CN113004139A - Method for synthesizing propionic acid by ethanol carbonyl under low water content - Google Patents
Method for synthesizing propionic acid by ethanol carbonyl under low water content Download PDFInfo
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Abstract
The invention discloses a method for synthesizing propionic acid by ethanol carbonyl under low water content, which comprises the following steps: raw material ethanol is carbonylated to synthesize propionic acid under the existence of rhodium main catalyst, accelerant hydriodic acid, ethyl iodide, alkali metal lithium salt and ligand organic diphosphorus compound. According to the method for synthesizing propionic acid by ethanol carbonylation under low water content, disclosed by the invention, the problems of reduced equipment production capacity, difficult product separation and the like caused by overhigh water content in the process of synthesizing propionic acid by ethanol carbonylation are solved by adding various promoters, the stability and high reaction activity of a rhodium catalyst can be still maintained under low water content, and the production cost can be effectively reduced. By adding organic diphosphine ligand, the activity of rhodium catalyst is improved, and the activity is greatly improvedThe space-time yield of propionic acid synthesized by ethanol carbonyl is up to 6.27 mol.L‑1h‑1。
Description
Technical Field
The invention belongs to the technical field of ethanol oxo synthesis of organic chemical products, and particularly relates to a method for synthesizing propionic acid by ethanol oxo under low water content.
Background
Propionic acid and its salt are widely used in the fields of synthetic fibers, plastics, medical intermediates, fruit essences, spices, etc., and also as esterification agents, special cellulose solvents, plasticizers, etc. Propionic acid is the most economical and safe additive among three generally accepted preservatives in the world, so that propionic acid is widely used for storage of foods, grains and feeds, and the demand is increasing.
The worldwide production of propionic acid is about 40 million tons per year, and the production process mainly adopts a propionaldehyde oxidation method and an ethylene carbonylation method (Reppe method) which take petroleum as raw materials. At present, the main production mode of propionic acid is propionaldehyde oxidation, and the process has been successfully industrialized in the sixties of the last century. The process is divided into two steps, the first step is to oxidize ethylene to prepare propionaldehyde, and the second step is to oxidize propionaldehyde by air to generate propionic acid. The process is divided into two types, cobalt catalyst high pressure carbonylation and rhodium (or titanium) catalyst low pressure carbonylation, according to the different catalysts used in the ethylene oxidation step. The catalyst adopted by the high-pressure method is generally cobalt carbonyl, and because the catalyst is expensive, the catalyst is sometimes replaced by chromium, nickel and the like, the reaction rate and the conversion rate are reduced, the reaction pressure is 20-28MPa, and the reaction temperature is 130-150 ℃. The process has harsh reaction conditions, high equipment operation cost, poor catalyst recovery effect and high consumption. In 1975, united states combined carbonization corporation developed a low pressure carbonylation process using a rhodium or titanium catalyst. The reaction temperature is about 100 ℃, the reaction pressure is 2MPa, the conditions are mild, the product is easy to separate, and the selectivity of propionaldehyde is high. The reaction of propionaldehyde oxidation to propionic acid can take place at 40-50 deg.C, and the side reaction is few, and the product is easy to separate, generally select manganese or cobalt as catalyst, propionic acid yield exceeds 96%. The ethylene carbonylation method is also called Reppe method, and can directly produce propionic acid by means of one-step reaction of ethylene, carbon monoxide and water, and the catalyst adopted is mainly nickel carbonyl complex, and can also use the complex of cobalt carbonyl, molybdenum carbonyl, etc. to substitute nickel carbonyl. The process is developed by German Pasteur company, the yield of propionic acid is high, the process flow is simple, but the reaction conditions are harsh, the requirement on the corrosion resistance of equipment is high, the reaction temperature is 250-.
In the eighties of the 20 th century, the Monsanto company uses rhodium iodide as a catalyst, and the preparation of acetic acid by methanol carbonylation is realized under relatively mild process conditions, so that the production cost is greatly reduced. The low pressure methanol carbonylation synthesis method is the mainstream technology for producing acetic acid at present and has strong competitiveness. As a similar reaction, BThe research on the preparation of propionic acid by alcohol homogeneous carbonylation is also gradually becoming a hot spot. The ethanol oxo-synthesis of propionic acid adopts halides of copper acetate, rhodium, nickel, manganese and cobalt as catalysts, and is firstly realized by DuPont in the United states at the temperature of 200-400 ℃ and the pressure of 35-70MPa, but the reaction conditions are harsh, so that large-scale industrialization is not realized. The preparation of propionic acid by ethanol carbonylation is firstly realized by DuPont in the United states, but the reaction condition is harsh, the catalyst cost is high, and the large-scale industrialization is not realized. In 1987, Jenner et al adopted RuCl3·H2O is a catalyst, iodine simple substance is an auxiliary agent, and the reaction conditions are as follows: the temperature is 200 ℃, the total pressure is 44.4MPa, the partial pressure of carbon monoxide is 30MPa, the conversion rate of ethanol is 92 percent, and the yield of propionic acid is 41 percent. In 2008, Chong et al examined the process of synthesizing propionic acid by carbonylation of ethanol using rhodium iodide as a catalyst and hydroiodic acid as an auxiliary agent. The reaction temperature is 185 ℃, the pressure is 4.5MPa, the reaction condition is mild, but the space-time yield of carbonyl is only 1 mol.L-1h-1. In addition, the ethanol oxo-synthesis of propionic acid has the requirement of minimum water content. In the report of Song inspection et al, the mass fraction of water in the reaction system was not less than 9%. However, too high a water content in the reaction solution has many disadvantages for the production, which not only reduces the production capacity of the equipment and increases the requirements for corrosion protection of the equipment, but also makes the subsequent separation process more difficult. Therefore, further improving the stability of the rhodium catalyst at low water content and increasing the space-time yield of carbonyl group are the technical problems to be solved by many researchers at present.
Disclosure of Invention
In order to overcome the defects of poor stability of a rhodium catalyst under the condition of low water content, low reaction activity of catalyzing ethanol carbonyl to synthesize propionic acid and low carbonyl space-time yield in the prior art, the invention aims to provide a novel method for synthesizing propionic acid by ethanol carbonyl under the condition of low water content.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect the present invention provides a process for the oxo synthesis of propionic acid from ethanol at low water content comprising the steps of: raw material ethanol is carbonylated to synthesize propionic acid under the existence of rhodium main catalyst, accelerant hydriodic acid, ethyl iodide, alkali metal lithium salt and ligand organic diphosphorus compound.
The method for synthesizing propionic acid by ethanol carbonylation under low water content comprises the following steps:
sequentially adding a rhodium main catalyst, an accelerant hydroiodic acid, ethyl iodide, an alkali metal lithium salt, a ligand organic diphosphorus compound, ethanol and a solvent propionic acid into a titanium high-pressure reaction kettle, sealing the reaction kettle, replacing air in the reaction kettle with carbon monoxide gas, pressurizing to 0.5MPa, keeping the pressure for 2 minutes, slowly emptying, repeatedly replacing for three times, introducing carbon monoxide after replacement is completed to enable the pressure of a reaction system to reach 0.5-1.5 MPa (preferably 0.6-1.0 MPa), starting stirring and heating, controlling the stirring speed to be 280-380 rpm, setting the temperature to be 40-50 ℃, slowly heating, measuring the temperature in the reaction kettle, keeping the temperature of the kettle to be 50 ℃ for 4 hours to activate the catalyst, heating to enable the reaction liquid to be rapidly heated to the reaction temperature of 150-220 ℃ after activation is finished, preferably 160-200 ℃, supplementing carbon monoxide to the reaction pressure of 2.0-4.5 MPa (preferably 2.2-3.8 MPa), the reaction was started when both the temperature and the pressure reached the set values, the sample was taken at a reaction time of 20 minutes, and the content of each component was determined by gas chromatography.
The precursor compound of the rhodium main catalyst is selected from RhI3、RhI3·3H2O、Rh(acac)(CO)2、RhCl3、RhCl3·3H2At least one of O.
The mass concentration of rhodium element in the rhodium main catalyst is 500-2500 ppm, preferably 800-2000 ppm, based on the total mass of the reaction system.
The alkali metal lithium salt is selected from LiI and LiI.3H2O、LiOAc、Li2CO3And LiCl.
The ligand organic diphosphorus compound is bis-diphenylphosphinomethane monosulfide (dppMS) and bis-diphenylphosphinomethane disulfide (dppMS)2) Bis (diphenylphosphinoethane) (dppe), bis (diphenylphosphinopropane) (dppp).
The molar ratio of the ligand organic diphosphorus compound to the rhodium main catalyst is (0.5-10): 1, preferably (0.5-5): 1.
The mass concentration of the hydriodic acid aqueous solution is 5 to 15 percent based on the total mass of the reaction system.
The mass concentration of the ethyl iodide is 2-18 percent based on the total mass of the reaction system.
The mass concentration of the alkali metal lithium salt is 5-20% based on the total mass of the reaction system.
The mass concentration of the ethanol is 10-30% based on the total mass of the reaction system.
The bis-diphenylphosphinomethane disulfide (dppmS)2) The preparation method comprises the following steps:
under the condition of no water and no oxygen, under the nitrogen atmosphere and with stirring, in an organic solvent (dichloromethane, THF or acetone), bis-diphenylphosphinomethane and twice the amount of elemental sulfur or 0.25 times the amount of S are sequentially added8Stirring the obtained solution for 1-12 h at the temperature of 30-100 ℃, and evaporating the solvent to obtain bis (diphenylphosphinomethane) disulfide (dppMS)2)。
The preparation method of the bis-diphenylphosphinomethane monosulfide (dppmS) comprises the following steps:
in a nitrogen atmosphere, stirring the mixture, and adding bis (diphenylphosphino) methane (dppm) and bis (diphenylphosphino) methane disulfide (dppmS) in a mass ratio of 1 (1.01-1.5)2) Dissolving the zinc salt in an organic solvent (dichloromethane, THF or acetone), and then adding a catalytic amount of zinc salt (the addition amount is 2.5-15 mol%, and the zinc salt is one of the following: zn (CF)3SO3)2、Zn(BF4)2、ZnCl2、ZnBr2Or ZnF2) The mixture is placed in the dark and continuously stirred at room temperature, the solution is evaporated to dryness after the reaction is completed, and bis-diphenylphosphinomethane monosulfide (dppmS) is obtained by column chromatography separation.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the invention relates to a method for synthesizing propionic acid by ethanol carbonyl under low water contentThe method overcomes the problems of reduced equipment production capacity, difficult product separation and the like caused by overhigh water content in the process of synthesizing propionic acid by ethanol carbonyl by adding a plurality of promoters, and has low water content<4.2 wt.%), the stability and high reaction activity of rhodium catalyst can be maintained, and production cost can be effectively reduced; by adding organic diphosphine ligand, the activity of rhodium catalyst is improved, the space-time yield of propionic acid synthesized by ethanol carbonylation is greatly improved, and the maximum reaches 6.27 mol.L-1h-1And has good commercial value.
The method for synthesizing propionic acid by ethanol carbonylation under low water content has good catalytic activity and selectivity and good stability under low water content, lower temperature and lower pressure, can efficiently catalyze ethanol carbonylation to synthesize propionic acid, and has the advantages that under the optimal reaction condition (example 9), by the reaction time of 20 minutes, the ethanol conversion rate is 99.0%, the propionic acid selectivity is 86.0%, the propionic acid yield reaches 85.1%, and the carbonyl space-time yield reaches 6.27 mol.L-1h-1The water content of the system was 4.06%.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The general experimental method of the batch reaction mode adopted in the embodiments 1 to 11 of the present invention is as follows:
the reaction is carried out in a titanium high-pressure reaction kettle with the volume of 0.5L, and the heating mode in the reaction process is external heating with temperature control. Accurately weighing a rhodium main catalyst, an accelerant hydroiodic acid, ethyl iodide, an alkali metal lithium salt, a ligand organic diphosphorus compound, ethanol and a solvent propionic acid, sequentially adding into a reaction kettle, and sealing the reaction kettle. Then replacing air in the reaction kettle with carbon monoxide gas, pressurizing to 0.5MPa, keeping for 2 minutes, slowly emptying, and repeatedly replacing for three times. And after the replacement is finished, introducing carbon monoxide to ensure that the pressure of the reaction system reaches 1MPa, starting stirring and heating, controlling the stirring rotating speed at 350rpm, setting the temperature at 50 ℃, slowly heating, measuring the temperature in the reaction kettle by a thermocouple, and keeping for 4 hours to activate the catalyst after the temperature of the kettle liquid reaches 50 ℃. After activation, adjusting the heating device to rapidly heat the reaction solution to a reaction temperature of 150-220 ℃, supplementing carbon monoxide to a reaction pressure of 2.0-4.5 MPa, and maintaining the reaction solution constant through a pressure reducing valve. When the temperature and the pressure reach set values, the reaction starts, when the reaction time is 20 minutes, a sampling valve is used for sampling, the obtained reaction liquid is used for measuring the content of each component through gas chromatography, and a Karl Fischer titrator is used for measuring the water content in the sample.
The carbonyl space-time yield (STY) is an important index of the production capacity of the device, the carbonyl space-time yield is taken as an index for measuring the reaction rate, and the carbonyl space-time yield (STY) is the amount n of the generated propionic acidPA(produced)The ratio of the reaction time t (h) to the volume of the reaction solution V (L) is calculated by the following formula:
the conditions of the gas chromatography were:
all samples were subjected to quantitative analysis of the product using an Agilent 7980 gas chromatograph, the measurement method being area normalization. The Agilent 7980 gas chromatograph uses an Elite Wax column (30 m. times.0.25 mm. times.6 m). The chromatographic detection conditions are as follows: the temperature of the gasification chamber was 200 deg.C, the temperature of the Flame Ionization Detector (FID) was 200 deg.C, high-purity nitrogen gas was used as carrier gas, and the constant flow rate was 2 mL/min-1. The flow rates of air and high-purity hydrogen in the FID detector are respectively 400 mL/min-1And 40mL min-1. The temperature of the column box adopts a temperature programming mode, the column box is kept for 2 minutes at 50 ℃, and the temperature is 10 ℃ per minute-1The temperature rise rate of (2) was increased to 200 ℃ and the analysis was terminated after 4 minutes at 200 ℃. The water content in the product could not be detected by gas chromatography, and the water content in the sample was determined by karl fischer titration.
The reactions in the following examples 1 to 11 were carried out in the batch reaction manner described above.
Example 1
0.94g of rhodium triiodide (the concentration of rhodium is 1400ppm, wherein the concentration of rhodium refers to the concentration of rhodium in a rhodium main catalyst based on the total mass of a reaction system, the same below), 10.81g of hydriodic acid aqueous solution (45 wt%), 17.89g of ethyl iodide, 10.73g of lithium iodide, 1.62g of bis (diphenylphosphine) methane monosulfide (dppmS), 15g of ethanol and 86.07g of solvent propionic acid are sequentially added into a titanium high-pressure reaction kettle (GCF500 type) with the volume of 0.5L, the total weight of the reaction solution is 143.06g, the molar ratio of the bis (diphenylphosphine) methane monosulfide to the rhodium triiodide is 2:1, the stirring speed is 350rpm, the pressure is 1MPa, and the temperature is 50 ℃ for activation for 4 hours, after the activation, the reaction temperature was kept at 180 ℃, the reaction pressure was 2.6MPa, and the sampling was performed for 20 minutes, resulting in 99.2% conversion of ethanol, 83.3% selectivity of propionic acid, and 6.21mol · L space-time yield of carbonyl.-1h-1. The yield of propionic acid was 82.6% and the water content of the system was 4.11%.
And subtracting the amount of the propionic acid solvent added before the reaction from the amount of the propionic acid in the product to obtain the amount of the generated propionic acid.
Example 2
Rh (acac) (CO) was sequentially added to a titanium autoclave having a capacity of 0.5L20.50g (rhodium concentration of 1400ppm), 10.81g of aqueous hydriodic acid (45 wt%), 17.89g of iodoethane, 10.73g of lithium iodide, 1.62g of bis (diphenylphosphinomethane) monosulfide (dppmS), 15g of ethanol and 86.51g of solvent propionic acid, the total weight of the reaction solution is 143.06g, bis (diphenylphosphinomethane) monosulfide and Rh (acac) (CO)2The molar ratio of (A) was 2:1, the stirring speed was 350rpm, the pressure was 1MPa, the temperature was 50 ℃ and the reaction temperature was kept at 180 ℃ after the activation, the reaction pressure was 2.6MPa, and the sampling was carried out for 20 minutes, whereby the ethanol conversion was 98.6%, the propionic acid selectivity was 78.3%, and the carbonyl space-time yield was 5.97 mol. L-1h-1. The yield of propionic acid was 77.2% and the water content of the system was 4.22%.
Example 3
0.81g of rhodium triiodide (rhodium concentration: 1200ppm), 10.81g of hydriodic acid aqueous solution (45 wt%), 17.89g of ethyl iodide, 10.73g of lithium iodide, and bis (diphenylphosphinomethane) monosulfide were sequentially added to a titanium autoclave having a volume of 0.5L1.40g of the product (dppMS), 15g of ethanol and 86.42g of propionic acid as a solvent, and the total weight of the reaction mixture was 143.06 g. The molar ratio of bis (diphenylphosphinomethane) monosulfide to rhodium triiodide was 2:1, the stirring speed was 350rpm, the pressure was 1MPa, the temperature was 50 ℃ and the activation was carried out for 4 hours, after the activation, the reaction temperature was kept at 180 ℃, the reaction pressure was 2.6MPa, and the reaction time was 20 minutes, and sampling was carried out, whereby the ethanol conversion was 98.5%, the propionic acid selectivity was 79.3%, and the carbonyl space-time yield was 5.83 mol. L-1h-1. The yield of propionic acid was 78.1%, and the water content of the system was 4.31%.
Example 4
0.67g of rhodium triiodide (rhodium concentration: 1000ppm), 10.81g of an aqueous hydroiodic acid solution (45 wt%), 17.89g of ethyl iodide, 10.73g of lithium iodide, 1.16g of bis (diphenylphosphinomethane) monosulfide (dppmS), 15g of ethanol, and 86.80g of propionic acid as a solvent were sequentially added to a titanium autoclave having a volume of 0.5L, and the total weight of the reaction solution was 143.06 g. The molar ratio of bis (diphenylphosphinomethane) monosulfide to rhodium triiodide was 2:1, the stirring speed was 350rpm, the pressure was 1MPa, the temperature was 50 ℃ and the activation was carried out for 4 hours, after the activation, the reaction temperature was kept at 180 ℃, the reaction pressure was 2.6MPa, and the reaction time was 20 minutes, and sampling was carried out, whereby the ethanol conversion was 97.7%, the propionic acid selectivity was 65.4%, and the carbonyl space-time yield was 4.97 mol. L-1h-1. The yield of propionic acid was 63.9%, and the water content of the system was 4.82%.
Example 5
0.94g of rhodium triiodide (with a rhodium concentration of 1400ppm), 10.81g of an aqueous hydroiodic acid solution (45 wt%), 17.89g of ethyl iodide, 10.73g of lithium iodide, 0.81g of bis (diphenylphosphinomethane) monosulfide (dppmS), 15g of ethanol and 86.88g of propionic acid as a solvent were sequentially added to a titanium autoclave having a volume of 0.5L, and the total weight of the reaction solution was 143.06 g. The molar ratio of bis (diphenylphosphinomethane) monosulfide to rhodium triiodide was 1:1, the stirring speed was 350rpm, the pressure was 1MPa, the temperature was 50 ℃ and the activation was carried out for 4 hours, after the activation, the reaction temperature was kept at 180 ℃, the reaction pressure was 2.6MPa, and the reaction time was 20 minutes, and sampling was carried out, whereby the ethanol conversion was 97.0%, the propionic acid selectivity was 59.8%, and the carbonyl space-time yield was 4.59 mol. L-1h-1. Yield of propionic acid58.1 percent and the water content of the system is 5.06 percent.
Example 6
0.94g of rhodium triiodide (with a rhodium concentration of 1400ppm), 10.81g of an aqueous hydroiodic acid solution (45 wt%), 17.89g of ethyl iodide, 10.73g of lithium iodide, 4.05g of bis (diphenylphosphinomethane) monosulfide (dppmS), 15g of ethanol and 83.64g of propionic acid as a solvent were sequentially added to a titanium autoclave having a volume of 0.5L, and the total weight of the reaction solution was 143.06 g. The molar ratio of bis (diphenylphosphinomethane) monosulfide to rhodium triiodide was 5:1, the stirring speed was 350rpm, the pressure was 1MPa, the temperature was 50 ℃ and the activation was carried out for 4 hours, after the activation, the reaction temperature was kept at 180 ℃, the reaction pressure was 2.6MPa, and the reaction time was 20 minutes, and sampling was carried out, whereby the ethanol conversion was 97.7%, the propionic acid selectivity was 72.1%, and the carbonyl space-time yield was 5.33 mol. L-1h-1. The yield of propionic acid was 70.5%, and the water content of the system was 4.60%.
Example 7
0.94g of rhodium triiodide (with a rhodium concentration of 1400ppm), 10.81g of an aqueous hydroiodic acid solution (45 wt%), 17.89g of ethyl iodide, 7.15g of lithium iodide, 1.62g of bis (diphenylphosphinomethane) monosulfide (dppmS), 15g of ethanol and 89.65g of propionic acid as a solvent were sequentially added to a titanium autoclave having a volume of 0.5L, and the total weight of the reaction solution was 143.06 g. The molar ratio of bis (diphenylphosphinomethane) monosulfide to rhodium triiodide was 2:1, the stirring speed was 350rpm, the pressure was 1MPa, the temperature was 50 ℃ and the activation was carried out for 4 hours, after the activation, the reaction temperature was kept at 180 ℃, the reaction pressure was 2.6MPa, and the reaction time was 20 minutes, and sampling was carried out, whereby the ethanol conversion was 98.6%, the propionic acid selectivity was 73.5%, and the carbonyl space-time yield was 5.66 mol. L-1h-1. The yield of propionic acid was 72.5%, and the water content of the system was 4.43%.
Example 8
0.94g of rhodium triiodide (with a rhodium concentration of 1400ppm), 10.81g of an aqueous hydroiodic acid solution (45 wt%), 17.89g of ethyl iodide, 10.73g of lithium iodide, 1.62g of bis (diphenylphosphinomethane) monosulfide (dppmS), 15g of ethanol and 86.07g of propionic acid as a solvent were sequentially added to a titanium autoclave having a volume of 0.5L, and the total weight of the reaction solution was 143.06 g. The molar ratio of bis (diphenylphosphinomethane) monosulfide to rhodium triiodide is 2:1The reaction was carried out at a stirring speed of 350rpm and a pressure of 1MPa for 4 hours at a temperature of 50 ℃ and at a reaction temperature of 190 ℃ after the completion of the activation, at a reaction pressure of 2.6MPa for 20 minutes, and sampling was carried out, whereby the conversion of ethanol was 98.8%, the selectivity of propionic acid was 77.9%, and the space-time yield of carbonyl was 5.89 mol. L-1h-1. The yield of propionic acid was 77.0% and the water content of the system was 4.30%.
Example 9
0.94g of rhodium triiodide (with a rhodium concentration of 1400ppm), 10.81g of an aqueous hydroiodic acid solution (45 wt%), 17.88g of ethyl iodide, 14.31g of lithium iodide, 1.62g of bis (diphenylphosphinomethane) monosulfide (dppmS), 15g of ethanol and 82.5g of propionic acid as a solvent were sequentially added to a titanium autoclave having a volume of 0.5L, and the total weight of the reaction solution was 143.06 g. The molar ratio of bis (diphenylphosphinomethane) monosulfide to rhodium triiodide was 2:1, the stirring speed was 350rpm, the pressure was 1MPa, the temperature was 50 ℃ and the activation was carried out for 4 hours, after the activation, the reaction temperature was kept at 180 ℃, the reaction pressure was 2.6MPa, and the reaction time was 20 minutes, and sampling was carried out, whereby the ethanol conversion was 99.0%, the propionic acid selectivity was 86.0%, and the carbonyl space-time yield was 6.27 mol. L-1h-1. The yield of propionic acid was 85.1%, and the water content of the system was 4.06%.
Example 10
0.94g of rhodium triiodide (with a rhodium concentration of 1400ppm), 10.81g of an aqueous hydroiodic acid solution (45 wt%), 14.31g of ethyl iodide, 10.73g of lithium iodide, 1.62g of bis (diphenylphosphinomethane) monosulfide (dppmS), 15g of ethanol and 89.65g of propionic acid as a solvent were sequentially added to a titanium autoclave having a volume of 0.5L, and the total weight of the reaction solution was 143.06 g. The molar ratio of bis (diphenylphosphinomethane) monosulfide to rhodium triiodide was 2:1, the stirring speed was 350rpm, the pressure was 1MPa, the temperature was 50 ℃ and the activation was carried out for 4 hours, after the activation, the reaction temperature was kept at 180 ℃, the reaction pressure was 2.6MPa, and the reaction time was 20 minutes, and sampling was carried out, whereby the ethanol conversion was 98.1%, the propionic acid selectivity was 69.4%, and the carbonyl space-time yield was 5.03 mol. L-1h-1. The yield of propionic acid was 68.1%, and the water content of the system was 4.81%.
Example 11
Titanium material with volume of 0.5L0.94g of rhodium triiodide (with a rhodium concentration of 1400ppm), 10.81g of an aqueous hydriodic acid solution (45 wt%), 17.89g of ethyl iodide, 10.73g of lithium iodide, and bis (diphenylphosphinomethane) disulfide (dppmS) were sequentially added to a high-pressure reaction vessel2)1.74g, 15g of ethanol and 85.95g of solvent propionic acid, wherein the total weight of the reaction liquid is 143.06 g. The molar ratio of bis (diphenylphosphinomethane) monosulfide to rhodium triiodide was 2:1, the stirring speed was 350rpm, the pressure was 1MPa, the temperature was 40 ℃ and the activation was carried out for 2 hours, after the activation, the reaction temperature was kept at 180 ℃, the reaction pressure was 2.6MPa and the reaction time was 20 minutes, and then sampling was carried out, whereby the ethanol conversion was 98.5%, the propionic acid selectivity was 75.4%, and the carbonyl space-time yield was 5.52 mol. L-1h-1. The yield of propionic acid was 74.3%, and the water content of the system was 4.52%.
Comparative example 1
0.94g of rhodium triiodide (with the rhodium concentration of 1400ppm), 25.12g of hydriodic acid aqueous solution (45 wt%), 17.89g of ethyl iodide, 15g of ligand-free ethanol and 84.11g of solvent propionic acid were sequentially added into a titanium high-pressure reaction kettle with the volume of 0.5L, and the total weight of the reaction solution was 143.06 g. The mixture was stirred at 350rpm, the pressure was 1MPa, the temperature was 50 ℃ and the reaction temperature was kept at 180 ℃ after the activation, the reaction pressure was 2.6MPa, and the reaction time was 20 minutes, and then sampling was carried out, whereby the conversion of ethanol was 95.7%, the selectivity of propionic acid was 34.4%, and the space-time yield of carbonyl was 2.67 mol. L-1h-1. The yield of propionic acid was 32.9%, and the water content of the system was 11.30%.
Comparing the experimental results of example 1 and comparative example 1, the catalyst of example 1 has higher ethanol conversion rate, propionic acid selectivity and carbonyl space time yield under the same reaction conditions, and the water content of the reaction system is low.
Comparative example 2
0.94g of rhodium triiodide (with a rhodium concentration of 1400ppm), 10.81g of an aqueous hydroiodic acid solution (45 wt%), 17.89g of ethyl iodide, 10.73g of lithium iodide, 15g of ligand-free ethanol and 87.69g of propionic acid as a solvent were sequentially added to a titanium autoclave having a volume of 0.5L, and the total weight of the reaction solution was 143.06 g. Stirring at 350rpm, activating at 1MPa and 50 deg.C for 4 hr, and maintaining the reaction temperature at 180 deg.CThe pressure was 2.6MPa, the reaction time was 20 minutes, and sampling was conducted, whereby the conversion of ethanol was 94.8%, the selectivity of propionic acid was 41.0%, and the space-time yield of carbonyl was 3.14 mol. multidot.L-1h-1. The yield of propionic acid was 38.9%, and the water content of the system was 5.78%.
Comparing the experimental results of example 1 and comparative example 2, the catalyst of example 1 has higher ethanol conversion, propionic acid selectivity and carbonyl space time yield under the same reaction conditions.
Comparative example 3
0.94g of rhodium triiodide (with a rhodium concentration of 1400ppm), 10.81g of an aqueous hydroiodic acid solution (45 wt%), 17.89g of ethyl iodide, no lithium iodide, 1.62g of bis (diphenylphosphinomethane) monosulfide (dppmS), 15g of ethanol, and 96.80g of propionic acid as a solvent were sequentially added to a titanium autoclave having a volume of 0.5L, and the total weight of the reaction solution was 143.06 g. The molar ratio of bis (diphenylphosphinomethane) monosulfide to rhodium triiodide was 1:1, the stirring speed was 350rpm, the pressure was 1MPa, the temperature was 50 ℃ and the activation was carried out for 4 hours, after the activation, the reaction temperature was kept at 180 ℃, the reaction pressure was 2.6MPa, and the reaction time was 20 minutes, and sampling was carried out, whereby the ethanol conversion was 96.2%, the propionic acid selectivity was 42.7%, and the carbonyl space-time yield was 3.28 mol. L-1h-1. The yield of propionic acid was 41.1%, and the water content of the system was 5.74%.
Comparing the experimental results of example 1 and comparative example 3, the catalyst of example 1 has higher ethanol conversion rate, propionic acid selectivity and carbonyl space time yield under the same reaction conditions, and the catalyst has no precipitate and good stability.
Bis-diphenylphosphinomethane monosulfide (dppMS) and bis-diphenylphosphinomethane disulfide (dppMS) used in the above examples2) The preparation method comprises the following steps:
the synthesis process adopts standard Schlenk technology, and the reaction is carried out under anhydrous and anaerobic conditions. Under nitrogen atmosphere, 6.00g of bis (diphenylphosphinomethane) (dppm) and twice the amount of elemental sulfur (or 0.25 times the amount of S) were added to 20mL of an acetone solution in this order with stirring8)1.00 g. The resulting solution was stirred at 40 ℃ for 6h, and after evaporation of the solvent, pure bis-diphenylphosphinomethane disulfide (dppmS) was obtained2) White, whiteColor solid, yield: 100% (7.00 g). Nuclear magnetic data:31P{1H}NMR(121.5MHz CDCl325 ℃ with 85% H3PO4As external standard) delta 35.1 ppm.
Under nitrogen atmosphere, 0.77g of bis-diphenylphosphinomethane (dppm) and bis-diphenylphosphinomethane disulfide (dppmS) were added with stirring2)0.81g was dissolved in acetone (50ml) and then zinc salt (2.5 mol%, one of the following was added: zn (CF)3SO3)2、Zn(BF4)2、ZnCl2、ZnBr2Or ZnF2). The mixture was left in the dark and stirred continuously at room temperature for 36 hours to prevent traces of oxygen dissolved in the solution from partially oxidizing the phosphine. The solution was evaporated to dryness and the resulting white mixture was isolated by column chromatography to give bis-diphenylphosphinomethane monosulfide (dppms), yield: 65 percent. The semi-quantitative product yields are according to31The integrated areas of the P NMR signals were estimated as dppm (. delta.22.1 ppm), dppmS (. delta.41.2 and 27.8ppm) and dppmS2(δ35.8ppm)。
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for synthesizing propionic acid by ethanol carbonyl under low water content is characterized by comprising the following steps: raw material ethanol is carbonylated to synthesize propionic acid under the existence of rhodium main catalyst, accelerant hydriodic acid, ethyl iodide, alkali metal lithium salt and ligand organic diphosphorus compound.
2. A process for the oxo synthesis of propionic acid from ethanol at low water content according to claim 1, comprising the steps of:
the method comprises the steps of sequentially adding a rhodium main catalyst, an accelerant hydroiodic acid, ethyl iodide, an alkali metal lithium salt, a ligand organic diphosphorus compound, ethanol and a solvent propionic acid into a reaction kettle, sealing the reaction kettle, replacing air in the reaction kettle with carbon monoxide gas for three times, introducing carbon monoxide after replacement is finished to enable the pressure of a reaction system to reach 0.5-1.5 MPa, starting stirring and heating, controlling the stirring speed to be 280-380 rpm, setting the temperature to be 40-50 ℃, slowly heating, measuring the temperature in the reaction kettle, keeping the temperature for 3-5 hours after the temperature of kettle liquid reaches 40-60 ℃ for catalyst activation, heating to enable the reaction liquid to quickly heat to the reaction temperature of 150-220 ℃ after activation is finished, supplementing carbon monoxide to the reaction pressure of 2.0-4.5 MPa, keeping constant, starting the reaction when the temperature and the pressure reach set values, sampling when the reaction time is 20 minutes, the content of each component was determined by gas chromatography.
3. A process for the oxo synthesis of propionic acid from ethanol at low water content as claimed in claim 2, wherein the precursor compound of the rhodium procatalyst is selected from RhI3、RhI3·3H2O、Rh(acac)(CO)2、RhCl3、RhCl3·3H2At least one of O;
the mass concentration of rhodium element in the rhodium main catalyst is 500-2500 ppm, and the mass concentration is calculated on the basis of the total mass of a reaction system.
4. A low water content process for the oxo synthesis of propionic acid from ethanol according to claim 2, wherein the alkali metal lithium salt is selected from LiI, LiI-3H2O、LiOAc、Li2CO3And LiCl.
5. A process for the oxo synthesis of propionic acid from ethanol at low water content according to claim 2, wherein the ligand organic bisphosphorus compound is at least one of bis-diphenylphosphinomethane monosulfide, bis-diphenylphosphinomethane disulfide, bis-diphenylphosphinoethane, bis-diphenylphosphinopropane.
6. A method for oxo synthesis of propionic acid from ethanol at low water content as claimed in claim 2, wherein the molar ratio of the ligand organodiphosphine compound to the rhodium procatalyst is (0.5-10): 1;
the mass concentration of the hydriodic acid aqueous solution is 5 to 15 percent based on the total mass of the reaction system.
7. A process for the oxo synthesis of propionic acid from ethanol at low water content as claimed in claim 2, wherein the mass concentration of ethyl iodide is 2% to 18% based on the total mass of the reaction system;
the mass concentration of the alkali metal lithium salt is 5-20% based on the total mass of the reaction system.
8. A process for the oxo synthesis of propionic acid from ethanol at low water content as claimed in claim 2, wherein the mass concentration of ethanol is 10% to 30% based on the total mass of the reaction system.
9. A process for the oxo synthesis of propionic acid from ethanol at low water content as claimed in claim 2, wherein the process for the preparation of bis diphenylphosphinomethane disulfide comprises the following steps:
under the anhydrous and oxygen-free conditions and in nitrogen atmosphere, under the condition of stirring, in the organic solvent, bis-diphenylphosphinomethane and twice the amount of elemental sulfur or 0.25 times the amount of S are added in turn8Stirring the obtained solution for 1-12 h at the temperature of 30-100 ℃, and evaporating the solvent to obtain the bis-diphenylphosphinomethane disulfide.
10. A process for the oxo synthesis of propionic acid from ethanol at low water content according to claim 9, wherein the process for the preparation of bis-diphenylphosphinomethane monosulfide comprises the following steps:
in a nitrogen atmosphere, dissolving bis-diphenylphosphinomethane and bis-diphenylphosphinomethane disulfide in a mass ratio of 1 (1.01-1.5) in an organic solvent under stirring, then adding a catalytic amount of zinc salt, placing the mixture in a dark place, continuously stirring at room temperature, evaporating the solution to dryness after complete reaction, and separating by column chromatography to obtain bis-diphenylphosphinomethane monosulfide.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85106097A (en) * | 1984-07-20 | 1987-01-14 | 联合碳化公司 | Produce carboxylic acid by using rhodium complex catalysts by alcohol |
| EP0460905A2 (en) * | 1990-06-04 | 1991-12-11 | Hoechst Celanese Corporation | Improved method for producing ibuprofen |
| CN1105013A (en) * | 1993-06-30 | 1995-07-12 | 英国石油化学品有限公司 | Process for the carbonylation of methanol or a reactive derivatives thereof |
| CN1823030A (en) * | 2003-05-14 | 2006-08-23 | 英国石油化学品有限公司 | Carbonylation process using metal-tridentate ligand catalysts |
| CN101954295A (en) * | 2010-09-26 | 2011-01-26 | 华陆工程科技有限责任公司 | Catalyst system for methanol low-pressure carbonyl synthesis of acetic acid and application thereof |
| CN102633836A (en) * | 2012-04-10 | 2012-08-15 | 濮阳惠成电子材料股份有限公司 | Method for synthesizing bis(diphenylphosphino)-alkane |
| CN102794198A (en) * | 2012-07-16 | 2012-11-28 | 江苏索普（集团）有限公司 | Preparation method of catalyst for synthesizing propionic acid by ethanol carbonylation, and application thereof |
| CN102911035A (en) * | 2012-11-02 | 2013-02-06 | 江苏索普（集团）有限公司 | Method for preparing propionic acid from ethyl acetate through carbonylation |
| CN103977834A (en) * | 2014-06-03 | 2014-08-13 | 江苏索普（集团）有限公司 | Preparation method of catalyst used in synthesizing of propionic acid by carbonylating ethyl alcohol and application of catalyst |
| US20160185701A1 (en) * | 2014-12-30 | 2016-06-30 | Eastman Chemical Company | Methyl-iodide-free carbonylation of an alcohol to its homologous aldehyde and/or alcohol |
-
2019
- 2019-12-18 CN CN201911306216.XA patent/CN113004139B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85106097A (en) * | 1984-07-20 | 1987-01-14 | 联合碳化公司 | Produce carboxylic acid by using rhodium complex catalysts by alcohol |
| EP0460905A2 (en) * | 1990-06-04 | 1991-12-11 | Hoechst Celanese Corporation | Improved method for producing ibuprofen |
| CN1105013A (en) * | 1993-06-30 | 1995-07-12 | 英国石油化学品有限公司 | Process for the carbonylation of methanol or a reactive derivatives thereof |
| CN1823030A (en) * | 2003-05-14 | 2006-08-23 | 英国石油化学品有限公司 | Carbonylation process using metal-tridentate ligand catalysts |
| CN101954295A (en) * | 2010-09-26 | 2011-01-26 | 华陆工程科技有限责任公司 | Catalyst system for methanol low-pressure carbonyl synthesis of acetic acid and application thereof |
| CN102633836A (en) * | 2012-04-10 | 2012-08-15 | 濮阳惠成电子材料股份有限公司 | Method for synthesizing bis(diphenylphosphino)-alkane |
| CN102794198A (en) * | 2012-07-16 | 2012-11-28 | 江苏索普（集团）有限公司 | Preparation method of catalyst for synthesizing propionic acid by ethanol carbonylation, and application thereof |
| CN102911035A (en) * | 2012-11-02 | 2013-02-06 | 江苏索普（集团）有限公司 | Method for preparing propionic acid from ethyl acetate through carbonylation |
| CN103977834A (en) * | 2014-06-03 | 2014-08-13 | 江苏索普（集团）有限公司 | Preparation method of catalyst used in synthesizing of propionic acid by carbonylating ethyl alcohol and application of catalyst |
| US20160185701A1 (en) * | 2014-12-30 | 2016-06-30 | Eastman Chemical Company | Methyl-iodide-free carbonylation of an alcohol to its homologous aldehyde and/or alcohol |
Non-Patent Citations (1)
| Title |
|---|
| 赖崇伟等: ""乙醇羰基化催化剂研究进展"", 《天然气化工》 * |
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