CN114471596B - Catalyst for preparing acrylic acid and method for preparing catalyst - Google Patents

Catalyst for preparing acrylic acid and method for preparing catalyst Download PDF

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CN114471596B
CN114471596B CN202011162701.7A CN202011162701A CN114471596B CN 114471596 B CN114471596 B CN 114471596B CN 202011162701 A CN202011162701 A CN 202011162701A CN 114471596 B CN114471596 B CN 114471596B
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catalyst
slurry
carrier
acrylic acid
solvent
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CN114471596A (en
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宋卫林
杨斌
徐文杰
王伟华
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • 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
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • 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
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J37/0213—Preparation of the impregnating solution
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The present application provides a catalyst for preparing acrylic acid, comprising: the catalyst comprises a carrier and active components distributed on the surface of the carrier and in the pore channels of the carrier, wherein the content of the carrier is 40-60 wt% based on the total weight of the catalyst, the content of the active components distributed on the surface of the carrier is 10-20 wt%, and the content of the active components distributed in the pore channels of the carrier is 20-50 wt%. The catalyst provided by the application has the characteristics of high acrolein conversion rate and high acrylic acid yield.

Description

Catalyst for preparing acrylic acid and method for preparing catalyst
Technical Field
The application relates to the technical field of preparation of acrylic acid, in particular to a catalyst for preparing acrylic acid and a method for preparing the catalyst.
Background
Acrolein is the simplest unsaturated aldehyde, is an important chemical synthesis intermediate, and is widely used for synthesizing important chemical products such as picoline, pyridine, glutaraldehyde, acrylic acid and the like. Acrylic acid is an important organic chemical raw material, is mainly used for manufacturing multifunctional polymer materials such as acrylic esters and the like, and is widely applied to the fields of papermaking, leather, paint, textile, plastics, rubber, oil additives, petroleum exploitation and the like. In recent years, the market demand for acrylic acid has increased worldwide, and the production of acrylic acid has been a hot spot of research.
The synthesis of acrylic acid by the acrolein oxidation method is currently used industrially on a large scale. The catalyst used for synthesizing acrylic acid by using the acrolein oxidation method is generally an oxide of Mo-V series, the basic elements of the catalyst are Mo and V, and other elements for improving the performance of the catalyst, such as Nb, sn, cr, W, fe, co, ni, sb and the like, are added.
US 7220698B2 describes a solution for introducing a small amount of catalyst poison into the catalyst preparation process, inhibiting thermal degradation of the catalyst and providing stability to the catalyst. US 7456129B2 describes a solution for modifying the acid content, controlling the acid strength and improving the catalyst performance in the preparation of a catalyst support. CN1697701a and CN1210511a propose a preparation method of a composite oxide catalyst, which is to coprecipitate mixed solutions of various element components (including Fe, co, mo, V, bi, ni, etc.), dry into powder, then tablet and extrude to form, finally bake to obtain the composite oxide catalyst.
The above methods can successfully prepare acrylic acid catalysts and improve catalyst performance, but the catalysts have poor mechanical strength and relatively low catalytic activity, so that practical application is limited.
The catalyst active components are loaded on the carrier with high pore space and high strength, so that the mechanical strength of the catalyst can be increased, the loading amount of the active components can be greatly increased, the active components of the catalyst can be exerted to a great extent through synergistic effect, and a proper mass and heat transfer channel is provided, so that the activity and selectivity of the catalyst can be improved.
CN1130172a (method for preparing acrylic acid) describes a method for preparing a spherical catalyst, in which a carrier is added to a mixed solution of active components, and evaporated to dryness, so that the active components are deposited on the surface of the carrier. CN108325533a also discloses a catalyst using an inert carrier to support an active component, which can improve the activity and selectivity of the catalyst.
However, the prior art impregnation slurry comprising the above document has low solid content and low active component loading, and the multi-impregnation method is adopted, and because materials are accumulated in the orifice during the drying process, the subsequent impregnation slurry cannot enter the carrier, so the catalytic activity of the supported acrylic acid catalyst is low. If too thick active ingredient is supported on the outer surface of the carrier, it is liable to peel off and fall off.
Disclosure of Invention
In view of the above problems in the prior art, it is an object of the present application to provide a catalyst for preparing acrylic acid, which has an active component content of up to 50wt% to 70wt%, and 20wt% to 50wt% of the active component is located in the pore channels of the carrier, so that the catalyst provided by the present application has the characteristics of high acrolein conversion rate and high acrylic acid yield.
The second object of the present application is to provide a method for preparing a catalyst corresponding to one of the objects.
It is a further object of the present application to provide a process for preparing a catalyst corresponding to the above object.
A fourth object of the present application is to provide a method for producing acrylic acid corresponding to the above object.
In order to achieve one of the above purposes, the technical scheme adopted by the application is as follows:
a catalyst for the preparation of acrylic acid comprising: the catalyst comprises a carrier and active components distributed on the surface of the carrier and in the pore channels of the carrier, wherein the content of the carrier is 30-50wt%, the content of the active components distributed on the surface of the carrier is 10-20wt% and the content of the active components distributed in the pore channels of the carrier is 30-60wt% based on the total weight of the catalyst.
In some preferred embodiments of the application, the support is selected from one or more of alumina, silica, magnesia and calcia; and/or the active component contains V, mo and Cu.
In some preferred embodiments of the application, the active ingredient has the general formula (1):
VMo a Cu b X c Y d O e (1)
In the formula (1), X is selected from one or more of Sb, nb, cr, W, la and Ce, Y is selected from one or more of K, na, rb and Cs, and a is 2.0-8.0; b is 0.2 to 0.8; c is 0.2-1.0; d is 0.05 to 1.2; e is the number of moles of oxygen atoms required to satisfy the valence of each element in the active component.
In order to achieve the second purpose, the technical scheme adopted by the application is as follows:
the preparation method of the catalyst for preparing acrylic acid comprises the following steps:
s1, dissolving a compound containing the active component in water, and concentrating to prepare first slurry;
s2, mixing the first slurry with a solvent to prepare second slurry;
s3, mixing the second slurry with the carrier to prepare a catalyst precursor; and
s4, roasting the catalyst precursor to obtain the catalyst;
wherein the solvent comprises water and a lower alcohol selected from one or more of methanol, ethanol, propanol and 1, 3-propanediol.
The inventor of the application discovers in the research that the problem that solid materials in a pure organic solvent are poorly dispersed, agglomerate and grow up and cannot enter a carrier pore canal can be avoided by adopting water-containing low-carbon alcohol, and the problem that slurry viscosity is too large and the fluidity difference cannot be impregnated when the solid content in an aqueous solution is improved is also avoided. The preparation method can realize high load capacity by one-time impregnation, and improve the activity and selectivity of the catalyst.
According to some embodiments of the application, in step S1, the concentration may be performed by evaporation with heating.
According to some specific embodiments of the application, in step S1, the water content in the first slurry is 15% to 18%.
In some preferred embodiments of the application, the lower alcohol is ethanol.
In some preferred embodiments of the present application, the water is present in an amount of 5wt% to 35wt% based on the total weight of the solvent.
In some preferred embodiments of the present application, the water is present in an amount of 10wt% to 30wt% based on the total weight of the solvent.
In some preferred embodiments of the present application, the water is present in an amount of 15wt% to 25wt% based on the total weight of the solvent.
In some preferred embodiments of the application, the volume ratio of the first slurry to the solvent is (1-3): 1.
In some preferred embodiments of the application, the volume ratio of the first slurry to the solvent is (1-2.5): 1.
In some preferred embodiments of the application, the volume ratio of the first slurry to the solvent is (1-2): 1.
In some embodiments of the application, the volume ratio of the first slurry to the solvent is (1.5-2): 1.
In some preferred embodiments of the present application, in step S2, the viscosity of the second paste is 100cP or less.
In some preferred embodiments of the present application, in step S2, the viscosity of the second paste is 80cP or less.
In some preferred embodiments of the present application, in step S2, the viscosity of the second paste is 1cP to 50cP.
According to the application, the viscosity may be measured by a brookfield dial viscometer at 80℃and 60 rpm.
In some preferred embodiments of the present application, in step S3, the support is calcined at 800 to 1200 ℃ to thereby pretreat the support.
In some preferred embodiments of the present application, in step S4, the temperature of the calcination treatment is 350 to 550 ℃, preferably 400 to 500 ℃; and/or the time of the calcination treatment is 0.5 to 5 hours, preferably 1 to 4 hours.
In some preferred embodiments of the present application, in step S4, before the calcination treatment is performed, a step of drying the catalyst precursor is further included, and the drying conditions include: the drying temperature is 80-150 ℃, preferably 100-130 ℃; and/or the drying time is 1h to 28h, preferably 5h to 15h.
In order to achieve the third purpose, the technical scheme adopted by the application is as follows:
the use of the above-described catalyst or of a catalyst prepared according to the above-described preparation method in the field of the preparation of acrylic acid, in particular in the field of the preparation of acrylic acid by oxidation of acrolein.
In order to achieve the fourth purpose, the technical scheme adopted by the application is as follows:
a method for preparing acrylic acid by oxidizing acrolein, comprising the following steps: contacting a feed stream comprising acrolein with the catalyst described above or a catalyst prepared according to the preparation method described above, thereby producing acrylic acid.
In some preferred embodiments of the application, the contacting conditions include: the temperature of the contact is 200 to 350 ℃, preferably 250 to 300 ℃.
The application has the advantages that: the catalyst of the application has the advantages that the conversion rate of the acrolein can reach more than 98 percent, the yield of the acrylic acid can reach more than 95 percent, and a better technical effect is obtained, thus being applicable to the industrial production of the acrylic acid.
Detailed Description
The present application will be described in detail with reference to examples, but the scope of the present application is not limited to the following description.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products available commercially without the manufacturer's knowledge.
The catalyst evaluation method of the application is as follows:
the reactor comprises: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 150mL;
reaction temperature: 280 ℃;
reaction time: 4 hours;
the volume ratio of the raw materials is as follows: acrolein: air: water vapor = 1:3.5:2;
total volume space velocity of raw materials: 1400 hours -1 。
The acrolein conversion and acrylic acid yield of the present application are defined as follows:
acrolein conversion= (molar amount of acrolein reaction/molar amount of total acrolein addition) ×100%;
acrylic acid yield = (molar amount of acrylic acid produced/molar amount of acrolein total added) ×100%.
The active components in the pore canal of the carrier are calculated as follows:
active component = (total active component loading-amount of active component on support surface)/total active component loading x 100% in support pore channels.
The amount of active ingredient on the surface of the support was measured by abrasion meter (by mechanical abrasion, weighing).
The viscosity of the slurry according to the application was measured by a brookfield dial viscometer at 80℃and 60 rpm.
Example 1
Step one: a total of 150 g of VO was weighed out 2 、MoO 3 、CuO、Sb 2 O 3 、Nb 2 O 3 、WO 3 、Cr 2 O 3 And Na (Na) 2 Ammonium metavanadate, ammonium heptamolybdate, copper nitrate, antimony trioxide, niobium oxalate, ammonium metatungstate, chromium nitrate and sodium nitrate (wherein the atomic ratios of Mo, cu, sb, nb, W, cr and K to V are 4.0, 0.5, 0.3, 0.1, 0.2 and 0.1, respectively) were dissolved in water, and concentrated by evaporation to give 100mL of slurry 1 (water content 16%, calculated as negative pressure loss on drying at 30 ℃).
Step two: to slurry 1, 50mL of a mixture of 20% ethanol and water was added, and slurry 2 was obtained by beating and dispersing, and the viscosity of slurry 2 was measured, and the results are shown in Table 1.
Step three: slurry 2 was mixed with 150 g of alumina support (pore volume 0.4 mL/g), rotary evaporated at 80 ℃ until no visible liquid was present, dried at 120 ℃ for 12 hours, and calcined in an air atmosphere at 450 ℃ for 2 hours to give a catalyst. The evaluation results of the catalyst are shown in Table 1.
Example 2
Step one: a total of 150 g of VO was weighed out 2 、MoO 3 、CuO、Sb 2 O 3 、Nb 2 O 3 、WO 3 、Cr 2 O 3 And Na (Na) 2 Ammonium metavanadate, ammonium heptamolybdate, copper nitrate, antimony trioxide, niobium oxalate, ammonium metatungstate, chromium nitrate and sodium nitrate (wherein the atomic ratios of Mo, cu, sb, nb, W, cr and K to V are 4.0, 0.5, 0.3, 0.1, 0.2 and 0.1, respectively) were dissolved in water, and concentrated by evaporation to give 100mL of slurry 1 (water content 16%, calculated as negative pressure loss on drying at 30 ℃).
Step two: to slurry 1, 50mL of water was added, and slurry 2 was obtained by beating and dispersing, and the viscosity of slurry 2 was measured, and the results are shown in Table 1.
Step three: slurry 2 was mixed with 150 g of alumina support (pore volume 0.4 mL/g), rotary evaporated at 80 ℃ until no visible liquid was present, dried at 120 ℃ for 12 hours, and calcined in an air atmosphere at 450 ℃ for 2 hours to give a catalyst. The evaluation results of the catalyst are shown in Table 1.
Example 3
Step one: a total of 150 g of VO was weighed out 2 、MoO 3 、CuO、Sb 2 O 3 、Nb 2 O 3 、WO 3 、Cr 2 O 3 And Na (Na) 2 Ammonium metavanadate, ammonium heptamolybdate, copper nitrate, antimony trioxide, niobium oxalate, ammonium metatungstate, chromium nitrate and sodium nitrate (wherein the atomic ratios of Mo, cu, sb, nb, W, cr and K to V are 4.0, 0.5, 0.3, 0.1, 0.2 and 0.1, respectively) were dissolved in water, and concentrated by evaporation to give 100mL of slurry 1 (water content 16%, calculated as negative pressure loss on drying at 30 ℃).
Step two: to slurry 1, 50mL of ethanol was added, and slurry 2 was obtained by beating and dispersing, and the viscosity of slurry 2 was measured, and the results are shown in Table 1.
Step three: slurry 2 was mixed with 150 g of alumina support (pore volume 0.4 mL/g), rotary evaporated at 80 ℃ until no visible liquid was present, dried at 120 ℃ for 12 hours, and calcined in an air atmosphere at 450 ℃ for 2 hours to give a catalyst. The evaluation results of the catalyst are shown in Table 1.
Example 4
Step one: a total of 150 g of VO was weighed out 2 、MoO 3 、CuO、Sb 2 O 3 、Nb 2 O 3 、WO 3 、Cr 2 O 3 And Na (Na) 2 Ammonium metavanadate, ammonium heptamolybdate, copper nitrate, antimony trioxide, niobium oxalate, ammonium metatungstate, chromium nitrate and sodium nitrate (wherein the atomic ratios of Mo, cu, sb, nb, W, cr and K to V are 4.0, 0.5, 0.3, 0.1, 0.2 and 0.1, respectively) were dissolved in water, and concentrated by evaporation to give 100mL of slurry 1 (water content 16%, calculated as negative pressure loss on drying at 30 ℃).
Step two: to slurry 1, 50mL of a mixture of ethanol and water containing 10% of water was added, and slurry 2 was obtained by beating and dispersing, and the viscosity of slurry 2 was measured, and the results are shown in Table 1.
Step three: slurry 2 was mixed with 150 g of alumina support (pore volume 0.4 mL/g), rotary evaporated at 80 ℃ until no visible liquid was present, dried at 120 ℃ for 12 hours, and calcined in an air atmosphere at 450 ℃ for 2 hours to give a catalyst. The evaluation results of the catalyst are shown in Table 1.
Example 5
Step one: a total of 150 g of VO was weighed out 2 、MoO 3 、CuO、Sb 2 O 3 、Nb 2 O 3 、WO 3 、Cr 2 O 3 And Na (Na) 2 Ammonium metavanadate, ammonium heptamolybdate, copper nitrate, antimony trioxide, niobium oxalate, ammonium metatungstate, chromium nitrate and sodium nitrate (wherein the atomic ratios of Mo, cu, sb, nb, W, cr and K to V are 4.0, 0.5, 0.3, 0.1, 0.2 and 0.1, respectively) were dissolved in water, and concentrated by evaporation to give 100mL of slurry 1 (water content 16%, calculated as negative pressure loss on drying at 30 ℃).
Step two: to slurry 1, 50mL of a mixture of ethanol and water containing 5% of water was added, and slurry 2 was obtained by beating and dispersing, and the viscosity of slurry 2 was measured, and the results are shown in Table 1.
Step three: slurry 2 was mixed with 150 g of alumina support (pore volume 0.4 mL/g), rotary evaporated at 80 ℃ until no visible liquid was present, dried at 120 ℃ for 12 hours, and calcined in an air atmosphere at 450 ℃ for 2 hours to give a catalyst. The evaluation results of the catalyst are shown in Table 1.
Example 6
Step one: a total of 150 g of VO was weighed out 2 、MoO 3 、CuO、Sb 2 O 3 、Nb 2 O 3 、WO 3 、Cr 2 O 3 And Na (Na) 2 Ammonium metavanadate, ammonium heptamolybdate, copper nitrate, antimony trioxide, niobium oxalate, ammonium metatungstate, chromium nitrate and sodium nitrate (wherein the atomic ratios of Mo, cu, sb, nb, W, cr and K to V are 4.0, 0.5, 0.3, 0.1, 0.2 and 0.1, respectively) were dissolved in water, and concentrated by evaporation to give 100mL of slurry 1 (water content 16%, calculated as negative pressure loss on drying at 30 ℃).
Step two: to slurry 1, 50mL of a mixture of 30% aqueous ethanol and water was added, and slurry 2 was obtained by beating and dispersing, and the viscosity of slurry 2 was measured, and the results are shown in Table 1.
Step three: slurry 2 was mixed with 150 g of alumina support (pore volume 0.4 mL/g), rotary evaporated at 80 ℃ until no visible liquid was present, dried at 120 ℃ for 12 hours, and calcined in an air atmosphere at 450 ℃ for 2 hours to give a catalyst. The evaluation results of the catalyst are shown in Table 1.
Example 7
Step one: a total of 150 g of VO was weighed out 2 、MoO 3 、CuO、Sb 2 O 3 、Nb 2 O 3 、WO 3 、Cr 2 O 3 And Na (Na) 2 Ammonium metavanadate, ammonium heptamolybdate, copper nitrate, antimony trioxide, niobium oxalate, ammonium metatungstate, chromium nitrate and sodium nitrate (wherein the atomic ratios of Mo, cu, sb, nb, W, cr and K to V are 4.0, 0.5, 0.3, 0.1, 0.2 and 0.1, respectively) were dissolved in water, and concentrated by evaporation to give 100mL of slurry 1 (water content 16%, calculated as negative pressure loss on drying at 30 ℃).
Step two: to slurry 1, 50mL of a mixture of ethanol and water containing 35% of water was added, and slurry 2 was obtained by beating and dispersing, and the viscosity of slurry 2 was measured, and the results are shown in Table 1.
Step three: slurry 2 was mixed with 150 g of alumina support (pore volume 0.4 mL/g), rotary evaporated at 80 ℃ until no visible liquid was present, dried at 120 ℃ for 12 hours, and calcined in an air atmosphere at 450 ℃ for 2 hours to give a catalyst. The evaluation results of the catalyst are shown in Table 1.
Example 8
Step one: a total of 150 g of VO was weighed out 2 、MoO 3 、CuO、Sb 2 O 3 、Nb 2 O 3 、WO 3 、Cr 2 O 3 And Na (Na) 2 Ammonium metavanadate, ammonium heptamolybdate, copper nitrate, antimony trioxide, niobium oxalate, ammonium metatungstate, chromium nitrate and sodium nitrate (wherein the atomic ratios of Mo, cu, sb, nb, W, cr and K to V are 4.0, 0.5, 0.3, 0.1, 0.2 and 0.1, respectively) were dissolved in water, and concentrated by evaporation to give 100mL of slurry 1 (water content 16%, calculated as negative pressure loss on drying at 30 ℃).
Step two: to slurry 1, 100mL of a mixture of 20% ethanol and water was added, and slurry 2 was obtained by beating and dispersing, and the viscosity of slurry 2 was measured, and the results are shown in table 1.
Step three: slurry 2 was mixed with 150 g of alumina support (pore volume 0.4 mL/g), rotary evaporated at 80 ℃ until no visible liquid was present, dried at 120 ℃ for 12 hours, and calcined in an air atmosphere at 450 ℃ for 2 hours to give a catalyst. The evaluation results of the catalyst are shown in Table 1.
Example 9
Step one: a total of 150 g of VO was weighed out 2 、MoO 3 、CuO、Sb 2 O 3 、Nb 2 O 3 、WO 3 、Cr 2 O 3 And Na (Na) 2 O ammonium metavanadate, ammonium heptamolybdate, copper nitrate, antimony trioxide, niobium oxalate, ammonium metatungstate, chromium nitrate and sodium nitrate (wherein the atomic ratio of Mo, cu, sb, nb, W, cr and K to V is 4.0, 0.5, 0.3, 0.1, 0.2 and 0.1 respectively) were dissolved in water, and concentrated by evaporation to give 100mL of slurry 1 (water content 16% toAnd (5) calculating the negative pressure drying weight loss at 30 ℃).
Step two: to slurry 1, 35mL of a mixture of 20% ethanol and water was added, and slurry 2 was obtained by beating and dispersing, and the viscosity of slurry 2 was measured, and the results are shown in table 1.
Step three: slurry 2 was mixed with 150 g of alumina support (pore volume 0.4 mL/g), rotary evaporated at 80 ℃ until no visible liquid was present, dried at 120 ℃ for 12 hours, and calcined in an air atmosphere at 450 ℃ for 2 hours to give a catalyst. The evaluation results of the catalyst are shown in Table 1.
TABLE 1
It should be noted that the above-described embodiments are only for explaining the present application and do not constitute any limitation of the present application. The application has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the application as defined in the appended claims, and the application may be modified without departing from the scope and spirit of the application. Although the application is described herein with reference to particular means, materials and embodiments, the application is not intended to be limited to the particulars disclosed herein, as the application extends to all other means and applications which perform the same function.

Claims (21)

1. A catalyst for the preparation of acrylic acid comprising: the catalyst comprises a carrier and active components distributed on the surface of the carrier and in pore channels of the carrier, wherein the content of the carrier is 40-60 wt% based on the total weight of the catalyst, the content of the active components distributed on the surface of the carrier is 10-20 wt%, and the content of the active components distributed in the pore channels of the carrier is 20-50 wt%;
the carrier is selected from one or more of aluminum oxide, silicon oxide, magnesium oxide and calcium oxide; and/or the active component contains V, mo and Cu;
the general formula of the active component is shown as a formula (1):
VMo a Cu b X c Y d O e (1)
In the formula (1), X is selected from one or more of Sb, nb, cr, W, la and Ce, Y is selected from one or more of K, na, rb and Cs, and a is 2.0-8.0; b is 0.2 to 0.8; c is 0.2-1.0; d is 0.05 to 1.2; e is the number of moles of oxygen atoms required to satisfy the valence of each element in the active component;
the preparation method of the catalyst for preparing acrylic acid comprises the following steps:
s1, dissolving a compound containing the active component in water, and concentrating to prepare first slurry;
s2, mixing the first slurry with a solvent to prepare second slurry;
s3, mixing the second slurry with the carrier to prepare a catalyst precursor; and
s4, roasting the catalyst precursor to obtain the catalyst;
wherein the solvent comprises water and a lower alcohol selected from one or more of methanol, ethanol, propanol and 1, 3-propanediol.
2. The catalyst of claim 1, wherein the pore volume of the support is from 0.1mL/g to 1.0mL/g.
3. The catalyst of claim 2, wherein the pore volume of the support is from 0.3mL/g to 0.5mL/g.
4. The catalyst of claim 1, wherein the lower alcohol is ethanol.
5. The catalyst according to claim 1, wherein the water content is 5 to 35wt%, calculated on the total weight of the solvent.
6. The catalyst of claim 5 wherein the water is present in an amount of 10wt% to 30wt% based on the total weight of the solvent.
7. The catalyst of claim 6 wherein the water is present in an amount of 15wt% to 25wt% based on the total weight of the solvent.
8. The catalyst of claim 1 wherein the volume ratio of the first slurry to the solvent is (1-3): 1.
9. The catalyst of claim 8 wherein the volume ratio of the first slurry to the solvent is (1-2): 1.
10. The catalyst of claim 1, wherein in step S2, the viscosity of the second slurry is 100cP or less.
11. The catalyst of claim 10, wherein in step S2, the viscosity of the second slurry is 80cP or less.
12. The catalyst of claim 11, wherein in step S2, the viscosity of the second slurry is from 1cP to 50cP.
13. The catalyst according to claim 1, wherein in step S4, the temperature of the calcination treatment is 350 ℃ to 550 ℃; and/or the roasting treatment time is 0.5-5 h.
14. The catalyst according to claim 13, wherein in step S4, the temperature of the calcination treatment is 400 ℃ to 500 ℃; and/or the roasting treatment time is 1-4 h.
15. The catalyst according to claim 1, further comprising a step of drying the catalyst precursor before the calcination treatment in step S4, wherein the drying conditions include: the drying temperature is 80-150 ℃; and/or the drying time is 1-28 h.
16. The catalyst of claim 15, wherein the drying temperature is from 100 ℃ to 130 ℃; and/or the drying time is 5-15 h.
17. Use of a catalyst according to any one of claims 1 to 16 in the field of the preparation of acrylic acid.
18. The use according to claim 17, wherein the catalyst is used in the field of the oxidation of acrolein to acrylic acid.
19. A method for preparing acrylic acid by oxidizing acrolein, comprising the following steps: contacting a feed stream comprising acrolein with a catalyst according to any one of claims 1-16, thereby producing acrylic acid.
20. The method of claim 19, wherein the contacting conditions comprise: the contact temperature is 200-350 ℃.
21. The method of claim 20, wherein the contacting is at a temperature of 250 ℃ to 300 ℃.
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