CN101497553A - Method for producing nine carbon alcohol from eight carbon olefin - Google Patents

Method for producing nine carbon alcohol from eight carbon olefin Download PDF

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Publication number
CN101497553A
CN101497553A CNA2009100099694A CN200910009969A CN101497553A CN 101497553 A CN101497553 A CN 101497553A CN A2009100099694 A CNA2009100099694 A CN A2009100099694A CN 200910009969 A CN200910009969 A CN 200910009969A CN 101497553 A CN101497553 A CN 101497553A
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processing step
hydroformylation
reactor
cobalt
alkene
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H·-G·卢肯
A·凯兹克
W·托特什
B·肖尔茨
W·德罗斯特
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Evonik Operations GmbH
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Oxeno Olefinchemie GmbH
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    • 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
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • 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
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions

Abstract

The invention relates to a method for preparing C<9>-alcohol from C<8>-olefin, comprising preparing C<9>-alcohol continuously from two-phase hydroformylation of C<8>-olefin in the presence of cobalt catalyst evenly dissolved in organic phase.

Description

From C 8-olefin production C 9The method of-alcohol
Technical field
The present invention relates to a kind of from C 8-alkene is by preparing C by means of the two stage hydroformylations of synthetic gas and the hydrogenation of gained reaction mixture in the presence of cobalt catalyst 9-alcohol, that is for example nonyl alcohol for example nonanol-and single branching and/or many branching nonyl alcohol of isononyl alcohol, isomery, hereinafter referred to as isononyl alcohol, the method for mixture.In addition, this method also can comprise multiple separating technology, for example is used to isolate unreacted alkene and/or by product and/or cobalt compound and is used to separate organic phase and water.
Background technology
Transition-metal catalyst for example in the presence of cobalt and the rhodium compound alkene and carbon monoxide and hydrogen carry out hydroformylation to form the aldehyde of many carbon atoms known as oxo process.Generally speaking, at C 8-olefin hydroformylation forms the non-branching aldehyde of seeking high share in the aldehyde process, and this is the intermediate product when producing important economically plastics with tenderizer alcohol and detergent alcohol.
The method of olefin hydroformylation has a large amount of descriptions in the literature.The reactivity of the alkene that uses is depended in the catalyst system that hydroformylation is used and the selection of optimum reaction condition.The structure of the alkene that uses to the influence of its hydroformylation reaction for example by J.Falbe " New Syntheses withCarbon Monoxide ", Springer Verlag, 1980, Berlin, Heidelberg, NewYork, 95 pages are risen to some extent and describe.
Although linear terminal olefin (so-called alpha-olefin) can be is very well carried out hydroformylation (J.Falbe " New Syntheses with Carbon Monoxide " with the rhodium or the cobalt catalyst of phosphine-modified; Springer Verlag; 1980; Berlin; Heidelberg; New York, 55 pages are risen), but for the alkene of low reactivity, preferably use unmodified cobalt and rhodium catalyst for internal olefin and for the branching internal olefin.
The hydroformylation of alkene mixture that contains the non-branching isomery of terminal internal olefin and branching internal olefin is advantageously carried out with unmodified cobalt catalyst.Compare with rhodium catalyst,, obtain the more high yield of the linear chain aldehyde seek especially with cobalt catalyst from same alkene.
Preferably the example that is reacted into the typical isomeric olefine mixture of corresponding carbonyl synthesizing aldehyde (OxoAldehyde) by the catalytic hydroformylation of cobalt is dimer, tripolymer and the tetramer of propylene, n-butene (1-butylene and 2-butylene) and iso-butylene.
Since developing oxo synthesis, the catalytic hydroformylation process of cobalt is continued to optimize and is improved.
Appearance until DE 196 54 340; the catalytic hydroformylation of cobalt is carried out with the rapid technology of the multistep that comprises following four processing steps: Preparation of Catalyst (pre-carbonylation); catalyst extraction, olefin hydroformylation and from reaction product, remove catalyzer (cobalt removal).The cobalt catalyst that DE 196 54 340 has described formation, the formation of cobalt catalyst first is extracted in the organic phase and these steps of hydroformylation of corresponding alkene can be carried out in a step.
DE-OS 21 39 630 is open: also additionally contain by product except containing target product aldehyde and alcohol, the reactor output object of the residual olefin of hydroformylation and cobalt catalyst is not depressurized to 0.1 and arrives 1.5MPa, and infeed the catalyzer post-processing stages subsequently.In cobalt is removed, the organic phase in the reactor output object in the presence of the process water that does not contain complex compound by removing the cobalt carbonylcomplex with oxygen or air handling.According to WO 93/24438, cobalt is removed and can carried out under 60 to 100 ℃ of temperature He under 0.1 to the 2.0MPa pressure.At this moment, the oxidized property of cobalt catalyst destruction, and the cobalt salt of gained by back extraction to aqueous phase.The cobalt saline solution of removing gained from cobalt is recycled to first processing step, promptly pre-carbonylation.Other embodiment that cobalt is removed is described among WO 93/24437 and the EP 0 183 546.Before destroying, the oxidisability of cobalt catalyst carries out gas purging herein, with synthetic gas or nitrogen.
DE 101 35 906 is open; alkene with 5 to 24 carbon atoms is in the presence of unmodified cobalt catalyst; in reactor, exist under water and the organic phase situation under 100 ℃ to 220 ℃ temperature and pressure and to carry out with single stage process that hydroformylation forms the aldehyde that has 6 to 25 carbon atoms accordingly and/or the method for alcohol is preferably carried out like this at 100bar to 400bar; promptly; make water-bed and organic phase thorough mixing in the reactor; the concentration of water-bed cobalt compound in mutually is in 0.4 to 1.7 quality % scope, and the level (Stand) of water-bed phase is a constant under steady state in the reactor.
After separating liquiding catalyst and gas phase and optional other sepn process that needs for example extracted and/or distill, the reaction product of hydroformylation for example was converted to corresponding alcohol in hydrogenation and the distillation in further process segment usually.
When aftertreatment reaction output object, often find that alkene transforms not exclusively in hydroformylation.Therefore developed the method that hydroformylation was wherein carried out with the multistage.
Therefore; DE 198 42 368 has described a kind of being used for from isomeric olefine mixture with 5 to 24 carbon atoms by carrying out the method that two stage hydroformylations prepare high-grade carbonyl synthetic alcohol (Oxo-Alkohole) in the presence of cobalt or the rhodium catalyst under high temperature and high pressure; wherein make the reaction mixture selective hydration in the first hydroformylation stage; hydrogenated mixture is separated into the thick pure and mild low-boiling-point substance of mainly being made up of alkene when distillation; described low-boiling-point substance was infeeded for the second hydroformylation stage; the reaction mixture in the second hydroformylation stage is once more by selectivity hydrogenation; this hydrogenated mixture is separated into thick pure and mild low-boiling-point substance when distillation; should thick alcohol processedly by distillation obtain pure alcohol, at least a portion low-boiling-point substance takes out with the discharging stable hydrocarbon from this process.The loss of alkene can take place in selective hydration.
The reaction output object that DE 198 42 371 has described a kind of wherein hydroformylation equally also is separated into unreacted alkene and pure method subsequently by selectivity hydrogenation.
Further developing of these methods is described among the DE 100 34 360.Will have the alkene multistage cobalt of 6 to 24 carbon atoms-or rhodium-catalysis hydroformylation form in this method of alcohol and/or aldehyde; alkene carries out hydroformylation to transformation efficiency in the first hydroformylation step be 20 to 98%; catalyzer is removed from the liquid reactor output object that obtains like this; the liquid hydrogen formylation mixture that obtains like this is separated into the low-boiling-point substance cut that contains alkene and paraffin and contains aldehyde and/or the tower bottom distillate of alcohol; the alkene that contains in the low-boiling-point substance cut is further reacting in the operation stage; and the tower bottom distillate of all operation stages is merged, and randomly carries out hydrogenation then.Therefore, omitted selective hydration in the method, replaced alcohols and aldehydes is separated from the hydroformylation mixture.
The hydrogenation of hydroformylation mixture is described many times.For example, EP 0 987 240 has described C 5-to C 24The hydrogenation of the reaction mixture of-olefin hydroformylation, wherein reaction mixture is evaporated and passes through on the DNAcarrier free Cu/Cr catalyzer with the steam attitude in the presence of hydrogen.
The reaction mixture that DE 100 62 448 has described a kind of hydroformylation from the alkene with 4 to 16 carbon atoms is containing the method for continuous hydrogenation on the fixed bed catalyst of at least a element in the periodic table of elements the 8th subgroup in even liquid phase; wherein the even liquid phase of reactor output object still contains 0.05 to 10 quality % water, and under the steady state of this technology input than 3 to 50% the hydrogen of manying that consumes owing to hydrogenation.
Each method improvement that proposes, although part has been described the preparation of isononyl alcohol in an embodiment, its existing way not optimizing to be used for from C as total method 8-olefin production C 9-alcohol.
Summary of the invention
Therefore the purpose of this invention is to provide a kind of from C 8-olefin production C 9The total method of replaceability of-alcohol, this method are convenient to implement on industrial technology, and preferably avoid one or more shortcomings of prior art.
Surprisingly find C 9-alcohol can be with plain mode from C 8-alkene makes, wherein, in two stage hydroformylation processes, C 8-alkene uniform dissolution be present in cobalt catalyst in the organic phase in the presence of react, wherein at the first hydroformylation stage, C in the presence of cobalt catalyst 8-olefin hydroformylation to transformation efficiency is 50 to 90%, and catalyzer is removed from the liquid reactor output object that is obtained, and the liquid hydrogen formylation mixture that does not contain catalyzer that obtains like this is separated into contains C 8-alkene and randomly contain the low-boiling-point substance cut of paraffin and contain aldehyde and randomly contain the tower bottom distillate of alcohol, contained C in the low-boiling-point substance cut 8-alkene reacted in the second hydroformylation stage, wherein C in this processing step 8-conversion of olefines rate is 55 to 98%; catalyzer is removed from the liquid reactor output object that is obtained; with the liquid hydrogen formylation mixture that does not contain catalyzer that obtains like this with from the hydroformylation mixture separation in the first hydroformylation stage and tower bottom distillate merge; and in even liquid phase, containing on the fixed bed catalyst of at least a element in the periodic table of elements 8-10 family and under 0.5 to 4MPa pressure and 120 to 220 ℃ of temperature, carry out hydrogenation, and from this hydrogenated products, isolate C by fractionation by distillation 9-alcohol, described cobalt catalyst pass through at C in two hydroformylation steps 8-alkene, C 9-alcohol and/or C 9-aldehyde exists to be made the cobalt saline solution that contains 0.7 to 3 quality % cobalt and synthetic gas react down and obtains, and the cobalt catalyst that forms in reaction passes through C 8-alkene, C 9-alcohol and/or C 9-aldehyde and being extracted into the organic phase from water, described reaction and extraction are carried out in the reactor that carries out hydroformylation, and the level of carrying out the water-bed phase in the reactor of hydroformylation therein is higher or lower than the outlet 0 to 1m of each mixing nozzle, cobalt saline solution, C 8-alkene and synthetic gas are introduced in the reactor through described mixing nozzle.
Method of the present invention has the advantage that is highly susceptible to controlling.This especially the level constant by water-bed phase in the reactor remain the outlet 0 to 1m that is higher or lower than mixing nozzle and realize.
Another advantage of the inventive method is, a hydrogenation must only be provided, and wherein the aldehyde that obtains when hydroformylation is hydrogenated to alcohol.
Become unreacted C by the hydroformylation mixture separation 8-alkene and C 9-aldehyde can be economized except that often causing C 8The selective hydration of-alkene loss.By using cobalt catalyst also to bring following advantage: needn't worry that product is polluted by extra catalystic material as the process condition of wherein using different catalysts in different steps two hydroformylation stages.
Being also advantageous in that of the inventive method can be set different reaction conditionss in the hydroformylation stage.This makes the hydroformylation condition can be matched with the reactivity of the alkene mixture that infeeds under every kind of situation.For subsequent products and by product are minimized, for example usefully, the friendly alkene of reaction is reacted under gentle as far as possible condition, therefore form subsequent products and by product hardly at this.In the subsequent reaction device, the remaining alkene mixture of mainly being made up of less reactive alkene more carries out hydroformylation under the exacting terms optional then.Therefore may be by the isomeric distribution of the formed aldehyde of differential responses condition influence in the reactor.
Below with exemplary description the inventive method with the product of the inventive method preparation, the present invention should not be limited to these exemplary embodiments.
Embodiment
In the presence of being present in cobalt catalyst in the organic phase, uniform dissolution passes through C 8Two stage hydroformylations of-alkene prepare C continuously 9-alcohol the inventive method be characterised in that,
A) C 8-alkene first hydroformylation in the stage in the presence of cobalt catalyst hydroformylation to transformation efficiency be 50 to 90%,
B) catalyzer is removed from the liquid reactor output object that obtains a) at processing step,
The liquid hydrogen formylation mixture that does not contain catalyzer that c) will obtain like this is separated into and contains C 8-alkene and randomly contain the low-boiling-point substance cut of paraffin and contain aldehyde tower bottom distillate and
D) make C contained in the low-boiling-point substance cut 8-alkene reacted in the second hydroformylation stage, wherein C in this processing step 8-conversion of olefines rate is 55 to 98%,
E) with catalyzer from processing step d) remove in the liquid reactor output object that obtains,
F) with the processing step c in the first hydroformylation stage) tower bottom distillate and from processing step e) the hydroformylation mixture that does not contain catalyzer merge; and on the fixed bed catalyst that in liquid phase, is containing at least a element in the periodic table of elements 8-10 family under 0.5 to 4MPa pressure and 120 to the 220 ℃ of temperature, carry out hydrogenation and
G) by fractionation by distillation with C 9-alcohol from processing step f) hydrogenated products separate,
Wherein, cobalt catalyst two processing steps a) and d) in following acquisition: at C 8-alkene, C 9-alcohol and/or C 9-aldehyde exists down reacts the cobalt saline solution and the synthetic gas that contain 0.7 to 3 quality % cobalt, and makes the cobalt catalyst that forms when reacting pass through C 8-alkene, C 9-alcohol and/or C 9-aldehyde and being extracted into the organic phase from water; described reaction and extraction are carried out carrying out in the reactor of hydroformylation therein; and the level of wherein carrying out water-bed phase in the reactor of hydroformylation is higher or lower than each mixing nozzle outlet 0 to 1m, cobalt saline solution, C 8-alkene and synthetic gas are introduced in the reactor through described mixing nozzle.
Processing step a) and d), the first and second hydroformylation stages
The formation of cobalt catalyst, formed cobalt catalyst be extracted in the organic phase and the hydroformylation of corresponding alkene the hydroformylation stage a) and d) in carry out simultaneously with single processing step.The instrument that can omit these operation stage complexity by this way separates.Therefore, cobalt catalyst processing step a) and d) in preferred also obtain like this, that is, cobalt saline solution is with fresh cobalt salt solution and/or from the form and the C of the cobalt salt solution of technology 8-alkene and synthetic gas are incorporated in the reactor simultaneously.Special preferred reactor has contained C 9-alcohol and/or C 9-aldehyde is as solvent.Very particularly preferably reactor contains isononyl alcohol.This can help improve the solvability of catalyst complex in reaction mixture.When the reaction beginning, preferred C 9The concentration of-alcohol in reaction mixture is 5 to 25 quality %, preferred 10 to 15 quality %.
As fresh cobalt saline solution, preferably use the aqueous solution of the carboxylic acid cobalt salt in cobaltous formate or cobaltous acetate or the water soluble.The preferred aqueous solution that uses cobaltous acetate.The cobalt contents of employed cobalt saline solution is preferably 0.9 to 1.5 quality %, is preferably 1.2 to 1.4 quality % especially, in metal.
Preferably in 2:1 to 1:2 scope, preferred 1.1:1 to 1:1.1 is preferably 1:1 to the volumetric ratio of carbon monoxide and hydrogen especially in the synthetic gas.Synthetic gas is advantageously with a small amount of excessive use, and is preferred excessive in 25%, more preferably excessive in 10%, based on required stoichiometry meter.
Hydroformylation step a) and d) preferably at 160 to 220 ℃, under preferred 170 to 210 ℃ of temperature, and 20 to 30MPa, carries out under preferred 23.8 to the 29.2MPa pressure.Two hydroformylation stages preferably carry out under essentially identical temperature and pressure.Two hydroformylations between the stage temperature or the maximum deviation of pressure be preferably 5K or 0.5MPa.
The reactor that wherein carries out hydroformylation can be identical or different at all operation stages.The example of spendable type of reactor is bubble-plate column, loop reactor, jet nozzle reactors, stirring reactor and tubular reactor, wherein can the part cascade and/or be equipped with internals.Hydroformylation step a) and d) for example can carry out in the known columniform upright high pressure bubble-column reactor usually, described reactor does not have or has, and preferably has to be installed in the top, preferred co-axial tubular stinger.At hydroformylation step a) and d) one of or two in advantageously can use its space reactor by at least one separating device reactor of separating such as sieve plate or porous plate for example.This separating device is preferably perpendicular to the flow direction of reactant flow and product stream and installation is set.Compare with simple bubble-plate column, obviously reduced back-mixing, and make flow behavior approach tubular reactor by reactor cascade.This industrial technology measure makes that the space-time yield of hydroformylation and selectivity can both be improved.
Because C 8The hydroformylation of-alkene is thermopositive reaction, so for the temperature in the limited reactions device, advantageously the heat that will produce is removed from reactor.Too high-temperature can cause by product formation to increase and catalyst deactivation, for example with the cobalt precipitated form.Therefore also usually wish isothermal as far as possible process, have a direct impact because temperature of reaction can be formed (for example n/i ratio) to product.
Heat radiation can realize by various industrial measures, for example pass through heat radiations such as reactor wall or embedded water cooler.Advantageously industrial, it is lower that the expense of heat radiation need keep.Yet, because when using alkene mixture the speed of response difference, particularly in the fs,, preferably react away herein because be easy to the component of hydroformylation owing to thermopositive reaction produces quite a large amount of heat releases.Therefore, the inventive method is brought following possibility: in the industrial scope of being convenient to control, particularly in first operation stage, by adaptive reaction conditions low catalyst concentration or add inert solvent and keep heat release for example.Preferably utilize built-in heat exchanger to remove reaction heat.It is particularly advantageous being designed to vaporific heat exchanger.
Processing step a) and d) in, the level of water-bed phase keeps constant or almost constant in the hydroformylation reaction device.This means: during steady state operation (constant operational condition), wherein disperse the lower aqueous of a part of organic phase and the top that wherein the disperses a part of water phase boundary between mutually to present its highly preferably level of fluctuation in mean value maximum ± 5% scope.In the methods of the invention, this mean value of phase boundary height can be higher or lower than mixing nozzle and go out open height or be in wherein, by described mixing nozzle described parent material is introduced in the reactor.Phase boundary is preferably placed at this and is higher or lower than mixing nozzle outlet 0 to 0.5m, preferred especially 0 to 0.2m place.
By the cobalt concentration fluctuation that makes separating layer in the reactor keep the constant aqueous phase of avoiding to cause operating troubles to take place.The absolute height of phase boundary is also influential to reflex action.For example can find that transformation efficiency reduces when phase boundary is significantly higher than mixing nozzle,, also find when phase boundary significantly is lower than mixing nozzle, can produce the local temperature peaks that can cause catalyst breakage because the jetting action of mixing nozzle is no longer in full force and effect.Therefore, in order to reach maximum yield and/or optionally the optimum height of separating layer depend on and for example depend on specific concentrations in the reactor cobalt concentration of aqueous phase, and depend on other processing parameter; Therefore, separating layer must be complementary with the operational condition that exists.
Advantageously, processing step a) with d) the bottom in the reactor in one or two accounts for 1 to 10% of liquid reactor inclusion mutually.
In order to keep the level of water in the reactor, can be with aqueous stream, fresh water, cobalt salt solution and/or the water that comes out in other position separating of described technology for example, input processing step a) or d) reactor in.The round-robin aqueous stream can contain parent material, product and cobalt compound.
Aqueous stream directly can be introduced reactor bottom.Another kind of possibility is that aqueous stream is imported with alkene and/or synthetic gas.In addition, aqueous stream can be pumped into the optional circulation loop that is used for the reactor water that exists.
In this way, even when water is emitted from reactor by the liquid hydrogen formylation mixture that is removed with by excessive synthetic gas, the water level in the reactor also can remain unchanged.Discharging amount depends on operating parameters for example pressure, temperature, catalyst concn and the residence time, but the more special composition that depends on the hydroformylation mixture, and described composition is auxiliary to be determined the water dissolution ability and therefore determines emitting of water.Especially, the alcohol that forms owing to aldehyde hydrogenation has increased water-soluble.In addition, emitting when start-up course or load variations of water changes.
Cobalt compound is also discharged from reactor.For the cobalt concentration of the conditioned reaction device bottom in mutually, cobalt compound can be metered into processing step a) and d) in.Cobalt compound can for example be dissolved in the solution form input in product, parent material or the water with solution.Preferably can use for example aqueous solution of cobaltous formate or cobaltous acetate of carboxylic acid cobalt salt.Can also use the solution that contains more than a kind of cobalt compound.Particularly preferred cobalt salt solution is those solution that produce from hydroformylation output object removal cobalt the time in technology itself.This solution that can also contain formic acid can directly use, or uses after concentrating, or uses after reducing formic acid concn, for example uses as among the German patent application DE 100 09 207.1.The aqueous stream that is metered into after measuring like this and after the amount of the cobalt that is metered into, that is, make the water level keep constant, and the cobalt concentration of water is 0.7 to 3 quality % in the reactor, preferred 0.9 to 1.7 quality %, preferred especially 1.0 to 1.5 quality % are in metal.Lower cobalt concentration is impracticable, and this is because speed of response became slow.To avoid higher cobalt concentration equally, because this can promote the sedimentation of cobalt compound or cobalt metal.Can occur like this blocking and can damaging the function of measuring and regulating instrument, thereby can cause operating troubles.Water-bed cobalt concentration in is mutually preferably advantageously monitored by on-line analysis.
In order to obtain high speed of response, mix with the same organic phase that exists mutually at the bottom in advantageously making parent material and being present in reactor.Avoid the concentration gradient of reaction partner by thorough mixing.In addition, water-bedly help formed catalyzer with being mixed with of organic phase and transfer in the organic phase of mainly carrying out hydroformylation.
Parent material (alkene, synthetic gas, cobalt saline solution) with itself and be present in the reactor water-bed mutually and the mixing of the organic phase of same existence undertaken by mixing nozzle.Therefore, preferably all three kinds of parent materials are infeeded in the reactor by one or more mixing nozzles together.
Described mixing is subjected to the influence of the jetting action of one or more mixing nozzles.Jetting action is depended on the level of phase boundary and is depended on from the momentum of the liquids and gases of mixing nozzle discharge.In order to obtain well blend, find, processing step a) and d) in one or two, the liquid velocity in the mixing nozzle exit is preferably 3 to 300m/s, is in particular 10 to 100m/s, it is particularly advantageous that the utmost point is in particular 15 to 70m/s.
Water-bed such as additional cycles by means of being installed on pump in the circulation loop.The mixing of water and water can be realized by the mixing nozzle that a part of water is used from reactor importing parent material with mixing also of organic phase and synthetic gas.This can realize by means of pump.Another kind of possibility is, makes a part of bottom suck mixing nozzle from reactor by material stream.
Processing step b) and e), catalyzer is removed
In order to remove processing step b) and e) in catalyzer, from processing step a) or d) the reaction output object adding under the acid cobalt saline solution situation preferably with air or oxygen, more preferably handle, be separated into organic phase that does not contain catalyzer that contains reaction product and the water that contains cobalt salt subsequently with air.From processing step a) and d) the reaction output object preferably take out in reactor head.For this purpose, reactor head quality award from the ministry apolegamy within it has the pipe of coaxial embedding form of tubes, and described length of tube is enough to take out from reactor being present in the reactor liquid phase under the gas buffer.Such pipe preferably has 0.5 to 2m length, more preferably from about the length of 1m.Can avoid pressure surge and level fluctuation in the reactor in this way.
The reaction output object preferably at first is relaxed 1.0 to 1.5MPa pressure after leaving reactor, and introduces the cobalt removal stage that is used to remove cobalt catalyst.By release excessive synthetic gas is removed from the reaction output object.Randomly can be with synthetic gas such as carrying out aftertreatment by settling vessel and/or scrubber, and infeed with further application, for example after compression, be re-used as air feed and be used for hydroformylation.Other applicable cases for example can prepare hydrogen by the reaction of the carbon monoxide that exists in the synthetic gas.In cobalt is removed, preferably under 110 to 180 ℃ of temperature, carry out with acid cobalt saline solution (process water) and air or oxygen processing reaction output object, react output object and do not contain the cobalt carbonylcomplex thereby make.The oxidized destruction of cobalt carbonylcomplex described in this is handled.The cobalt contents of acid cobalt saline solution (process water) is preferably 0.9 to 1.5 quality %, and preferred especially 1.2 to 1.4 quality % calculate with metal, and its pH value is 3 to 4.Acid cobalt saline solution is the aqueous solution of the aqueous solution of carboxylic acid, especially formic acid preferably.The pH value for example can be regulated by adding formic acid or acetate or sodium hydroxide solution.Cobalt is removed preferably at 100 to 150 ℃, more preferably carries out under 110 to 140 ℃ the temperature.Such advantage is that the acetal that forms by subsequent reactions resolves into desirable target product aldehyde and alcohol as far as possible fully again.
Cobalt is removed and can be carried out in having the conduit of hybrid element, for example carries out in the pressurized vessel that is filled with filler such as Raschig ring, produces high as far as possible phase exchange surface thus.The cobalt that the pressurized vessel of removing from cobalt obtains is removed mixture and is transferred to subsequently the separation vessel, and there, the organic hydroformylation mixture that has removed cobalt compound in cobalt is removed is as organic phase and the aqueous phase separation that contains cobalt.
Cobalt removal method is known, and describes in detail in the literature, and for example J.FALBE is at " NewSyntheses with Carbon Monoxide ", Springer Verlag (1980), and Berlin, Heidelberg, New York, the 158th page is risen.Other details that cobalt is removed can be obtained by this document.
At processing step b) and e) in the water that contains cobalt salt that obtains can be completely or partially, hydroformylation step a) and/or d are returned in circulation directly or after aftertreatment) in.Advantageously, circulation loop is by suitable measure, and for example adiabatic or companion's heat assembling like this makes the temperature of circulation water be not less than 40 ℃.Can avoid cobalt salt owing to the concentration that reaches capacity precipitates by this way as far as possible.
Remove (processing step b) by cobalt, e)) the hydroformylation mixture that obtains infeeded processing step c) randomly can move further aftertreatment technology before.Therefore the hydroformylation mixture especially can be further purified by filter method and other extracting process.
Especially preferably the hydroformylation mixture that obtains that is separated from cobalt is removed is at first further removed cobalt by continuous extraction.As extraction agent, preferably make water.By suitable technological design, can control the water supply and the draining of whole technology like this, promptly make not form extra waste water.For example this water can be used as process water and utilizes.Advantageously, then carry out filtration stage after the extraction, the particle that may contain cobalt can be removed from the hydroformylation mixture thus.As filtering medium, can use conventional filtering material and filtration types.
Processing step c)
From processing step b) the liquid hydrogen formylation mixture that does not contain catalyzer that obtains is at processing step c) preferably be separated into and contain C by distillation 8-alkene and randomly contain the low-boiling-point substance cut of paraffin and contain C 9-aldehyde, C 9-pure and mild the tower bottom distillate that randomly contains other high boiling component.This separation preferably has 10 to 25, carries out in the tower of preferred 14 to 18 theoretical separation levels.At this, the adding of hydroformylation mixture is preferably carried out so in the following manner gentle the carrying between the post of setting prop on the rectifying tower, promptly makes the gentle distribution of putting forward the theoretical plate number between the post of rising post be about 1/2.The preferred interior temperature of tower of regulating like this makes that promptly tower top temperature is 45 to 65 ℃, and preferred 50 to 60 ℃, column bottom temperature is 115 to 135 ℃, preferred 120 to 130 ℃.
The preferred distillation condition of selecting so promptly makes not form a large amount of by products during distilling.Because this mainly owing to the reaction of aldehyde under comparatively high temps, therefore can under low pressure distill, thereby keep the interior temperature of tower lower.But also can under normal pressure, distill.Distillation is to operate under 140 to 160hPa in the cat head absolute pressure preferably.The overhead product of tower can contain the aldehyde of maximum 10 weight %, preferred 5 weight %, the aldehyde of preferred especially 0.1-2 weight %.
The product that can contain at the bottom of the tower preferably contains paraffin and/or the alkene that is lower than 0.3 weight %, and special preferred concentration range for is paraffin and/or the alkene of 0.1-0.2 weight %.
Therefore will be from the C of first operation stage 9-aldehyde separates, and not be used in the hydroformylation reaction condition that subordinate phase stands to help subsequent reactions once more.
In distilation steps, removed C 9-aldehyde and the alcohol of choosing wantonly and the unreacted alkene of high boiling material are imported in the hydroformylation step of next operation stage subsequently.
Processing step d)
The C that in the low-boiling-point substance cut, contains 8-alkene reacted in the second hydroformylation stage, carried out like this at this this processing step, promptly made C 8-alkene is 55 to 98% with respect to the conversion of olefines rate that infeeds subordinate phase, preferred 70 to 95%.
Processing step d) hydroformylation in above-mentioned essentially identical condition under carry out.But the temperature in the reactor is preferably 160 to 220 ℃, preferred 175 to 195 ℃.Pressure is 20 to 30MPa.
Processing step e)
If there is not other explanation, processing step e) carry out like that as mentioned above.
Processing step f)
At processing step f) in; the tower bottom distillate of the first hydroformylation stage process step c) and merge from the hydroformylation mixture that does not contain catalyzer of the second hydroformylation stage process step e); and in liquid phase; in containing periodic table of elements 8-10 family, on the fixed bed catalyst of at least a element, under 0.5 to 4MPa pressure and 120 to 220 ℃ of temperature, carry out hydrogenation.Processing step f) the preferred thermal insulation of the hydrogenation in is carried out.Processing step f) hydrogenation in can a stage or the multistage carry out.The special selection process step f) multistage carries out.In the case, all reactors, suitable is tubular reactor, can adiabatic or almost isothermal ground operation, and one or more thermal insulation and other are almost operated on isothermal ground.Can make aldehyde or aldehyde mixture randomly in the presence of water, carry out hydrogenation in addition, with single passage or have product circulation and carry out.
Advantageously, the tower bottom distillate of the first hydroformylation stage process step c) and before infeeding hydrogenation, at first separately or be filtered at least once from the hydroformylation mixture that does not contain catalyzer of the second hydroformylation stage process step e) with merging.Can influence the active catalyzer poison of hydrogenation catalyst with this plain mode separates.For example filter bag or filter candle (they optional also can by back scrubbing) filter can to use conventional filtration material and filtration types.Pressure before the strainer is for example with pump or accessory is preferred regulates like this, promptly makes the pressure that reaches in the filtrate side at least corresponding to the required pressure of hydrogenation feed.Temperature when filtering is preferably 130-180 ℃, preferred 160-170 ℃ especially.
Processing step f) can in one or more hydrogenation reactors, carry out.Preferred two or three placed in-line reactors that use.Preferably operation in a looping fashion of first reactor in the case, one or more reactors subsequently are in a looping fashion and/or with single channel operation.As the reactor of operation in a looping fashion, for example can use the vertical heater or the bundled tube reactor that have heat exchanger in the circulation loop outside.
Processing step f) with drip phase (Rieselphase) or preferably with liquid phase in phase reactor and stream carry out, wherein hydrogen is finely divided in a manner known way in liquid aldehydes stream.In order to make the liquid uniform distribution, to remove reaction heat removal and higher space-time yield better, reactor is preferably with 15 to 120, and preferred 25 arrive 50m 3/ m 2Empty reactor cross-section/hour high liquid load operate.If reactor isothermal or false isothermal ground are under 2 to 5K and with single channel operation at the maximum difference between the entrance and exit, the value of the unit load of catalyzer (LHSV) is preferably 0.1 to 10h -1, preferred 0.5 to 5h -1, preferred especially 0.5 to 1h -1
Processing step f) hydrogenation in is 1.5 to 2.5MPa at pressure preferably, is 2.0 to 2.2MPa in inlet pressure preferably, is to carry out under the 2.1Mpa particularly preferably in inlet pressure.Carry out processing step f) temperature be preferably 140 to 200 ℃.Temperature in is preferably 165 to 180 ℃, and preferred especially 170 to 175 ℃, very particularly preferably 175 ℃.The adiabatic temperature raises and is preferably 15 to 20 ℃, is preferably 16 to 18 ℃, especially 17 ℃.This hydrogenant example is stated in patent application DE198 42 369 and DE 198 42 370.
Under the steady state of described method, preferably at processing step f) in input Duo 1 to 50mol% than the hydrogen that hydrogenation consumed, preferred 2 to 20mol%, preferred especially 3 arrive the hydrogen of 10mol%.
Advantageously, at processing step f) the even liquid phase of the hydrogenation output object that obtains contains the water of 1 to 5 quality %.At processing step f) water concentration in the output object that obtains can regulate by add entry in hydrogenation.
Mentioned water-content is meant that the water that does not rely on the water consumption that is caused by chemical reaction and do not rely on hydrogenation waste gas discharges.Under the hydrogenant reaction conditions, water mainly be present in organic starting material-product mutually in, have only small portion to be present in the gas phase.There is not other liquid water.The unit water yield in the organic phase by the vapour pressure of the solvability of water under the reaction conditions, water with compare (gas ratio liquid) decision.Required least quantity is for example manthanoate, full reduced aldehyde, enol ether, phenol formaldehyde condensation product and other optional hydrolyzable material water yield of being hydrolyzed and being consumed of high boiling material.If parent material contains a large amount of hydrolyzable compounds, then when beginning, must only add the required water of a part, to prevent in hydrogenation reactor, forming second water.Other parts are looked the input of water consumption situation during hydrogenation.When only using a reactor, this one or several position on reactor realizes, when using a plurality of placed in-line reactor, suitable is to carry out before each reactor.So just guaranteed that hydrogenated products still contains water, almost be not useable for hydrogenation without any aldehyde with hemiacetal or the protection of full reduced aldehyde form.
At processing step f) in, the aldehyde concentration that enters hydrogenation reactor is preferably 5 to 25 quality %.Aldehyde concentration for example can be regulated like this, that is, the hydrogenation output object circulation of suitable proportion is returned in the charging.
As fixed bed catalyst, can use for example copper, cobalt, copper/nickel, copper/chromium, copper/chromium/nickel, zinc/chromium, nickel/molybdenum catalyst, they are chosen wantonly can also contain other element.Catalyzer can be carrier-free, and perhaps the material of hydrogenation activity or its precursor can be coated on carrier for example on silicon-dioxide or the aluminum oxide.Optional described catalyzer can also obtain by deposition reaction.
As processing step f) in fixed bed catalyst, preferably use those on solid support material, to contain the catalyzer of 0.3 to 15 quality % copper, 0.3 to 15 quality % nickel, 0.05 to 3.5 quality % chromium and 0 to 1.8 quality % basic metal or alkaline-earth metal.The amount that provides is based on still unbated catalyzer meter.Basic metal or alkaline earth metal component are chosen wantonly.Advantageously at processing step f) in use and to contain silicon-dioxide and/or aluminum oxide fixed bed catalyst as solid support material.Particularly preferably in processing step f) in use the catalyzer of the cupric oxide of the nickel protoxide of chromium trioxide, 4 mass parts of the aluminum oxide that under minimizing state not, contains 85 mass parts, 1 mass parts and 9 mass parts.
Described catalyzer preferably uses with the form of bringing low flow resistance, for example uses with the form of particle, bead or formed body such as lamellar body, right cylinder, extrusion profile or ring bodies.They preferably are activated before use, for example activate by heating in hydrogen stream.They preferably are activated in hydrogenation reactor.For example in DE 199 33 348.3, stating with hydrogen activatory method in the presence of the liquid phase.
Processing step f) has series of advantages.In the presence of the water of uniform dissolution during the pure aldehyde of hydrogenation, productive rate and selectivity are corresponding to the productive rate and the selectivity of vapour phase hydrogenation in liquid phase, but energy expenditure is significantly lower.
If as processing step b) and acquisition aldehyde of product c) or aldehyde mixture, they contain manthanoate and/or high boiling material, and the latter mainly is made up of phenolic aldehyde product and acetal, and are hydrogenated in the presence of water in liquid phase, then manthanoate almost completely changes into alcohol, and high boiling material partly changes into alcohol.So just formed than the alcohol of volume more of normal aldehyde in the feed mixture.
According to the pure aldehyde of the inventive method hydrogenation or when lacking the aldehyde of high boiling material, high boiling material forms obvious minimizing during hydrogenation, so essence has been improved the hydrogenant selectivity.In order to obtain the effect that water improves selectivity and productive rate, must there be water in liquid phase.
Hydrogenated products preferably contains and is lower than 0.5 quality %, especially is lower than 0.3 quality %, especially preferably is lower than the residual aldehyde of 0.2 quality %.
Processing step g)
After the hydrogenation, the aftertreatment of gained hydrogenated products by fractionation by distillation.This can carry out at atmospheric or low pressure.
At processing step g) in, from processing step f) hydrogenated products that obtains becomes to contain C by fractionation by distillation 9-aldehyde and compare C 9Low-boiling low-boiling-point substance of-aldehyde and optional C 9The cut of-aldehyde and contain C 9-pure and mild the C that compares 9The cut of-pure difficult ebullient high boiling material.Choose wantonly and can also will contain C 9The thing cut that boils in-the aldehyde is drawn, and its circulation is returned before the hydrogenation.Can further improve the effect of whole technology by this way.Preferably have 20 to 70, separating in the tower of preferred 28 to 65 theoretical separation levels.Temperature is preferred in the tower regulates like this, makes that promptly tower top temperature is 85 to 110 ℃, and preferred 95 to 100 ℃, column bottom temperature is 175 to 200 ℃, preferred 185 to 193 ℃.As overhead product, isolate and contain stable hydrocarbon and the optional alkene and the low-boiling-point substance of aldehyde.The alkene that optionally separating is come out can circulate return processing step a) and/or d) one of in.As bottom product, obtain containing the C of high boiling material 9-pure cut.
Tower bottom distillate is optional can be changed in another distillation tower, and is separated into and contains C 9The cut of-alcohol and the C that contains high boiling material and choose wantonly 9The cut of-alcohol.This separation preferably has 8 to 35, carries out in the tower of preferred 10 to 30 theoretical separation levels.Temperature in this tower is preferred regulates like this, makes that promptly tower top temperature is 150 to 180 ℃, and preferred 160 to 170 ℃, and column bottom temperature is 180 to 205 ℃, preferred 185 to 195 ℃.As overhead product, can isolate the optional C that can contain the trace low-boiling-point substance 9-alcohol.As bottom product, can obtain choosing wantonly and can contain C 9The high boiling material of-alcohol.
In order to improve the economy of present method, optional high boiling material cut (tower bottom distillate) from this distillation tower can being changed in another distillation tower, and be separated into and contain C 9The overhead fraction of-alcohol and the tower bottom distillate that mainly contains high boiling material.Can also contain a small amount of C in this external tower bottom distillate 9-alcohol.This separation preferably has 15 to 35, carries out in the tower of preferred 20 to 30 theoretical separation levels.Temperature in the tower is preferred regulates like this, makes that promptly tower top temperature is 95 to 120 ℃, and preferred 100 to 110 ℃, and column bottom temperature is 160 to 190 ℃, preferred 165 to 175 ℃.Suitable is, the overhead fraction of these two towers is merged.
The theory of distillation tower is separated the overhead fraction purity and the residual C of progression, pure tower or high boiling material tower 9-pure content depends on required product purity.
In the methods of the invention can with processing step a) and/or b) in the excessive synthetic gas separated completely or partially circulate and return in the technology.Significant especially possibility is that the hydroformylation reaction device is operated under different pressures.The waste gas of first reactor that working pressure is higher than second reactor can separate under the working pressure that is higher than second reactor, so this waste gas can need not compression and promptly is used for second reactor.
Principal character of the present invention be with two stages to C 8-alkene carries out hydroformylation, mainly is to have more reactive alkene to react in the fs, mainly is to lack reactive alkene to react in subordinate phase.Another key character of the present invention is by fractionation by distillation from unreacting olefin hydroformylation product, that in low-boiling-point substance contain of fs with liquid emission, preferably separates after removing catalyzer.
Can use the C that obtains in the mode that varies in the methods of the invention 8-alkene.As parent material, C 8-alkene can use with pure form, perhaps with C 8-alkene mixture form is used, isomer mixture for example, and it can contain the C of branching and non-branching 8-alkene is perhaps to use with the alkene mixture form that other alkene of different C numbers forms.Appropriate C 8-alkene is especially at the mixture of butene dimerization or the isomer octene (dibutene) that produces when oligomeric.Can use the C that makes by other industrial technology in addition 8-alkene or C 8-alkene mixture.Preferred especially the use by the oligomeric C that obtains of n-butene on the nickel fixed bed catalyst 8The C of-alkene mixture form 8-alkene.
There are three kinds of methods to be used for oligomerization of butenes is become mainly to contain C in principle 8The mixture of-alkene.Disclosed already be on an acidic catalyst, carry out oligomeric, the industrial in this respect phosphoric acid that for example uses on zeolite or the carrier.Mainly be the isomer mixture (WO 92/13818) of the branched olefin of dimethyl hexene this moment.The method that a kind of same world wide adopts is to carry out oligomeric with solubility Ni complex compound, be known as DIMERSOL method (B.CORNILS, W.A.HERRMANN, " Applied Homogeneous Catalysis with Organicmetallic Compounds "; 1﹠amp; 2 volumes, VCH, Weinheim, New York 1996).The third method be on the nickel fixed bed catalyst, carry out oligomeric; This method is called as OCTOL technology (HydrocarbonProcess., Int.Ed. (1986) 65 (2.1 joint) 31-33 page or leaf) in the literature, also can find in DE 39 14 817 and EP 1 029 839.
For C produced according to the present invention 9-alcohol mixture, it is particularly suitable for preparing tenderizer, and preferred the use according to OCTOL technology used the C that obtains from linear butylene under the nickeliferous catalyzer situation 8-alkene mixture.
The alcohol that makes according to the inventive method is particularly suitable as the pure and mild detergent alcohol of tenderizer.Tenderizer alcohol can for example be used phthalic anhydride (PAN) by esterification, is reacted into for the common tenderizer of polyvinyl chloride (PVC).Described aldehyde also can be used to prepare carboxylic acid.

Claims (14)

1. in the presence of being present in cobalt catalyst in the organic phase, uniform dissolution passes through C 8Two stage hydroformylations of-alkene prepare C continuously 9The method of-alcohol, wherein,
A) C 8-alkene first hydroformylation in the stage in the presence of cobalt catalyst hydroformylation to transformation efficiency be 50 to 90%,
B) catalyzer is removed from the liquid reactor output object that obtains a) at processing step,
The liquid hydrogen formylation mixture that does not contain catalyzer that c) will obtain like this is separated into and contains C 8-alkene and randomly contain the low-boiling-point substance cut of paraffin and contain aldehyde tower bottom distillate and
D) make the C that in the low-boiling-point substance cut, contains 8-alkene reacted in the second hydroformylation stage, wherein C in this processing step 8-conversion of olefines rate is 55 to 98%,
E) with catalyzer from processing step d) remove in the liquid reactor output object that obtains,
F) with the processing step c in the first hydroformylation stage) tower bottom distillate and from processing step e) the hydroformylation mixture that does not contain catalyzer merge; and on the fixed bed catalyst that in liquid phase, is containing at least a element in the periodic table of elements 8-10 family under 0.5 to 4MPa pressure and 120 to the 220 ℃ of temperature, carry out hydrogenation and
G) by fractionation by distillation with C 9-alcohol from processing step f) hydrogenated products separate,
Wherein cobalt catalyst two processing steps a) and d) in following acquisition: at C 8-alkene, C 9-alcohol and/or C 9-aldehyde exists down reacts the cobalt saline solution and the synthetic gas that contain 0.7 to 3 quality % cobalt, and makes the cobalt catalyst that forms when reacting pass through C 8-alkene, C 9-alcohol and/or C 9-aldehyde and being extracted into the organic phase from water, described reaction and extraction are carried out in the reactor that carries out hydroformylation, and the level of wherein carrying out water-bed phase in the reactor of hydroformylation is higher or lower than each mixing nozzle outlet 0 to 1m, cobalt saline solution, C 8-alkene and synthetic gas are introduced in the reactor through described mixing nozzle.
2. according to the method for claim 1, it is characterized in that, at hydroformylation step a) and d) one of or two in use its space reactor by the separated reactor of at least one separating device.
3. according to the method for claim 1 or 2, it is characterized in that, cobalt catalyst two processing steps a) and d) in by cobalt saline solution, C 8-alkene and synthetic gas are incorporated into simultaneously in the reactor and obtain.
4. according at least one method among the claim 1-3, it is characterized in that, processing step a) with d) the bottom in the reactor in one or two accounts for 1 to 10% of liquid reactor inclusion mutually.
5. according at least one method among the claim 1-4, it is characterized in that, processing step a) and d) in one or two, the liquid velocity in the mixing nozzle exit is 10 to 100m/s.
6. according at least one method among the claim 1-5, it is characterized in that, in order to remove processing step b) and e) in catalyzer, from processing step a) or d) the reaction output object handle with air adding under the acid cobalt saline solution situation, and be separated into organic phase that does not contain catalyzer that contains reaction product and the water that contains cobalt salt.
7. according to the method for claim 6, it is characterized in that, at processing step b) and e) in the circulation directly or after aftertreatment of the water that contains cobalt salt that obtains return the hydroformylation step a) and the d of operation stage separately) in.
8. according at least one method among the claim 1-7, it is characterized in that, at processing step f) liquid phase of the hydrogenation output object that obtains contains the water of 1 to 5 quality %, and under the steady state of this technology in hydrogenation reactor input than 1 to 50% the hydrogen of manying that consumes owing to hydrogenation.
9. according at least one method among the claim 1-8, it is characterized in that, at processing step f) in use the fixed bed catalyst contain 0.3 to 15 quality % copper, 0.3 to 15 quality % nickel, 0.05 to 3.5 quality % chromium and 0 to 1.8 quality % basic metal or alkaline-earth metal.
10. according at least one method among the claim 1-9, it is characterized in that, at processing step f) in use and contain silicon-dioxide and/or aluminum oxide fixed bed catalyst as solid support material.
11., it is characterized in that, at processing step f according at least one method among the claim 1-10) in, the aldehyde concentration that enters hydrogenation reactor is 5 to 20%.
12. according at least one method among the claim 1-11, it is characterized in that, use by the oligomeric C that obtains on the nickel fixed bed catalyst 8The C of-alkene mixture form 8-alkene.
13. according at least one method among the claim 1-12, it is characterized in that, processing step a) and d) in hydroformylation under 160 to 220 ℃ temperature, carry out.
14. according at least one method among the claim 1-13, it is characterized in that, processing step a) and d) in hydroformylation under 20 to 30MPa pressure carry out.
CNA2009100099694A 2008-01-31 2009-01-24 Method for producing nine carbon alcohol from eight carbon olefin Pending CN101497553A (en)

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