CN114939417B - Preparation method of coating catalyst for preparing acrolein by propylene oxidation - Google Patents

Preparation method of coating catalyst for preparing acrolein by propylene oxidation Download PDF

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CN114939417B
CN114939417B CN202210517752.XA CN202210517752A CN114939417B CN 114939417 B CN114939417 B CN 114939417B CN 202210517752 A CN202210517752 A CN 202210517752A CN 114939417 B CN114939417 B CN 114939417B
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catalyst
acrolein
propylene
oxidation
nitrate
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CN114939417A (en
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张利杰
李贺
周鹏
夏继平
张尚强
姚烁
曾贤君
孙彦民
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China National Offshore Oil Corp CNOOC
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8876—Arsenic, antimony or bismuth
    • B01J35/397—
    • B01J35/51—
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a coating catalyst for preparing acrolein by propylene oxidation and a preparation method thereof. The preparation method of the catalyst comprises the following steps: adding a mixed solution of cobalt nitrate, nickel nitrate, ferric nitrate, bismuth nitrate and potassium nitrate into an ammonium molybdate aqueous solution to perform coprecipitation under high-speed stirring, and performing constant-temperature reaction and aging to prepare active precursor slurry; the active precursor is quickly dried and fired to obtain active component porous microspheres; mixing the active component powder with a binder, spraying polycarboxylic acid for roll coating molding, and drying and roasting the molded product after microwave treatment to obtain the catalyst. The catalyst of the invention forms a through pore canal and has the characteristics of high catalyst strength and high catalytic activity.

Description

Preparation method of coating catalyst for preparing acrolein by propylene oxidation
Technical Field
The invention belongs to the field of preparation of oxidation reaction catalysts, relates to a catalyst for preparing acrolein by propylene oxidation, and in particular relates to a preparation method of a coating catalyst for preparing acrolein by propylene oxidation, which has higher strength and higher activity.
Background
At present, the industrial production of acrolein mostly adopts a gas phase contact method process, takes Mo-Bi composite oxide as a catalyst, and is doped with auxiliary agent elements such as Co, ni and the like to improve the comprehensive performance of the catalyst. The catalyst is also mostly shaped as a cylinder, a hollow cylinder or a sphere. The method has the advantages that the strong heat is released in the reaction process of preparing the acrolein by propylene oxidation, and the reasonable distribution of the temperature of a catalyst bed layer is controlled by selecting proper reaction process conditions and proper performance of the catalyst, so that the product index is ensured, and the service performance of the catalyst is protected. In addition, the reaction space velocity of the acrolein preparation by propylene oxidation is higher, the surface of the catalyst is easily abraded due to long-time flushing of the high-flow raw material gas, so that the catalyst is pulverized and crushed, on one hand, the control difficulty of a pressure drop rising device of the reactor is increased, and on the other hand, part of inorganic powder enters a post-sentry acrolein absorption refining unit, and the stable operation of the device is not facilitated. Therefore, improving the mechanical strength of the catalyst is also one of the important subjects in the technical field of producing acrolein by oxidizing propylene.
In order to ensure that the catalyst has better mechanical strength, the traditional catalyst for preparing the acrolein by propylene oxidation is mostly formed by integrally forming active powder. The patent CN1697701A carries out coprecipitation on a nitrate mixed solution of iron, cobalt and nickel and an ammonium paramolybdate solution, the obtained slurry is aged, silicon dioxide and bismuth subcarbonate are added, the dried solid is crushed, and finally the crushed solid is pressed into a columnar particle catalyst. Patent CN1093021a uses the following procedure to prepare an acrolein catalyst: adding potassium nitrate, borax solution, silicon dioxide and molybdenum trioxide into Fe, co, ni, bi mixed nitrate solution in turn, fully stirring for reaction under a certain condition, heating and drying the slurry to obtain solid, crushing and grinding the solid, and extruding the solid to obtain the cylindrical catalyst with the thickness of 5mm multiplied by 5 mm. The columnar catalyst has higher mechanical strength, but the reaction heat is not easy to remove because of lower porosity of the bed layer, and larger bed layer resistance is also generated, so that the columnar catalyst is not suitable for the existing high space velocity reaction condition.
In order to reduce the resistance of the catalyst bed, the patent mostly prepares annular catalysts by opening holes in the center of a cylinder, the patent CN1255366C prepares active precursor slurry containing Mo, bi, W, fe, co, cs, simultaneously adds silica sol into the slurry, and prepares solid by stirring and drying, and then molds the annular catalysts into the annular catalysts with the diameter of 6mm multiplied by 2mm multiplied by 6mm after crushing. Similarly, the catalyst of patent CN113522301a was shaped into annular particles with a diameter of 5.5mm, a height of 5.0mm, and an inner bore of 2.0 mm. To prevent the central opening from adversely affecting the strength of the catalyst, the patent CN105026036a adds silica and alumina fibers to the active powder and then coats the surface of the annular support to improve the mechanical properties of the catalyst. The mechanical strength of the annular catalyst is improved to some extent by adding inorganic strength enhancers such as asbestos, graphite, silicon nitride, calcium silicate, magnesium silicate, sodium silicate, aluminum silicate, magnesium titanate, and potassium titanate in the patent CN112439442 a. In order to improve the activity of the catalyst, the patent CN112452336A adds carbon dioxide polyurea as a pore-forming agent in the catalyst forming process, so as to improve the number of pore channels in the catalyst and enhance the utilization rate of internal active components.
The cylindrical or annular catalyst with the integrally formed active components is widely applied to the early acrolein production field, but in recent years, along with the continuous improvement of the reaction load of an acrolein device, the high reaction space velocity has higher requirements on the mechanical strength and the activity of the catalyst. To solve this problem, some researchers have shifted the center of gravity to the coated catalyst.
The patent CN1210511A adopts a coprecipitation method to prepare active precursor slurry, firstly prepares aqueous solution of ammonium molybdate and potassium nitrate, then adds aqueous solution containing ferric nitrate, cobalt nitrate and acidified bismuth nitrate into the aqueous solution, uniformly mixes the aqueous solution, and dries the obtained slurry to obtain active powder. In order to ensure good mechanical strength of the catalyst, a certain amount of crystalline cellulose is mixed into the active powder, and the active powder is adhered to the surface of a spherical inert carrier with a certain size under the action of a glycerol aqueous solution serving as a binder, so that the spherical coating catalyst is obtained. The catalyst described in patent CN106732634B uses polyvinyl alcohol as a binder during the forming process to increase the strength of the catalyst. After the active powder is prepared by the patent CN1101273C, the liquid binder is selected from alcohols, mono-or polycarboxylic acids and other organic substances. The binder has the common characteristic of good water solubility, and the formed catalyst migrates along with moisture in the drying process, so that the binder is unevenly distributed to cause stress difference in the catalyst to cause cracking and abrasion of the product to be increased. The poor water-solubility of the binder also causes poor dispersibility and deformability, and large closed cells are formed in the catalyst, which results in a decrease in the strength and activity of the catalyst.
Disclosure of Invention
The invention aims to solve the technical problems of reduced catalyst strength and low activity of the existing preparation method, and provides a preparation method of a high-activity and high-strength coating catalyst for preparing acrolein by propylene oxidation. The swelling body can fully expand the through holes and improve the activity of the catalyst; on the other hand, the migration of water-soluble components in the drying and firing processes is avoided, and phenomena of catalyst damage, cracking, unshelling and the like caused by uneven binder distribution are prevented, so that the activity of the catalyst is improved, the mechanical property of the catalyst is improved, and the influence on the service life of the catalyst caused by abrasion of the catalyst in the transportation, filling and using processes is prevented.
The invention solves the technical problems and is realized by adopting the following technical scheme:
a preparation method of a coated catalyst for preparing acrolein by propylene oxidation is characterized by comprising the following steps:
(1) Adding a mixed solution of cobalt nitrate, ferric nitrate, nickel nitrate, potassium nitrate and bismuth nitrate into an ammonium molybdate aqueous solution under high-speed stirring, controlling the temperature to be 40-80 ℃ to obtain aqueous slurry, and aging the aqueous slurry at the constant temperature of 40-80 ℃ for 2-4 hours to obtain active precursor slurry; drying the active precursor slurry to obtain a composite oxide precursor, and roasting the composite oxide precursor at 350-450 ℃ to obtain composite metal oxide powder; adding polyvinyl alcohol accounting for 1-15% of the mass content of the powder into the composite metal oxide powder to obtain an active component;
(2) Putting the spherical carrier into a rotary drum granulator, spraying aqueous solution of polycarboxylic acid with the concentration of 0.5-10%, and simultaneously adding the active components into a forming machine in batches for forming; after the molding is finished, treating the obtained spheres by microwaves for 5-30 min, and baking the spheres under flowing atmosphere to obtain the coating catalyst for preparing the acrolein by propylene oxidation;
the catalyst is in a core-shell structure formed by active components and a spherical carrier, wherein the active component coating is a shell, the spherical carrier is a core, the active components in the shell are provided with through holes, and the mass ratio of the active components to the carrier is 1:3-3:1;
the active ingredient may be represented by the general formula:
Mo12BiaFebCocNidKeOx
taking the number of Mo atoms as a reference, wherein:
the value range of a is 0.6-2.0;
b has a value range of 1-2;
c has a value range of 2-9;
d has a value range of 0-3;
e is 0 to 0.1;
the value of x depends on the values of other elements.
In the preparation method of the coated catalyst of the present invention, the active precursor slurry is preferably spray-dried.
The mass content of the polyvinyl alcohol in the powder is preferably 2-10%.
In step 2) of the preparation method of the coated catalyst of the present invention, the polycarboxylic acid is preferably one or more of oxalic acid, citric acid, maleic acid, tartaric acid and maleic acid.
The concentration of the aqueous polycarboxylic acid solution is 0.5-10%, preferably 1-5%.
The roasting temperature is 400-600 ℃, preferably 450-550 ℃, and the roasting time is 2-10 h, preferably 2-5 h.
The invention further provides a coated catalyst prepared by the preparation method.
Furthermore, the invention also provides application of the coated catalyst in the reaction of preparing acrolein by propylene oxidation.
The preparation method of the coated catalyst provided by the invention ensures that the slurry is quickly dried and partially decomposed at a higher temperature in the spray drying process to form porous microspheres, and the porous microspheres can strengthen the adhesive effect of the adhesive. After the molding is finished, the product after the molding is treated by microwave radiation to crosslink the adhesive polyvinyl alcohol and the molding auxiliary agent polycarboxylic acid to generate a water-insoluble swelling body, and the swelling body is uniformly distributed in the catalyst to form a through pore canal. And after the molding, the catalyst is uniformly dried in the drying process, so that the problems of catalyst shelling, breakage, cracking and the like caused by moisture migration and uneven binder distribution are prevented. The prepared coating catalyst has the characteristics of high catalyst strength and high catalytic activity.
Detailed Description
The technical scheme of the invention is further described below by combining specific embodiments.
Example 1
(1) Adding 4L of deionized water and 584g of ammonium heptamolybdate into a reaction kettle, and heating to 60 ℃ under stirring to dissolve the ammonium heptamolybdate to prepare an ammonium heptamolybdate aqueous solution; adding 418g of cobalt nitrate, 225g of nickel nitrate, 200.5g of ferric nitrate and 2.7g of potassium nitrate into 1.4L of deionized water, stirring to dissolve, weighing 275mL of deionized water, acidifying with 37mL of concentrated nitric acid, adding 227.5g of bismuth nitrate, stirring to dissolve, and rapidly adding a bismuth nitrate solution into the cobalt nitrate, nickel nitrate, ferric nitrate and potassium nitrate solution to prepare a nitrate mixed solution; adding the mixed nitrate solution into the ammonium heptamolybdate solution at the temperature of 60 ℃ for coprecipitation, and continuing to age at the constant temperature of 60 ℃ for 3 hours after the precipitation is finished to obtain active precursor slurry. And (3) spray drying the precursor slurry, controlling the inlet temperature to be 360 ℃, and adjusting the feeding speed to keep the outlet temperature at 105 ℃. The dried product thus obtained was calcined at 420℃in an air atmosphere for 3 hours to obtain a composite oxide powder. Uniformly mixing 400g of the composite oxide powder with 8g of polyvinyl alcohol to prepare an active component;
(2) 400g of the spherical support were placed in a rotary drum granulator, a 1% aqueous solution of maleic acid was sprayed, and 408g of the active ingredient was added to the former in portions. And taking out the spheres after the molding is finished, treating the spheres by microwaves for 15min, drying the spheres in an oven at 120 ℃ for 5h, and roasting the dried products at 520 ℃ for 3h to obtain the acrolein coating catalyst prepared by propylene oxidation.
Example 2
"400g of the above-mentioned composite oxide powder was mixed with 8g of polyvinyl alcohol" in step (1) of example 1 was replaced with "400g of the above-mentioned composite oxide powder was mixed with 20g of polyvinyl alcohol";
the procedure of example 1 was repeated except that the "1% aqueous solution of maleic acid was sprayed" in step (2) of example 1 was replaced with "2.5% aqueous solution of maleic acid was sprayed".
Example 3
The procedure of example 1 was repeated except that the "1% aqueous solution of maleic acid was sprayed" in step (2) of example 1 was replaced with "1% aqueous solution of tartaric acid was sprayed".
Comparative example 1
(1) In the same embodiment (1)
(2) 400g of spherical carrier is put into a rotary drum granulator, 30% glycerol aqueous solution is sprayed, and 400g of active component and 20g of crystalline cellulose are mixed uniformly and then added into the forming machine in batches. And taking out the spheres after the molding is finished, airing for 20 hours, drying for 5 hours at the temperature of 100 ℃ in an oven, and roasting the dried products for 3 hours at the temperature of 520 ℃ to obtain the acrolein coating catalyst prepared by propylene oxidation.
Comparative example 2
The procedure of example 1 was followed except that the "microwave treatment for 15min" in step (2) of example 1 was replaced with "air-drying at room temperature for 20 h".
Catalyst performance evaluation method
The catalyst performance evaluation is carried out in a fixed bed tubular reactor, the inner diameter of a reaction tube is 20mm, and the length of the reaction tube is 2000mm, the catalyst is arranged in a constant temperature area of a reaction tube, the filling volume is 30ml, the reaction pressure is normal pressure, the reaction temperature is 330 ℃, and the propylene feeding airspeed is 120h -1 The volume fraction of propylene in the reaction raw materials is 8%, the volume fraction of oxygen is 13.5%, and the balance is nitrogen, and the reaction conversion rate and the yield result are analyzed by adopting a gas chromatography.
The physical properties of the catalysts of examples and comparative examples are shown in the following tables.
TABLE 1 mechanical catalyst Property results
TABLE 2 catalyst reaction Performance results
Catalyst Propylene conversion/% Acrolein yield/% Carbon oxide yield/%
Example 1 97.3 83.5 3.6
Example 2 98.5 83.9 3.8
Example 3 96.9 83.1 3.7
Comparative example 1 95.1 81.5 3.3
Comparative example 2 95.5 81.1 3.9
Table 1 shows the mechanical properties of the coated catalysts prepared by the process of the present invention compared to those prepared by conventional roll coating processes, and it can be seen that the catalysts prepared by the process of the present invention have lower mechanical strength, lower attrition and lower cracking ratio, and are more excellent in mechanical properties. Comparative example 1 the product of comparative example 2 was formed without microwave treatment, the binder did not form a crosslinked structure, and the physical properties of the formed product were poor in both forming schemes.
Table 2 shows the performance of the spherical coated catalysts prepared by different processes, and it can be seen that the catalyst prepared by the method of the invention has higher propylene conversion rate and higher acrolein yield.

Claims (8)

1. A method for preparing a coated catalyst for preparing acrolein by propylene oxidation, which is characterized in that the preparation process comprises the following steps:
(1) Adding a mixed solution of cobalt nitrate, ferric nitrate, nickel nitrate, potassium nitrate and bismuth nitrate into an ammonium molybdate aqueous solution under high-speed stirring, controlling the temperature to be 40-80 ℃ to obtain aqueous slurry, and aging the aqueous slurry at the constant temperature of 40-80 ℃ for 2-4 hours to obtain active precursor slurry; drying the active precursor slurry to obtain a composite oxide precursor, and roasting the composite oxide precursor at 350-450 ℃ to obtain composite metal oxide powder; adding polyvinyl alcohol with the mass content of 1-15% into the composite metal oxide powder to obtain an active component;
(2) Putting the spherical carrier into a rotary drum granulator, spraying aqueous solution of polycarboxylic acid with the concentration of 0.5-10%, and simultaneously adding the active components into a forming machine in batches for forming; after the molding is finished, treating the obtained spheres by microwaves for 5-30 min, drying the spheres in a flowing atmosphere, and roasting the spheres at 400-600 ℃ for 2-10 h to obtain a coating catalyst for preparing acrolein by propylene oxidation;
the coating catalyst for preparing the acrolein by propylene oxidation is formed into a core-shell structure by an active component and a spherical carrier, wherein the active component coating is a shell, the spherical carrier is a core, the active component in the shell is provided with a through pore canal, and the mass ratio of the active component to the carrier is 1:3-3:1;
the active component is represented by the following general formula:
Mo 12 Bi a Fe b Co c Ni d K e O x
taking the number of Mo atoms as a reference, wherein:
the value range of a is 0.6-2.0;
b has a value range of 1-2;
c has a value range of 2-9;
d has a value range of 0-3;
e is 0 to 0.1;
the value of x depends on the values of other elements.
2. The method for preparing a coated catalyst for the oxidation of propylene to acrolein according to claim 1, wherein the active precursor slurry in step (1) is dried by spray drying at an outlet temperature of 120 to 150 ℃.
3. The method for preparing a coated catalyst for the oxidation of propylene to acrolein according to claim 1, wherein the mass content of the polyvinyl alcohol in the step (1) is 2 to 10%.
4. The method for preparing a coated catalyst for the oxidation of propylene to acrolein according to claim 1, wherein the polycarboxylic acid in the step (2) is one or more of oxalic acid, tartaric acid, citric acid and maleic acid.
5. The method for producing a coated catalyst for the oxidation of propylene to acrolein according to claim 1, wherein the concentration of the aqueous polycarboxylic acid solution in the step (2) is 1 to 5%.
6. The method for preparing a coated catalyst for the oxidation of propylene to acrolein according to claim 1, wherein the firing temperature in step (2) is 450 to 550 ℃ and the firing time is 2 to 5 hours.
7. A coated catalyst prepared by the method of any one of claims 1 to 6.
8. Use of the coated catalyst according to claim 7 in a reaction for the oxidation of propylene to acrolein.
CN202210517752.XA 2022-05-14 2022-05-14 Preparation method of coating catalyst for preparing acrolein by propylene oxidation Active CN114939417B (en)

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