CN116474768A - Multiphase rhodium catalyst for catalyzing olefin hydroformylation and preparation method thereof - Google Patents
Multiphase rhodium catalyst for catalyzing olefin hydroformylation and preparation method thereof Download PDFInfo
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- CN116474768A CN116474768A CN202310341387.6A CN202310341387A CN116474768A CN 116474768 A CN116474768 A CN 116474768A CN 202310341387 A CN202310341387 A CN 202310341387A CN 116474768 A CN116474768 A CN 116474768A
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- rhodium
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- 239000010948 rhodium Substances 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 59
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 36
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 6
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 claims description 6
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 6
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 4
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229940069096 dodecene Drugs 0.000 claims description 3
- -1 ethylene, propylene, butene Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 3
- 229940095068 tetradecene Drugs 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- VQOXUMQBYILCKR-UHFFFAOYSA-N tridecaene Natural products CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims 2
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 150000001299 aldehydes Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 3
- 235000019838 diammonium phosphate Nutrition 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000005696 Diammonium phosphate Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011995 wilkinson's catalyst Substances 0.000 description 2
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 1
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a heterogeneous rhodium catalyst for catalyzing olefin hydroformylation, which is used for catalyzing olefin hydroformylation and has higher olefin conversion rate, aldehyde selectivity and stability. The invention also relates to a more feasible preparation method of the multiphase rhodium catalyst for catalyzing olefin hydroformylation, which has the advantages of simple process, low-cost and easily-obtained raw materials, easy separation and recovery, realization of continuous reaction operation and contribution to engineering application.
Description
Technical Field
The invention belongs to a catalyst preparation technology, and relates to a multiphase rhodium catalyst for efficiently catalyzing olefin hydroformylation and a preparation method thereof.
Background
Aldehydes are intermediates for most fine chemicals, which can be synthesized into chemicals such as alcohols, carboxylic acids, amines, esters, etc. by catalytic hydrogenation, oxidation, reductive amination, addition, etc., and are used in the fields of foods, pharmaceuticals, cosmetics, etc. The preparation of aldehydes by hydroformylation of olefins is a great route to industrial aldehydes. The olefin is mainly produced by petroleum catalytic pyrolysis in industry, and the petroleum belongs to primary energy, so that the olefin is utilized more efficiently, and the method has important application value. Hydroformylation is a typical example of atomic economy, is a reaction advocated in green chemistry, and is a significant measure of rational use and energy conservation.
At present, the hydroformylation has become one of the largest homogeneous catalysis industrial processes, and the homogeneous rhodium catalyst has the characteristics of high activity, high selectivity, mild reaction conditions and the like, such as a Wilkinson catalyst, but is not easy to separate after the reaction, so that Rh and ligand are lost more, the reaction cannot be continuously operated, rhodium is not easy to exploit because of low abundance in the crust, so that market price is high, even ppm-level loss is not negligible, and engineering application is not facilitated. In contrast, the heterogeneous rhodium catalyst has the characteristic of easy separation, can realize continuous reaction, but has low activity and selectivity.
Therefore, the development of the heterogeneous rhodium catalyst and the optimization of the catalytic performance of the heterogeneous rhodium catalyst have important research significance and practical value.
Disclosure of Invention
One of the purposes of the present invention is to overcome the shortcomings in the prior art, and to provide a heterogeneous rhodium catalyst for catalyzing the hydroformylation of olefins, which is used for catalyzing the hydroformylation of olefins and has high conversion rate of olefins, aldehyde selectivity and stability.
The invention aims to provide a more feasible preparation method of the multiphase rhodium catalyst for catalyzing olefin hydroformylation, which has the advantages of simple process, low-cost and easily-obtained raw materials, easy separation and recovery, realization of continuous reaction operation and contribution to engineering application.
To this end, the present invention provides in a first aspect a rhodium catalyst for the hydroformylation of olefins, which is a heterogeneous rhodium catalyst.
In some embodiments of the invention, the heterogeneous rhodium catalyst has an olefin conversion of 80% or more; the aldehyde selectivity of the heterogeneous rhodium catalyst is more than or equal to 85 percent.
In a second aspect, the present invention provides a process for the preparation of a heterogeneous rhodium catalyst according to the first aspect of the invention, comprising:
step A, dispersing a carrier in rhodium chloride aqueous solution, carrying out ultrasonic treatment for 1-5 h, and standing at room temperature overnight;
step B, volatilizing moisture of the product in the step A, and drying in an oven;
and C, roasting the solid obtained in the step B to obtain the multi-phase rhodium catalyst.
According to the invention, in step A, the concentration of the rhodium chloride aqueous solution is 0.001-10mol/L; preferably, the volume-mass ratio of the rhodium chloride aqueous solution to the carrier is 10-80 mL/g.
In some embodiments of the invention, the mass fraction of rhodium in the heterogeneous rhodium catalyst is between 0.01% and 20%.
In the invention, the carrier is one or more of alumina, zirconia, titania, ceria and hydroxyapatite.
In some embodiments of the invention, the firing temperature is 300 to 600 ℃; and/or the roasting time is 1-8 h.
According to some embodiments of the invention, the method further comprises sequentially subjecting the heterogeneous rhodium catalyst to a reduction treatment and an oxidation treatment to obtain an activated heterogeneous rhodium catalyst.
In some embodiments of the invention, the temperature of the reduction treatment is 200-600 ℃; and/or the time of the reduction treatment is 1-6h.
In other embodiments of the invention, the temperature of the oxidation treatment is 100-800 ℃; and/or the time of the oxidation treatment is 0.25-24h.
In a third aspect, the present invention provides the use of a heterogeneous rhodium catalyst as described in the first aspect of the invention or as prepared by a process as described in the second aspect of the invention in the efficient catalytic hydroformylation of olefins.
In the present invention, the olefin includes one or more of styrene, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene and hexadecene.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts a simpler regulation and control method to regulate and control the chemical environment where Rh species are located, so that the activity of the heterogeneous rhodium catalyst is greatly improved, and the heterogeneous rhodium catalyst can be compared with a homogeneous Wilkinson catalyst, and has wide application prospect.
(2) The method for preparing the catalyst is simple, the raw materials are cheap and easy to obtain, and the catalyst is easy to separate and recycle, can realize continuous reaction operation, and is beneficial to engineering application.
(3) The heterogeneous rhodium catalyst prepared by the invention has higher stability, and the catalyst can be regenerated through a simple roasting procedure.
Drawings
The invention is described in further detail below with reference to the accompanying drawings:
FIG. 1 shows an autoclave for the hydroformylation of olefins.
Detailed Description
In order that the invention may be readily understood, a detailed description of the invention will be provided below with reference to the accompanying drawings and examples. Before the present invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Where a range of values is provided, it is understood that each intervening value, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.
Unless defined otherwise, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described.
I, terminology
The term "water" as used herein refers to deionized water, distilled water or ultrapure water unless otherwise specified or defined.
The terms "about," "substantially," and "primarily" as used herein in connection with a range of an element, concentration, temperature, or other physical or chemical property or characteristic, cover a variation that may exist in the upper and/or lower limit of the range of the property or characteristic, including, for example, variations caused by rounding off, measurement methods, or other statistical variation. For example, as described herein, a numerical value in relation to amount, weight, etc., is defined as "about" being 1% plus or minus all numerical values of each particular value, e.g., the term "about 10%" is to be understood as "9% to 11%".
II, embodiment
In order to solve the technical problems, the invention adopts the following solutions: the preparation method of the multiphase rhodium catalyst for catalyzing olefin hydroformylation is more feasible, and comprises the following steps:
(1) Adding the carrier powder into rhodium chloride aqueous solution, carrying out ultrasonic treatment for 1-5 h, and standing at room temperature overnight. The volume mass ratio of the rhodium chloride aqueous solution to the carrier is 10-80 mL/g; the mass fraction of rhodium is 0.01% -20%.
(2) Roasting the solid obtained in the step (1) for 1-8 hours at the temperature of 300-600 ℃ to obtain the heterogeneous rhodium catalyst.
(3) Reducing the prepared heterogeneous rhodium catalyst for 1-6h at 200-600 ℃; oxidation treatment is carried out, oxidation is carried out for 0.25 to 24 hours at the temperature of 100 to 800 ℃, and the catalyst is used in the hydroformylation reaction.
The carrier in the invention comprises one or more of alumina, zirconia, titania, cerium oxide and hydroxyapatite.
The invention has no special limitation on the sources of the carriers, and can be purchased commercially or self-made; for example, in some examples, the hydroxyapatite carrier may be prepared by a co-precipitation method, in particular as follows:
first, calcium nitrate tetrahydrate is dissolved in deionized water to prepare a calcium nitrate solution, and diammonium phosphate is dissolved in deionized water to prepare a diammonium phosphate solution.
Secondly, the calcium nitrate solution and the diammonium hydrogen phosphate solution are simultaneously added into a beaker filled with deionized water under intense stirring by using a syringe pump, and concentrated ammonia water is dropwise added during the period to control the pH value of the solution to be 7-11. Then, the beaker was placed in an oil bath and stirred, cooled to room temperature, suction-filtered, washed with a large amount of water, and dried. And finally, placing the filter cake in a muffle furnace and roasting for 1-6h at 300-600 ℃.
In the invention, the rhodium catalyst for catalyzing the hydroformylation of olefin prepared by the preparation method is a heterogeneous rhodium catalyst.
Research results show that the olefin conversion rate of the heterogeneous rhodium catalyst is more than or equal to 80%; the aldehyde selectivity of the heterogeneous rhodium catalyst is more than or equal to 85 percent.
The application of the heterogeneous rhodium catalyst or the heterogeneous rhodium catalyst prepared by the preparation method in the invention for efficiently catalyzing olefin hydroformylation can be understood as a method for catalyzing olefin hydroformylation by using the heterogeneous rhodium catalyst or the heterogeneous rhodium catalyst prepared by the preparation method.
In the present invention, the olefin includes one or more of styrene, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene and hexadecene.
In some specific embodiments, the method of applying the heterogeneous rhodium catalyst prepared in the present invention to olefin hydroformylation reactions comprises:
using a high pressure reactor (YZPR-100, shanghai rock sign) as shown in FIG. 1, 1mg of heterogeneous rhodium catalyst was added followed by 20mmol of substrate olefin and solvent, and the reactor was sealed. And 3MPa of synthesis gas is filled at room temperature, and the air in the kettle is exhausted in a pressurizing and pressure releasing mode. The reaction kettle is placed in a heating sleeve, and the reaction temperature is set at 100 ℃ for 4 hours. After the reaction is finished, adding internal standard bromobenzene and n-decane, carrying out product analysis by using gas chromatography, and calculating the conversion rate of olefin and the corresponding aldehyde selectivity. The solvent is toluene or anisole.
It should be understood by those skilled in the art that the autoclave shown in fig. 1 is not merely used for olefin hydroformylation, but is actually a slurry bed reaction system, and can be used as a reaction system for testing and evaluating the activity of the heterogeneous rhodium catalyst for catalyzing olefin hydroformylation. Accordingly, the above-described reaction conditions or parameters of the method for carrying out the hydroformylation of olefins using the reaction vessel shown in fig. 1 are also applicable to the test for evaluating the activity of the heterogeneous rhodium catalyst for catalyzing the hydroformylation of olefins.
Examples
The present invention will be specifically described below by way of specific examples. The experimental methods described below, unless otherwise specified, are all laboratory routine methods. The experimental materials described below, unless otherwise specified, are commercially available.
The catalysts according to the invention were successfully prepared by the following examples and were used in the hydroformylation of styrene. The reaction conditions and results in examples 1-15 are shown in Table 1 below.
TABLE 1
Table 1, below
From the data in Table 1, the invention adopts a simple process to prepare and optimize the heterogeneous rhodium catalyst, shows higher activity and phenylpropionaldehyde selectivity in catalyzing the styrene hydroformylation reaction, and provides a new thought for the design strategy of the heterogeneous rhodium catalyst.
It should be noted that the above-mentioned embodiments are merely preferred embodiments of the present invention, for illustration, to facilitate understanding of 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 (10)
1. A rhodium catalyst for catalyzing the hydroformylation of olefins, which is a heterogeneous rhodium catalyst.
2. The heterogeneous rhodium catalyst according to claim 1, wherein the olefin conversion of the heterogeneous rhodium catalyst is greater than or equal to 80%; the aldehyde selectivity of the heterogeneous rhodium catalyst is more than or equal to 85 percent.
3. A process for preparing the heterogeneous rhodium catalyst according to claim 1 or 2, which comprises:
step A, dispersing a carrier in rhodium chloride aqueous solution, carrying out ultrasonic treatment, and standing overnight at room temperature to obtain rhodium chloride aqueous solution containing the carrier;
step B, volatilizing moisture from rhodium chloride aqueous solution containing a carrier, and drying in an oven to obtain a heterogeneous rhodium catalyst precursor;
and C, roasting the heterogeneous rhodium catalyst precursor to obtain the heterogeneous rhodium catalyst.
4. The process according to claim 3, wherein in the step A, the molar concentration of the rhodium trichloride aqueous solution is 0.001 to 10mol/L; preferably, the volume-mass ratio of the rhodium chloride aqueous solution to the carrier is 10-80 mL/g.
5. The preparation method according to claim 3, wherein the mass fraction of rhodium in the heterogeneous rhodium catalyst is 0.01% -20%; and/or the carrier comprises one or more of alumina, zirconia, titania, ceria and hydroxyapatite.
6. The method according to claim 3, wherein the baking temperature is 300 to 600 ℃; and/or the roasting time is 1-8 h.
7. The production method according to any one of claims 3 to 6, further comprising subjecting the heterogeneous rhodium catalyst to a reduction treatment and an oxidation treatment in this order to obtain an activated heterogeneous rhodium catalyst.
8. The method of claim 7, wherein,
the temperature of the reduction treatment is 200-600 ℃; and/or the time of the reduction treatment is 1-6h;
and/or the temperature of the oxidation treatment is 100-800 ℃; and/or the time of the oxidation treatment is 0.25-24h.
9. Use of a heterogeneous rhodium catalyst according to claim 1 or 2 or a heterogeneous rhodium catalyst prepared by a process according to any of claims 3 to 8 for the hydroformylation of olefins.
10. The use according to claim 9, wherein the olefins comprise one or more of styrene, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene and hexadecene.
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