CN117943098A - Oxidation-esterification catalyst, preparation method and application - Google Patents

Oxidation-esterification catalyst, preparation method and application Download PDF

Info

Publication number
CN117943098A
CN117943098A CN202410050173.8A CN202410050173A CN117943098A CN 117943098 A CN117943098 A CN 117943098A CN 202410050173 A CN202410050173 A CN 202410050173A CN 117943098 A CN117943098 A CN 117943098A
Authority
CN
China
Prior art keywords
copper
catalyst
silicon
molecular sieve
vanadium
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.)
Pending
Application number
CN202410050173.8A
Other languages
Chinese (zh)
Inventor
王旭
方子来
张永鹏
何光文
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.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Priority to CN202410050173.8A priority Critical patent/CN117943098A/en
Publication of CN117943098A publication Critical patent/CN117943098A/en
Pending legal-status Critical Current

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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • 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
    • 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
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention provides an oxidation esterification catalyst, a preparation method and application thereof, wherein the catalyst consists of a copper silicon vanadium molecular sieve carrier and an alkaline earth metal oxide modified active component loaded on the carrier, and the carrier is a copper silicon vanadium molecular sieve porous pellet embedded with SO 4 2‑; the active component is composite oxide powder of cerium and molybdenum. The catalyst of the invention has the oxidation and esterification functions. The catalyst provided by the invention realizes the function of preparing methyl methacrylate by oxidizing and esterifying the methacrolein in one reactor, effectively reduces equipment investment and has industrial value.

Description

Oxidation-esterification catalyst, preparation method and application
Technical Field
The invention belongs to the technical field of organic synthesis catalysts, and particularly relates to an oxidation esterification catalyst, a preparation method and application thereof in preparation of methyl methacrylate by oxidation esterification of methacrolein.
Background
Methyl Methacrylate (MMA) is an important chemical raw material, can be used for producing polymethyl methacrylate (PMMA) plastics and other engineering plastics, PVC modifiers, adhesives, surface coatings and the like, and has very broad market prospect. The current industrial processes for producing MMA mainly comprise a C4 method, an acetone cyanohydrin method and an ethylene method.
The main process flow of the C4 method is as follows: the isobutene and oxygen are oxidized under the action of a molybdenum-based catalyst to prepare methacrolein, the methacrolein is oxidized again to prepare methacrylic acid, and the methacrylic acid and methanol are further esterified to generate MMA. The acetone cyanohydrin process is limited by the high pollution and high toxicity of the raw material hydrofluoric acid. The main flow of the ethylene method is as follows: ethylene reacts with methanol to produce methyl propionate, which reacts with formaldehyde to produce methyl methacrylate and methyl ester.
Patent CN115532280A reports a catalyst for continuously preparing methyl methacrylate by oxidative esterification, and a preparation method and application thereof, wherein the catalyst is prepared by loading a main catalytic component and a co-catalytic component on a catalyst carrier; wherein: the catalyst carrier raw material is one of particles CaCO 3, mgO, znO or Al 2O3, the particle size is 0.1-10 mu m, and attapulgite with the mass ratio of 2-20% is added in the catalyst carrier forming process; the main catalytic component is one of Pd or Pt; the auxiliary catalytic component is one or two of Pb, bi, fe or La. The catalyst is used in a fixed bed reactor, can complete one-step oxidation-esterification reaction of methacrolein, and meets the requirement of a continuous process for preparing methyl methacrylate. Before the catalyst prepared by the process is put into use, formaldehyde solution is introduced at normal temperature and normal pressure for reduction or hydrogen is introduced at normal pressure for reduction, formaldehyde is introduced in the production process of the continuous device, and meanwhile, the running cost of the device is increased.
Patent CN112823876B reports a catalyst for preparing MMA by direct oxidative esterification, which is composed of a carrier and an active component modified by an oxidizing agent and supported on the carrier, and a preparation method thereof; the carrier is a porous porcelain ball embedded with alkaline earth metal. In the preparation process of the catalyst, an oxidant such as ozone, hydrogen peroxide, hypochlorous acid and the like is introduced, and meanwhile, noble metal gold is used as an active component, so that the production cost of the catalyst is increased.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the catalyst for preparing MMA by direct oxidation and esterification and the preparation method thereof, the preparation method of the catalyst is simple, the copper-silicon-vanadium molecular sieve improves the stability and activity of the catalyst, and the introduction of copper and vanadium ions improves the conversion rate of esterification reaction; SO 4 2- with a catalyst pore canal is embedded, SO that the rate of esterification reaction is further improved; the cerium molybdenum oxide component loaded on the surface of the sphere improves the activity of the oxidation reaction and the selectivity of methacrylic acid which is an oxidation reaction target product.
It is a further object of the present invention to provide the use of such a catalyst in the oxidative esterification of MMA.
In order to achieve the above object, the present invention has the following technical scheme:
The oxidation and esterification catalyst comprises a copper silicon vanadium molecular sieve carrier and an alkaline earth metal oxide modified active component loaded on the carrier, wherein the carrier is a copper silicon vanadium molecular sieve porous pellet embedded with SO 4 2-; the active component is composite oxide powder of cerium and molybdenum.
In the catalyst, the mass percent of the carrier is 85-90%, such as 85%, 86%, 87%, 88%, 89%, 90%, etc., and the mass percent of the alkaline earth metal oxide modified active component is 10-15%, such as 10%, 11%, 12%, 13%, 14%, 15%, etc.;
Preferably, the molar ratio of vanadium, silicon, copper, cerium and molybdenum in the catalyst is 1: (40-100): (20-50): (2-4): (10-40), for example 1: (40, 50, 60, 70, 80, 90, 100): (20, 30, 40, 50): (2, 3, 4): any one of the ratio combinations of (10, 20, 30, 40), preferably 1: (60-80): (35-45): (2.5-3.5): (25-35).
In another aspect, a method for preparing the one-step oxidative esterification catalyst comprises the steps of:
1) Preparation of porous pellets of a carrier molecular sieve:
i) Adding a hard template agent into a silicon source solution, stirring uniformly, adding a vanadium source and a copper source, stirring at room temperature under a closed condition to obtain a mixed solution, centrifugally separating and filtering the mixed solution, washing a filter cake with deionized water, roasting, and removing the hard template agent to obtain the copper-silicon-vanadium molecular sieve;
ii) mixing the copper silicon vanadium molecular sieve with water and a pore-forming agent to prepare a ball with a pore canal inside; drying and roasting to obtain porous molecular sieve pellets;
iii) Placing the porous pellets in sulfate aqueous solution, and impregnating to obtain copper silicon vanadium molecular sieve porous pellets embedded with SO 4 2-;
2) Preparing composite oxide powder:
uniformly stirring a cerium source and a molybdenum source in water, standing, and then drying, roasting and crushing to obtain composite oxide powder;
3) Placing the SO 4 2- -embedded copper-silicon-vanadium molecular sieve porous pellets of the step 2) into a coating machine, enabling the composite oxide powder of the step 3) to be attached to the porous pellets under centrifugal force, drying and roasting to obtain a catalyst finished product.
In some specific embodiments, the silicon source in i) of step 1) is at least one of white carbon black, silica sol, solid silica gel, organosilicate, water glass, preferably silica sol;
The copper source is one or two or more of copper nitrate, copper chloride, copper sulfate monohydrate, copper sulfate pentahydrate, copper oxide, copper acetate, cuprous chloride, copper oxalato, copper oxalate and basic copper carbonate, preferably at least one of copper nitrate, copper oxide and copper acetate;
The vanadium source is vanadate, preferably at least one of metavanadate, orthovanadate, pyrovanadate and decavanadate, preferably sodium vanadate; among these are metavanadate MVO 3, orthovanadate M 3VO4 and pyrovanadate M 4V2O7, vanadate containing (V 3O9)3- or (the ion of V 4O12)4- is also called metavanadate, and vanadate containing (the ion of V 10O28)6- is called decavanadate).
The hard template agent is carbon nano material and/or foam carbon; preferably, the carbon nanomaterial is a carbon nanotube, carbon nanofiber and/or nanocarbon sphere; the density of the carbon foam is 0.08-0.80g/cm 3, such as 0.1g/cm3、0.2g/cm3、0.3g/cm3、0.4g/cm3、0.6g/cm3、0.7g/cm3, etc., preferably 0.2-0.5g/cm 3; in the invention, the hard template agent is preferably a carbon nanotube (also called a Barbary tube), the typical diameter of a single-wall tube of the carbon nanotube is 0.6-2nm, the innermost layer of the multi-wall tube can reach 0.4nm, the coarsest layer can reach hundreds of nanometers, but the typical tube diameter is 2-100nm. Mesoporous carbon nanotubes with diameters of 2-50nm are preferred in the present invention.
In some preferred embodiments, the vanadium source: silicon source: copper source: the molar ratio of the hard template agent is 1: (300-500): (100-300): (50 to 100), preferably 1: (360-460): (150-250): (60-80);
in some preferred embodiments, the stirring is at room temperature for 4 to 8 hours;
the roasting is carried out for 12-16 hours at 450-550 ℃ in a muffle furnace.
In some specific embodiments, the molar ratio of vanadium, silicon and copper in the prepared copper silicon vanadium molecular sieve is 1: (40-100): (20 to 50), preferably 1: (60-80): (35-45);
preferably, the diameter of the prepared copper silicon vanadium molecular sieve pellets is 3-5 mm, preferably 3.5-4.5 mm.
In some specific embodiments, the pore-forming agent in ii) of step 1) is at least one of polymethyl methacrylate microspheres, polypropylene microspheres, polyethylene microspheres, aminopolymethyl methacrylate microspheres, carboxy polymethyl methacrylate microspheres, preferably polymethyl methacrylate microspheres;
Preferably, the pore-forming agent has a diameter of 5 to 20. Mu.m, preferably 10 to 15. Mu.m;
More preferably, the mass ratio of the copper silicon vanadium molecular sieve to water and pore-forming agent is (8-10): (2:4): 1, for example 8:2: 1. 9:3: 1. 10:4: 1. 9:4:1, etc.
In some specific embodiments, the aqueous solution of sulfate salt in iii) of step 1) is one or more of sodium sulfate, potassium sulfate, ammonium sulfate, magnesium sulfate, preferably the aqueous solution of sulfate salt has a concentration of 10 to 20wt%, preferably 10wt% aqueous solution of sodium sulfate.
In some specific embodiments, the cerium source in step 2) is one or more of cerium sulfate, cerium nitrate, cerium chloride, cerium oxide, preferably cerium oxide;
the molybdenum source is one or more of ammonium polymolybdate, molybdenum trioxide, molybdic acid and molybdenum disulfide, preferably molybdenum trioxide;
Preferably, the stirring is uniform and the mixture is kept stand, the stirring is uniform at the temperature of 40-80 ℃, and the mixture is kept stand for 12-24 hours at the constant temperature;
More preferably, the molar ratio of cerium to molybdenum in the prepared oxide-loaded powder is 1: (5-10), preferably 1: (6.5-8.5); the diameter of the prepared catalyst particles is 3-5 mm, preferably 3.5-4.5 mm.
In some specific embodiments, the drying in step 3) is at a temperature of 150 to 200 ℃ for a period of 12 to 24 hours;
The roasting is carried out at the temperature of 450-550 ℃ for 12-24 hours.
In yet another aspect, the use of the oxidative esterification catalyst described above or the oxidative esterification catalyst prepared by the method described above in the oxidative esterification of methacrolein to prepare methyl methacrylate.
In some specific embodiments, the method comprises the steps of filling the oxidative esterification catalyst particles into a fixed bed reactor, and introducing methacrolein, methanol and air into the reactor for oxidative esterification reaction to prepare methyl methacrylate;
Preferably, the methacrolein liquid phase feed space velocity is from 0.5 to 2.5h -1, preferably from 0.8 to 1.5h -1;
the molar ratio of methacrolein to methanol was 1:1.05 to 1.3, preferably 1: (1-1.2);
The molar ratio of methacrolein to oxygen is 1:0.6 to 0.7, preferably 1: (0.64-0.66);
the reaction temperature is 100-150 ℃, and the reaction pressure is 0.05-0.2 MPa.
Compared with the prior art, the application has the following beneficial effects:
The invention innovatively realizes that one catalyst has two catalytic performances at the same time, and realizes two-step reactions of oxidizing and esterifying the methacrolein in the same reactor. The raw material methacrolein adopts liquid phase feeding, and can be subjected to two-step reaction of oxidation and esterification simultaneously or respectively in a reactor according to actual production conditions, so that the flexibility of the reaction is improved.
Drawings
FIG. 1 is a schematic illustration of the process flow of methyl methacrylate according to the invention.
Wherein, 1 is tower reactor, 2 is circulating pump, 3 is heater, 4 is methyl alcohol, 5 is nitrogen gas, 6 is air, 7 is methacrolein, 8 is overhead extraction, 9 is tower cauldron extraction.
Detailed description of the preferred embodiments
The invention is further described below with reference to the accompanying drawings, but the invention is not limited thereto.
A method for preparing an oxidative esterification catalyst, comprising the steps of:
a. Preparation of catalyst support pellets: adding a hard template agent into a silicon source solution, stirring uniformly, adding a vanadium source and a copper source, stirring for 4-8 hours at room temperature under a closed condition to obtain a mixed solution, centrifugally separating and filtering the solution, washing a filter cake with deionized water, placing the filter cake in a muffle furnace, roasting at 500 ℃ for 12-16 hours, and removing the hard template agent to obtain the copper-silicon-vanadium molecular sieve; mixing the molecular sieve with water and pore-forming agent, and making into pellets with pore channels; placing the pellets into a muffle furnace for drying and roasting to obtain porous pellets; placing the porous pellets into an SO 4 2- aqueous solution, and dipping to obtain porous ceramic pellets embedded with SO 4 2-;
b. Preparing composite oxide powder, uniformly stirring a cerium source and a molybdenum source in deionized water at 40-80 ℃, keeping the temperature for 12-24 hours, and then drying, roasting and crushing to obtain the composite oxide powder;
c. Placing the porous pellets embedded with SO 4 2- into a coating machine, enabling active components to be attached to pellet carriers under centrifugal force, drying and roasting to obtain a catalyst finished product;
d. The catalyst particles are filled into a fixed bed reactor, and the methyl acraldehyde, the methanol and the air are introduced into the reactor for oxidation and esterification reaction to prepare the methyl methacrylate.
FIG. 1 is a schematic diagram of a process flow of methyl methacrylate of the invention, in a tower reactor 1, methyl acrolein 7 is introduced, in order to ensure that methanol and methacrylic acid are fully contacted, methanol 4 is fully and uniformly mixed by two feed materials, air 6 and nitrogen 5 and then enters the reactor, three materials are subjected to oxidation esterification reaction in the reactor to prepare methyl methacrylate, a part of materials at the tower bottom is returned to a reaction tower through a circulating pump 2 and a heater 3, a part of materials at the tower bottom are extracted 9, and materials at the tower top are extracted 8 from the tower top.
The following examples were mainly prepared from the following raw materials:
Template agent: the Baki tube is purchased from Zhongkerui, the external diameter is 10-30nm, the internal diameter is 2-4nm, and the length is 5-15um; the carbon content is more than 95 percent.
Other raw materials not specifically described are available directly from the market.
The analytical instrument and method employed in the examples were as follows:
the catalyst comprises the following components in percentage by weight: nuclear magnetism, varian-NMR 300;
Oxidative conversion and esterification conversion:
Gas chromatograph: agilent-7820;
Gas chromatographic column: DB-5 capillary column with the thickness of 0.25mm multiplied by 30m, detector FID, vaporizing chamber temperature of 280 ℃, column box temperature of 280 ℃, FID detector temperature of 300 ℃, argon current-carrying capacity of 2.1mL/min, hydrogen flow of 30mL/min, air flow of 400mL/min and sample injection amount of 1.0 mu L. The conversion of the alkene and the selectivity of the product were calculated using an area normalization method. Heating program: preheating to 40 deg.C, maintaining for 5min, and heating from 40 deg.C to 280 deg.C at 15 deg.C/min for 2min.
Example 1: catalyst preparation
(1) Preparation of carrier pellets:
① Under the condition of airtight stirring, 3672g of silica sol (SiO 2*8H2 O) is added into 5000g of deionized water, meanwhile, after 42g of buckytube is added and fully and uniformly mixed, 9.2g of sodium vanadate and 800g of copper oxide are added, stirring is carried out for 6 hours at room temperature, a mixed solution is obtained, centrifugal separation and filtration are carried out on the solution, a filter cake is washed by deionized water, and then the solution is placed in a muffle furnace for roasting for 16 hours at 500 ℃, and the buckytube is removed, thus obtaining the copper-silicon-vanadium molecular sieve.
② Taking 500g of the copper-silicon-vanadium molecular sieve, adding 10g of polymethyl methacrylate microspheres, adding 200g of water, and preparing a pill with a pore canal inside by a pill making machine; placing the pellets into a muffle furnace for drying and roasting to obtain porous pellets with the diameter of 4 mm;
③ Placing the pellets into a 10% sodium sulfate solution, uniformly stirring, soaking for 10 hours, placing the pellets into a muffle furnace, and roasting for 8 hours at 500 ℃ to obtain porous pellets embedded with SO 4 2-;
(2) Preparing catalyst pellets:
Taking 15.6g of cerium oxide and 93.6g of molybdenum trioxide, uniformly stirring in 200g of deionized water at 40-80 ℃, keeping the temperature for 12-24 hours, vacuum drying at 200 ℃ for 8 hours, and crushing to obtain active component powder. 30g of active component is attached to 300g of carrier in a centrifugal way on a high-speed coating machine, 5g of ethanol is added as a binder in the process, and then the catalyst pellets are obtained by drying at 150 ℃ for 2h and roasting at 500 ℃ for 4 h. Herein simply referred to as catalyst 1.
Example 2:
preparation procedure with reference to example 1, except that copper oxide was added in an amount of 600g to prepare catalyst pellets, abbreviated herein as catalyst 2.
Example 3:
the preparation process was conducted in accordance with example 1, except that 1000g of copper oxide was added to prepare catalyst pellets, which were abbreviated as catalyst 3 herein.
Example 4:
preparation procedure referring to example 1, except that molybdenum trioxide was added in an amount of 122.4g, catalyst pellets, herein abbreviated as catalyst 4, were prepared.
Comparative example 1:
(1) Preparation of carrier pellets:
① Under the condition of airtight stirring, 3672g of silica sol (SiO 2*8H2 O) is added into 5000g of deionized water, meanwhile, after 42g of buckytube is added and fully and uniformly mixed, 9.2g of sodium vanadate and 800g of copper oxide are added, stirring is carried out for 6 hours at room temperature, a mixed solution is obtained, centrifugal separation and filtration are carried out on the solution, a filter cake is washed by deionized water, and then the solution is placed in a muffle furnace for roasting for 16 hours at 500 ℃, and the buckytube is removed, thus obtaining the copper-silicon-vanadium molecular sieve.
② Taking 500g of the copper-silicon-vanadium molecular sieve, adding 10g of polymethyl methacrylate microspheres, adding 200g of water, and preparing a pill with a pore canal inside by a pill making machine; placing the pellets into a muffle furnace for drying and roasting to obtain porous pellets with the diameter of 4 mm;
(2) Preparing catalyst pellets:
Taking 15.6g of cerium oxide and 93.6g of molybdenum trioxide, uniformly stirring in 200g of deionized water at 40-80 ℃, keeping the temperature for 12-24 hours, vacuum drying at 200 ℃ for 8 hours, and crushing to obtain active component powder. 30g of active component is attached to 300g of carrier in a centrifugal way on a high-speed coating machine, 5g of ethanol is added as a binder in the process, and then the catalyst pellets are obtained by drying at 150 ℃ for 2h and roasting at 500 ℃ for 4 h. Here simply referred to as catalyst 5.
Comparative example 2: preparation of carrier pellets:
① Under the condition of airtight stirring, 3672g of silica sol (SiO 2*8H2 O) is added into 5000g of deionized water, meanwhile, after 42g of buckytube is added and fully and uniformly mixed, 9.2g of sodium vanadate and 800g of copper oxide are added, stirring is carried out for 6 hours at room temperature, a mixed solution is obtained, centrifugal separation and filtration are carried out on the solution, a filter cake is washed by deionized water, and then the solution is placed in a muffle furnace for roasting for 16 hours at 500 ℃, and the buckytube is removed, thus obtaining the copper-silicon-vanadium molecular sieve.
② Taking 500g of the copper-silicon-vanadium molecular sieve, adding 10g of polymethyl methacrylate microspheres, adding 200g of water, and preparing a pill with a pore canal inside by a pill making machine; placing the pellets into a muffle furnace for drying and roasting to obtain porous pellets with the diameter of 4 mm;
③ Placing the pellets into a 10% sodium sulfate solution, stirring uniformly, soaking for 10 hours, placing the pellets into a muffle furnace, and roasting for 8 hours at 500 ℃ to obtain porous pellets embedded with SO 4 2-. Here simply referred to as catalyst 6.
Comparative example 3: preparation of Carrier pellets
① Under the condition of airtight stirring, 3672g of silica sol (SiO 2*8H2 O) is added into 5000g of deionized water, meanwhile, after 42g of buckytube is added and fully and uniformly mixed, 9.2g of sodium vanadate and 800g of copper oxide are added, stirring is carried out for 6 hours at room temperature, a mixed solution is obtained, centrifugal separation and filtration are carried out on the solution, a filter cake is washed by deionized water, and then the solution is placed in a muffle furnace for roasting for 16 hours at 500 ℃, and the buckytube is removed, thus obtaining the copper-silicon-vanadium molecular sieve.
② Taking 500g of the copper-silicon-vanadium molecular sieve, adding 10g of polymethyl methacrylate microspheres, adding 200g of water, and preparing a pill with a pore canal inside by a pill making machine; placing the pellets into a muffle furnace for drying and roasting to obtain porous pellets with the diameter of 4 mm; here simply referred to as catalyst 7.
Example 5:
5L of the catalyst 1 prepared in example 1 was placed in a fixed bed reactor, the upper and lower layers were packed and the heights were uniform, 4.2kg/h of methacrolein was fed into the reactor at a space velocity corresponding to 1h -1 and 2.11kg/h of methanol, and at the same time, air was fed into the reactor at a flow rate of 4.2Nm 3/h, and the temperature was raised to 100 ℃.
Example 6:
The procedure is as in example 5, except that the methacrolein feed amount is 5kg/h, the corresponding liquid phase feed space velocity is 1.2h -1, the methanol feed amount is 2.51kg/h, and the air feed amount is 4.9Nm 3/h.
Example 7:
The procedure was as in example 5, except that the catalyst was catalyst 2 of example 2.
Example 8:
the procedure was as in example 6, except that the catalyst was catalyst 2 of example 2.
Example 9:
The procedure was as in example 5, except that the catalyst was catalyst 3 of example 3.
Example 10:
The procedure was as in example 6, except that the catalyst was catalyst 3 of example 3.
Example 11:
The procedure was as in example 5, except that the catalyst was catalyst 4 of example 4.
Example 12:
The procedure was as in example 6, except that the catalyst was catalyst 4 of example 4.
Comparative example 4
The procedure was as in example 5, except that the catalyst was catalyst 5 of comparative example 1.
Comparative example 5
The procedure was as in example 6, except that the catalyst was catalyst 5 of comparative example 1.
Comparative example 6
The procedure was as in example 5, except that the catalyst was catalyst 6 of comparative example 2.
Comparative example 7
The procedure was as in example 6, except that the catalyst was catalyst 6 of comparative example 2.
Comparative example 8
The procedure was as in example 5, except that the catalyst was catalyst 7 of comparative example 3.
Comparative example 9
The procedure was as in example 6, except that the catalyst was catalyst 7 of comparative example 3. The conversion of methacrolein oxidative esterification in the same reactor is shown in the following table:
the foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.

Claims (11)

1. The oxidation and esterification catalyst is characterized by comprising a copper silicon vanadium molecular sieve carrier and an alkaline earth metal oxide modified active component loaded on the carrier, wherein the carrier is a copper silicon vanadium molecular sieve porous pellet embedded with SO 4 2-; the active component is composite oxide powder of cerium and molybdenum.
2. The oxidative esterification catalyst according to claim 1, wherein the mass percentage of the carrier is 85 to 90%, and the mass percentage of the alkaline earth metal oxide modified active component is 10 to 15%;
Preferably, the molar ratio of vanadium, silicon, copper, cerium and molybdenum in the catalyst is 1: (40-100): (20-50): (2-4): (10-40).
3. A method for preparing the oxidative esterification catalyst according to claim 1 or 2, comprising the steps of:
1) Preparation of porous pellets of a carrier molecular sieve:
i) Adding a hard template agent into a silicon source solution, stirring uniformly, adding a vanadium source and a copper source, stirring at room temperature under a closed condition to obtain a mixed solution, centrifugally separating and filtering the mixed solution, washing a filter cake with deionized water, roasting, and removing the hard template agent to obtain the copper-silicon-vanadium molecular sieve;
ii) mixing the copper silicon vanadium molecular sieve with water and a pore-forming agent to prepare a ball with a pore canal inside; drying and roasting to obtain porous molecular sieve pellets;
iii) Placing the porous pellets in sulfate aqueous solution, and impregnating to obtain copper silicon vanadium molecular sieve porous pellets embedded with SO 4 2-;
2) Preparing composite oxide powder:
uniformly stirring a cerium source and a molybdenum source in water, standing, and then drying, roasting and crushing to obtain composite oxide powder;
3) Placing the SO 4 2- -embedded copper-silicon-vanadium molecular sieve porous pellets of the step 2) into a coating machine, enabling the composite oxide powder of the step 3) to be attached to the porous pellets under centrifugal force, drying and roasting to obtain a catalyst finished product.
4. The method according to claim 3, wherein the silicon source in step 1) i) is at least one of white carbon black, silica sol, solid silica gel, organosilicate, and water glass; and/or
The copper source is one or two or more of copper nitrate, copper chloride, copper sulfate monohydrate, copper sulfate pentahydrate, copper oxide, copper acetate, cuprous chloride, copper oxalato, copper oxalate and basic copper carbonate, preferably at least one of copper nitrate, copper oxide and copper acetate; and/or
The vanadium source is vanadate, preferably at least one of metavanadate, orthovanadate, pyrovanadate and decavanadate; and/or
The hard template agent is carbon nano material and/or foam carbon; preferably, the carbon nanomaterial is a carbon nanotube, carbon nanofiber and/or carbon nanosphere, preferably a carbon nanotube; the density of the carbon foam is 0.08-0.80g/cm 3, preferably 0.2-0.5g/cm 3;
Preferably, the vanadium source: silicon source: copper source: the molar ratio of the hard template agent is 1: (300-500): (100-300): (50-100);
More preferably, the stirring is carried out at room temperature for 4 to 8 hours; and/or
The roasting is carried out for 12-16 hours at 450-550 ℃ in a muffle furnace.
5. The preparation method according to claim 3 or 4, wherein the molar ratio of vanadium, silicon and copper in the prepared copper-silicon-vanadium molecular sieve is 1: (40-100): (20-50);
Preferably, the diameter of the prepared copper silicon vanadium molecular sieve pellets is 3-5 mm.
6. The method according to claim 3, wherein the pore-forming agent in step 1) ii) is at least one of polymethyl methacrylate microspheres, polypropylene microspheres, polyethylene microspheres, amino polymethyl methacrylate microspheres, and carboxyl polymethyl methacrylate microspheres;
preferably, the pore-forming agent has a diameter of 5-20 μm;
More preferably, the mass ratio of the copper silicon vanadium molecular sieve to water and pore-forming agent is (8-10): (2-4): 1.
7. A process according to claim 3, wherein the aqueous solution of sulphate in step iii) of step 1) is one or more of sodium sulphate, potassium sulphate, ammonium sulphate, magnesium sulphate, preferably the aqueous solution of sulphate has a concentration of 10% to 20% wt.
8. The method according to claim 3, wherein the cerium source in step 2) is one or more of cerium sulfate, cerium nitrate, cerium chloride, and cerium oxide; and/or
The molybdenum source is one or more of ammonium polymolybdate, molybdenum trioxide, molybdic acid and molybdenum disulfide;
Preferably, the stirring is uniform and the mixture is kept stand, the stirring is uniform at the temperature of 40-80 ℃, and the mixture is kept stand for 12-24 hours at the constant temperature;
More preferably, the molar ratio of cerium to molybdenum in the prepared oxide-loaded powder is 1: (5-10); the diameter of the prepared catalyst particles is 3-5 mm.
9. The method according to claim 3, wherein the drying in step 3) is performed at a temperature of 150 to 200 ℃ for a time of 12 to 24 hours; and/or
The roasting is carried out at the temperature of 450-550 ℃ for 12-24 hours.
10. Use of the one-step oxidative esterification catalyst according to claim 1 or 2 or the one-step oxidative esterification catalyst produced by the production method according to any one of claims 3 to 8 for producing methyl methacrylate by oxidative esterification of methacrolein.
11. The use according to claim 10, wherein the oxidative esterification catalyst particles are filled in a fixed bed reactor, and methacrolein, methanol and air are introduced into the reactor for oxidative esterification reaction to obtain methyl methacrylate;
Preferably, the space velocity of the methacrolein liquid phase feed is 0.5 to 2.5h -1; and/or
The molar ratio of methacrolein to methanol was 1:1.05 to 1.3; and/or
The molar ratio of methacrolein to oxygen is 1:0.6 to 0.7; and/or
The reaction temperature is 100-150 ℃, and the reaction pressure is 0.05-0.2 MPa.
CN202410050173.8A 2024-01-15 2024-01-15 Oxidation-esterification catalyst, preparation method and application Pending CN117943098A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202410050173.8A CN117943098A (en) 2024-01-15 2024-01-15 Oxidation-esterification catalyst, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202410050173.8A CN117943098A (en) 2024-01-15 2024-01-15 Oxidation-esterification catalyst, preparation method and application

Publications (1)

Publication Number Publication Date
CN117943098A true CN117943098A (en) 2024-04-30

Family

ID=90804357

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202410050173.8A Pending CN117943098A (en) 2024-01-15 2024-01-15 Oxidation-esterification catalyst, preparation method and application

Country Status (1)

Country Link
CN (1) CN117943098A (en)

Similar Documents

Publication Publication Date Title
CN109304176B (en) Synthesis method of cyclohexanol compound
CN1153136A (en) Method for selective oxidation of sulphur compounds to elemental sulphur
CN107008492A (en) A kind of high dispersive beaded catalyst synthesized for hydrogen peroxide and its preparation method and application
CN1301793C (en) Nano carbon material modified copper base catalyst and its preparing method
CN110075835B (en) Catalyst for preparing methyl methacrylate by one-step oxidation esterification method and preparation method and application thereof
CN110314685B (en) Preparation method of core-shell structure catalyst for low-temperature catalytic oxidation of toluene
CN105712461A (en) Catalytic wet oxidation method for acrylic acid and ester wastewater
CN117943098A (en) Oxidation-esterification catalyst, preparation method and application
CN113713824B (en) Catalyst for preparing methacrolein by selective oxidation and preparation method and application thereof
CN101322943B (en) Ti2O nano tube supported V2O5 composite catalyst
CN114405493B (en) Preparation method of high-strength large-aperture alumina-titania composite carrier
CN112191244B (en) Activated carbon-supported gold-based catalyst, preparation method thereof and application thereof in acetylene hydrogenation
CN114308108A (en) Metal loaded MXene/C3N4Heterogeneous microsphere photocatalyst and preparation method and application thereof
JP2003519067A (en) Method for the selective oxidation of carbon monoxide in hydrogen-containing streams
CN113751042B (en) Carbon-coated nickel oxide nano composite material and preparation method and application thereof
CN112823876B (en) Catalyst for preparing MMA (methyl methacrylate) through direct oxidative esterification and preparation method thereof
CN102658179A (en) Preparation method of stannous chloride immobilized catalyst
CN109395725B (en) Au/TiO2-C nanotube catalyst, preparation method and application thereof
CN108067224A (en) The preparation method of catalytic wet oxidation catalyst
JPH0810621A (en) Production of catalyst for producing unsaturated carboxylic acid
Han et al. Deposition of Pd–Fe nanoparticles onto carbon spheres with controllable diameters and applied for CO catalytic oxidation
CN110538671B (en) Catalyst with catalytic oxidation function, preparation method thereof and cyclohexane oxidation method
JP3867305B2 (en) Carbon monoxide conversion catalyst
CN110538670B (en) Catalytic oxidation catalyst, preparation method thereof and cyclohexane oxidation method
JP2005515064A (en) Method for preparing micro ellipsoidal catalyst

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