CN112547044A - Catalyst for acrylic acid synthesis and preparation method and application thereof - Google Patents
Catalyst for acrylic acid synthesis and preparation method and application thereof Download PDFInfo
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- CN112547044A CN112547044A CN201910918136.3A CN201910918136A CN112547044A CN 112547044 A CN112547044 A CN 112547044A CN 201910918136 A CN201910918136 A CN 201910918136A CN 112547044 A CN112547044 A CN 112547044A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 21
- 238000001308 synthesis method Methods 0.000 title description 3
- 239000013078 crystal Substances 0.000 claims abstract description 36
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 39
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 19
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 239000002002 slurry Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 229910001868 water Inorganic materials 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000007493 shaping process Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002905 metal composite material Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920000247 superabsorbent polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- 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 invention discloses a catalyst for acrylic acid synthesis, which comprises Mo with a general formula12VaOgThe active ingredient of the rod-like crystal of (1), wherein a is 0.5 to 10.0. The invention also discloses a preparation method of the catalyst, which comprises the step of crystallizing the dispersion liquid of the oxysalt containing the V element, the oxysalt of one or more elements selected from Cu, W and Sb and the oxysalt of the Mo element.
Description
Technical Field
The invention belongs to the technical field of acrylic acid synthesis methods, and particularly relates to a catalyst for propylene synthesis, and a preparation method and application of the catalyst for propylene synthesis.
Background
The acrylic acid and the esters thereof have wide application, wherein the crude acrylic acid is mainly used for producing water-soluble paint and adhesive, and the high-purity acid is mainly used for producing super absorbent polymer SAP. With the development of building, electronic and automobile industries, the demand and capacity of acrylic acid are increasing worldwide, especially the domestic acrylic acid production capacity is increased sharply in recent years, and the domestic production capacity has increased from 14 ten thousand tons in 2000 to 300 ten thousand tons by 2018.
The current method for industrially producing acrylic acid is a two-step oxidation method of propylene, which comprises oxidizing propylene to acrolein and then oxidizing acrolein to acrylic acid under the action of a catalyst. One type of catalyst commonly used in the two-step oxidation process is a metal composite oxide catalyst, such as a molybdenum-vanadium (Mo-V) composite oxide, a molybdenum-bismuth (Mo-Bi) composite oxide, and the like, and the activity of different types of metal composite oxide catalysts and the yield of acrylic acid obtained have a large difference.
At present, the commonly used method for preparing the metal composite oxide catalyst mostly adopts the processes of preparing a metal compound into a solution, adding an insoluble oxide for heating and evaporation, and then calcining, crushing and forming, and the catalyst obtained by the preparation methods usually lacks a stable crystal form, has short service life, low conversion rate and selectivity of the catalyst and low product yield.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the catalyst used in the reaction for synthesizing acrylic acid by acrolein oxidation in the prior art has short service life and low product yield, and the catalyst has long service life and high acrylic acid yield.
The second technical problem to be solved by the invention is that the preparation method in the prior art is difficult to prepare the catalyst for synthesizing acrylic acid by acrolein oxidation, which has uniform and stable crystal form and high product yield, and provides the preparation method of the catalyst which can obtain a stable rod-shaped crystal structure, and has long service life and high product yield.
The third technical problem to be solved by the present invention is to provide a method for synthesizing acrylic acid using the catalyst described in one of the above technical problems.
In order to solve one of the above technical problems, the present invention first provides the following technical solutions:
a catalyst for synthesizing acrylic acid contains Mo12VaOgThe rod-like crystal of (1), wherein,
a＝0.5～10.0；
g is a number determined by the total valence of the elements in the formula other than oxygen.
In the above scheme, Mo, V, and O represent the elements molybdenum, vanadium, and oxygen, respectively, and a and g represent their respective atomic ratios.
Compared with the metal composite catalyst commonly used in the prior art, the Mo in the invention12VaOgUnder certain preparation conditions, a stable rod-like crystal structure can be obtained, and the structure can be kept stable in long-term repeated application. In the catalytic reaction, Mo12VaOgThe rod-shaped crystal has larger specific surface area, and is difficult to agglomerate, so that the catalyst has higher catalytic efficiency and longer service life compared with amorphous or other crystal-shaped catalysts.
In some embodiments of the catalyst of the present invention, the Mo is12VaOgWherein a is 4.
In some embodiments of the catalyst of the present invention, the rod-like crystals have a diameter of 0.1 to 5 μm.
In some embodiments of the catalyst of the present invention, the rod-like crystals have a length of 1 to 50 μm.
In some embodiments of the catalyst of the present invention, the rod-like crystals have an aspect ratio of 3 to 100.
In some embodiments of the catalyst of the present invention, it further comprises a support on which the above rod-shaped crystals are supported.
In some embodiments of the catalyst of the present invention, it comprises 20 to 90 parts by mass of the rod-like crystals and 10 to 80 parts by mass of the carrier.
The carrier with different shapes, sizes and components can be selected by the person skilled in the art according to actual needs, for example, the carrier can be selected from SiO2、Al2O3、ZrO2And TiO2But not limited to, the above options.
In order to solve the second technical problem, the invention provides the following technical scheme:
a method for preparing a catalyst for acrylic acid synthesis, comprising a step of crystallizing a dispersion of a raw material compound, wherein the raw material compound comprises an oxysalt of a V element, an oxysalt of one or more elements selected from Cu, W and Sb, and an oxysalt of a Mo element, and the ratio of the amounts of the Mo element and the V element in the raw material compound is 12 (0.5-10.0), and preferably the dispersion is an aqueous dispersion. Preferably, the oxysalt of the Mo element is added to the dispersion after the oxysalt of the V element.
In the above scheme, the crystallization refers to a process of converting an amorphous substance into a crystal.
In the above embodiment, the aqueous dispersion is a dispersion in which the solvent is water, and is obtained by adding an oxysalt of a V element, an oxysalt of a W element, and an oxysalt of a Mo element to water.
The inventors have surprisingly found that crystallization in an inert atmosphere can be obtained by controlling the order of addition of the starting compounds, in particular by controlling the way in which the oxysalt of the element Mo is added to the solvent after the oxysalt of the element V, followed by crystallization in an inert atmosphereMo having rod-like crystal structure12VaOgA compound is provided.
In some embodiments of the preparation method of the present invention, the crystallization temperature is 80 to 250 ℃, preferably 90 to 150 ℃, such as but not limited to 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃ or 145 ℃. In some embodiments of the preparation method of the present invention, the crystallization time is 2 to 168 hours, preferably, the crystallization time is 10 to 160 hours, such as, but not limited to, 10 hours, 20 hours, 30 hours, 50 hours, 100 hours or 150 hours.
In some embodiments of the preparation method of the present invention, the crystallization is performed in a closed container in an inert atmosphere, which may be provided by an atmosphere of nitrogen, argon, helium, or the like.
In some embodiments of the preparation method of the present invention, the raw material compound includes ammonium heptamolybdate and/or a hydrate thereof, ammonium metavanadate and/or a hydrate thereof, and ammonium tungstate and/or a hydrate thereof.
In some embodiments of the preparation method of the present invention, the dispersion liquid contains 1 to 50 wt%, more preferably 2 to 15 wt% of ammonium heptamolybdate and/or a hydrate thereof. In one embodiment, the ammonium heptamolybdate and/or the hydrate thereof is added to the mixed aqueous solution of ammonium metavanadate and ammonium tungstate in the form of an aqueous solution of ammonium heptamolybdate.
In some specific embodiments of the preparation method of the present invention, the catalyst for acrylic acid synthesis is obtained by mixing the crystallized crystals or crystallized dispersion with a carrier raw material, and then calcining and molding, wherein the calcining temperature is 200 to 1000 ℃, and/or the calcining time is 0.5 to 100 hours.
In some embodiments of the preparation method of the present invention, the temperature of the calcination is 400 to 700 ℃, such as, but not limited to, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃.
In some embodiments of the preparation method of the present invention, the roasting time is 3 to 10 hours.
In some embodiments of the preparation method of the present invention, the time for the calcination can be selected from, but not limited to, the following values: 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 10 hours, 20 hours, or 30 hours.
In some embodiments of the preparation method of the present invention, the calcination may be carried out in an oxidizing atmosphere, preferably an oxygen-containing atmosphere, such as, but not limited to, water vapor, oxygen, air, oxygen-containing gas and N, or in an inert atmosphere2(and/or inert gas); the inert atmosphere is preferably nitrogen and/or an inert gas, such as, but not limited to, He, Ne, and/or Ar.
Preferably, the firing is performed in an air atmosphere.
In some embodiments of the preparation method of the present invention, the raw material of the carrier is SiO2、Al2O3、ZrO2、TiO2And their precursors.
The precursor is a substance which can be converted into a corresponding oxide through simple reactions such as dehydration, oxidation and the like, such as a hydrate and the like.
Preferably, the catalyst for acrylic acid synthesis comprises 20 to 90 parts by mass of the crystal and 10 to 80 parts by mass of the carrier.
Preferably, the carrier raw material further contains graphite.
In some embodiments of the preparation method of the present invention, the forming can be selected according to actual requirements, such as but not limited to rolling ball, extruding bar or tabletting, and during the forming process, the addition of forming auxiliary agent can be reasonably selected according to requirements.
The shape of the molded catalyst can be spherical, Raschig ring or cylindrical and the like, wherein the spherical diameter can be preferably 3-5 mm; the outer diameter of the raschig ring can be preferably 4-7 mm, the inner diameter is preferably 1.5-3 mm, and the length is preferably 3-5 mm; the cylindrical outer diameter can be preferably 4-7 mm, and the length is preferably 3-5 mm.
In order to solve the third technical problem, the invention further provides the following technical scheme:
the catalyst for acrylic acid synthesis and/or the catalyst prepared by the method are applied to acrylic acid synthesis, in particular to the process of preparing acrylic acid by acrolein oxidation.
In some embodiments of the use of the present invention, the catalyst is contacted with acrolein at 240 to 320 ℃.
In some embodiments of the application of the invention, the volume space velocity of the acrolein is 100-150 mL-h-1·g-1。
In some embodiments of the use of the present invention, the reaction temperature of the catalyst with acrolein is 270 ℃, and the volume space velocity of the acrolein is 110 mL-h-1·g-1In the embodiment, the conversion rate of the acrolein can reach 99.5%, the yield of the product acrylic acid can reach 93.2%, and the catalytic effect of the catalyst is not obviously reduced in a 500-hour life test.
The invention has the following beneficial effects:
(1) the catalyst for acrylic acid synthesis of the present invention contains Mo having a rod-like crystal structure12VaOgThe catalyst has high catalytic activity, high product yield and long service life, and the catalytic effect is not obviously reduced after the catalyst is used for 500 hours;
(2) the preparation method has simple process and convenient operation, and the obtained catalyst has stable and uniform rod-shaped crystal as an active component, and has higher catalytic efficiency, longer service life and better selectivity compared with the catalyst with an amorphous or other crystal structure as the active component;
(3) the application of the invention can efficiently convert the acrolein into the acrylic acid at 240-320 ℃, the product yield is more than 90%, and the acrolein conversion rate is more than 99%.
Drawings
FIG. 1 is an SEM image of a catalyst for acrylic acid synthesis obtained in example 1 of the present invention;
FIG. 2 is an SEM image of a catalyst for acrylic acid synthesis obtained in example 2 of the present invention;
FIG. 3 is an SEM image of the catalyst obtained in comparative example 1 of the present invention;
FIG. 4 is an SEM image of the catalyst obtained in comparative example 2 of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples. It should be understood that the embodiments and examples described herein are only for illustrating and explaining the present invention and are not to be construed as limiting the present invention.
The catalyst evaluation methods used in the following examples were:
introducing a reactant acrolein into a fixed bed reactor filled with a catalyst to be detected, absorbing a product after reaction by using dilute acid at 0 ℃, analyzing by using a gas chromatography, calculating carbon balance in the analysis process, and selecting data when the carbon balance is 95-105% as effective data, wherein the reaction conditions are as follows:
a reactor: a fixed bed reactor with an inner diameter of 25.4 mm and a length of 750 mm;
catalyst loading: 150 g;
reaction temperature: 270 ℃;
reaction time: 500 hours;
the volume ratio of raw materials is as follows: acrolein, air, water vapor 1:3.2: 2.1;
acrolein volume space velocity: 110 mL. h-1·g-1。
[ example 1 ]
43.9 g of ammonium metavanadate (NH)4VO3) 38.2 g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 1000g of aqueous solution, transferring the obtained slurry into a closed reaction kettle, introducing high-purity nitrogen (99.9%) for replacement for 5 times, heating to 150 ℃, crystallizing for 24 hours, and transferring the slurry to a flat bottomPutting the mixture into a tray, drying the mixture for 24 hours in an oven at 130 ℃, and then crushing the mixture to obtain powder.
160 g of the obtained powder and 160 g of Al are taken2O31.6g of graphite and 3.2g of deionized water are uniformly mixed, the tabletting pressure is set to be 3kN by a tablet machine, the round flaky shaped catalyst with the diameter of 5mm and the thickness of 4mm is obtained by tabletting, and finally the catalyst is roasted for 4 hours at 395 ℃ to obtain the catalyst for synthesizing acrylic acid.
The microstructure of the obtained catalyst is observed by a scanning electron microscope SEM, and as shown in figure 1, the active component in the obtained catalyst is a regular rod-shaped crystal structure, the diameter of the crystal is about 1 μm, the length of the crystal is about 5 μm, and the major axis of the crystal is 5.
The obtained catalyst was evaluated by the catalyst evaluation method described above, and the results are shown in table 1.
[ example 2 ]
43.9 g of ammonium metavanadate (NH)4VO3) 38.2 g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 1000g of aqueous solution, transferring the obtained slurry into a closed reaction kettle, introducing high-purity nitrogen (99.9%) for replacement for 5 times, heating to 130 ℃, crystallizing for 24 hours, transferring the slurry into a flat bottom plate, drying in an oven at 130 ℃ for 24 hours, and then crushing to obtain powder.
160 g of the obtained powder and 160 g of Al are taken2O31.6g of graphite and 3.2g of deionized water are uniformly mixed, the tabletting pressure is set to be 3kN by a tablet machine, the round flaky shaped catalyst with the diameter of 5mm and the thickness of 4mm is obtained by tabletting, and finally the catalyst is roasted for 4 hours at 395 ℃ to obtain the catalyst for synthesizing acrylic acid.
The microstructure of the obtained catalyst is observed by a scanning electron microscope SEM, as shown in figure 2, the active component in the obtained catalyst is a regular rod-shaped crystal structure, the diameter of the crystal is 0.5 μm, the length of the crystal is 6 μm, and the length-diameter ratio of the crystal is 12.
The obtained catalyst was evaluated by the catalyst evaluation method described above, and the results are shown in table 1.
[ example 3 ]
43.9 g of ammonium metavanadate (NH)4VO3) 38.2 g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 1000g of aqueous solution, transferring the obtained slurry into a closed reaction kettle, introducing high-purity nitrogen (99.9%) for replacement for 5 times, heating to 110 ℃, crystallizing for 24 hours, transferring the slurry into a flat bottom plate, drying in an oven at 130 ℃ for 24 hours, and then crushing to obtain powder.
160 g of the obtained powder and 160 g of Al are taken2O31.6g of graphite and 3.2g of deionized water are uniformly mixed, the tabletting pressure is set to be 3kN by a tablet machine, the round flaky shaped catalyst with the diameter of 5mm and the thickness of 4mm is obtained by tabletting, and finally the catalyst is roasted for 4 hours at 395 ℃ to obtain the catalyst for synthesizing acrylic acid.
The obtained catalyst was evaluated by the catalyst evaluation method described above, and the results are shown in table 1.
[ example 4 ]
43.9 g of ammonium metavanadate (NH)4VO3) 38.2 g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 1000g of aqueous solution, transferring the obtained slurry into a closed reaction kettle, introducing high-purity nitrogen (99.9%) for replacement for 5 times, heating to 90 ℃, crystallizing for 24 hours, transferring the slurry into a flat bottom plate, drying in an oven at 130 ℃ for 24 hours, and then crushing to obtain powder.
160 g of the obtained powder and 160 g of Al are taken2O31.6g of graphite and 3.2g of deionized water are uniformly mixed, the tabletting pressure is set to be 3kN through a tablet press, and circular tablets with the diameter of 5mm and the tablet thickness of 4mm are obtained through tablettingAnd (3) calcining the catalyst at 395 ℃ for 4 hours to obtain the catalyst for synthesizing the acrylic acid.
The obtained catalyst was evaluated by the catalyst evaluation method described above, and the results are shown in table 1.
[ example 5 ]
43.9 g of ammonium metavanadate (NH)4VO3) 38.2 g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 1000g of aqueous solution, transferring the obtained slurry into a closed reaction kettle, introducing high-purity argon (99.9%) for replacement for 5 times, heating to 130 ℃, crystallizing for 24 hours, transferring the slurry into a flat bottom plate, drying in an oven at 130 ℃ for 24 hours, and then crushing to obtain powder.
160 g of the obtained powder and 160 g of Al are taken2O31.6g of graphite and 3.2g of deionized water are uniformly mixed, the tabletting pressure is set to be 3kN by a tablet machine, the round flaky shaped catalyst with the diameter of 5mm and the thickness of 4mm is obtained by tabletting, and finally the catalyst is roasted for 4 hours at 395 ℃ to obtain the catalyst for synthesizing acrylic acid.
The obtained catalyst was evaluated by the catalyst evaluation method described above, and the results are shown in table 1.
[ example 6 ]
43.9 g of ammonium metavanadate (NH)4VO3) 38.2 g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 1000g of aqueous solution, transferring the obtained slurry into a closed reaction kettle, introducing high-purity argon (99.9%) for replacement for 5 times, heating to 130 ℃, crystallizing for 72 hours, transferring the slurry into a flat bottom plate, drying in an oven at 130 ℃ for 24 hours, and then crushing to obtain powder.
160 g of the obtained powder and 160 g of Al are taken2O31.6g of graphite and 3.2g of deionized water are uniformly mixed, the tabletting pressure is set to be 3kN by a tablet machine, the round flaky shaped catalyst with the diameter of 5mm and the thickness of 4mm is obtained by tabletting, and finally the catalyst is roasted for 4 hours at 395 ℃ to obtain the catalyst for synthesizing acrylic acid.
The obtained catalyst was evaluated by the catalyst evaluation method described above, and the results are shown in table 1.
Comparative example 1
43.9 g of ammonium metavanadate (NH)4VO3) 38.2 g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 1000g of an aqueous solution, transferring the slurry into an oven to dry for 24 hours at 130 ℃, and then crushing to obtain powder.
160 g of the obtained powder and 160 g of Al are taken2O31.6g graphite, 3.2g deionized water misce bene, set up preforming pressure 3kN through the tablet press, the circular sheet shaping catalyst that the preforming shaping obtained the diameter to be 5mm, 4mm is thick on the piece, at last the calcination 4 hours at 395 ℃, obtain contrast catalyst.
The microstructure of the comparative catalyst is observed by a scanning electron microscope SEM, as shown in figure 3, it can be seen that the active component in the obtained catalyst is powdery, has no uniform and stable crystal structure, and has an agglomeration phenomenon.
The comparative catalysts were evaluated by the catalyst evaluation methods described above, and the results are shown in table 1.
Comparative example 2
43.9 g of ammonium metavanadate (NH)4VO3) 38.2 g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 1000g of aqueous solution, transferring the obtained slurry into a closed reaction kettle, heating to 200 ℃ for crystallization for 24 hours, and transferring into an oven 13Drying at 0 deg.C for 24h, and pulverizing to obtain powder.
160 g of the obtained powder and 160 g of Al are taken2O31.6g graphite, 3.2g deionized water misce bene, set up preforming pressure 3kN through the tablet press, the circular sheet shaping catalyst that the preforming shaping obtained the diameter to be 5mm, 4mm is thick on the piece, at last the calcination 4 hours at 395 ℃, obtain required catalyst, obtain contrast catalyst.
The microstructure of the comparative catalyst is observed by a scanning electron microscope SEM, and as shown in figure 4, the active component in the obtained catalyst has no uniform and stable crystal structure and has an agglomeration phenomenon.
The catalyst was evaluated by the above evaluation method, and the results are shown in table 1.
Comparative example 3
200 g of ammonium heptamolybdate ((NH)4)6Mo7O24·4H2O) and 38.2 g ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 4.39 wt% of ammonium metavanadate (NH) was added thereto4VO3) 1000g of aqueous solution, transferring the obtained slurry into a closed reaction kettle, introducing high-purity nitrogen (99.9%) for replacement for 5 times, heating to 200 ℃, crystallizing for 24 hours, transferring into an oven for drying at 130 ℃ for 24 hours, and then crushing to obtain powder.
160 g of the obtained powder and 160 g of Al are taken2O31.6g graphite, 3.2g deionized water misce bene, set up preforming pressure 3kN through the tablet press, the circular sheet shaping catalyst that the preforming shaping obtained the diameter to be 5mm, 4mm is thick on the piece, at last the calcination 4 hours at 395 ℃, obtain required catalyst, obtain contrast catalyst.
The microstructure of the comparative catalyst is observed by a scanning electron microscope SEM, so that the catalyst has no uniform and stable crystal structure and has obvious agglomeration phenomenon.
The catalyst was evaluated by the above evaluation method, and the results are shown in table 1.
TABLE 1
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A catalyst for synthesizing acrylic acid contains Mo12VaOgThe active component of the rod-like crystal of (1), wherein a is 0.5 to 10.0; g is a number determined by the total valence of the elements in the formula other than oxygen.
2. The catalyst for acrylic acid synthesis according to claim 1, characterized in that: the diameter of the rod-shaped crystal is 0.1-5 micrometers, the length of the rod-shaped crystal is 1-50 micrometers, and/or the length-diameter ratio of the rod-shaped crystal is 3-100.
3. The catalyst for acrylic acid synthesis according to claim 1 or 2, characterized in that: the catalyst also comprises a carrier for supporting the active component, preferably the carrier is selected from SiO2、Al2O3、ZrO2And TiO2One or more of (a).
4. The catalyst for acrylic acid synthesis according to any one of claims 1 to 3, characterized in that: the catalyst comprises 20-90 parts by mass of an active component and 10-80 parts by mass of a carrier.
5. A method for producing a catalyst for acrylic acid synthesis, comprising crystallizing a dispersion of a raw material compound, wherein the raw material compound comprises an oxysalt of a V element, an oxysalt of one or more elements selected from Cu, W and Sb, and an oxysalt of a Mo element, and the ratio of the amounts of the Mo element and the V element in the raw material compound is 12 (0.5 to 10.0), preferably, the oxysalt of the Mo element is added to the dispersion after the oxysalt of the V element, and the dispersion is an aqueous dispersion.
6. The method of claim 5, wherein: the crystallization temperature is 80-250 ℃, preferably 90-150 ℃, and/or the crystallization time is 2-168 hours, preferably 10-160 hours, the crystallization is carried out in an inert atmosphere, preferably, the crystallization is carried out in a closed container in the inert atmosphere.
7. The production method according to claim 5 or 6, characterized in that: the crystallization temperature is selected from 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃ or 145 ℃; and/or the time of crystallization is selected from 10 hours, 20 hours, 30 hours, 50 hours, 100 hours, or 150 hours.
8. The production method according to any one of claims 5 to 7, characterized in that: the raw material compound comprises ammonium heptamolybdate and/or a hydrate thereof, ammonium metavanadate and/or a hydrate thereof, and ammonium tungstate and/or a hydrate thereof, and preferably, the dispersion liquid contains 1-50 wt%, more preferably 2-15 wt% of ammonium heptamolybdate and/or a hydrate thereof.
9. The production method according to any one of claims 5 to 8, characterized in that: mixing the crystallized crystal or crystallized dispersion liquid with a carrier raw material, roasting, and forming to obtain the catalyst for acrylic acid synthesis, wherein the roasting temperature is 200-1000 ℃, and/or the roasting time is 0.5-100 hours;
preferably, the raw material of the carrier is SiO2、Al2O3、ZrO2、TiO2And one of their precursorsOne or more kinds;
preferably, the catalyst for acrylic acid synthesis comprises 20-90 parts by mass of crystals and 10-80 parts by mass of a carrier;
preferably, the roasting temperature is 400-700 ℃, more preferably 450 ℃, 500 ℃, 550 ℃, 600 ℃ and 650 ℃;
preferably, the roasting time is 3-10 hours; or preferably, the calcination time is 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 10 hours, 20 hours, 30 hours.
10. Use of the catalyst for acrylic acid synthesis according to any one of claims 1 to 4 and/or the catalyst prepared by the preparation method according to any one of claims 5 to 9 in acrylic acid synthesis, preferably, the use comprises contacting the catalyst with acrolein at a reaction temperature of 240 to 320 ℃, and/or contacting the catalyst with a volume space velocity of 100 to 150 mL-h-1·g-1Acrolein contact; preferably, the reaction temperature is 270 ℃ and the volume space velocity is 110 mL-h-1·g-1。
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