CN1023797C - Prepn. process for producing alcohol from alkenes - Google Patents
Prepn. process for producing alcohol from alkenes Download PDFInfo
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- CN1023797C CN1023797C CN89100610A CN89100610A CN1023797C CN 1023797 C CN1023797 C CN 1023797C CN 89100610 A CN89100610 A CN 89100610A CN 89100610 A CN89100610 A CN 89100610A CN 1023797 C CN1023797 C CN 1023797C
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Abstract
The present invention discloses a technical process for preparing alcohol, and olefin with 9 to 15 carbon atoms is processed by hydroformylation, and n-alkanol is generated in one step and is a main product. The entire process is divided into three working sections, a catalyst regeneration working section is before a reaction working section, and the catalyst regeneration working section is propitious to increase the concentration of active substances of a cobalt-phosphine compound catalyst, increase reaction activity and reduce catalyst consumption figure and alcohol production cost. Two film evaporators can be connected in series so as to reduce the stay time of the catalyst at vacuum high temperature.
Description
The invention relates to continuous process, promptly so-called olefin hydroformylation continuous process with alkene and carbon monoxide and H-H reaction generation alcohol.
Olefin hydroformylation is a kind of well-known technological process, and wherein with alkene, normally normal olefine in the presence of suitable catalyzer, with carbon monoxide and hydrogen, reacts by following formula, and a step generates alcohol:
R
1, R
2General proxy one hydrogen atom or an alkyl, R
2Be generally hydrogen atom.
Raw material olefin also can be mixed olefins, as C9～C10, C11～C12, C13～C14, C15～C16 or the like, or wherein olefin(e) centent is about 80%(weight) alkene mixture.Use reduction that this class raw material can be by a relatively large margin to produce the cost of alcohol and enlarge the source of raw material olefin widely.
For realizing above-mentioned technological process, people have proposed various embodiments and technical solution from all many-sides such as catalyzer, reaction conditions, technological processs, to reach economical, to obtain the purpose of alcohol from alkene rationally, easily.
The catalyzer of bringing into use is the transition-metal-carbonyl-complexes of no phosphine ligand, for example HCo(CO)
4Deng.Use the advantage of the technological process of this class catalyzer to be, adaptable olefin feedstock source broad, no matter be to hold position alkene or internal olefin or branched-chain alkene all to can be used as the raw material of preparation alcohol, its main drawback is that the straight chain rate of product is lower, has influence on the range of application of product alcohol.Because unless special purposes is arranged, it is n-alkanol that the general expectation of people obtains.And, using this class catalyzer, the first step product is an aldehyde, also needs for second step aldehyde hydrogenation was become alcohol, catalyzer also must destructively reclaim.
Afterwards, it is found that the carbonylic cobalt compound catalyzer that adopts the organic phosphine modification, not only reaction pressure can drop to 5.0～8.0MPa, and single step reaction can mainly generate alcohol by alkene, significantly reduced the burden of back end hydrogenation, made the back end hydrogenation technological process reduce to less important attached technological process, simultaneously by main technique, the ratio of the n-alkanol in the product alcohol of this technology also obviously improves, and the general content of n-alkanol in product alcohol is not less than 80%.BP1191015 and US3420898 are one of representatives of this class technological process.This class technological process must not reclaim cobalt complex catalyst breakage ground, just under suitable condition, from reaction stream, isolate catalyzer after, mother liquor directly recycles.This improvement has not only saved the recovery system of many cobalt metals or salt, and has reduced the consumption of catalyzer in reaction one partitioning cycle process.
Obviously, adopt the technological process of organophosphite ligand compound transition-metal catalyst, how to guarantee that cobalt salt and ligand do not decompose in recycling repeatedly, and alap degree is reduced in their loss is very important, can reduces the cost of producing alcohol so effectively.
In above-mentioned technological process, catalyzer and reaction product all are present in in a kind of reaction solution in the homogeneous catalytic reaction process, need from reaction solution, separate product or portion of product, with catalyzer or catalyzer mother liquor together with solvent recycled to reactive system.Have in order to the method for finishing this sepn process many, for example: simple distillation, underpressure distillation, flash distillation and the pressure distillation under synthetic gas protection etc.The subject matter that above-mentioned each method exists is that cobalt metal and its esters and organic phosphine coordination body loses in sepn process more, and particularly when preparing higher alcohols, catalyst loss is even more serious.
In order to address the above problem, US4060557 proposes molecular distillation equipment is used for separating of alkene system higher alcohols product and catalyzer.
The principle of molecular distillation and technology are listed in many books of teaching as known technology.The molecular distillation equipment separating mixture, it is low to have separation temperature, the advantage that residence time of material is short and efficient is high, to separating thermographic compound, for example transition-metal-carbonyl-complexes catalyzer etc. has more obvious effects.Reason is that this quasi-molecule distillation plant is to operate under higher vacuum tightness, to reduce separation temperature as far as possible.But, component broad when mixed solution to be separated, boiling spread is bigger, particularly not only contain higher-boiling compound but also contained and do not coagulated component when (as: containing carbon monoxide and hydrogen in the reaction solution), requiring at first will not coagulate component separates, and then carry out molecular distillation and separate, otherwise will reduce the distillation efficiency of the unit surface of molecular distillation equipment greatly, perhaps impel distillation temperature to raise significantly, cause a large amount of decomposition of thermographic compound-homogeneous catalyst, lost the meaning of using molecular distillation equipment.Under negative pressure, in the reaction solution overwhelming majority such as dissolved carbon monoxide and hydrogen not condensate from liquid phase, overflow, carbonyl-complexes cobalt transition-metal catalyst is also taken off carbonyl and is changed salt into, and this salt very easily is decomposed into cobalt metal under higher temperature, causes the permanent inactivation of catalyzer.The also easy and alkene of this salt, the compound that alkynes, nitrile, amine etc. have coordination ability generates more stable title complex.Even this title complex in the presence of carbon monoxide and hydrogen, also is difficult for being transformed into as the required cobalt carbonyl-complexes catalyzer of hydroformylation of olefin, reduced the utilization ratio of catalyzer.
The present invention seeks a kind of technological process that generates the improvement alkene oxo process system alcohol of C10 to C16 alcohol from the alkene of C9 to C15, this technological process makes the catalyzer mother liquor after negative pressure is separated change into the carbonyl-complexes of alkene oxo catalyst again in the short as far as possible time, the alkene etc. of avoiding having coordination ability with separate after the contact of catalyzer mother liquor, guarantee organic phosphine coordination body and cobalt-carbonyl making full use of as catalyzer.The present invention also further seeks in the sepn process of catalyzer mother liquor and product alcohol, reduce the separation efficiency of lock out operation temperature and raising separator unit surface, to reduce the loss of organic phosphine coordination and cobalt atom, adaptation mixed olefins or olefin(e) centent are lower than 80% hydrocarbon mixture as the needs of making raw polyol.
The use olefin(e) centent is lower than 80% hydrocarbon mixture as the system raw polyol, compare with using pure alkene, have advantages such as low price, raw material sources be extensive, but the low or mixed olefins of raw material olefin content, cause bigger pressure for undoubtedly reactive system, particularly separation system.As oleaginousness 8%(weight) the prepared alkene of wax cracking, its olefin(e) centent is generally in 80%(weight) about owing in the olefin feedstock 20%(weight is arranged still) inert substance, increased burden for the refining and aftertreatment of product.Another object of the present invention promptly is to improve sepn process and the technology in the prior art, with alleviate use olefin(e) centent less than 80% alkene the burden of product aftertreatment during as the raw material of system alcohol.
Purpose of the present invention can realize by following measure:
According to the present invention; can provide a kind of with the alkene of 9 to 15 carbon atoms or their mixture, the mixture of perhaps above-mentioned alkene and other hydro carbons (alkane, naphthenic hydrocarbon etc.) carries out olefin hydroformylation; produce the continuous process of the alcohol of 10 to 16 carbon atoms, this technological process comprises:
Provide the RS Regenerator Section hydroformylation of olefin section of a hydroformylation of olefin section, a product segregation section and a recycling catalyst to form by several placed in-line shell and tube gas and liquid flowing bubble towers:
To the fluid that above-mentioned alkene hydroformylation reaction section provides, be actually the liquid olefin hydroformylation medium of pre-determined volume, wherein contain equally distributed; (a) contain and carbon monoxide and organic phosphine coordination body title complex olefin hydroformylation catalyzer with fit system bonded cobalt; (b) free ligand; (c) free carboxy acid's root and alkaline promoter;
Provide synthetic gas, H continuously to above-mentioned hydroformylation of olefin section
2/ CO=2～2.3: the 1(mol ratio);
Provide above-mentioned any substituted olefine or mixed olefins continuously to above-mentioned hydroformylation of olefin section;
The above-mentioned hydroformylation of olefin section of operation under the olefin hydroformylation condition;
Product segregation section is made up of low gas-liquid separator, an external-cooling type thin-film evaporator and an inner-cooled film evaporator;
Feed hydroformylation of olefin stream to above-mentioned product segregation section;
Separation and Recovery gas phase carbon monoxide and hydrogen in the low-pressure gas-liquid separator of above-mentioned segregation section;
Separation and Recovery is dissolved in carbon monoxide and hydrogen and most of by product alkane, unreacted alkene and other inert substances of reaction solution in the external-cooling type thin-film evaporator of above-mentioned segregation section;
In the inner-cooled film evaporator of above-mentioned segregation section, isolate product alcohol, comprise whole catalyzer one cobalt and its esters and ligand in the residuum with certain proportion;
At above-mentioned segregation section, by the evaporation conditions of different isolates, operate above-mentioned segregation section,
To the above-mentioned gas-liquid flow of the continuous circulation of above-mentioned hydroformylation of olefin section;
The catalyst regeneration section is made up of catalyst recirculation jar and a filler bubble tower revivifier that has steam jacket;
Charge into the synthetic gas that is actually predetermined amount to above-mentioned catalyst recirculation jar;
From recycling catalyst solution and the synthetic gas of catalyst recirculation jar, replenish the raw catalyst of predetermined amount simultaneously to above-mentioned catalyst filling bubble tower injection predetermined amount of flow;
The above-mentioned RS Regenerator Section of operation under regeneration condition.
By the hydroformylation of olefin device that several placed in-line shell and tube gas and liquid flowing bubble towers are formed, can only adorn a reactor, also can adorn more than two or two.All enter reactor from the effusive catalyst solution in revivifier top and synthetic gas and reaction raw materials alkene from reactor bottom, reaction mixture passes through each reactor in the mode of gas and liquid flowing, comprise from the reaction stream that last reactor flows out: inert substance that product alcohol, by product alkane and a small amount of dipolymer, catalyzer, unreacted alkene, raw material olefin are contained and remaining synthetic gas etc., above-mentioned gas-liquid mixture all injects segregation section.
The gas-liquid separator of segregation section is the gas step-down disposal facilities with predetermined volume, and the vapor phase stream in the reaction solution emits with certain pressure in this container.The liquid phase stream of reaction stream enters the external-cooling type thin-film evaporator then, in this equipment, not only remove dissolved carbon monoxide and hydrogen etc. in the reaction solution, and remove the lower boiling inert substance that most of by product alkane, unreacted alkene and raw material are brought into, from the effusive liquid of this base of evaporator mainly is product alcohol and heavy constituent material, also has catalyzer.These mixtures continue to enter inner-cooled film evaporator, and product alcohol steams with certain proportion in this equipment, comprise whole catalyzer one cobalt and its esters and ligand in the residuum.
From the catalyzer that inner-cooled film evaporator obtains, the inflow catalyst circulation tank, two arranged side by side of this circulation tank has one to be in collection catalyst in two circulation tanks all the time.Another carries the working order of catalyzer, and two regularly switch.After treating that receipts are full, charge into synthetic gas, with pump or air pressure catalyzer is sent into revivifier, revivifier is that a filler bubble tower that has steam jacket is formed, volume is equivalent to 1/10th to 1/8th of reactor volume, inject the recycling catalyst solution and the synthetic gas of predetermined amount of flow from the bottom, inject a little raw catalyst solution simultaneously, gas-liquid two-phase is simultaneously from the revivifier overhead stream toward conversion zone.
The reader in present technique field will appreciate that the present invention does not belong to the invention category of any new olefin hydroformylation building-up reactions or the pure system of new principles of chemistry system, and the present invention only improves the technological process of prior art.That is: the two-stage process with prior art (US3,448,157, US3,369,050) is improved to three segment process, and the present invention characterizes by the original position spectrographic and the contrast of example, has fully confirmed to set up before conversion zone the necessity of a RS Regenerator Section.In addition, be lower than 80% mixed fraction needs for adapting to olefin(e) centent as the pure raw materials for production of system, use external-cooling type film under vacuum vaporizer to replace prior art (US4,060,557) vacuum degassing tower, and the recycle unit and the technology of the catalyst solution of improvement from segregation section to the revivifier, above-mentioned improvement of the present invention, not only reduced of the decomposition of cobalt carbonyl-complexes catalyzer to greatest extent at segregation section, and make the catalyst activity species that have catalytic activity most: phosphine coordinate hydrogenized carbonyl cobalt component fully contacts with alkene, so not only improved the efficient of catalyzer and reaction unit, and catalyzer is reduced to gratifying degree in the decomposition of conversion zone, alleviated again simultaneously owing to use low concentration of olefin cut to give product aftertreatment (alkali cleaning as the system raw polyol, washing, distillation etc.) burden that increases.
Originally, to decompose in the part of reaction when workshop section such as separating and recycle be inevitable to cobalt phosphine carbon back composition catalyst.Its decomposing cause: be oxygen and the sulphur that raw material is brought on the one hand, destroyed the valence state of phosphorus atom, make it to become pentavalent, lose coordination ability by trivalent; Be under the vacuum state on the other hand, originally be present in the reaction solution as the catalyst activity thing and with these catalyst activity phase balances or all overflow as the coordination carbonyl in catalyst activity thing predecessor's the carbonyl-complexes, cobalt atom has lost stable pentacoordinate body structure, very easily forms cobalt metal and is deposited on the wall of container.Adopt the in-situ ft-ir of the reaction solution of in-situ infrared technology test reaction section, spectrogram as shown in Figure 2, the ownership of each absorption peak is as follows:
A:2045cm
-1, 1970cm
-1Belong to HCo(CO)
3L
B:2010cm
-1, 1998cm
-1Belong to Co
2(CO)
7L
C:1950cm
-1Belong to Co
2(CO)
6L
2
D:1923cm
-1Belong to HCo(CO)
2L
2
E:1910cm
-1Belong to [Co(CO)
4]
-
F:1880cm
-1, 1620cm
-1Belong to RCH=CH
2
G:1740cm
-1Belong to RCHO
H:1710cm
-1Belong to RCOOH
Wherein: 2045～1910
-1The interval is the absorption band of cobalt phosphine carbonyl-complexes.2045～1910cm under the segregation section vacuum state
-1The interval in-situ ft-ir band (see figure 3) that all disappears shows that cobalt phosphine carbonyl-complexes does not all exist separating residual solution or steam in the liquid, and cobalt atom may generate a kind of naphthenic acid cobalt salt of organic phosphine coordination with free organic phosphine and cycloalkanes acid group.About the character of such salt, existing detailed argumentation.This cobalt salt then generates unsettled novel complexes as contacting with alkene; can decomposite cobalt metal being higher than under the mitigation temperature of room temperature; cause permanent inactivation; if with contact with synthetic gas before alkene contacts; about 120 ℃, promptly generate carbonyl-complexes such as A, B, C, D, E; Fig. 4 has clearly illustrated that this variation, and it is catalytic activity things that these title complexs have some, and is issued to balance with other title complex in the hydroformylation reaction condition.Because the existence of these catalytic activity things, just can make conversion of olefines is alcohol.Obviously, because the present invention has improved the technology that recycling catalyst directly enters conversion zone in the prior art from segregation section, increase volume in the conversion zone front little, the simple again RS Regenerator Section of structure, can fully reduce the decomposition of catalyzer at conversion zone, alkene is directly contacted with the catalyst activity species one phosphine coordinate hydrogenized carbonyl cobalt that has most catalytic activity etc., rather than directly contact with catalyzer that segregation section reclaims, to improving reaction efficiency, the loss that reduces catalyzer is useful so undoubtedly.In the technology of prior art; first reactor be the bottom of this reactor particularly; be actually the revivifier of catalyzer; it should be noted that; when the catalyzer that reclaims from segregation section; after carbon monoxide and hydrogen and olefin feedstock enter first reactor; the catalyzer that reclaims must contact with synthetic gas earlier and be converted into catalytic active species; could carry out hydroformylation reaction by catalyzed alkene; but when catalyzer contacts with synthetic gas; also contact with the alkene that enters reactor with synthetic gas inevitably, the hazardness of this contact we narrated very clear.The adding of RS Regenerator Section in the technology of the present invention, avoided catalyzer before producing active specy with the contacting of alkene, not only improved the utilization ratio of first reactor lower part effectively, the more important thing is the consumption that has reduced catalyzer.By above-mentioned improvement, we have realized one of purpose of the present invention.
This technological process can be adapted to the alkene of 9 to 15 carbon atoms, and this type of alkene not only can be end position alkene or internal olefin, also can be mixed olefins, particularly is adapted to the hydrocarbon mixture of olefin(e) centent less than 80%.That is, can have one or several substituent chemical formula is-CH=CH
2Or C=CH
2α-thiazolinyl or
Interior thiazolinyl.Representational alkene comprises, 1-nonene, 2-nonene, 3-nonene, 1-decene, 2-decene, 3-decene, 1-hendecene, 3-hendecene, 1-laurylene, 4-laurylene, 1-tridecylene, 3-tridecylene, 4-tridecylene, 1-tetradecylene, 1-ten pentaenes, 3-ten pentaenes or the like.Raw material olefin of the present invention is the cut of optional self-contained other hydro carbons also, and this class alkene is usually from wax cracking, thermal cracking of heavy oil and polymer gasoline etc.When the present invention used above-mentioned olefin(e) centent to be lower than 80% raw material, its typical component was approximately: C9～C14 normal olefine 76%(weight), and C9～C14 alkane 15%, C9～C14 isomeric olefine 3%, C9～C14 diolefin or alkynes 3%, C9～C14 aromatic hydrocarbons 3%, chief constituent 1%.Certainly we expect to have in the raw material normal olefine of high level.
Obviously, use the raw material olefin of different carbon numbers and structure, should select the phosphine ligand of different structure and boiling point for use, the boiling point of phosphine ligand should be higher than the boiling point of product alcohol usually.The ligand that the present invention selects for use has:
Trialkyl tertiary phosphine class: three positive its phosphines of fourth, tri-n-octyl phosphine, three n-hexadecyl phosphines or diethyl hexadecyl phosphine, dibutyl hexadecyl phosphine.
Trialkyl aryl phosphine class: diethyl phenyl phosphine, ethyl diphenylphosphine, dibutyl Phenylphosphine, butyl diphenyl phosphine, diethyl naphthyl phosphine or dibutyl naphthyl phosphine.
Cyclic phosphines class: 9-phosphine bicyclic nonane octadecyl phosphine and encircle single phosphine or two phosphines of many rings etc. more.
Comprise the cobalt phosphine carbonyl-complexes catalyzer of forming with fit system and carbon monoxide and phosphine ligand in the reaction medium.This catalyzer can be in reaction medium produced in situ, also can make in advance, preferably make in advance, when the technical process running of the present invention, catalyzer is actually and makes in advance in revivifier, and then introduces reaction medium.Certainly, the method for preparing active catalyst is being well-known in the art.
The content of cobalt in reaction medium is calculated as 0.2～0.6%(weight by cobalt metal) or greater than 0.6%, but from considering that economically still 0.40～0.45% scope is good.The source of cobalt can be selected cobalt naphthenate, carbonyl acid cobalt salt, cobalt octacarbonyl, diphosphine six carbonyl diurethane cobalts and cobaltous carbonate etc. for use.
In reaction medium, ligand is normally excessive: P: the Co(atom)=4: 1～3: 1, ratio is P: Co=2 preferably: 1.Common yardstick is that every mole of cobalt catalyst has the free ligand that contains at least more than 1.5 moles.
The above-mentioned technological process of operation is produced alcohol under the olefin hydroformylation condition, can select the conversion zone condition, segregation section condition and the RS Regenerator Section condition that suit according to raw material olefin, ligand, cobalt concentration and other efficiency factor.RS Regenerator Section is selected conditions such as identical or close temperature, pressure for use with conversion zone.Conversion zone usually adopts at 170～190 ℃, 5.0～8.0MPa and H
2/ CO=2～2.3(mole) under the condition, reacted 6～12 hours, preferable reaction conditions is at 175～185 ℃, and 5.0～6.0MPa operated 7～9 hours down.RS Regenerator Section adopts 165～175 ℃ usually, 5.0～7.0MPa, H
2/ CO=2～2.3, the condition of 30～60 minutes recovery times.Two tandem thin-film vaporizers of segregation section are also selected identical or close working pressure for use, be generally 0.1～50mmHg, second thin-film evaporator operated under higher vacuum tightness than first, separation temperature is different and different according to isolating object, common first thin-film evaporator is than low 20～30 ℃ of second service temperature, must not surpass 120 ℃ and second temperature is the highest, otherwise can cause that catalyzer decomposes in a large number.Lower working pressure and temperature are expectations of the present invention, if there is not other negative consequence.
When using different raw material olefins and catalyzer, the operation of this technological process is also different.As use the raw material of olefin(e) centent point about 80%, from the effusive reaction stream more complicated of conversion zone, comprise inert substance and the aforesaid liquid institute dissolved synthetic gas brought in product alcohol, by product alkane, unreacted alkene, free ligand, catalyzer, a small amount of heavy constituent, the raw material, and, the alkene higher with using purity is different as raw material, the concentration of alcohol only reaches 60～65% in its reaction stream, rather than 85～90%.Press prior art, use degassing tower to remove the synthetic gas that is dissolved in the reaction solution, and then make reaction solution enter the separation that thin-film evaporator carries out the pure and mild catalyzer of product, owing to differ 80～100 ℃ with the hydro carbons of carbon number and the boiling point of alcohols, in thin-film evaporator, must there be the part heating surface to be used for low boiling point hydrocarbon evaporation and have reduced the evaporation area that is used for evaporate alcohol, and with the increase of hydrocarbon content, it reduces more very.For the productive rate that guarantees that catalyzer is stable and pure, its way is to increase evaporation area, prolongs catalyzer in the residence time of steaming under the product alcohol, or improves vaporization temperature.Obviously, above-mentioned measure is unfavorable factor for the stability of thermo-sensitivity catalyzer and parent thereof.The present invention adopts an external-cooling type thin-film evaporator to replace the efficient degassing tower of prior art, its function is not merely for removing the synthetic gas in the reaction solution, in addition, still most of hydro carbons is separated in this equipment, hydro carbons is different with the carbonatoms of alcohol in the visual response liquid, selects suitable service temperature.Shorten the residence time of catalyzer under vacuum and comparatively high temps like this, reduced the decomposition of catalyzer, reduced the calmness of cobalt on the thin film evaporation wall, prolonged the cleaning interval of vaporizer, also alleviated the burden of pure crude product aftertreatment in addition.
Above-mentioned improvement of the present invention, the raw material that olefin(e) centent is low or composition is complicated that suited preferably, the boiling point of each main component of reaction solution that following table is listed just is being to use the reflection of this class coarse raw materials:
The carbon boiling point (℃) boiling point of 0.1mmHg (℃)
Number alkane alkene-n alcohol-n alkane alkene-n alcohol-n
C5 36.1 30 137.3
748，50
13/ / /
C6 68.7 63.3 158 / / /
C7 98.4 93.6 176.3，78-9
15/ / ～0
C8 125.6 121.3 194-195 / / ～17
C9 150.7 149.9 215 / / ～30
C10 174 172 232.9 / / ～43
C11 195.6 192-195 243 ～17 ～15～17 ～50
C12 213 213 259 ～32 ～32 ～60
C13 235.4 232.8 274 ～45 ～43 ～70
C14 253.7 246 170-3
20～55 ～51 ～81～85
C15 270.5 268.2 299 ～65 ～62 ～85
C16 287 284.5 190
15～76 ～75 ～106
As use the higher raw material olefin of purity, its reaction solution component to want simple many, at this moment, certainly consider only to use a thin-film evaporator.
For understanding the present invention better, we propose following embodiment.
Example 1:
This example is with or without regenerators a comparison example.
In the technological process of Fig. 1 and device, as solvent, cobalt naphthenate and octadecyl dicyclo phosphine in the ninth of the ten Heavenly Stems are the raw material of controlling catalyst with 2-Ethylhexyl Alcohol, and the good cobalt contents of in-situ preparing is a 0.4%(weight) cobalt phosphine carbonyl-complexes catalyzer, its reaction result is:
There is revivifier not have revivifier
Cobalt metal content (weight %) 0.4 0.4
P/Co（mol） 2 2
H
2/CO（mol） 2 2
Regenerator temperature (℃) 107 ± 5/
Revivifier pressure (MPa) 5.0/
Temperature of reactor (℃) 180 ± 5 180 ± 5
Reactor pressure (MPa) 5.0 5.0
Olefin(e) centent 76% 76%
（C9～C14）
Continuous operation time (hour) 400 400
Olefin conversion 94% 90%
Primary alconol yield (weight) 103 98
Alkane yield (weight) 8.01 8.1
Organic phosphine consumes 1.98 2.56
(kilogram/ton alcohol)
Example 2
In autoclave, add 90 parts of 4.5 parts of cobalt naphthenates, 4.5 parts of tributylphosphines, promotor KOH1 part and solvent 2-Ethylhexyl Alcohols successively, stir and heat up, charge into special 170 ℃ of synthetic gas dimension, 4.0MPa condition 4 hours, qualified through In-situ Infrared monitoring, that is: 1970 and 2045cm
-1Absorption reach capacity.The catalyst solution of making, warp 18 and pump 34 mix with recycling catalyst, add catalyst regeneration one reaction cycle system.
Raw material olefin (line 2) is boosted behind preheater 36 by high-pressure metering pump 33, with synthetic gas (line 1, the H behind the purifying
2CO is 2～2.1) enter reactor 22 after converging, effusive catalyzer in revivifier 21 tops and synthetic gas spray into reactor 22 through sinking to the bottom pipe 65 and sparger 62 from the bottom, react under 170～180 ℃, 5.0～7.0MPa condition.Reactor 22 effusive reaction solutions are through sinking to the bottom pipe 66 and gas-liquid distributor 63 inflow reactors 23, and reactor 23 effusive reaction solutions enter reactor 24 through sinking to the bottom pipe 67 and sparger 64.Reaction heat is removed by the chuck of each reactor and the temperature adjustment water in the interior cold tubulation.Intensification water (line 68) decompression back flows into drum 32, separates low-pressure steam (line 19), replenishes corresponding cold water (line 20), boosts and interchanger 40,41 is adjusted to temperature adjustment water through pump 35.Last reactor 24 effusive gas-liquid mixture enters gas-liquid separator 25, enters the fuel gas house steward after unreacted synthetic gas (line 5) decompression.Reaction solution enters external-cooling type thin-film evaporator 26 after water cooler 37 temperature adjustments, the control vaporization temperature is 60～70 ℃, pressure 15mmHg(absolute pressure), reaction solution dissolved synthetic gas and most of alkane, alkene and reaction product alcohol and catalyzer are separated, and the alkane that evaporates, alkene are through water cooler 38 cooling back receptions.Unevaporated a small amount of alkane, alkene and alcohol, catalyzer etc. flow into inner-cooled film evaporator 27, are 90～95 ℃ in vaporization temperature, pressure 0.1～0.5mmHg(absolute pressure) under the condition, be separated into two strands of materials of thick pure and mild catalyzer.Thick alcohol mixes with alkane, the hydrocarbon hydrocarbon that vaporizer 26 steams, and send follow-up workshop section to make refinement treatment.Catalyzer is lowered the temperature through water cooler 39, is received by receiving tank 28,29, with 30, the 31 supporting switchings of catalyst recirculation jar, realizes the continuous circulation of catalyzer, and regularly quantitative discharge unit spent catalyst (line 15).Circulation tank 30,31 fills the synthetic gas protection of 0.2～0.4MPa.Intermittently the live catalyst (line 18) that replenishes, boost through volume pump 34 with recycling catalyst and to mix, mix with a small amount of synthetic gas again and inject revivifier, keep 160～170 ℃, the regeneration condition of 5.0～7.0MPa, liquid stopped after 0.5～1 hour, in the gas-liquid mixture mode by the revivifier top through reactor bottom sparger 62 injecting reactors.
With the olefin(e) centent is 79%(weight), alkane content is 15%(weight) C9～C11 mixed olefins fraction be raw material, catalyst cobalt concentration is 0.4%(weight), phosphine cobalt ratio is 2: 1(mol), synthetic gas and alkene ratio are 4～5: 1(mol), recycling catalyst/alkene ratio is 0.67～2.5: the 1(volume ratio, be generally 1.6: 1), the liquid total reaction residence time is under 7.7～12 hours (being generally 9 hours) conditions, in said apparatus, continuous operation 1000 hours, the weight in average yield of C10～C12 alcohol is 90%.
Example 3
Phosphine ligand is 16 to 20 mixed alkyls-9-phosphine bicyclic nonane mixture, is 76%(weight with alpha-olefin content).Alkane is 10～15%, isomeric alkane, alkene and unknown material are that 10～14% C8～C16 mixed olefins of forming are raw material, and wherein C11～C14 alkene accounts for 85%.Adopt and example 2 described same procedure and devices, 1), synthetic gas/alkene is 4.69～8.63 in the liquid total residence time is 6.72～10.22 hours (better 9～10 hours), recycling catalyst and alkene volume ratios 0.54～2: 1(is preferably 0.54～0.67:: 1(mol) (be preferably 4.5～5.0: 1) under the condition, continuous operation 1000 hours, the average yield 99.54%(weight of C9～C17 alcohol), under above-mentioned preferable reaction conditions, the weight yield of higher alcohols can reach 100～105%.In this running, the evaporation conditions of external-cooling type thin-film evaporator is 70～80 ℃ of temperature, pressure is the 10mmHg(absolute pressure) operational condition of inner-cooled film evaporator is 95～105 ℃ of temperature, pressure 0.2mmHg(absolute pressure).
Claims (9)
1, any substituted olefine with 9 to 15 carbon numbers carries out olefin hydroformylation, produces the continuous process of the alcohol of 10 to 16 carbon numbers, and this technology comprises:
A hydroformylation of olefin section, a product separation section are provided;
The hydroformylation of olefin section is made up of several placed in-line shell and tube gas and liquid flowing bubble towers;
The fluid that provides to above-mentioned hydroformylation of olefin section, be actually the olefin hydroformylation catalyst liquid of pre-determined volume, wherein contain equally distributed: (1) is contained and carbon monoxide and the organic phosphine coordination body title complex olefin hydroformylation catalyzer with fit system bonded cobalt; (2) free ligand; (3) free carboxy acid's root and alkaline promoter;
Provide carbon monoxide and hydrogen continuously to above-mentioned alkene hydrogen first section;
To above-mentioned olefin hydroformylation section above-mentioned any substituted olefine without interruption;
The above-mentioned hydroformylation of olefin section of operation under the olefin hydroformylation condition;
Segregation section is made of low-pressure gas-liquid separator and thin-film evaporator serial group;
Feed hydroformylation of olefin stream to above-mentioned product segregation section;
The above-mentioned segregation section of operation under separation condition;
To the above-mentioned gas-liquid flow of the continuous circulation of above-mentioned hydroformylation of olefin;
It is characterized in that:
The equipment of the liquid between a catalyst regeneration section and circulation segregation section and the RS Regenerator Section is provided;
The catalyst regeneration section is made up of the filler bubble tower revivifier that catalyst recirculation jar and of the synthetic gas that charges into 0.2～0.4MPa has steam jacket, the bubble tower volume be overall reactor long-pending 1/10～1/8;
Provide by the thin-film evaporator of an external-cooling type thin-film evaporator and an inner-cooled film evaporator serial group and form, external-cooling type is lower 20～30 ℃ than inner-cooled film evaporator, and inner-cooled film evaporator is not more than under 120 ℃ the condition and operates;
Inject the recycling catalyst solution of predetermined amount and synthetic gas, replenish the raw catalyst of predetermined amount simultaneously to catalyst regenerator from the catalyst recirculation jar;
The catalyst regeneration condition is under 185～175 ℃ and the 5.0～7.0MPa, to operate 0.5～1.0 hour.
2,, it is characterized in that any substituted olefine has 9 to 15 carbon atoms according to the technological process of claim 1.
3,, it is characterized in that any substituted olefine is selected from oleaginousness and is not more than 8%(weight according to the technological process of claim 1 or 2) wax cracking alkene, thermal cracking of heavy oil alkene, polymer gasoline alkene and contain the mixed olefins of other hydro carbons.
4, according to the technological process of claim 1, it is characterized in that any substituted olefine is selected from the wax cracking cut, it consists of: C
9～C
10Normal olefine 78%(weight), C
9～C
10Alkane 15%, C
9～C
10Isomeric olefine 3%, C
9～C
10Diolefin or alkynes 3%, other cut 4%, and ligand is a kind of trialkyl tertiary phosphine.
5, according to the technological process of claim 1, it is characterized in that any substituted olefine is selected from the wax cracking cut, it consists of: C
11～C
14Normal olefine 78%(weight), C
11～C
14Alkane 15%, C
11～C
14Isomeric olefine 3%, C
11～C
14Diolefin or alkynes 3%, C
11～C
14Aromatic hydrocarbons 3%, other component 1%, and ligand is a kind of dicyclo phosphine Heterocyclylalkyl tertiary phosphine.
6, according to the technological process of claim 1, wherein the olefin hydroformylation medium contains, and presses cobalt metal and calculates, and about cobalt of 0.2 to 0.6 and one mole of cobalt catalyst have 1.5～2 moles free ligand at least.
7, technological process according to Claim 8 is characterized in that the scope of cobalt concentration in olefin hydroformylation Jie formylation medium is 0.4～0.45%(weight).
8, according to the technological process of claim 1, it is characterized in that the olefin hydroformylation condition is: 175～185 ℃ of temperature, pressure 5.0～8.0MPa operated 6～12 hours down.
9, according to the technological process of claim 7, it is characterized in that the hydroformylation condition is: at 175～185 ℃ of pressure 5.0～6 of temperature, 0MPa operated 7～9 hours down.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89100610A CN1023797C (en) | 1989-01-28 | 1989-01-28 | Prepn. process for producing alcohol from alkenes |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89100610A CN1023797C (en) | 1989-01-28 | 1989-01-28 | Prepn. process for producing alcohol from alkenes |
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| Publication Number | Publication Date |
|---|---|
| CN1044452A CN1044452A (en) | 1990-08-08 |
| CN1023797C true CN1023797C (en) | 1994-02-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89100610A Expired - Fee Related CN1023797C (en) | 1989-01-28 | 1989-01-28 | Prepn. process for producing alcohol from alkenes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106831297A (en) * | 2017-02-24 | 2017-06-13 | 中国科学院上海高等研究院 | A kind of synthesis gas directly alkene processed oil-phase product separate processing method and system |
| CN110981692A (en) * | 2019-12-25 | 2020-04-10 | 中国科学院兰州化学物理研究所 | Method and system for co-producing isononyl alcohol and carbon octaalkane |
| CN114478215A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Method and device for continuously preparing aldehyde and alcohol |
| CN114656343B (en) * | 2020-12-23 | 2024-05-17 | 中国石油化工股份有限公司 | Method for preparing aldehyde and alcohol |
| CN115701418B (en) * | 2021-08-02 | 2024-05-17 | 中国石油化工股份有限公司 | Aldol composition and preparation method thereof, and method for continuously preparing aldehyde and alcohol |
| CN116063168A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Method for hydroformylation of olefins |
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1989
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