CN112742454B - Preparation method of supported heteropoly acid catalyst - Google Patents

Preparation method of supported heteropoly acid catalyst Download PDF

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CN112742454B
CN112742454B CN201911048910.6A CN201911048910A CN112742454B CN 112742454 B CN112742454 B CN 112742454B CN 201911048910 A CN201911048910 A CN 201911048910A CN 112742454 B CN112742454 B CN 112742454B
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heteropoly acid
catalyst
impregnation
carrier
preparation
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CN112742454A (en
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姜睿
吕清林
霍稳周
包洪洲
祁文博
张霞
王振宇
王丽博
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • 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
    • B01J29/48—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 containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract

A preparation method of a supported heteropolyacid catalyst comprises the following steps: ultrasonically mixing a porous carrier with a nonpolar solvent with the size smaller than the size of an inner pore passage of the porous carrier, and carrying out primary impregnation; after the completion, placing the porous carrier in a heteropoly acid solution for secondary impregnation; and after the secondary impregnation is finished, carrying out microwave drying, and roasting to obtain the supported heteropolyacid catalyst. In the invention, the catalyst carrier is soaked in advance by using the nonpolar solvent which is insoluble in water, on one hand, the nonpolar solvent cyclohexane and the like have low dielectric constant, and can be filled in the carrier pore channel and not heated, thereby avoiding the damage of the pore channel caused by the rapid temperature rise of water in the microwave drying process of the traditional aqueous solution dipping method and protecting the pore channel structure of the catalyst; on the other hand, microwave drying and temperature rise are efficient, and separation of heteropoly acid in a traditional heating mode is avoided. Therefore, the preparation method enables the heteropoly acid to be more efficiently and uniformly loaded on the surface of the carrier, and improves the acidity and the catalytic efficiency of the catalyst; meanwhile, the operation efficiency and stability of the catalyst are guaranteed; in addition, microwave drying also reduces energy consumption.

Description

Preparation method of supported heteropoly acid catalyst
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a supported heteropolyacid catalyst.
Background
The heteropoly acid is used as a high-efficiency catalyst with both acidity and redox performance, and has wide application in the fields of petrochemical industry, organic synthesis and the like.
Keggin first proposed a Keggin-type heteropolyacid configuration in 1934 by a young physicist j.f. Keggin of the Bragg group of manchester, uk, and began a study of heteropolyacids and their applications. The industrialization of propylene hydration to produce isopropanol in Japan in the last 70 th century has been successfully realized by adopting heteropoly acid, and since then, heteropoly acid has been widely noticed by people as a catalyst in organic synthesis and petrochemical industry.
The specific surface area of the heteropoly acid is small compared with that of the molecular sieve catalyst, so in practical application, the heteropoly acid is usually loaded on a suitable carrier to improve the specific surface area and increase the reaction efficiency. The preparation method of the supported heteropolyacid catalyst generally comprises an impregnation method and an adsorption method.
The dipping method adopts a general dipping method, a certain amount of heteropoly acid is taken and dissolved in water, a certain amount of carrier is added, the mixture is stirred for a plurality of hours at a fixed temperature, the heteropoly acid is dipped into the carrier, and then a sample is dried in a water bath. The adsorption method comprises the steps of putting a certain amount of carrier into a beaker, adding a heteropoly acid aqueous solution with a certain content into the beaker, heating for a certain time, standing, pouring out liquid, measuring the amount of heteropoly acid adsorbed in the catalyst by using the residual mother liquor, and drying the prepared solid heteropoly acid catalyst for later use.
The research institute of petrochemical industry for the well-being and petrochemical industry is dedicatedThe method provides a reaction for preparing tert-butylamine by direct amination of isobutene under catalysis of heteropoly acid as a catalyst in CN99113280.7, and the conversion per pass of isobutene can reach 12%. The american german corporation also reported in its patent US05304681A the better catalytic effect of heteropolyacid catalysts on isobutylene amination. Also, in its patent, it is stated that the TiO base is based on 2 The supported hydrogen fluoride and fluorophosphoric acid catalyst also have catalytic action for isobutene amination reaction.
Microwave heating is mainly to heat materials by converting electromagnetic energy into heat energy through dipole steering polarization and interface polarization of high-frequency electromagnetic waves (2450 MHz). According to different requirements of the heating process, the corresponding electric field intensity, namely the temperature, can be provided for material drying, low-temperature shaping and sintering by adjusting the power of the equipment. Different from the traditional method of heating materials from outside to inside through heat radiation by an external heat source in a conduction mode, microwave heating is to conduct microwave energy to atoms or molecules in the materials through a space or a medium in an electromagnetic wave mode, the excited molecules oscillate 24.5 hundred million times per second to generate rotation energy level transition to generate heat, the materials are heated inside and outside the medium in an electromagnetic field at the same time, and the heated materials become a heat source under the action of high-frequency electromagnetic waves, so that chemical products of various materials can be dried.
In patent CN108126751A, a hierarchical-level molecular sieve is used to mix with a metal acid salt and a phosphate aqueous solution, microwave treatment is adopted for 5-120 min to remove residual moisture, and the mixture is dried and roasted to obtain a multilevel-level molecular sieve supported heteropolyacid catalyst which is used in the alkylation conversion process of gasoline sulfide, wherein the highest sulfur removal rate reaches 97%.
However, microwave drying is closely related to complex dielectric coefficient of raw materials, introduction of microwaves may bring about local heating or rapid heating effect of a reaction system, thereby causing hot spots or thermal runaway phenomenon, and the violent local heating effect undoubtedly plays a role in promoting the disruption of the pore structure of the material caused by microwave heating, especially the part of the pore structure which is permeated by a solution is selectively heated and disrupted due to good absorption capacity of water to microwaves, thereby causing great reduction of the specific surface area, the specific surface area of micropores and the pore volume of the catalyst. At the same time, a part of the newly formed larger pores is blocked by the material fragments, and the space of the secondarily formed pores is insufficient to compensate for the lost part of the microporous structure, thereby causing a decrease in pore volume and an increase in average pore diameter.
Disclosure of Invention
In order to solve the problems of low loading capacity and easy damage to catalyst pore channels in the microwave heating preparation process of the supported heteropolyacid catalyst in the prior art, the invention provides a preparation method of the supported heteropolyacid catalyst, which adopts two-step impregnation and then utilizes microwave drying to carry out rapid and efficient drying to obtain the catalyst which has large heteropolyacid loading capacity, uniform loading and undamaged pore channel structure.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a supported heteropolyacid catalyst comprises the following steps:
ultrasonically mixing a porous carrier with a nonpolar solvent with the size smaller than the size of an inner pore passage of the porous carrier, and carrying out primary impregnation; after the completion, placing the porous carrier in a heteropoly acid solution for secondary impregnation; and after the secondary impregnation is finished, carrying out microwave drying, and roasting to obtain the supported heteropolyacid catalyst.
Further, the nonpolar solvent is selected from at least one of cyclohexane, hexane, and benzene.
Further, the porous carrier is a commonly used carrier for catalysts in the prior art, comprises a porous carrier compounded or modified by a plurality of components, and is selected from molecular sieves, activated carbon, alumina, ion exchange resin and TiO as a specific technical scheme 2 And a layered column material, more preferably a molecular sieve such as ZSM-5 or MCM-41.
Further, the heteropoly acid is a common water-soluble heteropoly acid used for catalyst modification in the prior art, and is selected from H as a specific technical scheme 2 SO 4 、H 3 PO 4 Heteropolyacids having Keggin structure or Dawson structure and salts derived therefromWherein the heteropoly acid with Keggin structure preferably has a general formula of HnAB 12 O 40 ·xH 2 The structure of O is preferably H as a more specific means 4 [Si(W 3 O 10 ) 4 ]·xH 2 O、H 3 PW 12 O 40 ·xH 2 O and derived salts thereof, wherein the derived salts are copper salts and sodium salts.
Further, the temperature of the first impregnation is 0-60 ℃, preferably 0-50 ℃, and most preferably 10-40 ℃; the ultrasonic dipping time is 0.5-48 h, preferably 1-24 h, and most preferably 4-12 h.
Further, the temperature of the secondary impregnation is 10-80 ℃, preferably 15-70 ℃, most preferably 40-60 ℃, and the impregnation time is 1-24 h, preferably 2-12 h, most preferably 4-10 h. The volume ratio of the heteropoly acid solution to the carrier is 1: 1-10: 1, preferably 3: 1-8: 1, and most preferably 4: 1-5: 1. The concentration of the heteropoly acid in the heteropoly acid solution is 1-90%, preferably 3-20%.
Further, the microwave drying is vacuum microwave drying, the microwave frequency is 2500 minus MHz, the microwave drying time is 30-600 min, and the microwave power is 800 minus 1500W.
Further, the roasting temperature is 100-600 ℃, preferably 150-450 ℃, and most preferably 200-300 ℃; the roasting time is 1-24h, preferably 3-10 h.
In the above method, it should be understood by those skilled in the art that the first impregnation with the nonpolar solvent smaller than the size of the pore channels inside the carrier is performed by ultrasonic impregnation, so that the nonpolar solvent and the heteropoly acid solution are not mutually soluble, and the heteropoly acid solution cannot completely enter the pore channels of the molecular sieve during the second impregnation, so that the heteropoly acid solution is sufficiently adsorbed on the surface of the carrier. The dielectric constant of a nonpolar solvent such as cyclohexane and the like is very low, the nonpolar solvent cannot be heated to raise the temperature under microwave radiation, only the heteropoly acid aqueous solution subjected to secondary impregnation is dried during microwave drying, and the heteropoly acid precipitation caused by conventional heating is avoided by the microwave drying mode, so that the loading capacity and uniform loading of the heteropoly acid on the surface of the carrier are ensured; the cyclohexane does not destroy the pores of the carrier during the drying and calcination processes.
Compared with the prior art, the invention has the following advantages:
in the invention, a catalyst carrier is soaked in advance by using a nonpolar solvent which is insoluble in polar solvents such as water and the like, so that a small molecular solvent enters a carrier pore channel, and then the heteropoly acid is soaked, when microwave drying is used, on one hand, due to the low dielectric constant of the nonpolar solvent cyclohexane and the like, the carrier pore channel is filled with the nonpolar solvent and cannot be heated, the damage of the pore channel caused by the rapid temperature rise of water in the microwave drying process of the traditional aqueous solution soaking method is avoided, and the pore channel structure of the catalyst is protected; on the other hand, microwave drying and temperature rise are efficient, and separation of heteropoly acid in a traditional heating mode is avoided. Therefore, the preparation method enables the heteropoly acid to be more efficiently and uniformly loaded on the surface of the carrier, and improves the acidity and the catalytic efficiency of the catalyst; meanwhile, the operation efficiency and stability of the catalyst are guaranteed; in addition, microwave drying also reduces energy consumption.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. In the following examples and comparative examples, all the raw materials used were commercially available unless otherwise specified.
Comparative example 1
Mixing 38g of ZSM-5 zeolite with 28gSB powder, adding 60g of 15% dilute phosphoric acid, kneading on a strip extruding machine, extruding and molding to obtain a strip catalyst carrier with the diameter of 1.5mm, drying in an oven at 120 ℃ for 12 hours, and roasting in a muffle furnace at 550 ℃ for 6 hours to prepare the catalyst A. gamma-Al in catalyst 2 O 3 The content is 31 percent, and the ZSM-5 zeolite content is 68 percent.
Comparative example 2
The catalyst A obtained in the comparative example 1 is directly soaked in 80g of 5 percent silicotungstic acid aqueous solution by ultrasonic for 8 hours, dried in an oven at 120 ℃ for 12 hours and then roasted at 250 ℃ for 8 hours to obtain a modified catalyst B, wherein gamma-Al in the catalyst 2 O 3 Content of 31%, ZSM-5 zeolite contentThe amount was 68%.
Comparative example 3
Performing ultrasonic impregnation on the catalyst A by adopting cyclohexane for 8 hours, filtering the impregnated catalyst, performing ultrasonic impregnation on the catalyst A by adopting 80mL of 5 percent silicotungstic acid aqueous solution for 8 hours, drying the catalyst in an oven at 120 ℃ for 12 hours, and then roasting the catalyst at 250 ℃ for 8 hours to obtain a modified catalyst C, wherein gamma-Al in the catalyst 2 O 3 The content is 31 percent, and the content of ZSM-5 zeolite is 68 percent.
Comparative example 4
And (3) carrying out ultrasonic impregnation on the catalyst A by using 80g of 5% silicotungstic acid aqueous solution for 8 hours, drying in a 2450MHz vacuum microwave dryer for 60 minutes, and roasting at 250 ℃ for 8 hours to obtain a modified catalyst D. gamma-Al in catalyst 2 O 3 The content is 30.5 percent, and the content of ZSM-5 zeolite is 68 percent.
Example 1
Ultrasonically dipping a catalyst A60mL in cyclohexane for 8 hours, filtering the dipped catalyst, ultrasonically dipping the catalyst in 80mL of 5% silicotungstic acid aqueous solution for 8 hours, drying the catalyst in a 2450MHz vacuum microwave dryer for 60 minutes, and roasting the catalyst at 250 ℃ for 8 hours to obtain a modified catalyst E, wherein gamma-Al in the catalyst 2 O 3 The content is 30.5 percent, and the content of ZSM-5 zeolite is 68 percent.
Example 2
Mixing 40g of H beta zeolite and 30g of SB powder, adding 40g of 16% nitric acid aqueous solution, kneading on a strip extruding machine, extruding and molding to obtain a catalyst carrier with the diameter of 1.5mm, drying in an oven at 120 ℃ for 12 hours, and roasting in a muffle furnace at 550 ℃ for 6 hours to prepare the catalyst carrier. Performing ultrasonic impregnation on a catalyst carrier by adopting cyclohexane for 8 hours, filtering to obtain 60mL of the catalyst carrier, performing ultrasonic impregnation on the catalyst carrier by adopting a 5% phosphotungstic acid aqueous solution of 80mL for 8 hours, drying the catalyst carrier in a 2450MHz vacuum microwave dryer for 60 minutes, and then roasting the catalyst carrier for 8 hours at 250 ℃ to obtain a modified catalyst F, wherein gamma-Al in the catalyst 2 O 3 The content is 31 percent, and the content of beta zeolite is 67.5 percent.
Examples 3 to 5
According to the preparation method of the catalyst in the embodiment 1, the concentration and the volume of the heteropoly acid aqueous solution in the secondary impregnation process are improved, 60mL, 100mL and 150mL of 10% silicotungstic acid aqueous solution are respectively adopted for ultrasonic impregnation for 8 hours, a 2450MHz vacuum microwave dryer is used for drying for 60 minutes, and then the catalyst G, H and I after modification are obtained after roasting for 8 hours at 250 ℃. The contents of heteropoly acids were 3.2%, 5.1% and 8.3%, respectively.
The heteropoly acid content is determined by adding water solution containing given amount of heteropoly acid, soaking, filtering, measuring heteropoly acid content in mother liquor, and determining the amount of heteropoly acid adsorbed in the catalyst carrier. The contents of heteropoly acids and the analysis results in the examples are shown in Table 1.
Examples 6 to 8
According to the preparation method of the catalyst in the embodiment 2, the concentration and the volume of the heteropoly acid in the heteropoly acid aqueous solution in the secondary impregnation process are improved, 60mL, 100mL and 150mL of 10% phosphotungstic acid aqueous solution are respectively adopted for ultrasonic impregnation for 8 hours, a 2450MHz vacuum microwave dryer is used for drying for 60 minutes, and then the catalyst J, K and L are roasted for 8 hours at 250 ℃, so that the modified catalyst J, K and L are obtained. The contents of heteropoly acid are 3.4%, 5.8% and 8.6%, respectively. The results of the catalyst analyses in examples 6 to 8 are shown in Table 1
Determination of the catalyst Performance:
(1) the content, pore volume and specific surface area of heteropoly acid in the above catalysts were measured, and the results are shown in Table 1.
TABLE 1
Figure DEST_PATH_IMAGE001
(2) The catalysts of examples 1-8 and comparative examples 1-4 were used to catalyze isobutylene reaction to prepare tert-butylamine:
the direct amination reaction of isobutene adopts a fixed bed reactor, the size of the fixed bed reactor is phi 20mm multiplied by 1000mm, and the fixed bed reactor is made of a stainless steel single tube. The reactor is filled in three sections, a certain amount of quartz sand is filled at the bottom, 50mL of the catalyst prepared in the examples 1-8 and the catalysts prepared in the comparative examples 1-4 are respectively filled at the middle section, and the quartz sand is filled at the top until the catalyst is filled. Replacing air in the fixed bed reactor with mixed gas of nitrogen and ammonia gas for 24 hr before reaction, preheating the reaction material, and reactingThe reaction materials enter the fixed bed reactor, the reaction temperature is 180 ℃, the reaction pressure is 4.0MPa, the amino-olefin ratio is 1:1, and the isobutene liquid hourly space velocity is 0.5 h -1 The reaction is carried out under the conditions of (1), the reaction product is decompressed and cooled and then enters a product tank for separation, unreacted olefin and ammonia are discharged from the top, the liquid phase material at the bottom is weighed, and the isobutene conversion rate and the tert-butylamine selectivity are calculated by analyzing through gas chromatography, and the results are shown in table 2.
TABLE 2
Figure 537880DEST_PATH_IMAGE002

Claims (13)

1. A preparation method of a supported heteropolyacid catalyst comprises the following steps:
ultrasonically mixing a porous carrier with a nonpolar solvent with the size smaller than the size of an inner pore channel of the porous carrier, and carrying out primary impregnation, wherein the nonpolar solvent is selected from at least one of cyclohexane, hexane and benzene; after the completion, placing the porous carrier in a heteropoly acid solution for secondary impregnation; and after the secondary impregnation is finished, carrying out microwave drying, and roasting to obtain the supported heteropolyacid catalyst.
2. The method of claim 1, wherein the non-polar solvent is cyclohexane.
3. The method according to claim 1, wherein the porous support is selected from the group consisting of molecular sieves, activated carbon, alumina, ion exchange resins, and TiO 2 At least one of (1).
4. The method according to claim 1, wherein the heteropoly acid is selected from heteropoly acids having a Keggin structure or a Dawson structure.
5. The method according to claim 1, wherein the heteropoly acid is a heteropoly acid having a Keggin structure with a general open pore structureFormula H n AB 12 O 40 ·xH 2 The structure of O.
6. A method according to claim 1, wherein said heteropoly acid is selected from H 4 [Si(W 3 O 10 ) 4 ]·xH 2 O or H 3 PW 12 O 40 ·xH 2 O。
7. The preparation method of claim 1, wherein the temperature of the first impregnation is 0 ℃ to 60 ℃, and the ultrasonic impregnation time is 0.5h to 48 h.
8. The preparation method of claim 1, wherein the temperature of the secondary impregnation is 10 ℃ to 80 ℃, and the impregnation time is 1h to 24 h.
9. The method according to claim 1, wherein the volume ratio of the heteropoly acid solution to the carrier is 1:1 to 10: 1.
10. The method according to claim 1, wherein the concentration of the heteropoly acid in the heteropoly acid solution is 1% to 90%.
11. The method according to claim 10, wherein the concentration of heteropoly acid in the heteropoly acid solution is 3% to 20%.
12. The method as claimed in claim 1, wherein the microwave drying is vacuum microwave drying, the microwave frequency is 2500MHz, the microwave drying time is 30-600 min, and the microwave power is 800-1500W.
13. The preparation method of claim 1, wherein the roasting temperature is 100 ℃ to 600 ℃, and the roasting time is 1 to 24 hours.
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