CN113070069A - Catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation and preparation method and application thereof - Google Patents
Catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation and preparation method and application thereof Download PDFInfo
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- CN113070069A CN113070069A CN202110190734.0A CN202110190734A CN113070069A CN 113070069 A CN113070069 A CN 113070069A CN 202110190734 A CN202110190734 A CN 202110190734A CN 113070069 A CN113070069 A CN 113070069A
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- catalyst
- soluble salt
- preparing
- cyclohexanone
- cyclohexanol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 36
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 10
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 9
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 5
- 230000032683 aging Effects 0.000 claims description 37
- 150000003839 salts Chemical class 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 15
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical group [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 230000010355 oscillation Effects 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012686 silicon precursor Substances 0.000 claims description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000007790 solid phase Substances 0.000 description 10
- 230000003472 neutralizing effect Effects 0.000 description 5
- 230000002431 foraging effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000000975 co-precipitation Methods 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
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J23/002—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
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- 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
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention discloses a catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation, a preparation method and application thereof, wherein the catalyst is prepared from Al2O3The active component consists of CuO and SiO2And Cr2O3The structural auxiliary agent is La2O3Or CeO2The mass content of the active component CuO is 30-45%, and the mass content of the active component SiO is210-20% of active component Cr2O3The mass content of the structural auxiliary agent is 10-20%, and the mass content of the structural auxiliary agent is 2-6%. The catalyst of the invention is used for preparing cyclohexanone by cyclohexanol dehydrogenation, and has good activity, selectivity and stability in a wider temperature range.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation, and a preparation method and application thereof.
Background
Cyclohexanone is an important organic chemical raw material, and is a main intermediate for producing nylon-6 and nylon-66. At present, dehydrogenation catalysts can be mainly classified into two types, namely Zn-based catalysts and Cu-based catalysts according to the active components of the catalysts. The Zn-based catalyst has the advantages of high conversion rate, high reaction temperature generally at 350-400 ℃, poor selectivity and short service life. The Cu-based catalyst has the advantages of good selectivity, but in the using process of the Cu-based catalyst, the sintering of copper can be accelerated when the reaction temperature is increased to more than 280 ℃, the active surface area is reduced, the carrier structure is obviously changed, so the activity of the catalyst is obviously reduced, and the stability of the catalyst is poor. Therefore, the development of new cyclohexanol dehydrogenation catalysts is of great interest.
Patent CN103861626A discloses a catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation and application thereof, wherein the catalyst takes phosphide of metallic iron, cobalt or nickel and oxide of tungsten as active components, and Al is used2O3、SiO2Or the porous ceramic is used as a carrier material, and alkali metal or alkaline earth metal oxide is also added to modify the catalyst, and the catalyst is prepared by adopting a multi-step impregnation method.
Patent CN103285847A discloses a dehydrogenation catalyst, its preparation method and application, and a method for preparing cyclohexanone by dehydrogenation of cyclohexanol, wherein active components of the catalyst are mainly Zn, Ca and Ba, under the condition of coprecipitation, soluble salts of the dehydrogenation active components and a precipitant capable of precipitating cations of the soluble salts are borrowed in water and then filtered to obtain solid precipitates, and the precipitates are dried or not dried and then calcined to obtain the catalyst.
The conversion rate and the selectivity of the cyclohexanol dehydrogenation catalyst prepared by the prior art can not be optimized at the same time, and the conversion rate is low due to dehydrogenation at a lower temperature; while at higher temperatures dehydrogenation, cyclohexanone selectivity generally decreases and the catalyst is easily deactivated.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a catalyst for preparing cyclohexanone by dehydrogenating cyclohexanol is prepared from Al2O3The active component consists of CuO and SiO2And Cr2O3The structural auxiliary agent is La2O3Or CeO2The mass content of the active component CuO is 30-45%, and the mass content of the active component SiO is210-20% of active component Cr2O3The mass content of (A) is 10-20%, the mass content of the structural auxiliary agent is 2-6%, and the balance is Al2O3。
The invention also discloses a preparation method of the catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation, which comprises the following steps:
(a) adjusting the pH value of a silicon precursor to 10-12 by using an alkali solution, and treating at 60-90 ℃ for 1-4 h to obtain a mixed solution A;
(b) adding soluble salt of copper and soluble salt of chromium into the mixed solution A under stirring, and then aging and precipitating to obtain precipitate B for later use;
(c) mixing soluble salt of lanthanum or cerium and soluble salt of aluminum with alkaline solution under stirring, and then aging and precipitating to obtain precipitate C for later use;
(d) under the ultrasonic oscillation condition with the frequency of 60-120 KHz, mixing the precipitate B and the precipitate C, and filtering and separating to obtain a solid D;
(e) and drying and roasting the solid D, adding graphite into a roasted product, and then tabletting and forming to obtain the catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation.
Preferably, the silicon precursor is at least one of silica sol, tetraethyl silicate, tetrapropyl silicate and tetrabutyl silicate.
Preferably, the soluble salt of copper is copper nitrate, the soluble salt of chromium is chromium nitrate, the soluble salt of aluminum is aluminum nitrate, the soluble salt of lanthanum is lanthanum nitrate, and the soluble salt of cerium is cerium nitrate.
Preferably, the alkali solution is at least one of a potassium hydroxide solution and a sodium hydroxide solution; the alkaline solution is at least one of sodium carbonate and potassium carbonate.
Preferably, the mass ratio of the silicon precursor to the soluble salt of copper to the soluble salt of chromium to the soluble salt of aluminum to the soluble salt of lanthanum or to the soluble salt of cerium is 1: 1-2.5: 0.1-1: 0.05-0.3: 0.2-3.
Preferably, the stirring speed in the step (b) is 100-400 rpm, the aging time is 20-80 min, the aging temperature is 30-70 ℃, and the precipitation end point pH value is 7.2-9.0; the stirring speed in the step (c) is 200-400 rpm, the aging time is 40-80 min, the aging temperature is 30-70 ℃, and the precipitation end point pH value is 6.8-7.5.
Preferably, the drying temperature is 110-160 ℃, the drying time is 8-20 h, the roasting temperature is 350-600 ℃, the roasting time is 4-16 h, and the adding amount of the graphite is 0.1-0.3% of the quality of the roasted product.
The invention also discloses an application of the catalyst in preparation of cyclohexanone, and the specific application method comprises the following steps: under the action of a catalyst, carrying out dehydrogenation reaction on cyclohexanol to prepare cyclohexanone, wherein the temperature of the dehydrogenation reaction is 210-280 ℃, the pressure is 0.1-0.3 MPa, and the space velocity of cyclohexanol is 0.6-1.8 h-1。
Preferably, before the dehydrogenation reaction, the catalyst is reduced by using a mixed gas of hydrogen and nitrogen, the temperature of the reduction treatment is 120-300 ℃, the time is 40-180 h, and the volume concentration of the hydrogen in the mixed gas is 0.1-20%.
Compared with the prior art, the invention has the following beneficial effects:
1. the catalyst has good activity, and the catalyst has good anti-pulverization stability and improved activity by optimizing the formula and preparation parameters of the catalyst, and the active component and the structural auxiliary agent in the prepared catalyst are mutually cooperated, so that the catalyst has good activity, selectivity and stability in a wider temperature range, the conversion rate of cyclohexanol is above 66.7%, and the selectivity of cyclohexanone is above 99.1%.
2. The preparation process is simple, the operation of the preparation process of the catalyst is simple, the reaction is mild, and the preparation process is obviously optimized.
Detailed Description
The technical solution of the present invention is further described in detail by the following examples, but the present invention is not limited to the following examples.
Example 1
First, 128.1g of silica Sol (SiO)230 percent of mass content), adjusting the pH value to 11.0 by using 0.5mol/L sodium hydroxide aqueous solution, and treating for 2 hours at the temperature of 80 ℃ to form mixed liquid A; (b) under stirring, 241.2g of copper nitrate, 60.5g of chromium nitrate and the mixed solution A are contacted for aging treatment, wherein the stirring speed is 200rpm, the aging time is 20min, the aging temperature is 70 ℃, and the pH value of the final precipitation point is controlled to be 8.5, so that a precipitate B is obtained; (c) under stirring, neutralizing 24.3g of cerium nitrate and 133.5g of aluminum nitrate with 1mol/L of potassium carbonate aqueous solution, and performing aging treatment, wherein the stirring speed is 300rpm, the aging time is 40min, the aging temperature is 40 ℃, and the pH value of the final precipitation point is controlled to be 7.2 to obtain a precipitate C; (d) under the ultrasonic oscillation condition with the frequency of 80KHz, fully mixing the precipitate B and the precipitate C, and filtering to obtain a solid phase D; (e) drying the solid phase D at 120 ℃ for 10h, then roasting at 400 ℃ for 8h, adding graphite with the mass of 0.1% of that of the roasted product into the roasted product, and then tabletting and forming to obtain the catalyst
(h) The cylindrical catalyst of (1). Based on the mass of the prepared catalyst, SiO215% by mass of (A), 40% by mass of CuO, and Cr2O3Is 15% by mass of CeO2Is 5% by mass, Al2O3The content is 25%.
Example 2
Firstly, 121.5g of tetraethyl silicate is adjusted to pH value of 10.5 by 0.8mol/L potassium hydroxide aqueous solution and then treated for 4 hours at the temperature of 70 ℃ to form a mixed solution A; (b) under stirring, 246.4g of copper nitrate, 109.2g of chromium nitrate and mixed solution A were contacted and agedThe stirring speed is 300rpm, the aging time is 20min, the aging temperature is 60 ℃, and the pH value of the precipitation end point is controlled to be 8.1 to obtain a precipitate B; (c) neutralizing 9.1g of lanthanum nitrate and 277.2g of aluminum nitrate with 0.5mol/L of sodium carbonate aqueous solution under stirring, and performing aging treatment, wherein the stirring speed is 200rpm, the aging time is 30min, the aging temperature is 70 ℃, and the pH value at the end point of precipitation is controlled to be 7.1 to obtain precipitation C; (d) under the ultrasonic oscillation condition with the frequency of 100KHz, fully mixing the precipitate B and the precipitate C, and filtering to obtain a solid phase D; (e) drying the solid phase D at 130 ℃ for 16h, then roasting at 500 ℃ for 10h, adding graphite with the mass of 0.3% of that of the roasted product into the roasted product, and then tabletting and forming to obtain the catalyst
(h) The cylindrical catalyst of (1). Based on the mass of the prepared catalyst, SiO210% by mass of (A), 30% by mass of CuO, and Cr2O3Is 20% by mass of La2O3Is 2.6% by mass, Al2O3The content was 37.4%.
Example 3
First 106.3g of silica Sol (SiO)230 percent of mass content), adjusting the pH value to 12.0 by using 1.2mol/L potassium hydroxide aqueous solution, and treating for 2 hours at the temperature of 60 ℃ to form a mixed solution A; (b) under stirring, 164.3g of copper nitrate, 44.2g of chromium nitrate and the mixed solution A are contacted for aging treatment, wherein the stirring speed is 200rpm, the aging time is 60min, the aging temperature is 50 ℃, and the pH value of the final precipitation point is controlled to be 7.6 to obtain a precipitate B; (c) under stirring, neutralizing 11.3g of lanthanum nitrate, 129.5g of aluminum nitrate and 0.8mol/L of sodium carbonate aqueous solution, and performing aging treatment, wherein the stirring speed is 300rpm, the aging time is 40min, the aging temperature is 70 ℃, and the pH value of the precipitation endpoint is controlled to be 7.2 to obtain a precipitate C; (d) under the ultrasonic oscillation condition with the frequency of 60KHz, fully mixing the precipitate B and the precipitate C, and filtering to obtain a solid phase D; (e) drying the solid phase D at 110 ℃ for 12h, then roasting at 600 ℃ for 8h, adding graphite with the mass of 0.2% of that of the roasted product into the roasted product, and then tabletting and forming to obtain the catalyst
(h) The cylindrical catalyst of (1). Based on the mass of the prepared catalyst, SiO215.7% by mass of (B), 34.3% by mass of CuO, and Cr2O3Has a mass content of 13.9% and La2O35.6% by mass of Al2O3The content was 30.5%.
Example 4
Firstly, 154.4g of tetrapropyl silicate is adjusted to pH value of 10.1 by 2mol/L of potassium carbonate aqueous solution and then treated for 3 hours at the temperature of 70 ℃ to form a mixed solution A; (b) under stirring, 185.5g of copper nitrate, 41.4g of chromium nitrate and the mixed solution A are contacted for aging treatment, wherein the stirring speed is 200rpm, the aging time is 50min, the aging temperature is 40 ℃, and the pH value of the final precipitation point is controlled to be 8.4 to obtain a precipitate B; (c) under stirring, neutralizing 10.4g of cerium nitrate and 62.1g of aluminum nitrate with 0.2mol/L of sodium hydroxide aqueous solution, and performing aging treatment, wherein the stirring speed is 300rpm, the aging time is 60min, the aging temperature is 40 ℃, and the precipitation end point pH value is 7.2 to obtain a precipitate C; (d) under the ultrasonic oscillation condition with the frequency of 80KHz, fully mixing the precipitate B and the precipitate C, and filtering to obtain a solid phase D; (e) drying the solid phase D at 150 ℃ for 8h, then roasting at 450 ℃ for 14h, adding graphite with the mass of 0.2% of that of the roasted product into the roasted product, and then tabletting and forming to obtain the catalyst
(h) The cylindrical catalyst of (1). Based on the mass of the prepared catalyst, SiO220% by mass of (A), 45% by mass of CuO, and Cr2O3Is 15% by mass of CeO2Is 3% by mass, Al2O3The content was 17%.
Example 5
First 125.5g of silica Sol (SiO)230 percent of mass content), adjusting the pH value to 11.5 by using 0.8mol/L sodium hydroxide aqueous solution, and treating for 2 hours at the temperature of 70 ℃ to form mixed liquid A; (b) under stirring, 206.3g of copper nitrate, 39.9g of chromium nitrate andcontacting the mixed solution A for aging treatment, wherein the stirring speed is 400rpm, the aging time is 80min, the aging temperature is 30 ℃, and the pH value of the precipitation end point is controlled to be 8.8 to obtain a precipitate B; (c) under stirring, neutralizing 11.6g of lanthanum nitrate, 108.2g of aluminum nitrate and 0.2mol/L of sodium hydroxide aqueous solution, and performing aging treatment, wherein the stirring speed is 400rpm, the aging time is 80min, the aging temperature is 30 ℃, and the pH value at the end point of precipitation is controlled to be 7.4 to obtain a precipitate C; (d) under the ultrasonic oscillation condition with the frequency of 100KHz, fully mixing the precipitate B and the precipitate C, and filtering to obtain a solid phase D; (e) drying the solid phase D at 120 ℃ for 10h, then roasting at 400 ℃ for 8h, adding graphite with the mass of 0.2% of that of the roasted product into the roasted product, and then tabletting and forming to obtain the catalyst
(h) The cylindrical catalyst of (1). Based on the mass of the prepared catalyst, SiO217.7% by mass of (B), 41.3% by mass of CuO, and Cr2O3Is 12% by mass, La2O35.5% by mass of Al2O3The content was 23.5%.
The catalyst of the invention is used for preparing cyclohexanone by cyclohexanol dehydrogenation:
the catalyst in the embodiment 1-5 is loaded into a fixed bed reactor and is subjected to reduction treatment by using a mixed gas of hydrogen and nitrogen, wherein the reduction treatment conditions are as follows: the temperature is 280 ℃, the reduction time is 60h, and the volume concentration of hydrogen in the mixed gas is 0.5%. And after the reduction treatment is finished, introducing the raw material cyclohexanol into a fixed bed reactor to perform dehydrogenation reaction to prepare cyclohexanone. The catalyst activity evaluation was carried out under the following reaction conditions, respectively, while changing the reaction conditions, and the results are shown in table 1:
the reaction conditions (1) are as follows: the hourly space velocity of the raw material cyclohexanol liquid is 0.8h-1The reaction temperature is 220 ℃, and the reaction pressure is normal pressure;
the reaction conditions (2) are as follows: the hourly space velocity of the raw material cyclohexanol liquid is 1.2h-1The reaction temperature is 260 ℃, and the reaction pressure is 0.1 MPa;
the reaction conditions (3) are as follows: when the raw material is cyclohexanol liquidThe space velocity is 1.5h-1The reaction temperature is 240 ℃ and the reaction pressure is 0.3MPa
TABLE 1 evaluation results of cyclohexanol dehydrogenation catalyst
As can be seen from the catalytic reaction performance data in Table 1, the catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation has good activity, selectivity and stability in a wider temperature range.
Claims (10)
1. The catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation is characterized in that the catalyst is prepared from Al2O3The active component consists of CuO and SiO2And Cr2O3The structural auxiliary agent is La2O3Or CeO2The mass content of the active component CuO is 30-45%, and the mass content of the active component SiO is210-20% of active component Cr2O3The mass content of (A) is 10-20%, the mass content of the structural auxiliary agent is 2-6%, and the balance is Al2O3。
2. The method for preparing the catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation, according to claim 1, comprising the steps of:
(a) adjusting the pH value of a silicon precursor to 10-12 by using an alkali solution, and treating at 60-90 ℃ for 1-4 h to obtain a mixed solution A;
(b) adding soluble salt of copper and soluble salt of chromium into the mixed solution A under stirring, and then aging and precipitating to obtain precipitate B for later use;
(c) mixing soluble salt of lanthanum or cerium and soluble salt of aluminum with alkaline solution under stirring, and then aging and precipitating to obtain precipitate C for later use;
(d) under the ultrasonic oscillation condition with the frequency of 60-120 KHz, mixing the precipitate B and the precipitate C, and filtering and separating to obtain a solid D;
(e) and drying and roasting the solid D, adding graphite into a roasted product, and then tabletting and forming to obtain the catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation.
3. The method for preparing the catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation according to claim 2, wherein the silicon precursor is at least one of silica sol, tetraethyl silicate, tetrapropyl silicate and tetrabutyl silicate.
4. The method for preparing the catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation, according to claim 2, wherein the soluble salt of copper is copper nitrate, the soluble salt of chromium is chromium nitrate, the soluble salt of aluminum is aluminum nitrate, the soluble salt of lanthanum is lanthanum nitrate, and the soluble salt of cerium is cerium nitrate.
5. The method for preparing the catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation according to claim 2, wherein the alkali solution is at least one of a potassium hydroxide solution and a sodium hydroxide solution; the alkaline solution is at least one of sodium carbonate and potassium carbonate.
6. The method for preparing the catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation, according to claim 2, wherein the mass ratio of the silicon precursor, the soluble salt of copper, the soluble salt of chromium, the soluble salt of aluminum, the soluble salt of lanthanum or the soluble salt of cerium is 1: 1-2.5: 0.1-1: 0.05-0.3: 0.2-3.
7. The method for preparing catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation according to claim 2, wherein the stirring rotation speed in step (b) is 100-400 rpm, the aging time is 20-80 min, the aging temperature is 30-70 ℃, and the precipitation end point pH value is 7.2-9.0; the stirring speed in the step (c) is 200-400 rpm, the aging time is 40-80 min, the aging temperature is 30-70 ℃, and the precipitation end point pH value is 6.8-7.5.
8. The method for preparing the catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation according to claim 2, wherein the drying temperature is 110-160 ℃, the drying time is 8-20 h, the roasting temperature is 350-600 ℃, the roasting time is 4-16 h, and the addition amount of graphite is 0.1-0.3% of the quality of a roasted product.
9. The use of the catalyst of claim 1 for the preparation of cyclohexanone by a specific method comprising: under the action of a catalyst, carrying out dehydrogenation reaction on cyclohexanol to prepare cyclohexanone, wherein the temperature of the dehydrogenation reaction is 210-280 ℃, the pressure is 0.1-0.3 MPa, and the space velocity of cyclohexanol is 0.6-1.8 h-1。
10. The use of claim 9, wherein the catalyst is subjected to reduction treatment by using a mixed gas of hydrogen and nitrogen before the dehydrogenation reaction, the temperature of the reduction treatment is 120-300 ℃, the time is 40-180 h, and the volume concentration of hydrogen in the mixed gas is 0.1-20%.
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| CN114797882A (en) * | 2022-04-01 | 2022-07-29 | 衢州巨化锦纶有限责任公司 | Catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation and preparation method and application thereof |
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| CN1500007A (en) * | 2001-03-29 | 2004-05-26 | �Ϸ���ѧ��ý��ʽ���� | Catalyst for dehydrogenation of cyclohexanol and method for preparaiton thereof |
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| CN1500007A (en) * | 2001-03-29 | 2004-05-26 | �Ϸ���ѧ��ý��ʽ���� | Catalyst for dehydrogenation of cyclohexanol and method for preparaiton thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114797882A (en) * | 2022-04-01 | 2022-07-29 | 衢州巨化锦纶有限责任公司 | Catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation and preparation method and application thereof |
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