Nothing Special   »   [go: up one dir, main page]

CN118204123B - Amination supported heteropolyacid catalyst, preparation method and application thereof - Google Patents

Amination supported heteropolyacid catalyst, preparation method and application thereof Download PDF

Info

Publication number
CN118204123B
CN118204123B CN202410444516.9A CN202410444516A CN118204123B CN 118204123 B CN118204123 B CN 118204123B CN 202410444516 A CN202410444516 A CN 202410444516A CN 118204123 B CN118204123 B CN 118204123B
Authority
CN
China
Prior art keywords
carrier
heteropolyacid
catalyst
equal
amination
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202410444516.9A
Other languages
Chinese (zh)
Other versions
CN118204123A (en
Inventor
李彦君
杨树斌
田晖
管嘉豪
刘媛媛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yantai University
Original Assignee
Yantai University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yantai University filed Critical Yantai University
Priority to CN202410444516.9A priority Critical patent/CN118204123B/en
Publication of CN118204123A publication Critical patent/CN118204123A/en
Application granted granted Critical
Publication of CN118204123B publication Critical patent/CN118204123B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Toxicology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention belongs to the field of materials, and particularly relates to an amination supported heteropolyacid catalyst, a preparation method and application thereof. The amination supported heteropolyacid catalyst comprises heteropolyacid and a carrier, wherein the heteropolyacid has the following chemical expression: PA xByC12‑nVnO40; the carrier is subjected to amination modification through low-temperature plasma treatment. The invention utilizes the low-temperature plasma technology to carry out modification treatment on the carrier, and can introduce amino functional groups on the surface of the carrier in a short time. Compared with the traditional supported catalyst, the preparation method provided by the invention can avoid the problem of agglomeration and easy loss of the catalytic active components on the carrier, and the prepared catalyst has the advantages of strong thermal stability, high catalytic efficiency, simple process, low cost and convenient separation, can be applied to catalyzing the oxidation of high-carbon aliphatic aldehyde into high carbonic acid, and improves the conversion rate and selectivity of the reaction.

Description

Amination supported heteropolyacid catalyst, preparation method and application thereof
Technical Field
The invention belongs to the field of materials, and particularly relates to a catalyst, in particular to an amination supported heteropolyacid catalyst, a preparation method and application thereof.
Background
2-Ethylhexanoic acid (2-Ethylhexanoic Acid, 2-EHA), commonly known as isooctanoic acid, is an important synthetic saturated branched fatty acid. The product has high purity and light color, and can be widely used for preparing paint drier, PVC stabilizer, medical salifying agent and the like by generally reacting with various metal compounds to generate isooctanoic acid metal salt; esters thereof are also used in bactericides, cosmetics, plasticizers and the like. With the rapid development of fields such as domestic high-grade light-colored paint, high-grade printing ink and the like, the demand of the isooctanoic acid can be in a future period.
There are generally two types of industrial processes for producing isooctanoic acid: one is an isooctanol oxidation method, the raw materials of the method are easy to obtain, the operation is simple, but the method has the problems of long process flow, large three-waste discharge, small production scale and the like, and a newly built device does not use the process to manufacture isooctanoic acid; the other is a butyraldehyde condensation hydrogenation oxidation method, which takes n-butyraldehyde as a raw material, produces 2-ethyl hexenal through condensation dehydration, then hydrogenates to obtain 2-ethyl hexanal, and finally oxidizes to obtain isooctanoic acid. The method has continuous production, high yield and easy mass production, is a main flow process for producing the isooctanoic acid at present, but the 2-ethylhexanal oxidation reaction process generally uses a traditional KMnO 4 and other strong oxidants, and the method can obtain higher target product yield but has serious environmental pollution. Therefore, the development of an environment-friendly synthesis process is a key for green production of isooctanoic acid in the future.
Patent CN1357527a discloses a method for preparing isooctanoic acid by oxidizing 2-ethylhexanal, which uses oxygen as oxidant to make reaction in a bubbling tower under the action of catalyst, but the lower reaction temperature increases engineering temperature control energy consumption. The patent CN1410407A, CN1422840A, CN111620772A uses a falling film reactor, a filler reaction tower and a microbubble oxidation reactor to replace a bubbling tower for reaction on the basis, and the reaction can be carried out at 25-50 ℃, but the structure of a reaction device is complex, the production investment cost is high, and the selectivity is not obviously improved.
Patent CN102701944A, US5739352 and CN110773234A, CN109433270A respectively adopt phosphomolybdic vanadium heteropolyacid, amine or amine-N-oxide, nano Jin Danhua carbon and porphyrin bionic supported catalyst to prepare isooctanoic acid. However, the above catalyst has the problems of difficult post-treatment of homogeneous catalyst (such as phosphomolybdic vanadium heteropolyacid, amine or amine-N-oxide), high catalyst preparation cost, poor mass transfer effect, long reaction time (such as nano Jin Danhua carbon and porphyrin bionic supported catalyst) and the like, and is difficult to industrialize.
Therefore, there is a need to develop a highly efficient catalyst for preparing isooctanoic acid by oxidizing 2-ethylhexanal, which achieves the continuous process flow and low-cost operation goals.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an amination supported heteropolyacid catalyst, a preparation method and application thereof. Compared with the traditional supported catalyst, the preparation method provided by the invention can avoid the problems of agglomeration and easy loss of the catalytic active components on the carrier, and the prepared catalyst has the advantages of strong thermal stability, high catalytic efficiency, simple process, low cost and convenient separation.
The specific technical scheme is as follows:
One of the purposes of the invention is to provide an amination supported heteropolyacid catalyst which comprises heteropolyacid and a carrier, wherein the heteropolyacid has the following chemical expression: PA xByC12-nVnO40;
wherein: a is at least one of K, rb and Cs; b is at least one of Ni, cu, zn, fe, co, mn, la, ce, sb, sn elements; c is Mo or/and W element;
wherein: x, y and z are mole coefficients, x is more than or equal to 0.01 and less than or equal to 6,0.01 y is less than or equal to 2, n is more than or equal to 0 and less than or equal to 3;
the carrier is subjected to amination modification through low-temperature plasma treatment.
Further, the carrier is preferably an oxide carrier, and specifically, is preferably at least one of nano silica, nano titania, nano zirconia, diatomaceous earth, and molecular sieve.
Further, the carrier is subjected to amination modification by low-temperature plasma treatment and then is subjected to quaternization treatment.
Further, the amination supported heteropolyacid catalyst preferably comprises 4-45 parts of heteropolyacid and 55-96 parts of carrier according to parts by weight.
Further preferably, in the chemical expression: x is more than or equal to 0.1 and less than or equal to 4,0.05 and y is more than or equal to n is more than or equal to 1.5 and less than or equal to 0 and less than or equal to 2.5.
Still more preferably, in the chemical expression: x is more than or equal to 0.2 and less than or equal to 3, and x is more than or equal to 0.1 and less than or equal to 3 y is less than or equal to 1, n is more than or equal to 0 and less than or equal to 2.
Specifically, the supported heteropolyacid catalyst is preferably at least one of the following chemical formulas:
PCs1.5Cu0.2Fe0.3Mo11VO40/TiO2-NH2；
PCs1.5Cu0.2Fe0.3Mo11VO40/SiO2-NH2；
PCs1.5Cu0.2Fe0.3Mo11VO40/ZrO2-NH2；
PCs1.5Cu0.2Fe0.3W11VO40/TiO2-NH2；
PCs3Ni0.1Mo11VO40/MCM41-NH2。
PCs0.2Ce0.8Mo10V2O40/TiO2-NH2；
PCs1.5Sn0.5Sb0.3Mo12O40/TiO2-NH2；
PK1.5MnMo11VO40/TiO2-NH2。
the second object of the present invention is to provide a method for preparing the aminated supported heteropolyacid catalyst, comprising the steps of:
S1, roasting: roasting the carrier;
S2, modification: the method comprises the steps of carrying out low-temperature plasma treatment on the roasted carrier to enable the carrier to be aminated and modified;
S3, heteropolyacid impregnation: immersing the modified carrier in heteropoly acid impregnating solution, adding a compound containing B element and a compound containing A element after impregnation, and drying to obtain catalyst powder; the heteropoly acid impregnating solution is an aqueous solution of at least one of phosphomolybdic acid, phosphotungstic acid, phosphomolybdic vanadic acid and phosphotungstic vanadic acid;
S4, roasting again: and roasting the catalyst powder to obtain the catalyst.
The invention innovatively utilizes the low-temperature plasma technology, and generates high-energy plasma through discharge so that the high-energy plasma can complete the amino grafting activation treatment on the surface of the carrier in a short time, thereby improving the synthesis efficiency, avoiding using an organic solvent and high-temperature and high-pressure reaction conditions, reducing the influence on the environment and uniformly loading amino functional groups on the surface of the carrier. In addition, the porous structure and the larger specific surface area of the carrier are beneficial to the adsorption and reaction of reactant molecules, the use amount of heteropoly acid can be reduced, more active sites are exposed, and the reaction activity of the heteropoly acid is improved.
Further, in step S1, specific conditions for firing are preferably: roasting for 2-24 h at 300-700 ℃. The calcination is preferably carried out in an air atmosphere.
Further, in step S1, the specific conditions for firing are preferably: roasting for 4-12 hours at 400-600 ℃.
Further, in step S2: after the low-temperature plasma modification treatment, the carrier after amination modification is preferably reacted with an alkyl halide and alkali or/and alkali salt, and the carrier is subjected to quaternization treatment to obtain a quaternized carrier.
The amino on the surface of the carrier can be further converted into quaternary ammonium salt through quaternization, so that the stability of the amino immobilized on the surface of the carrier is greatly improved; the heteropolyacid takes the quaternary ammonium salt functional group grafted on the surface of the carrier as an active falling site, and is firmly combined with the negatively charged heteropolyacid root under the extremely strong positive electric attraction of the quaternary ammonium salt to form the heteropolyacid ammonium salt, so that the bonding strength of the heteropolyacid and the carrier is improved, the problem that the heteropolyacid is easy to run off on the carrier is solved, meanwhile, the uniform quaternary ammonium salt distribution can regulate and control the solid-carrying mode of the heteropolyacid, and the agglomeration problem caused by the simple physical adsorption of the heteropolyacid is solved.
Further, in step S2, the conditions for the quaternization treatment are preferably: and (3) placing the amination modified carrier into an organic solvent, adding alkyl halide and sodium hydroxide, heating and stirring for 2-8 hours at 30-70 ℃, filtering, washing and drying to obtain the quaternary ammonium salt carrier.
Wherein, the alkyl halide is preferably at least one of bromomethane, bromoethane, iodomethane and iodoethane.
Wherein the organic solvent is preferably at least one of ethanol, dichloromethane, N-dimethylformamide, N-dimethylacetamide and toluene.
In the quaternization, the mass ratio of the carrier after the amination modification to the alkyl halide is preferably (0.2 to 0.8): 1.
In the quaternization treatment, the mass ratio of the carrier after amination modification to sodium hydroxide is preferably 1 (0.25-1).
Further, the conditions of the low temperature plasma modification treatment are as follows:
The carrier is placed in a radio frequency plasma generator, and is treated at 100-600 ℃ in an inert atmosphere and an ammonia atmosphere sequentially by using 5-150 kHz glow (radio frequency) plasma under the conditions that the power is 50-800W, the gas flow rate is 10-100 mL/min and the pressure in a plasma cavity is 5-150 Pa.
The treatment time of the carrier in the inert atmosphere is preferably 1 to 30min, more preferably 3 to 15min.
The carrier is preferably treated for 1-4 times, more preferably 2-3 times in an ammonia atmosphere; the treatment time is preferably 1 to 30 minutes, more preferably 3 to 15 minutes, per treatment.
The power of the RF plasma generator is more preferably 100-500W.
Wherein the gas flow rate is more preferably 20-80 mL/min.
Wherein the pressure in the plasma cavity is more preferably 10-100 Pa.
The frequency of the radio frequency plasma generator is more preferably 10-100 kHz.
Wherein the inert atmosphere preferably contains Ar.
The ammonia gas atmosphere is preferably a mixed gas of NH 3-N2, and the content of NH 3 in the mixed gas is preferably 5-20% (volume percent).
Wherein the temperature of the treatment in the ammonia atmosphere is more preferably 200-400 ℃.
And after the treatment of the radio frequency plasma generator is finished, continuing ventilation for 1-10 min for cooling.
Further, in step S3: the compound containing the element A and the compound containing the element B are at least one of nitrate, carbonate, sulfate, acetate, oxalate, chloride, hydroxide and oxide of corresponding elements.
Specifically, in step S3: dissolving heteropoly acid in water to prepare heteropoly acid impregnating solution, placing the modified carrier into the impregnating solution, stirring for a period of time, adding a compound solution containing B element into the mixed suspension, continuing stirring, adding a compound solution containing A element, continuing stirring, filtering and drying to obtain the supported heteropoly acid powder.
The preparation method of the heteropoly acid impregnating solution is preferably as follows: and adding the heteropolyacid into water, and stirring for 10-30 min at 25-50 ℃ to enable the heteropolyacid to be completely dissolved in the water.
In the step S3, the mass ratio of the modified carrier to the heteropoly acid in the heteropoly acid impregnating solution is preferably (1.5-25): 1.
In the step S3, the modified carrier is placed into heteropoly acid impregnating solution, and then heated and stirred for 1-4 hours at the temperature of 40-70 ℃ preferably.
In the step S3, after adding the compound containing the B element, heating and stirring are preferably performed at 50-90 ℃ for 30 min-2 h.
In the step S3, after adding the compound containing the element A, heating and stirring are preferably performed at 50-90 ℃ for 30 min-2 h.
In step S3, the water used is preferably deionized water.
In the step S3, the drying temperature is preferably 100-120 ℃, and the drying time is preferably 6-24 hours.
Further, in step S4, specific conditions for firing are preferably: roasting for 2-24 h at 200-400 ℃. The calcination is preferably carried out in an air atmosphere. The temperature rising rate of the roasting is preferably 2-10 ℃/min.
The invention further aims to provide an application of the amination supported heteropoly acid catalyst in catalyzing oxidation of high-carbon aliphatic aldehyde into high carbonic acid.
Test results prove that the amination supported heteropolyacid catalyst can improve the conversion rate and the selectivity of the reaction.
Wherein the carbon number of the high-carbon aliphatic aldehyde is more than or equal to 8. Preferably, the number of carbon atoms is 8 to 12, more preferably 8 to 9.
Further, the high-carbon fatty aldehyde is at least one of 2-ethylhexyl aldehyde (isooctyl aldehyde), n-octyl aldehyde, n-nonyl aldehyde and isononyl aldehyde.
The beneficial effects of the invention are as follows:
(1) According to the invention, the carrier is modified by utilizing a low-temperature plasma technology, amino functional groups can be introduced into the surface of the carrier in a short time, after the carrier is further processed into quaternary ammonium salt, the active component heteropolyacid is firmly immobilized on the carrier by utilizing an acid-base chemical reaction between the carrier and the heteropolyacid, and the supported heteropolyacid catalyst obtained by utilizing a chemical reaction mode has more ideal active component distribution, and further forms the heteropolyacid ammonium salt with higher thermal stability through subsequent roasting, so that the loading stability and the anti-loss property of the catalyst are greatly improved, the reduction of the catalytic activity caused by the agglomeration of the catalyst on the carrier is avoided, the dosage of the heteropolyacid can be reduced, and the use cost is reduced.
(2) The carrier is rich in pore channel structure and large in specific surface area, the diffusion and adsorption capacity of reactant molecules and oxygen are increased, the mass transfer effect of materials can be greatly promoted under the condition of gas-solid phase catalytic reaction, the reaction rate is increased, the residence time of the materials in the reactor is greatly shortened, the large-scale continuous production is easier to carry out, the phenomenon of selective reduction caused by excessive oxidation is reduced, and the yield of target products is improved. Under the process, the catalyst and the reaction system have no separation problem, and the post-treatment step of the catalyst under a liquid-solid system is avoided.
(3) The A element contained in the heteropoly acid catalyst can play a role in improving the thermal stability of the heteropoly acid catalyst and prolonging the catalytic life; the B element has the effect of accelerating electron transfer, and enhances the oxidation-reduction performance of the catalyst; the V element can improve the selectivity. Under the synergistic effect of the elements, the catalyst prepared by the invention has good catalytic effect, the conversion rate can reach more than 99.5%, and the selectivity can reach more than 90%.
Drawings
FIG. 1 is an X-ray diffraction pattern of the catalyst obtained in example 1 and comparative example 1 of the present invention;
FIG. 2 is a Fourier transform infrared spectrum of the catalyst obtained in example 1 and comparative example 1 of the present invention.
Detailed Description
The principles and features of the present invention are described below in connection with examples, which are set forth only to illustrate the present invention and not to limit the scope of the invention. The experimental methods used in the following examples are conventional methods unless otherwise specified. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
The preparation method of the amination supported heteropolyacid catalyst comprises the following steps:
S1, placing 30g of nano titanium dioxide into a roasting furnace, and roasting at a high temperature of 500 ℃ for 8 hours in air.
S2, preparing a modified carrier:
(1) Amination: cooling the roasted nano titanium dioxide to room temperature, placing the nano titanium dioxide in a radio frequency plasma generator with power of 100W, using Ar plasma with gas speed of 20mL/min, controlling the pressure in a generator cavity at 10Pa, and treating the nano titanium dioxide at 15kHz and 200 ℃ for 15min; performing ammonia gas atmosphere treatment, switching to NH 3-N2 plasma with ammonia gas content of 15%, and treating for 10min at 200 ℃ under the same condition; and (3) after ventilation for 10min and cooling, repeatedly treating the mixture once under the same ammonia gas atmosphere, and cooling to room temperature after ventilation for 10min to obtain the amination carrier.
(2) Quaternization: adding 12g of amination carrier into 200mL of absolute ethyl alcohol, adding 20g of bromomethane, adding 5.6g of sodium hydroxide, heating and stirring for 4 hours at 50 ℃, filtering, washing with absolute ethyl alcohol for three times, filtering and drying to obtain the quaternary ammonium salt carrier.
S3, dissolving 4.9g of phosphomolybdic vanadium heteropolyacid H 4PMo11VO40·10H2 O in 100mL of deionized water, and stirring for 20min at 40 ℃; 11.4g of quaternary ammonium salt carrier is put into the phosphomolybdic vanadium heteropolyacid solution to form suspension, and the suspension is stirred at 50 ℃ for 2h; dropwise adding 15 mL water mixture containing 0.12 g copper nitrate trihydrate and 0.3g ferric nitrate nonahydrate into the suspension, and stirring at 70deg.C for 30min; then 10mL of an aqueous solution containing 0.61g of cesium carbonate is added dropwise to the suspension, and stirring is continued for 2h at 70 ℃; drying at 100 deg.c for 18 hr to obtain the catalyst powder.
And S4, heating the catalyst powder to 380 ℃ at a heating rate of 10 ℃/min in an air atmosphere, and roasting 6 h to obtain the supported heteropolyacid catalyst.
The composition of the obtained catalyst is PCs 1.5Cu0.2Fe0.3Mo11VO40/TiO2-NH2, the X-ray diffraction diagram is shown in figure 1, and the Fourier transform infrared spectrum is shown in figure 2.
Example 2
Referring to example 1, the difference from example 1 is that: the nano titanium dioxide is replaced by nano silicon dioxide in equal mass. Other technical features are the same as those of embodiment 1.
The composition of the resulting catalyst was PCs 1.5Cu0.2Fe0.3Mo11VO40/SiO2-NH2.
Example 3
Referring to example 1, the difference from example 1 is that: the nano titanium dioxide is replaced by nano zirconium dioxide in equal mass. Other technical features are the same as those of embodiment 1.
The composition of the resulting catalyst was PCs 1.5Cu0.2Fe0.3Mo11VO40/ZrO2-NH2.
Example 4
Referring to embodiment 1, the difference from embodiment 1 is that in step S3: 4.9g of phosphomolybdic vanadium heteropolyacid H 4PMo11VO40·10H2 O was replaced by 7.3g of phosphotungstic vanadium heteropolyacid H 4PW11VO40·10H2 O. Other technical features are the same as those of embodiment 1.
The composition of the resulting catalyst was PCs 1.5Cu0.2Fe0.3W11VO40/TiO2-NH2.
Example 5
Referring to example 1, the difference from example 1 is that:
replacing the MCM41 molecular sieve with nano titanium dioxide in equal mass;
The step S3 is as follows: 4.9g of phosphomolybdic vanadium heteropolyacid H 4PMo11VO40·10H2 O is dissolved in 100mL of deionized water and stirred for 20min at 40 ℃; 19.6g of quaternary ammonium salt carrier is put into the phosphomolybdic vanadium heteropolyacid solution to form suspension, and the suspension is stirred at 50 ℃ for 2 h; dropwise adding 10mL aqueous solution containing 0.073g nickel nitrate hexahydrate into the suspension, and stirring at 90 ℃ for 1h; then 15mL of an aqueous solution containing 1.22g of cesium carbonate is added into the suspension in a dropwise manner, and stirring is continued for 1h at 90 ℃; drying at 100 ℃ for 18 hours to obtain catalyst powder;
The step S4 is as follows: and heating the catalyst powder to 200 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and roasting 24 h to obtain the amination supported heteropolyacid catalyst.
Other technical features are the same as those of embodiment 1.
The composition of the resulting catalyst was PCs 3Ni0.1Mo11VO40/MCM41-NH2.
Example 6
The preparation method of the amination supported heteropolyacid catalyst comprises the following steps:
S1, placing 30g of nano titanium dioxide into a roasting furnace, and roasting at a high temperature of 500 ℃ for 8 hours in air.
S2, preparing an amination carrier:
(1) Amination: cooling the roasted nano titanium dioxide to room temperature, placing the nano titanium dioxide in a radio frequency plasma generator with power of 300W, using Ar plasma and gas speed of 50mL/min, controlling the pressure in a generator cavity at 100Pa, and treating the nano titanium dioxide at 100kHz and 100 ℃ for 3min; performing ammonia gas atmosphere treatment, switching to NH 3-N2 plasma with ammonia gas content of 15%, and treating for 15min at 360 ℃ under the same condition; and (3) after ventilation for 5min and cooling, repeatedly treating for two times under the same ammonia gas atmosphere, and cooling to room temperature after ventilation for 15min to obtain the amination carrier.
(2) Quaternization: adding 12g of the amination carrier into 200mL of absolute ethyl alcohol, adding 40g of methyl iodide, adding 11.3g of sodium hydroxide, heating and stirring for 8 hours at 50 ℃, filtering, washing with the absolute ethyl alcohol for three times, filtering, and drying to obtain the quaternary ammonium salt carrier.
S3, dissolving 4.8g of phosphomolybdic vanadium heteropolyacid H 5PMo10V2O40·10H2 O in 100mL of deionized water, and stirring at 40 ℃ for 20min; 11.2g of quaternary ammonium salt carrier is put into the phosphomolybdic vanadium heteropolyacid solution to form suspension, and the suspension is stirred for 4 hours at 50 ℃; dropwise adding a 20 mL aqueous solution containing 1.1 g ammonium cerium nitrate into the suspension, and stirring for 1h at 90 ℃; then 10mL of water solution containing 0.082g of cesium carbonate is added into the suspension in a dropwise manner, and stirring is continued for 2h at 90 ℃; drying at 120 ℃ for 24 hours to obtain catalyst powder.
And S4, heating the catalyst powder to 380 ℃ at a heating rate of 10 ℃/min in an air atmosphere, and roasting 6 h to obtain the amination supported heteropolyacid catalyst.
The composition of the resulting catalyst was PCs 0.2Ce0.8Mo10V2O40/TiO2-NH2.
Example 7
Referring to embodiment 1, the difference from embodiment 1 is that step S3 is: 4.9g of phosphomolybdic vanadium heteropolyacid H 4PMo11VO40·10H2 O is dissolved in 100mL of deionized water and stirred for 20min at 40 ℃; 11.4g of quaternary ammonium salt carrier is put into the phosphomolybdic vanadium heteropolyacid solution to form suspension, and the suspension is stirred at 50 ℃ for 2h; to the suspension were added dropwise 5mL of a 20 mL aqueous solution containing 0.33g of tin tetrachloride and a 0.1M hydrochloric acid solution containing 0.17g of antimony trichloride, and the mixture was stirred at 90℃for 1 hour; then 10mL of aqueous solution containing 0.61g of cesium carbonate is added into the suspension in a dropwise manner, and stirring is continued for 2h at 90 ℃; drying at 100 deg.c for 18 hr to obtain the catalyst powder.
Other technical features are the same as those of embodiment 1.
The composition of the resulting catalyst was PCs 1.5Sn0.5Sb0.3Mo12O40/TiO2-NH2.
Example 8
The preparation method of the amination supported heteropolyacid catalyst comprises the following steps:
S1, placing 30g of nano titanium dioxide into a roasting furnace, and roasting at a high temperature of 500 ℃ for 8 hours in air.
S2, preparing an amination carrier:
(1) Amination: and (3) cooling the roasted nano titanium dioxide to room temperature, placing the nano titanium dioxide in a radio frequency plasma generator with power of 500W, using Ar plasma, controlling the pressure in the generator cavity at 50Pa and treating the nano titanium dioxide at 400 ℃ for 10min at the glow plasma of 50 kHz. Performing ammonia gas atmosphere treatment, switching to NH 3-N2 plasma with ammonia gas content of 15%, and treating for 3min at 400 ℃ under the same condition; and (3) after ventilation for 5min and cooling, repeatedly treating for three times under the same ammonia gas atmosphere, and cooling to room temperature after ventilation for 3min to obtain the amination carrier.
(2) Quaternization: 48g of the amination carrier is added into 400mL of absolute ethyl alcohol, 80g of ethyl iodide is added, 20.6g of sodium hydroxide is added, heating and stirring are carried out for 2 hours at 70 ℃, filtering is carried out, the amination carrier is washed three times by the absolute ethyl alcohol, filtering is carried out, and the quaternary ammonium salt amination carrier is obtained after drying.
S3, dissolving 2.45g of phosphomolybdic vanadium heteropolyacid H 4PMo11VO40·10H2 O in 200mL of deionized water, and stirring at 40 ℃ for 20min; putting 46.55g of quaternary ammonium salt carrier into the phosphomolybdic vanadium heteropolyacid solution to form suspension, and stirring for 30min at 50 ℃; dropwise adding 10mL aqueous solution containing 0.335g manganese acetate dihydrate into the suspension, and stirring at 70 ℃ for 30min; then 10mL of aqueous solution containing 0.14g of potassium chloride is added into the suspension in a dropwise manner, and stirring is continued for 1h at 70 ℃; drying at 100 deg.c for 18 hr to obtain the catalyst powder.
And S4, heating the catalyst powder to 380 ℃ at a heating rate of 10 ℃/min in an air atmosphere, and roasting 6 h to obtain the supported heteropolyacid catalyst.
The composition of the resulting catalyst was PK 1.5MnMo11VO40/TiO2-NH2.
Example 9
Referring to example 1, the difference from example 1 is that: step S2 (2) is not included, namely: the quaternized carrier in the subsequent step S3 is replaced by the aminated carrier obtained in the step S2 (1) in terms of quality without quaternization. Other technical features are the same as those of embodiment 1.
Comparative example 1
Referring to example 1, the difference from example 1 is that: and (3) without the step (S3), directly roasting the quaternary ammonium salt carrier obtained in the step (S2). Other technical features are the same as those of embodiment 1.
The X-ray diffraction diagram of the obtained catalyst is shown in figure 1, and the Fourier transform infrared spectrum is shown in figure 2.
Comparative example 2
Referring to example 1, the difference from example 1 is that: step S2 is not included, namely: and (3) not preparing a modified carrier, and replacing the quaternary ammonium salt carrier in the subsequent step S3 with the roasting carrier obtained in the step S1 in equal mass. Other technical features are the same as those of embodiment 1.
Comparative example 3
Referring to embodiment 1, the difference from embodiment 1 is that step S3 is: 4.9g of phosphomolybdic vanadium heteropolyacid H 4PMo11VO40·10H2 O is dissolved in 100mL of deionized water and stirred for 20min at 40 ℃; 11.4g of quaternary ammonium salt carrier is put into the phosphomolybdic vanadium heteropolyacid solution to form suspension, and the suspension is stirred at 50 ℃ for 2h;10 mL of an aqueous solution containing 0.61g of cesium carbonate was added dropwise to the suspension, and stirring was continued at 70℃for 2 hours; drying at 100 deg.c for 18 hr to obtain the catalyst powder. Namely: no compound containing B element was added.
The other technical features are the same as those of example 1.
Comparative example 4
Referring to embodiment 9, the difference from embodiment 9 is that in step S2: the low-temperature plasma modification is replaced by amination modification of the carrier by cetyl trimethyl ammonium bromide, and the method specifically comprises the following steps: 30g of the carrier obtained in the step S1 was dispersed in 200mL of toluene, 15g of cetyltrimethylammonium bromide was added, and the mixture was refluxed and stirred at 80℃for reaction for 12 hours, filtered, washed with absolute ethanol 3 times, and dried at 120℃for 10 hours to obtain an aminated carrier.
The other technical features are the same as those of example 9.
Test 1
The catalysts obtained in examples 1 to 9 and comparative examples 1 to 4 were evaluated for activity by a micro fixed bed reactor. The catalyst is crushed into particles with 20-40 meshes, 15mL of the catalyst is measured and is filled into a reactor, 5mL of quartz sand is filled up and down respectively, mixed gas containing 3.5% of 2-ethylhexanal, 46.5% of air, 25% of nitrogen and 25% of water vapor in volume fraction is introduced for reaction under the conditions of normal pressure and 220 ℃ of reaction temperature at the space velocity of 1000h -1, after the reaction is carried out for 100h, sampling is carried out, and quantitative analysis is carried out by using a gas chromatography by adopting an internal standard method, and the results are shown in the table 1.
Table 1 evaluation results of the reaction Performance of the catalyst for catalyzing the oxidation of 2-ethylhexanal to Isooctanoic acid
Experiment number Conversion of 2-ethylhexanal/% Isooctanoic acid selectivity/%
Example 1 99.8 90.6
Example 2 99.6 89.9
Example 3 99.8 89.5
Example 4 99.5 86.4
Example 5 99.7 86.3
Example 6 99.5 85.6
Example 7 99.7 90.4
Example 8 90.8 87.2
Example 9 92.6 85.3
Comparative example 1 70.2 36.3
Comparative example 2 81.3 73.4
Comparative example 3 92.5 80.7
Comparative example 4 83.1 77.6
As can be seen from Table 1, compared with comparative example 1, the addition of the heteropoly acid in example 1 significantly improved both the 2-ethylhexanal conversion and the isooctanoic acid selectivity of the resulting catalyst; compared with comparative example 2, the plasma treatment technique was used in example 1, and the 2-ethylhexanal conversion rate and isooctanoic acid selectivity of the obtained catalyst were both significantly improved. The 2-ethylhexanal conversion and isooctanoic acid selectivity of the resulting catalyst were better when elemental B was added as compared to comparative example 3, example 1. The 2-ethylhexanal conversion and isooctanoic acid selectivity of the resulting catalyst were significantly improved using plasma treatment techniques as compared to comparative example 4, example 9. Compared with example 8, the heteropoly acid loading in example 1 is higher, and the 2-ethylhexanal conversion rate is obviously increased; whereas the addition of the alkyl halide in example 1 for the quaternization compared to example 9 significantly increased the 2-ethylhexanal conversion and isooctanoic acid selectivity of the resulting catalyst.
Test 2
The supported heteropolyacid catalyst obtained in example 1 was evaluated for its catalytic performance for selective oxidation of other higher aliphatic aldehydes to the corresponding higher fatty acids to examine its applicability, and the results are shown in table 2. Preparation of n-octanoic acid, n-nonanoic acid, isononanoic acid referring to test 1, the equimolar amounts of 2-ethylhexanal were replaced with the reactants in Table 2, respectively.
TABLE 2 oxidative reactivity of amination supported heteropoly acid catalysts to catalyze other higher aliphatic aldehydes
Reactants Conversion/% Selectivity/%
N-octyl aldehyde 99.6 91.3
N-nonanal 99.5 90.8
Isononal 99.3 88.6
As can be seen from Table 2, the catalyst of the present invention is suitable for catalyzing the oxidation of other high-carbon aliphatic aldehydes to high-carbonic acid, and has high conversion rate and selectivity.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.

Claims (7)

1. An amination supported heteropolyacid catalyst comprises heteropolyacid and a carrier, and is characterized in that the heteropolyacid has the following chemical expression: PA xByC12-nVnO40;
wherein: a is at least one of K, rb and Cs; b is at least one of Ni, cu, zn, fe, co, mn, la, ce, sb, sn elements; c is Mo or/and W element;
wherein: x, y and z are mole coefficients, x is more than or equal to 0.01 and less than or equal to 6,0.01 y is less than or equal to 2, n is more than or equal to 0 and less than or equal to 3;
the carrier is an oxide carrier;
the carrier is subjected to amination modification through low-temperature plasma treatment;
the carrier is subjected to amination modification by low-temperature plasma treatment and then is subjected to quaternization treatment.
2. The supported aminated heteropolyacid catalyst according to claim 1, wherein the supported aminated heteropolyacid catalyst comprises 4-45 parts by weight of heteropolyacid and 55-96 parts by weight of carrier.
3. The aminated supported heteropolyacid catalyst according to claim 1, wherein: x is more than or equal to 0.1 and less than or equal to 4,0.05 and y is more than or equal to n is more than or equal to 1.5 and less than or equal to 0 and less than or equal to 2.5.
4. A method for preparing the aminated supported heteropolyacid catalyst according to any one of claims 1 to 3, comprising the steps of:
S1, roasting: roasting the carrier;
S2, modification: carrying out low-temperature plasma treatment on the roasted carrier to enable the carrier to be aminated and modified; after the low-temperature plasma modification treatment, the carrier reacts with alkyl halide and alkali or/and alkali salt, and quaternization treatment is carried out on the carrier;
S3, heteropolyacid impregnation: immersing the carrier in heteropoly acid impregnating solution, adding a compound containing B element and a compound containing A element after immersing, and drying to obtain catalyst powder; the heteropoly acid impregnating solution is an aqueous solution of at least one of phosphomolybdic acid, phosphotungstic acid, phosphomolybdic vanadic acid and phosphotungstic vanadic acid;
S4, roasting again: and roasting the catalyst powder to obtain the catalyst.
5. The method according to claim 4, wherein the alkyl halide is at least one of methyl bromide, ethyl bromide, methyl iodide and ethyl iodide.
6. The method according to claim 4, wherein in step S2, the conditions for the low-temperature plasma modification treatment are as follows:
The carrier is placed in a radio frequency plasma generator, and is treated at 100-600 ℃ in an inert atmosphere and an ammonia atmosphere sequentially under the conditions that the power is 50-800W, the gas flow rate is 10-100 mL/min and the pressure in a plasma cavity is 5-150 Pa and by using 5-150 kHz glow plasma.
7. Use of the aminated supported heteropoly acid catalyst according to any one of claims 1-3 for catalyzing oxidation of high-carbon aliphatic aldehydes to high-carbonic acid.
CN202410444516.9A 2024-04-15 2024-04-15 Amination supported heteropolyacid catalyst, preparation method and application thereof Active CN118204123B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202410444516.9A CN118204123B (en) 2024-04-15 2024-04-15 Amination supported heteropolyacid catalyst, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202410444516.9A CN118204123B (en) 2024-04-15 2024-04-15 Amination supported heteropolyacid catalyst, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN118204123A CN118204123A (en) 2024-06-18
CN118204123B true CN118204123B (en) 2024-10-22

Family

ID=91450373

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202410444516.9A Active CN118204123B (en) 2024-04-15 2024-04-15 Amination supported heteropolyacid catalyst, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN118204123B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111744518A (en) * 2020-07-09 2020-10-09 烟台大学 Amino acid modified supported heteropolyacid salt catalyst and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5319119A (en) * 1991-03-15 1994-06-07 Asahi Kasei Kogyo Kabushiki Kaisha Oleophilic molybdenum compound for use in hydroconversion of a hydrocarbon and a method for producing the same
CN1814348A (en) * 2005-01-31 2006-08-09 中国科学院化学研究所 Solid-phase photocatalyst utilizing visible light and its preparing method
CN105289675A (en) * 2015-10-21 2016-02-03 中国科学院过程工程研究所 Nanometer heteropolyacid catalyst used for preparing methacrylic acid through oxidation of methacrolein
CN106519298B (en) * 2016-10-26 2019-02-15 河南工程学院 A kind of preparation method of PA66 grafting carbon nanotube
CN109046452B (en) * 2018-05-29 2022-02-08 南京大学 Immobilized heteropolyacid catalyst and preparation method and application thereof
CN117160534B (en) * 2023-11-03 2023-12-29 烟台大学 Heteropolyacid composite oxide catalyst and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111744518A (en) * 2020-07-09 2020-10-09 烟台大学 Amino acid modified supported heteropolyacid salt catalyst and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杂多酸盐类催化剂催化正丙醇氧化制备丙酸的研究;刘敏雪;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20220115(第1期);第17页2.1；第22-23页，2.6.2 *

Also Published As

Publication number Publication date
CN118204123A (en) 2024-06-18

Similar Documents

Publication Publication Date Title
CN103638956A (en) Catalyst for synthesizing methyl acrylate by trioxymethylene or paraformaldehyde and acetic acid and acetic acid aqueous solution, its preparation and its application method
CN100457263C (en) Catalyst for synthesizing low-carbon carboxylate
CN104001543B (en) A kind of catalyst of the oxidation of aldehydes methacrylic acid processed of metering system and preparation method thereof
CN103586067B (en) Method for synthesizing acrylic acid by aqueous formaldehyde solution and acetic acid
CN106391001A (en) Active carbon loaded ruthenium-platinum bimetallic composite catalyst, preparation method and application
CN111744518B (en) Amino acid modified supported heteropolyacid salt catalyst and preparation method thereof
CN101455976A (en) Effective catalyst used in hydrogenation of dimethyl oxalate to synthesizing ethylene glycol and production method thereof
CN111229265B (en) Metal modified hydroxyapatite catalyst and preparation and application thereof
CN115646501B (en) Cobalt monoatomic catalyst synthesized by molten salt method and application thereof
CN104353465B (en) A kind of catalyst used by formaldehyde through catalytic oxidation and preparation method thereof
CN114210372B (en) Fe-based denitration ammonia synthesis catalyst and preparation method and application thereof
CN118204123B (en) Amination supported heteropolyacid catalyst, preparation method and application thereof
CN111229266B (en) Supported hydroxyapatite catalyst and preparation and application thereof
CN112479875A (en) Method for preparing alpha-oxo-carboxylic ester by selective oxidation of alpha-hydroxy-carboxylic ester
CN112387272B (en) Titanium-manganese-cerium co-oxide catalytic material, preparation method thereof and application thereof in synthesis of methacrylonitrile
CN114210352B (en) Preparation method and application of transition metal doped aluminum phosphate catalyst
CN114425367B (en) Catalyst system for preparing acrylic ester by carbonylation of acetylene, preparation and application thereof
CN112569945B (en) Metal-loaded dolomite catalyst for preparing ethanol by glycerol dehydration and preparation thereof
CN114349973A (en) Lanthanum-manganese bimetal quasi-organic framework material and preparation method and application thereof
CN112206800B (en) Nitrogen-sulfur doped carbon material supported palladium catalyst, preparation method thereof and application thereof in tetrahydrophthalic anhydride hydrogenation reaction
CN111514930B (en) Ionic liquid stable monoatomic catalyst and preparation method and application thereof
CN109225227A (en) A kind of order mesoporous C catalyst and preparation method thereof being used to prepare hexahydrophthalic anhydride
CN113398917A (en) Preparation method of hydrotalcite-like molybdenum oxide catalyst and application of hydrotalcite-like molybdenum oxide catalyst in synthesis of methacrylic acid from isobutyraldehyde
CN113457700B (en) Vanadium-phosphorus-oxygen catalyst for aldol condensation and preparation method and application thereof
CN118527170B (en) Molecular sieve encapsulated heteropolyacid salt composite catalyst, preparation method and application thereof

Legal Events

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