CN115286495A - Method for preparing acrolein by catalytic oxidation of glycerol through ZSM-5 molecular sieve membrane - Google Patents
Method for preparing acrolein by catalytic oxidation of glycerol through ZSM-5 molecular sieve membrane Download PDFInfo
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 266
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000012528 membrane Substances 0.000 title claims abstract description 91
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 68
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 23
- 230000003647 oxidation Effects 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
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- 238000003912 environmental pollution Methods 0.000 abstract description 3
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- 238000010924 continuous production Methods 0.000 abstract description 2
- 235000011187 glycerol Nutrition 0.000 description 81
- 238000006297 dehydration reaction Methods 0.000 description 30
- 230000018044 dehydration Effects 0.000 description 24
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 239000012466 permeate Substances 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- 239000003225 biodiesel Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QYRVPBBOQIPGGV-UHFFFAOYSA-N benzene propane-1,2,3-triol Chemical compound OCC(O)CO.c1ccccc1 QYRVPBBOQIPGGV-UHFFFAOYSA-N 0.000 description 1
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- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- -1 rare earth pyrophosphate Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
-
- 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
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the technical field of molecular sieve membrane catalysis and separation, and provides a method for preparing acrolein by catalytic oxidation of glycerol through a ZSM-5 molecular sieve membrane, which comprises the following steps: s1, sealing one end of a ZSM-5 molecular sieve membrane, connecting the other end of the ZSM-5 molecular sieve membrane with a vacuum pump, assembling the ZSM-5 molecular sieve membrane into a membrane component for catalytic oxidation of glycerol, and placing the membrane component into a reactor; s2, adding glycerol and hydrogen peroxide into the reactor to immerse the ZSM-5 molecular sieve membrane in the feed liquid, uniformly stirring, and heating to 30-95 ℃ to perform glycerol oxidation reaction; and S3, providing power on the permeation side of the membrane by using a vacuum pump, pushing the reactant in the feed liquid side to pass through the ZSM-5 molecular sieve membrane to react and reach the permeation side, and collecting a reaction product on the permeation side of the ZSM-5 molecular sieve membrane. The method has the advantages of simple operation, high acrolein yield, less environmental pollution, continuous production and the like, and is beneficial to solving the problems of difficult separation and easy inactivation of the catalyst in the reaction process of preparing the acrolein by dehydrating the glycerol.
Description
Technical Field
The invention relates to the technical field of molecular sieve membrane catalysis and separation, in particular to a method for preparing acrolein by catalytic oxidation of glycerol through a ZSM-5 molecular sieve membrane.
Background
In recent years, non-renewable energy sources such as fossil fuels are gradually exhausted, and the problem of environmental pollution generated in the process of resource utilization is increasingly serious, so that a green and renewable energy source is urgently needed. The biodiesel has the advantages of reproducibility, degradability, environmental protection, good safety and the like. However, about 1kg of glycerin is by-produced per 10kg of biodiesel produced, and therefore, the rapid development of the biodiesel industry inevitably leads to an excess in the glycerin market. With the increase in biodiesel production, glycerol appears to be a major by-product in its production process, leading to market saturation. The glycerin is reasonably developed and utilized, and is converted into chemicals with high added values, so that the problem of market saturation of the glycerin can be solved, and the economic benefit of the biodiesel industry can be improved. The catalytic selective dehydration of glycerol to prepare acrolein is a very promising approach, and the acrolein is simple unsaturated aldehyde, is an important intermediate product of a plurality of compounds, and is widely applied to industries of oil fields, pharmacy, coatings, paper making, organic synthesis and the like.
The preparation of acrolein by glycerol dehydration can be divided into gas phase and liquid phase methods, wherein the gas phase method usually causes polymerization and pipe blockage, which easily causes catalyst carbon deposition and rapid inactivation, and these factors greatly restrict the development of the reaction taking acrolein as an intermediate product. The glycerol is subjected to liquid phase dehydration reaction to obtain the acrolein in one step, so that adverse factors in the propylene oxidation process can be eliminated, and a new green and environment-friendly process route is provided for the acrolein.
The reaction conditions for preparing the acrolein by glycerol liquid phase dehydration are harsh, the key point is that the yield of the acrolein is improved by a proper catalyst, the reaction can be divided into homogeneous phase catalytic reaction and heterogeneous catalytic reaction, and common catalysts comprise inorganic acid and salt thereof, rare earth pyrophosphate, metal oxide, heteropoly acid, molecular sieve and the like. The molecular sieve catalyst has a high specific surface area and good thermal stability, can provide a large number of acid sites, is an excellent glycerol dehydration catalyst, particularly a ZSM-5 molecular sieve, and is concerned due to high selectivity and catalytic stability for producing acrolein. However, the dehydration reaction of glycerol is generally over 300 ℃, and severe coking is easy to cause the deactivation of the catalyst. The existing production process for preparing acrolein by glycerol dehydration has the problems of harsh reaction conditions, low acrolein yield, poor safety, difficult separation of a catalyst, easy poisoning and the like.
Disclosure of Invention
The invention aims to overcome at least one of the defects of the prior art and provide a method for preparing acrolein by catalytic oxidation of glycerol by adopting a ZSM-5 molecular sieve membrane. The purpose of the invention is realized based on the following technical scheme:
the invention provides a method for preparing acrolein by catalytic oxidation of glycerol by adopting a ZSM-5 molecular sieve membrane, which comprises the following steps:
s1, sealing one end of a ZSM-5 molecular sieve membrane, connecting the other end of the ZSM-5 molecular sieve membrane with a vacuum pump, assembling the ZSM-5 molecular sieve membrane into a membrane component for catalytic oxidation of glycerol, and placing the membrane component into a reactor;
s2, adding glycerol and hydrogen peroxide into the reactor to immerse the ZSM-5 molecular sieve membrane in the feed liquid, uniformly stirring, and heating to 30-95 ℃ to perform glycerol oxidation reaction;
and S3, providing power on the permeation side of the membrane by using a vacuum pump, pushing the reactant in the feed liquid side to pass through the ZSM-5 molecular sieve membrane to react and reach the permeation side, and collecting a reaction product on the permeation side of the ZSM-5 molecular sieve membrane.
The research adopts a high-aluminum ZSM-5 molecular sieve membrane as a heterogeneous catalyst for preparing acrolein by glycerol liquid phase dehydration, and simultaneously adopts hydrogen peroxide as a green oxidant for glycerol oxidation dehydration. The hydrogen peroxide is a green and mild oxidant, the final product after application is water, no pollution is caused to the environment, and the application field is wider and wider. On one hand, the porous carrier loaded high-alumina ZSM-5 molecular sieve membrane has pore channel structures of different levels and acidic catalytic active sites, and can be used as a high-efficiency catalyst for preparing acrolein by oxidizing glycerol with hydrogen peroxide for dehydration; on the other hand, the high-aluminum ZSM-5 molecular sieve adopted in the research has a proper pore structure and good hydrophilicity, can remove water generated in the reaction of preparing the acrolein by dehydrating the glycerol on line, breaks the dynamic balance of chemical reaction, and improves the conversion rate of the glycerol and the yield of the acrolein, thereby realizing the high-efficiency reactor integrating catalytic reaction and separation coupling. In addition, compared with the traditional heterogeneous catalyst, the high-aluminum ZSM-5 molecular sieve membrane reactor has the advantages of higher reuse rate, easiness in separation, simplicity and convenience in recovery, continuity in production and the like. Therefore, the invention develops a reaction by adopting a high-performance ZSM-5 molecular sieve membrane, and provides a foundation for realizing industrial application and popularization of the technology of preparing the acrolein by catalyzing the dehydration of the glycerol by using the high-aluminum ZSM-5 molecular sieve membrane.
Preferably, the ZSM-5 molecular sieve membrane in the step S1 is a high-aluminum ZSM-5 molecular sieve membrane, and the Si/Al ratio is 8-100.
Preferably, the ZSM-5 molecular sieve membrane in step S1 is tubular.
Preferably, the reactor in step S1 is a three-port glass tube.
Preferably, the reactor in step S1 is further connected to a condensing device.
Preferably, the molar ratio of glycerol to hydrogen peroxide in step S2 is 1: [0.2,5 ].
Preferably, the temperature of the glycerol oxidation reaction in step S2 is 40-80 ℃.
Preferably, the ratio of the area of the high-aluminum ZSM-5 molecular sieve membrane to the volume of the reaction liquid in the step S2 is 0.005-0.5m 2 ·L -1 。
Preferably, the concentration of the hydrogen peroxide in the step S2 is 20wt% -50wt%.
Preferably, the vacuum pump maintains the vacuum degree in the membrane reactor apparatus at 200Pa or less in step S3.
Preferably, the reaction product in step S3 is collected after condensation, for example, by pumping through a glass tube connected to a ZSM-5 molecular sieve membrane into a cold trap with liquid nitrogen condensation.
Preferably, step S4 is further included after step S3: taking out the reaction product at the membrane permeation side every other hour by taking the reaction temperature as a timing starting point, weighing and then carrying out gas phase analysis.
The invention can obtain at least one of the following beneficial effects:
the invention provides a method for preparing acrolein by coupling a membrane reactor and glycerol dehydration reaction, which combines a ZSM-5 molecular sieve membrane into a pervaporation membrane reactor for catalyzing the reaction of preparing the acrolein by glycerol dehydration. The method has the advantages of simple operation, high acrolein yield, less environmental pollution, continuous production and the like, and is beneficial to solving the problems of difficult separation and easy inactivation of the catalyst in the reaction process of preparing the acrolein by dehydrating the glycerol. The high-performance ZSM-5 molecular sieve membrane reactor and the reaction for preparing the acrolein by dehydrating the benzene glycerol are coupled, and the catalysis and the separation can be integrated into a pervaporation membrane reactor. The operating principle of the pervaporation membrane reactor is that reactant molecules in the feed liquid measurement are pushed to pass through the membrane by pressure difference generated by a vacuum pump, and glycerin molecules are catalyzed and oxidized into acrolein by high-activity acid catalytic sites and hydrogen peroxide in the pore passages of a high-aluminum ZSM-5 molecular sieve; in addition, the high-aluminum ZSM-5 molecular sieve membrane adopted by the invention utilizes the pore channel restriction and the hydrophilicity to remove the water of a reaction product into a reaction solution, thereby promoting the continuous reaction and improving the conversion rate of the glycerol and the yield of the acrolein.
Drawings
FIG. 1 is a schematic diagram of an apparatus for catalytic oxidation of glycerol to acrolein for use in a high alumina ZSM-5 molecular sieve membrane reactor in a preferred embodiment of the present invention;
FIG. 2 is a graph showing the change in permeate side glycerol conversion, permeate side acrolein selectivity, permeate side acrolein content, and membrane permeation flux over time for example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The device for preparing acrolein by coupling pervaporation and glycerin catalytic oxidation reaction is shown in figure 1, and comprises a vacuum pump 1, a second cold trap 2, a first cold trap 3, a ZSM-5 molecular sieve membrane 4, a reactor 5, a condenser pipe 6, an oil bath pot 7, a magnet 8 and a vacuum gauge 9, wherein: the reactor 5 adopts three glass tubes and is arranged in an oil bath pot 7; the reaction liquid 7 is placed in the reactor 5, the magneton 8 and the ZSM-5 molecular sieve membrane 4 are directly placed in the reaction liquid, one end of the ZSM-5 molecular sieve membrane 4 is closed, the other end of the ZSM-5 molecular sieve membrane 4 is connected with a three-way valve of a vacuum line through a latex tube, the other two ends of the three-way valve are respectively connected with a first cold trap 3 condensed by liquid nitrogen, a second cold trap 2 is arranged between the first cold trap 3 and the vacuum pump 1, the other end of the second cold trap 2 is connected with the vacuum pump 1, the first cold trap 3 is used for collecting the reaction liquid and membrane penetrating fluid, and the second cold trap 2 is used for preventing the penetrating fluid from being pumped into the vacuum pump; the vacuum degree of the apparatus was measured by a vacuum gauge 9.
Heating an oil bath pot, weighing glycerol and 30wt% hydrogen peroxide solution in a molar ratio of 1, placing the glycerol and the 30wt% hydrogen peroxide solution in a three-port glass tube, starting stirring to perform glycerol oxidation reaction, directly placing a high-aluminum ZSM-5 molecular sieve membrane (Si/Al = 9) in glycerol oxidation reaction liquid, sealing one end of the ZSM-5 molecular sieve membrane, connecting a three-way valve of a vacuum line through a latex tube at the other end of the ZSM-5 molecular sieve membrane, and maintaining the vacuum degree of the system to be below 100Pa by a vacuum pump. Heating reaction solution of glycerol and hydrogen peroxide to 50 deg.C, wherein the volume ratio of membrane area to reaction solution is 0.07cm 2 /cm 3 . Collecting reaction liquid and membrane penetrating liquid from the first cold trap 3 every other hour, measuring the component content of the reaction liquid and the membrane penetrating liquid by using gas chromatography, and calculating the conversion rate of reactants, the yield of products and the selective separation performance of a membrane according to an analysis result; after the reaction is completed, the molecular sieve membrane is taken out and washed by distilled water until the pH value is approximately equal to 7, and the structure and the performance of the molecular sieve membrane can be characterized or reused after the molecular sieve membrane is dried for 12 hours at 80 ℃.
The glycerol oxidation dehydration products (water, acrolein and the like) enter a cold trap under the pushing of negative pressure in a mode of permeating steam through a molecular sieve membrane, are switched every hour through a three-way valve, and are rapidly condensed and collected through liquid nitrogen. An electronic pressure sensor is connected to the vacuum line to detect the system vacuum.
The degree of progress of the oxidation dehydration reaction of glycerin and the catalytic performance of the molecular sieve membrane were measured by the conversion of glycerin, the conversion of acrolein and the permeation flux (in kg. M) -2 ·h -1 ) To show that:
the glycerol conversion of the reactants in the esterification reaction, the acrolein conversion, and the permeation flux and acrolein content of the permeate are plotted as a function of time in FIG. 2. As shown in the figure, the conversion of glycerol and the selectivity to acrolein were both 100% on the permeate side, and the permeate flux remained stable after 4 hours. In addition, the high-aluminum ZSM-5 molecular sieve membrane not only has good catalytic effect, but also can remove water generated by reaction and promote the continuous reaction, the substance on the permeation side is an aqueous solution of acrolein, and the content of the acrolein can be maintained at 7.88wt%.
Example 2
The glycerin oxidative dehydration conditions were the same as in step example 1 except that the reaction temperature was 60 ℃. The data of the glycerol oxidative dehydration are shown in table 1, and the conversion of glycerol and the selectivity of acrolein are both 100% under the reaction conditions. The substance on the permeation side was an aqueous solution of acrolein, and the content of acrolein was maintained at 7.25wt%.
Example 3
Glycerol oxidative dehydration conditions were the same as in example 1 except that the ratio of the membrane area to the volume of the reaction solution was 0.15cm 2 /cm 3 . The data of the glycerol oxidative dehydration are shown in table 1, and the conversion of glycerol and the selectivity of acrolein are both 100% under the reaction conditions. The substance on the transmission side was an aqueous solution of acrolein, and the acrolein content was maintained at 7.45wt%.
Example 4
The glycerin oxidative dehydration conditions were the same as in step example 1, except that the molar ratio of hydrogen peroxide to glycerin in the reaction stock solution was 1:2.5. as shown in Table 1, the conversion of glycerin and the selectivity of acrolein were 11.06% and 94.29%, respectively, under the reaction conditions, the substance on the permeation side was an aqueous solution of acrolein, and the content of acrolein was maintained at 7.93% by weight.
Example 5
The glycerin oxidative dehydration conditions were the same as in step example 1, except that the molar ratio of hydrogen peroxide to glycerin in the reaction stock solution was 2.5:1. as shown in Table 1, the conversion of glycerin and the selectivity of acrolein were 94.67% and 10.13%, respectively, under the reaction conditions, and the acrolein content in the permeate side was maintained at 9.25wt%.
Example 6
The glycerol oxidative dehydration conditions were the same as in step example 1, except that: the molar ratio of hydrogen peroxide to glycerol is 2:1, the reaction temperature is 70 ℃, and the ratio of the membrane area to the volume of the reaction solution is 0.03cm 2 /cm 3 . As shown in Table 1, the conversion of glycerin and the selectivity of acrolein were 100% and 35.47%, respectively, under the reaction conditions, and the acrolein content in the permeate side was maintained at 6.92wt%.
Example 7
The glycerol oxidative dehydration conditions were the same as in step example 1, except that: the molar ratio of hydrogen peroxide to glycerol is 1:2, the reaction temperature is 80 ℃, and the ratio of the membrane area to the volume of the reaction solution is 0.2cm 2 /cm 3 . As shown in Table 1, the conversion of glycerin and the selectivity of acrolein were 81.61% and 100%, respectively, under the reaction conditions, and the acrolein content in the permeate side was maintained at 8.13wt%.
Example 8
The glycerin oxidative dehydration conditions were the same as in step example 1, except that the molar ratio of hydrogen peroxide to glycerin in the reaction stock solution was 1:1.5. as shown in Table 1, the conversion of glycerin and the selectivity of acrolein were 95.36% and 100%, respectively, under the reaction conditions, the substance on the permeation side was an aqueous solution of acrolein, and the content of acrolein was maintained at 8.79% by weight.
Example 9
The glycerin oxidative dehydration conditions were the same as in step example 1, except that the molar ratio of hydrogen peroxide to glycerin in the reaction stock solution was 1.5:1. as shown in Table 1, the conversion of glycerol and the selectivity to acrolein under these reaction conditions were 100% and 65.32%, respectively, and the acrolein content in the permeate side was maintained at 8.55wt%.
Comparative example 1
The conditions for the oxidative dehydration of glycerin were the same as those in example 1 except that only glycerin was contained in the reaction liquid. The data of the glycerol oxidative dehydration reaction are shown in table 1, and when hydrogen peroxide is not added as an oxidizing agent in the reaction, the conversion rate of glycerol and the selectivity of acrolein under the reaction conditions are both 0.
Comparative example 2
The glycerin oxidative dehydration conditions were the same as in step example 1, except that the molar ratio of hydrogen peroxide to glycerin in the reaction stock solution was 5:1. as shown in Table 1, the conversion of glycerin and the selectivity of acrolein were respectively 100% and 0 under the above reaction conditions, and the content of acrylic acid was maintained at 8.25wt% while the substance on the permeation side was deeply oxidized to acrylic acid due to the excess of hydrogen peroxide and the selectivity of acrylic acid was 100%, and the substance on the permeation side was an aqueous solution of acrylic acid.
Comparative example 3
The oxidation dehydration conditions of glycerin were the same as in example 1, except that the reaction stock solution was not placed in a high alumina ZSM-5 molecular sieve membrane as the catalytic membrane reactor. The data of the glycerol oxidative dehydration reaction are shown in table 1, and the conversion of glycerol and the selectivity of acrolein under the reaction conditions were 16.89% and 5.36%.
TABLE 1
Note: the data for reaction 6h are shown in the table, and the data for 1-6h are similar with only minor fluctuations.
As can be seen from the data in Table 1, the high-alumina ZSM-5 molecular sieve membrane adopted by the invention removes the water of the reaction product from the reaction liquid by utilizing the pore channel limitation and the hydrophilicity, promotes the reaction to be continuously carried out, finally realizes the preparation of the acrolein by catalyzing the oxidation of the glycerol at a lower temperature by controlling the experimental parameters, and improves the conversion rate of the glycerol and the yield of the acrolein.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still make modifications to the technical solutions described in the foregoing embodiments, or make equivalent substitutions and improvements to part of the technical features of the foregoing embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing acrolein by catalytic oxidation of glycerol by adopting a ZSM-5 molecular sieve membrane is characterized by comprising the following steps:
s1, sealing one end of a ZSM-5 molecular sieve membrane, connecting the other end of the ZSM-5 molecular sieve membrane with a vacuum pump, assembling a membrane component for catalyzing and oxidizing glycerol, and placing the membrane component into a reactor;
s2, adding glycerol and hydrogen peroxide into the reactor to immerse the ZSM-5 molecular sieve membrane in the feed liquid, uniformly stirring, and heating to 30-95 ℃ to perform glycerol oxidation reaction;
and S3, providing power on the permeation side of the membrane by using a vacuum pump, pushing the reactant in the feed liquid side to pass through the ZSM-5 molecular sieve membrane to react and reach the permeation side, and collecting a reaction product on the permeation side of the ZSM-5 molecular sieve membrane.
2. The method for preparing acrolein through catalytic oxidation of glycerol with ZSM-5 molecular sieve membrane according to claim 1, wherein the ZSM-5 molecular sieve membrane in step S1 is a high alumina acid-resistant ZSM-5 molecular sieve membrane, and the Si/Al ratio is 8-100.
3. The method for preparing acrolein according to claim 1, wherein the ZSM-5 molecular sieve membrane in step S1 is tubular.
4. The method for preparing acrolein by catalytic oxidation of glycerol with ZSM-5 molecular sieve membrane according to claim 1, wherein the reactor in step S1 is a three-port glass tube.
5. The method for preparing acrolein by catalytic oxidation of glycerol with ZSM-5 molecular sieve membrane according to claim 1, wherein the molar ratio of glycerol/hydrogen peroxide in step S2 is 1: [0.2,5 ].
6. The method for preparing acrolein by catalytic oxidation of glycerol with ZSM-5 molecular sieve membrane according to claim 1, wherein the temperature of the glycerol oxidation reaction in the step S2 is 40-80 ℃.
7. The method of claim 1, wherein the area of the high alumina ZSM-5 zeolite membrane to the volume of the reaction solution in step S2 is 0.005 to 0.5m 2 ·L -1 。
8. The method for preparing acrolein by catalytic oxidation of glycerol through ZSM-5 molecular sieve membrane according to claim 1, wherein the concentration of hydrogen peroxide in step S2 is 20wt% -50wt%.
9. The method of claim 1, wherein the vacuum pump maintains the vacuum in the membrane reactor at 200Pa or less in step S3.
10. The method of claim 1, wherein the reaction product obtained in step S3 is collected after being condensed.
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