CN118307395A - Continuous production method for preparing propionic acid by oxidation of n-propanol - Google Patents
Continuous production method for preparing propionic acid by oxidation of n-propanol Download PDFInfo
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- CN118307395A CN118307395A CN202410734282.1A CN202410734282A CN118307395A CN 118307395 A CN118307395 A CN 118307395A CN 202410734282 A CN202410734282 A CN 202410734282A CN 118307395 A CN118307395 A CN 118307395A
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 title claims abstract description 171
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 235000019260 propionic acid Nutrition 0.000 title claims abstract description 83
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 title claims abstract description 83
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000010924 continuous production Methods 0.000 title claims abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 230000003197 catalytic effect Effects 0.000 claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 239000012043 crude product Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002808 molecular sieve Substances 0.000 claims abstract description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 238000002360 preparation method Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 208000012839 conversion disease Diseases 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 tetramethyl dipentaerythritol Chemical compound 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The application relates to the technical field of propionic acid production, and particularly discloses a continuous production method for preparing propionic acid by using n-propanol oxidation. The production method specifically comprises the following steps: mixing n-propanol and 30wt% hydrogen peroxide, and feeding the mixture into a continuous tubular reactor filled with a catalyst, and converting the mixture into crude product propionic acid through catalytic oxidation; extracting the crude product propionic acid by using an extracting agent, and separating and purifying an extraction phase to obtain high-purity propionic acid; the molar ratio of the n-propanol to the 30wt% hydrogen peroxide is 1 (1.5-3.5); the temperature of the catalytic oxidation reaction is 30-80 ℃; the catalyst is titanium silicalite molecular sieve. The production process provided by the application has the advantages of simple flow, easiness in operation, mild reaction conditions, high reaction conversion rate and high yield, and realizes efficient, continuous and low-energy-consumption preparation of propionic acid.
Description
Technical Field
The application relates to the technical field of propionic acid production, in particular to a continuous production method for preparing propionic acid by utilizing n-propanol oxidation.
Background
Propionic acid is a colorless oily liquid with rancid and pungent smell, and is widely used in the manufacture of food spices, medicines, pesticides, mildew inhibitors and other products. Furthermore, propionic acid can also be used to produce propionate esters and derivatives thereof. Therefore, the application and the demand of the propionic acid are continuously expanding, and the n-propanol is rich and easy to obtain, so the development of the production method for preparing the propionic acid by using the oxidation of the n-propanol has higher value.
At present, two methods for industrially producing propionic acid by using propanol as a raw material are generally available. One is the dehydrogenation of propanol to propanal followed by the reoxidation to propionic acid; the other is to oxidize propanol directly into propionic acid, such as nitric acid and hydrogen peroxide, but the conversion rate and selectivity are not ideal.
The related art discloses a method for preparing propionic acid by catalyzing hydrogen peroxide to oxidize n-propanol by using heteropolyacid salt, which takes [ (CH 3)3N(n-C12H25)]2Na5PW11O39) as a catalyst, and reacts for 6 hours under the conditions that the molar ratio of n-propanol to the catalyst is 50:1, the molar ratio of n-propanol to 30wt% hydrogen peroxide is 1:3 and the temperature is 60 ℃, and the yield of propionic acid is 58%.
The related art also discloses a method for optimizing the preparation of propionic acid by oxidizing propanol with caustic soda, which adopts white oil as a solvent, so that the temperature of a reaction system can be rapidly increased to 300-310 ℃, the white oil has an emulsifying effect at high temperature, the dehydrogenation reaction speed of molten caustic soda and alcohol is increased, the generation of side reaction is reduced, the selectivity is more than 99%, and the conversion rate of reaction quality is more than 90%. Although the conversion is improved over the prior art, the reaction temperature is still high.
Based on the above, there is no production process for preparing propionic acid from propanol which can combine mild reaction conditions, high reaction conversion and high yield.
Disclosure of Invention
In view of the above related analysis, the present application provides a continuous production method for preparing propionic acid by oxidation of n-propanol. The production process is simple in flow, easy to operate, mild in reaction condition, high in reaction conversion rate and high in yield, and realizes efficient, continuous and low-energy-consumption preparation of propionic acid.
The application provides a continuous production method for preparing propionic acid by oxidizing n-propanol, which adopts the following technical scheme:
A continuous production method for preparing propionic acid by using n-propanol oxidation specifically comprises the following steps:
Mixing n-propanol and 30wt% hydrogen peroxide, and feeding the mixture into a continuous tubular reactor filled with a catalyst, and converting the mixture into crude product propionic acid through catalytic oxidation; extracting the crude product propionic acid by using an extracting agent, and separating and purifying an extraction phase to obtain high-purity propionic acid;
The molar ratio of the n-propanol to the 30wt% hydrogen peroxide is 1 (1.5-3.5);
the temperature of the catalytic oxidation reaction is 30-80 ℃;
The catalyst is titanium silicalite molecular sieve.
The production method provided by the application has the advantages of low reaction temperature and low energy consumption. The continuous reaction process of the tubular reactor is adopted, so that the continuous, efficient, rapid and low-energy-consumption preparation of the propionic acid is realized. Meanwhile, the catalyst and the product used in the application are easy to separate, the catalyst has long service life, low production cost, simple operation, less waste, safety and environmental protection, and is suitable for large-scale industrial production.
The application removes the water in the crude product propionic acid and the hydrogen peroxide which is not completely reacted by using the extractant extraction. And separating and purifying the extract phase to remove the extractant in the extract phase, thereby obtaining the high-purity propionic acid of the target product. The extracted extractant can be recycled.
The detection analysis shows that the propionic acid prepared by taking the n-propanol as the raw material has high yield and good product quality, the conversion rate of the n-propanol is 100%, the highest selectivity of the propionic acid can reach 97.1%, and the purity of the propionic acid is higher than 99.5%.
In a specific embodiment, the catalytic oxidation reaction is at a temperature of 30 ℃, 40 ℃,55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃.
In some embodiments, the catalytic oxidation reaction is at a temperature of 30-40℃、30-55℃、30-60℃、30-65℃、30-70℃、30-75℃、40-55℃、40-60℃、40-65℃、40-70℃、40-75℃、40-80℃、55-60℃、55-65℃、55-70℃、55-75℃、55-80℃、60-65℃、60-70℃、60-75℃、60-80℃、65-70℃、65-75℃、65-80℃、70-75℃、70-80℃、75-80℃.
In a specific embodiment, the molar ratio of the n-propanol to the 30wt% hydrogen peroxide is 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5.
In some embodiments, the molar ratio of the n-propanol to the 30wt% hydrogen peroxide is 1 (1.5-2), 1 (1.5-2.5), 1 (1.5-3.5), 1 (2-2.5), 1 (2-3), 1 (2-3.5), 1 (2.5-3), 1 (2.5-3.5), 1 (3-3.5).
Optionally, the titanium silicalite molecular sieve comprises one or more of TS-1, TS-2, ti-MWW.
In a specific embodiment, the titanium silicalite molecular sieve is of the type TS-1.
In a specific embodiment, the titanium silicalite molecular sieve is of the type TS-2.
In a specific embodiment, the titanium silicalite molecular sieve is of the type Ti-MWW.
Optionally, the titanium-silicon molecular sieve has a titanium-silicon ratio of 0.03-0.08 and a specific surface area of 250-1200m 2/g.
Alternatively, the n-propanol and the 30wt% hydrogen peroxide are mixed into the continuous tube reactor by pressurizing with a pump into the continuous tube reactor.
Alternatively, the feeding modes include a horizontal continuous feeding mode and a vertical continuous feeding mode according to the feeding modes.
Optionally, the vertical continuous feeding mode comprises an upper feeding mode and a lower feeding mode.
In a specific embodiment, the feed mode is a horizontal continuous feed mode.
In a specific embodiment, the feed mode is an upper feed mode.
In a specific embodiment, the feed mode is a lower feed mode.
Optionally, the liquid hourly space velocity of the catalytic oxidation reaction is 0.1-5h -1.
In a specific embodiment, the liquid hourly space velocity of the catalytic oxidation reaction is 0.1h -1、0.2h-1、0.9h-1、1.5h-1、3h-1、5h-1.
In some embodiments, the catalytic oxidation reaction has a liquid hourly space velocity of 0.1-0.2h-1、0.1-0.9h-1、0.1-1.5h-1、0.1-3h-1、0.2-0.9h-1、0.2-1.5h-1、0.2-3h-1、0.2-5h-1、0.9-1.5h-1、0.9-3h-1、0.9-5h-1、1.5-3h-1、1.5-5h-1、3-5h-1.
Optionally, the pressure of the catalytic oxidation reaction is 0-0.5MPa.
In a specific embodiment, the catalytic oxidation reaction is carried out at a pressure of 0MPa, 0.1MPa, 0.2MPa, 0.5MPa.
In some embodiments, the catalytic oxidation reaction is at a pressure of 0-0.1MPa, 0-0.2MPa, 0.1-0.5MPa, 0.2-0.5MPa.
Optionally, the extractant comprises one or more of ethyl acetate, dichloromethane, toluene, benzene, cyclohexane, methyl tert-butyl ether, tetramethyl dipentaerythritol and ethylene glycol monomethyl ether.
Optionally, the extraction is one or more countercurrent extractions.
Optionally, the volume ratio of the crude product propionic acid to the extractant is 1 (1-3).
The application can realize at least the following beneficial effects:
(1) The method adopts a continuous reaction process, and the propionic acid product prepared by taking the n-propanol as the raw material has the advantages of high reaction conversion rate, high yield and high product quality, simple process flow, easy operation, mild reaction conditions and realization of high-efficiency, continuous and low-energy-consumption preparation of propionic acid.
(2) Meanwhile, the catalyst used by the application is easy to separate from the product, the catalyst has long catalytic life, low production cost, simple operation, less waste, safety and environmental protection, and is suitable for large-scale industrial production.
(3) In addition, the production method provided by the application has the advantages that the reaction temperature is easy to control, the reaction rate can be accelerated by slightly regulating the reaction temperature within a controllable range, the raw material conversion rate and the product selectivity are greatly improved, and the production cost is reduced.
Drawings
FIG. 1 is a schematic of a continuous tube reactor with horizontal feed.
FIG. 2 is a schematic of a continuous tube reactor with upper feed.
FIG. 3 is a schematic of a continuous tube reactor with lower feed.
Detailed Description
Before describing embodiments of the application in detail, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this term belongs.
The application provides a continuous production method for preparing propionic acid by oxidation of n-propanol, which comprises the following steps:
Mixing n-propanol and 30wt% hydrogen peroxide, and feeding the mixture into a continuous tubular reactor filled with a catalyst, and converting the mixture into crude product propionic acid through catalytic oxidation; extracting the crude product propionic acid by using an extracting agent, and separating and purifying an extraction phase to obtain high-purity propionic acid;
The molar ratio of the n-propanol to the 30wt% hydrogen peroxide is 1 (1.5-3.5);
the temperature of the catalytic oxidation reaction is 30-80 ℃;
The catalyst is titanium silicalite molecular sieve.
Alternatively, the catalytic oxidation reaction is carried out at a temperature of 55-80 ℃. Further, the temperature of the catalytic oxidation reaction is 60-70 ℃.
Alternatively, the molar ratio of n-propanol to 30wt% hydrogen peroxide is 1 (2-3). Further, the molar ratio of n-propanol to 30wt% hydrogen peroxide is 1 (2-2.5).
Alternatively, the liquid hourly space velocity of the catalytic oxidation reaction is from 0.1 to 5h -1. Further, the liquid hourly space velocity of the catalytic oxidation reaction is 0.2-3h -1. Still further, the liquid hourly space velocity of the catalytic oxidation reaction is 0.5-1.5h -1.
Alternatively, the catalytic oxidation reaction is carried out at a pressure of 0-0.5MPa. Further, the pressure of the catalytic oxidation reaction is 0.1-0.4MPa. Still further, the pressure of the catalytic oxidation reaction is 0.1-0.2MPa.
The feeding modes include a horizontal feeding mode and a vertical feeding mode. The vertical feeding mode includes an upper feeding mode and a lower feeding mode. The continuous tubular reactor can be a continuous tubular reactor with double-line feeding, and a heat exchange device is arranged outside the continuous tubular reactor. The heat exchange device is provided with a heat exchange medium inlet and a heat exchange medium outlet. The heat exchange medium can be water, and in particular can be steam or circulating water. The outlet and the inlet of each section of the tubular reactor can be communicated with each other through a pipeline.
In the application, crude product propionic acid and an extracting agent are extracted and separated to remove water in the crude product propionic acid, and an extraction phase is subjected to subsequent separation and purification to obtain the target product high-purity propionic acid. Wherein the extractant comprises one or more of ethyl acetate, dichloromethane, toluene, benzene, cyclohexane, methyl tertiary butyl ether, tetramethyl dipentamethyleneketone and ethylene glycol monomethyl ether. Alternatively, the extractant is methyl tert-butyl ether (MTBE).
Optionally, the volume ratio of crude propionic acid to extractant is 1 (1-3). Further, the volume ratio of the crude product propionic acid to the extractant is 1 (1-1.5).
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described below. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application.
The raw materials adopted by the application are all commercial products unless specified.
The present application will be described in further detail with reference to examples and performance test results.
In the following examples, the continuous tube reactor shown in FIG. 1 was used as the horizontal feed, the continuous tube reactor shown in FIG. 2 was used as the upper feed, and the continuous tube reactor shown in FIG. 3 was used as the lower feed.
Examples
Example 1
The present example provides a continuous production process for the preparation of propionic acid using oxidation of n-propanol.
The production method specifically comprises the following steps:
Catalyst titanium silicalite TS-1 13g (volume about 20mL, titanium silicalite ratio about 0.074, specific surface area 1173.2068 m. Mu.m/g) was charged into a continuous tube reactor.
N-propanol and 30wt.% hydrogen peroxide are mixed according to a molar ratio of 1:3 and then introduced into a continuous tubular reactor for catalytic oxidation reaction, and a horizontal feeding mode is selected as a feeding mode. In the catalytic oxidation reaction process, the liquid hourly space velocity is 0.9 h -1, the temperature is 80 ℃, the material system is controlled to react for 20min under normal pressure (namely 0.1 MPa), and the material at the outlet of the continuous tube reactor is collected, so that the crude product propionic acid is obtained.
Extracting the crude product propionic acid by using an extractant methyl tert-butyl ether (MTBE) according to a volume ratio of 1:1, and rectifying and separating the extract phase for multiple times to obtain colorless liquid, namely the target product high-purity propionic acid.
Examples 2 to 28
Examples 2-28 provide a continuous process for the preparation of propionic acid by oxidation of n-propanol, respectively. The above embodiment differs from embodiment 1 in that: the parameters involved in the production process were different, as shown in Table 1, and the rest was the same as in example 1.
Examples 1-28 differ in particular as follows:
Examples 1-8 differ in that: the catalytic oxidation reaction temperature is different.
Examples 10 to 13 differ from example 4 in that: the molar ratio of n-propanol to 30wt.% hydrogen peroxide is different.
Example 9 differs from example 12 in that: the catalytic oxidation reaction temperature is different.
Examples 14-15 differ from example 12 in that: the feeding modes are different. Specifically, the feeding mode of example 14 is an upper feeding mode, the feeding mode of example 15 is a lower feeding mode, and the feeding mode of example 12 is a horizontal feeding mode.
Examples 16 to 17 differ from example 12 in that: the types of titanium silicalite molecular sieves vary.
Examples 18-21 differ from example 12 in that: the catalytic oxidation reaction pressure is different.
Examples 22-26 differ from example 12 in that: the liquid hourly space velocities of the catalytic oxidation reactions are different.
Examples 27-28 differ from example 12 in that: the extractant is different.
Table 1 examples 1-28 provide parameters involved in the production process
Comparative example
Comparative example 1
This comparative example provides a method for preparing propionic acid. In particular to a method for preparing propionic acid by catalyzing hydrogen peroxide to oxidize n-propanol by heteropolyacid salt in the background technology. The yield of propionic acid was 58%.
Comparative example 2
This comparative example provides a method for preparing propionic acid. In particular to a method for optimizing the preparation of propionic acid by oxidizing propanol with caustic soda, which is mentioned in the background of the application. The conversion rate of the n-propanol exceeds 90%, the selectivity of the propionic acid exceeds 99%, the yield of the propanol is more than 89.1%, but the temperature of a reaction system is 300-310 ℃.
Detection test
The selectivity of the crude product propionic acid prepared in the above examples, the conversion of n-propanol, and the purity of the target product high-purity propionic acid were each analyzed by gas chromatography. The analysis results are shown in Table 1.
The production method provided by the application effectively improves the yield of propionic acid compared with the method of comparative example 1. Compared with the method of comparative example 2, the production method provided by the application has the advantages that the temperature of the reaction system is between 30 and 80 ℃, and the temperature of the reaction system of comparative example 2 is between 300 and 310 ℃, so that the temperature of the reaction system is greatly reduced. Based on the above, the production method provided by the application has mild reaction conditions, high reaction conversion rate and high yield, and realizes efficient, continuous and low-energy-consumption preparation of propionic acid.
As is clear from Table 1, the results of the test in comparative examples 1 to 8 show that the conversion of n-propionic acid was 100% at a temperature of 30 to 80 ℃. Further, when the temperature of the catalytic oxidation reaction is 55-80 ℃, the yield of propionic acid is more than 88%. Still further, the yield of propionic acid is greater than 92% when the temperature of the catalytic oxidation reaction is between 60 and 70 ℃.
As is clear from the results of comparison of example 4 with examples 10 to 13, when the molar ratio of n-propanol to 30wt% hydrogen peroxide was 1 (1.5 to 3.5), the conversion of n-propionic acid was 100%. Further, when the molar ratio of n-propanol to 30wt% hydrogen peroxide is 1 (2-3), the yield of propionic acid is more than 93.3%. Still further, when the molar ratio of n-propanol to 30wt% hydrogen peroxide is 1 (2-2.5), the yield of propionic acid is greater than 95.7%.
As is clear from the results of comparison between example 9 and example 12, the catalytic oxidation reaction temperature was 65℃and the yield of propionic acid was more improved than 70 ℃.
As is evident from the results of the examination of examples 14 to 15 and example 12, the feeding mode had a certain effect on the yield of propionic acid, and the yield of propionic acid was lower in the upper feeding mode or the lower feeding mode than in the horizontal feeding mode.
As is clear from the results of the tests of examples 16 to 17, examples 18 to 21, examples 22 to 26, examples 27 to 28 and example 12, respectively, the kinds of the titanium silicalite molecular sieves, the pressure of the catalytic oxidation reaction, the liquid hourly space velocity of the catalytic oxidation reaction and the kind of the extractant have less influence on the yield of propionic acid.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and are not limiting; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present application.
Claims (10)
1. The continuous production method for preparing propionic acid by using n-propanol oxidation is characterized by comprising the following steps of:
Mixing n-propanol and 30wt% hydrogen peroxide, and feeding the mixture into a continuous tubular reactor filled with a catalyst, and converting the mixture into crude product propionic acid through catalytic oxidation; extracting the crude product propionic acid by using an extracting agent, and separating and purifying an extraction phase to obtain high-purity propionic acid;
The molar ratio of the n-propanol to the 30wt% hydrogen peroxide is 1 (1.5-3.5);
the temperature of the catalytic oxidation reaction is 30-80 ℃;
The catalyst is titanium silicalite molecular sieve.
2. The continuous production process for producing propionic acid using oxidation of n-propanol according to claim 1, wherein the manner in which the n-propanol and the 30wt% hydrogen peroxide are mixed into the continuous tube reactor is by pressurizing the continuous tube reactor with a pump.
3. The continuous production method for producing propionic acid by oxidation of n-propanol according to claim 1, wherein the kinds of titanium silicalite molecular sieves include one or more of TS-1, TS-2, ti-MWW.
4. The continuous production method for preparing propionic acid by using n-propanol oxidation according to claim 1, wherein the titanium-silicon molecular sieve has a titanium-silicon ratio of 0.03-0.08 and a specific surface area of 250-1200 m 2/g.
5. The continuous production method for producing propionic acid by oxidation of n-propanol according to claim 1, wherein the feeding means comprises a horizontal continuous feeding means and a vertical continuous feeding means according to feeding means.
6. The continuous process for producing propionic acid using n-propanol oxidation according to claim 1, wherein the vertical continuous feed mode comprises an upper feed mode and a lower feed mode.
7. The continuous production method for producing propionic acid by oxidation of n-propanol according to claim 1, wherein the liquid hourly space velocity of the catalytic oxidation reaction is 0.1-5h -1.
8. The continuous production method for producing propionic acid by oxidation of n-propanol according to claim 1, wherein the pressure of the catalytic oxidation reaction is 0 to 0.5MPa.
9. The continuous production method for producing propionic acid by oxidation of n-propanol according to claim 1, wherein the extractant comprises one or more of ethyl acetate, dichloromethane, toluene, benzene, cyclohexane, methyl tert-butyl ether, tetramethyl dipentamethyleneone, and ethylene glycol monomethyl ether.
10. The continuous production process for producing propionic acid by oxidation of n-propanol according to claim 1, wherein the extraction is one or more counter-current extraction; the volume ratio of the crude product propionic acid to the extractant is 1 (1-3).
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| CN102452918A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing corresponding dicarboxylic acid by catalytic oxidation of hydroxy acid |
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| CN113563179A (en) * | 2021-07-22 | 2021-10-29 | 青岛科技大学 | A kind of method for preparing propionic acid by oxidation of n-propanol |
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