CN114471592B - Catalyst for acrolein synthesis and preparation method and application thereof - Google Patents
Catalyst for acrolein synthesis and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 8
- 238000001308 synthesis method Methods 0.000 title description 2
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 15
- 239000011258 core-shell material Substances 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 239000004480 active ingredient Substances 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 21
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical group 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 20
- 150000002751 molybdenum Chemical class 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 13
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 13
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000012018 catalyst precursor Substances 0.000 claims description 9
- 239000012798 spherical particle Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000003756 stirring Methods 0.000 description 16
- 238000010304 firing Methods 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 238000001694 spray drying Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- 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)
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- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for acrolein synthesis, a preparation method and application thereof. The catalyst for synthesizing acrolein provided by the invention comprises a catalyst with a general formula of Mo 12 Bi a Ni b Co c O g Is an active ingredient of (a). The active component in the catalyst provided by the invention has a core-shell structure, and compared with the catalyst with an amorphous or other crystal structure as the active component, the catalyst has the advantages of higher catalytic efficiency, longer service life and better selectivity.
Description
Technical Field
The invention relates to a catalyst for acrolein synthesis and a preparation method and application thereof.
Background
Acrolein is the simplest unsaturated aldehyde, has active chemical properties, is widely applied to organic synthesis and resin production, is an intermediate product of acrylic acid industrial production, and has a domestic production scale of about 5 ten thousand tons per year and an acrylic acid production scale of about 300 ten thousand tons per year.
The current industrial acrolein production method uses propylene oxidation method, and the reaction is carried outIn the reactor, under the action of Mo-Bi composite oxide catalyst, propylene is oxidized to generate acrolein, and CO are generated simultaneously 2 Byproducts such as acetaldehyde and acetic acid, and emits a large amount of heat. The existing common method for preparing the catalyst mostly adopts the processes of preparing a metal compound into a solution, adding an insoluble oxide for evaporation, and then calcining, crushing and forming, and the catalyst obtained by the preparation method is generally low in activity, low in conversion rate and selectivity of the catalyst and low in product yield.
In addition, in order to improve the performance of the catalyst and extend its service life, for example, patent CN1210511 discloses a method for preparing a composite oxide by co-precipitation. The active components in the composite oxide prepared by the coprecipitation method are uniformly distributed in the catalyst and on the surface, and the molybdate of cobalt in the catalyst prepared by the method lacks a beta-phase structure which is more effective for reaction, so that the synergistic effect between the active components of the catalyst is difficult to be exerted to a large extent, and the activity and the stability of the catalyst are inhibited.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the catalyst used in the reaction of synthesizing acrolein by propylene oxidation in the prior art has low yield, and the catalyst with high acrolein yield is provided.
The second technical problem to be solved by the invention is to provide a preparation method of the catalyst corresponding to one of the technical problems to be solved.
The first aspect of the present invention provides a catalyst for acrolein synthesis, comprising a catalyst having the general formula Mo 12 Bi a Ni b Co c O g Wherein the active ingredient of the composition comprises, in the active ingredient,
a＝0.5-5.0，
b＝0.1-10.0，
c＝0.1-10.0，
g is a number determined by the total valence of the elements other than oxygen in the formula.
According to some embodiments of the invention, the active component is a spherical particle having a core-shell structure.
According to some embodiments of the invention, the core-shell structure has at least two layers of structure.
According to some embodiments of the invention, the spherical particles have a diameter of 10-55 microns.
According to some embodiments of the invention, the spherical particles have a shell thickness of 1-10 microns and a core diameter of 5-45 microns.
According to some embodiments of the invention, the catalyst further comprises a support carrying the active component.
According to some embodiments of the invention, the support is selected from the group consisting of SiO 2 、Al 2 O 3 、CeO 2 And TiO 2 One or more of the following.
According to some embodiments of the invention, the catalyst includes 20 to 90 parts by mass of the active component and 10 to 80 parts by mass of the support.
In a second aspect, the present invention provides a method for producing a catalyst for acrolein synthesis, comprising the steps of:
s1: pre-roasting powder of a raw material compound containing Mo, bi, ni and Co elements to obtain a catalyst precursor (I);
s2: and (3) immersing the catalyst precursor (I) in an impregnating solution containing soluble molybdenum salt, and drying to obtain a catalyst precursor (II).
In the invention, the catalyst precursor (II) is the active component of the catalyst.
According to some embodiments of the invention, the method further comprises step S3: and mixing the catalyst precursor (II) with a carrier, and then forming and roasting to obtain the catalyst for synthesizing the acrolein.
According to some embodiments of the invention, the feedstock compound comprises oxygen-containing salts of Mo, bi, ni and Co elements.
According to some embodiments of the invention, the starting compounds further comprise an oxygen-containing salt of one or more elements selected from Cu, W, ca, fe, ce, mn, K and Nb.
According to some embodiments of the invention, the feedstock compound comprises ammonium heptamolybdate and/or a hydrate thereof, bismuth nitrate and/or a hydrate thereof, cobalt nitrate and/or a hydrate thereof, and nickel nitrate and/or a hydrate thereof.
According to some embodiments of the invention, the total concentration of the starting compounds is from 5 to 70% by weight, more preferably from 20 to 50% by weight.
According to some embodiments of the invention, the soluble molybdenum salt is selected from ammonium heptamolybdate and/or a hydrate thereof.
According to some embodiments of the invention, the support is selected from the group consisting of SiO 2 、Al 2 O 3 、CeO 2 、TiO 2 And one or more of their precursors.
According to some embodiments of the present invention, the molar ratio of the oxygen-containing salt of Mo, bi, ni, and Co elements in the raw material compound is 12 (0.5 to 5.0): 0.1 to 10.0, based on Mo, bi, ni, and Co elements.
According to some embodiments of the invention, the catalyst comprises 20 to 90 parts by mass of the active component and 10 to 80 parts by mass of the carrier.
According to some embodiments of the invention, in S1, a powder is obtained by spraying a dispersion of a raw material compound containing Mo, bi, ni, and Co elements.
According to some embodiments of the invention, the dispersion is an aqueous dispersion.
According to some embodiments of the invention, in S2, the impregnation is an isovolumetric impregnation.
According to some embodiments of the invention, the concentration of the soluble molybdenum salt in the impregnation fluid is in the range of 1 to 50wt%.
According to a preferred embodiment of the invention, the concentration of the soluble molybdenum salt in the impregnation fluid is in the range of 20-35wt%.
According to some embodiments of the invention, the impregnating solution is an aqueous solution.
According to some embodiments of the invention, the molar ratio of the dispersion to the soluble molybdenum salt in the impregnation fluid is from 2 to 50:1, for example, may be 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, and any value therebetween.
According to some embodiments of the invention, the molar ratio of the dispersion to the soluble molybdenum salt in the impregnation fluid is from 2 to 20:1.
according to a preferred embodiment of the invention, the molar ratio of the dispersion to the soluble molybdenum salt in the impregnation fluid is between 2 and 10:1.
according to a further preferred embodiment of the invention, the molar ratio of the dispersion to the soluble molybdenum salt in the impregnation fluid is from 3 to 5:1.
according to some embodiments of the invention, in S1, the pre-firing temperature is 200-1000 ℃.
According to some embodiments of the invention, in S1, the pre-firing time is 0.5 to 100 hours.
According to some embodiments of the invention, in S1, the pre-firing temperature is 300-600 ℃.
According to some embodiments of the invention, in S1, the pre-firing temperature may be 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ and any value therebetween.
According to some embodiments of the invention, in S1, the pre-firing time is 4-30 hours.
According to some embodiments of the invention, in S1, the pre-firing time is 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, and any value therebetween.
According to some embodiments of the invention, in S3, the firing temperature is 200-1000 ℃.
According to some embodiments of the invention, in S3, the firing time is 0.5 to 100 hours.
According to some embodiments of the invention, in S3, the firing temperature is 300-600 ℃.
According to some embodiments of the invention, in S3, the firing temperature may be 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ and any value therebetween.
According to some embodiments of the invention, in S3, the firing time is 4 to 30 hours.
According to some embodiments of the invention, in S3, the firing time is 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, and any value therebetween.
According to some embodiments of the invention, the temperature of the pre-firing in S1 is lower than the temperature of the firing in S3.
In the catalyst obtained by the preparation method, the active component is spherical particles with a core-shell structure.
According to some embodiments of the invention, the core-shell structure has at least two layers of structure.
According to some embodiments of the invention, the spherical particles have a diameter of 10-55 microns.
According to some embodiments of the invention, the spherical particles have a shell thickness of 1-10 microns and a core diameter of 5-45 microns.
In a third aspect, the present invention provides the use of a catalyst according to the first aspect or a catalyst prepared according to the preparation method of the second aspect in the synthesis of acrolein.
According to some embodiments of the invention, the application comprises contacting the catalyst with propylene.
According to some embodiments of the invention, the contacting temperature is 350-420 ℃.
According to some embodiments of the invention, the propylene has a volume space velocity of from 90 to 150 ml.h -1 ·g -1 。
According to some embodiments of the invention, the contacting conditions include: the temperature is 370 ℃, and the volume space velocity of propylene is 110 mL.h -1 ·g -1 。
The invention has the following beneficial effects:
(1) The catalyst of the invention contains Mo with the general formula 12 Bi a Ni b Co c O g The active components of the catalyst have 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 disclosed by the invention is simple in process and convenient to operate, and the active component in the obtained catalyst has a core-shell structure, 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.
Drawings
Fig. 1 shows the microstructure of the catalyst prepared according to example 1 of the present invention.
Fig. 2 shows the microstructure of the catalyst prepared according to example 1 of the present invention.
Fig. 3 shows the microstructure of the catalyst prepared according to example 2 of the present invention.
Fig. 4 shows the microstructure of the catalyst prepared according to example 2 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention in any way.
The catalyst evaluation methods used in the following examples were:
introducing reactant propylene into a fixed bed reactor filled with a catalyst to be detected, absorbing the reacted product by using dilute acid at 0 ℃, analyzing by using 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:
the reactor comprises: a fixed bed reactor with an inner diameter of 25.4 mm and a length of 750 mm;
catalyst loading: 150 g;
reaction temperature: 400 ℃;
reaction time: 500 hours;
the volume ratio of the raw materials is as follows: propylene to air water vapor = 1:7.6:1.7;
propylene volume space velocity: 110 mL.h -1 ·g -1 。
[ example 1 ]
91.6 g of bismuth nitrate, 109 g of cobalt nitrate, 69.3 g of nickel nitrate were dissolved in 100g of water, to which 25% by weight of ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 ·4H 2 650g of aqueous solution, stirring for 10min, spray drying, and roasting the obtained powder in a muffle furnace at 400 ℃ for 8 hours to obtain a precursor (I).
Then 25wt% of ammonium heptamolybdate ((NH) was added to the precursor (I) 4 ) 6 Mo 7 O 24 ·4H 2 And O) 150g of aqueous solution, uniformly stirring, and drying at 80 ℃ for 24 hours to obtain a precursor (II).
400g of the obtained precursor (II) and 100g of Al are taken 2 O 3 Uniformly mixing 5g of graphite and 10g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round flaky formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 505 ℃ for 8 hours to obtain the catalyst for synthesizing acrolein.
The microstructure of the obtained catalyst was observed by SEM, and as shown in fig. 1 and 2, it can be seen that the active component in the obtained catalyst was catalyst particles having a core-shell structure.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 2 ]
91.6 g of bismuth nitrate, 109 g of cobalt nitrate, 69.3 g of nickel nitrate were dissolved in 100g of water, to which 25% by weight of ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 ·4H 2 O) 800g of an aqueous solution, stirring for 10min, spray drying, and roasting the obtained powder in a muffle furnace at 505 ℃ for 4 hours to obtain a precursor.
400g of the obtained precursor and 100g of Al are taken 2 O 3 Uniformly mixing 5g of graphite and 10g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round flaky formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 505 ℃ for 8 hours to obtain the catalyst for synthesizing acrolein. Through a scanning electron microscope SThe microstructure of the obtained catalyst was observed by EM, and as shown in fig. 3 and 4, it can be seen that the active component of the obtained catalyst was catalyst particles of solid structure. The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 3 ]
91.6 g of bismuth nitrate, 109 g of cobalt nitrate, 69.3 g of nickel nitrate were dissolved in 100g of water, to which 25% by weight of ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 ·4H 2 O) 400g of an aqueous solution, stirring for 10min, spray drying, and roasting the obtained powder in a muffle furnace at 400 ℃ for 8 hours to obtain a precursor (I).
Then 25wt% of ammonium heptamolybdate ((NH) was added to the precursor (I) 4 ) 6 Mo 7 O 24 ·4H 2 O) 400g of an aqueous solution, and after stirring uniformly, drying at 80 ℃ for 24 hours to obtain a precursor (II).
400g of the obtained precursor (II) and 100g of Al are taken 2 O 3 Uniformly mixing 5g of graphite and 10g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round flaky formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 505 ℃ for 8 hours to obtain the catalyst for synthesizing acrolein.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 4 ]
91.6 g of bismuth nitrate, 109 g of cobalt nitrate, 69.3 g of nickel nitrate were dissolved in 100g of water, to which 25% by weight of ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 ·4H 2 And O) 720g of aqueous solution, stirring for 10min, spray drying, and roasting the obtained powder in a muffle furnace at 400 ℃ for 8 hours to obtain a precursor (I).
Then 25wt% of ammonium heptamolybdate ((NH) was added to the precursor (I) 4 ) 6 Mo 7 O 24 ·4H 2 O) 80g of aqueous solution, and after stirring uniformly, drying at 80 ℃ for 24 hours to obtain a precursor (II).
400g of the precursor (II) obtained was taken) 100g of Al 2 O 3 Uniformly mixing 5g of graphite and 10g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round flaky formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 505 ℃ for 8 hours to obtain the catalyst for synthesizing acrolein.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 5 ]
91.6 g of bismuth nitrate, 109 g of cobalt nitrate, 69.3 g of nickel nitrate were dissolved in 100g of water, to which 25% by weight of ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 ·4H 2 760g of aqueous solution, stirring for 10min, spray drying, and roasting the obtained powder in a muffle furnace at 400 ℃ for 8 hours to obtain a precursor (I).
Then 25wt% of ammonium heptamolybdate ((NH) was added to the precursor (I) 4 ) 6 Mo 7 O 24 ·4H 2 O) 40g of an aqueous solution, and after stirring uniformly, drying at 80 ℃ for 24 hours to obtain a precursor (II).
400g of the obtained precursor (II) and 100g of Al are taken 2 O 3 Uniformly mixing 5g of graphite and 10g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round flaky formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 505 ℃ for 8 hours to obtain the catalyst for synthesizing acrolein.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 6 ]
91.6 g of bismuth nitrate, 109 g of cobalt nitrate, 69.3 g of nickel nitrate were dissolved in 100g of water, to which 25% by weight of ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 ·4H 2 O) 780g of an aqueous solution, stirring for 10min, spray drying, and roasting the obtained powder in a muffle furnace at 400 ℃ for 8 hours to obtain a precursor (I).
Then 25wt% of ammonium heptamolybdate ((NH) was added to the precursor (I) 4 ) 6 Mo 7 O 24 ·4H 2 And O) 20g of aqueous solution, uniformly stirring, and drying at 80 ℃ for 24 hours to obtain a precursor (II).
400g of the obtained precursor (II) and 100g of Al are taken 2 O 3 Uniformly mixing 5g of graphite and 10g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round flaky formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 505 ℃ for 8 hours to obtain the catalyst for synthesizing acrolein.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 7 ]
91.6 g of bismuth nitrate, 109 g of cobalt nitrate, 69.3 g of nickel nitrate were dissolved in 100g of water, to which 25% by weight of ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 ·4H 2 790g of aqueous solution, stirring for 10min, spray drying, and roasting the obtained powder in a muffle furnace at 400 ℃ for 8 hours to obtain the precursor (I).
Then 25wt% of ammonium heptamolybdate ((NH) was added to the precursor (I) 4 ) 6 Mo 7 O 24 ·4H 2 O) 10g of aqueous solution, and after stirring uniformly, drying at 80 ℃ for 24 hours to obtain a precursor (II).
400g of the obtained precursor (II) and 100g of Al are taken 2 O 3 Uniformly mixing 5g of graphite and 10g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round flaky formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 505 ℃ for 8 hours to obtain the catalyst for synthesizing acrolein.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 8 ]
54.1 g of bismuth nitrate, 109 g of cobalt nitrate, 69.3 g of nickel nitrate were dissolved in 100g of water, to which 25% by weight of ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 ·4H 2 O) 800g of aqueous solution, stirring for 10min, spray drying, and roasting the obtained powder in a muffle furnace at 400 ℃ for 8 hours to obtainA precursor (I).
Then 150g of 25wt% bismuth nitrate aqueous solution is added into the obtained precursor (I), and the mixture is stirred uniformly and then dried at 80 ℃ for 24 hours, thus obtaining the precursor (II).
400g of the obtained precursor (II) and 100g of Al are taken 2 O 3 Uniformly mixing 5g of graphite and 10g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round flaky formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 505 ℃ for 8 hours to obtain the catalyst for synthesizing acrolein.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 9 ]
91.6 g of bismuth nitrate, 71.5 g of cobalt nitrate, 69.3 g of nickel nitrate were dissolved in 100g of water, to which 25% by weight of ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 ·4H 2 O) 800g of an aqueous solution, stirring for 10min, spray drying, and roasting the obtained powder in a muffle furnace at 400 ℃ for 8 hours to obtain a precursor (I).
And 160g of 25wt% cobalt nitrate aqueous solution is added into the obtained precursor (I), and the mixture is uniformly stirred and dried at 80 ℃ for 24 hours to obtain a precursor (II).
400g of the obtained precursor (II) and 100g of Al are taken 2 O 3 Uniformly mixing 5g of graphite and 10g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round flaky formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 505 ℃ for 8 hours to obtain the catalyst for synthesizing acrolein.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 10 ]
91.6 g of bismuth nitrate, 109 g of cobalt nitrate, 31.8 g of nickel nitrate were dissolved in 100g of water, to which 25% by weight of ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 ·4H 2 O) 800g of aqueous solution, stirring for 10min, spray drying, and roasting the obtained powder in a muffle furnace at 400 ℃ for 8 hours to obtainTo precursor (I).
Then 160g of 25wt% nickel nitrate aqueous solution is added into the obtained precursor (I), and the mixture is uniformly stirred and dried at 80 ℃ for 24 hours to obtain a precursor (II).
400g of the obtained precursor (II) and 100g of Al are taken 2 O 3 Uniformly mixing 5g of graphite and 10g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round flaky formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 505 ℃ for 8 hours to obtain the catalyst for synthesizing acrolein.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
TABLE 1
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention 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 invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (27)
1. A catalyst for synthesizing acrolein includes a catalyst having a general formula Mo 12 Bi a Ni b Co c O g Wherein the active ingredient of the composition comprises, in the active ingredient,
a=0.5-5.0，
b=0.1-10.0，
c=0.1-10.0，
g is a number determined by the total valence of the elements other than oxygen in the formula;
the active component is spherical particles with a core-shell structure;
the preparation method of the catalyst comprises the following steps:
s1: pre-roasting powder of a raw material compound containing Mo, bi, ni and Co elements to obtain a catalyst precursor (I); in S1, a powder is obtained by spraying a dispersion of a raw material compound containing Mo, bi, ni, and Co elements;
s2: impregnating the catalyst precursor (I) in impregnating solution containing soluble molybdenum salt, and drying to obtain a catalyst precursor (II);
the molar ratio of the dispersion liquid to the soluble molybdenum salt in the impregnating liquid is 2-50:1.
2. The catalyst of claim 1, wherein the core-shell structure has at least a two-layer structure.
3. The catalyst of claim 2 wherein the spherical particles have a diameter of 10 to 55 microns.
4. A catalyst according to claim 3, wherein the spherical particles have a shell thickness of 1 to 10 microns and a core diameter of 5 to 45 microns.
5. The catalyst of claims 1-4, further comprising a support supporting the active component.
6. The catalyst of claim 5 wherein the support is selected from the group consisting of SiO 2 、Al 2 O 3 、CeO 2 And TiO 2 One or more of the following.
7. The catalyst according to claim 6, characterized in that the catalyst comprises 20 to 90 parts by mass of the active component and 10 to 80 parts by mass of the carrier.
8. The catalyst according to claim 7, wherein the method for preparing the catalyst further comprises step S3: and mixing the catalyst precursor (II) with a carrier, and then forming and roasting to obtain the catalyst for synthesizing the acrolein.
9. The catalyst of claim 8, wherein the catalyst is,
the raw material compound comprises oxygen-containing salts of Mo, bi, ni and Co elements and optionally one or more elements selected from Cu, W, ca, fe, ce, mn, K and Nb; and/or
The soluble molybdenum salt is selected from ammonium heptamolybdate and/or a hydrate thereof; and/or
The carrier is selected from SiO 2 、Al 2 O 3 、CeO 2 、TiO 2 And one or more of their precursors.
10. Catalyst according to claim 9, characterized in that the starting compounds comprise ammonium heptamolybdate and/or a hydrate thereof, bismuth nitrate and/or a hydrate thereof, cobalt nitrate and/or a hydrate thereof and nickel nitrate and/or a hydrate thereof.
11. The catalyst of claim 10, wherein the total concentration of each feedstock compound is from 5 to 70wt%.
12. The catalyst of claim 11, wherein the total concentration of each feedstock compound is from 20 to 50wt%.
13. The catalyst according to any one of claims 8 to 12, wherein the molar ratio of the oxygen-containing salts of Mo, bi, ni and Co elements in the raw material compound is 12 (0.5 to 5.0): (0.1 to 10.0) in terms of Mo, bi, ni and Co elements.
14. The catalyst of claim 13, wherein the dispersion is an aqueous dispersion; and/or, in S2, the impregnation adopts isovolumetric impregnation;
and/or, in S1, the temperature of the pre-roasting is 200-1000 ℃;
and/or, in S1, the pre-roasting time is 0.5-100 hours;
and/or, in S3, the roasting temperature is 200-1000 ℃,
and/or, in S3, the roasting time is 0.5-100 hours.
15. The catalyst of claim 14, wherein in S1, the pre-calcination time is from 4 to 30 hours.
16. The catalyst of claim 15, wherein in S3, the calcination is for a period of 4 to 30 hours.
17. The catalyst of claim 16, wherein in S1, the pre-calcination temperature is 300-600 ℃.
18. The catalyst of claim 17, wherein in S3 the calcination temperature is 300-600 ℃.
19. The catalyst of any one of claims 14-18, wherein the pre-calcination temperature in S1 is lower than the calcination temperature in S3.
20. The catalyst of claim 19, wherein the concentration of soluble molybdenum salt in the impregnation fluid is from 1 to 50wt%.
21. The catalyst of claim 20, wherein the concentration of soluble molybdenum salt in the impregnation fluid is from 20 to 35wt%.
22. The catalyst of claim 21 wherein the impregnating solution is an aqueous solution.
23. The catalyst of claim 22, wherein the molar ratio of the dispersion to the soluble molybdenum salt in the impregnation is from 2 to 20:1.
24. The catalyst of claim 23, wherein the molar ratio of the dispersion to the soluble molybdenum salt in the impregnation is from 2 to 10:1.
25. Use of a catalyst according to any one of claims 1-24 in the synthesis of acrolein.
26. The use according to claim 25, wherein the use comprises contacting the catalyst with propylene.
27. The use according to claim 26, wherein the temperature of the contacting is 350-420 ℃, and/or the volumetric space velocity of the propylene is 90-150 ml.h -1 •g -1 。
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| US5144090A (en) * | 1990-06-06 | 1992-09-01 | Mitsui Toatsu Chemicals, Incorporated | Method for preparing acrolein or methacrolein |
| JP2002273228A (en) * | 2001-03-19 | 2002-09-24 | Nippon Kayaku Co Ltd | Catalyst and method for manufacturing acrolein and acrylic acid |
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| CN101690900A (en) * | 2009-10-21 | 2010-04-07 | 中国海洋石油总公司 | Method for preparing catalyst for acrolein and acrylic acid |
| JP2018158314A (en) * | 2017-03-23 | 2018-10-11 | 三菱ケミカル株式会社 | Method for producing composite oxide catalyst |
| CN109304171A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | The catalyst of methacrylaldehyde acrylic acid |
| CN109305910A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | Methacrylaldehyde acrylic acid |
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2020
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5144090A (en) * | 1990-06-06 | 1992-09-01 | Mitsui Toatsu Chemicals, Incorporated | Method for preparing acrolein or methacrolein |
| JP2002273228A (en) * | 2001-03-19 | 2002-09-24 | Nippon Kayaku Co Ltd | Catalyst and method for manufacturing acrolein and acrylic acid |
| CN101239316A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Methane selective oxidation making formaldehyde catalyst and preparation and application thereof |
| CN101690900A (en) * | 2009-10-21 | 2010-04-07 | 中国海洋石油总公司 | Method for preparing catalyst for acrolein and acrylic acid |
| JP2018158314A (en) * | 2017-03-23 | 2018-10-11 | 三菱ケミカル株式会社 | Method for producing composite oxide catalyst |
| CN109304171A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | The catalyst of methacrylaldehyde acrylic acid |
| CN109305910A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | Methacrylaldehyde acrylic acid |
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