CN108129289A - The preparation method of carbonylation synthesis propionic acid under a kind of ethyl alcohol low pressure - Google Patents
The preparation method of carbonylation synthesis propionic acid under a kind of ethyl alcohol low pressure Download PDFInfo
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- CN108129289A CN108129289A CN201611091346.2A CN201611091346A CN108129289A CN 108129289 A CN108129289 A CN 108129289A CN 201611091346 A CN201611091346 A CN 201611091346A CN 108129289 A CN108129289 A CN 108129289A
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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Abstract
The invention belongs to the field of chemical synthesis, and in particular to the preparation method of carbonylation synthesis propionic acid under a kind of ethyl alcohol low pressure.The method includes the steps：Make ethyl alcohol under the conditions of existing for rhodium major catalyst, catalyst stabilizer metal Ru salt, accelerating agent alkali metal lithium salts, hydroiodic acid, water, synthesizing propionic acid by carbonylation.The present invention preparation method have the special feature that for：It is reacted with ethyl alcohol and hydroiodic acid instead of co-catalyst iodoethane, not directly using the larger iodoethane of toxicity.
Description
Technical field
The invention belongs to the field of chemical synthesis, and in particular to the preparation method of carbonylation synthesis propionic acid under a kind of ethyl alcohol low pressure.
Background technology
Propionic acid is one of widely used three big consumption preservatives, is generally acknowledged most economical economical, most safe in the world
Effective consumption preservative；Propionic acid is also important fine chemical material, is widely used in rubber, plastics, paint, perfume (or spice)
The numerous areas such as material, medicine, pesticide, printing.
Propionic acid industrialized producing technology mainly has propionic aldehyde oxidizing process and Reppe methods.Propionic aldehyde oxidation legal system propionic acid, therein third
Aldehyde is synthesized by ethene hydroformylation, can be realized in the presence of cobalt or rhodium catalyst.When making catalyst with carbonyl cobalt, ethylene hydrogen formyl
The temperature of change be 403~423K, synthesis atmospheric pressure be 28~30MPa, ethylene once by conversion ratio be 95%, propionic aldehyde yield with
Ethylene meter is not more than 91%.When making catalyst with rhodium, hydroformylation temperature is 373-393K, and synthesis atmospheric pressure is 1~3.5MPa,
Ethylene is once 99% by conversion ratio, and propionic aldehyde yield is 98~99%, and by-product is seldom.It is to be catalyzed that propionic aldehyde, which is oxidized to propionic acid,
It is realized under agent manganese acetate or manganese acetate-copper acetate effect, reaction temperature 333K, reaction pressure 0.65MPa.Propionic aldehyde once passes through
Conversion ratio is 87~98%, and propionic acid selectivity 87~94%, yield of propionic acid is 90% or so.Reppe methods are using ethylene as original
Material generates propionic acid under catalyst action with carbon monoxide and one step of water.This method using transition metal Ni, Co, Fe, Rh,
Ir, Pt, Pd, Ru, Mo-Ni, W-Ni etc. are catalyst.The catalyst temperature of early application is 473~573K, pressure for 20~
30MPa.In recent years, Rh, Ir, Pb, Co (pyridine co-catalysis) also constantly have been reported that, reaction condition is mild compared to before.Germany
BASF AG produces propionic acid using this method.[Jiang great Zhi, Jiang Jing propionic acid synthetic method [C] Zhengzhou：14th national chemical fertilizer
Methanol technology annual meeting, 2005.46-56.]
Late 1960s, Monsanto companies of the U.S. are successfully developed by the technique of low-pressure methanol synthesizing acetic acid by carbonylation.
Similar therewith, 1962, N.V.Kutepow etc. used H first3P04, Fe, Co, Ni complex compound for catalyst carry out ethanol carbonylation
Propionic acid synthesized research, as a result yield is very low, and needs to pressurize.1969, F.E.Paulik et al. was in patent US3487112
In report soluble RhCI3·nH2O/ iodide catalysis ethanol synthesizing propionic acid by carbonylation, activity and selectivity all increase,
The ethanol carbonylation effect of Rh loaded catalysts is also preferable.DuPont Corporation obtains propionic acid, temperature 180 using this method first
~400 DEG C, 35.5~70.9MPa of reaction pressure.Chinese invention patent application 201010521509.2 discloses a kind of carbonyl and closes
Into the preparation method of propionic acid, this method is using the derivative of ethyl alcohol or ethyl alcohol as raw material, with liquid reaction composition (rhodium or iridium main reminder
Agent, iodoethane co-catalyst, ethyl propionate, propionic acid, water and the 1st and the 2nd salt compounded of iodine as accelerating agent) temperature 140~
It is propionic acid synthesized under conditions of 220 DEG C and 2.0~8.0MPa of pressure.Patent is proposed by adding in the 1st and the 2nd liang into reaction system
Kind salt compounded of iodine, improves the stability of rhodium or iridium major catalyst and the catalytic activity that ethyl alcohol carbonylation is propionic acid synthesized.But at this
Iodoethane is all employed as co-catalyst in a little technologies.
Invention content
In order to overcome the problems of in the prior art, the purpose of the present invention is to provide carbonyls under a kind of ethyl alcohol low pressure
Propionic acid synthesized preparation method.
To achieve these goals and other related purposes, the present invention adopt the following technical scheme that：
The present invention provides a kind of method of synthesizing propionic acid by carbonylation, including step：Make ethyl alcohol in rhodium major catalyst, catalyst
Under the conditions of stabilizer metals ruthenium salt, accelerating agent alkali metal lithium salts, hydroiodic acid, water are existing, synthesizing propionic acid by carbonylation.
Preferably, reaction temperature is 160~260 DEG C.It is further preferred that 180~210 DEG C.
Preferably, reaction pressure is 2.0~10.0Mpa.More preferable 2.5~4.5MPa.
Preferably, counted based on reaction solution total weight, in the rhodium major catalyst shared by rhodium element a concentration of 300~
3000ppm.It is further preferred that 1000~2000ppm.
Preferably, the precursor compound of the rhodium major catalyst is selected from, but not limited to, RhI3、RhI3·3H2O、RhCl3、
RhCl3·3H2O、[Rh(CO)2Cl]2、[Rh(CO)2I]2、Rh(OAc)3、Rh(acac)(CO)2、Rh4(CO)12Or Rh6(CO)16In
One or more.It is highly preferred that the precursor compound of the rhodium major catalyst is selected from RhI3Or RhI3·3H2One kind in O or
Two kinds.
Preferably, it is counted based on reaction system total weight, in the catalyst stabilizer metal Ru salt shared by ruthenium element
A concentration of 300~3000ppm, preferably 500~1500ppm.
Preferably, the catalyst stabilizer metal Ru salt is selected from, but not limited to, RuI3、RuCl3、RuCl3·3H2O、
RuBr3、Ru(HCOO)3、Ru(OAc)3、Ru(CH3CH2COO)3、Ru(CH3CH2CH2COO)3、[Ru(CO)3I3]-H+、Ru(CO)5With
Ru3(CO)12One or more of.It is highly preferred that the catalyst stabilizer metal Ru salt is selected from RuI3Or Ru
(CH3CH2COO)3One or both of.
Preferably, it is counted based on reaction system total weight, it is dense shared by elemental lithium in the accelerating agent alkali metal lithium salts
It spends for 500~5000ppm.More preferable 2500~3500ppm.
Preferably, the accelerating agent alkali metal lithium salts is selected from, but not limited to, LiI, LiI3H2O、LiCl、LiBr、LiOAc
Or Li2CO3One or more of.It is highly preferred that the accelerating agent alkali metal lithium salts is selected from LiI or LiI3H2One kind in O
Or two kinds.
Preferably, it is counted based on reaction system total weight, the content of the hydroiodic acid is 1~30wt%.More preferable 5~
20wt%.The content of the water is 1~30wt%.More preferable 8~18wt%.The content of the ethyl alcohol is 10~30%.It is more excellent
Select 12~20%.Remaining reaction liquid is solvent propionic acid.
Preferably, it is reacted under conditions of there are carbon monoxide.
Compared with prior art, the present invention has the advantages that：
(1) the larger iodoethane of toxicity is replaced with ethyl alcohol and hydroiodic acid, can effectively reduces environmental risk；(2) with ethyl alcohol and
Hydroiodic acid does not reduce the space-time yield of ethyl alcohol carbonylation synthesis propionic acid instead of co-catalyst iodoethane.
Specific embodiment
Before further describing the specific embodiments of the present invention, it should be appreciated that protection scope of the present invention is not limited to down
State specific specific embodiment；It is also understood that the term used in the embodiment of the present invention is specific specific in order to describe
Embodiment, the protection domain being not intended to be limiting of the invention.The test method of actual conditions is not specified in the following example,
Usually according to normal condition or the condition proposed by according to each manufacturer.
When embodiment provides numberical range, it should be appreciated that except non-present invention is otherwise noted, two ends of each numberical range
Any one numerical value can be selected between point and two endpoints.Unless otherwise defined, in the present invention all technologies for using and
Scientific terminology is identical with the normally understood meaning of those skilled in the art of the present technique.Except used in embodiment specific method, equipment,
Outside material, according to record of the those skilled in the art to the grasp of the prior art and the present invention, it can also use and this
Any method, equipment and the material of the similar or equivalent prior art of method, equipment described in inventive embodiments, material come real
The existing present invention.
Unless otherwise stated, disclosed in this invention experimental method, detection method, preparation method using this technology lead
The routine techniques in domain, these technologies existing perfect explanation in the prior art.
The present invention replaces co-catalyst iodoethane, carbonylation synthesis by the way of intermittent reaction, with ethyl alcohol and hydroiodic acid
Propionic acid.Specific method includes：
This experiment carries the zirconium material reaction kettle (i.e. carbonylation reactor) of blender using volume 250ml, and reaction process adds
Hot mode is with temperature controlled electrical heating.Zirconium material cooling water coil is connected in kettle, reaction solution is contributed to be quickly cooled down.It is accurate to claim
Quantitative response component：Rhodium major catalyst, catalyst stabilizer metal Ru salt, accelerating agent alkali metal lithium salts, hydroiodic acid, water, ethyl alcohol and
Reaction dissolvent propionic acid.Above each material is sequentially added in reaction kettle in proportion, then in carbon monoxide replacement reaction kettle
Air is pressurized to 0.5MPa, after by pressure in kettle, slowly emptying to prevent the loss of volatile matter in reaction solution, uses an oxidation
Carbon is replaced three times repeatedly.Being passed through carbon monoxide after completion displacement makes reaction system boost to 3.0MPa.Confirming reaction kettle sealing
It is slowly vented after all right No leakage, pressure drops to 0.6MPa, closes blow valve and starts to stir and heat, speed of agitator control
800rpm is made as, reaction temperature sets 190 DEG C.Observing response kettle heats up and pressure changing.When temperature is raised to 190 DEG C,
It opens air intake valve and is passed through carbon monoxide to 3.0MPa, maintain 190 ± 2 DEG C of reaction temperature, start to react.Pass through gas mass flow
Gauge observes the integrated flux and instantaneous flow of carbon monoxide, and inlet pressure maintains 3.0MPa.When the instantaneous flow of carbon monoxide
When dropping to below 100ml/min, stop air inlet and stop heating, be passed through cooling water and " Quench " processing, fast quickly cooling are carried out to reaction
But.Treat that reaction temperature is cooled to room temperature, remaining gas is slowly released in reaction kettle pressure release, and with nitrogen displacement three times, is opened anti-
Kettle is answered, pour out reaction solution and weighs, sample, the content that reaction solution passes through gas Chromatographic Determination each component.It is measured and reacted by ICP
The content of metal rhodium, ruthenium, lithium in liquid.
The transient absorption rate of carbon monoxide calculates the instantaneous space-time yield of reaction during being carried out with reaction, during with unit
Between the molal quantity of propionic acid that is generated by carbonylation in unit reaction volume calculate the average space-time yield of reaction.This experiment
Using instantaneous space-time yield, unit mol/ (Lh), calculation formula is as follows：
STY=(R60)/(22.4V)
Wherein, R be carbon monoxide absorption rate, unit L/min；Volumes of the V for reaction solution, unit L.
Embodiment 1
Rhodium triiodid 1.06g (rhodium concentration 1500ppm, rhodium concentration tool herein are sequentially added into 250ml zirconium material reaction kettles
Body refers to the rhodium concentration in reaction solution system, similarly hereinafter), (ruthenium concentration 1200ppm, ruthenium concentration herein refer specifically to triiodide ruthenium 0.86g
Ruthenium concentration in reaction solution system, similarly hereinafter), (lithium concentration 3000ppm, lithium concentration herein refer specifically to react three water lithium iodide 12g
Lithium concentration in liquid system, similarly hereinafter), hydriodic acid aqueous solution (58wt%) 28g, pure water 2g, ethyl alcohol 18.5g and solvent propionic acid
87.58g, reaction solution gross weight 150g.Keep 190 DEG C of reaction temperature, reaction pressure 3.0MPa.The highest monitored in reaction process
Instantaneous space-time yield is 1.729mol/ (Lh).
Embodiment 2
RhCl is sequentially added into 250ml zirconium material reaction kettles30.31g (rhodium concentration 1000ppm), RuCl3(ruthenium is dense by 0.15g
Spend 500ppm), LiI 7.13g (lithium concentration 2500ppm), hydroiodic acid (58wt%) 12.9g, pure water 5.5g, ethyl alcohol 18g and solvent
Propionic acid 106.01g, reaction solution gross weight 150g.Keep 180 DEG C of reaction temperature, reaction pressure 4.5MPa.It is monitored in reaction process
The instantaneous space-time yield of highest be 1.021mol/ (Lh).
Embodiment 3
[Rh (CO) is sequentially added into 250ml zirconium material reaction kettles2Cl]20.57g (rhodium concentration 2000ppm), RuBr3
0.76g (ruthenium concentration 1500ppm), LiCl 3.19g (lithium concentration 3500ppm), hydroiodic acid (58wt%) 51.7g, pure water 3g, second
Alcohol 30g and solvent propionic acid 60.78g, reaction solution gross weight 150g.Keep 210 DEG C of reaction temperature, reaction pressure 2.5MPa.It reacted
The instantaneous space-time yield of highest monitored in journey is 2.554mol/ (Lh).
Embodiment 4
Rh (acac) (CO) is sequentially added into 250ml zirconium material reaction kettles20.56g (rhodium concentration 1500ppm), Ru
(CH3CH2COO)30.57g (ruthenium concentration 1200ppm), Li2CO32.38g (lithium concentration 3000ppm), hydroiodic acid (58wt%)
28g, pure water 2g, ethyl alcohol 18.5g and solvent propionic acid 97.99g, reaction solution gross weight 150g.Keep 190 DEG C of reaction temperature, reaction pressure
Power 3.0MPa.The instantaneous space-time yield of highest monitored in reaction process is 1.768mol/ (Lh).
Embodiment 5
Rh is sequentially added into 250ml zirconium material reaction kettles4(CO)120.54g (rhodium concentration 2000ppm), Ru (OAc)3
0.50g (ruthenium concentration 1200ppm), three water lithium iodide 12g (lithium concentration 3000ppm), hydroiodic acid (58wt%) 28g, pure water 2g, second
Alcohol 18.5g and solvent propionic acid 88.46g, reaction solution gross weight 150g.Keep 190 DEG C of reaction temperature, reaction pressure 3.0MPa.Reaction
The instantaneous space-time yield of highest monitored in the process is 2.514mol/ (Lh).
Embodiment 6
Rh is sequentially added into 250ml zirconium material reaction kettles6(CO)160.26g (rhodium concentration 1000ppm), Ru (CO)5
0.43g (ruthenium concentration 1200ppm), three water lithium iodide 12g (lithium concentration 3000ppm), hydroiodic acid (58wt%) 28g, pure water 2g, second
Alcohol 18.5g and solvent propionic acid 88.81g, reaction solution gross weight 150g.Keep 190 DEG C of reaction temperature, reaction pressure 3.0MPa.Reaction
The instantaneous space-time yield of highest monitored in the process is 1.257mol/ (Lh).
Reference examples A
Rhodium triiodid 1.06g (rhodium concentration 1500ppm), triiodide ruthenium 0.86g are sequentially added into 250ml zirconium material reaction kettles
(ruthenium concentration 1200ppm), three water lithium iodide 12g (lithium concentration 3000ppm), iodoethane 12g, hydroiodic acid (58wt%) 10g, pure water
12g, ethyl alcohol 15g and solvent propionic acid 87g, reaction solution gross weight 150g.Keep 190 DEG C of reaction temperature, reaction pressure 3.0MPa.Reaction
The instantaneous space-time yield of highest monitored in the process is 1.768mol/ (Lh).
Reference examples B
Rhodium triiodid 1.06g (rhodium concentration 1500ppm), triiodide ruthenium 0.86g are sequentially added into 250ml zirconium material reaction kettles
(ruthenium concentration 1200ppm), three water lithium iodide 12g (lithium concentration 3000ppm), iodoethane 12g, hydroiodic acid (58wt%) 10g, pure water
12g, ethyl alcohol 15g and solvent propionic acid 87g, reaction solution gross weight 150g.Keep 185 DEG C of reaction temperature, reaction pressure 3.0MPa.Reaction
The instantaneous space-time yield of highest monitored in the process is 1.414mol/ (Lh).
Reference examples C
Rhodium triiodid 1.06g (rhodium concentration 1500ppm), triiodide ruthenium 0.86g are sequentially added into 250ml zirconium material reaction kettles
(ruthenium concentration 1200ppm), three water lithium iodide 12g (lithium concentration 3000ppm), iodoethane 12g, hydroiodic acid (58wt%) 10g, pure water
12g, ethyl alcohol 15g and solvent propionic acid 87g, reaction solution gross weight 150g.Keep 195 DEG C of reaction temperature, reaction pressure 3.0MPa.Reaction
The instantaneous space-time yield of highest monitored in the process is 2.357mol/ (Lh).
Reference examples D
Rhodium triiodid 1.06g (rhodium concentration 1500ppm), three water lithium iodide 12g are sequentially added into 250ml zirconium material reaction kettles
(lithium concentration 3000ppm), iodoethane 12g, hydroiodic acid (58wt%) 10g, pure water 12g, ethyl alcohol 15g and solvent propionic acid 88g, reaction
Liquid gross weight 150g.Keep 190 DEG C of reaction temperature, reaction pressure 3.0MPa.The instantaneous space-time production of highest monitored in reaction process
Rate is 1.846mol/ (Lh).
Reference examples E
Rhodium triiodid 0.7g (rhodium concentration 1000ppm), acetic acid ruthenium 3.85g (rutheniums are sequentially added into 250ml zirconium material reaction kettles
Concentration 1200ppm), three water lithium iodide 12g (lithium concentration 3000ppm), iodoethane 12g, hydroiodic acid (58wt%) 10g, pure water
10g, ethyl alcohol 15g and solvent propionic acid 86g, reaction solution gross weight 150g.Keep 195 DEG C of reaction temperature, reaction pressure 3.0MPa.Reaction
The instantaneous space-time yield of highest monitored in the process is 1.493mol/ (Lh).
In addition to the addition of rhodium triiodid is different, the experimental procedure of reference examples F-reference examples L, experiment condition tests component
Identical with reference examples E with addition, acquired results are as shown in table 1.
Table 1
Reference examples M
Rhodium triiodid 0.7g (rhodium concentration 1000ppm), acetic acid ruthenium 3.85g (rutheniums are sequentially added into 250ml zirconium material reaction kettles
Concentration 1200ppm), three water lithium iodide 12g (lithium concentration 3000ppm), iodoethane 12g, hydroiodic acid (58wt%) 10g, pure water
15g, ethyl alcohol 15g and solvent propionic acid 81g, reaction solution gross weight 150g.Keep 195 DEG C of reaction temperature, reaction pressure 3.0MPa.Reaction
The instantaneous space-time yield of highest monitored in the process is 1.493mol/ (Lh).
In addition to the addition of pure water is different, the experimental procedure of reference examples N-reference examples S, experiment condition is tested component and is added
It is identical with reference examples M to enter amount, acquired results are as shown in table 2.
Table 2
Reference examples T
Rhodium triiodid 1.06g (rhodium concentration 1500ppm), triiodide ruthenium 0.86g are sequentially added into 250ml zirconium material reaction kettles
(ruthenium concentration 1200ppm), three water lithium iodide 12g (lithium concentration 3000ppm), iodoethane 12g, hydroiodic acid (58wt%) 10g, pure water
12g, ethyl alcohol 15g and solvent propionic acid 87g, reaction solution gross weight 150g.Keep 190 DEG C of reaction temperature, reaction pressure 4.0MPa.Reaction
The instantaneous space-time yield of highest monitored in the process is 1.807mol/ (Lh).
The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that for those skilled in the art, under the premise of the method for the present invention is not departed from, can also make
Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are the equivalent embodiment of the present invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution of any equivalent variations that above-described embodiment is made still fall within the range of technical scheme of the present invention
It is interior.
Claims (10)
1. a kind of method of synthesizing propionic acid by carbonylation, including step：Make ethyl alcohol in rhodium major catalyst, catalyst stabilizer metal Ru
Under the conditions of salt, accelerating agent alkali metal lithium salts, hydroiodic acid, water are existing, synthesizing propionic acid by carbonylation.
2. according to the method described in claim 1, it is characterized in that, reaction temperature is 160~260 DEG C, preferably 180~210 DEG C.
3. according to the method described in claim 1, it is characterized in that, reaction pressure be 2.0~10.0Mpa, preferably 2.5~
4.5MPa。
4. it according to the method described in claim 1, it is characterized in that, is counted based on reaction system total weight, the rhodium main reminder
A concentration of 300~3000ppm in agent shared by rhodium element, preferably 1000~2000ppm.
5. according to the method described in claim 1, it is characterized in that, the precursor compound of the rhodium major catalyst is selected from RhI3、
RhI3·3H2O、RhCl3、RhCl3·3H2O、[Rh(CO)2Cl]2、[Rh(CO)2I]2、Rh(OAc)3、Rh(acac)(CO)2、Rh4
(CO)12Or Rh6(CO)16One or more of.
6. it according to the method described in claim 1, it is characterized in that, is counted based on reaction system total weight, the catalyst
A concentration of 300~3000ppm in stabilizer metals ruthenium salt shared by ruthenium element, preferably 500~1500ppm.
7. according to the method described in claim 1, it is characterized in that, the catalyst stabilizer metal Ru salt is selected from RuI3、
RuCl3、RuCl3·3H2O、RuBr3、Ru(HCOO)3、Ru(OAc)3、Ru(CH3CH2COO)3、Ru(CH3CH2CH2COO)3、[Ru
(CO)3I3]-H+、Ru(CO)5And Ru3(CO)12One or more of.
8. it according to the method described in claim 1, it is characterized in that, is counted based on reaction system total weight, the accelerating agent
A concentration of 500~5000ppm in alkali metal lithium salts shared by elemental lithium, preferably 2500~3500ppm.
9. according to the method described in claim 1, it is characterized in that, the accelerating agent alkali metal lithium salts be selected from, but not limited to, LiI,
LiI·3H2O, LiCl, LiBr, LiOAc or Li2CO3One or more of.
10. it according to the method described in claim 1, it is characterized in that, is counted based on reaction solution total weight, the method is also wrapped
Include any one of following characteristics or multinomial：(1) content of the hydroiodic acid is 1~30wt%, preferably 5~20wt%；And/or
(2) content of the water is 1~30wt%, more preferable 8~18wt%；And/or the content of (3) described ethyl alcohol is 10~30%,
More preferable 12~20%；Remaining reaction liquid is solvent propionic acid.
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Application publication date: 20180608 |