal and/or acetal from olefins with a high conversion rate and a high selectivity. The present invention provides a method for producing a ketal and/or acetal by allowing olefins having at least one ethylenic double bond to react with oxygen and a polyhydric alcohol in the presence of a catalyst, which comprises carrying out the reaction in the presence of (a) palladium, (b) at least one metal other than palladium belonging to the groups 8, 9, 10 and 14 of the periodic table and (c) a halogen as the catalyst and a method for producing a ketone and/or aldehyde by hydrolyzing the ketal and/or acetal obtained by the above method in the presence of an acid catalyst.
Description
Technical field
The present invention relates to a kind of method of producing ketal and/or acetal with the oxygen molecule olefin oxide.
Background technology
The corresponding aldehydes or ketones of being produced with the oxygen molecule olefin oxide is industrial useful compound, and for a long time, they synthesize by various catalyzed reactions always.Useful especially in all methods is the reaction that is commonly referred to the Watts Wacker reaction.In other words, a kind of like this method of industrial employing always is with containing PdCl
2And CuCl
2The aqueous solution as catalyzer, produce acetaldehyde by the oxygen molecule oxidation by ethene, by production of propylene acetone.Yet, in this tradition Wal gram reaction, the aqueous solution is under the strong acid condition and has high corrosion hydrochloric acid, is confined to rudimentary hydro carbons such as ethene and propylene so consider reactor and peripheral unit requirement advanced material and reactant, this always not industrial advantageous method.
As a kind of reaction that is similar to traditional Watts Wacker reaction, the alkene of also studying the hydroperoxidation complex compound (Pd-OOH chemical seed) by Pd becomes reactive ketone, and (JP-A-57-156428 is (corresponding to United States Patent (USP) 4,400,544), JP-A-60-92236, JP-A-61-60621; Here employed " JP-A " is meant " unexamined, disclosed Japanese patent application ").In this reaction, be used as the water that reaction medium replaces use in the gram reaction of traditional Wal such as methyl alcohol or alcoholic acid monohydroxy-alcohol, the metal-salt of Pd and Cu and/or Fe is as catalyzer simultaneously, but as commercial run, it is low and when the fatal shortcoming precipitation takes place reaction conditions Pd metal when high temperature side moves that this reaction exists selectivity such as product ketone or aldehyde.Above-mentioned document description arrives, and promotor Cu and Fe have equivalent action.
Also have, point out in the J.Org.Chem. volume 34,3949 (1969), 1,4-dioxy spiral shell [4,5] decane can pass through with PdCl
2And CuCl
2Produce with high yield by tetrahydrobenzene as reaction solvent as catalyzer and with polyvalent alcohol such as ethylene glycol or glycerine, yet do not provide in the literary composition such as the details with example explanation yield.The document is not referred to the application of molysite as catalyst component, does not disclose any solution Pd yet and precipitates this way as the critical defect of commercial run.
As mentioned above, current present situation is that the industrial effective means that is synthesized corresponding aldehydes or ketones by alkene does not find as yet.
Particularly, production as the useful pimelinketone of caprolactam precursors is adopted, hexanaphthene carries out oxidation in the presence of certain catalyzer that depends on the circumstances, the method of pimelinketone-hexalin mixture dehydrogenation subsequently, perhaps adopt cyclohexene hydration to obtain hexalin, the method for dehydrogenation reaction takes place in hexalin again.Yet, because oxidation then takes place in preceding a kind of product that reacts generation easily during cyclohexane oxidation, therefore transformation efficiency must be controlled at quite low level and allow a large amount of unnecessary unreacted hexanaphthenes circulate, cause this method to become the low method of a kind of energy efficiency.A kind of method in back also has problems, promptly, the yield deficiency of hydration reaction, so a large amount of energy expenditures the extraction of tetrahydrobenzene from the very approaching benzol-cyclohexane of boiling point with separate, perhaps consume very high from boiling point mole pimelinketone-hexalin mixture such as approximate and isolate separately in the process of pimelinketone.
As seen, a kind ofly prepare aldehydes or ketones by corresponding alkene such as tetrahydrobenzene if having, particularly pimelinketone, highly selective and synthetic method efficiently, its meaning will be quite big.
For solving these problems that relate in the olefin hydrocarbon oxidation reaction, the inventor has carried out further investigation and has found, Pd precipitates that this industrial fatal phenomenon can be prevented and the decline of catalyst selectivity can be inhibited, only need in the process of react by alkene and oxygen and polyvalent alcohol generation ketal and/or acetal, except with (a) palladium with (c) the halogen, also use (b) to belong at least a non-metallic palladium of 8,9,10 and 14 families of the periodic table of elements as catalyzer, so finished the present invention.
Summary of the invention
In sum, of the present inventionly to be intended to following aspects:
(1) alkene by having at least one olefinic double bonds and oxygen and polyvalent alcohol react in the presence of catalyzer and produce the method for ketal and/or acetal, this method be included in (a) palladium, (b) belong to the periodic table of elements 8,9,10 and 14 families at least a non-metallic palladium and (c) halogen implement this reaction down as the existence of catalyzer.
(2) the production ketal described in (1) and/or the method for acetal wherein are reflected in the liquid phase of having dissolved catalyzer and carry out.
(3) the production ketal described in (1) and (2) and/or the method for acetal comprise also that wherein copper is as catalyzer.
(4) the production ketal described in (3) and/or the method for acetal, wherein the catalyst compound that uses as the copper source is at least a in cuprous chloride and the cupric chloride.
(5) the production ketal described in (3) or (4) and/or the method for acetal, wherein the consumption of copper is 0.1～100 times of at least a non-metallic palladium of (b) 8,9,10 and 14 families of belonging to the periodic table of elements, by mole.
(6) as the method for any one described production ketal and/or acetal in (1)～(5), wherein (b) belongs at least a non-metallic palladium chosen from Fe, cobalt, nickel and the tin of 8,9,10 and 14 families of the periodic table of elements.
(7) the production ketal described in (6) and/or the method for acetal, wherein (b) to belong at least a non-metallic palladium of 8,9,10 and 14 families of the periodic table of elements be iron.
(8) as the method for any one described production ketal and/or acetal in (1)～(7), wherein (c) halogen is a chlorine.
(9) as the method for any one described production ketal and/or acetal in (1)～(8), wherein the concentration of palladium in reaction soln is 0.001～10 weight %.
(10) as the method for any one described production ketal and/or acetal in (1)～(9), wherein (b) belongs at least a non-metallic palladium of 8,9,10 and 14 families of the periodic table of elements and the mol ratio of palladium is 0.1～100 in the reaction soln.
(11) as the method for any one described production ketal and/or acetal in (1)～(10), wherein the mol ratio of (c) halogen and palladium is 0.1～100 in the reaction soln.
(12) as the method for any one described production ketal and/or acetal in (1)～(11), wherein the employed catalyst compound in source as (a) palladium is a Palladous chloride.
(13) as the method for any one described production ketal and/or acetal in (1)～(12), wherein the employed catalyst compound in source as (a) palladium is the compound of divalence palladium.
(14) as the method for any one described production ketal and/or acetal in (1)～(13), wherein the employed catalyst compound in source as (a) palladium is nitrile compounds-coordination compound.
(15) as the method for any one described production ketal and/or acetal in (1)～(14), wherein the catalyst compound in source of at least a non-metallic palladium that belongs to 8,9,10 and 14 families of the periodic table of elements as (b) is a muriate.
(16) as the method for any one described production ketal and/or acetal in (1)～(15), wherein the chlorine as (c) halogen is used as (a) or muriate (b).
(17) as the method for any one described production ketal and/or acetal in (1)～(16), wherein alkene is the cyclenes that contains 4～10 carbon atoms.
(18) method of production ketal and/or acetal described in (17), wherein alkene is tetrahydrobenzene.
(19) as the method for any one described production ketal and/or acetal in (1)～(16), wherein alkene is the terminal olefine that contains 2～25 carbon atoms.
(20) as the method for any one described production ketal and/or acetal in (1)～(16), wherein alkene is the internal olefin that contains 4～25 carbon atoms.
(21) as the method for any one described production ketal and/or acetal in (1)～(20), wherein polyvalent alcohol is aliphatic series or alicyclic diol.
(22) as the method for any one described production ketal and/or acetal in (1)～(21), wherein the consumption of polyvalent alcohol is 1～100 times of alkene, by mole.
(23) method of a kind of ketal that will produce by any one described method in claim (1)～(22) and/or acetal hydrolysis production ketone and/or aldehyde in the presence of acid catalyst.Invention optimum implementation (catalyzer)
Catalyzer of the present invention is made up of the component that comprises following material, and (a) palladium, (b) belong at least a non-metallic palladium and (c) halogen of 8,9,10 and 14 families of the periodic table of elements.In such cases, component (a)～(c) can any form such as dissociative ion, salt or molecule exist in reaction system.
(a) palladium can be in divalence～tetravalence form, and can randomly be selected from known and commercially available compound.Its example comprises halogenation palladium such as Palladous chloride and palladium bromide, mineral acid or organic acid palladium salt such as Palladous nitrate, palladous sulfate, acid chloride, palladium trifluoroacetate and palladium acetylacetonate, and inorganic palladium such as palladous oxide and palladium hydroxide.Useful also has by these metal-salt deutero-alkali coordination compounds, for example [Pd (en)
2] Cl
2, [Pd (phen)
2] Cl
2, [Pd (CH
3CN)
2] Cl
2, [Pd (C
6H
5CN)
2] Cl
2, [Pd (C
2O
4)
2]
2, [PdCl
2(NH
3)
2] and [Pd (NO
2)
2(NH
3)
2] (wherein en represents quadrol; Phen represents 1, the 10-phenanthroline), but be not limited to these.In these palladium sources, better adopt divalence palladium source, especially muriate or nitrile compounds-coordination compound.
The interaction of the effect of palladium in catalyst system available it and iron ion and polyvalent alcohol is represented, but action condition still imperfectly understands.In view of essence is that palladium is expressed its activity by constituting spike with other catalyst components, so be enough to induce the palladium source of this kind essence just enough as long as exist in the system.
Belong at least a non-metallic palladium of 8,9,10 and 14 families of the periodic table of elements as (b), can enumerate iron, cobalt, nickel, ruthenium and tin, wherein iron is preferred.
Can divalence or the existence of trivalent form as the catalyst compound that source of iron is used.For example, it can various salt form be used for this reaction, comprise muriate such as iron protochloride and iron(ic) chloride, bromide such as ferrous bromide and iron bromide, inorganic acid salt such as ferrous sulfate and ferric sulfate, Iron nitrate and iron nitrate and the salt such as ferrous acetate, ironic acetate, Ferrox, ironic oxalate, ironic formiate and ferric acetyl acetonade, perhaps its coordination compound form.Be similar to the situation of palladium, essence is that Tie Tong crosses and constitutes spike with other catalyst components and express its activity, therefore is enough to induce the source of iron of this kind essence just enough as long as exist in system.
Can take divalence, trivalent or quaternary form as the catalyst compound that cobalt, nickel, ruthenium or Xi Yuan use.As an example, can use various salt, comprise its halogenide such as muriate and bromide, inorganic acid salt such as vitriol and nitrate and such as salt such as acetate, oxalate, formate and acetylacetonate, perhaps its coordination compound.When component (b) is cobalt, nickel or tin, be preferably, it further is used in combination with copper.
Main effect of the present invention is, the precipitation of palladium is owing to the adding of component (b) is significantly suppressed, and further adds therein such as CuCl or CuCl
2And so on copper compound then will bring into play other advantageous effects as commercial run, that is, and the improvement of speed of reaction and the minimizing of by product such as halogenide.
Halogen (c) is chlorine (Cl) and/or bromine (Br), but chlorine (Cl) is particularly preferred.Halogen can be used as the phase pair anion of Pd and/or Fe in reaction system.Also can be with it as the muriate of other catalyst components or with the definite form supply response system such as HCl and HBr, but prerequisite is that under any circumstance this kind compound all should exist with ionic species in reaction system.
According to the present invention, ketal and/or acetal react in the liquid phase of having dissolved above-mentioned catalyzer by alkene and oxygen and polyvalent alcohol and make.(alkene)
The alkene that uses among the present invention is aliphatic series or the alicyclic organic compound that contains at least one olefinic double bonds.As chain alkene, can enumerate to contain usually and equal or more than 2, preferred 2～25, the more preferably alkene of 3～10 carbon atoms, for example ethene, propylene, butylene, amylene, hexene and octene.In such cases, the position of two keys both can also can be in inside at the end of the chain, but under the situation of terminal olefine the main ketal that forms acetal or methyl ketone, and at the next main corresponding ketal that obtains of the situation of internal olefin.
The example of cyclenes comprises having 4～10, preferred 5～8 carbon atoms, and contain the compound of at least one olefinic double bonds, and for example cyclopentenes, tetrahydrobenzene, cyclohexadiene, suberene and cyclooctene, wherein cyclopentenes and tetrahydrobenzene are the industrial compounds that is particularly useful.When during as alkene, generating 1 as product with tetrahydrobenzene, 4-dioxy spiral shell [4,5] decane (below be called the pimelinketone ketal).
At least a substituting group, for example alkyl, alkoxyl group, aryl, phenyl group, carboxylic group, halogen atom or nitro can be present in any position of these alkene main chains.For example, have the alkene of functional group in the 2-position such as vinyl cyanide, propenal, vinylformic acid or vinylchlorid, perhaps vinylbenzene or vinyl toluene are fit to take place this reaction.In addition, have the compound of fused rings, for example 3, the 4-dialin also can use if it has the words of olefinic double bonds.(polyvalent alcohol)
Polyvalent alcohol is generally binary～quaternary, and glycol is particularly suitable.Under the situation of glycol, it has 2 or more a plurality of carbon atom usually, but when considering cost, stability or when being easy to generate factor such as acetal or ketal, preferred 2～10, more preferably 3～8 carbon atoms, the preferred descriptions example of these glycol comprises ethylene glycol, 1, ammediol, 1,2-dihydroxyl butane, 1, the 2-dihydroxypropane, 1, the 4-butyleneglycol, 1,4 cyclohexane dimethanol, 1, the 2-cyclohexanedimethanol, glycol ether, 1,2-is trans-the ring pentanediol, 2, the 4-pentanediol, styrene glycol, 1,5-dihydroxyl cyclooctane, 1,4-dihydroxyl cyclooctane, 2,5-dihydroxyl norbornane, 2,6-dihydroxyl norbornane, 1,4-dihydroxyl-2,3-dimethylbutane, 1,5-dihydroxyl-2, the 4-dimethylpentane, tetramethylene-1, the 2-dimethanol, hexanaphthene-1, the 3-dimethanol, 1,4-dihydroxyl-2,3-dichlorobutane and 2, the 5-dihydroxy-hexane is wherein with ethylene glycol, 1, ammediol, 1,2-dihydroxyl butane, 1, the 2-dihydroxypropane, 1, the 4-butyleneglycol, 1, the 4-cyclohexanedimethanol, 1, the 2-cyclohexanedimethanol, glycol ether, 1, the trans ring pentanediol of 2-, 2, the 4-pentanediol, styrene glycol is preferred.Can be with two in the middle of them or more kinds of being used in combination.
Though the present invention must use the reason of polyvalent alcohol still to imperfectly understand, but it is believed that, exist with bivalent form such as muriate when palladium begins, generate divalence peroxo-complex subsequently as a kind of new active ingredient, think that again alcohol is for inducing this kind spike to play useful effect.Except this effect, it also reacts with the aldehydes or ketones that generates and generates corresponding acetal or ketal, and the result obtains the stability of the much higher antioxygen oxygenizement of a kind of specific ionization aldehyde and ketone.Like this, target product is kept remarkable high selectivity just becomes possibility.
When using such as methyl alcohol, ethanol or propyl alcohol monohydroxy-alcohol to replace polyvalent alcohol, product mainly is the aldehydes or ketones compound, and the generation of corresponding acetal or ketal is then few.Unstable under the condition that oxygen exists in view of these free aldehydes or ketones, they will be then oxidized, cause the yield of target aldehydes or ketones can not guarantee very high.In contrast, when use comprises the polyvalent alcohol of the dibasic alcohol such as ethylene glycol, propylene glycol and butyleneglycol, can obtain corresponding acetal or ketal as primary product.In view of subsequent oxidation takes place under oxidation reaction condition hardly for the acetal of so producing or ketal, therefore the yield of producing aldehydes or ketones by the former hydrolysis obviously comes highly.(reaction conditions)
According to the present invention, the use of oxygen-containing gas is a prerequisite, but in view of existing oxygen and organic compound at specified temp, particular pressure range and the possibility that forms explosive mixture in the definite composition scope are so must avoid this kind danger.If oxygen partial pressure is 0.001MPa or higher, this reaction can be carried out, but speed of reaction will be too slow, and catalyzer is crossed in oxygen partial pressure and also is tending towards passivation when hanging down simultaneously.In the present invention, oxygen partial pressure is preferably at 0.01～10MPa, more preferably 0.05～5MPa, but most preferred pressure should be selected according to safety and economic aspect.
When temperature of reaction is 0 ℃ or when higher, reaction can be carried out, but in view of the present invention very big to the temperature dependency of reaction, so higher temperature is satisfying.Though the selection of reactant should be taken into account the formation condition of explosive mixture and the increase that the free radical autoxidation causes by product, the speed of reaction that has an economic benefit can be at general 20～200 ℃, and preferred 40～180 ℃ temperature range obtains.The stagnation pressure of reaction can be to be equal to or greater than the pressure of keeping liquid phase, but is generally 0.1MPa～20MPa, preferred 0.1MPa～15MPa.Also have, the reaction times (residence time) is generally 5s～20h, preferred 10s～10h.
(a) palladium is 0.001～10 weight % as catalyst concentration, and preferred 0.01～5 weight % is by [Pd
2+] meter and be benchmark with the reaction soln gross weight.Under the high density condition, speed of reaction shows the concentration dependent that is different under low consistency conditions, and catalytic efficiency aggravates, and therefore concentration should be selected according to economic principle efficiently.
(b) concentration of at least a non-metallic palladium M that belongs to 8,9,10 and 14 families of the periodic table of elements can be described the relative concentration of (a) palladium with it.Here it is, and it can be chosen in, the scope of general 0.1＜[M]/[Pd]＜100 (mol ratio), preferred 0.1＜[M]/[Pd]＜10 (mol ratio).Concentration then will cause the speed of reaction downward trend if be lower than this scope, and precipitate inhibiting downward trend as the Pd of the main effect of metal (b).On the other hand, if its add-on is excessive, then may not can suppresses this reaction itself, but can cause the limited trend of its meltage in reaction system.
Halogen (c) is generally 1＜[Cl and/or Br]/[Pd]＜100 (mol ratio) with respect to the relative concentration of palladium, in the scope of preferred 0.3＜[Cl and/or Br]/[Pd]＜50 (mol ratio).In view of the water in the reactor under high halogen concentration condition might cause the reactor material corrosion, preferably halogen concentration is chosen in the alap level that guarantees that catalyst system normally plays a role.Also have, in some cases, may generate as the part of by product and to contain the derive component of halogen of catalyzer, and in this case, preferably with the form of for example its metal-salt halogen that falls of supplement consumed continuously or periodically.
The amount of polyvalent alcohol in reaction system can be to be the theoretical amount (1mol) of benchmark with alkene, but according to the present invention, it is desirable to also use it as reaction solvent simultaneously.Its amount is generally 1～99% (volume), and preferred 5～99% (volumes) are benchmark with the total reaction volume.Have, the amount of polyvalent alcohol is that benchmark is generally 1～100mol with alkene, preferred 2～50mol again.The amount of alkene in reaction system can be chosen in, and general 1～99% (volume) is in preferred 1～50% (volume) scope.
When the concentration of polyvalent alcohol is low relatively, that is, when the relative concentration of alkene is too high, has in mutually and cause the sedimentary trend of palladium easily because the part catalyst component has been assigned to alkene.On the other hand, if polyvalent alcohol concentration is excessive, then the concentration of the alkene of being supplied is corresponding reduction, therefore often brings the trend of the performance difficulty that is separated after the low and reaction of productivity.Under this type of situation, can regulate the relative concentration of polyvalent alcohol and alkene and further improve the characteristic that is separated by the 3rd component that in reaction system, adds " oxidation-inertia ".
According to the present invention, can improve activity and reactivity by adding another kind of component again.For example, can add a kind of additive, for example copper compound or basic metal, alkaline-earth metal or rare earth metal with promotes oxidn reactivity.Have again, also can take to add free radical and capture the method that agent is inhibited side reaction.
In high volume production process, especially as producing in the method for pimelinketone in the middle of all reactions of the present invention, when considering the material balance of whole process, require to separate impurity effectively by tetrahydrobenzene, even trace.For example, the difficult especially generation that separates and may have the impurity of disadvantageous effect such as cyclonene, cyclohexenol, chlorine pimelinketone, pimelinketone ketal to product should be controlled at alap level.
Reaction of the present invention can be implemented according to general oxidizing reaction.When every kind of catalyst component existed with solution state, oxidizing reaction can adopt batch reactor and allow alkene contact specific time with oxygen-containing gas and realize, perhaps adopted the external phase reactor and realized by oxygen-containing gas without interruption and alkene.On the other hand, when catalyst component of the present invention is fixed, can adopt liquid phase reaction, perhaps adopt so-called trickle bed system, wherein catalyzer is filled in the fixed bed, and corresponding alkene and oxygen are with the liquid form supply.
Supply about oxygen, can adopt the technology of oxygen dissolution in the reaction soln system that make, for example utilize agitating vane that oxygen-containing gas is broken up technology into rill, the baffle plate that utilization is arranged in the reactor is broken up technology into rill with oxygen-containing gas, perhaps utilize high linear speed with gas by jet technology in system of nozzle.(processing after the oxidizing reaction)
Reaction product solution after the oxidizing reaction comprises raw material olefin, as ketal and/or acetal, catalyst component and the polyvalent alcohol of product.When reaction product solution is in the band pressure condition, can reduce pressure by release to a certain degree.When the boiling point of alkene in the reaction product solution and ketal and/or acetal was more much lower than polyol solvent, these low boiling components (alkene and ketal and/or acetal) can be separated from reaction product solution by distilling directly.Acquisition contains the polyhydric alcohol solutions of catalyst component, its capable of circulation turning back in the oxidation step as the distillatory bottom product.
Also have, when the boiling point of alkene and ketal and/or acetal is higher than polyol solvent, then add such as forming the biphase organic solvent as extraction solvent with polyvalent alcohol, reach two by extraction then and be separated, thereby be divided into extraction solvent that contains alkene and ketal and/or acetal and the polyvalent alcohol that contains catalyst component mutually.Then, reclaim alkene and ketal and/or acetal mutually, and then can take out ketal and/or acetal by fractionation by distillation from extraction solvent.Mutually capable of circulation the turning back in the oxidation step of polyvalent alcohol that contains catalyst component.In two are separated, when the extraction solvent side that contains alkene and ketal and/or acetal is stain by the trace catalyst component, the catalyst component in this extraction phase can by with polyol solvent to extraction solvent carry out mutually two or more times extraction its residual quantity is reduced to the level of ignoring.Can also adopt a kind of like this technology, wherein at the two-phase after separating first time, by distillation alkene and ketal and/or acetal are separated mutually from extraction solvent, with this remainder catalyst concentration of extraction solvent in mutually is increased to a certain degree, and then implements extraction.
In addition, because although subsequent oxidation slight, will generate water in the reactor during ketal generates.Be preferably the water of from reaction system, removing generation like this as much as possible, but nonetheless, when halogen component such as chlorine remained in the system, its possibility that participates in reactor corrosion was still very big.Therefore, Bi Yao part must use the material that the caustic acid example hydrochloric acid is had high corrosion resistance.
Material such as glass, pottery and teflon can be used for the not too high zone of reaction pressure, but under the situation of high-response pressure, the preferred container that uses as corrosion-resistant reactor usually that uses, promptly, by the Stainless Steel Alloy that particularly is referred to as hastelloy such as Stainless Steel Alloy usually, contain titanium alloy or contain the container that zirconium alloy is made, perhaps with these alloy-coated or be pressed together on the container of surperficial gained.Though this reactor has the corrosion possibility extra high round, when having arranged again to leave standstill container and separation vessel in addition, these parts also have the very high danger that is corroded.In addition, carry out under the distillatory situation containing product oil phase, when catalyst component remains, exist halogen component spissated may, thereby also have the corrosive of generation excessive risk.It is desirable to, determine according to the corrosive degree that may take place in the viable economically scope, the pipeline that these main container neutralizations are attached thereto adopts corrosion resistant material without exception.
The polyvalent alcohol that exists as necessary component in the reaction system is not that oxidizing reaction is complete inertia.Moreover although quantity is few, some compound that the subsequent oxidation by alkene generates has the polarity close with polyvalent alcohol.So, when prolonged and repeated when carrying out rhythmic reaction or under the situation in successive reaction, some derive with alkene by polyvalent alcohol but not necessarily the desirable component of this reaction will the alcohol that contains catalyst component mutually in accumulation.For reaching the stable operation of process, control overall material balance in time.Therefore, need contain the new soln that the catalyzer polyvalent alcohol comes the make-up catalyst material mutually by take out a part from system, its speed should be corresponding with the generating rate of the generating rate of these impurity and subsequent oxidation component.In this case, the ratio that shifts out of the catalyst component that takes out from system causes very greatly and therefore than the large economy burden, therefore must reclaim these catalyst components.Its method is not limit, but comprises that the technology in being recovered in of the shifting out of organic substance, washing and metal component is effective.
When by distillation from the extraction solvent that comprises two-phase separated product (ketal and/or acetal) mutually during the extraction solvent of recovery such as organic solvent, the productive set of impurity equally also can take place, therefore, the old extraction solvent of an also extensible in this case part adds new extraction solvent.
Ketal and/or the acetal produced by the present invention are converted into corresponding ketone and/or aldehyde by being hydrolyzed in the presence of water and acid.The acid that can be used in this kind situation comprises mineral acid for example hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, polyacid such as heteropolyacid, and solid acid such as ion exchange resin, zeolite and clay.Interesting aldehyde and ketone can separate aldehyde, purify and produce efficiently as expecting compound with ketone then by recycle-water and polyvalent alcohol from the reaction product solution that is rich in aldehyde and/or ketone of acquisition like this.
Also have, ketal and/or the acetal produced by the present invention can be converted into alcohol corresponding efficiently by carry out hydrogenation in the presence of water, hydrogen source and hydrogenation catalyst.The example of hydrogen source comprises hydrogen, formalin and hydrogen boronation disodium (disodium borohydride) (NaBH
4), the example of hydrogenation catalyst comprises Raney nickel, Raney cobalt; Contain the oxide compound of Cu-Cr, by 8 family's metal such as Pd, Pt or Ru are stated from the catalyzer that constitutes on the carrier, and with 8 family's metals such as Ru, Pt or the Pd complex catalyst as central metal.Interested alcohol can efficiently be produced by following method, and the alcohol that is obtained and be rich in recycle-water in the reaction product solution of alcohol by hydrogenation and generated by acetal and/or ketal separates alcohol, purify as expecting compound subsequently.
Below, will more specifically describe the present invention by embodiment, yet the invention is not restricted to these embodiment.
Examples Example 1
In having cydariform vulval vycol reactor magnetic stirrer and gas inlet tube, internal diameter 40mm, high 12mm, add 0.1mmol Pd (CH
3CN)
2Cl
2, 0.1mmolCuCl
2, 0.1mmol FeCl
3, 10mL ethylene glycol and 20mmol tetrahydrobenzene, with pure oxygen replaced air, then reaction under agitation, 40 ℃ carry out 5h.Mark compound in adding in reaction soln adopts the gas-chromatography art to carry out product analysis.As a result, the transformation efficiency of tetrahydrobenzene is 2.5%, and the pimelinketone ketal obtains with 2.5% yield.TOF is 1.0/h.TOF per hour is meant the generating rate of per 1 mole of palladium pimelinketone and pimelinketone ketal.In such cases, only generated the pimelinketone ketal.After the reaction, do not find the precipitation of palladium in the solution.Do not generate the chlorine hexanaphthene yet.Example 2
Reaction is implemented according to the program of example 1, and different is not add CuCl
2As a result, the transformation efficiency of tetrahydrobenzene is 2.5%, and the pimelinketone ketal obtains with 2.5% yield.TOF is 1.0/h.Found with the pimelinketone ketal to be the by product chlorine hexanaphthene of benchmark 1.0mol%.After the reaction, do not find the precipitation of palladium in the solution.Comparative Examples 1
Reaction is implemented according to the program of example 1, and different is not add FeCl
3As a result, the transformation efficiency of tetrahydrobenzene is 2.3%, and the pimelinketone ketal obtains with 2.3% yield.TOF is 0.92/h.After the reaction, reaction soln is muddy because of the thin black powder that contains palladium black, and finds the precipitation of palladium on reactor bottom and inwall.
Table 1
| Palladium compound | Iron cpd | Copper compound | The CHE transformation efficiency ★ | The ketal yield ★★ | ??TOF ★★★ | Remarks | |
| Example 1 | ?0.1mmol | ?0.1mmol | ??0.1mmol | ????2.5％ | ????2.5％ | 1.0/ hour | Do not have the palladium precipitation, do not generate the chlorine hexanaphthene |
| Example 2 | ?0.1mmol | ?0.1mmol | Do not use | ????2.5％ | ????2.5％ | 1.0/ hour | Do not have the palladium precipitation, generate the chlorine hexanaphthene |
| Comparative Examples 1 | ?0.1mmol | Do not use | ??0.1mmol | ????2.3％ | ????2.3％ | 0.92/ hour | The palladium precipitation |
★: the tetrahydrobenzene transformation efficiency
★ ★: pimelinketone ketal yield
★ ★ ★: the generating rate of per hour per 1 mole of palladium pimelinketone and pimelinketone ketal
With example 1 and 2 and Comparative Examples 1 compare as can be seen, the precipitation of palladium is owing to the adding of Fe is inhibited.Can find out that also the generation of chlorine hexanaphthene is owing to the other adding of copper compound is inhibited.Example 3
The drum type brake teflon beaker that has magnetic stick, internal diameter 40mm, a high 15mm be inserted into withstand voltage 100kG, size just with the SUS-316 autoclave of beaker coupling in, the condition of the feed composition that reaction employing and example 1 are identical, depress at 80 ℃ temperature of reaction and 7kG oxygen and to carry out 1h.As a result, obtain reaction product speed=24.8 of pimelinketone ketal/pimelinketone, and pimelinketone ketal/cyclonene=26.1, wherein the tetrahydrobenzene transformation efficiency is 30%, TOF is 60/h.After reaction is finished, do not find the precipitation of palladium.Example 4
Reaction is implemented according to the mode identical with example 3, and different is not use CuCl.As a result, the tetrahydrobenzene transformation efficiency is 34%, and TOF is 67/h.The growing amount of chlorine hexanaphthene is that benchmark is 1mol% with the ketal.After reaction is finished, do not find the precipitation of palladium.Comparative Examples 2
Reaction is implemented according to the mode identical with example 4, and different is not use FeCl
3, and CuCl
2Or then quantity use in accordance with regulations of CuCl.The results are shown in table 2.All find the precipitation of palladium in all cases.
Table 2
*: the generating rate of per hour per 1 mole of palladium pimelinketone and pimelinketone ketal
| Copper compound | The tetrahydrobenzene transformation efficiency | TOF* (/ hour) |
| CuCl(0.1mmol) CuCl 2(0.1mmol) CuCl 2(0.2mmol) | ????13.5％ ????21.0％ ????45.0％ | ????27 ????42 ????90 |
As can be seen from the above results, when iron was present in the system, precipitation did not take place in palladium and catalyzer can work efficiently, even reach under the situation of high numerical value in oxygen concn raising and tetrahydrobenzene transformation efficiency.Example 5
Reaction according to example 1 in the same way as described implement, different is replaces ethylene glycol with the mixing solutions of 5mL ethanol+2.5g ethylene glycol.As a result, the tetrahydrobenzene transformation efficiency is 22%; (pimelinketone+pimelinketone ketal) yield is 21.0%; (pimelinketone ketal+pimelinketone) selectivity is 95%; TOF is 8.4/h.After the reaction, do not find the precipitation of palladium in the solution.Example 6
Reaction according to example 1 in the same way as described implement, different is replaces ethylene glycol with the mixing solutions of 5mL methyl alcohol+2.5g ethylene glycol.As a result, pimelinketone ketal and pimelinketone obtain with 17.6 ratio, and the tetrahydrobenzene transformation efficiency is 10.0%; (pimelinketone+pimelinketone ketal) yield is 10.0%; TOF is 4.0/h.After the reaction, do not find the precipitation of palladium in the solution.Example 7
Reaction according to example 1 in the same way as described implement, different is use 7.5g1, the mixing solutions replacement ethylene glycol of 4-butyleneglycol+2.5g ethylene glycol.As a result, the tetrahydrobenzene transformation efficiency is 22%; TOF is 8.0/h.After the reaction, do not find the precipitation of palladium in the solution.Example 8
Reaction according to example 1 in the same way as described implement, different is with 1, ammediol replacement ethylene glycol.As a result, obtain reaction product pimelinketone ketal/pimelinketone=2.87, pimelinketone ketal/cyclonene=16.1, the tetrahydrobenzene transformation efficiency is 16%.As for the generating rate of (pimelinketone+ketal), TOF is 6.4/h.After the reaction, do not find the precipitation of palladium in the solution.Example 9
Reaction according to example 1 in the same way as described implement, different is with 1,4-butyleneglycol replacement ethylene glycol.As a result, obtain reaction product pimelinketone ketal/pimelinketone=0.41, pimelinketone ketal/cyclonene=4.93, the tetrahydrobenzene transformation efficiency is 27%.(pimelinketone+ketal) selectivity is 79%, and TOF is 8.5/h.After the reaction, do not find the precipitation of palladium in the solution.Example 10
Reaction according to example 1 in the same way as described implement, different is with 2,3-butyleneglycol replacement ethylene glycol.As a result, the tetrahydrobenzene transformation efficiency is 7%.(pimelinketone ketal+pimelinketone) selectivity is 91.5%, and TOF is 2.6/h.After the reaction, do not find the precipitation of palladium in the solution.Example 11
Reaction according to example 1 in the same way as described implement, different is with 1,2-cyclohexanediol replacement ethylene glycol.As a result, the tetrahydrobenzene transformation efficiency is 12%.Pimelinketone ketal/pimelinketone is 3.7, and (pimelinketone ketal+pimelinketone) selectivity is 90%, and TOF is 4.3/h.After the reaction, do not find the precipitation of palladium in the solution.Comparative Examples 3
Reaction according to example 1 in the same way as described implement, different is to replace ethylene glycol with ethanol.As a result, the tetrahydrobenzene transformation efficiency is 35%.The pimelinketone yield is 17%.The selectivity of pimelinketone is 51%.Do not find the precipitation of palladium on the reactor wall.Do not generate the pimelinketone acetal.
The result of example 5～11 and Comparative Examples 3 is shown in following table 3 in the lump together with the result of example 1.
Table 3
*: pimelinketone ketal/pimelinketone * *: the generating rate of the pimelinketone of per hour per 1 mole of palladium and pimelinketone ketal
| Alcohol | CHN ketal/CHN* | ??TOF** | Remarks | |
| Example 1 | Ethylene glycol (EG) 10mL | ????100 | ??1.0/h | No palladium precipitation, no chlorine hexanaphthene |
| Example 5 | Ethanol 5mL+EG 2.5g | ????＞10 | ??8.4/h | No palladium precipitation |
| Example 6 | Methyl alcohol 5mL+EG 2.5g | ????17.6 | ??4.0/h | No palladium precipitation |
| Example 7 | 1,4-butyleneglycol (BG) 7.5g+EG 2.5g | ????＞10 | ??8.0/h | No palladium precipitation |
| Example 8 | 1, ammediol 10mL | ????2.87 | ??6.4/h | No palladium precipitation |
| Example 9 | 1,4-butyleneglycol (BG) 10mL | ????0.41 | ??8.5/h | No palladium precipitation |
| Example 10 | 2,3-butyleneglycol 10mL | ????5-10 | ??2.6/h | No palladium precipitation |
| Example 11 | 1,2-cyclohexanediol 10mL | ????3.7 | ??4.3/h | No palladium precipitation |
| Comparative Examples 3 | Ethanol 10mL | ????0 | ??6.8/h | No palladium precipitation, no ketal generates |
By example 1 and 5～11 with the comparison of Comparative Examples 3, when having polyvalent alcohol, have the CHN ketal to generate as can be seen.Compare with CHN in view of CHN ketal in reaction system subsequent oxidation takes place hardly, so, it is desirable to obtain the product of high CHN ketal/CHN ratio for (CHN+CHN ketal) selectivity.Example 12
Reaction according to example 7 in the same way as described implement, different is with Pd (BzCN)
2Cl
2Replace Pd (CH
3CN)
2Cl
2As a result, the transformation efficiency of tetrahydrobenzene is 5%; TOF is 2/h.After the reaction, in solution, do not find the precipitation of palladium.Example 13
Reaction according to example 7 in the same way as described implement, different is to use PdCl
2Replace Pd (CH
3CN)
2Cl
2As a result, the transformation efficiency of tetrahydrobenzene is 4%; TOF is 1.6/h.After the reaction, in solution, do not find the precipitation of palladium.Example 14
The drum type brake teflon beaker that has magnetic stick, internal diameter 40mm, a high 15mm is inserted in the SUS-316 autoclave that withstand voltage 100kG, size mate with beaker just, the feed composition condition identical with example 1 adopted in reaction, depresses at 70,80,90 or 100 ℃ temperature of reaction and 7kG oxygen and carries out 1h.After reaction is finished, do not find the precipitation of palladium in the solution.The results are shown in table 4.As can be seen, speed of reaction depends on temperature of reaction or oxygen pressure to a great extent.
Table 4
*: the generating rate example 15 of per hour per 1 mole of palladium pimelinketone and pimelinketone ketal
| Temperature of reaction (℃) | The tetrahydrobenzene transformation efficiency | ????TOF* | Ketal/pimelinketone | Ketal/cyclonene |
| ????70 ????80 ????90 ????100 | ????21％ ????30％ ????50％ ????58％ | ????42 ????58 ????93 ????110 | ????＞40 ????24.8 ????28.5 ????18.3 | ????＞1000 ????26.1 ????12.3 ????15.7 |
Reaction according to example 14 in the same way as described implement, different is that the mixture of 4-butyleneglycol is 40,60,80 or 90 ℃ as reaction solvent and temperature of reaction with 2.5g ethylene glycol+7.5g1.After the reaction, in solution, do not find the precipitation of palladium.The results are shown in table 5.
Table 5
*: the generating rate of per hour per 1 mole of palladium pimelinketone and pimelinketone ketal
| Temperature of reaction | The tetrahydrobenzene transformation efficiency | ????TOF* | Ketal/pimelinketone | Ketal/cyclonene |
| ????40 ????60 ????80 ????90 | ????4％ ????13％ ????46％ ????87％ | ????8 ????24 ????84 ????154 | ????5.3 ????2.6 ????2.3 ????1.1 | ????12.5 ????8.0 ????7.2 ????3.7 |
As can be seen, speed of reaction increases sharply with the increase of temperature of reaction.Example 16
The reaction of embodiment 14, temperature of reaction that different is are fixed on 80 ℃ and change the add-on of tetrahydrobenzene.After the reaction, in solution, do not find the precipitation of palladium.The results are shown in table 6.
Table 6
*: the generating rate example 17 of per hour per 1 mole of palladium pimelinketone and pimelinketone ketal
| Tetrahydrobenzene/palladium | Reaction times | The tetrahydrobenzene transformation efficiency | ????TOF* ????(/h) | Ketal/pimelinketone | Ketal/cyclonene |
| ????200 ????400 | ????1.0 ????3.0 ????1.0 ????3.0 | ????26％ ????70.5％ ????37％ ????60％ | ????50 ????43 ????47 ????37 | ????24.8 ????11.7 ????27.6 ????17.2 | ????26.1 ????10.4 ????19.0 ????11.9 |
The reaction of embodiment 15, different is, temperature of reaction is fixed on 90 ℃, and each add-on of palladium, copper and iron all is fixed as 0.025mmol.As a result, the tetrahydrobenzene transformation efficiency is 58%; The TOF value is 425/h; Pimelinketone ketal/pimelinketone ratio is 4.4; Pimelinketone ketal/cyclonene ratio is 8.5.After the reaction, do not find the precipitation of palladium in the solution.Example 18
Implement the oxidizing reaction identical with example 3, different is FeCl
3Change the promotor shown in the table 7 into.As a result, the product great majority are pimelinketone ketals.The TOF value is as shown in table 7.
Table 7
Acac: acetylacetonate example 19
| Promotor | ????TOF/h | The palladium black precipitation | |
| Example 3 | ????FeCl 3 | ????60 | Do not have |
| Example 18 | ????FeCl 3 | ????70 | Slightly |
| ????CoCl 3 | ????57 | Slightly | |
| ????Sn(acac) 2Br 2 | ????27 | Do not have | |
| ????Ni(acac) 2 | ????4 | Do not have |
The drum type brake teflon beaker that has magnetic stick, internal diameter 40mm, a high 15mm is inserted in the SUS-316 autoclave that withstand voltage 100kG, size be complementary with beaker just, is reflected at 80 ℃ temperature of reaction and 7kG oxygen and depresses the identical feed composition of employing and example 1 and add under the cinnamic condition of 20mmol and carry out.Behind the reaction 1h, take out material and analyze with gas-chromatography.As a result, the TOF value is 154/h; The EG acetal compound selectivity of phenylacetic aldehyde is 54%; The EG ketal compound selectivity of methyl phenyl ketone is 11%; (phenylacetic aldehyde+methyl phenyl ketone) selectivity is 25%.After the reaction, do not find the precipitation of palladium in the solution.Example 20
Reaction is implemented according to the mode identical with example 19, and different is that alpha-methyl styrene is used to replace vinylbenzene.As a result, the TOF value is 54/h; Only generate 2-phenylpropyl aldehyde and EG acetal compound thereof.Acetal/aldehyde ratio is 2.5.After the reaction, do not find the precipitation of palladium in the solution.Example 21
Reaction is implemented according to the mode identical with example 19, and different is, and 3, the 4-dialin is used to replace vinylbenzene.As a result, the TOF value is 90/h.After the reaction, do not find the precipitation of palladium in the solution.Example 22
Reaction is implemented according to the mode identical with example 19, and different is that the 1-octene is used to replace vinylbenzene.As a result, the TOF value is 46/h; (ketal compound+acetal compound) selectivity is 70%; And the primary product that obtains is the ketal compound of the corresponding ketone compound of the octene that transfer takes place two keys in the octene.After the reaction, do not find the precipitation of palladium in the solution.Example 23
Reaction is implemented according to the mode identical with example 22, and different is that the 2-octene is used to replace the 1-octene.As a result, the TOF value is 40/h; (ketal compound+acetal compound) selectivity is 84%.The distribution that generates product is identical with the situation of example 22.After the reaction, do not find the precipitation of palladium in the solution.(using the embodiment of the mixture of cyclooctene and benzene) example 24
The drum type brake teflon beaker that has magnetic stick, internal diameter 40mm, a high 15mm be inserted into withstand voltage 100kG, size just with the SUS-316 autoclave of beaker coupling in, take the operating mode of benzene coexistence, adding 2.2g benzene, 2g tetrahydrobenzene, 0.3mmol Pd (CH
3CN)
2Cl
2, 0.3mmol CuCl
2, 0.3mmol FeCl
3And 6.2g1, the 4-butyleneglycol.Being reflected at 70 ℃ temperature of reaction depresses with various different oxygen shown in the following table and carries out.Primary product except that pimelinketone and pimelinketone ketal is a cyclonene.The results are shown in table 8.
Table 8
Selectivity=pimelinketone+pimelinketone ketal example 25
| Oxygen is pressed (kG) | Reaction times (minute) | Tetrahydrobenzene transformation efficiency (%) | Selectivity (%) |
| ????4 ????5 ????6 ????7 ????8 ????9 | ????24 ????20 ????22 ????24 ????9 ????11 | ????63 ????67 ????68 ????62 ????72 ????85 | ????71 ????72 ????77 ????84 ????70 ????74 |
Use the conversion unit identical, take the operating mode with the benzene coexistence, adding 2.2g benzene, 2g tetrahydrobenzene, 0.6mmol Pd (CH with example 24
3CN)
2Cl
2, 0.6mmol CuCl
2, 0.6mmolFeCl
3And 6.2g1, the 4-butyleneglycol.The oxygen that is reflected at 7kG press and following table shown in carry out under the various differential responses temperature.Primary product except that pimelinketone and pimelinketone ketal is a cyclonene.The result is stated from table 9.
Table 9
Selectivity=pimelinketone+pimelinketone ketal example 26
| Temperature of reaction (℃) | Reaction times (minute) | Tetrahydrobenzene transformation efficiency (%) | Selectivity (%) |
| ????70 ????65 ????60 | ????8 ????11 ????28 | ????80 ????75 ????72 | ????70 ????76 ????79 |
Use the conversion unit identical, take the operating mode with the benzene coexistence, adding 1.1g benzene, 1g tetrahydrobenzene, 0.3mmol Pd (CH with example 24
3CN)
2Cl
2, 0.3mmol CuCl
2, 0.3mmolFeCl
3And 6.2g1, the 4-butyleneglycol.The oxygen that is reflected at 7kG press and 80 ℃ temperature of reaction under carry out 3.5min.As a result, the transformation efficiency of tetrahydrobenzene is 92%; The selectivity of pimelinketone and pimelinketone ketal is 70%.Primary product except that pimelinketone and pimelinketone ketal is a cyclonene.Example 27
Material and catalyst component join in the conversion unit according to the mode identical with example 24, and different is that with 1, the 2-cyclohexanedimethanol replaces 1, the 4-butyleneglycol.Being reflected at 70 ℃ temperature of reaction and 7kG oxygen depresses and carries out 32min.As a result, the tetrahydrobenzene transformation efficiency is 52%; The selectivity of pimelinketone and pimelinketone ketal is 84%.Pimelinketone ketal/pimelinketone ratio is 3.Example 28
Material and catalyst component join in the conversion unit according to the mode identical with example 27, and different is, 2.3g1, and 2-cyclohexanedimethanol and 3.9g1, the 4-cyclohexanedimethanol is used to replace 6.2g1, the 2-cyclohexanedimethanol.Being reflected at 70 ℃ temperature of reaction and 7kG oxygen depresses and carries out 20min.As a result, the tetrahydrobenzene transformation efficiency is 70%; The selectivity of pimelinketone and pimelinketone ketal is 63%.Pimelinketone ketal/pimelinketone ratio is 1.Industrial operability
According to the present invention, can high conversion and highly selective by olefin production ketal and/or acetal, the precipitation of palladium is inhibited, so it has very high industrial utility value.
Though described the present invention in conjunction with specific embodiments of the present invention above, it will be apparent to those skilled in the art that under the prerequisite that does not depart from spirit and scope of the invention from wherein also formulating various variation and modification.
The Japanese patent application 2000-125535 that the application submits to based on 2000-04-26 receives its full content for referencial use at this.
Claims (23)
1. alkene and oxygen and the polyvalent alcohol by having at least one olefinic double bonds reacts in the presence of catalyzer and produces the method for ketal and/or acetal, this method be included in (a) palladium, (b) belong to the periodic table of elements 8,9,10 and 14 families at least a non-metallic palladium and (c) halogen implement this reaction down as the existence of catalyzer.
2. according to the production ketal of claim 1 and/or the method for acetal, wherein be reflected in the liquid phase of having dissolved catalyzer and carry out.
3. according to the production ketal of claim 1 or 2 and/or the method for acetal, comprise also that wherein copper is as catalyzer.
4. according to the production ketal of claim 3 and/or the method for acetal, wherein the catalyst compound that uses as the copper source is at least a in cuprous chloride and the cupric chloride.
5. according to the production ketal of claim 3 or 4 and/or the method for acetal, wherein the consumption of copper is 0.1～100 times of at least a non-metallic palladium of (b) 8,9,10 and 14 families of belonging to the periodic table of elements, by mole.
6. according to the method for any one described production ketal and/or acetal in the claim 1～5, wherein (b) belongs at least a non-metallic palladium chosen from Fe, cobalt, nickel and the tin of 8,9,10 and 14 families of the periodic table of elements.
7. according to the production ketal of claim 6 and/or the method for acetal, wherein (b) to belong at least a non-metallic palladium of 8,9,10 and 14 families of the periodic table of elements be iron.
8. according to the method for any one described production ketal and/or acetal in the claim 1～7, wherein (c) halogen is a chlorine.
9. according to the production ketal of any one and/or the method for acetal in the claim 1～8, wherein the concentration of palladium in reaction soln is 0.001～10 weight %.
10. according to the production ketal of any one and/or the method for acetal in the claim 1～9, wherein (b) belongs at least a non-metallic palladium of 8,9,10 and 14 families of the periodic table of elements and the mol ratio of palladium is 0.1～100 in the reaction soln.
11. according to the production ketal of any one and/or the method for acetal in the claim 1～10, wherein the mol ratio of (c) halogen and palladium is 0.1～100 in the reaction soln.
12. according to the production ketal of any one and/or the method for acetal in the claim 1～11, wherein the catalyst compound that uses as the source of (a) palladium is a Palladous chloride.
13. according to the production ketal of any one and/or the method for acetal in the claim 1～12, wherein the catalyst compound that uses as the source of (a) palladium is the compound of divalence palladium.
14. according to the production ketal of any one and/or the method for acetal in the claim 1～13, wherein the catalyst compound that uses as the source of (a) palladium is nitrile compounds-coordination compound.
15. according to the production ketal of any one and/or the method for acetal in the claim 1～14, wherein the catalyst compound in source of at least a non-metallic palladium that belongs to 8,9,10 and 14 families of the periodic table of elements as (b) is a muriate.
16. according to the production ketal of any one and/or the method for acetal in the claim 1～15, wherein the chlorine as (c) halogen is used as (a) or muriate (b).
17. according to the production ketal of any one and/or the method for acetal in the claim 1～16, wherein alkene is the cyclenes that contains 4～10 carbon atoms.
18. according to the production ketal of claim 17 and/or the method for acetal, wherein alkene is tetrahydrobenzene.
19. according to the production ketal of any one and/or the method for acetal in the claim 1～16, wherein alkene is the terminal olefine that contains 2～25 carbon atoms.
20. according to the production ketal of any one and/or the method for acetal in the claim 1～16, wherein alkene is the internal olefin that contains 4～25 carbon atoms.
21. according to the production ketal of any one and/or the method for acetal in the claim 1～20, wherein polyvalent alcohol is aliphatic series or alicyclic diol.
22. according to the production ketal of any one and/or the method for acetal in the claim 1～21, wherein the consumption of polyvalent alcohol is 1～100 times of alkene, by mole.
23. a method of producing ketone and/or aldehyde, it produces ketone and/or aldehyde by hydrolysis in the presence of the catalyzer for the ketal produced by the method for any one in the claim 1～22 by hydrolysis in the presence of acid catalyst and/or acetal.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000125535 | 2000-04-26 | ||
| JP125535/2000 | 2000-04-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1426384A true CN1426384A (en) | 2003-06-25 |
| CN1217885C CN1217885C (en) | 2005-09-07 |
Family
ID=18635478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN018087175A Expired - Fee Related CN1217885C (en) | 2000-04-26 | 2001-04-25 | Method for producing ketal and/or acetal |
Country Status (7)
| Country | Link |
|---|---|
| KR (1) | KR100779888B1 (en) |
| CN (1) | CN1217885C (en) |
| AU (1) | AU2001252577A1 (en) |
| MY (1) | MY141282A (en) |
| TW (1) | TWI294423B (en) |
| WO (1) | WO2001081276A2 (en) |
| ZA (1) | ZA200207686B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109819658A (en) * | 2016-07-01 | 2019-05-28 | 科莱恩国际有限公司 | Synergistic acetal compositions and methods for scavenging sulfides and mercaptans |
| US11555140B2 (en) | 2017-12-22 | 2023-01-17 | Clariant International Ltd | Synergized hemiacetals composition and method for scavenging sulfides and mercaptans |
| US11603497B2 (en) | 2017-12-22 | 2023-03-14 | Clariant International Ltd | Synergized acetals composition and method for scavenging sulfides and mercaptans |
| CN115779463A (en) * | 2021-09-08 | 2023-03-14 | 中国科学院大连化学物理研究所 | Ketal synthesis reaction device and production method |
| CN115779463B (en) * | 2021-09-08 | 2025-02-21 | 中国科学院大连化学物理研究所 | Ketal synthesis reaction device and production method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020124433A1 (en) * | 2018-12-19 | 2020-06-25 | Rhodia Operations | Process for preparing acetals or ketals |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60331B2 (en) * | 1981-03-20 | 1985-01-07 | 工業技術院長 | Method for producing cyclohexanone |
-
2001
- 2001-04-25 MY MYPI20011932A patent/MY141282A/en unknown
- 2001-04-25 WO PCT/JP2001/003579 patent/WO2001081276A2/en active Application Filing
- 2001-04-25 KR KR1020027014188A patent/KR100779888B1/en not_active IP Right Cessation
- 2001-04-25 CN CN018087175A patent/CN1217885C/en not_active Expired - Fee Related
- 2001-04-25 AU AU2001252577A patent/AU2001252577A1/en not_active Abandoned
- 2001-04-26 TW TW090109988A patent/TWI294423B/en not_active IP Right Cessation
-
2002
- 2002-09-25 ZA ZA200207686A patent/ZA200207686B/en unknown
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109819658A (en) * | 2016-07-01 | 2019-05-28 | 科莱恩国际有限公司 | Synergistic acetal compositions and methods for scavenging sulfides and mercaptans |
| CN109819658B (en) * | 2016-07-01 | 2021-03-09 | 科莱恩国际有限公司 | Synergistic acetal compositions and methods for scavenging sulfides and mercaptans |
| US11530347B2 (en) | 2016-07-01 | 2022-12-20 | Clariant International Ltd | Synergized acetals composition and method for scavenging sulfides and mercaptans |
| US11555140B2 (en) | 2017-12-22 | 2023-01-17 | Clariant International Ltd | Synergized hemiacetals composition and method for scavenging sulfides and mercaptans |
| US11603497B2 (en) | 2017-12-22 | 2023-03-14 | Clariant International Ltd | Synergized acetals composition and method for scavenging sulfides and mercaptans |
| CN115779463A (en) * | 2021-09-08 | 2023-03-14 | 中国科学院大连化学物理研究所 | Ketal synthesis reaction device and production method |
| CN115779463B (en) * | 2021-09-08 | 2025-02-21 | 中国科学院大连化学物理研究所 | Ketal synthesis reaction device and production method |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI294423B (en) | 2008-03-11 |
| KR20030005295A (en) | 2003-01-17 |
| CN1217885C (en) | 2005-09-07 |
| ZA200207686B (en) | 2003-09-25 |
| AU2001252577A1 (en) | 2001-11-07 |
| KR100779888B1 (en) | 2007-11-28 |
| MY141282A (en) | 2010-04-16 |
| WO2001081276A2 (en) | 2001-11-01 |
| WO2001081276A3 (en) | 2002-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1196660C (en) | Process for preparing cumene which is used in the preparation of phenol | |
| TW201538475A (en) | Process for producing methyl methacrylate | |
| CN1304112C (en) | Preparation of ruthenium/iron catalyst loaded onto carbon | |
| CN110078684B (en) | Method for continuously synthesizing epichlorohydrin by using microchannel reactor | |
| CN104650008B (en) | A kind of technique and system being prepared expoxy propane by oxygen, hydrogen direct oxidation propylene | |
| CN104628548A (en) | Method for preparing acetophenone by bionic catalytic oxidation of ethylbenzene | |
| CN104387236B (en) | A kind of propilolic alcohol, 1,4-butynediols and methenamine three coproduction continuous producing method | |
| CN109704944B (en) | Method for preparing menthone from citronellal and catalyst system used in method | |
| CN1239449C (en) | Catalytic process for the production of alkanediol with recycle of reactor product | |
| CN1217885C (en) | Method for producing ketal and/or acetal | |
| CN1416949A (en) | Metal oxide catalyst for synthesizing methyl carbonate by urea process and its prepn | |
| CN1310042A (en) | Process for producing catalyst, and the same catalyst using for catalytic oxidation reaction | |
| CN102093180B (en) | Method for continuously producing unsaturated aldehyde compound | |
| CN102234223A (en) | Method for synthesizing dichloropropanol by reaction of glycerol and hydrogen chloride | |
| CN1481348A (en) | Process for prepn. of polyhydric alcohols | |
| CN107266290A (en) | A kind of method of methyl methacrylate coproducing methyl allyl alcohol | |
| CN1025731C (en) | Anhydrous diluents for isobutylene oxidation reaction to methacrolein and methacrolein oxidation to methacrylic acid | |
| CN104109095B (en) | The method that oxalate hydrogenation produces ethyl glycolate | |
| CN1277800C (en) | Method for preparing saturated carboxylic acid with one to four carbon atoms by 2-butanone gas-phase oxidation | |
| JP4019670B2 (en) | Method for producing ketal and / or acetal | |
| CN111393273A (en) | A kind of system and method for preparing benzaldehyde from PTA oxidation residue | |
| CN1298858A (en) | Process for synthesizing aldehyde from olefine, CO and hydrogen | |
| CN103145538A (en) | Method for synthesizing o-vanillin through utilizing 5-aldehyde vanillin | |
| CN1243702C (en) | Method of dehydrogenating triisopropylbenzene and diisopropylbenzene | |
| JP4032663B2 (en) | Method for producing ketal and / or acetal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050907 Termination date: 20150425 |
|
| EXPY | Termination of patent right or utility model |