WO2023130930A1 - 一种制备甲基异丁基酮的方法 - Google Patents
一种制备甲基异丁基酮的方法 Download PDFInfo
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- WO2023130930A1 WO2023130930A1 PCT/CN2022/139038 CN2022139038W WO2023130930A1 WO 2023130930 A1 WO2023130930 A1 WO 2023130930A1 CN 2022139038 W CN2022139038 W CN 2022139038W WO 2023130930 A1 WO2023130930 A1 WO 2023130930A1
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- copper
- zinc
- reaction
- oxide
- methyl isobutyl
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 title claims abstract description 55
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 114
- 239000003054 catalyst Substances 0.000 claims abstract description 93
- -1 methyl isobutyl Chemical group 0.000 claims abstract description 70
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 claims abstract description 54
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 claims abstract description 54
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 26
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N iso-butyl alcohol Natural products CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229940035429 isobutyl alcohol Drugs 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000009471 action Effects 0.000 claims abstract description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 48
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 32
- 239000005751 Copper oxide Substances 0.000 claims description 32
- 229910000431 copper oxide Inorganic materials 0.000 claims description 32
- 239000011787 zinc oxide Substances 0.000 claims description 24
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 19
- 238000011049 filling Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000009833 condensation Methods 0.000 description 12
- 230000005494 condensation Effects 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- 238000010926 purge Methods 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 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
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
-
- 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
Definitions
- the present invention relates to a kind of method of preparing methyl isobutyl ketone, more specifically, relate to a kind of method of preparing methyl isobutyl ketone in one step from mesityl oxide and methyl isobutyl alcohol.
- Methyl isobutyl ketone also known as 4-methyl-2-pentanone
- MIBK is a colorless and stable flammable liquid with a pleasant smell. Its explosion range in air is 1.4% to 7.5%. The source of fire is close, and airtight containers must be used for storage, stored at low temperature, and long-term contact with skin should be avoided. MIBK is slightly soluble in water, but completely miscible with some organic solvents, and is an excellent solvent.
- MIBK is slightly soluble in water, but completely miscible with some organic solvents, and is an excellent solvent.
- a kind of methyl isobutyl ketone production technique and equipment thereof as CN103274913A comprise the following steps: (a) raw material acetone and hydrogen are sent into fixed bed tube reactor to react, adopt B621 catalyzer; Reaction obtained after reaction The product is first condensed and separated to obtain hydrogen; the condensed solution enters the subsequent separation system; (b) the product solution is sent to the light component tower for separation, and the bottom still liquid enters the acetone tower for separation; (c) the acetone tower The pressure is controlled as a slight negative pressure, and the heavy components obtained at the bottom of the tower are sent to the dehydration tower for water removal; (d) the light components obtained at the top of the dehydration tower are sent to the waste water tower for treatment to obtain organic light components; the dehydration tower The product obtained at the bottom is sent to the product tower for purification, and the product methyl isobutyl ketone is obtained at the top of the product tower.
- CN105130778A adopts the strongly acidic cation exchange resin catalyst treated with palladium acetate, optimizes the separation process, and purifies the by-product diisobutyl ketone (DIBK), which realizes the increase of organic matter yield and the decrease of energy consumption.
- DIBK diisobutyl ketone
- the present invention provides a brand-new method from raw material to catalytic system for preparing methyl isobutyl ketone, so as to realize cost advantages.
- the invention adopts mesityl oxide (MO) and methyl isobutyl alcohol (MIBC) to carry out in-situ transfer of hydrogen under the action of a copper-based catalyst to prepare methyl isobutyl ketone in one step.
- MO mesityl oxide
- MIBC methyl isobutyl alcohol
- the whole reaction process does not need an external hydrogen system, the reaction is carried out under normal pressure, the process flow is short, and it has the advantages of high atom utilization rate and high safety, and is suitable for popularizing industrial applications.
- the present invention provides a method for preparing methyl isobutyl ketone, said method comprising reacting mesityl oxide and methyl isobutyl alcohol under the action of a copper-based catalyst to generate methyl isobutyl ketone.
- the copper-based catalyst includes copper oxide, and the mass of copper oxide accounts for more than 50% of the total mass of the copper-based catalyst.
- the copper-based catalyst is a copper-zinc-aluminum catalyst.
- the copper zinc aluminum catalyst comprises copper oxide, zinc oxide and aluminum oxide.
- the mass of copper oxide accounts for more than 50% of the total mass of the copper-zinc-aluminum catalyst.
- the mass of copper oxide is 50%-70% of the total mass of the copper-zinc-aluminum catalyst
- the mass of zinc oxide is the total mass of the copper-zinc-aluminum catalyst 10%-30% of the total mass of the aluminum oxide is 5%-15% of the total mass of the copper-zinc-aluminum catalyst.
- the mass of copper oxide is 54%-64% of the total mass of the copper-zinc-aluminum catalyst
- the mass of zinc oxide is the total mass of the copper-zinc-aluminum catalyst
- the mass of the alumina is 7.8%-8% of the total mass of the copper-zinc-aluminum catalyst.
- the molar ratio of mesityl oxide to methyl isobutyl alcohol is (0.1-2):1, preferably (0.8-1.2):1.
- methyl isobutyl ketone is added to the reaction system.
- the temperature of the reaction is 140°C-250°C, preferably 180 ⁇ 20°C.
- the pressure of the reaction is atmospheric pressure.
- the volume space velocity of the reaction is 0.05-0.2h -1 , preferably 0.1 ⁇ 0.02h -1 .
- no hydrogen gas is introduced during the reaction.
- the reaction is performed in a fixed bed reactor, such as a single tube reactor.
- the reaction is performed under the protection of an inert gas.
- the method includes: heating a reactor filled with a copper-based catalyst to the reaction temperature, feeding homogeneously mixed mesityl oxide and methyl isobutyl alcohol from the bottom of the reactor, The upper part of the reactor discharges the material for reaction.
- the uniformly mixed mesityl oxide and methyl isobutyl alcohol are preheated to the reaction temperature before being sent into the reactor for reaction.
- the reactor is a single-tube reactor with a diameter of 20 ⁇ 2 mm and a height of 700 ⁇ 100 mm, and the bed filling height of the copper-based catalyst is 500 ⁇ 50 mm.
- Fig. 1 is the synoptic diagram that mesityl oxide and methyl isobutyl alcohol prepare methyl isobutyl ketone in one step.
- percentages refer to mass percentages
- ratios refer to mass ratios
- the invention provides a brand-new method from raw material to catalytic system for preparing methyl isobutyl ketone.
- the present invention uses mesityl oxide and methyl isobutyl alcohol to carry out the in-situ transfer of hydrogen under the action of a copper-based catalyst to prepare methyl isobutyl ketone in one step.
- the whole reaction process does not need an external hydrogen system, the reaction is carried out under normal pressure, the process flow is short, and it has the advantages of high atom utilization rate and high safety, and is suitable for popularizing industrial applications.
- the method for preparing methyl isobutyl ketone of the present invention comprises making mesityl oxide and methyl isobutyl alcohol undergo hydrogen transfer reaction in situ under the action of a copper-based catalyst.
- the copper-based catalyst includes copper oxide, and the mass of copper oxide accounts for more than 50% of the total mass of the copper-based catalyst, such as >50%, 54%, or 64%.
- the copper-based catalyst is preferably a copper-zinc-aluminum catalyst.
- the main components of the copper-zinc-aluminum catalyst are copper oxide, aluminum oxide and zinc oxide, and the remaining components can be activated carbon.
- the copper zinc aluminum catalyst consists of copper oxide, aluminum oxide, zinc oxide, and activated carbon.
- the copper oxide content can be 50%-70% of the total mass of the catalyst, such as 52%, 54%, 60%, 64%, 65%, preferably 54%-64%
- the zinc oxide content can be 10%-30% of the total mass of the catalyst, such as 12%, 14%, 20%, 24%, 25%, preferably 14%-24%
- the alumina content can be 5%-15% of the total mass of the catalyst, such as 7%, 8%, 9%, 10%, preferably 7.8%-8%. Keeping the composition and ratio of the catalyst within the above range is conducive to the in-situ transfer of hydrogen, and the process flow is short.
- Copper-based catalysts suitable for use in the present invention are commercially available.
- the present invention uses a copper zinc aluminum catalyst with 54% copper oxide, 24% zinc oxide, and 8% aluminum oxide, or 64% copper oxide, 14% zinc oxide, A copper-zinc-aluminum catalyst with an alumina content of 7.8%.
- the catalyst used in the present invention may be cylindrical.
- the molar ratio of mesityl oxide to methyl isobutyl alcohol can be 0.1:1 to 2:1, such as 0.5:1 to 1.5:1, preferably 0.8:1 to 1.2:1, such as 1 : About 1. Adopting the preferred molar ratio of feed is beneficial to improve the conversion rate of mesityl oxide and methyl isobutyl alcohol and the selectivity of methyl isobutyl ketone.
- methyl isobutyl ketone may optionally exist in the initial reaction system.
- mesityl oxide, methyl isobutyl alcohol, and methyl isobutyl ketone may be mixed for reaction, or only mesityl oxide and methyl isobutyl alcohol may be mixed for reaction.
- the initial reaction system includes methyl isobutyl ketone
- the initial molar number of methyl isobutyl ketone added can be 0.5 to 2 times the total molar number of mesityl oxide and methyl isobutyl alcohol, such as 1 times.
- the reaction pressure can be normal pressure, which has high safety.
- the reaction temperature may be 140°C-250°C, such as 140°C, 160°C, 180°C, 200°C, 250°C, preferably around 180°C.
- the reaction volume space velocity can be 0.05-0.2h -1 , such as 0.06h -1 , 0.08h -1 , 0.1h -1 , 0.12h -1 , 0.15h -1 , preferably about 0.1h -1 .
- reaction process of the present invention there is no need to feed hydrogen.
- the reaction is carried out under the protection of an inert gas, such as nitrogen.
- an inert gas such as nitrogen.
- the air in the reactor can be replaced with an inert gas before the reaction.
- the reaction of the present invention is preferably carried out in a fixed-bed reactor, that is, preferably, the catalyst is fixedly filled in the reactor, and the flowing raw material occurs in the process of passing through the catalyst.
- the fixed bed reactor may be a tubular reactor, such as a single tube reactor.
- the reactor filled with the copper-based catalyst can be heated to the reaction temperature, and the uniformly mixed mesityl oxide and methyl isobutyl alcohol are fed from the bottom of the reactor and discharged from the upper part of the reactor for reaction.
- the evenly mixed mesityl oxide and methyl isobutyl alcohol can be preheated to the reaction temperature before being sent into the reactor for reaction.
- a single-tube reactor with a diameter of 20 ⁇ 2mm and a height of 700 ⁇ 100mm can be used, and the bed filling height of the copper-based catalyst in it can be 500 ⁇ 50mm.
- the method for preparing methyl isobutyl ketone of the present invention comprises: after heating the reactor filled with the copper-based catalyst to the reaction temperature, the reactor is purged with an inert gas, and the mixture is uniformly
- the mesityl oxide, methyl isobutyl alcohol and optional methyl isobutyl ketone are sent to the preheating system to be preheated to the reaction temperature, and then sent to the reactor for reaction.
- the rate at which the raw material enters the preheating system may be 0.125-0.5 mL/min, such as 0.25 mL/min.
- the present invention does not require external hydrogen and high-pressure circulation system, and the whole reaction is carried out under normal pressure, which has high safety;
- the present invention adopts a relatively cheap copper-based catalyst to replace the expensive palladium noble metal catalyst, and the production cost is greatly reduced;
- the present invention is a brand-new method for synthesizing MIBK, which is different from traditional techniques, and the product components are relatively single, and subsequent product separation and purification are easier to realize.
- the present invention will be further described in the form of specific examples below. It should be understood that these examples are illustrative only and not intended to limit the scope of the present invention.
- the methods and reagents used in the examples, unless otherwise stated, are conventional methods and reagents in the art.
- the copper-zinc-aluminum columnar catalyst with a ratio of copper oxide, zinc oxide and aluminum oxide of 54:24:8 was purchased from the market, and the model was Chuanhua CB-5; copper oxide, zinc oxide, aluminum oxide
- the copper-zinc-aluminum columnar catalyst with a ratio of 64:14:7.8 was purchased from a commercial channel, and the model was Chuanhua AF104.
- a certain amount of copper-zinc-aluminum cylindrical catalyst (the content of copper oxide is 54%, the content of zinc oxide is 24%, and the content of aluminum oxide is 8%) is filled into a single-tube reactor with a diameter of 20 mm and a height of 700 mm, so that the catalyst bed The filling height is 500mm. Turn on the heating system to raise the temperature of the reaction device. After the temperature reaches 140°C, blow dry nitrogen gas from the top to purge the reactor for 10 minutes.
- a certain amount of copper-zinc-aluminum cylindrical catalyst (the content of copper oxide is 54%, the content of zinc oxide is 24%, and the content of aluminum oxide is 8%) is filled into a single-tube reactor with a diameter of 20 mm and a height of 700 mm, so that the catalyst bed The filling height is 500mm. Turn on the heating system to raise the temperature of the reaction device. After the temperature reaches 160°C, blow dry nitrogen gas from the top to purge the reactor for 10 minutes.
- a certain amount of copper-zinc-aluminum cylindrical catalyst (the content of copper oxide is 54%, the content of zinc oxide is 24%, and the content of aluminum oxide is 8%) is filled into a single-tube reactor with a diameter of 20 mm and a height of 700 mm, so that the catalyst bed The filling height is 500mm. Turn on the heating system to raise the temperature of the reaction device. After the temperature reaches 180°C, blow dry nitrogen gas from the top to purge the reactor for 10 minutes.
- a certain amount of copper-zinc-aluminum cylindrical catalyst (the content of copper oxide is 54%, the content of zinc oxide is 24%, and the content of aluminum oxide is 8%) is filled into a single-tube reactor with a diameter of 20 mm and a height of 700 mm, so that the catalyst bed The filling height is 500mm. Turn on the heating system to raise the temperature of the reaction device. After the temperature reaches 200°C, blow dry nitrogen gas from the top to purge the reactor for 10 minutes.
- a certain amount of copper-zinc-aluminum cylindrical catalyst (the content of copper oxide is 54%, the content of zinc oxide is 24%, and the content of aluminum oxide is 8%) is filled into a single-tube reactor with a diameter of 20 mm and a height of 700 mm, so that the catalyst bed The filling height is 500mm. Turn on the heating system to raise the temperature of the reaction device. After the temperature reaches 250°C, blow dry nitrogen gas from the top to purge the reactor for 10 minutes.
- a certain amount of copper-zinc-aluminum cylindrical catalyst (the content of copper oxide is 54%, the content of zinc oxide is 24%, and the content of aluminum oxide is 8%) is filled into a single-tube reactor with a diameter of 20 mm and a height of 700 mm, so that the catalyst bed The filling height is 500mm. Turn on the heating system to raise the temperature of the reaction device. After the temperature reaches 180°C, blow dry nitrogen gas from the top to purge the reactor for 10 minutes.
- a certain amount of copper-zinc-aluminum cylindrical catalyst (the content of copper oxide is 54%, the content of zinc oxide is 24%, and the content of aluminum oxide is 8%) is filled into a single-tube reactor with a diameter of 20 mm and a height of 700 mm, so that the catalyst bed The filling height is 500mm. Turn on the heating system to raise the temperature of the reaction device. After the temperature reaches 180°C, blow dry nitrogen gas from the top to purge the reactor for 10 minutes.
- a certain amount of copper-zinc-aluminum cylindrical catalyst (the content of copper oxide is 54%, the content of zinc oxide is 24%, and the content of aluminum oxide is 8%) is filled into a single-tube reactor with a diameter of 20 mm and a height of 700 mm, so that the catalyst bed The filling height is 500mm. Turn on the heating system to raise the temperature of the reaction device. After the temperature reaches 180°C, blow dry nitrogen gas from the top to purge the reactor for 10 minutes.
- a certain amount of copper-zinc-aluminum cylindrical catalyst (the content of copper oxide is 54%, the content of zinc oxide is 24%, and the content of aluminum oxide is 8%) is filled into a single-tube reactor with a diameter of 20 mm and a height of 700 mm, so that the catalyst bed The filling height is 500mm. Turn on the heating system to raise the temperature of the reaction device. After the temperature reaches 180°C, blow dry nitrogen gas from the top to purge the reactor for 10 minutes.
- a certain amount of copper-zinc-aluminum cylindrical catalyst (the content of copper oxide is 64%, the content of zinc oxide is 14%, and the content of aluminum oxide is 7.8%) is filled into a single-tube reactor with a diameter of 20 mm and a height of 700 mm, so that the catalyst bed The filling height is 500mm. Turn on the heating system to raise the temperature of the reaction device. After the temperature reaches 180°C, blow dry nitrogen gas from the top to purge the reactor for 10 minutes.
- a certain amount of copper-zinc-aluminum cylindrical catalyst (the content of copper oxide is 64%, the content of zinc oxide is 14%, and the content of aluminum oxide is 7.8%) is filled into a single-tube reactor with a diameter of 20 mm and a height of 700 mm, so that the catalyst bed The filling height is 500mm. Turn on the heating system to raise the temperature of the reaction device. After the temperature reaches 180°C, blow dry nitrogen gas from the top to purge the reactor for 10 minutes. Mix MO and MIBC at a molar ratio of 1:1, pump the mixture into the preheating system with a constant flow pump at a speed of 0.25mL/min, and enter from the bottom of the reactor after preheating to 180°C.
- the reaction volume space velocity is 0.1h -1 , discharge from the upper part, take a sample after condensation, and analyze it by GC.
- the MIBC conversion rate was 98.72%
- the MO conversion rate was 97.93%
- the MIBK selectivity was 98.15%.
- the present invention uses mesityl oxide and methyl isobutyl alcohol to carry out in-situ transfer of hydrogen under the action of a copper-based catalyst to prepare methyl isobutyl ketone in one step.
- the whole reaction process does not need an external hydrogen system, the reaction is carried out under normal pressure, the process flow is short, and a good MIBC conversion rate, MO conversion rate and selectivity have been achieved. It has the advantages of high atom utilization and high safety, and is suitable for the promotion of industrial application.
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Abstract
Description
Claims (10)
- 一种制备甲基异丁基酮的方法,其特征在于,所述方法包括使异丙叉丙酮和甲基异丁基醇在铜系催化剂的作用下进行反应生成甲基异丁基酮。
- 如权利要求1所述的方法,其特征在于,所述铜系催化剂包含氧化铜,氧化铜的质量占所述铜系催化剂总质量的50%以上。
- 如权利要求1所述的方法,其特征在于,所述铜系催化剂为铜锌铝催化剂;优选地,所述铜锌铝催化剂包含氧化铜、氧化锌和氧化铝。
- 如权利要求3所述的方法,其特征在于,所述铜锌铝催化剂中,氧化铜的质量占所述铜锌铝催化剂总质量的50%以上;优选地,所述铜锌铝催化剂中,氧化铜的质量为所述铜锌铝催化剂总质量的50%-70%,氧化锌的质量为所述铜锌铝催化剂总质量的10%-30%,所述氧化铝的质量为所述铜锌铝催化剂总质量的5%-15%;更优选地,所述铜锌铝催化剂中,氧化铜的质量为所述铜锌铝催化剂总质量的54%-64%,氧化锌的质量为所述铜锌铝催化剂总质量的14%-24%,所述氧化铝的质量为所述铜锌铝催化剂总质量的7.8%-8%。
- 如权利要求1所述的方法,其特征在于,所述反应中,异丙叉丙酮和甲基异丁基醇的投料摩尔比为(0.1-2)∶1,优选(0.8-1.2)∶1。
- 如权利要求1所述的方法,其特征在于,所述反应开始时,反应体系中添加有甲基异丁基酮。
- 如权利要求1所述的方法,其特征在于,所述反应具有以下一项或多项特征:所述反应的温度为140℃-250℃,优选180±20℃;所述反应的压力为常压;所述反应的体积空速为0.05-0.2h -1,优选0.1±0.02h -1;所述反应过程中不通入氢气;所述反应在固定床反应器、例如单管反应器中进行;所述反应在惰性气体保护下进行。
- 如权利要求1所述的方法,其特征在于,所述方法包括:将填充有铜系催化剂的反应器加热至反应温度,将混合均匀的异丙叉丙酮和甲基异丁基醇由反应器底部进料、反应器上部出料进行反应。
- 如权利要求7所述的方法,其特征在于,先将混合均匀的异丙叉丙酮和甲基异丁基醇预热至反应温度后,再送入反应器进行反应。
- 如权利要求7所述的方法,其特征在于,所述反应器为直径为20±2mm、高700±100mm的单管反应器,所述铜系催化剂的床层填充高度为500±50mm。
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