CN116474758B - Catalyst for preparing 1-octene by octanol dehydration, preparation method and application - Google Patents

Catalyst for preparing 1-octene by octanol dehydration, preparation method and application Download PDF

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CN116474758B
CN116474758B CN202310516701.XA CN202310516701A CN116474758B CN 116474758 B CN116474758 B CN 116474758B CN 202310516701 A CN202310516701 A CN 202310516701A CN 116474758 B CN116474758 B CN 116474758B
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octene
octanol
dehydration
tho
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CN116474758A (en
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梁菁菁
李巍
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Dalian Wankang Industrial Technology Co ltd
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
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Abstract

The invention discloses a catalyst for preparing 1-octene by octanol dehydration, a preparation method and application, wherein the catalyst for preparing 1-octene by octanol dehydration is a thorium oxide bimetallic oxide catalyst, and the composition of the catalyst is MO X ‑ThO 2 Wherein M represents a metal element, X is the total number of oxygen atoms satisfying the valence of the metal element, M is selected from one of Al, ce, zr, la or Ta, and MO is selected from the group consisting of X And ThO 2 The molar ratio of (1-5) to (1-5). The invention discloses a catalyst for preparing 1-octene by octanol dehydration, a preparation method and application thereof, wherein n-octanol is used as a raw material, and intramolecular dehydration is carried out by suspension catalytic rectification to obtain 1-octene. The preparation method has the advantages of simple and easy realization of the preparation process, simple and safe operation, environmental protection, easy control of technological parameters, and high purity of the obtained 1-octene, and can be used as a comonomer.

Description

Catalyst for preparing 1-octene by octanol dehydration, preparation method and application
Technical Field
The invention relates to the technical field of preparation of organic chemical materials, in particular to a catalyst for preparing 1-octene by octanol dehydration, a preparation method and application.
Background
With the explosive growth of the polyolefin industry, there is an increasing demand for 1-octene long chain alpha-olefins that can be used as comonomers. Based on the existing mainstream scheme for synthesizing long-chain alpha-olefin by olefin oligomerization, the alcohol selective dehydration synthesis method can be used as an alternative synthesis route. The rapid development of Fischer-Tropsch synthesis and other technologies has the opportunity to solve the source of long-chain alcohols, so that the route has a certain industrial prospect. In the process of preparing olefin by dehydrating long-chain fatty alcohol on the surface of a catalyst, side reactions such as: the intermolecular dehydration produces ether, the alcohol dehydrogenation produces aldehyde and the olefin shift produces internal olefin, which results in low selectivity and low target yield of long-chain alpha-olefin prepared by dehydration reaction of long-chain primary alcohol.
Chinese patent publication No. CN101108792A discloses a method for producing dimethyl ether by continuous catalytic rectification of methanol, which adopts cation exchange resin as a catalyst, and carries out methanol dehydration reaction in a catalytic rectifying tower, so that the methanol can be completely converted under lower temperature and pressure conditions, and the equipment investment, the operation cost and the production cost are reduced. Because the intermolecular dehydration generates ether, the long-chain primary alcohol dehydration reaction is low in selectivity and target yield for preparing long-chain alpha-olefin.
Chinese patent publication No. CN 113198519B discloses a method for producing high purity alpha-olefin by using a knapsack type reactive distillation apparatus. The method takes olefin as raw material and utilizes a knapsack type reaction rectification device to produce high-purity alpha-olefin. ZnO-ZrO is filled in the knapsack reactor 2 The ZSM molecular sieve serves as an isomerization catalyst to iso-form alpha-olefins from internal olefins. The patent converts internal olefins to alpha-olefins and employs catalytic distillation to enhance them. Because the application generates olefin shift to generate internal olefin, the long-chain primary alcohol dehydration reaction is low in selectivity and target yield for preparing long-chain alpha-olefin.
Chinese patent publication No. CN103333038B discloses a process for producing long chain alpha-linear olefins. The method uses a fixed bed process to carry out dehydration reaction, the olefin yield is 99.5%, and the alpha-olefin yield is 90-98%. In the patent, the alcohol dehydration reaction and the olefin hydration reaction are reversible reactions, so that long-chain alcohol cannot be completely converted, and the purity of olefin products is affected.
Disclosure of Invention
Aiming at the problem of low target yield of long-chain alpha-olefin prepared by long-chain primary alcohol dehydration reaction in the prior art, the invention aims to provide a catalyst for preparing 1-octene by octanol dehydration, a preparation method and application thereof, and the catalyst takes n-octanol obtained by byproduct n-octanol in the Fischer-Tropsch synthesis process or coconut oil hydrogenation product as a raw material, and obtains 1-octene by intramolecular dehydration through suspension catalytic rectification. The preparation method has the advantages of simple and easy realization of the preparation process, simple and safe operation, environmental protection, easy control of technological parameters, and high purity of the obtained 1-octene, and can be used as a comonomer.
In order to achieve the above purpose, the present invention provides the following technical solutions: a catalyst for preparing 1-octene by dewatering octanol is thorium oxide bimetallic oxide catalyst with MO composition X -ThO 2 Wherein M represents a metal element, X is the total number of oxygen atoms satisfying the valence of the metal element, M is selected from one of Al, ce, zr, la or Ta, and MO is selected from the group consisting of X And ThO 2 The molar ratio of (1-5) to (1-5).
Further, the metal element M also comprises alkali metal, and the alkali metal in the metal element M accounts for 1wt%.
Further, the alkali metal is selected from any one of Li, na, K, rb or Cs.
Further, the catalyst size is 50-200um.
Further, the catalyst is prepared by adopting a precipitation method, and specifically comprises the following steps: dissolving nitrate solution containing metal M and thorium nitrate in glycol-water solution with volume ratio of 2:1, adding precipitant, maintaining pH between 9-10, and stirring at 80deg.C for 24 hr to obtain precipitate;
washing and filtering the precipitate to obtain a filter cake;
drying the filter cake at 110 ℃ for 12 hours and calcining to obtain a thorium oxide bimetallic oxide catalyst;
the calcination conditions are as follows: roasting at 550 ℃ for 3 hours.
Still further, the precipitant is selected from at least one of LiOH, naOH, KOH, rbOH or CsOH.
In order to achieve the above purpose, the present invention provides the following technical solutions: the application of the catalyst in the reaction of preparing 1-octene by octanol dehydration specifically comprises the following steps:
s1: taking 1-octanol as a raw material, and uniformly mixing the catalyst and the 1-octanol raw material to obtain a mixed solution;
s2: introducing the mixed solution prepared in the step S1 into a suspension catalytic rectifying tower, carrying out dehydration rectifying reaction, distilling 1-octene from a top discharge hole of the suspension catalytic rectifying tower, and distilling unreacted raw materials and byproducts from the bottom;
s3: and (2) separating the mixture distilled from the bottom in the step (S2) by a solid-liquid separator, introducing the mixture into a stripping section, dehydrating a side reaction product octyl ether by using the distilled alcohol from the bottom of the stripping section, and circularly pumping unreacted raw materials distilled from a discharge hole at the top of the column into a suspension catalytic rectifying tower to continuously carry out dehydration rectifying reaction.
Further, in step S1, the mass ratio of the raw material to the catalyst is (500-10000): 1.
further, in steps S2 and S3, the operating conditions of the suspension catalytic rectification column: the temperature of the tower top is 120-125 ℃, the temperature of the reaction section is 280-360 ℃, the reflux ratio of the tower top is 0.3-5, the operating pressure is 0.1MPa, and the space velocity of the feeding volume is 0.3-1h -1 The stripping section temperature of the stripping section is 200-250 ℃.
Further, in step S3, the solid-liquid separator separates a liquid and a solid, the liquid is introduced into the stripping tower, the solid and the raw material are mixed as a new raw material, and the operation of S1 is repeated.
Further, in step S2, a 1-octene product having a purity of 95wt% or more is produced from the top of the column.
In summary, the invention has the following beneficial effects:
first, the invention adopts the metal element and thorium oxide composite oxide as the dehydration catalyst, because the metal oxide mainly carries out alcohol dehydration to alpha-olefin, but ThO 2 Mainly adsorb the formed alpha-olefin, avoid olefin shift and further isomerization of the alpha-olefin, and further processAnd a high alpha-olefin yield is obtained.
Secondly, the method takes the n-octanol which is a byproduct of the Fischer-Tropsch synthesis process or a hydrogenated product of coconut oil as a raw material, and obtains 1-octene through intramolecular dehydration by suspension catalytic rectification. The preparation method has the advantages of simple and easy realization of the preparation process, simple and safe operation, environmental protection, easy control of technological parameters, and high purity of the obtained 1-octene, and can be used as a comonomer.
Thirdly, the catalyst prepared by the method is applied to the preparation of 1-octene by octanol dehydration, the catalytic rectification process is adopted to carry out alcohol dehydration reaction, the alcohol intramolecular dehydration reaction and the product rectification separation process are coupled to improve the conversion efficiency of alcohol dehydration equilibrium reaction, and the special alcohol dehydration catalyst is adopted to greatly improve the yield of alpha-olefin, wherein the yield of the alpha-olefin is more than 95%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it will be obvious that the drawings in the following description are some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a process flow diagram employed in the method of the present invention.
In the figure: 1. a suspension catalytic rectifying tower; 11. a reaction section; 12. a rectifying section; 2. a solid-liquid separator; 3. stripping section.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to fig. 1 of the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples
Example 1
Al (aluminum) alloy 2 O 3 -ThO 2 The specific preparation method of the catalyst comprises the following steps: al (NO) was added at a metal molar ratio of 1:1 3 ) 3 And Th (NO) 3 ) 4 ·4H 2 O is dissolved in glycol-water solution with the volume ratio of 2:1 and stirred for 30min, wherein the mass concentration of metal salt is 10%, then NaOH solution with the mass concentration of 20% is added into the solution dropwise until the pH is kept between 9 and 10, and the mixture is stirred for 24h at 80 ℃ to obtain precipitate. The resulting precipitate was repeatedly rinsed with deionized water several times and dried at 110℃for 12h. Roasting the dried sample at 550 ℃ for 3 hours to obtain Al 2 O 3 -ThO 2 The catalyst is ground for 10min, then pressed into tablets, broken and sieved by a 100-200 mesh sieve.
Example 2
CeO (CeO) 2 -ThO 2 The specific preparation method of the catalyst comprises the following steps: ce (NO) was added at a metal molar ratio of 1:1 3 ) 3 And Th (NO) 3 ) 4 ·4H 2 O is dissolved in glycol-water solution with volume ratio of 2:1 and stirred for 30min, wherein the concentration of metal salt is 10wt%, then NaOH solution with mass concentration of 20% is added into the solution dropwise until the pH is kept between 9 and 10, and the mixture is stirred for 24h at 80 ℃ to obtain precipitate. The resulting precipitate was repeatedly rinsed with deionized water several times and dried at 110℃for 12h. Roasting the dried sample at 550 ℃ for 3 hours to obtain CeO 2 -ThO 2 The catalyst is ground for 10min, then pressed into tablets, broken and sieved by a 100-200 mesh sieve.
Example 3
ZrO (ZrO-like grain) 2 -ThO 2 The specific preparation method of the catalyst comprises the following steps: zr (NO) was added in a metal molar ratio of 1:1 3 ) 4 And Th (NO) 3 ) 4 4H2O was dissolved in an ethylene glycol-water solution having a volume ratio of 2:1 and stirred for 30min, wherein the mass concentration of the metal salt was 10wt%, then a 20% NaOH solution was added dropwise to the above solution, the pH was kept between 9 and 10, and stirred at 80℃for 24 hours to obtain a precipitate. The obtained precipitate is used forThe ionic water was repeatedly washed several times and dried at 110℃for 12h. Roasting the dried sample at 550 ℃ for 3 hours to obtain ZrO 2 /ThO 2 ZrO in a molar ratio of 1:1 2 -ThO 2 The catalyst is ground for 10min, then pressed into tablets, broken and sieved by a 100-200 mesh sieve.
Example 4
La (La) 2 O 3 -ThO 2 The specific preparation method of the catalyst comprises the following steps: la (NO 3 ) 3 And Th (NO) 3 ) 4 4H2O was dissolved in an ethylene glycol-water solution having a volume ratio of 2:1 and stirred for 30min, wherein the metal salt concentration was 10wt%, then a 20% NaOH solution was added dropwise to the above solution, the pH was kept between 9 and 10, and the mixture was stirred at 80℃for 24 hours to obtain a precipitate. The resulting precipitate was repeatedly rinsed with deionized water several times and dried at 110℃for 12h. Roasting the dried sample at 550 ℃ for 3 hours to obtain La 2 O 3 -ThO 2 The catalyst was ground for 10min, then tabletted and broken up, and the catalyst was sieved with a 20-40 mesh sieve.
Example 5
Ta (Ta) 2 O 5 -ThO 2 The specific preparation method of the catalyst comprises the following steps: ta (OH) in a metal molar ratio of 1:1 5 And Th (NO) 3 ) 4 4H2O was dissolved in an ethylene glycol-water solution in a volume ratio of 2:1 and stirred for 30min, wherein the mass concentration of the metal salt was 10wt%, then a 20% NaOH solution was added dropwise to the above solution, the pH was kept between 9 and 10, and stirred for 24H at 80 ℃. The resulting precipitate was repeatedly rinsed with deionized water several times and dried at 110℃for 12h. Roasting the dried sample at 550 ℃ for 3 hours to obtain Ta 2 O 5 -ThO 2 The catalyst is ground for 10min, then pressed into tablets, broken and sieved by a 100-200 mesh sieve.
Example 6
Differs from example 3 only in that ZrO 2 /ThO 2 The molar ratio was 5:1.
Example 7
The only difference from example 3 is that,ZrO 2 /ThO 2 the molar ratio was 3:1.
Example 8
Differs from example 3 only in that ZrO 2 /ThO 2 The molar ratio was 1:3.
Example 9
Differs from example 3 only in that ZrO 2 /ThO 2 The molar ratio was 1:5.
Example 10
Li + Modified ZrO 2 -ThO 2 The specific preparation method of the catalyst comprises the following steps: zr (NO) was added in a metal molar ratio of 1:1 3 ) 4 And Th (NO) 3 ) 4 4H2O is dissolved in an ethylene glycol-water solution with a volume ratio of 2:1 and stirred for 30min, wherein the mass concentration of the metal salt is 10wt%, then a LiOH solution with a mass concentration of 20% is added dropwise to the solution, the pH is kept between 9 and 10, and the mixture is stirred for 24H at 80 ℃ to obtain a precipitate. The resulting precipitate was repeatedly rinsed with deionized water several times and dried at 110℃for 12h. Roasting the dried sample at 550 ℃ for 3 hours to obtain ZrO 2 /ThO 2 ZrO in a molar ratio of 1:1 2 -ThO 2 The catalyst is ground for 10min, then pressed into tablets, broken and sieved by a 100-200 mesh sieve.
Example 11
Na + Modified ZrO 2 -ThO 2 The specific preparation method of the catalyst comprises the following steps: zr (NO) was added in a metal molar ratio of 1:1 3 ) 4 And Th (NO) 3 ) 4 4H2O was dissolved in a 2:1 volume ratio of ethylene glycol-water solution and stirred for 30min, wherein the mass concentration of the metal salt was 10wt%, however, a 20% NaOH solution was added dropwise to the above solution, the pH was kept between 9 and 10, and stirred for 24H at 80 ℃. The resulting precipitate was repeatedly rinsed with deionized water several times and dried at 110℃for 12h. Roasting the dried sample at 550 ℃ for 3 hours to obtain ZrO 2 /ThO 2 ZrO in a molar ratio of 1:1 2 -ThO 2 Catalyst, grinding the catalyst for 10min, tabletting, breaking, and sieving with 100-200 mesh sieve.
Example 12
K + Modified ZrO 2 -ThO 2 The specific preparation method of the catalyst comprises the following steps: zr (NO) was added in a metal molar ratio of 1:1 3 ) 4 And Th (NO) 3 ) 4 4H2O was dissolved in an ethylene glycol-water solution in a volume ratio of 2:1 and stirred for 30min, wherein the mass concentration of the metal salt was 10wt%, then a KOH solution in a mass concentration of 20% was added dropwise to the above solution, the pH was kept between 9 and 10, and stirred for 24H at 80 ℃. The resulting precipitate was repeatedly rinsed with deionized water several times and dried at 110℃for 12h. Roasting the dried sample at 550 ℃ for 3 hours to obtain ZrO 2 /ThO 2 ZrO in a molar ratio of 1:1 2 -ThO 2 The catalyst is ground for 10min, then pressed into tablets, broken and sieved by a 100-200 mesh sieve.
Example 13
Rb + Modified ZrO 2 -ThO 2 The specific preparation method of the catalyst comprises the following steps: zr (NO) was added in a metal molar ratio of 1:1 3 ) 4 And Th (NO) 3 ) 4 4H2O was dissolved in an ethylene glycol-water solution at a volume ratio of 2:1 and stirred for 30min, wherein the mass concentration of the metal salt was 10wt%, then a 20% RbOH solution was added dropwise to the above solution, the pH was kept between 9 and 10, and stirred for 24H at 80 ℃. The resulting precipitate was repeatedly rinsed with deionized water several times and dried at 110℃for 12h. Roasting the dried sample at 550 ℃ for 3 hours to obtain ZrO 2 /ThO 2 ZrO in a molar ratio of 1:1 2 -ThO 2 The catalyst is ground for 10min, then pressed into tablets, broken and sieved by a 100-200 mesh sieve.
Example 14
Cs + Modified ZrO 2 -ThO 2 The specific preparation method of the catalyst comprises the following steps: zr (NO) was added in a metal molar ratio of 1:1 3 ) 4 And Th (NO) 3 ) 4 4H2O was dissolved in an ethylene glycol-water solution in a volume ratio of 2:1 and stirred for 30min, wherein the mass concentration of the metal salt was 10%, then a CsOH solution in a mass concentration of 20% was added dropwise to the above solution, the pH was kept between 9 and 10, and stirred for 24H at 80 ℃. Repeatedly using deionized water to obtain precipitateRinsed several times and dried at 110 ℃ for 12h. Roasting the dried sample at 550 ℃ for 3 hours to obtain ZrO 2 /ThO 2 ZrO in a molar ratio of 1:1 2 -ThO 2 The catalyst is ground for 10min, then pressed into tablets, broken and sieved by a 100-200 mesh sieve. .
Comparative example
Comparative example 1
Al (aluminum) alloy 2 O 3 The specific preparation method of the catalyst comprises the following steps: al (NO) 3 ) 3 Dissolving in a glycol-water solution with a volume ratio of 2:1 and stirring for 30min, wherein the mass concentration of the metal salt is 10%, however, dropwise adding a 20% NaOH solution into the solution, keeping the pH between 9 and 10, and stirring for 24h at 80 ℃. The resulting precipitate was repeatedly rinsed with deionized water several times and dried at 110℃for 12h. Roasting the dried sample at 550 ℃ for 3 hours to obtain Al 2 O 3 The catalyst is ground for 10min, then pressed into tablets, broken and sieved by a 100-200 mesh sieve.
Comparative example 2
CeO (CeO) 2 The specific preparation method of the catalyst comprises the following steps: ce (NO) 3 ) 3 Dissolving in a glycol-water solution with a volume ratio of 2:1 and stirring for 30min, wherein the mass concentration of the metal salt is 10%, however, dropwise adding a 20% NaOH solution into the solution, keeping the pH between 9 and 10, and stirring for 24h at 80 ℃. The resulting precipitate was repeatedly rinsed with deionized water several times and dried at 110℃for 12h. Roasting the dried sample at 550 ℃ for 3 hours to obtain CeO 2 The catalyst is ground for 10min, then pressed into tablets, broken and sieved by a 100-200 mesh sieve. .
Comparative example 3
ZrO (ZrO-like grain) 2 The specific preparation method of the catalyst comprises the following steps: zr (NO) 3 ) 3 Dissolving in a glycol-water solution with a volume ratio of 2:1 and stirring for 30min, wherein the mass concentration of the metal salt is 10%, however, dropwise adding a 20% NaOH solution into the solution, keeping the pH between 9 and 10, and stirring for 24h at 80 ℃. Repeatedly washing the obtained precipitate with deionized water for several times, anddrying at 110℃for 12h. Roasting the dried sample at 550 ℃ for 3 hours to obtain ZrO 2 The catalyst is ground for 10min, then pressed into tablets, broken and sieved by a 100-200 mesh sieve. .
Comparative example 4
La (La) 2 O 3 The specific preparation method of the catalyst comprises the following steps: la (NO) 3 ) 3 Dissolving in a glycol-water solution with a volume ratio of 2:1 and stirring for 30min, wherein the mass concentration of the metal salt is 10mol%, however, adding 20% NaOH dropwise to the solution, keeping the pH between 9 and 10, and stirring for 24h at 80 ℃. The resulting precipitate was repeatedly rinsed with deionized water several times and dried at 110℃for 12h. Roasting the dried sample at 550 ℃ for 3 hours to obtain La 2 O 3 The catalyst is ground for 10min, then pressed into tablets, broken and sieved by a 100-200 mesh sieve. .
Comparative example 5
Ta (Ta) 2 O 5 The specific preparation method of the catalyst comprises the following steps: dissolving metal tantalum sheet in mixed acid of nitric acid and hydrofluoric acid, precipitating with ammonia water, washing with water, oven drying, and calcining to obtain Ta 2 O 5 The catalyst is ground for 10min, then pressed into tablets, broken and sieved by a 100-200 mesh sieve.
Comparative example 6
ThO (methyl ethyl ketone) 2 The specific preparation method of the catalyst comprises the following steps: th (NO) 3 ) 4 4H2O was dissolved in a 2:1 volume ratio of glycol-water solution with a metal salt concentration of 10mol% and stirred for 30min, however, to the above solution was added dropwise NaOH with a mass concentration of 20% and a pH maintained between 9 and 10 and stirred for 24H at 80 ℃. The resulting precipitate was repeatedly rinsed with deionized water several times and dried at 110℃for 12h. Roasting the dried sample at 550 ℃ for 3 hours to obtain ThO 2 The catalyst is ground for 10min, then pressed into tablets, broken and sieved by a 100-200 mesh sieve.
Application example
The specific preparation method of the catalyst applied to the reaction of preparing 1-octene by dehydrating octanol is as follows:
s1: taking 1-octanol as a raw material, uniformly mixing a catalyst and the 1-octanol raw material, and suspending the catalyst in the raw material to obtain a catalyst particle suspension;
s2: referring to FIG. 1, the catalyst particle suspension prepared in the step S1 is added into a reaction section 11 of a suspension catalytic rectifying tower 1 from the middle part, the suspension is subjected to catalytic dehydration reaction in the reaction section 11 to obtain a light component mixture and a heavy component mixture, the light component mixture enters a rectifying section 12 from the upper end of the reaction section 11 to be rectified, 1-octene with the purity of more than 95wt% is obtained at the top of the tower, and intermediate byproduct components (such as octanal) with the boiling point between 1-octene (122-123 ℃) and 1-octanol (196 ℃) are extracted from a side line; the bottom of the tower is obtained with a heavy component mixture (such as internal alkene and octyl ether);
s3: the suspension liquid coming out from the lower end of the reaction section 11 of the suspension catalytic rectifying tower 1 in the step S2 enters a solid-liquid separator 2, the catalyst is recycled after being separated from the liquid phase in the solid-liquid separator 2 and regenerated, and the operation of the step S1 is repeated;
and sending the clear liquid separated by the solid-liquid separator 2 into a stripping section 3 for purification, distilling alcohol dehydration side reaction product octyl ether from the bottom of the stripping section 3, circularly pumping internal alkene distilled from a discharge hole at the top of the tower into a reaction section 11 of the suspension catalytic rectifying tower from the lower end, and continuously carrying out dehydration rectifying reaction.
Suspension catalytic rectifying tower: the temperature of the reaction section is 340 ℃, the temperature of the rectifying section is 120-125 ℃, the temperature of the stripping section is 250 ℃, the reflux ratio of the tower top is 2, the operating pressure is 0.1MPa, and the space velocity of the feeding volume is 0.5h -1 。
The product yield and catalyst conversion referred to in this application were analyzed separately using an Agilent 7890 gas chromatograph, fitted with an HP-5 universal chromatographic column.
Table 1 preparation of the ingredients of application examples 1 to 5
TABLE 2 analytical data for application examples 1-5
Analysis data Catalyst yield (%) 1-octene selectivity (%) Internal alkene Selectivity (%) Octanal selectivity (%) Octyl ether selectivity (%)
Application example 1 98.9 89.2 10.6 0 0.2
Application example 2 93.1 95.2 4.7 0.1 0
Application example 3 95.2 98.5 1.4 0.1 0
Application example 4 85.2 94.1 4.5 1.3 0.1
Application example 5 84.3 90.2 7.6 2.1 0.1
As can be seen from tables 1-2, the use of the thorium oxide bimetallic oxide catalyst plays an important role in the catalytic dehydration reaction of 1-octanol, the metal oxide is used as a carrier, and the metal oxide in the catalyst not only plays a role of the carrier, but also has a catalytic effect, and surface vacancies for embedding thorium ions exist on the surface of the metal oxide, so that when the thorium oxide is loaded, strong alkali sites can be generated without strong interaction with the carrier, the damage to the carrier structure can be avoided, and the direct dehydration of 1-octanol to olefin can be generated due to the synergistic effect of acid-base centers in the thorium oxide bimetallic oxide catalyst structure. The thorium oxide bimetallic oxide catalyst significantly improves the yield of 1-octene in the form of ZrO 2 -ThO 2 The selectivity of 1-octene can reach 98.5% at most for dehydration catalyst.
Table 3 burdening Table of application examples 6 to 9
Raw materials/g Application example 6 Application example 7 Application example 8 Application example 9
1-octanol 500 1000 5000 10000
Catalyst (example 3) 1 1 1 1
Table 4 analytical data for application examples 6-9
Analysis data Catalyst yield (%) 1-octene selectivity (%) Internal alkene Selectivity (%) Octanal selectivity (%) Octyl ether selectivity (%)
Application example 6 99.8 95.4 4.3 0.3 0
Application example 7 98.7 97.0 2.9 0.1 0
Application example 8 82.1 99.4 0.5 0.1 0
Application example 9 75.8 99.6 0.3 0.1 0
Application examples 6 to 9 differ from application example 3 only in the mass ratio of the raw material to the catalyst.
As can be seen from tables 3 to 4, as the mass ratio of the raw material to the catalyst increases, the selectivity for 1-octene gradually increases, but the conversion of the catalyst decreases, and when the mass ratio of the raw material to the catalyst is 2000:1, the selectivity for 1-octene can reach 98.5%, and when the mass ratio exceeds 2000:1, the selectivity for 1-octene does not significantly change, but the conversion of the catalyst significantly decreases.
Table 5 application examples 10-13 batching Table
TABLE 6 analytical data for application examples 10-13
Application examples 10 to 13 differ from application example 3 in that the ZrO in the catalyst 2 /ThO 2 The molar ratios are different.
As can be seen from tables 5 to 6, due to ZrO 2 Mainly through alcohol dehydration to alpha-olefin, while ThO 2 Mainly adsorbs the formed alpha-olefin, and avoids olefin shift and further isomerization of the alpha-olefin. Therefore, in order to avoid the generation of internal olefins and to maintain a high conversion, zrO is required 2 /ThO 2 Suitable molar ratios are 3:1-1:1.
table 7 burdening Table of application examples 14 to 18
TABLE 8 analytical data for application examples 14-18
Application examples 14 to 18 differ from application example 3 in that the catalyst was modified with an alkali metal and the modified alkali metal was different.
As is clear from tables 7 to 8, since thorium ion is noble metal, its d-orbital is not filled with electrons and has high catalytic activity, and when alkali metal is supported, alkali metal can participate in dehydration reaction, and also has catalytic action in the course of reaction, and since alkali metal can weaken acidity of catalyst, reduce double bond shift of alpha-olefin to form internal olefin, excessive alkali metal can generate strong base site, so that it can promote alcohol dehydrogenation to produce aldehyde, therefore, terminal alkene selectivity can be raised by doping alkali metal ion, but proper proportion is required to prevent alcohol dehydrogenation reaction.
TABLE 9 reaction conditions for application examples 19-22
Reaction conditions Application example 19 Application example 20 Application example 21 Application example 22
Reaction section temperature (. Degree. C.) 280 300 320 360
Airspeed (h) -1 ) 0.5 0.5 0.5 0.5
Table 10 analytical data for application examples 19 to 22
Application examples 19 to 22 differ from application example 3 in that the reaction zone temperatures are different.
As is clear from tables 9 to 10, since octanol dehydration is an endothermic reaction, an increase in reaction temperature is advantageous for the reaction to proceed rightward, and for the dehydration reaction to occur, while a high temperature reduces intramolecular dehydrogenation in the intermolecular dehydrator of side reactions, therefore, the temperature for octanol dehydration needs to be greater than 340 ℃.
Table 11 reaction conditions of application examples 23 to 25
Reaction conditions Application example 23 Application example 24 Application example 25
Reaction section temperature (. Degree. C.) 340 340 340
Airspeed (h) -1 ) 0.3 0.75 1
Table 12 analytical data for application examples 23 to 25
Application examples 23-25 differ from application example 3 in the feed volume space velocity.
As can be seen from tables 11 to 12, since the space velocity is the reciprocal of the contact time, the space velocity differs, the contact time of the catalyst with the substrate n-octanol differs, the conversion of the substrate differs at different contact times, and therefore the space velocity for the dehydration of octanol needs less than 0.5h -1 。
Table 13 burdening Table comparing application examples 1 to 5
Table 14 compares analytical data for application examples 1-5
Comparative examples 1 to 6 differ from example 3 in the catalysts.
As can be seen from tables 13 to 14, thO 2 The dehydration catalyst has an optimal 1-octene yield, but has a problem of low 1-octanol conversion rate.
In summary, the present application is directed to the optimization of catalyst, zrO 2 /ThO 2 The molar ratio, the reaction condition of the reactive rectifying tower and the mass ratio of the raw materials to the catalyst regulate and control the coupling of the dehydration reaction and the rectification separation process in the alcohol molecule, and improve the conversion efficiency of the equilibrium reaction. According to the scheme, the catalyst conversion rate and the product yield are both greatly improved, meanwhile, 1-octanol is used as a raw material, the raw material is low in price, the route is simple, and the reaction process is environment-friendly.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (7)

1. The application of the thorium oxide bimetallic oxide catalyst in the reaction of preparing 1-octene by octanol dehydration is characterized by comprising the following steps:
s1: taking 1-octanol as a raw material, and uniformly mixing the catalyst and the 1-octanol raw material to obtain a mixed solution;
s2: introducing the mixed solution prepared in the step S1 into a suspension catalytic rectifying tower (1), carrying out dehydration rectifying reaction, distilling 1-octene from a top discharge hole of the suspension catalytic rectifying tower (1), and distilling unreacted raw materials and byproducts from the bottom of the suspension catalytic rectifying tower;
s3: the mixture distilled from the bottom of the step S2 is introduced into a stripping section (3) after being separated by a solid-liquid separator (2), and the unreacted raw materials distilled from a discharge hole at the top of the stripping section (3) are circularly fed into a suspension catalytic rectifying tower (1) to carry out dehydration rectifying reaction continuously;
the catalyst is thorium oxide bimetallic oxide catalyst, and the composition of the catalyst is MO X -ThO 2 Wherein M represents a metal element, X is the total number of oxygen atoms satisfying the valence of the metal element, M is selected from any one of Ce, zr, la or Ta, and MO X And ThO 2 The molar ratio of (1-5) to (1-5); the metal element M also comprises alkali metal, wherein the alkali metal accounts for 1 weight percent, and the alkali metal is selected from any one of Li, na, K, rb or Cs.
2. The use according to claim 1, wherein the catalyst size is 50-200um.
3. The use according to claim 1, wherein the catalyst is prepared by precipitation, comprising in particular the steps of:
dissolving nitrate solution containing metal M and thorium nitrate in glycol-water solution with volume ratio of 2:1, adding precipitant, maintaining pH between 9-10, and stirring at 80deg.C for 24 hr to obtain precipitate;
washing and filtering the precipitate to obtain a filter cake;
drying the filter cake at 110 ℃ for 12 hours and calcining to obtain a thorium oxide bimetallic oxide catalyst;
the calcination conditions are as follows: roasting at 550 ℃ for 3 hours.
4. The use according to claim 1, characterized in that in step S1 the mass ratio of raw material to catalyst is (500-10000): 1.
5. use according to claim 1, characterized in that in steps S2 and S3, the operating conditions of the suspension catalytic rectification column (1): the temperature of the tower top is 120-125 ℃, the temperature of the reaction section is 280-360 ℃, the reflux ratio of the tower top is 0.3-5, the operating pressure is 0.1MPa, and the space velocity of the feeding volume is 0.3-1h -1 The temperature of the stripping section is 200-250 ℃.
6. Use according to claim 1, characterized in that in step S3 the solid-liquid separator (2) separates a liquid and a solid, the liquid is introduced into the stripping column, the solid and the raw material are mixed as new raw material, and the operation of S1 is repeated.
7. Use according to claim 1, characterized in that in step S2 a 1-octene product having a purity of 95% by weight or more is taken off from the top of the column.
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