CN102304019B - Method for removing propyl propionate in process for preparing normal propyl alcohol by hydrogenating propionaldehyde - Google Patents
Method for removing propyl propionate in process for preparing normal propyl alcohol by hydrogenating propionaldehyde Download PDFInfo
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- CN102304019B CN102304019B CN 201110194172 CN201110194172A CN102304019B CN 102304019 B CN102304019 B CN 102304019B CN 201110194172 CN201110194172 CN 201110194172 CN 201110194172 A CN201110194172 A CN 201110194172A CN 102304019 B CN102304019 B CN 102304019B
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- propyl alcohol
- propyl
- propionate
- propyl propionate
- normal propyl
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Abstract
The invention discloses a method for removing propyl propionate in a process for preparing normal propyl alcohol by hydrogenating propionaldehyde. The method comprises the following steps of: inputting the normal propyl alcohol containing propyl propionate into a hydrolyzing kettle to be mixed with added alkaline substances; heating and agitating; and continuously distilling on the top of the hydrolyzing kettle, wherein the temperature in the kettle is controlled in a range of 95-115 DEG C and the distilling temperature on the top of the kettle is controlled in a range of 90-95 DEG C; condensing and dewatering the normal propyl alcohol on the top of the kettle to obtain the normal propyl alcohol with high purity. The method provided by the invention has the advantages of simple process and convenience in operation; more importantly, the method improves the output of the normal propyl alcohol, effectively reduces the content of the propyl propionate, saves a lightness-removing column and a weight-removing column in the process of refining the normal propyl alcohol, and greatly reduces the energy consumption. The method provided by the invention is applied to the process for preparing normal propyl alcohol by hydrogenating propionaldehyde and is also applied to a process for producing corresponding alcohols by hydrogenating butanol, n-amyl alcohol and isovaleraldehyde.
Description
Technical field
The present invention relates to the removal method of by product propyl propionate in a kind of preparing normal propyl alcohol by propionaldehyde hydrogenation technology.
Background technology
The main application of n-propyl alcohol is to be used as solvent and chemical intermediate, is used as the special solvent of flexographic ink, especially for the printing of polyene and polyamide layer.Can be used as the carboxymethylated solvent of fiber in addition, the jelling agent of cellulose acetate and softening agent etc. can be produced n-propyl acetate, di-n-propylamine, propyl alcohol urea etc. with n-propyl alcohol.
Because it is later that domestic mass-producing n-propyl alcohol device is set up, and in output with all be difficult to qualitatively meet the need of market, therefore domestic n-propyl alcohol production technology remains further raising.Adopt the synthetic propionic aldehyde of water-soluble rhodium phosphine catalyst, propionic aldehyde after the rectifying contains the water about 2% approximately, utilize the direct hydrogenation of this moisture propionic aldehyde to synthesize n-propyl alcohol, reduced the propionic aldehyde process for refining, and the water in the propionic aldehyde can play the effect that suppresses the part side reaction, but produces a certain amount of propyl propionate by product inevitably.CN101225018A discloses the removal method of by product propyl propionate in a kind of preparing normal propyl alcohol by propionaldehyde hydrogenation technology, the water formation ternary azeotropic that makes n-propyl alcohol, propyl propionate and mend by an amount of moisturizing when thick propyl alcohol enters distillation system removes propyl propionate in lightness-removing column.This technology will certainly be lost a certain amount of n-propyl alcohol in removing the process of propyl propionate.
CN101225019A discloses the production technique of preparing normal propyl alcohol by propionaldehyde hydrogenation under a kind of copper zinc catalyst, and thick propyl alcohol removes light constituent and heavy constituent respectively through lightness-removing column and weight-removing column, obtains the product n-propyl alcohol.Do not show in this invention that the light constituent that removes is the concrete treatment process of hair oil.
Summary of the invention
Goal of the invention: the objective of the invention is at the deficiencies in the prior art, a kind of method of not losing the output of n-propyl alcohol and will adopt the by product propyl propionate in the preparing normal propyl alcohol by propionaldehyde hydrogenation technology to remove is provided.
Technical scheme: the removal method of propyl propionate in the preparing normal propyl alcohol by propionaldehyde hydrogenation technology of the present invention, the n-propyl alcohol that will contain propyl propionate feeds in the hydrolysis kettle and mixes with the alkaline matter that adds, heating, stir and in the still jacking row continuous still battery of hydrolysis kettle, wherein, temperature in the kettle control is at 95～115 ℃, distillation temperature control in still top is at 90～95 ℃, again still tops n-propyl alcohol carried out condensation, dewatering process obtains highly purified n-propyl alcohol.
Relatively good for distilling effect, one section rectifying section can be set on the top of hydrolysis kettle, still-process carries out in the rectifying section on hydrolysis kettle top.
Alkaline matter of the present invention is preferably sodium hydroxide solution, potassium hydroxide solution, solid oxidation sodium or solid oxidation potassium, can certainly select some other alkaline matter for use, but treatment effect is not best.
The mol ratio of sodium hydroxide described in the present invention or potassium hydroxide and propyl propionate is 1～2:1; The mol ratio of described solid oxidation sodium or solid oxidation potassium and described propyl propionate is 0.5～1:1.Alkaline matters such as certain sodium hydroxide or potassium hydroxide can add more more, but do not save economically, also can be less a little, but complete inadequately to the processing of propyl propionate.
The concentration of above-mentioned sodium hydroxide solution is preferably 20% to saturated solution, by percentage to the quality.Rarer solution can increase the time of follow-up dewatering process.
In like manner, the concentration of described potassium hydroxide solution also is preferably more than 20% to saturated solution, by percentage to the quality.
The present invention compared with prior art, its beneficial effect is: 1, the inventive method technology is simple, easy and simple to handle, the more important thing is and has improved n-propyl alcohol output, effectively reduces the wherein content of propyl propionate, save lightness-removing column and weight-removing column during n-propyl alcohol is refining simultaneously, greatly reduced energy consumption; The present invention is applicable to hydrogenation of propionaldehyde production n-propyl alcohol technology, also is applicable to the technology that butyraldehyde, valeraldehyde, isovaleric aldehyde hydrogenation are produced correspondent alcohol simultaneously; 2, after the inventive method was handled, the purity of n-propyl alcohol was than higher, and the propyl propionate content in the n-propyl alcohol is reduced to by original about 0.3% ~ 2.5% and is lower than 0.1%, took off the loss that can not cause n-propyl alcohol in the process of ester; 3, the inventive method is applicable to the light constituent in the traditional technology lightness-removing column simultaneously, and it is about 60% to contain n-propyl alcohol in the light constituent that lightness-removing column comes out, propyl propionate about 10%, water about 27% ~ 30%, after the inventive method processing, the content of propyl propionate is reduced to below 0.1%, and the purity of n-propyl alcohol is higher than 99%.
Description of drawings
Fig. 1 is the processing flow chart of the inventive method.
Embodiment
Below technical solution of the present invention is elaborated, but protection scope of the present invention is not limited to described embodiment.Following content and concentration are all by percentage to the quality.
Embodiment 1:Moisture propionic aldehyde from the ethene hydroformylation device mixes with hydrogen; gasification is by the tar trap; enter fixed-bed reactor by the bottom after removing the oil content in the reaction gas; 110 ~ 130 ℃ of temperature ins; reaction pressure 0.4 ~ 0.6MPa carries out hydrogenation reaction under the Cu-series catalyst effect, this reaction is thermopositive reaction; the heat that reaction produces is taken away by thermal oil, to keep the reaction hot(test)-spot temperature at 160 ~ 195 ℃.The material that comes out from reactor head ℃ removes separating tank through condenser condenses to 30 ~ 50, realizes separating of thick propyl alcohol and unreacting hydrogen in separating tank.After unreacting hydrogen left separating tank, part directly entered the pressurization of hydrogen pressure machine, recycle, and pressurization utilized after another part was then purified by pressure swing adsorption technique.Separating tank bottom then obtains thick propyl alcohol and anhydrates and separate degreasing technology.
According to the inventive method this thick propyl alcohol is carried out skimming treatment below: thick propyl alcohol and sodium hydroxide are fed hydrolysis kettle continuously, propyl propionate content 0.3% in the thick propyl alcohol, naoh concentration is 30%, sodium hydroxide and propyl propionate mol ratio are 2:1, to hydrolysis kettle heating, stirring, and continuous still battery, the still temperature control is at 95 ℃, the distillation tower top temperature is at 95 ℃, propyl propionate in the thick propyl alcohol issues the reaction of unboiled water solution at alkaline condition and generates Sodium Propionate, the overhead fraction n-propyl alcohol is through condensation, dewatering process, thus acquisition high purity n-propyl alcohol product.Propyl propionate content is 0.04% in the finished product n-propyl alcohol, and the purity of n-propyl alcohol is 99.93%.
Embodiment 2:The source of thick propyl alcohol is with embodiment 1, and difference is propyl propionate content 1% in the thick propyl alcohol.
According to the inventive method this thick propyl alcohol is carried out skimming treatment below, thick propyl alcohol and sodium oxide are added hydrolysis kettle, the naoh concentration that sodium oxide reaction back forms is about 40%, sodium hydroxide and propyl propionate mol ratio are 1.6:1, to hydrolysis kettle heating, stirring, and continuous still battery, the still temperature control is at 115 ℃, the distillation tower top temperature is at 92 ℃, propyl propionate in the thick propyl alcohol issues the reaction of unboiled water solution at alkaline condition and generates Sodium Propionate, the overhead fraction n-propyl alcohol is through condensation, dewatering process, thus acquisition high purity n-propyl alcohol product.Propyl propionate content is 0.08% in the finished product n-propyl alcohol, and the purity of n-propyl alcohol is 99.89%.
Embodiment 3:The source of thick propyl alcohol is with embodiment 1, and difference is propyl propionate content 1.8% in the thick propyl alcohol.
According to the inventive method this thick propyl alcohol is carried out skimming treatment below, thick propyl alcohol and potassium oxide are added hydrolysis kettle, the potassium hydroxide that potassium oxide reaction back forms is saturated solution, potassium hydroxide and propyl propionate mol ratio are 1:1, to hydrolysis kettle heating, stirring, and continuous still battery, the still temperature control is at 110 ℃, the distillation tower top temperature is at 94 ℃, propyl propionate in the thick propyl alcohol issues the reaction of unboiled water solution at alkaline condition and generates potassium propionate, the overhead fraction n-propyl alcohol is through condensation, dewatering process, thus acquisition high purity n-propyl alcohol product.Propyl propionate content is 0.05% in the finished product n-propyl alcohol, and the purity of n-propyl alcohol is 99.91%.
Embodiment 4:The source of thick propyl alcohol is with embodiment 1, and difference is propyl propionate content 2.5% in the thick propyl alcohol.
According to the inventive method this thick propyl alcohol is carried out skimming treatment below, thick propyl alcohol and potassium hydroxide are fed hydrolysis kettle continuously, concentration of potassium hydroxide is 20%, potassium hydroxide and propyl propionate mol ratio are 1.4:1, to hydrolysis kettle heating, stirring, and continuous still battery, the still temperature control is at 115 ℃, the distillation tower top temperature is at 90 ℃, propyl propionate in the thick propyl alcohol issues the reaction of unboiled water solution at alkaline condition and generates potassium propionate, the overhead fraction n-propyl alcohol is through condensation, dewatering process, thus acquisition high purity n-propyl alcohol product.Propyl propionate content is 0.1% in the finished product n-propyl alcohol, and the purity of n-propyl alcohol is 99.85%.
Embodiment 5:Adopt the synthetic propionic aldehyde of water-soluble rhodium phosphine catalyst, propionic aldehyde after the rectifying contains the water about 2% approximately, utilize the direct hydrogenation of this moisture propionic aldehyde to synthesize n-propyl alcohol, reduced the propionic aldehyde process for refining, and the water in the propionic aldehyde can play and suppress the part side reaction, but produces a certain amount of propyl propionate inevitably, forms ternary azeotropic with water and n-propyl alcohol in lightness-removing column, remove as light constituent, cause n-propyl alcohol to lose in a large number.It is about 60% to contain n-propyl alcohol in this light constituent, and propyl propionate is about 10%, water about 27% ~ 30%.
The present invention handles this light constituent, be that 35% potassium hydroxide feeds hydrolysis kettle continuously with the concentration of this light constituent and adding, the mol ratio of potassium hydroxide and propyl propionate is 2:1, to hydrolysis kettle heating, stirring, and continuous still battery, the still temperature control is at 114 ℃, the distillation tower top temperature is at 95 ℃, make propyl propionate wherein change into propyl alcohol and propionic salt fully, it is about 70% to obtain overhead fraction propyl alcohol content by distillation, and water-content is about 30%.Further carry out condensation, dehydration purification, i.e. n-propyl alcohol in the recyclable lightness-removing column.Propyl propionate content is 0.05% in the finished product n-propyl alcohol, and the purity of n-propyl alcohol is 99.87%.
As mentioned above, although represented and explained the present invention that with reference to specific preferred embodiment it shall not be construed as the restriction to the present invention self.Under the spirit and scope of the present invention prerequisite that does not break away from the claims definition, can make various variations in the form and details to it.
Claims (4)
1. the removal method of propyl propionate in the preparing normal propyl alcohol by propionaldehyde hydrogenation technology, it is characterized in that: the n-propyl alcohol that will contain propyl propionate feeds in the hydrolysis kettle and mixes with the alkaline matter that adds, heating, stir and in the still jacking row continuous still battery of hydrolysis kettle, wherein, described alkaline matter is sodium hydroxide solution, potassium hydroxide solution, solid oxidation sodium or solid oxidation potassium, temperature in the kettle control is at 95～115 ℃, distillation temperature control in still top is at 90～95 ℃, again still tops n-propyl alcohol carried out condensation, dewatering process obtains highly purified n-propyl alcohol.
2. the removal method of propyl propionate in the preparing normal propyl alcohol by propionaldehyde hydrogenation technology according to claim 1, it is characterized in that: the mol ratio of described sodium hydroxide or potassium hydroxide and propyl propionate is 1～2:1; The mol ratio of described solid oxidation sodium or solid oxidation potassium and described propyl propionate is 0.5～1:1.
3. the removal method of propyl propionate in the preparing normal propyl alcohol by propionaldehyde hydrogenation technology according to claim 1, it is characterized in that: the concentration of described sodium hydroxide solution is more than 20%, by percentage to the quality.
4. the removal method of propyl propionate in the preparing normal propyl alcohol by propionaldehyde hydrogenation technology according to claim 1, it is characterized in that: the concentration of described potassium hydroxide solution is more than 20%, by percentage to the quality.
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| CN 201110194172 CN102304019B (en) | 2011-07-12 | 2011-07-12 | Method for removing propyl propionate in process for preparing normal propyl alcohol by hydrogenating propionaldehyde |
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| CN 201110194172 CN102304019B (en) | 2011-07-12 | 2011-07-12 | Method for removing propyl propionate in process for preparing normal propyl alcohol by hydrogenating propionaldehyde |
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| CN102304019B true CN102304019B (en) | 2013-09-11 |
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| CN102887815B (en) * | 2012-07-25 | 2014-09-17 | 江苏九天高科技股份有限公司 | N-propanol refining technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866725A (en) * | 1997-12-11 | 1999-02-02 | Celanese International Corporation | Process for the production of n-propanol |
| CN101225018A (en) * | 2008-01-31 | 2008-07-23 | 淄博诺奥化工有限公司 | Method for removing byproduct propyl propionate during preparation process of n-propanol by hydrogenation of propionaldehyde |
| CN101225019A (en) * | 2008-01-31 | 2008-07-23 | 淄博诺奥化工有限公司 | Process for preparing n-propanol by hydrogenation of propionaldehyde with cu-zn catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866725A (en) * | 1997-12-11 | 1999-02-02 | Celanese International Corporation | Process for the production of n-propanol |
| CN101225018A (en) * | 2008-01-31 | 2008-07-23 | 淄博诺奥化工有限公司 | Method for removing byproduct propyl propionate during preparation process of n-propanol by hydrogenation of propionaldehyde |
| CN101225019A (en) * | 2008-01-31 | 2008-07-23 | 淄博诺奥化工有限公司 | Process for preparing n-propanol by hydrogenation of propionaldehyde with cu-zn catalyst |
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Effective date of registration: 20181227 Address after: Room 1129, 11th floor, Traffic Bureau Building, 95 Yingbin Avenue, Xinhua Street, Huadu District, Guangzhou City, Guangdong 510800 Patentee after: Guangzhou New Century New Energy Development Co., Ltd. Address before: 210047 Fangshui Road 168-095, Chemical Industry Park, Liuhe District, Nanjing City, Jiangsu Province Patentee before: Nanjing Rongxin Chemical Co., Ltd. |
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Effective date of registration: 20201211 Address after: 210047 -095, Fang Shui Road, Nanjing Chemical Industrial Park, Nanjing, Jiangsu, China, 168 Patentee after: NANJING RONGXIN CHEMICAL INDUSTRIAL Co.,Ltd. Address before: Room 1129, 11th floor, Traffic Bureau Building, 95 Yingbin Avenue, Xinhua Street, Huadu District, Guangzhou City, Guangdong 510800 Patentee before: GUANGZHOU XINSHIJI NEW ENERGY DEVELOPMENT Co.,Ltd. |
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