CN112892584B - Catalyst for preparing 3-hydroxypropionaldehyde by acrolein hydration, preparation method and application thereof - Google Patents
Catalyst for preparing 3-hydroxypropionaldehyde by acrolein hydration, preparation method and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
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Abstract
The application discloses a catalyst for preparing 3-hydroxypropionaldehyde by acrolein hydration, a preparation method and application thereof. The catalyst is applied to the reaction of preparing 3-hydroxypropionaldehyde by acrolein hydration, can effectively inhibit the occurrence of side reaction, and improves the selectivity of a target product and the stability of the catalyst.
Description
Technical Field
The application relates to a method for preparing 3-hydroxypropionaldehyde by acrolein hydration, belonging to the field of catalyst materials.
Background
1, 3-propylene glycol is an important chemical raw material and is mainly used for producing chemical products such as polyester, plasticizer, polyurethane and the like. The most predominant use of 1, 3-propanediol is in the polymerization with terephthalic acid to form polytrimethylene terephthalate (PTT). PTT is a novel thermoplastic polyester material with excellent performance, and can be widely applied to the fields of engineering plastics, textile fibers, carpets and the like. At present, the main production methods of 1, 3-propanediol include biological fermentation, glycerol hydrogenation, acrolein hydration and hydrogenation. Wherein, the preparation of 3-hydroxypropionaldehyde by acrolein hydration is an important step in the preparation of 1, 3-propylene glycol by acrolein hydration hydrogenation.
Patent US5015789 discloses a process for the hydration of acrolein with a chelating ion exchange resin as catalyst, in which the selectivity of 3-hydroxypropanal can reach 82% at an acrolein conversion of 40.8%. In addition to ion exchange resin catalysts, molecular sieves have also been used for the hydration of acrolein. However, the molecular sieve used as the acrolein hydration catalyst at present has the defects of low reaction conversion rate, low selectivity, poor stability and the like, and the performance of the catalyst needs to be further optimized and improved.
Disclosure of Invention
According to an aspect of the present application, there is provided a catalyst for preparing 3-hydroxypropanal by hydration of acrolein, which can effectively suppress the occurrence of side reactions, improve the selectivity of a target product, and improve the stability of the catalyst, when used in a reaction for preparing 3-hydroxypropanal by hydration of acrolein.
The catalyst for preparing 3-hydroxypropionaldehyde by acrolein hydration contains a metal-modified silicon-aluminum molecular sieve.
Optionally, the silica-alumina molecular sieve has a silica-alumina ratio of 15 to 30.
Optionally, the loading amount of metal in the catalyst for preparing 3-hydroxypropionaldehyde by acrolein hydration is 0.3-3 wt%.
Preferably, the metal loading in the catalyst for preparing 3-hydroxypropanal by acrolein hydration is 0.5-1.5 wt%.
Optionally, the metal is selected from at least one of alkali metals, alkaline earth metals, transition metals.
Optionally, the silicoaluminophosphate molecular sieve comprises one of a ZSM-5 molecular sieve, a Y-type molecular sieve, a Beta molecular sieve.
Preferably, the alkali metal comprises at least one of sodium and potassium; the alkaline earth metal comprises at least one of magnesium and calcium; the transition metal comprises at least one of manganese, iron, cobalt, nickel, copper and zinc.
Optionally, the catalyst for preparing 3-hydroxypropanal by acrolein hydration contains a binder; the content of the binder in the catalyst for preparing the 3-hydroxypropionaldehyde by acrolein hydration is 60-70%.
Preferably, the binder is alumina.
According to another aspect of the present application, there is also provided a method of preparing a catalyst for preparing 3-hydroxypropanal by hydration of acrolein, the method comprising:
mixing a raw material containing a silicon-aluminum molecular sieve with a solution containing metal ions, and carrying out ion exchange to obtain the catalyst for preparing the 3-hydroxypropionaldehyde by acrolein hydration.
Alternatively, the method for preparing the catalyst for preparing 3-hydroxypropanal by acrolein hydration at least comprises the following steps:
(1) mixing a silicon-aluminum molecular sieve with an ammonium salt or inorganic acid solution, carrying out ion exchange, filtering the molecular sieve, drying the molecular sieve for 10-20 hours at 100-120 ℃, and then roasting the molecular sieve for 3-6 hours at 500-600 ℃;
(2) mixing the sample obtained in the step (1) with a binder and nitric acid, extruding into strips, forming, drying at 100-120 ℃ for 10-20 h, roasting at 500-600 ℃ for 3-6 h, crushing the roasted strip catalyst, and sieving to obtain a granular sample;
(3) preparing a solution containing metal ions, mixing the solution with a granular sample, carrying out ion exchange at the temperature of 80-95 ℃ for 20-60 min, filtering the sample, drying the sample at the temperature of 100-120 ℃ for 10-20 h, and then roasting the sample at the temperature of 500-600 ℃ for 3-6 h to obtain the catalyst.
The purpose of the step (1) is to obtain the hydrogen type molecular sieve.
Alternatively, a catalyst of a target loading may be prepared by repeating step (3).
The application also provides a method for preparing 3-hydroxypropionaldehyde by acrolein hydration, which at least comprises the following steps: the raw material containing acrolein and water is contacted with a catalyst for reaction to obtain 3-hydroxy propionaldehyde; wherein the catalyst comprises a metal-modified silicoaluminophosphate molecular sieve.
Alternatively, the catalyst is selected from at least one of the above-mentioned catalyst for preparing 3-hydroxypropanal by hydration of acrolein and the catalyst for preparing 3-hydroxypropanal by hydration of acrolein prepared according to the above-mentioned method.
Optionally, the reaction conditions are: the reaction temperature is 40-80 ℃; the mass ratio of the acrolein to the water in the raw materials is 10: 90-30: 70; the mass space velocity of the acrolein is 0.5-3.0 h-1。
Preferably, the mass ratio of the acrolein to the water in the raw material is 15: 85-25: 75.
Preferably, the reaction conditions are: the reaction temperature is 50-70 ℃.
Optionally, the raw materials also comprise a polymerization inhibitor; the polymerization inhibitor comprises at least one of hydroquinone, p-hydroxyanisole and phenothiazine, and the mass ratio of the polymerization inhibitor to the acrolein is 0.5: 100-3: 100.
Optionally, the reaction is carried out in a reactor; the reactor is a fixed bed reactor.
The following describes a specific procedure for the preparation of 3-hydroxypropanal by hydration of acrolein in a fixed bed reactor: putting catalyst particles into a fixed bed tubular reactor, raising the temperature to 50-70 ℃, then introducing an acrolein aqueous solution containing 0.02-0.9% polymerization inhibitor and having a concentration of 15-30 wt% into the reactor, wherein the mass space velocity of the acrolein in the reaction is 0.5-2.0 h-1And cooling and collecting the reaction effluent.
Optionally, the composition of the product is analyzed using a gas chromatograph.
The beneficial effects that this application can produce include: the molecular sieve is an important solid acid catalyst and can be used for catalyzing hydration reaction of carbon-carbon double bonds. For acrolein hydration reaction, the molecular sieve catalyst has strong acidity, so that various side reactions such as oligomerization and the like are easily catalyzed in the acrolein hydration reaction, and the reaction selectivity is reduced. The oligomers formed by the side reactions cover the active sites of the catalyst, which makes the catalyst less stable. The acid center strength and distribution of the molecular sieve catalyst modified by alkali metal, alkaline earth metal and transition metal can effectively inhibit the occurrence of side reaction and improve the selectivity of target products and the stability of the catalyst.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and solvents in the examples of the present application were all purchased commercially.
Wherein the molecular sieves were purchased from Nankai catalyst works.
The gas chromatograph used in this application is agilent 7890B.
The conversion, selectivity in the examples of the present application are calculated as follows:
EXAMPLE 1 preparation of the catalyst
30g of ZSM-5 molecular Sieve (SiO)2/Al2O325) was added to 150ml of a 1M ammonium chloride aqueous solution for ion exchange. After three times of exchange, the molecular sieve is filtered, dried for 12 hours at 120 ℃ and roasted for 4 hours at 500 ℃. The obtained sample was mixed with 70g of alumina and 20g of concentrated nitric acid (68% in concentration), extruded and molded, and then the extruded sample was dried at 120 ℃ for 12 hours and baked at 500 ℃ for 4 hours. After roasting, the strip catalyst is crushed and sieved to obtain a granular sample. The prepared granular sample was ion-exchanged in 150ml of 0.5M aqueous sodium nitrate solution at 90 ℃ for 30 min. Then the sample is filtered, dried for 12 hours at 120 ℃, and roasted for 4 hours at 500 ℃ to prepare the catalyst A.
EXAMPLE 2 preparation of the catalyst
The metal ion solution used in example 2 was a potassium nitrate solution, the other reaction steps and conditions were the same as those in example 1, and the obtained catalyst was designated as catalyst B.
EXAMPLE 3 preparation of the catalyst
The metal ion solution used in example 3 was a magnesium nitrate solution, the other reaction steps and conditions were the same as in example 1, and the obtained catalyst was designated as catalyst C.
EXAMPLE 4 preparation of the catalyst
The metal ion solution used in example 4 was calcium nitrate solution, the other reaction steps and conditions were the same as in example 1, and the obtained catalyst was designated as catalyst D.
EXAMPLE 5 preparation of the catalyst
The metal ion solution used in example 5 was a potassium nitrate solution, the other reaction steps and conditions were the same as those in example 1, and the obtained catalyst was designated as catalyst E.
EXAMPLE 6 preparation of the catalyst
The metal ion solution used in example 6 was an iron nitrate solution, the other reaction steps and conditions were the same as in example 1, and the obtained catalyst was designated as catalyst F.
EXAMPLE 7 preparation of the catalyst
The molecular sieve used in example 7 was a Y-type molecular Sieve (SiO)2/Al2O33.7), the other reaction steps and conditions were the same as in example 5, and the obtained catalyst was designated as catalyst G.
EXAMPLE 8 preparation of the catalyst
The molecular sieve used in example 8 was Beta molecular Sieve (SiO)2/Al2O3Equal to 10), the other reaction steps and conditions were the same as in example 5, and the obtained catalyst was denoted as catalyst H.
EXAMPLE 9 preparation of the catalyst
30g of ZSM-5 molecular Sieve (SiO)2/Al2O325) was added to 150ml of a 1M hydrochloric acid solution for ion exchange. After three times of exchange, the molecular sieve is filtered, dried for 12 hours at 120 ℃ and roasted for 4 hours at 500 ℃. Mixing the obtained sample with 70g of alumina and 20g of concentrated nitric acid, extruding and forming, drying the extruded sample at 120 ℃ for 12 hours, and roasting at 500 ℃ for 4 hours. After roasting, the strip catalyst is crushed and sieved to obtain a granular sample. The prepared granular samples were ion-exchanged in 150ml of a 1.0M potassium nitrate solution for 30min at an ion-exchange temperature of 90 ℃. Then the sample is filtered, dried for 12 hours at 120 ℃, and roasted for 4 hours at 500 ℃ to prepare the catalyst I.
EXAMPLE 10 preparation of catalyst
30g of ZSM-5 molecular Sieve (SiO)2/Al2O325) was added to 150ml of 1M ammonium chloride solution for ion exchange. After three times of exchange, the molecular sieve is filtered, dried for 12 hours at 120 ℃ and roasted for 4 hours at 500 ℃. The resulting sample was mixed with 70g of aluminaMixing with 20g of concentrated nitric acid, extruding and forming, drying the extruded sample at 120 ℃ for 12 hours, and roasting at 500 ℃ for 4 hours. After roasting, the strip catalyst is crushed and sieved to obtain a granular sample. The prepared granular samples were ion-exchanged in 150ml of a 1.0M potassium nitrate solution for 30min at 90 ℃ for two total exchanges. Then the sample is filtered, dried for 12 hours at 120 ℃ and roasted for 4 hours at 500 ℃ to prepare the catalyst J.
EXAMPLE 11 preparation of the catalyst
30g of ZSM-5 molecular Sieve (SiO)2/Al2O325) was added to 150ml of a 1M ammonium chloride solution for ion exchange. After three times of exchange, the molecular sieve is filtered, dried for 12 hours at 120 ℃ and roasted for 4 hours at 500 ℃. The obtained sample is mixed with 70g of alumina and 20g of concentrated nitric acid, extruded into strips and molded, and then the extruded sample is dried at 120 ℃ for 12 hours and roasted at 500 ℃ for 4 hours. After roasting, the strip catalyst is crushed and sieved to obtain a granular sample. The prepared granular samples were ion-exchanged in 150ml of a 1.0M potassium nitrate solution for 30min at an ion-exchange temperature of 90 ℃ for three times. Then the sample is filtered, dried for 12 hours at 120 ℃ and roasted for 4 hours at 500 ℃ to prepare the catalyst K. The content of metallic potassium in the catalyst was 1.68 wt%.
Example 12 testing of Metal loadings in catalysts
X-ray fluorescence elemental analysis tests were performed on the catalysts A to K obtained in examples 1 to 11, and the results are summarized in Table 1.
TABLE 1 Supports of metals in catalysts in examples 1-11
| Catalyst numbering | Amount of support (wt%) |
| A | 0.39 |
| B | 0.37 |
| C | 0.36 |
| D | 0.33 |
| E | 0.34 |
| F | 0.34 |
| G | 0.45 |
| H | 0.47 |
| I | 0.76 |
| J | 1.35 |
| K | 1.68 |
Example 13 catalytic Performance testing of the catalyst
1g of catalyst A particles are charged into a fixed bed tubular reactor, the temperature is raised to 350 ℃ for pretreatment for 1 hour, and the reactor temperature is lowered to 60 ℃. Introducing an acrolein aqueous solution with the concentration of 20 wt% and containing 0.2% of hydroquinone polymerization inhibitor into a reactor for reaction, wherein the mass space velocity of the acrolein is 1.0h-1. After 1 hour of reaction, the effluent was collected by cooling and the product composition was analyzed by gas chromatography.
The catalyst A was replaced with catalysts B to K, respectively, and the above procedure was repeated.
The results of the analysis calculation of the reaction for preparing 3-hydroxypropanal by hydrating acrolein using the catalysts A to K are shown in Table 2.
TABLE 2 acrolein conversion and 3-hydroxypropanal selectivity using the catalyst of example 111
| Catalyst and process for preparing same | Acrolein conversion (%) | 3-hydroxypropanal Selectivity (%) |
| A | 88 | 93 |
| B | 85 | 95 |
| C | 86 | 92 |
| D | 81 | 87 |
| E | 84 | 90 |
| F | 82 | 89 |
| G | 67 | 90 |
| H | 80 | 87 |
| I | 84 | 96 |
| J | 82 | 97 |
| K | 65 | 94 |
EXAMPLE 14 testing of the stability of the catalyst
1g of catalyst I granules are charged into a fixed-bed tubular reactor, the temperature is increased to 350 ℃ for 1 hour of pretreatment and the reactor temperature is reduced to 60 ℃. And introducing an acrolein aqueous solution with the concentration of 20 wt% and containing 0.2% of hydroquinone polymerization inhibitor into the reactor for reaction, wherein the mass space velocity of the acrolein is 1.0h < -1 >. After 100 hours of reaction, the effluent was collected by cooling and the product composition was analyzed by gas chromatography. The reaction results are shown in Table 3.
By replacing the catalyst I with the catalysts in other examples in the application and repeating the above process, similar results to those obtained by using the catalyst I are obtained, the conversion rate of the acrolein and the selectivity of the 3-hydroxypropionaldehyde are not obviously changed after 100 hours of reaction, and the catalyst in the application is proved to be stable when being used for preparing the 3-hydroxypropionaldehyde by acrolein hydration.
TABLE 3 acrolein conversion and 3-hydroxypropanal selectivity using the catalyst of example 9
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (8)
1. A process for the preparation of 3-hydroxypropanal by hydration of acrolein, comprising at least the following steps:
the raw material containing acrolein and water is contacted with a catalyst for reaction to obtain 3-hydroxy propionaldehyde;
wherein the catalyst comprises a metal-modified silicoaluminophosphate molecular sieve;
the metal is at least one of alkali metal, alkaline earth metal and transition metal;
the silicon-aluminum molecular sieve comprises one of a ZSM-5 molecular sieve, a Y-type molecular sieve and a Beta molecular sieve;
the alkali metal comprises at least one of sodium and potassium; the alkaline earth metal comprises at least one of magnesium and calcium; the transition metal comprises at least one of manganese, iron, cobalt, nickel, copper and zinc.
2. The process according to claim 1, characterized in that the reaction conditions are: the reaction temperature is 40-80 ℃;
the mass ratio of acrolein to water in the raw material is 10: 90-30: 70;
the mass space velocity of the acrolein is 0.5-3.0 h-1。
3. The method of claim 1, wherein the feedstock further comprises a polymerization inhibitor; the polymerization inhibitor comprises at least one of hydroquinone, p-hydroxyanisole and phenothiazine; the mass ratio of the polymerization inhibitor to the acrolein is 0.5: 100-3: 100.
4. the process according to claim 1, characterized in that the reaction is carried out in a reactor; the reactor is a fixed bed reactor.
5. The method according to claim 1, wherein the loading of the metal in the catalyst is 0.3 to 3 wt%.
6. The method according to claim 5, wherein the loading of the metal in the catalyst is 0.5 to 1.5 wt%.
7. The method of claim 1, wherein the catalyst comprises a binder;
the content of the binder in the catalyst is 60-70 wt%.
8. The method of claim 1, wherein the catalyst is prepared by a method comprising:
mixing the raw material containing the silicon-aluminum molecular sieve with a solution containing metal ions, and carrying out ion exchange to obtain the catalyst.
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