CN116239445A - Method for synthesizing 1, 3-propylene glycol by propiolactone ring-opening hydrogenation - Google Patents

Method for synthesizing 1, 3-propylene glycol by propiolactone ring-opening hydrogenation Download PDF

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CN116239445A
CN116239445A CN202310013754.XA CN202310013754A CN116239445A CN 116239445 A CN116239445 A CN 116239445A CN 202310013754 A CN202310013754 A CN 202310013754A CN 116239445 A CN116239445 A CN 116239445A
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propiolactone
ring
hydrogenation
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黄文学
冉建锋
严成岳
庞海洋
谢硕
刘泽超
黎源
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Wanhua Chemical Group Co Ltd
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • C07C31/205—1,3-Propanediol; 1,2-Propanediol
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract

The invention provides a method for synthesizing 1,3-propanediol by ring-opening hydrogenation of beta-propiolactone. The method comprises the steps of continuously reacting alcohol and beta-propiolactone under the catalysis of strong alkaline resin and auxiliary agent to obtain a 3-hydroxy propionate intermediate, then pumping the intermediate into a hydrogenation kettle, and reducing hydrogen to obtain a 1,3-propanediol product. Firstly, the invention innovatively takes beta-propiolactone as a raw material, and obtains 1,3-propanediol through continuous ring opening and hydrogenation reaction; the 3-hydroxy propionate intermediate is obtained by the alcoholysis and ring opening of the beta-propiolactone, so that the generation of byproducts such as propionic acid and the like during the direct hydrogenation of the beta-propiolactone is avoided; secondly, the invention adopts strong alkaline resin to catalyze the alcoholysis reaction of alcohol on beta-propiolactone, and overcomes the defects of large catalyst consumption, more three wastes and the like when sodium methoxide, sulfuric acid and the like are adopted for catalysis in the prior art; finally, the ring-opening reaction and the hydrogenation reaction are continuously carried out, the production efficiency is high, the process is stable, and the labor is saved.

Description

Method for synthesizing 1, 3-propylene glycol by propiolactone ring-opening hydrogenation
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a method for synthesizing 1, 3-propylene glycol by ring-opening hydrogenation of propiolactone.
Background
1,3-Propanediol (PDO) is a very important linear diol compound, and currently the main industrial use is to produce polytrimethylene terephthalate (PTT); besides the chemical stability of the ethylene terephthalate, the PTT also has good rebound performance and pollution resistance, and has good application prospect in the fields of textiles and the like. Besides being used for producing PTT, PDO has certain application in the fields of antifreeze, emulsifying agent, medicine, antioxidant and the like. At present, most of PDO manufacturers are centralized abroad, the global productivity is about 30 ten thousand tons/year, main manufacturers have Degusai, shell, duPont and the like, domestic manufacturers are fewer, the productivity is relatively smaller, and the market demand cannot be met.
There are various processes for producing PDO, such as ethylene oxide process, acrolein process, fermentation process, etc. The shell adopts ethylene oxide to produce PDO, the ethylene oxide reacts with synthesis gas under the action of a cobalt catalyst to obtain 3-hydroxy propanal, and then hydrogenation is carried out to obtain PDO. Shell lewis An Nazhou cover horses in the united states have a set of PDO units using this production to produce 13.6 ten thousand tons/year. Calculated by ethylene oxide, the yield of the process PDO can reach 85-90%, the key of the process is that a cobalt carbonyl catalyst is used in the hydroformylation process, and various ligands (phosphine ligands) and auxiliary agents (tetrabutyl phosphonium acetate, butyl amyl pyridine and the like) are adopted, so that the reaction yield of the step is effectively improved.
Figure BDA0004038600380000021
PDO is produced by an acrolein hydration method of companies such as Desoxhlet and DuPont: firstly, acrolein reacts with water to obtain 3-hydroxy-propanal, and the 3-hydroxy-propanal is hydrogenated and reduced to obtain PDO. The first reaction step is a key step in the process, and the conversion of acrolein is reported to be only-82% and the selectivity of 3-hydroxypropanal to 80%. Because of the active chemical nature of acrolein and the difficulty in transportation, the production process generally requires matching acrolein resources, and the acrolein is generally used as an intermediate for producing acrylic acid. The capacity of the Germany acrolein hydration plant of Desoxhlet corporation is 6.8 ten thousand tons/year; dupont has also been reported to have an acrolein hydration plant in germany with a capacity of about 1.8 ten thousand tons/year.
Figure BDA0004038600380000022
In addition to the above processes, dupont developed a biological fermentation process for PDO, which has a set of 6 ten thousand tons/year biological fermentation equipment in the united states, and uses starch, glucose, etc. as raw materials to perform fermentation production of PDO; related researches on synthesizing PDO by fermentation methods are also carried out at the university of Qinghua in China, double-strain and two-step fermentation are adopted, and then PDO with purity of more than 99% is obtained through procedures such as flocculation, concentration and rectification, and the yield is reported to be more than 90%. Some domestic enterprises such as Cheneria and crown organisms are also producing PDO by fermentation, but the production scale is relatively small. Recently, some researches report that PDO is produced by adopting a glycerol hydrogenolysis method, but the method is still in a preliminary research stage at present, and the condition of mass production is not provided.
In summary, PDO is a very important diol monomer, and although there are a plurality of synthetic routes to prepare PDO at present, the yields and the cost of these routes are not ideal, and further optimization and promotion are still needed at present, so that development of a new and more efficient PDO synthetic route is still very important.
Disclosure of Invention
The invention aims to provide a novel continuous preparation method of 1,3-Propanediol (PDO), which has novel route, takes simple and easily obtained beta-propiolactone as a starting raw material, and obtains a PDO product through alcoholysis ring opening and hydrogenation reduction; the two-step reactions of ring opening and hydrogenation are carried out in a continuous mode, the process is stable, the operation is simple and convenient, and the total yield of the route is high.
In order to achieve the above purposes and achieve the above technical effects, the present invention adopts the following technical scheme:
a method for synthesizing 1,3-propanediol by continuous ring-opening hydrogenation of beta-propiolactone, comprising the following steps:
s1: in a tubular reactor, under the catalysis of strong alkaline resin and auxiliary agent, beta-propiolactone and alcohol continuously react, and ring opening is carried out to obtain 3-hydroxy propionate;
s2: under the action of a hydrogenation catalyst, the methyl 3-hydroxypropionate is subjected to continuous hydrogenation reaction to obtain the 1, 3-propanediol.
The reaction route is shown below, and the schematic diagram of the reaction device is shown in the attached figure 1:
Figure BDA0004038600380000031
in the invention, the strong basic resin S1 is styrene type strong basic anion resin and/or acrylic acid type strong basic anion resin, preferably one or more of D201, D202, D280, 201, 202, 203, ambersep 900OH and Amberlyst-26 (OH).
In the invention, the auxiliary agent S1 contains a pyridine structure, preferably pyridine with electron-donating substituent groups on an aromatic ring, more preferably one or more of 4-methylpyridine, 4-dimethylaminopyridine, 4-pyrrolidinylpyridine and 4-piperidinylpyridine; preferably, the dosage of the auxiliary agent is 10-100ppm based on the total mass of the feed liquid; the addition of the auxiliary agent can promote the ring-opening esterification of the beta-propiolactone, because the pyridine has stronger nucleophilicity, can generate pyridine salt with the beta-propiolactone, and the pyridine salt can quickly react with alcohol to obtain 3-hydroxy propionate and regenerate the pyridine auxiliary agent.
In the invention, the feeding mole ratio of the beta-propiolactone to the alcohol in S1 is 1:4.0-10.0.
In the present invention, the alcohol of S1 is an alkyl alcohol, preferably one or more of methanol, ethanol, propanol, butanol.
In the present invention, the reaction of S1 is carried out in a tubular reactor.
In the invention, the beta-propiolactone and alcohol are mixed uniformly and then enter a reactor, and the mixture is bottom-in and top-out.
In the invention, the weight hourly space velocity of the S1 ring-opening reaction liquid is 0.6 to 3.0h -1 Preferably 0.6-2.0h -1 . The weight hourly space velocity is the mass of feed per hour divided by the mass of catalyst charged.
In the invention, the temperature of the S1 ring-opening reaction is 60-100 ℃, and the reaction pressure is normal pressure or micro-positive pressure.
In the invention, the hydrogenation catalyst in S2 is one or more of Raney nickel, raney cobalt, ruthenium carbon, platinum oxide and supported copper catalyst, preferably supported copper catalyst.
In the invention, the catalyst content in the S2 hydrogenation reaction liquid is 0.5-2.0wt%.
In the invention, the hydrogenation reaction of S2 is carried out in a continuous mode in an autoclave, and the ring-opening reaction liquid of S1 is directly introduced into the hydrogenation reaction kettle; preferably, the residence time of the reaction liquid in the S2 in the hydrogenation reaction kettle is 4.0-10.0h.
And/or the hydrogen pressure in S2 is 2.0-5.0MPaG.
And/or the reaction temperature in S2 is 150-220 ℃.
It is another object of the present invention to provide a 1,3-propanediol product.
The 1,3-propanediol is prepared by the method, and the 1,3-propanediol is synthesized by continuous ring-opening hydrogenation of beta-propiolactone.
In the present invention, the pressures are gauge pressures unless otherwise indicated.
Compared with the prior art, the invention has the following positive effects:
1. the synthetic route is novel, the simple and easily obtained beta-propiolactone is taken as the raw material, the cost is low, and the synthetic route has potential popularization and application values;
2. the invention adopts the strong alkaline resin catalyst beta-propiolactone alcoholysis ring opening, overcomes the common catalysts such as sodium methoxide, sulfuric acid and the like reported in the prior literature, has high catalytic activity, can stably run for a long time, saves operation and cost, does not need neutralization, and avoids the generation of waste salt and wastewater.
3. The invention realizes continuous operation of alcoholysis ring opening and hydrogenation by the serial application of tubular reaction and kettle reaction, and overcomes the defects of frequent intermittent operation and unstable process conditions.
4. The beta-propiolactone is subjected to alcoholysis ring opening to obtain 3-hydroxy propionate, and then hydrogenation is carried out, so that the defect of more propionic acid and propanol which are byproducts of direct hydrogenation reduction of the beta-propiolactone is greatly reduced.
Drawings
FIG. 1 is a schematic view of a reaction apparatus according to the present invention.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
The main raw material information is as follows:
beta-propiolactone, self-made, 99%; methanol, 99.6%, alar Ding Shiji; strong alkaline resins D201, D202 and 201, and Dandelion with purity of 98-99%; amberlyst-26 (OH), microphone, 98%; auxiliary agent 4-dimethylamino pyridine, 4-pyrrolidinyl pyridine, 4-piperidinyl pyridine, ara Ding Shiji, 99%. Copper-cadmium-lithium catalyst, copper-zinc-lithium catalyst, copper-molybdenum-lithium catalyst, self-made and alumina-supported; raney nickel catalyst, wanhua chemistry. Absolute ethanol, 99%, enoKai reagent.
The gas chromatography test conditions of the present invention are as follows: the conversion rate and the selectivity are measured by an internal standard method, and n-tetradecane is used as an internal standard;
instrument model: agilent 5975C; chromatographic column: capillary column HP-5 (30 m. Times.0.30 mm. Times.0.25 μm); the initial temperature is 100 ℃, and the temperature is increased to 200 ℃ at the speed of 10 ℃/min; then the temperature is raised to 240 ℃ at the speed of 20 ℃/min and kept for 10min. The carrier gas is high-purity nitrogen, the split ratio is 30:1, and the split flow is 45mL/min. Carrier gas saving: 20mL/min, and a wait time of 2min was started. The sample injection temperature is 280 ℃, the detector is FID, the detector temperature is 280 ℃, the air flow rate is 350mL/min, the hydrogen flow rate is 35mL/min, the tail blowing flow rate is 30mL/min, and the sample injection amount is 0.2 mu L.
Example 1
And (3) preparing a hydrogenation catalyst.
Copper acetate aqueous solution (14.6 mL) having a concentration of 2.0wt% was weighed at room temperature, zinc nitrate (74 mg), lithium chloride (10 mg) and polyvinylpyrrolidone K10 (0.1 g) were sequentially added, and the mixture was uniformly mixed for use. Alumina powder (5.1 g) was weighed, washed 3 times with 5wt% aqueous citric acid (10 mL), and then washed 2 times with deionized water, pH of the aqueous solution>And 6, judging that the product is qualified. The alumina powder after acid washing was added to a copper acetate solution (14.6 mL) prepared in advanceIn the process, a suspension is obtained, stirring and adsorption are continued for 3 hours at room temperature, water is evaporated, the obtained solid powder is roasted for 2 hours at a high temperature of 500 ℃, and then the solid powder is mixed with hydrogen and nitrogen (10 v.% H) 2 +90v.％N 2 ) And (3) carrying out reduction roasting treatment for 2 hours at 140 ℃ in an air atmosphere to obtain 5.2g of the target alumina-supported copper-zinc-lithium catalyst.
By adopting the preparation method, zinc nitrate is changed into cadmium nitrate and molybdenum nitrate, and the aluminum oxide supported copper-cadmium-lithium catalyst and the aluminum oxide supported copper-molybdenum-lithium catalyst can be respectively prepared.
Example 2
The beta-propiolactone is subjected to ring opening and hydrogenation to obtain 1, 3-propanediol.
Adopting a tubular reactor to carry out ring-opening reaction, wherein the length of a reaction tube is 50cm, the inner diameter is 2.2cm, the middle part of the reaction tube is filled with spherical D201 strong alkaline resin catalyst (100 g, purity is 99%), the top end and the low end of the reaction tube are respectively filled with ceramic ring filler, and the resin catalyst is fixed and supported; the middle of the reaction tube is provided with a temperature measuring pipeline, and total four temperature measuring points are arranged. After the catalyst is filled, a fixed bed reactor power supply is started, beta-propiolactone (252.2 g,3.5 mol), methanol (448.6 g,14.0 mol) and auxiliary agent 4-dimethylaminopyridine (70 mg,0.6 mmol) are added into a feed tank, a feed advection pump is started after the three materials are uniformly mixed, the feed speed of raw material liquid is 1.0g/min, the lower inlet and the upper outlet are carried out, and the weight hourly space velocity is 0.6h -1 . After the reaction tube is filled with the raw material liquid and is completely infiltrated, a heating sleeve of the reaction tube is started, the temperature of the reaction tube is slowly increased to 60 ℃, the feeding speed and the temperature are kept constant, continuous reaction is started, and the temperature of two temperature measuring points at the lower end of the reaction is found to be 62 ℃ in the reaction process, which is the part where the main ring-opening reaction occurs. And after the reaction liquid is discharged out of the reaction tube, cooling the reaction liquid by a condenser, and then, entering a ring-opening reaction liquid buffer tank. Samples were taken at the outlet of the condenser at regular intervals, and after addition of the internal standard n-decane, the reaction was chromatographed by GC, which indicated a reaction conversion of 93% and a selectivity of 99% (relative to beta-propiolactone). HRMS-EI M + Calcd for C 4 H 8 O 3 :104.0473,found 104.0473。
Pumping the ring-opening reaction liquid in the buffer tank into a continuous hydrogenation reaction kettle by using a advection pump, wherein the feeding speed is 0.5g/min, and paving is added into the kettle in advanceThe bottom solvent methanol (300 g), the powdered copper-cadmium-lithium catalyst (1.5 g, alumina load) and the hydrogen in the kettle are maintained at 5.0MPa, the temperature is maintained at 220 ℃, and the stirring speed is 600rpm/min. And (3) continuously discharging through an inner bottom filter in the kettle while feeding, wherein the discharging speed and the feeding speed are kept balanced, the liquid level in the kettle is kept unchanged, and the residence time of the ring-opening reaction liquid in the kettle is stable (10 h). In the reaction process, sampling and analysis are carried out regularly, after an internal standard n-decane is added, the content of raw material methyl 3-hydroxypropionate and product 1,3-propanediol in hydrogenation reaction liquid is analyzed by GC chromatography. The results showed that the conversion of methyl 3-hydroxypropionate was 99% and the selectivity of the product 1,3-propanediol was 100%. HRMS-EI M + Calcd for C 3 H 8 O 2 :76.0524,found 76.0522。
Example 3
The beta-propiolactone is subjected to ring opening and hydrogenation to obtain 1, 3-propanediol.
Adopting a tubular reactor to carry out ring-opening reaction, wherein the length of a reaction tube is 50cm, the inner diameter is 2.2cm, the middle part of the reaction tube is filled with spherical D201 strong alkaline resin catalyst (100 g, purity is 99%), the top end and the low end of the reaction tube are respectively filled with ceramic ring filler, and the resin catalyst is fixed and supported; the middle of the reaction tube is provided with a temperature measuring pipeline, and total four temperature measuring points are arranged. After the catalyst is filled, a fixed bed reactor power supply is started, beta-propiolactone (201.8 g,2.8 mol), methanol (538.3 g,16.8 mol) and auxiliary agent 4-dimethylaminopyridine (37 mg,0.3 mmol) are added into a feed tank, a feed advection pump is started after the three components are uniformly mixed, the feed speed of raw material liquid is 1.67g/min, the lower inlet and the upper outlet are performed, and the weight hourly space velocity is 1.0h -1 . After the reaction tube is filled with the raw material liquid and is completely infiltrated, a heating sleeve of the reaction tube is started, the temperature of the reaction tube is slowly increased to 100 ℃, the feeding speed and the temperature are kept constant, continuous reaction is started, and the temperature of two temperature measuring points at the lower end of the reaction is found to be 100-103 ℃ in the reaction process, which is the part where the main ring-opening reaction occurs. And after the reaction liquid is discharged out of the reaction tube, cooling the reaction liquid by a condenser, and then, entering a ring-opening reaction liquid buffer tank. Samples were taken at the outlet of the condenser at regular intervals, and after addition of the internal standard n-decane, the reaction was chromatographed by GC, which indicated a conversion of 100% and a selectivity of 98% (relative to beta-propiolactone).
The ring-opening reaction liquid in the buffer tank is pumped into a continuous hydrogenation reaction kettle by a advection pump, the feeding speed is 1.8g/min, the kettle is added with bottom solvent methanol (432 g), powdery copper-cadmium-lithium catalyst (8.6 g and alumina load) in advance, the hydrogen in the kettle is maintained at 2.0MPa, the temperature is maintained at 150 ℃, and the stirring speed is 600rpm/min. And (3) continuously discharging through the bottom filter in the kettle while feeding, wherein the discharging speed and the feeding speed are kept balanced, the liquid level in the kettle is kept unchanged, and the residence time of the ring-opening reaction liquid in the kettle is stable (4 h). In the reaction process, sampling and analysis are carried out regularly, after an internal standard n-decane is added, the content of raw material methyl 3-hydroxypropionate and product 1,3-propanediol in hydrogenation reaction liquid is analyzed by GC chromatography. The results showed that the conversion of methyl 3-hydroxypropionate was 98% and the selectivity of the product 1,3-propanediol was 100%.
Example 4
The beta-propiolactone is subjected to ring opening and hydrogenation to obtain 1, 3-propanediol.
Adopting a tubular reactor to carry out ring-opening reaction, wherein the length of a reaction tube is 50cm, the inner diameter is 2.2cm, the middle part of the reaction tube is filled with spherical D201 strong alkaline resin catalyst (100 g, purity is 99%), the top end and the low end of the reaction tube are respectively filled with ceramic ring filler, and the resin catalyst is fixed and supported; the middle of the reaction tube is provided with a temperature measuring pipeline, and total four temperature measuring points are arranged. After the catalyst is filled, a fixed bed reactor power supply is started, beta-propiolactone (223.4 g,3.1 mol), methanol (993.3 g,31.0 mol) and auxiliary agent 4-dimethylaminopyridine (12 mg,0.1 mol) are added into a feed tank, a feed advection pump is started after the beta-propiolactone, methanol (993.3 g,31.0 mol) and auxiliary agent 4-dimethylaminopyridine are uniformly mixed, the feed speed of raw material liquid is 3.33g/min, the lower inlet and upper outlet are carried out, and the weight hourly space velocity is 2.0h -1 . After the reaction tube is filled with the raw material liquid and is completely infiltrated, a heating sleeve of the reaction tube is started, the temperature of the reaction tube is slowly increased to 80 ℃, the feeding speed and the temperature are kept constant, continuous reaction is started, and the temperature of two temperature measuring points at the lower end of the reaction is found to be 80-83 ℃ in the reaction process, which is the part where the main ring-opening reaction occurs. And after the reaction liquid is discharged out of the reaction tube, cooling the reaction liquid by a condenser, and then, entering a ring-opening reaction liquid buffer tank. Samples were taken at the outlet of the condenser at regular intervals, and after addition of the internal standard n-decane, the reaction was chromatographed by GC, which indicated 100% conversion and 100% selectivity (relative to beta-propiolactone).
The ring-opening reaction liquid in the buffer tank is pumped into a continuous hydrogenation reaction kettle by a advection pump, the feeding speed is 1.5g/min, the kettle is added with a bottom solvent methanol (720 g), a powdery copper-cadmium-lithium catalyst (7.2 g and alumina load) in advance, the hydrogen in the kettle is maintained at 4.0MPa, the temperature is maintained at 200 ℃, and the stirring speed is 600rpm/min. And (3) continuously discharging through an inner bottom filter in the kettle while feeding, wherein the discharging speed and the feeding speed are kept balanced, the liquid level in the kettle is kept unchanged, and the residence time of the ring-opening reaction liquid in the kettle is stable (8 h). In the reaction process, sampling and analysis are carried out regularly, after an internal standard n-decane is added, the content of raw material methyl 3-hydroxypropionate and product 1,3-propanediol in hydrogenation reaction liquid is analyzed by GC chromatography. The results showed that the conversion of methyl 3-hydroxypropionate was 100% and the selectivity of the product 1,3-propanediol was 100%.
Example 5
The beta-propiolactone is subjected to ring opening and hydrogenation to obtain 1, 3-propanediol.
Adopting a tubular reactor to carry out ring-opening reaction, wherein the length of a reaction tube is 50cm, the inner diameter is 2.2cm, the middle part of the reaction tube is filled with spherical D202 strong alkaline resin catalyst (100 g, purity is 99%), the top end and the low end of the reaction tube are respectively filled with ceramic ring filler, and the resin catalyst is fixed and supported; the middle of the reaction tube is provided with a temperature measuring pipeline, and total four temperature measuring points are arranged. After the catalyst is filled, a fixed bed reactor power supply is started, beta-propiolactone (252.2 g,3.5 mol), methanol (785.0 g,24.5 mol) and auxiliary agent 4-pyrrolidinyl pyridine (83 mg,0.7 mmol) are added into a feed tank, a feed advection pump is started after the three materials are uniformly mixed, the feed speed of raw material liquid is 3.33g/min, the lower inlet and the upper outlet are carried out, and the weight hourly space velocity is 2.0h -1 . After the reaction tube is filled with the raw material liquid and is completely infiltrated, a heating sleeve of the reaction tube is started, the temperature of the reaction tube is slowly increased to 70 ℃, the feeding speed and the temperature are kept constant, continuous reaction is started, and the temperature of two temperature measuring points at the lower end of the reaction is found to be 70-74 ℃ in the reaction process, which is the part where the main ring-opening reaction occurs. And after the reaction liquid is discharged out of the reaction tube, cooling the reaction liquid by a condenser, and then, entering a ring-opening reaction liquid buffer tank. Samples were taken at the outlet of the condenser at regular intervals, and after addition of the internal standard n-decane, the reaction was chromatographed by GC, which indicated 100% conversion and 100% selectivity (relative to beta-propiolactone).
The ring-opening reaction liquid in the buffer tank is pumped into a continuous hydrogenation reaction kettle by a advection pump, the feeding speed is 1.7g/min, the kettle is added with a bottom solvent methanol (714 g), a powdery copper zinc lithium catalyst (7.1 g and alumina load) in advance, the hydrogen in the kettle is maintained at 4.0MPa, the temperature is maintained at 200 ℃, and the stirring speed is 600rpm/min. And (3) continuously discharging through an inner bottom filter in the kettle while feeding, wherein the discharging speed and the feeding speed are kept balanced, the liquid level in the kettle is kept unchanged, and the residence time of the ring-opening reaction liquid in the kettle is stable (7 h). In the reaction process, sampling and analysis are carried out regularly, after an internal standard n-decane is added, the content of raw material methyl 3-hydroxypropionate and product 1,3-propanediol in hydrogenation reaction liquid is analyzed by GC chromatography. The results showed that the conversion of methyl 3-hydroxypropionate was 100% and the selectivity of the product 1,3-propanediol was 100%.
Example 6
The beta-propiolactone is subjected to ring opening and hydrogenation to obtain 1, 3-propanediol.
Adopting a tubular reactor to carry out ring-opening reaction, wherein the length of a reaction tube is 50cm, the inner diameter is 2.2cm, the middle part of the reaction tube is filled with spherical 202 strong alkaline resin catalyst (100 g, purity is 99%), the top end and the low end of the reaction tube are respectively filled with ceramic ring filler, and the resin catalyst is fixed and supported; the middle of the reaction tube is provided with a temperature measuring pipeline, and total four temperature measuring points are arranged. After the catalyst is filled, a fixed bed reactor power supply is started, beta-propiolactone (209.0 g,2.9 mol), methanol (650.5 g,20.3 mol) and auxiliary agent 4-piperidylpyridine (69 mg,0.6 mmol) are added into a feed tank, a feed advection pump is started after the three materials are uniformly mixed, the feed speed of raw material liquid is 3.33g/min, the lower inlet and the upper outlet are performed, and the weight hourly space velocity is 2.0h -1 . After the reaction tube is filled with the raw material liquid and is completely infiltrated, a heating sleeve of the reaction tube is started, the temperature of the reaction tube is slowly increased to 70 ℃, the feeding speed and the temperature are kept constant, continuous reaction is started, and the temperature of two temperature measuring points at the lower end of the reaction is found to be 70-74 ℃ in the reaction process, which is the part where the main ring-opening reaction occurs. And after the reaction liquid is discharged out of the reaction tube, cooling the reaction liquid by a condenser, and then, entering a ring-opening reaction liquid buffer tank. Samples were taken at the outlet of the condenser at regular intervals, and after addition of the internal standard n-decane, the reaction was chromatographed by GC, which indicated 100% conversion and 100% selectivity (relative to beta-propiolactone).
The ring-opening reaction liquid in the buffer tank is pumped into a continuous hydrogenation reaction kettle by a advection pump, the feeding speed is 2.1g/min, the bottom solvent methanol (756 g), the powdery Raney nickel catalyst (7.1 g) and the hydrogen in the kettle are added in advance, the temperature is maintained at 200 ℃, and the stirring speed is 600rpm/min. And (3) continuously discharging through an inner bottom filter in the kettle while feeding, wherein the discharging speed and the feeding speed are kept balanced, the liquid level in the kettle is kept unchanged, and the residence time of the ring-opening reaction liquid in the kettle is stable (6 h). In the reaction process, sampling and analysis are carried out regularly, after an internal standard n-decane is added, the content of raw material methyl 3-hydroxypropionate and product 1,3-propanediol in hydrogenation reaction liquid is analyzed by GC chromatography. The results showed that the conversion of methyl 3-hydroxypropionate was 100% and the selectivity of the product 1,3-propanediol was 100%.
Example 7
The beta-propiolactone is subjected to ring opening and hydrogenation to obtain 1, 3-propanediol.
Adopting a tubular reactor to carry out ring-opening reaction, wherein the length of a reaction tube is 50cm, the inner diameter is 2.2cm, the middle part of the reaction tube is filled with spherical Amberlyst-26 (OH) strong alkaline resin catalyst (100 g, purity is 99%), the top end and the low end of the reaction tube are respectively filled with ceramic ring filler, and the resin catalyst is fixed and supported; the middle of the reaction tube is provided with a temperature measuring pipeline, and total four temperature measuring points are arranged. After the catalyst is filled, a fixed bed reactor power supply is started, beta-propiolactone (252.2 g,3.5 mol), ethanol (1128.0 g,24.5 mol) and auxiliary agent 4-dimethylaminopyridine (73 mg,0.6 mmol) are added into a feed tank, a feed advection pump is started after the beta-propiolactone, ethanol (1128.0 g,24.5 mol) and auxiliary agent 4-dimethylaminopyridine are uniformly mixed, the feed speed of raw material liquid is 5.0g/min, the lower inlet and upper outlet are carried out, and the weight hourly space velocity is 3.0h -1 . After the reaction tube is filled with the raw material liquid and is completely infiltrated, a heating sleeve of the reaction tube is started, the temperature of the reaction tube is slowly increased to 70 ℃, the feeding speed and the temperature are kept constant, continuous reaction is started, and the temperature of two temperature measuring points at the lower end of the reaction is found to be 70-74 ℃ in the reaction process, which is the part where the main ring-opening reaction occurs. And after the reaction liquid is discharged out of the reaction tube, cooling the reaction liquid by a condenser, and then, entering a ring-opening reaction liquid buffer tank. Samples were taken at the outlet of the condenser at regular intervals, and after addition of the internal standard n-decane, the reaction was chromatographed by GC, which indicated 100% conversion and 100% selectivity (relative to beta-propiolactone).
The ring-opening reaction liquid in the buffer tank is pumped into a continuous hydrogenation reaction kettle by a horizontal pump, the feeding speed is 2.3g/min, the bottom-laying solvent ethanol (828 g), the powdery copper-molybdenum-lithium catalyst (7.1 g and alumina load) and hydrogen in the kettle are added in advance, the temperature is maintained at 220 ℃, and the stirring speed is 600rpm/min. And (3) continuously discharging through an inner bottom filter in the kettle while feeding, wherein the discharging speed and the feeding speed are kept balanced, the liquid level in the kettle is kept unchanged, and the residence time of the ring-opening reaction liquid in the kettle is stable (6 h). In the reaction process, sampling and analysis are carried out regularly, after an internal standard n-decane is added, the contents of raw material 3-ethyl hydroxy propionate and product 1,3-propanediol in hydrogenation reaction liquid are analyzed by GC chromatography. The results showed 100% conversion of ethyl 3-hydroxypropionate and 100% selectivity to 1, 3-propanediol.
Comparative example 1
The resin alone catalyzes the ring opening of beta-propiolactone.
Adopting a tubular reactor to carry out ring-opening reaction, wherein the length of a reaction tube is 50cm, the inner diameter is 2.2cm, the middle of the reaction tube is filled with spherical Amberlyst-26 (OH) strong alkaline resin catalyst (100 g, purity is 99%), the top end and the low end of the reaction tube are respectively filled with ceramic ring filler, and the resin catalyst is fixed and supported; after the catalyst is filled, a fixed bed reactor power supply is started, beta-propiolactone (252.2 g,3.5 mol) and ethanol (1128.0 g,24.5 mol) are added into a feed tank, a feed advection pump is started after the beta-propiolactone and the ethanol are uniformly mixed, the feed speed of raw material liquid is 5.0g/min, the raw material liquid is fed into and discharged from the lower part, and the weight hourly space velocity is 3.0h -1 . After the reaction tube is filled with the raw material liquid and is completely infiltrated, a heating sleeve of the reaction tube is started, the temperature of the reaction tube is slowly increased to 70 ℃, the feeding speed and the temperature are kept constant, and continuous reaction is started. After the reaction liquid is discharged out of the reaction tube, the reaction liquid is cooled by a condenser and then enters a buffer tank. Samples were taken at regular intervals at the condenser, and after addition of the internal standard n-decane, the reaction was chromatographed with 83% conversion and 97% selectivity (relative to beta-propiolactone).
Comparative example 2
The organic base catalyzes the ring opening of beta-propiolactone.
The ring-opening reaction is carried out by adopting a tubular reactor, the length of a reaction tube is 50cm, the inner diameter is 2.2cm, and a ball is filled in the middleA shaped theta ring filler promotes the mixing and mass transfer of the reaction liquid in the tube; after filling, a fixed bed reactor power supply is started, beta-propiolactone (252.2 g,3.5 mol), ethanol (1128.0 g,24.5 mol), organic base tetramethylguanidine (20.2 g,0.175 mol) and auxiliary agent 4-dimethylaminopyridine (73 mg,0.6 mmol) are added into a feed tank, after the raw materials are uniformly mixed, a feed advection pump is started, the feeding speed of raw material liquid is 5.0g/min, the feeding speed of raw material liquid is lower, the feeding speed of raw material liquid is upper and lower, and the weight hourly space velocity is 3.0h -1 . After the reaction tube is filled with the raw material liquid and is completely infiltrated, a heating sleeve of the reaction tube is started, the temperature of the reaction tube is slowly increased to 100 ℃, the feeding speed and the temperature are kept constant, and continuous reaction is started. After the reaction liquid is discharged out of the reaction tube, the reaction liquid is cooled by a condenser and then enters a buffer tank. Samples were taken at regular intervals at the condenser, and after addition of the internal standard n-decane, the reaction was chromatographed with 26% conversion and 96% selectivity (relative to beta-propiolactone).
Comparative example 3
And hydrogenating the methyl 3-hydroxypropionate to obtain 1, 3-propanediol.
A mixed solution of methyl 3-hydroxypropionate (312.3 g,3.0 mol) and methanol (1200 g) is pumped into a continuous hydrogenation reaction kettle by a advection pump, the feeding speed is 2.3g/min, the kettle is added with a bottom solvent methanol (828 g), a powdery Raney nickel catalyst (7.1 g) in advance, the hydrogen in the kettle is maintained at 4.0MPa, the temperature is maintained at 220 ℃, and the stirring speed is 600rpm/min. And (3) continuously discharging through an inner bottom filter in the kettle while feeding, wherein the discharging speed and the feeding speed are kept balanced, the liquid level in the kettle is kept unchanged, and the residence time of the ring-opening reaction liquid in the kettle is stable (6 h). In the reaction process, sampling and analysis are carried out regularly, after an internal standard n-decane is added, the content of raw material methyl 3-hydroxypropionate and product 1,3-propanediol in hydrogenation reaction liquid is analyzed by GC chromatography. The results showed that the conversion of methyl 3-hydroxypropionate was 85.3% and the selectivity of 1,3-propanediol was 79.8%.

Claims (7)

1. A method for synthesizing 1,3-propanediol by continuous ring-opening hydrogenation of beta-propiolactone, which is characterized by comprising the following steps:
s1: under the catalysis of strong alkaline resin and auxiliary agent, beta-propiolactone and alcohol continuously react, and ring opening is carried out to obtain 3-hydroxy propionate;
s2: under the action of a hydrogenation catalyst, the methyl 3-hydroxypropionate is subjected to continuous hydrogenation reaction to obtain the 1, 3-propanediol.
2. The method according to claim 1, wherein the strongly basic resin of S1 is a styrene-type strongly basic anionic resin and/or an acrylic-type strongly basic anionic resin, preferably one or more of D201, D202, D280, 201, 202, 203, ambersep 900OH, amberlyst-26 (OH);
and/or the auxiliary agent of S1 contains a pyridine structure, preferably pyridine with electron donating substituents on an aromatic ring, more preferably one or more of 4-picoline, 4-dimethylaminopyridine, 4-pyrrolidinylpyridine and 4-piperidinylpyridine;
preferably, the amount of the auxiliary agent is 10-100ppm based on the total mass of the feed liquid.
3. The process according to claim 1 or 2, wherein the molar ratio of β -propiolactone to alcohol feed in S1 is from 1:4.0 to 10.0;
and/or the alcohol in S1 is alkyl alcohol, preferably one or more of methanol, ethanol, propanol and butanol.
4. A process according to any one of claims 1 to 3, wherein the reaction of S1 is carried out in a tubular reactor;
and/or, uniformly mixing the beta-propiolactone and alcohol in S1, and then entering a reactor, and entering from bottom to top;
and/or the weight hourly space velocity of the S1 ring-opening reaction liquid is 0.6-3.0h -1 Preferably 0.6-2.0h -1 ；
And/or the temperature of the S1 ring-opening reaction is 60-100 ℃, and the reaction pressure is normal pressure or micro-positive pressure.
5. The process according to claim 1, wherein S2 the hydrogenation catalyst is one or more of raney nickel, raney cobalt, ruthenium carbon, platinum oxide, supported copper catalyst, preferably supported copper catalyst;
and/or the catalyst content in the S2 hydrogenation reaction liquid is 0.5-2.0wt%.
6. The process according to claim 1 or 5, wherein the hydrogenation reaction of S2 is carried out in a continuous manner in an autoclave, and the ring-opening reaction liquid of S1 is directly introduced into the hydrogenation reaction kettle;
preferably, the residence time of the reaction solution in the S2 in the hydrogenation reaction kettle is 4.0-10.0h;
and/or the hydrogen pressure in S2 is 2.0-5.0MPaG;
and/or the reaction temperature in S2 is 150-220 ℃.
7.1, 3-propanediol obtained by the process of any one of claims 1-6, wherein the 1,3-propanediol is synthesized by continuous ring-opening hydrogenation of beta-propiolactone.
CN202310013754.XA 2023-01-05 2023-01-05 Method for synthesizing 1, 3-propylene glycol by propiolactone ring-opening hydrogenation Pending CN116239445A (en)

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