CN113087605B - Method for preparing octenal - Google Patents

Method for preparing octenal Download PDF

Info

Publication number
CN113087605B
CN113087605B CN201911341663.9A CN201911341663A CN113087605B CN 113087605 B CN113087605 B CN 113087605B CN 201911341663 A CN201911341663 A CN 201911341663A CN 113087605 B CN113087605 B CN 113087605B
Authority
CN
China
Prior art keywords
activated alumina
octenal
reaction
producing
butyraldehyde
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911341663.9A
Other languages
Chinese (zh)
Other versions
CN113087605A (en
Inventor
钱震
高源�
李俊诚
陈浩庭
张晓龙
菅青娥
武靖为
王海国
刘宏宇
梁颖堃
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Inner Mongolia Yitai Coal Based New Materials Research Institute Co Ltd
Original Assignee
Inner Mongolia Yitai Coal Based New Materials Research Institute Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Inner Mongolia Yitai Coal Based New Materials Research Institute Co Ltd filed Critical Inner Mongolia Yitai Coal Based New Materials Research Institute Co Ltd
Priority to CN201911341663.9A priority Critical patent/CN113087605B/en
Publication of CN113087605A publication Critical patent/CN113087605A/en
Application granted granted Critical
Publication of CN113087605B publication Critical patent/CN113087605B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C45/67—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 isomerisation; by change of size of the carbon skeleton
    • C07C45/68—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 isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—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 isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—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 isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a method for preparing octenal by catalyzing n-butyraldehyde condensation by activated alumina. The invention provides a novel catalyst, namely activated alumina activated by specific activation conditions, which has higher activity and selectivity in the reaction for preparing octenal, is environment-friendly, can be recycled, has low catalyst cost, and meanwhile, the obtained reaction product is easy to separate.

Description

Method for preparing octenal
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a method for preparing octenal by catalyzing n-butyraldehyde condensation by activated alumina.
Background
Octenal is an important organic intermediate, is mainly used for preparing isooctyl alcohol in industry, is an important basic organic chemical raw material, is mainly used as a plasticizer for plastic production, such as dioctyl phthalate and diisooctyl sebacate, and can be used as an antifoaming agent in the industries of photography, papermaking, paint, printing and dyeing, etc., as a dispersing agent for ceramic industry and glaze slurry, a mineral dressing agent, a detergent, a petroleum additive, etc.
The preparation of 2-ethyl-2-hexenal (octenal) by self-condensation of n-butyraldehyde is a typical aldol condensation reaction. The oxygen atom has stronger electronegativity, so that the carbonyl has an electron-withdrawing induction effect; in addition, the hydrocarbon bond on the carbonyl alpha carbon has sigma-pi super conjugation effect with carbonyl. The combined effect of the induction effect and the super-conjugation effect enables hydrogen on the alpha carbon atoms to be active, and the active alpha hydrogen can move between the alpha carbon and the carbonyl oxygen. Thus, carbonyl compounds exist as a pair of tautomers, i.e., keto and enol, which co-exist in an equilibrium system. The aldol condensation is the nucleophilic addition of an enol or enol salt to a carbonyl carbon. Under the action of an acid catalyst, firstly, acid protons are combined with carbonyl oxygen, and the protonated carbonyl has stronger electron-withdrawing effect, so that the acidity of alpha hydrogen is enhanced, and the alpha hydrogen is promoted to be dissociated into enol. Under the action of the alkaline catalyst, the alkali can be directly combined with alpha hydrogen to form a carbanion, and negative charge on carbon can be transferred to oxygen to form enol anions through the transfer of electron pairs. The enol or the enol anion is subjected to nucleophilic addition with the carbonyl of another molecule of aldehyde to form a new carbon-carbon bond, so as to obtain beta-hydroxyaldehyde. Because the alpha hydrogen atom is relatively active, the beta-hydroxyaldehyde containing the alpha hydrogen atom easily loses a molecule of water to form more stable alpha, beta-unsaturated aldehyde with a conjugated double bond structure.
The chemical reaction process can be represented by the following reaction formula:
Figure BDA0002331045190000011
patent CN201210256983.6 describes a process for preparing 2-ethyl-2-hexenal (octenal) by self-condensation of n-butyraldehyde catalyzed by heteropoly acid, which comprises fixing heteropoly acid on adsorbent such as molecular sieve to form solid catalyst, and catalyzing by solid-liquid catalysis, so as to avoid damaging the environment by using alkaline catalyst, and reuse the catalyst, wherein the activity of the catalyst is reduced with the increase of the number of times of use, thus not having the condition of industrial production.
Patent CN200910047404.5 describes a process for the reaction of n-butyraldehyde to octenal and the use of a polyethylene glycol, by adding a co-catalyst polyethylene glycol to an alkaline NaOH solution to increase the efficiency of the conversion of n-butyraldehyde to octenal, which essentially still catalyzes the n-butyraldehyde reaction in an alkaline environment, with the following four drawbacks: (1) The concentration of the liquid alkali is too low, the condensation reaction is not complete, and the conversion rate is low; (2) The concentration of liquid alkali is too high, aldol condensation reaction is more severe, trimer or polymer is easy to generate, and byproducts are more, so that the selectivity is lower; (3) The alkali-containing wastewater has large discharge amount, so that on one hand, the environment is polluted, and on the other hand, the treatment cost is high; (4) The cost is high, firstly, a large amount of NaOH is lost along with the wastewater, so that the consumption of the catalyst is high; secondly, after the reaction is finished, the water phase contains a large amount of products, and extraction and other processes are needed to be carried out, so that the cost is increased; thirdly, a large amount of acid liquor and the like are consumed for treating the wastewater, so that the cost is increased.
In view of the above problems that in the method for preparing octenal by condensing n-butyraldehyde, the environment and economic benefits are greatly affected by adopting a liquid alkaline catalyst, or an immature solid catalyst is adopted, the catalyst is deactivated after multiple uses and cannot be put into industrial production, so that an environment-friendly preparation method of octenal by adopting a stable solid catalyst is urgently needed.
Disclosure of Invention
The invention aims to solve the problems of low activity, incapability of recycling, difficult separation of products, high cost, environmental pollution and the like of a catalyst adopted in the existing method for preparing octenal by condensing n-butyraldehyde, and provides solid catalyst activated alumina which is used in the reaction for preparing octenal after being activated under specific activation conditions, has higher activity and selectivity, is environment-friendly, can be recycled, has low catalyst cost, and meanwhile, the obtained reaction product is easy to separate.
To this end, the first aspect of the present invention provides a method for producing octenal, comprising the step of catalyzing n-butyraldehyde to undergo condensation reaction with activated alumina as a catalyst to produce octenal.
In some embodiments of the invention, the activation conditions of the activated alumina are: the activation temperature is 400-750 ℃ and the activation time is 3-15 h.
In some preferred embodiments of the invention, the activation conditions of the activated alumina are: the activation temperature is 450-650 ℃ and the activation time is 3-10 h.
In other preferred embodiments of the present invention, the activation conditions of the activated alumina are: the activation temperature is 500-600 ℃ and the activation time is 4-9 h.
In some further preferred embodiments of the present invention, the activation conditions of the activated alumina are: the activation temperature is 500-600 ℃, and the activation time is 4-6 h.
In some embodiments of the invention, the condensation reaction is performed with a mass ratio of n-butyraldehyde to the activated alumina of (20-300) to 1.
In some preferred embodiments of the present invention, the condensation reaction is performed with a mass ratio of n-butyraldehyde to the activated alumina of (20-150) to 1.
In some further preferred embodiments of the present invention, the condensation reaction is performed with a mass ratio of n-butyraldehyde to the activated alumina of (30-90) to 1.
In some embodiments of the invention, the activated alumina has a specific surface area of 200-400m 2 /g。
In some preferred embodiments of the present invention, the activated alumina has a specific surface area of 300-400m 2 /g。
In some further preferred embodiments of the present invention, the specific surface area of the activated alumina is 360-400m 2 /g。
In some embodiments of the invention, the activated alumina has a pore volume of 0.38 to 0.46cm 3 /g。
In some embodiments of the invention, the activated alumina is 50-1000 mesh in size.
In some preferred embodiments of the invention, the activated alumina has a size of 50-200 mesh.
In some further preferred embodiments of the present invention, the activated alumina has a size of 80 to 150 mesh.
In some embodiments of the invention, the reaction temperature of the condensation reaction is from 80 ℃ to 200 ℃.
In some preferred embodiments of the invention, the reaction temperature of the condensation reaction is from 80 ℃ to 150 ℃.
In some further preferred embodiments of the present invention, the reaction temperature of the condensation reaction is from 100 ℃ to 130 ℃.
In other embodiments of the invention, the reaction time of the condensation reaction is from 3h to 6h.
In other preferred embodiments of the present invention, the reaction time of the condensation reaction is 3h to 5h.
In still further preferred embodiments of the present invention, the reaction time of the condensation reaction is from 3.5h to 4.5h.
In some embodiments of the invention, the condensation reaction has a reaction pressure of 2 to 10MPa.
In some preferred embodiments of the invention, the reaction pressure of the condensation reaction is from 2 to 8MPa.
In some further preferred embodiments of the present invention, the reaction pressure of the condensation reaction is 3-6MPa.
In some embodiments of the invention, the reaction conditions of the condensation reaction are: the reaction temperature is 80-200 ℃, the reaction time is 3-6 h, and the reaction pressure is 2-10MPa.
In some preferred embodiments of the invention, the reaction conditions of the condensation reaction are: the reaction temperature is 80-150 ℃, the reaction time is 3-5 h, and the reaction pressure is 2-8MPa.
In some further preferred embodiments of the present invention, the reaction conditions of the condensation reaction are: the reaction temperature is 100-130 ℃, the reaction time is 3.5-4.5 h, and the reaction pressure is 3-6MPa.
In some embodiments of the invention, the condensation reaction is performed under anaerobic conditions.
In a second aspect, the invention provides the use of activated alumina to catalyze n-butyraldehyde to make octenal.
In some embodiments of the invention, the activation conditions of the activated alumina are: the activation temperature is 400-750 ℃ and the activation time is 3-15 h.
In some preferred embodiments of the invention, the activation conditions of the activated alumina are: the activation temperature is 450-650 ℃ and the activation time is 3-10 h.
In other preferred embodiments of the present invention, the activation conditions of the activated alumina are: the activation temperature is 500-600 ℃ and the activation time is 4-9 h.
In some further preferred embodiments of the present invention, the activation conditions of the activated alumina are: the activation temperature is 500-600 ℃, and the activation time is 4-6 h.
In some embodiments of the invention, the condensation reaction is performed with a mass ratio of n-butyraldehyde to the activated alumina of (20-300) to 1.
In some preferred embodiments of the present invention, the condensation reaction is performed with a mass ratio of n-butyraldehyde to the activated alumina of (20-150) to 1.
In some further preferred embodiments of the present invention, the condensation reaction is performed with a mass ratio of n-butyraldehyde to the activated alumina of (30-90) to 1.
In some embodiments of the invention, the activated alumina has a specific surface area of 200-400m 2 /g。
In some preferred embodiments of the present invention, the activated alumina has a specific surface area of 300-400m 2 /g。
In some further preferred embodiments of the present invention, the specific surface area of the activated alumina is 360-400m 2 /g。
In some embodiments of the invention, the activated alumina has a pore volume of 0.38 to 0.46cm 3 /g。
In some embodiments of the invention, the activated alumina is 50-1000 mesh in size.
In some preferred embodiments of the invention, the activated alumina has a size of 50-200 mesh.
In some further preferred embodiments of the present invention, the activated alumina has a size of 80 to 150 mesh.
The existing method for preparing octenal by condensing n-butyraldehyde is not mature enough, and the catalyst is deactivated after multiple use in a solid-liquid two-phase catalysis mode, so that the catalyst cannot be put into industrial production. The alkaline liquid catalyst has the following disadvantages: (1) The concentration of the liquid alkali is too low, the condensation reaction is not complete, and the conversion rate is low; (2) The concentration of liquid alkali is too high, aldol condensation reaction is more severe, trimer or polymer is easy to generate, and byproducts are more, so that the selectivity is lower; (3) The alkali-containing wastewater has large discharge amount, so that on one hand, the environment is polluted, and on the other hand, the treatment cost is high; (4) The cost is high, firstly, a large amount of NaOH is lost along with the wastewater, so that the consumption of the catalyst is high; secondly, after the reaction is finished, the water phase contains a large amount of products, and extraction and other processes are needed to be carried out, so that the cost is increased; thirdly, a large amount of acid liquor and the like are consumed for treating the wastewater, so that the cost is increased.
In the prior art, a set of solid catalyst which can stably run and ensure the conversion rate is not available, and the developed octenal solid catalyst has low conversion rate of n-butyraldehyde or high byproduct content or is easy to deactivate, and the conversion rate is reduced by repeated use.
Based on the inventor, the inventor creatively discovers that the solid catalyst activated alumina has higher activity and selectivity when being used in the reaction for preparing octenal after being activated under specific activation conditions, is environment-friendly, can be recycled, has low catalyst cost, and meanwhile, the obtained reaction product is easy to separate. The n-butyraldehyde conversion rate of the catalyst reaches more than 90%, the activated alumina can be used for multiple times and put into experiments, and when the activity of the activated alumina is reduced, the activated alumina can be reused only by being put into a muffle furnace again for regeneration.
Drawings
The invention will be described below with reference to the accompanying drawings.
FIG. 1 shows chromatographic data before a condensation reaction is carried out in example 10 of the present invention;
FIG. 2 shows the chromatographic data at the end of the condensation reaction carried out in example 10 of the present invention.
Detailed Description
The technical scheme of the invention is described below through specific examples. However, these examples are for illustrative purposes only and are not meant to limit the scope of the present invention thereto.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Example 1
The pretreatment (activation) process of the activated alumina is as follows:
100 mesh activated alumina (specific surface area 300m 2 Per g, pore volume 0.38cm 3 And/g) adding the mixture into a muffle furnace at 500 ℃ for high-temperature treatment for 4 hours to obtain activated alumina after activation.
Example 2
The pretreatment (activation) process of the activated alumina is as follows:
100 mesh activated alumina (specific surface area 400m 2 Per g, pore volume 0.46cm 3 And/g) adding the mixture into a muffle furnace at 600 ℃ for high-temperature treatment for 9 hours to obtain activated alumina.
Example 3
The pretreatment (activation) process of the activated alumina is as follows:
100 mesh activated alumina (specific surface area 300m 2 Per g, pore volume 0.38cm 3 And/g) adding the mixture into a muffle furnace at 500 ℃ for high-temperature treatment for 9 hours to obtain activated alumina after activation.
Example 4
The pretreatment (activation) process of the activated alumina is as follows:
100 mesh activated alumina (specific surface area 400m 2 Per g, pore volume 0.46cm 3 And/g) adding the mixture into a muffle furnace at 600 ℃ for high-temperature treatment for 9 hours to obtain activated alumina.
Example 5
The pretreatment (activation) process of the activated alumina is as follows:
100 mesh activated alumina (specific surface area 400m 2 Per g, pore volume 0.46cm 3 And/g) adding the mixture into a muffle furnace at 550 ℃ for high-temperature treatment for 6 hours to obtain activated alumina.
Comparative example 1
The pretreatment (activation) process of the activated alumina is as follows:
100 mesh activated alumina (specific surface area 400m 2 Per g, pore volume 0.46cm 3 And/g) adding the mixture into a muffle furnace at 800 ℃ for high-temperature treatment for 6 hours to obtain activated alumina.
Example 6
80g of N-butyraldehyde and 2.4g of activated alumina activated in example 1 were weighed into a 300ml autoclave, N 2 The reaction was carried out under 5MPa at 100℃for 4h after 5 times of displacement, and the sample was analyzed. As can be seen from the chromatographic data, the conversion of n-butyraldehyde was 93% and the yield of octenal was 90%.
Example 7
80g of N-butyraldehyde and 2.4g of activated alumina activated in example 2 were weighed into a 300ml autoclave, N 2 The reaction was carried out under 5MPa at 100℃for 4h after 5 times of displacement, and the sample was analyzed. As can be seen from the chromatographic data, the conversion of n-butyraldehyde was 97% and the yield of octenal was 93%.
Example 8
80g of N-butyraldehyde and 2.4g of activated alumina activated in example 3 were weighed into a 300ml autoclave, N 2 The reaction was carried out under 5MPa at 100℃for 4h after 5 times of displacement, and the sample was analyzed. As can be seen from the chromatographic data, the conversion of n-butyraldehyde was 98% and the yield of octenal was 93%.
Example 9
80g of N-butyraldehyde and 2.4g of activated alumina activated in example 4 were weighed into a 300ml autoclave, N 2 The reaction was carried out under 5MPa at 100℃for 4h after 5 times of displacement, and the sample was analyzed. As can be seen from the chromatographic data, the conversion of n-butyraldehyde was 98% and the yield of octenal was 95%.
Example 10
80g of N-butyraldehyde and 2.4g of activated alumina activated in example 5 were weighed into a 300ml autoclave, N 2 The reaction was carried out under 5MPa at 100℃for 4h after 5 times of displacement, and the sample was analyzed. As can be seen from the chromatographic data (see fig. 1 and 2), the conversion of n-butyraldehyde was 99% and the octenal yield was 96%.
Example 11
80g of N-butyraldehyde and 0.9g of activated alumina activated in example 5 were weighed into a 300ml autoclave, N 2 The reaction was carried out under 5MPa at 100℃for 4h after 5 times of displacement, and the sample was analyzed. As can be seen from the chromatographic data (not shown), the conversion of n-butyraldehyde was 90% and the yield of octenal was 90%.
Comparative example 2
80g of N-butyraldehyde and 2.4g of activated alumina obtained in comparative example 1 were weighed into a 300ml autoclave, N 2 The reaction was carried out under 5MPa at 100℃for 4h after 5 times of displacement, and the sample was analyzed. From chromatographic data (not shown), n-butyraldehyde conversion was 80%, octeneThe yield of aldehyde was 83%.
Comparative example 3
80g of N-butyraldehyde and 0.2g of activated alumina activated in example 5 were weighed into a 300ml autoclave, N 2 The reaction was carried out under 5MPa at 100℃for 4h after 5 times of displacement, and the sample was analyzed. As can be seen from the chromatographic data (not shown), the conversion of n-butyraldehyde was 40% and the yield of octenal was 50%.
Example 12
The activated alumina of example 5 was repeatedly used, and the conversion of n-butyraldehyde and the yield of octenal were measured in the same manner as in example 10. The results are shown in Table 1 below:
TABLE 1
Number of times of use Conversion of n-butyraldehyde% Octenal yield% Alumina state
1 99 96 ——
2 97 95 ——
5 88 89 ——
8 (reactivation) 98 96 Reactivation of
As can be seen from Table 1, the catalytic activity of activated alumina gradually worsened with increasing number of uses, but the conversion and yield recovered to the original state after reactivation.
The activated alumina activated under the activation condition of the invention is used in the reaction of preparing octenal by condensing n-butyraldehyde, the n-butyraldehyde conversion rate reaches more than 90% after actual use, and the activated alumina can be put into experiment for multiple times, and can be reused only by putting the activated alumina into a muffle furnace again for reactivation when the catalytic activity of the activated alumina is reduced.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (31)

1. A method for preparing octenal, which is characterized by comprising the step of catalyzing n-butyraldehyde to perform condensation reaction by using activated alumina as a catalyst, wherein the activation condition of the activated alumina is as follows: the activation temperature is 400-650 ℃ and the activation time is 3-9 h;
the specific surface area of the activated alumina is 200-400m 2 Per g, pore volume of 0.38-0.46cm 3 /g。
2. The method for producing octenal according to claim 1, wherein the activation conditions of the activated alumina are: the activation temperature is 450-650 ℃.
3. The method for producing octenal according to claim 2, wherein the activation conditions of the activated alumina are: the activation temperature is 500-600 ℃.
4. The method for producing octenal according to claim 1, wherein the activation conditions of the activated alumina are: the activation time is 4-9 h.
5. The method for producing octenal according to claim 1, wherein the mass ratio of n-butyraldehyde to the activated alumina is (20 to 300): 1 when the condensation reaction is carried out.
6. The method for producing octenal according to claim 1, wherein the mass ratio of n-butyraldehyde to the activated alumina is (20 to 150): 1 when the condensation reaction is carried out.
7. The method for producing octenal according to claim 1, wherein the mass ratio of n-butyraldehyde to the activated alumina is (30-90): 1 when the condensation reaction is carried out.
8. The method for producing octenal according to any one of claims 1 to 7, wherein the specific surface area of the activated alumina is 300 to 400m 2 /g。
9. The method for producing octenal according to any one of claims 1 to 7, wherein the activated alumina360-400m specific surface area 2 /g。
10. The method for producing octenal according to any one of claims 1 to 7, wherein the activated alumina has a size of 50 to 1000 mesh.
11. The method for producing octenal according to any one of claims 1 to 7, wherein the activated alumina has a size of 50 to 200 mesh.
12. The method for producing octenal according to any one of claims 1 to 7, wherein the activated alumina has a size of 80 to 150 mesh.
13. The method for producing octenal according to any one of claims 1 to 7, wherein the reaction conditions of the condensation reaction are: the reaction temperature is 80-200 ℃, the reaction time is 3h-6h, and the reaction pressure is 2-10MPa.
14. The method for producing octenal according to any one of claims 1 to 7, wherein the reaction conditions of the condensation reaction are: the reaction temperature is 80-150 ℃.
15. The method for producing octenal according to any one of claims 1 to 7, wherein the reaction conditions of the condensation reaction are: the reaction temperature is 100-130 ℃.
16. The method for producing octenal according to any one of claims 1 to 7, wherein the reaction conditions of the condensation reaction are: reaction time 3h-5h.
17. The method for producing octenal according to any one of claims 1 to 7, wherein the reaction conditions of the condensation reaction are: the reaction time is 3.5h-4.5h.
18. The method for producing octenal according to any one of claims 1 to 7, wherein the reaction conditions of the condensation reaction are: the reaction pressure is 2-8MPa.
19. The method for producing octenal according to any one of claims 1 to 7, wherein the reaction conditions of the condensation reaction are: the reaction pressure is 3-6MPa.
20. The process according to any one of claims 1 to 7, wherein the condensation reaction is carried out under anaerobic conditions.
21. The application of activated alumina in catalyzing n-butyraldehyde to prepare octenal is characterized in that the activation conditions of the activated alumina are as follows: the activation temperature is 400-650 ℃ and the activation time is 3-9 h;
the specific surface area of the activated alumina is 200-400m 2 Per g, pore volume of 0.38-0.46cm 3 /g。
22. The use according to claim 21, wherein the activated alumina is activated under the following conditions: the activation temperature is 450-650 ℃.
23. The use according to claim 21, wherein the activated alumina is activated under the following conditions: the activation temperature is 500-600 ℃.
24. The use according to claim 21, wherein the activated alumina is activated under the following conditions: activation time 4h-9h.
25. The use according to any of claims 21 to 24, characterized in that the mass ratio of n-butyraldehyde to activated alumina is (20 to 300): 1 when the condensation reaction is carried out.
26. The use according to any of claims 21 to 24, characterized in that the mass ratio of n-butyraldehyde to activated alumina is (20 to 150): 1 when the condensation reaction is carried out.
27. The use according to any one of claims 21 to 24, wherein the mass ratio of n-butyraldehyde to activated alumina is (30-90): 1 when performing the condensation reaction.
28. The use according to any one of claims 21 to 24, wherein the activated alumina has a specific surface area of 300 to 400m 2 /g。
29. The use according to any one of claims 21 to 24, wherein the activated alumina has a size of 50 to 1000 mesh.
30. The use according to any one of claims 21 to 24, wherein the activated alumina has a size of 50 to 200 mesh.
31. The use according to any one of claims 21 to 24, wherein the activated alumina has a size of 80 to 150 mesh.
CN201911341663.9A 2019-12-23 2019-12-23 Method for preparing octenal Active CN113087605B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911341663.9A CN113087605B (en) 2019-12-23 2019-12-23 Method for preparing octenal

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911341663.9A CN113087605B (en) 2019-12-23 2019-12-23 Method for preparing octenal

Publications (2)

Publication Number Publication Date
CN113087605A CN113087605A (en) 2021-07-09
CN113087605B true CN113087605B (en) 2023-05-26

Family

ID=76663906

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911341663.9A Active CN113087605B (en) 2019-12-23 2019-12-23 Method for preparing octenal

Country Status (1)

Country Link
CN (1) CN113087605B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102746129A (en) * 2012-07-23 2012-10-24 河北工业大学 Process method for preparing 2-ethyl-2-hexenal by catalyzing self-condensation of n-butanal with heteropoly acid
CN102924251A (en) * 2012-11-30 2013-02-13 河北工业大学 Method for preparing 2-ethyl-2-hexenoic aldehyde through n-butyl aldehyde self-condensation under catalysis of solid acid

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE285392T1 (en) * 1998-11-25 2005-01-15 Johnson Matthey Plc ALDOL CONDENSATION

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102746129A (en) * 2012-07-23 2012-10-24 河北工业大学 Process method for preparing 2-ethyl-2-hexenal by catalyzing self-condensation of n-butanal with heteropoly acid
CN102924251A (en) * 2012-11-30 2013-02-13 河北工业大学 Method for preparing 2-ethyl-2-hexenoic aldehyde through n-butyl aldehyde self-condensation under catalysis of solid acid

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
Adsorption and surface reactions of acetaldehyde on TiO2, CeO2 and Al2O3;J. Rasko等;《Applied Catalysis A: General》;20051231;第287卷;252-260 *
KF-γ-Al_2O_3催化正丁醛自缩合合成辛烯醛;刘肖红等;《石油学报(石油加工)》;20151225(第06期);92-97 *
La-Al_2O_3催化正丁醛自缩合合成辛烯醛反应;刘肖红等;《化工学报》;20161231(第05期);258-265 *
n-Butyraldehyde self-condensation catalyzed by Ce-modified γ-Al2O3;Chao Xiong等;《RSC Adv.》;20151231;第5卷;第103524页第2.1-2.3节,第103525页第3.1节 *
TiO_2催化正丁醛自缩合反应机理;郑广宗等;《化学反应工程与工艺》;20190825(第04期);20-28 *
正丁醛自缩合合成辛烯醛反应催化剂研究进展;陈翠娜等;《化学通报》;20130418(第04期);28-33 *

Also Published As

Publication number Publication date
CN113087605A (en) 2021-07-09

Similar Documents

Publication Publication Date Title
CN104355975B (en) A kind of method of acetone two step synthesis methyl iso-butyl ketone (MIBK)
Mao et al. Heterogeneous cobalt catalysts for selective oxygenation of alcohols to aldehydes, esters and nitriles
CN102372600A (en) Separation method for glycol, propylene glycol and butylene glycol
CN108126748B (en) Alkaline monolithic catalyst with regular pore channels and preparation method and application thereof
WO2020192477A1 (en) Catalyst and method for preparing isopentyl diol
CN113087605B (en) Method for preparing octenal
CN114085136A (en) Method for preparing cyclopentanone by catalyzing furfural
CN112206808B (en) Catalyst for synthesizing isobutyl isobutyrate and preparation method and application thereof
CN101260035B (en) Technique for producing acrylic acid and ester thereof by biomass lactic acid ester dehydration
CN108017510B (en) Preparation method of hydroxyl pivalic aldehyde and application of hydroxyl pivalic aldehyde in preparation of neopentyl glycol
CN108927203B (en) Regeneration method of phenol hydrogenation Pd @ CN catalyst
CN110698438A (en) Method for preparing tetrahydrofuran by dehydrating 1, 4-butanediol under catalysis of solid catalyst
CN105111044A (en) Method for synthesizing isopentenol from butenol
CN113663725B (en) Mesoporous metal organic phosphonate catalyst, preparation method thereof and application thereof in preparation of 3-hydroxy-propanal
CN102924251B (en) Method for preparing 2-ethyl-2-hexenoic aldehyde through n-butyl aldehyde self-condensation under catalysis of solid acid
CN107188789A (en) A kind of method that catalytic reaction rectification produces polymethoxy dialkyl ether
CN1721385A (en) Process for producing alkylene glycol
CN114425367A (en) Catalyst system for preparing acrylate through acetylene carbonylation, preparation and application thereof
CN109384654B (en) Method for producing ethylene glycol mono-tert-butyl ether
CN101391942A (en) Process for preparing citral
CN104262143B (en) A kind of method of synthesizing alkene ester
CN104355976B (en) A kind of method of acetone through one-step method synthesis mesityl oxide
CN114031495B (en) Product separation method for preparing glycollic acid by glycol oxidation
CN113145172B (en) High-performance catalyst for preparing glycol by hydration of alkylene oxide, preparation method and application
CN105175230A (en) Method of synthesizing isopentenol from butenol

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant