CN109651084B - Method for treating aqueous solution of 3-hydroxypropanal mixture containing carboxylic acid and metal cation and application thereof - Google Patents
Method for treating aqueous solution of 3-hydroxypropanal mixture containing carboxylic acid and metal cation and application thereof Download PDFInfo
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- 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
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- C07C29/141—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 a —CHO group with hydrogen or hydrogen-containing gases
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Abstract
The present invention relates to a process for treating an aqueous solution of a mixture of 3-hydroxypropanal containing carboxylic acid and metal cations and a process for preparing 1, 3-propanediol comprising: the 3-hydroxypropionaldehyde mixture aqueous solution is contacted with an acidic medium and then contacted with an alkaline medium, and the treated 3-hydroxypropionaldehyde mixture aqueous solution is hydrogenated to prepare the 1, 3-propanediol. The method for treating the 3-hydroxypropionaldehyde mixture aqueous solution containing the carboxylic acid and the metal cations greatly improves the recovery rate of the 3-hydroxypropionaldehyde, the recovery rate can reach more than 99 percent, the influence of impurities in the 3-hydroxypropionaldehyde aqueous solution on a hydrogenation catalyst is effectively reduced, and the service life of the catalyst is prolonged.
Description
Technical Field
The invention relates to the field of raw material treatment processes, in particular to a method for treating a 3-hydroxypropanal mixture aqueous solution containing carboxylic acid and metal cations and application thereof.
Background
1, 3-propanediol is an important chemical raw material and is used for polymerizing with terephthalic acid to obtain PTT polyester. The PTT polyester has excellent performance, good rebound resilience, easy processability, easy dyeing, fluffiness and the like, and has wide market prospect.
Two-step processes are known to prepare PDO: (1) the ethylene oxide is subjected to hydroformylation reaction to generate an intermediate 3-hydroxy propionaldehyde; (2) hydrogenating the 3-hydroxypropionaldehyde to obtain the 1, 3-propanediol. The following characteristics exist in the hydrogenation product in the method for preparing 1, 3-propylene glycol by hydrogenating the intermediate 3-hydroxypropionaldehyde:
(1) the 3-hydroxypropionaldehyde is active in chemical property, and can generate organic acids such as 3-hydroxypropionic acid, acrylic acid and the like in the hydroformylation process;
(2) dissolving part of hydroformylation catalyst in the aqueous solution in the process of separating the 3-hydroxypropionaldehyde aqueous solution;
the pretreatment of the 3-hydroxypropionaldehyde aqueous solution has obvious influence on the subsequent hydrogenation and separation.
In the patent U.S.2004/0087819, alkali liquor is added to neutralize the organic acid in the aqueous solution of 3-hydroxypropanal, and although the process can effectively neutralize the organic acid in the aqueous solution of 3-hydroxypropanal, the addition of alkali liquor is not sufficient to stir, so that the pH distribution of the aqueous solution is not uniform, and aldehydes are easily condensed to form acetal or aldol condensation products under the condition of high pH, thereby reducing the yield of the final 1, 3-propanediol and affecting the rectification of the products.
The key to the process is whether the aqueous 3-hydroxypropanal mixture is pretreated to produce aldehyde condensation and loss.
Disclosure of Invention
Aiming at the technical defects of the prior art, the invention provides a method for treating a 3-hydroxypropanal mixture aqueous solution containing carboxylic acid and metal cations and a method for preparing 1, 3-propanediol, wherein the loss of the 3-hydroxypropanal is effectively reduced by the treatment method, the service life and the stability of a hydrogenation catalyst are prolonged, and the method has a great industrial application value.
The invention is realized by the following technical scheme:
a process for treating an aqueous solution of a mixture of 3-hydroxypropanal comprising a carboxylic acid and a metal cation, comprising the steps of:
1) contacting the 3-hydroxypropionaldehyde mixture aqueous solution with an acidic medium to obtain a first 3-hydroxypropionaldehyde-containing mixture aqueous solution;
2) contacting the first aqueous mixture solution containing 3-hydroxypropanal with an alkaline medium to obtain a second aqueous mixture solution containing 3-hydroxypropanal.
The 3-hydroxypropionaldehyde mixture water solution containing carboxylic acid and metal cations is a mixture water solution obtained by subjecting ethylene oxide to hydroformylation reaction, and mainly comprises the 3-hydroxypropionaldehyde, the carboxylic acid and the metal cations, wherein the carboxylic acid accounts for 0.1-5 wt%, and the metal cations account for less than 3 mmol/L.
Preferably, in step 1), the acidic medium is an acidic zeolite or an acidic cation exchange resin.
More preferably, the acidic cation exchange resin is a carboxylic acid-based cation exchange resin and/or a sulfonic acid-based cation exchange resin. More preferably a carboxylic acid-based cation exchange resin. For example, the acidic cation exchange resin is selected from one or more of SQD-80, D113, Amberlyst-15, C150 and D113.
Preferably, in step 2), the basic medium is a metal oxide or a basic anion exchange resin.
More preferably, the basic anion exchange resin is an organic amine anion exchange resin and/or a quaternary ammonium anion exchange resin. More preferably, the organic amine-based anion exchange resin. For example, the basic anion exchange resin is selected from one or more of D301, D311, 213 and CTA190 Plus.
More preferably, the metal oxide is Al2O3。
Preferably, one or more of the following technical features are also included:
1) in the step 1), the pH value of the 3-hydroxypropionaldehyde mixture aqueous solution is 3-5, such as 3-3.6, 3.6-3.9, 3.9-4.1, 4.1-4.5, 4.5-4.8 or 4.8-5, and more preferably 3.5-4.5;
2) in step 2), the pH value of the second aqueous solution of the mixture containing 3-hydroxypropanal is 5 to 6, such as 5 to 5.1, 5.1 to 5.2, 5.2 to 5.3, 5.3 to 5.6, 5.6 to 5.85, 5.85 to 5.9, or 5.9 to 6, more preferably 5 to 5.5;
3) based on the 3-hydroxypropionaldehyde mixture aqueous solution, the liquid hourly space velocity in the step 1) is 1-6h-1E.g. 1-2h-1、2-2.5h-1、2.5-4h-1Or 4-6h-1More preferably 1 to 3 hours-1；
4) Based on the first mixture water solution containing 3-hydroxypropionaldehyde, the liquid hourly space velocity in the step 2) is 1-8h-1E.g. 1-2h-1、2-2.5h-1、2.5-4h-1、4-6h-1Or 6 to 8h-1More preferably 2 to 4 hours-1；
5) The treatment pressure in step 1) and step 2) is 0.1-2MPa, such as 0.1-0.5MPa, 0.5-1MPa or 1-2MPa, more preferably 0.1-0.5 MPa;
6) the treatment temperature in step 1) and step 2) is 20-60 deg.C, such as 20-25 deg.C, 25-30 deg.C, 30-40 deg.C, 40-50 deg.C or 50-60 deg.C, more preferably 20-30 deg.C;
7) in step 1), the concentration of 3-hydroxypropanal in the aqueous 3-hydroxypropanal mixture is 7 to 30 wt%, such as 7 to 11 wt%, 11 to 20 wt%, 20 to 22 wt%, 22 to 25 wt%, or 25 to 30 wt%, more preferably 15 to 25 wt%;
8) the carboxylic acid in the 3-hydroxypropionaldehyde mixture aqueous solution is one or a mixture of more of C2-C5 carboxylic acids, and 3-hydroxypropionic acid and/or acrylic acid are more preferable.
Preferably, the metal cation in the aqueous 3-hydroxypropanal mixture is cobalt ion.
In a second aspect, the present invention provides a process for the preparation of 1, 3-propanediol comprising the steps of:
1) subjecting an aqueous solution of a mixture of 3-hydroxypropanal comprising a carboxylic acid and a metal cation to a process as described in any one of the preceding claims;
2) hydrogenating the 3-hydroxypropionaldehyde mixture aqueous solution treated in the step 1) to obtain the 1, 3-propanediol.
The invention has the beneficial effects that: the 3-hydroxypropionaldehyde mixture aqueous solution is contacted with an acidic medium and then contacted with an alkaline medium, so that the condensation of the 3-hydroxypropionaldehyde is reduced, the recovery rate of the 3-hydroxypropionaldehyde is greatly improved and can reach over 99 percent, the 3-hydroxypropionaldehyde mixture aqueous solution obtained by treatment is subjected to hydrogenation to prepare the 1, 3-propanediol, the influence of metal ions and organic acid on a hydrogenation catalyst is reduced, the service life of the catalyst is prolonged, and the economic benefit is improved.
Drawings
FIG. 1 is a process flow diagram of the process of the present invention for preparing 1, 3-propanediol.
Reference numerals are as follows:
c-1: an acidic medium treatment section;
c-2: an alkaline medium treatment section;
r-101: a first hydrogenation section;
r-102: a second hydrogenation section.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Examples 1 to 13
1) Contacting a 3-hydroxypropionaldehyde mixture aqueous solution obtained by subjecting ethylene oxide to hydroformylation reaction with an acidic medium (placed in a fixed bed reactor C-1) to obtain a first 3-hydroxypropionaldehyde-containing mixture aqueous solution;
2) contacting the first aqueous solution of the mixture containing 3-hydroxypropionaldehyde with an alkaline medium (placed in a fixed bed reactor C-2) to obtain a second aqueous solution of the mixture containing 3-hydroxypropionaldehyde;
3) carrying out two-stage hydrogenation on the second mixture water solution containing 3-hydroxypropionaldehyde, wherein the hydrogenation process conditions are as follows: first-stage reaction temperature: 55 ℃; second-stage reaction temperature: 120 ℃; liquid hourly space velocity: 0.8h-1(ii) a The ratio of hydrogen to aldehyde: 30, of a nitrogen-containing gas; 3-hydroxypropanal concentration: 18 wt%; hydrogenation catalyst: a nickel-based catalyst.
Step 1) and step 2) are carried out at 0.1MPa, 25 ℃ and 2h-1In the case of (2), pretreatment was carried out, and different types of media were used, and the results are shown in tables 1 and 2.
TABLE 1 comparison of results in different acidic media
Note: hydrogenation of 13-hydroxypropanal to 1, 3-propanediol
2 the service life of the catalyst is based on that the yield of the 1, 3-propylene glycol is more than or equal to 90 percent.
TABLE 2 comparison of results in different alkaline media
Note: hydrogenation of 13-hydroxypropanal to 1, 3-propanediol
2 the service life of the catalyst is based on that the yield of the 1, 3-propylene glycol is more than or equal to 90 percent.
Example fourteen
1) Contacting a 3-hydroxypropionaldehyde mixture aqueous solution obtained by subjecting ethylene oxide to hydroformylation reaction with an acidic medium D113 (placed in a fixed bed reactor C-1) to obtain a first 3-hydroxypropionaldehyde-containing mixture aqueous solution; the cobalt ion of the 3-hydroxypropionaldehyde mixture aqueous solution obtained by the hydroformylation reaction of the ethylene oxide is 1.58mmol/L, the pH is 3.9, and the concentration of the 3-HPA is 20 wt%;
2) contacting the first aqueous solution containing the 3-hydroxypropanal mixture with an alkaline medium D301 (placed in a fixed bed reactor C-2) to obtain a second aqueous solution containing the 3-hydroxypropanal mixture;
step 1) and step 2) are carried out at 0.1MPa, 30 ℃ and 2.5h-1Carrying out pretreatment;
after the pretreatment of the step 1) and the step 2), the recovery rate of the 3-hydroxypropionaldehyde is 99.89%, the cobalt ion content is 0.018mmol/L, and the pH value is 5.1;
3) subjecting the second aqueous solution containing the 3-hydroxypropionaldehyde mixture to two-stage hydrogenation: first-stage reaction temperature: 55 ℃; second-stage reaction temperature: 120 ℃; liquid hourly space velocity: 0.8h-1(ii) a The ratio of hydrogen to aldehyde: 30, of a nitrogen-containing gas; hydrogenation catalyst: a nickel-based catalyst; the yield of the 1, 3-propylene glycol is more than or equal to 95 percent, and the service life of the catalyst is more than 500 h.
Example fifteen
1) Contacting a 3-hydroxypropionaldehyde mixture aqueous solution obtained by subjecting ethylene oxide to hydroformylation reaction with an acidic medium D113 (placed in a fixed bed reactor C-1) to obtain a first 3-hydroxypropionaldehyde-containing mixture aqueous solution; the cobalt ion of the 3-hydroxypropionaldehyde mixture aqueous solution obtained by the hydroformylation reaction of the ethylene oxide is 1.58mmol/L, the pH is 3.9, and the concentration of the 3-HPA is 20 wt%;
2) contacting the first aqueous solution containing the 3-hydroxypropionaldehyde mixture with an alkaline medium D301 (placed in a fixed bed reactor C-2) to obtain a second aqueous solution containing the 3-hydroxypropionaldehyde mixture;
step 1) and step 2) are carried out at 0.1MPa, 30 ℃ and 6h-1In the case of (3), a pretreatment is performed;
after the pretreatment of the step 1) and the step 2), the recovery rate of the 3-hydroxypropionaldehyde is 99.83 percent, the cobalt ion is 0.78mmol/L, and the pH value is 5.1;
3) subjecting the second aqueous solution containing the 3-hydroxypropanal mixture to two-stage hydrogenation: first-stage reaction temperature: 55 ℃; second-stage reaction temperature: 120 ℃; liquid hourly space velocity: 0.8h-1(ii) a The ratio of hydrogen to aldehyde: 30, of a nitrogen-containing gas; hydrogenation catalyst: a nickel-based catalyst; the yield of the 1, 3-propylene glycol is more than or equal to 95 percent, the service life of the catalyst is as follows: 192 h.
Example sixteen
1) Contacting a 3-hydroxypropionaldehyde mixture aqueous solution obtained by subjecting ethylene oxide to hydroformylation reaction with an acidic medium D113 (placed in a fixed bed reactor C-1) to obtain a first 3-hydroxypropionaldehyde-containing mixture aqueous solution; the cobalt ion of the 3-hydroxypropionaldehyde mixture aqueous solution obtained by the hydroformylation reaction of the ethylene oxide is 1.78mmol/L, the pH is 3.9, and the concentration of the 3-HPA is 20 wt%;
2) contacting the first aqueous solution containing the 3-hydroxypropionaldehyde mixture with an alkaline medium D301 (placed in a fixed bed reactor C-2) to obtain a second aqueous solution containing the 3-hydroxypropionaldehyde mixture;
step 1) and step 2) are carried out at 0.5MPa, 40 ℃ and 4h-1Carrying out pretreatment;
after the pretreatment of the step 1) and the step 2), the recovery rate of the 3-hydroxypropionaldehyde is 90.12 percent, the cobalt ion is 0.36mmol/L, and the pH value is 5.2;
3) subjecting the second aqueous solution containing the 3-hydroxypropanal mixture to two-stage hydrogenation: first-stage reaction temperature: 55 ℃; second-stage reaction temperature: 120 ℃; liquid hourly space velocity: 0.8h-1(ii) a The ratio of hydrogen to aldehyde: 30, of a nitrogen-containing gas; hydrogenation catalyst: a nickel-based catalyst; the yield of the 1, 3-propylene glycol is more than or equal to 95 percent, the service life of the catalyst is as follows: 160 h.
Example seventeen
1) Contacting a 3-hydroxypropionaldehyde mixture aqueous solution obtained by subjecting ethylene oxide to hydroformylation reaction with an acidic medium D113 (placed in a fixed bed reactor C-1) to obtain a first 3-hydroxypropionaldehyde-containing mixture aqueous solution; the cobalt ion of the 3-hydroxypropionaldehyde mixture aqueous solution obtained by the hydroformylation reaction of the ethylene oxide is 1.82mmol/L, the pH is 4.8, and the concentration of the 3-HPA is 25 wt%;
2) contacting the first aqueous solution containing the 3-hydroxypropanal mixture with an alkaline medium D301 (placed in a fixed bed reactor C-2) to obtain a second aqueous solution containing the 3-hydroxypropanal mixture;
step 1) and step 2) are carried out at 1.0MPa, 40 ℃ and 4h-1Carrying out pretreatment;
after the pretreatment of the step 1) and the step 2), the recovery rate of the 3-hydroxypropionaldehyde is 98.76 percent, the cobalt ion is 0.65mmol/L, and the pH value is 5.6;
3) subjecting the second aqueous solution containing the 3-hydroxypropanal mixture to two-stage hydrogenation: first-stage reaction temperature: 55 ℃; second-stage reaction temperature: 120 ℃; liquid hourly space velocity: 0.8h-1(ii) a The ratio of hydrogen to aldehyde: 30, of a nitrogen-containing gas; hydrogenation catalyst: a nickel-based catalyst; the yield of the 1, 3-propylene glycol is more than or equal to 95 percent, the service life of the catalyst is as follows: 132 h.
EXAMPLE eighteen
1) Contacting a 3-hydroxypropionaldehyde mixture aqueous solution obtained by subjecting ethylene oxide to hydroformylation reaction with an acidic medium D113 (placed in a fixed bed reactor C-1) to obtain a first 3-hydroxypropionaldehyde-containing mixture aqueous solution; the cobalt ion of the 3-hydroxypropionaldehyde mixture aqueous solution obtained by the hydroformylation reaction of the ethylene oxide is 1.76mmol/L, the pH is 4.5, and the concentration of the 3-HPA is 22 wt%;
2) contacting the first aqueous solution containing the 3-hydroxypropionaldehyde mixture with an alkaline medium D301 (placed in a fixed bed reactor C-2) to obtain a second aqueous solution containing the 3-hydroxypropionaldehyde mixture;
step 1) and step 2) are carried out at 2.0MPa, 30 ℃ and 4h-1Carrying out pretreatment;
after the pretreatment of the step 1) and the step 2), the recovery rate of the 3-hydroxypropionaldehyde is 95.23 percent, the cobalt ion is 0.71mmol/L, and the pH value is 5.9;
3) subjecting the second aqueous solution containing the 3-hydroxypropanal mixture to two-stage hydrogenation: first-stage reaction temperature: 55 ℃; second-stage reaction temperature: 120 deg.C(ii) a Liquid hourly space velocity: 0.8h-1(ii) a The ratio of hydrogen to aldehyde: 30, of a nitrogen-containing gas; hydrogenation catalyst: a nickel-based catalyst; the yield of the 1, 3-propylene glycol is more than or equal to 94 percent, the service life of the catalyst is as follows: 154 h.
Example nineteen
1) Contacting a 3-hydroxypropionaldehyde mixture aqueous solution obtained by subjecting ethylene oxide to hydroformylation reaction with an acidic medium D113 (placed in a fixed bed reactor C-1) to obtain a first 3-hydroxypropionaldehyde-containing mixture aqueous solution; the cobalt ion of the 3-hydroxypropionaldehyde mixture aqueous solution obtained by the hydroformylation reaction of the ethylene oxide is 1.76mmol/L, the pH is 4.1, and the concentration of the 3-HPA is 22 wt%;
2) contacting the first aqueous solution containing the 3-hydroxypropanal mixture with an alkaline medium D301 (placed in a fixed bed reactor C-2) to obtain a second aqueous solution containing the 3-hydroxypropanal mixture;
step 1) and step 2) are carried out at 1.0MPa, 50 ℃ and 4h-1Carrying out pretreatment;
after the pretreatment of the step 1) and the step 2), the recovery rate of the 3-hydroxypropionaldehyde is 95.27 percent, the cobalt ion is 0.43mmol/L, and the pH value is 5.2;
3) subjecting the second aqueous solution containing the 3-hydroxypropanal mixture to two-stage hydrogenation: first-stage reaction temperature: 55 ℃; second-stage reaction temperature: 120 ℃; liquid hourly space velocity: 0.8h-1(ii) a The ratio of hydrogen to aldehyde: 30, of a nitrogen-containing gas; hydrogenation catalyst: a nickel-based catalyst; the yield of the 1, 3-propylene glycol is more than or equal to 94 percent, the service life of the catalyst is as follows: 136 h.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (3)
1. A process for treating an aqueous solution of a mixture of 3-hydroxypropanal containing a carboxylic acid and a metal cation, comprising the steps of:
1) contacting the 3-hydroxypropionaldehyde mixture aqueous solution with an acidic medium to obtain a first 3-hydroxypropionaldehyde-containing mixture aqueous solution; the acidic medium is acidic zeolite or acidic cation exchange resin; the pH value of the 3-hydroxypropionaldehyde mixture aqueous solution is 3.5-4.5; based on the 3-hydroxypropionaldehyde mixture aqueous solution, the liquid hourly space velocity in the step 1) is 1-2h-1(ii) a The carboxylic acid in the 3-hydroxypropanal mixture aqueous solution is C2-C5One or a mixture of more of carboxylic acids; the acidic cation exchange resin is carboxylic acid cation exchange resin and/or sulfonic acid cation exchange resin; the concentration of the 3-hydroxypropionaldehyde in the 3-hydroxypropionaldehyde mixture aqueous solution is 7-11 wt%;
2) contacting the first aqueous solution of the mixture containing 3-hydroxypropanal with an alkaline medium to obtain a second aqueous solution of the mixture containing 3-hydroxypropanal; the alkaline medium is alkaline anion exchange resin; the basic anion exchange resin is organic amine anion exchange resin and/or quaternary ammonium anion exchange resin; the pH value of the second aqueous solution of the mixture containing 3-hydroxypropionaldehyde is 5-6; based on the first mixture water solution containing 3-hydroxypropionaldehyde, the liquid hourly space velocity in the step 2) is 1-8h-1；
The treatment pressure of the step 1) and the step 2) is 0.1-2 Mpa;
the treatment temperature of the step 1) and the step 2) is 20-60 ℃.
2. The process of claim 1, wherein the metal cation in the aqueous 3-hydroxypropanal mixture is cobalt ion.
3. A process for preparing 1, 3-propanediol comprising the steps of:
1) subjecting an aqueous solution of a mixture of 3-hydroxypropanal containing a carboxylic acid and a metal cation to the process of claim 1 or 2;
2) hydrogenating the 3-hydroxypropionaldehyde mixture aqueous solution treated in the step 1) to obtain the 1, 3-propanediol.
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