CN116041158A - Method for preparing methyl isobutyl ketone by liquid phase hydrogenation of 4-methyl-3-pentene-2-one - Google Patents
Method for preparing methyl isobutyl ketone by liquid phase hydrogenation of 4-methyl-3-pentene-2-one Download PDFInfo
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- SHOJXDKTYKFBRD-UHFFFAOYSA-N 4-Methyl-3-penten-2-one, 9CI Chemical compound CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 44
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 31
- 239000007791 liquid phase Substances 0.000 title claims abstract description 12
- 239000004005 microsphere Substances 0.000 claims abstract description 61
- 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 59
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 150000001298 alcohols Chemical class 0.000 claims description 11
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 4
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 150000002576 ketones Chemical class 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 24
- 238000009826 distribution Methods 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 13
- 238000004846 x-ray emission Methods 0.000 description 12
- 230000009471 action Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 8
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- -1 aldehyde ketone Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of unsaturated ketone hydrogenation, and discloses a method for preparing methyl isobutyl ketone by liquid phase hydrogenation of 4-methyl-3-pentene-2-ketone. The method comprises the following steps: in the presence of a catalyst, 4-methyl-3-pentene-2-ketone is contacted with hydrogen to carry out hydrogenation reaction; wherein the catalyst is prepared by the following method: (1) Contacting the alumina microspheres with a polymer solution to couple the polymer to the alumina microspheres; (2) And (3) loading the metal active component on the alumina microsphere coupled with the polymer obtained in the step (1) under the condition that the polymer is not decomposed. The method for preparing the methyl isobutyl ketone by carrying out liquid phase hydrogenation on the 4-methyl-3-pentene-2-one can ensure the conversion rate of the 4-methyl-3-pentene-2-one and improve the selectivity of the methyl isobutyl ketone.
Description
Technical Field
The invention relates to the technical field of unsaturated ketone hydrogenation, in particular to a method for preparing methyl isobutyl ketone by liquid phase hydrogenation of 4-methyl-3-pentene-2-ketone.
Background
The reaction of selective hydrogenation of alpha, beta-unsaturated aldehyde ketone to saturated aldehyde ketone is a very important chemical reaction, and the product alpha, beta-saturated aldehyde ketone is an important raw material for synthesizing various flavors, fragrances, medicines, pesticides and organic intermediates. Methyl isobutyl ketone is colorless transparent liquid, is volatile and has camphor-like smell, and has wide application in paint, rubber, wax eliminating agent, surfactant, organic synthesis and other fields.
Industrial methyl isobutyl ketone is generally prepared by acetone hydrogenation, and the method mainly comprises an acetone one-step method, an acetone two-step method and an acetone three-step method. The acetone one-step method is mainly characterized in that: under the action of a high-performance catalyst, the raw material acetone and hydrogen simultaneously complete three-step reactions of acetone condensation, diacetone alcohol dehydration and 4-methyl-3-pentene-2-ketone selective hydrogenation in one device to obtain the target product methyl isobutyl ketone. The main flow of the acetone two-step method is as follows: firstly, in a fixed bed reactor or a catalytic rectifying tower, two molecules of acetone undergo condensation and dehydration reactions under the action of a solid catalyst to generate 4-methyl-3-pentene-2-one and water; and secondly, selectively hydrogenating the 4-methyl-3-pentene-2-ketone under the action of a hydrogenation catalyst to generate methyl isobutyl ketone. The main flow of the acetone three-step method is as follows: firstly, condensing two molecules of acetone under the action of an alkaline catalyst to generate one molecule of diacetone alcohol; secondly, dehydrating diacetone alcohol under the action of an acid catalyst to generate 4-methyl-3-pentene-2-ketone; and thirdly, selectively hydrogenating the 4-methyl-3-pentene-2-ketone under the action of a catalyst to generate the methyl isobutyl ketone. It is thus seen that the selective hydrogenation of 4-methyl-3-penten-2-one is the most important step in the preparation of methyl isobutyl ketone, directly related to the yield of methyl isobutyl ketone.
The selective hydrogenation catalyst used in the industrial production is Pd/resin, the selectivity of methyl isobutyl ketone reaches about 96 percent [ Liu Jiadong, zheng Jincheng, the summer is the same as that of any Cohn, zhao Hongbin. The technological research on the synthesis of methyl isobutyl ketone by acetone is advanced [ J ]. Zhejiang chemical, 2020,51 (06): 15-20 ]. In addition, CN100998953A, CN107400046a and US3953517 disclose that the selectivity for methyl isobutyl ketone is between 90-96% by ion exchange of a catalyst supporting noble metal palladium with a strongly acidic cation exchange resin as a carrier. However, these resin carriers require complicated modification methods, and the ion exchange method causes low metal utilization rate and unstable load, which causes metal loss during use.
CN102190568A discloses the use of an organic calcium salt modified alumina supported palladium as a catalyst for the preparation of methyl isobutyl ketone, but with a lower hydrogenation selectivity of 94.01%. CN107159263a discloses a hydrotalcite supported Pd hydrogenation catalyst with a selectivity of 93% in the preparation of methyl isobutyl ketone by selective hydrogenation.
As can be seen, the selectivity of the selective hydrogenation of 4-methyl-3-penten-2-one to methyl isobutyl ketone is still further improved.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a method for preparing methyl isobutyl ketone by liquid phase hydrogenation of 4-methyl-3-pentene-2-one.
In order to achieve the above object, the present invention provides a method for preparing methyl isobutyl ketone by liquid phase hydrogenation of 4-methyl-3-penten-2-one, said method comprising: in the presence of a catalyst, 4-methyl-3-pentene-2-ketone is contacted with hydrogen to carry out hydrogenation reaction;
wherein the catalyst is prepared by the following method:
(1) Contacting the alumina microspheres with a polymer solution to couple the polymer to the alumina microspheres;
(2) And (3) loading the metal active component on the alumina microsphere coupled with the polymer obtained in the step (1) under the condition that the polymer is not decomposed.
The method for preparing the methyl isobutyl ketone by carrying out liquid phase hydrogenation on the 4-methyl-3-pentene-2-one can ensure the conversion rate of the 4-methyl-3-pentene-2-one and improve the selectivity of the methyl isobutyl ketone. The reason is probably because the metal active component Pd is loaded on the alumina microsphere coupled with the polymer, and the existence of N element in the polymer has coordination effect with the metal active component Pd, so that the loss of the metal active component Pd can be avoided, and the stability of the metal active component Pd is improved; meanwhile, the outermost electron density of Pd metal is increased, and the hydrogenation selectivity is improved, so that the selectivity of methyl isobutyl ketone is improved.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, unless otherwise specified, the diameter of alumina microspheres refers to the average diameter of alumina microspheres.
The invention provides a method for preparing methyl isobutyl ketone by liquid phase hydrogenation of 4-methyl-3-pentene-2-one, which comprises the following steps: in the presence of a catalyst, 4-methyl-3-pentene-2-ketone is contacted with hydrogen to carry out hydrogenation reaction;
wherein the catalyst is prepared by the following method:
(1) Contacting the alumina microspheres with a polymer solution to couple the polymer to the alumina microspheres;
(2) And (3) loading the metal active component on the alumina microsphere coupled with the polymer obtained in the step (1) under the condition that the polymer is not decomposed.
According to the present invention, preferably, the alumina microspheres have a particle diameter of 200 to 800 μm and a coefficient of variation of 3 to 8%.
According to the present invention, the source of the alumina microspheres is not particularly limited as long as the particle diameter and the coefficient of variation of the alumina microspheres satisfy the defined ranges. The alumina microspheres can be prepared by the method described in CN110203953B or CN 110282642B. Preferably, the preparation method of the alumina microsphere comprises the following steps: the preparation method comprises the steps of taking aluminum sol as a disperse phase, taking an organic solvent as a continuous phase, enabling the disperse phase to form liquid drops under the shearing action of the continuous phase, solidifying to obtain gel microspheres, and drying and roasting to obtain the aluminum oxide microspheres.
In the method for preparing alumina microspheres according to the present invention, preferably, the alumina sol has a solid content of 5 to 8wt%.
In the method for preparing alumina microspheres according to the present invention, preferably, a monohydric saturated alcohol having an organic solvent of C1 to C10, preferably octanol, is used in the preparation of alumina microspheres.
In the method for preparing alumina microspheres according to the present invention, the drying temperature may be 100 to 120 ℃ and the drying time may be 3 to 15 hours.
In the method for preparing alumina microspheres according to the present invention, the firing temperature may be 550 to 1200 ℃ and the firing time may be 4 to 10 hours.
According to the present invention, preferably, the alumina microspheres are prepared in a microchannel reactor. The type of the microchannel reactor is not particularly limited, and the microchannel reactor may be a single-channel reactor and/or a multi-channel reactor.
According to a further preferred embodiment of the present invention, the multi-channel reactor is an eight-channel reactor. The eight-channel reactor comprises a continuous phase distribution layer, a first liquid drop generation layer, a second liquid drop generation layer and a disperse phase distribution layer, wherein the continuous phase distribution layer consists of petal-shaped resistance distribution channels, eight fluid outlets at the tail end of the petal-shaped resistance distribution channels, a continuous phase vertical inlet and four positioning holes, fluid is called one stage after each branch, a certain resistance is added before each stage of fluid branch, and the width of the channels is reduced along with the increase of the radius of the circumference of the starting end of each stage; the first liquid drop generation layer is provided with eight T-shaped channels, four positioning holes and eight through holes so as to meet the requirement of continuous phase flowing from the distribution layer to the generation layer, the second liquid drop generation layer is similar to the first liquid drop generation layer in structure, and eight liquid drop outlets are distributed at the tail end of a main channel of the T-shaped channel; the disperse phase distribution layer has a similar structure to the continuous phase distribution layer, and besides petal-shaped resistance distribution channels and eight disperse phase outlets at the tail end of the petal-shaped resistance distribution channels, the disperse phase distribution layer also has a disperse phase fluid inlet and 8 product outlets.
According to the present invention, the process of preparing alumina microspheres of the present invention is preferably illustrated with an eight-pass reactor. The preparation method comprises the steps of taking aluminum sol as a disperse phase, taking an organic solvent as a continuous phase, adjusting the flow rate of the continuous phase, enabling the continuous phase to be full of a continuous phase distribution layer and flow into a liquid drop generation layer, then flowing out from an outlet, enabling the flow rate of the continuous phase to be stabilized at 6-10mL/min, adjusting the flow rate of the disperse phase to be 1-4mL/min, enabling the disperse phase to be full of the disperse phase distribution layer and flow into the liquid drop generation layer, further generating liquid drops under the shearing action of the continuous phase, solidifying the liquid drops in an oil column to obtain gel microspheres, drying, and roasting to obtain the aluminum oxide microspheres with the diameters of 200-800 mu m and the variation coefficients of 3-8%.
The amount of the polymer may be selected within a wide range according to the present invention, but in order to enhance the selectivity of methyl isobutyl ketone, it is preferable that the amount of the polymer is 0.1 to 1g (for example, may be 0.1g, 0.2g, 0.3g, 0.4g, 0.5g, 0.6g, 0.7g, 0.8g, 0.9g, 1 g) with respect to 100g of the alumina microsphere.
According to the present invention, the conditions of the alumina microspheres and the polymer solution may be selected within a wide range, and preferably, the conditions of the contacting in step (1) include: the temperature is 100-120 ℃ and the time is 4-10h.
According to the present invention, preferably, step (1) further comprises subjecting the product of the contact of the alumina microspheres with the polymer solution to a first drying, more preferably, the first drying is performed at a temperature of 60 to 80 ℃ for a time of 4 to 12 hours.
According to the present invention, the kind of the polymer may be selected within a wide range, and preferably, the polymer in the polymer solution is an azacyclic ring-containing polymer, preferably at least one of polyvinylimidazole, polyvinylpyridine and polyvinylpyrrolidone, and more preferably polyvinylimidazole.
According to the present invention, the concentration of the polymer in the polymer solution is not particularly limited, but in order to further improve the selectivity of methyl isobutyl ketone, it is preferable that the concentration of the polymer in the polymer solution is 0.1 to 1wt%. (e.g., may be 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1 wt%).
According to the invention, the solvent in the polymer solution is preferably an alcohol, preferably a saturated alcohol of C1-C4, more preferably methanol and/or ethanol.
According to the present invention, it is preferable that the metal active component is used in an amount of 0.002 to 0.2g in terms of metal element with respect to 20g of the polymer-coupled alumina microsphere.
According to the present invention, preferably, the metal active component is Pd.
According to the present invention, preferably, the metal active component is supported on the polymer-coupled alumina microspheres in the step (2) in such a manner that: the alumina microsphere coupled with the polymer is impregnated with a solution containing a metal active component, and then the impregnated product is contacted with borohydride for reduction.
According to the present invention, it is preferable that the step (2) further comprises subjecting the impregnation product of the solution containing the metal active component impregnated with the polymer-coupled alumina microspheres to a second drying, more preferably, the second drying is carried out at a temperature of 60 to 80 ℃ for a time of 4 to 12 hours.
According to the present invention, preferably, the metal-containing active ingredient-containing solution is prepared by dissolving a water-soluble salt of a metal in water, and more preferably, the metal-containing active ingredient-containing solution has a mass percentage of the water-soluble salt of the metal of 0.01 to 1wt%.
According to the present invention, the conditions of the impregnation may be selected within a wide range, preferably the conditions of the impregnation include: the temperature is 30-40 ℃ and the time is 1-5h.
According to the present invention, preferably, the borohydride is used in an amount of 0.5 to 5g, relative to 20g of the alumina microsphere coupled with the polymer.
According to the present invention, preferably, the borohydride is sodium borohydride;
according to the present invention, preferably, the conditions of the reduction include: the temperature is 10-40 ℃ and the time is 4-6h.
According to the invention, preferably the borohydride is contacted with the impregnation product in the form of a solution, the solvent in the borohydride solution being an alcohol, preferably a saturated alcohol of C1-C4, more preferably methanol and/or ethanol. More preferably, the mass percent of borohydride in the borohydride solution is 0.5-5wt%.
According to the present invention, preferably, the hydrogenation reaction conditions include: the temperature is 50-200deg.C, preferably 80-100deg.C, the hydrogen pressure is 0.5-8MPa, preferably 3-5MPa, and the liquid hourly space velocity of 4-methyl-3-penten-2-one is 0.01-5h -1 Preferably 0.1-1h -1 The method comprises the steps of carrying out a first treatment on the surface of the The molar ratio of the hydrogen to the 4-methyl-3-penten-2-one is 5-10:1.
According to the present invention, preferably, the 4-methyl-3-penten-2-one is contacted with hydrogen in the form of a solution, the solvent in the 4-methyl-3-penten-2-one solution being a saturated alcohol of C1-C10.
According to the present invention, preferably, the weight ratio of 4-methyl-3-penten-2-one to C1-C10 saturated alcohol in the 4-methyl-3-penten-2-one solution is 1:5-10.
According to the present invention, preferably, the saturated alcohol of C1-C10 is ethanol.
The present invention will be described in detail by examples. In the following examples of the present invention,
the room temperature was about 25 ℃.
Conversion of 4-methyl-3-penten-2-one = (moles of 4-methyl-3-penten-2-one in starting material-moles of unreacted 4-methyl-3-penten-2-one)/(moles of 4-methyl-3-penten-2-one in starting material × 100%).
Methyl isobutyl ketone selectivity = moles of methyl isobutyl ketone in the product/(moles of 4-methyl-3-penten-2-one in the starting material-moles of unreacted 4-methyl-3-penten-2-one) ×100%.
The diameter of the alumina microsphere is tested by adopting a scanning electron microscope.
The method for testing the variation coefficient comprises the following steps: the number of the alumina microspheres in the unit area is measured by a scanning electron microscope, the diameter of each alumina microsphere is measured, and then the alumina microspheres are calculated according to a formula of a variation coefficient.
The coefficient of variation is calculated according to the following formula:
CV: coefficient of variation, n: counting alumina microsphere particles, X i : the particle diameter of the single alumina microsphere is equal to that of the single alumina microsphere,
all alumina microsphere particle diameters average. />
Preparation example
The preparation of alumina microsphere is carried out by adopting a microstructure reactor device, the dispersed phase is alumina sol with 7.5wt% of solid content, the continuous phase and liquid in an oil column are organic solvent octanol, the flow rate of the continuous phase is firstly regulated, the continuous phase is filled in a continuous phase distribution layer and flows into a liquid drop generation layer, then flows out from an outlet, and the flow rate of the continuous phase is finally stabilized at 6-10mL/min. And then adjusting the flow rate of the disperse phase to be 1-4mL/min, so that the disperse phase is filled in the disperse phase distribution layer and flows into the liquid drop generation layer, and further liquid drops are generated under the shearing action of the continuous phase. The droplets are solidified in an oil column to obtain gel microspheres, and the gel microspheres are dried at 120 ℃ for 12 hours and baked at 600 ℃ for 4 hours to obtain alumina microspheres with diameter of 345 mu m and variation coefficient of 7.2 percent.
Example 1
(1) 100g of the alumina microspheres obtained in the preparation example were immersed in an ethanol solution of polyvinyl imidazole having a concentration of 1wt% (wherein the amount of polyvinyl imidazole was 1 g), then transferred to a hydrothermal kettle, reacted at 100℃for 10 hours, cooled and filtered, and dried at 80℃for 4 hours to obtain a support (polymer-coupled alumina microspheres).
(2) 20g of the support was placed in a 0.01% by weight aqueous palladium nitrate solution (wherein the amount of palladium nitrate used is 0.002 g) based on the metal element, the support was taken out after immersing at 40℃for 1 hour, drained, dried at 80℃for 4 hours, and reduced at room temperature with a 0.5% by weight aqueous sodium borohydride solution (wherein the amount of borohydride used is 0.5 g) for 5 hours to obtain a catalyst.
The palladium loading in the catalyst was 0.0097wt% as characterized by X-ray fluorescence spectroscopy (XRF).
Example 2
Step (1) is the same as in example 1.
(2) 20g of the support was placed in a 0.1% by weight aqueous palladium nitrate solution (wherein the amount of palladium nitrate used is 0.02 g) in terms of metal element, the support was taken out after impregnating at 40℃for 1 hour, drained, dried at 80℃for 4 hours, and reduced at room temperature with a 1% by weight aqueous sodium borohydride solution (wherein the amount of borohydride used is 1 g) for 5 hours to obtain a catalyst.
The palladium loading in the catalyst was 0.098wt% as characterized by X-ray fluorescence spectroscopy (XRF).
Example 3
Step (1) is the same as in example 1.
(2) 20g of the support was placed in a 1wt% aqueous palladium nitrate solution (wherein the amount of palladium nitrate used was 0.2g in terms of metal element), the support was taken out after immersing at 40℃for 1 hour, drained, dried at 80℃for 4 hours, and reduced at room temperature with a 5wt% sodium borohydride ethanol solution (the amount of borohydride was 5 g) for 5 hours to obtain a catalyst.
The palladium loading in the catalyst was 0.99wt% as characterized by X-ray fluorescence spectroscopy (XRF).
Example 4
(1) 100g of the alumina microspheres obtained in the preparation example were immersed in an ethanol solution of 0.1wt% of polyvinylimidazole (the amount of polyvinylimidazole used was 0.1 g), then transferred to a hydrothermal kettle, reacted at 120℃for 4 hours, cooled and filtered, and dried at 60℃for 12 hours to obtain a support (polymer-coupled alumina microspheres).
(2) 20g of the carrier was put in a 1wt% aqueous palladium nitrate solution (wherein the amount of palladium nitrate is 0.2g in terms of metal element), the carrier was taken out after immersing at 30℃for 5 hours, drained, dried at 60℃for 12 hours, and reduced at room temperature with a 5wt% sodium borohydride ethanol solution (the amount of borohydride is 5 g) for 5 hours to obtain a catalyst.
The palladium loading in the catalyst was 0.99wt% as characterized by X-ray fluorescence spectroscopy (XRF).
Comparative example 1
The catalyst preparation was carried out as in example 3, except that the support was replaced with alumina dental spheres (purchased from enoki biotechnology ltd, particle size 3-4 mm).
The palladium loading in the catalyst was 0.99wt% as characterized by X-ray fluorescence spectroscopy (XRF).
Comparative example 2
The catalyst preparation was carried out as in example 3, except that the process of coupling the alumina microspheres with the polymer in step (1) was not included.
The palladium loading in the catalyst was 0.98wt% as characterized by X-ray fluorescence spectroscopy (XRF).
Test case
The catalysts of the above examples and comparative examples were tested for the performance of liquid phase hydrogenation of 4-methyl-3-penten-2-one to prepare methyl isobutyl ketone, 20mL of the catalyst was charged into a fixed bed reactor, and hydrogen, liquid 4-methyl-3-penten-2-one and a solvent (ethanol) were continuously fed, and the reaction temperature, the pressure of hydrogen, the liquid hourly space velocity of 4-methyl-3-penten-2-one and the weight ratio of 4-methyl-3-penten-2-one to the solvent were shown in Table 1. The test results are shown in Table 1.
TABLE 1
Note that: the ketene in Table 1 refers to 4-methyl-3-penten-2-one.
As can be seen from the results in Table 1, the method for preparing methyl isobutyl ketone by liquid phase hydrogenation of 4-methyl-3-penten-2-one can improve the selectivity of methyl isobutyl ketone while ensuring the conversion rate of 4-methyl-3-penten-2-one.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method for preparing methyl isobutyl ketone by liquid phase hydrogenation of 4-methyl-3-pentene-2-one, comprising the steps of: in the presence of a catalyst, 4-methyl-3-pentene-2-ketone is contacted with hydrogen to carry out hydrogenation reaction;
wherein the catalyst is prepared by the following method:
(1) Contacting the alumina microspheres with a polymer solution to couple the polymer to the alumina microspheres;
(2) And (3) loading the metal active component on the alumina microsphere coupled with the polymer obtained in the step (1) under the condition that the polymer is not decomposed.
2. The method of claim 1, wherein the polymer is used in an amount of 0.1-1g relative to 100g of alumina microspheres;
and/or, the contacting conditions in step (1) include: the temperature is 100-120 ℃ and the time is 4-10h.
3. The method according to claim 1, wherein the polymer in the polymer solution is an azacyclic ring-containing polymer, preferably at least one of polyvinylimidazole, polyvinylpyridine and polyvinylpyrrolidone, more preferably polyvinylimidazole;
and/or the concentration of the polymer in the polymer solution is 0.1 to 1wt%;
and/or the solvent in the polymer solution is an alcohol, preferably a saturated alcohol of C1-C4, more preferably methanol and/or ethanol.
4. The method according to claim 1, wherein the metal active component is used in an amount of 0.002 to 0.2g in terms of metal element relative to 20g of the polymer-coupled alumina microspheres;
and/or, the metal active component is Pd.
5. The method of claim 1, wherein the metal active component is supported on the polymer-coupled alumina microspheres in step (2) by: the alumina microsphere coupled with the polymer is impregnated with a solution containing a metal active component, and then the impregnated product is contacted with borohydride for reduction.
6. The method of claim 5, wherein the conditions of the impregnating include: the temperature is 30-40 ℃ and the time is 1-5h;
and/or, the borohydride is used in an amount of 0.5 to 5g relative to 20g of the alumina microsphere coupled with the polymer;
and/or, the borohydride is sodium borohydride;
and/or, the conditions of the reduction include: the temperature is 10-40 ℃ and the time is 4-6h.
7. A process according to claim 5, wherein the borohydride is contacted with the impregnation product in the form of a solution, the solvent in the borohydride solution being an alcohol, preferably a saturated alcohol of C1-C4, more preferably methanol and/or ethanol.
8. The process of claim 1, wherein the hydrogenation reaction conditions comprise: the temperature is 50-200deg.C, preferably 80-100deg.C, the hydrogen pressure is 0.5-8MPa, preferably 3-5MPa, and the liquid hourly space velocity of 4-methyl-3-penten-2-one is 0.01-5h -1 Preferably 0.1-1h -1 The method comprises the steps of carrying out a first treatment on the surface of the Mole of hydrogen and 4-methyl-3-penten-2-oneThe ratio is 5-10:1.
9. the process of claim 8, wherein the 4-methyl-3-penten-2-one is contacted with hydrogen in the form of a solution, the solvent in the 4-methyl-3-penten-2-one solution being a saturated alcohol of C1-C10.
10. The method of claim 9, wherein the weight ratio of 4-methyl-3-penten-2-one to C1-C10 saturated alcohol in the 4-methyl-3-penten-2-one solution is 1:5-10;
and/or, the saturated alcohol of C1-C10 is ethanol.
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