CN1308281C - Continuously producing method for proplonic acid by oxidizing propionic aldehyde - Google Patents
Continuously producing method for proplonic acid by oxidizing propionic aldehyde Download PDFInfo
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- CN1308281C CN1308281C CNB2005100540829A CN200510054082A CN1308281C CN 1308281 C CN1308281 C CN 1308281C CN B2005100540829 A CNB2005100540829 A CN B2005100540829A CN 200510054082 A CN200510054082 A CN 200510054082A CN 1308281 C CN1308281 C CN 1308281C
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Abstract
The present invention relates to a method for continuously producing propionic acid by oxidizing propylaldehyde, and a reaction tower thereof. The production method comprises the steps: firstly, of propylaldehyde and catalysts as raw materials are mixed; secondly, the mixed propylaldehyde and catalysts and air or oxygen are delivered to the bottom of the reaction tower to react in the reaction tower at a reaction temperature of 80 to 100 DEG C, the gradually generated propionic acid through reaction is overflowed from the upper part of the reaction tower to obtain primary coarse propionic acid. The production method has the characteristics of simple process flow, high catalyst activity, low reaction pressure and reaction temperature, short reaction time and good selectivity, and is suitable for large-scale industrialization production, and the obtained propionic acid product has the advantages of stable property, high purity, good quality, etc. The reaction tower for continuously producing propionic acid enables the oxidation efficiency to be improved, and favorable for the production method, and the conversion rate of the propylaldehyde and the selectivity and the yield of the propionic acid in the present invention respectively achieve 95%, 97% and more than 92%.
Description
One, technical field:
The present invention relates to the propionic aldehyde is production method and the reaction unit thereof that the continuous oxidation of main raw material makes propionic acid, is a kind of continuously producing method for proplonic acid by oxidizing propionic aldehyde and reaction tower thereof.
Two, background technology:
Propionic acid is a kind of very important industrial chemicals, and propionic acid and its esters are widely used in aspects such as food, feed anticorrosion agent, at present very shortage at home.The domestic continuous production device that does not have proplonic acid by oxidizing propionic aldehyde, laboratory study work in this respect is also considerably less, through inquiries such as domestic and international patent documentations, does not have relevant patent documentation report.
The production of propionic acid both at home and abroad at present mainly adopts the batch still formula to produce, for example: the partial continuous method of U.S. combinating carbide company (UCC) is produced propionic acid, require the purity higher (generally being equal to or greater than 99%) of main raw material propionic aldehyde, adopt the stirring-type reactor of rhythmic reaction, its technical process is complicated, equipment is more, require high to equipment and pipe material, its propionic aldehyde transformation efficiency is 75%, its propionic acid yield is 67.5%, its production quality control instability, batch still formula production technique and device are not suitable for large-scale industrial production.
Three, summary of the invention:
The invention provides a kind of continuously producing method for proplonic acid by oxidizing propionic aldehyde, overcome the problem that above-mentioned prior art exists, realized with the propionic aldehyde being main raw material continuous production propionic acid, it is applicable to suitability for industrialized production.
The present invention also provides a kind of reaction tower that is used for continuously producing method for proplonic acid by oxidizing propionic aldehyde, and it helps the realization of production method of the present invention.
One of technical scheme of the present invention realizes by following measure: a kind of continuously producing method for proplonic acid by oxidizing propionic aldehyde, at first with raw material propionic aldehyde and catalyst mix, secondly blended propionic aldehyde and catalyzer and air or oxygen are sent into bottom the reaction tower, react under 80 ℃ to 100 ℃ of reaction tower inner reaction temperature then, the propionic acid that generates of reaction overflows from reaction tower top and obtains once thick propionic acid gradually; Wherein:
Catalyzer comprises Primary Catalysts and promotor, Primary Catalysts is propionic salt or acetate or naphthenate, promotor is a phosphoric acid, and propionic aldehyde is 1000 to 0.5 to 3.0 with the weight proportion of Primary Catalysts, and propionic aldehyde is 1000 to 0.5 to 6.0 with the weight proportion of promotor;
Propionic aldehyde is 1 to 1 to 8 with the mol ratio of air or oxygen;
The pressure that the mixing liquid of propionic aldehyde and catalyzer is gone into before the reaction tower is 0.6MPa to 2.0Mpa;
The pressure of going into before the reaction tower of air or oxygen is 0.6MPa to 2.0Mpa;
Propionic aldehyde and catalyzer and air or oxygen from go into reaction tower to the residence time that goes out the reaction tower be 2 hours to 8 hours.
Be further optimization and/or improvements below to one of the invention described above technical scheme:
Can feed rare gas element on above-mentioned reaction tower top.
Above-mentioned rare gas element can adopt nitrogen or argon gas or helium.
The above-mentioned thick propionic acid that overflows can obtain the thick propionic acid of secondary through low pressure separation pot.
Above-mentioned once thick propionic acid or the thick propionic acid of secondary can carry out rectifying and obtain smart propionic acid under normal pressure, under 138 ℃ to 142 ℃.
Two of technical scheme of the present invention realizes by following measure: a kind of reaction tower that is used for above-mentioned continuously producing method for proplonic acid by oxidizing propionic aldehyde, it comprises the reaction king-post, propionic aldehyde inlet and gas inlet are arranged in the bottom of this reaction king-post, on the top of this reaction king-post overflow port, nitrogen inlet and vapor pipe are arranged, in this reaction king-post, filler is housed, outside this reaction king-post, is useful on the chuck of controlled temperature or/and in this reaction tower, be useful on the cooling tube of controlled temperature.
Be two further optimization and/or improvements below to the invention described above technical scheme:
In the reaction king-post between above-mentioned overflow port and filler broken foam filler can be arranged.
At above-mentioned gas inlet or/and nitrogen inlet can adopt conventional tree state sparger or conventional annular distribution device.
Above-mentioned filler can adopt ceramic packing or/and Stainless Steel Helices or/and glass filler.
Filler in the above-mentioned reaction king-post can adopt bulk form.
The safety blasting mouth can be arranged at the top at above-mentioned reaction king-post.
On above-mentioned safety blasting mouth, the safety blasting valve can be installed.
Production method of the present invention has characteristics: technical process is simplified, the catalyst activity height, and reaction pressure and temperature of reaction are low, reaction times is short, selectivity is good, is applicable to large-scale industrial production, products obtained therefrom propionic acid stable in properties, product purity height, good product quality etc.The reasonable and compact in structure of reaction tower of the present invention is utilized this continuous production propionic acid reaction tower, and oxidation efficiency is improved, and helps production method of the present invention.The selectivity of the transformation efficiency of propionic aldehyde, propionic acid and yield reach respectively more than 95%, 97% and 92% among the present invention.
Four, description of drawings
Accompanying drawing 1 is the structural representation of the most preferred embodiment of reaction tower of the present invention,
Coding in the accompanying drawing is respectively: 1 is the propionic aldehyde inlet, and 2 is gas inlet, and 3 is overflow port, 4 is nitrogen inlet, and 5 is vapor pipe, and 6 is filler, 7 is chuck, and 8 is cooling tube, and 9 is the safety blasting mouth, 10 are broken foam filler, 11 is Jacket inlet, and 12 is Jacket outlet, and 13 is conventional tree state sparger or conventional annular distribution device, 14 are the cooling tube inlet, and 15 are the cooling tube outlet.
Five, embodiment
The present invention is not subjected to the restriction of following embodiment, can determine concrete embodiment according to technical scheme of the present invention and practical situation.
Below in conjunction with embodiment and accompanying drawing the present invention is further described:
As shown in Figure 1, this reaction tower comprises the reaction king-post, propionic aldehyde inlet 1 and gas inlet 2 are arranged in the bottom of this reaction king-post, on the top of this reaction king-post overflow port 3 is arranged, nitrogen inlet 4 and vapor pipe 5, in this reaction king-post, filler 6 is housed, outside this reaction king-post, be useful on the chuck 7 of controlled temperature or/and in this reaction tower, be useful on the cooling tube 8 (that is: only outside this reaction king-post, be useful on the chuck 7 of controlled temperature or in this reaction tower, be useful on the cooling tube 8 of controlled temperature, perhaps outside this reaction king-post, be useful on the chuck 7 of controlled temperature and in this reaction tower, be useful on the cooling tube 8 of controlled temperature) of controlled temperature; Wherein, gas inlet 2 also can be described as oxygen intake.
In order further to improve the performance of reaction tower of the present invention, as follows to above-mentioned embodiment further optimization and/or improvements: as shown in Figure 1, safety blasting mouth 9 is preferably arranged at the top at the reaction king-post, the safety blasting valve preferably is installed on safety blasting mouth 9, thereby plays the safeguard protection effect; As shown in Figure 1, (that is: gas inlet 2 or nitrogen inlet 4 adopt conventional tree state sparger or conventional annular distribution device to gas inlet 2 or/and nitrogen inlet 4 adopts conventional tree state sparger or conventional annular distribution device, gas inlet 2 and nitrogen inlet 4 adopt conventional tree state sparger or conventional annular distribution device), thereby help the thorough mixing of air and propionic aldehyde and react, help nitrogen and play sufficient explosive-proof protector effect with the gas phase thorough mixing that will discharge; As shown in Figure 1, broken foam filler 10 is arranged preferably in the reaction king-post between overflow port 3 and filler 6, thereby significantly reduce the thick propionic acid in the gas phase and the content liquid of propionic aldehyde; According to actual needs, filler can adopt ceramic packing or/and Stainless Steel Helices or/and glass filler; Filler in the reaction king-post preferably adopts bulk form.
Above technical characterictic has constituted the most preferred embodiment of reaction tower of the present invention, and it has stronger adaptability and best implementation result, can increase and decrease non-essential technical characterictic according to actual needs, satisfies the demand of different situations.
The embodiment of continuously producing method for proplonic acid by oxidizing propionic aldehyde of the present invention is as follows:
Embodiment 1, at first with raw material propionic aldehyde and catalyst mix, secondly blended propionic aldehyde and catalyzer and air or oxygen are sent into bottom the reaction tower, react under 80 ℃ or 90 ℃ or 100 ℃ of reaction tower inner reaction temperature then, the propionic acid that generates of reaction overflows from reaction tower top and obtains once thick propionic acid gradually; Wherein:
Catalyzer comprises Primary Catalysts and promotor, Primary Catalysts is propionic salt or acetate or naphthenate, promotor is a phosphoric acid, propionic aldehyde is 1000 to 0.5 or 1000 to 0.8 or 1000 to 1.0 or 1000 to 1.5 or 1000 to 2.0 or 1000 to 2.5 or 1000 to 3.0 with the weight proportion of Primary Catalysts, and propionic aldehyde is 1000 to 0.5 or 1000 to 0.8 or 1000 to 1.2 or 1000 to 1.8 or 1000 to 2.5 or 1000 to 3.2 or 1000 to 4.0 or 1000 to 4.8 or 1000 to 5.2 or 1000 to 6.0 with the weight proportion of promotor;
Propionic aldehyde is 1 to 1 or 1 to 3 or 1 to 5 or 1 to 8 with the mol ratio of air or oxygen;
The pressure that the mixing liquid of propionic aldehyde and catalyzer is gone into before the reaction tower is 0.6MPa or 0.8Mpa or 1.0MPa or 1.2MPa or 1.5MPa or 1.8Mpa or 2.0Mpa;
The pressure of going into before the reaction tower of air or oxygen is 0.6MPa or 0.8Mpa or 1.0MPa or 1.2MPa or 1.5MPa or 1.8Mpa or 2.0Mpa;
Propionic aldehyde and catalyzer and air or oxygen from go into reaction tower to the residence time that goes out the reaction tower be 2 hours or 3 hours or 4 hours or 5 hours or 6 hours or 7 hours or 8 hours.
Embodiment 2, are with the difference of embodiment 1: in embodiment 2, the thick propionic acid that overflows is obtained the thick propionic acid of secondary through low pressure separation pot.
Embodiment 3, are with the difference of embodiment 1 and embodiment 2: in embodiment 3, the once thick propionic acid in the above-mentioned embodiment or the thick propionic acid of secondary can be obtained smart propionic acid carrying out rectifying under the normal pressure, under 138 ℃ or 140 ℃ or 142 ℃.
In above-mentioned Primary Catalysts:
Propionic salt can be preferably Cobaltous propionate or Manganese dipropionate, perhaps is Cobaltous propionate and Manganese dipropionate.
Acetate can be preferably Cobaltous diacetate or manganese acetate, perhaps is Cobaltous diacetate and manganese acetate.
Naphthenate can be preferably cobalt naphthenate or manganese naphthenate, perhaps is cobalt naphthenate and manganese naphthenate.
In the above-described embodiment, in order further to improve the security equal fruit of continuously producing method for proplonic acid by oxidizing propionic aldehyde of the present invention, further optimization and/or improvements are as follows: preferably feed rare gas element on reaction tower top, and rare gas element can adopt nitrogen or argon gas or helium.
In the invention described above continuously producing method for proplonic acid by oxidizing propionic aldehyde of the present invention, can adopt the embodiment of above-mentioned reaction tower, preferably adopt reaction tower as shown in Figure 1; But also can adopt other existing popular response tower that is applicable to this production method as required.
In the above-described embodiment: to used main raw material propionic aldehyde, available content is equal to or higher than 98% industrial propionic aldehyde.
Above technical characterictic has constituted the most preferred embodiment of continuously producing method for proplonic acid by oxidizing propionic aldehyde of the present invention, and it has stronger adaptability and best implementation result, can increase and decrease non-essential technical characterictic according to actual needs, satisfies the demand of different situations.
Resulting smart propionic acid in the above-mentioned embodiment is carried out check and analysis by GB GB10615-89, and it all meets or exceeds the following table measured value, and following table is the contrast table of GB GB10615-89 and measured value:
| Product specification (food grade) | Index (GB10615-89) | Measured value |
| Propionic acid purity/m% | ≥99.5 | ≥99.6 |
| Propionic aldehyde content/m% | ＜0.05 | Qualified |
| Oxidable thing (in formic acid)/m% | ＜0.05 | Qualified |
| Water/m% | ＜0.15 | 0.03 |
| Non-volatile residue/m% | ＜0.01 | Qualified |
| As/10 -6 | ＜3 | ＜3 |
| Pb/10 -6 | ＜10 | ＜10 |
| Colourity { platinum cobalt colorimetric } | ＜25 | Qualified |
| Relative density (20/20) | 0.993～0.997 | Qualified |
| Boiling range (0.1Mpa)/℃ | 138.5～142.5 | 139.5～141.5 |
As can be known from the above table: the resulting smart propionic acid of the present invention has reached the requirement of GB GB10615-89, has reached the purity requirement of food grade propionic acid.
According to GB GB10615-89, and by detecting and calculating is learnt: the transformation efficiency of propionic aldehyde, the selectivity of propionic acid and yield meet or exceed 95%, 97% and 92% respectively, and the purity of products obtained therefrom propionic acid is higher, foreign matter content is very low.
In sum, technical process of the present invention is simplified, the catalyst activity height, and reaction pressure and temperature of reaction are low, and the reaction times is short, and selectivity is good, is applicable to large-scale industrial production.Producing propionic acid with the partial continuous method of U.S. combinating carbide company (UCC) compares: in the present invention, its main raw material propionic aldehyde can adopt the propionic aldehyde of 98% purity, do not need to adopt the stirring-type reactor of rhythmic reaction, its propionic aldehyde transformation efficiency is higher more than 20% than U.S. union carbide corporation, and its propionic acid yield is higher more than 24.5% than U.S. union carbide corporation.
Claims (10)
1, a kind of continuously producing method for proplonic acid by oxidizing propionic aldehyde, it is characterized in that at first with raw material propionic aldehyde and catalyst mix, secondly blended propionic aldehyde and catalyzer and air or oxygen are sent into bottom the reaction tower, react under 80 ℃ to 100 ℃ of reaction tower inner reaction temperature then, the propionic acid that generates of reaction overflows from reaction tower top and obtains once thick propionic acid gradually; Wherein:
Catalyzer comprises Primary Catalysts and promotor, Primary Catalysts is propionic salt or acetate or naphthenate, promotor is a phosphoric acid, and propionic aldehyde is 1000 to 0.5 to 3.0 with the weight proportion of Primary Catalysts, and propionic aldehyde is 1000 to 0.5 to 6.0 with the weight proportion of promotor;
Propionic aldehyde is 1 to 1 to 8 with the mol ratio of air or oxygen;
The pressure that the mixing liquid of propionic aldehyde and catalyzer is gone into before the reaction tower is 0.6MPa to 2.0Mpa;
The pressure of going into before the reaction tower of air or oxygen is 0.6MPa to 2.0Mpa;
Propionic aldehyde and catalyzer and air or oxygen from go into reaction tower to the residence time that goes out the reaction tower be 2 hours to 8 hours.
2, continuously producing method for proplonic acid by oxidizing propionic aldehyde according to claim 1 is characterized in that reaction tower top feeds rare gas element.
3, continuously producing method for proplonic acid by oxidizing propionic aldehyde according to claim 2 is characterized in that rare gas element adopts nitrogen or argon gas or helium.
4,, it is characterized in that the thick propionic acid that overflows obtains the thick propionic acid of secondary through low pressure separation pot according to claim 1 or 2 or 3 described continuously producing method for proplonic acid by oxidizing propionic aldehyde.
5, according to claim 1 or 2 or 3 described continuously producing method for proplonic acid by oxidizing propionic aldehyde, it is characterized in that once thick propionic acid under normal pressure, under 138 ℃ to 142 ℃, carry out rectifying and obtain smart propionic acid.
6, continuously producing method for proplonic acid by oxidizing propionic aldehyde according to claim 4, it is characterized in that the thick propionic acid of secondary under normal pressure, under 138 ℃ to 142 ℃, carry out rectifying and obtain smart propionic acid.
7, a kind of reaction tower that is used for above-mentioned continuously producing method for proplonic acid by oxidizing propionic aldehyde, it is characterized in that comprising the reaction king-post, propionic aldehyde inlet and gas inlet are arranged in the bottom of this reaction king-post, on the top of this reaction king-post overflow port, nitrogen inlet and vapor pipe are arranged, in this reaction king-post, filler is housed, outside this reaction king-post, is useful on the chuck of controlled temperature or/and in this reaction tower, be useful on the cooling tube of controlled temperature.
8, reaction tower according to claim 7 is characterized in that broken foam filler is arranged in the reaction king-post between overflow port and the filler.
9, according to claim 7 or 8 or described continuous production propionic acid reaction tower, it is characterized in that gas inlet or/and nitrogen inlet adopts conventional tree state sparger or conventional annular distribution device; Or/and, filler adopt ceramic packing or/and Stainless Steel Helices or/and glass filler; Or/and the filler in the reaction king-post adopts bulk form; Or/and, on the top of reaction king-post the safety blasting mouth is arranged.
10, continuous production propionic acid reaction tower according to claim 9 is characterized in that being equipped with on the safety blasting mouth safety blasting valve.
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| CNB2005100540829A CN1308281C (en) | 2005-03-02 | 2005-03-02 | Continuously producing method for proplonic acid by oxidizing propionic aldehyde |
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| CNB2005100540829A CN1308281C (en) | 2005-03-02 | 2005-03-02 | Continuously producing method for proplonic acid by oxidizing propionic aldehyde |
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| CN1308281C true CN1308281C (en) | 2007-04-04 |
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| CN105254484A (en) * | 2015-11-10 | 2016-01-20 | 天津大学 | Continuous production method and device for preparing propionic acid through air oxidation of propionaldehyde |
| CN115041114B (en) * | 2022-06-19 | 2024-02-09 | 中海油天津化工研究设计院有限公司 | System and process method for preparing organic acid by continuous oxidation of aldehyde |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU793988A1 (en) * | 1979-03-23 | 1981-01-07 | Ордена Ленина Институт Химическойфизики Ah Cccp | Method of preparing propionic acid |
| SU1020423A1 (en) * | 1981-07-06 | 1983-05-30 | Институт Химической Физики Ан Армсср | Process for preparing propionic acid |
| CN1569798A (en) * | 2003-07-15 | 2005-01-26 | 中国石油化工股份有限公司齐鲁分公司 | Method for preparation of propionic acid |
| CN1597654A (en) * | 2003-09-15 | 2005-03-23 | 中国石油天然气股份有限公司 | Catulyst for preparing propionic acid by propionaldehyde oxidation and its method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU793988A1 (en) * | 1979-03-23 | 1981-01-07 | Ордена Ленина Институт Химическойфизики Ah Cccp | Method of preparing propionic acid |
| SU1020423A1 (en) * | 1981-07-06 | 1983-05-30 | Институт Химической Физики Ан Армсср | Process for preparing propionic acid |
| CN1569798A (en) * | 2003-07-15 | 2005-01-26 | 中国石油化工股份有限公司齐鲁分公司 | Method for preparation of propionic acid |
| CN1597654A (en) * | 2003-09-15 | 2005-03-23 | 中国石油天然气股份有限公司 | Catulyst for preparing propionic acid by propionaldehyde oxidation and its method |
Non-Patent Citations (1)
| Title |
|---|
| 《丙酸的生产应用与市场分析》 贺以乐，《化工科技市场》，第10卷 2003 * |
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