CN112979416A - Preparation method of high-selectivity methyl isobutyl alcohol - Google Patents
Preparation method of high-selectivity methyl isobutyl alcohol Download PDFInfo
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- CN112979416A CN112979416A CN202110255700.5A CN202110255700A CN112979416A CN 112979416 A CN112979416 A CN 112979416A CN 202110255700 A CN202110255700 A CN 202110255700A CN 112979416 A CN112979416 A CN 112979416A
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- Prior art keywords
- methyl isobutyl
- catalyst
- isobutyl ketone
- hydrogen
- isobutyl alcohol
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- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N iso-butyl alcohol Natural products CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229940035429 isobutyl alcohol Drugs 0.000 title claims abstract description 42
- -1 methyl isobutyl Chemical group 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 99
- 239000003054 catalyst Substances 0.000 claims abstract description 86
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims abstract description 83
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 54
- 239000001257 hydrogen Substances 0.000 claims abstract description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 230000009471 action Effects 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 229910052804 chromium Inorganic materials 0.000 claims description 22
- 239000011651 chromium Substances 0.000 claims description 22
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 16
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 238000002309 gasification Methods 0.000 claims 1
- 239000007790 solid phase Substances 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 9
- 239000006200 vaporizer Substances 0.000 description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 8
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000002576 ketones Chemical class 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction 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
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
Abstract
The invention relates to a preparation method of high-selectivity methyl isobutyl alcohol with mild process conditions and high product selectivity and raw material conversion rate, which comprises the steps of carrying out reaction in a gas-solid phase fixed reactor, gasifying the raw material methyl isobutyl ketone, and carrying out hydrogenation reaction with hydrogen under the action of a catalyst to prepare the methyl isobutyl alcohol.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, relates to synthesis of methyl isobutyl alcohol, and particularly relates to a preparation method of high-selectivity methyl isobutyl alcohol, which has mild process conditions and high product selectivity and raw material conversion rate.
Background
Methyl isobutyl carbinol (MIBC), an excellent medium boiling point solvent, and a wide range of applications, and can be used as solvents for dyes, petroleum, rubber, resins, paraffin, nitrocellulose, ethyl cellulose, and the like; used as brake fluid and raw material for organic synthesis; as mineral flotation agents, such as for example for extracting silicon and copper sulphate; the organic solvent is used as an inert solvent of the nitrocellulose paint, can increase the luster and the smoothness of the paint, and improves the reddening property; used as a solvent in the production of a lubricating oil additive.
With the continuous increase of the domestic MIBK device capacity, the profitability of the MIBK device is greatly weakened, and a plurality of devices are in a production stop or low-load operation state. The industry has begun to search for downstream products of MIBK to improve the profitability and risk resistance of the plant, one of the important products is methyl isobutyl alcohol (MIBC), which is in increasing demand and expensive, and has a good market value.
Patent No. CN 1325837A discloses a method for preparing corresponding alcohol by ketone hydrogenation, in a fixed bed reactor, raw material ketone contacts with a hydrogenation catalyst, and the raw material ketone and hydrogen undergo hydrogenation reaction to generate alcohol with the same carbon atom number as the raw material ketone. The raw material ketone is selected from acetone, methyl isopropyl ketone, methyl isobutyl ketone and diisobutyl ketone, and the hydrogenation catalyst comprises 10-80% of CuO and 2-85% of Al2O30.1 to 5.0% of an alkali metal oxide and 0 to 60% of an oxide of Zn, Mg, Cr or a mixture thereof. The reaction temperature is 100-250 ℃, the reaction pressure is normal pressure-6.0 MPa, the molecular ratio of hydrogen and ketone in the feeding is 1-6, and the liquid hourly space velocity of the feeding ketone is 0.2-5.0 h-1. In an embodiment of the present invention,100mL of catalyst is added into a fixed bed reactor with the diameter of 20mm, and the liquid hourly volume space velocity of the methyl isobutyl ketone is 1.0h-1The hydrogen-ketone ratio is 5:1, the reaction temperature is 180 ℃, the pressure is 2.0MPa, the MIBK conversion rate is 89.4 percent, and the MIBC selectivity is 99.9 percent.
Patent No. CN 110871076 a discloses a catalyst for preparing methyl isobutyl alcohol, a preparation method and an application thereof, and provides a catalyst for preparing methyl isobutyl alcohol, which comprises: the total weight of the catalyst is 100 parts, and the weight of nickel is 10-25 parts; 75-90 parts of gallium modified alumina carrier; the content of gallium in the alumina carrier is 0.5-5 wt%; the gallium modified alumina carrier is prepared by molding pseudo-boehmite powder into the alumina carrier, roasting, and spraying or dipping soluble gallium salt on the surface of the alumina carrier. The catalyst is loaded in a reactor, a methyl isobutyl ketone raw material and hydrogen are respectively preheated and then mixed and are fed into the upper end of the reactor, the mass ratio of the methyl isobutyl ketone to the hydrogen is 2: 1-8: 1 during feeding, and the liquid hourly space velocity of the methyl isobutyl ketone is 0.1-1.0 h-1Carrying out hydrogenation reaction under the reaction pressure of 1.0-3.0 MPa and the reaction temperature of 110-160 ℃, and controlling the preheating temperature of the methyl isobutyl ketone and the hydrogen to ensure that the liquid phase amount of the methyl isobutyl ketone accounts for 10-40% of the total amount of the methyl isobutyl ketone after the methyl isobutyl ketone and the hydrogen are mixed, the maximum MIBK conversion rate is 99.88%, and the MIBC selectivity is 100%.
The MIBK conversion rate of the process disclosed in patent No. CN 1325837A is only 89.4%, which is unfavorable for subsequent separation and high in production cost; the MIBK conversion rate and the MIBC selectivity of the process disclosed in the patent No. CN 1325837A reach higher levels, but the preparation process of the catalyst is complex and is not beneficial to industrialization, and the production process conditions are reduced compared with those of the process disclosed in the patent No. CN 1325837A, but from the implementation data, the high conversion rate is realized on the premise that the reaction temperature and pressure are increased and the space velocity is reduced.
Disclosure of Invention
The invention aims to solve the defects of high production cost, complex catalyst preparation and high temperature and high pressure of production process conditions of the existing preparation method of methyl isobutyl alcohol, and provides the preparation method of the high-selectivity methyl isobutyl alcohol, which has simpler process, milder production process conditions and keeps the high conversion rate of MIBK and the high selectivity of MIBC under the working condition of larger load.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing methyl isobutyl alcohol with high selectivity, take methyl isobutyl ketone as raw materials, take hydrogenation reaction with hydrogen under the influence of catalyst after gasifying to get methyl isobutyl alcohol; the catalyst is prepared by taking an aluminum oxide and a nickel oxide as carriers and loading cocatalyst copper and chromium, wherein in the catalyst composition, the nickel accounts for 10-30% of the final catalyst, the copper accounts for 1-10%, the chromium accounts for 1-10%, and the balance is the aluminum oxide.
The invention is a reaction carried out in a gas-solid phase fixed reactor, and the methyl isobutyl alcohol is prepared by gasifying the raw material methyl isobutyl ketone and then carrying out hydrogenation reaction with hydrogen under the action of a catalyst, compared with the prior art, the method has the characteristics of mild process conditions, high product selectivity and high raw material conversion rate, the conversion rate of the methyl isobutyl ketone is more than 99.50 percent, and the product selectivity of the methyl isobutyl alcohol is more than 99.7 percent.
In a preferred embodiment of the present invention, the molar ratio of the methyl isobutyl ketone to the hydrogen is 1: 2-10.
In a preferred embodiment of the present invention, the molar ratio of the methyl isobutyl ketone to the hydrogen is 1: 5-8.
As a preferred embodiment of the present invention, the reaction conditions are: the reaction temperature is 90-140 ℃, and the liquid space velocity is 0.1-1h-1The pressure is normal pressure-1.0 MPa.
As a preferred embodiment of the present invention, the reaction conditions are: the reaction temperature is 100 ℃ and 120 ℃, and the liquid space velocity is 0.5-0.7h-1The pressure is 0.5-0.7 MPa.
In a preferable scheme of the invention, in the catalyst composition, nickel accounts for 20-25% of the weight of the final catalyst, copper accounts for 2-5%, chromium accounts for 1-3%, and the balance is aluminum oxide.
As a preferable scheme of the invention, the preparation method of the catalyst comprises the following steps:
1) directly mixing one or more of aluminum oxide, nickel oxide or nickel protoxide with water, and rolling and molding;
2) roasting the raw materials in the step 1) to obtain a catalyst carrier;
3) loading copper and chromium serving as promoters on the surface of the catalyst carrier obtained in the step 2) by an impregnation method;
4) reducing the catalyst carrier loaded with the cocatalyst and obtained in the step 3) in a reducing gas atmosphere to obtain a catalyst finished product.
As a preferable scheme of the invention, in the step 2), the roasting temperature is 400-700 ℃, and the roasting time is 4-6 h.
In a preferred embodiment of the present invention, in the step 4), the reducing gas is hydrogen, and the temperature of the reduction is 400-.
In a preferable embodiment of the present invention, in the step 3), one of nitrate, acetate or carbonate is used as the promoter copper and chromium.
The catalyst and the preparation method thereof improve the interaction between metal components and alumina, so that metal nickel, cocatalyst copper and chromium are more easily and uniformly dispersed on the surface of a carrier and are more easily reduced, the particle size of nickel can be reduced after the copper and the chromium are added, nickel crystal grains are not easy to aggregate and grow in the using process, the active site on the inner surface of the catalyst is better, the catalyst has stronger hydrogenation function, the activity of the catalyst is improved, and the catalyst has stable performance in a stable period in a wider temperature range, so that the hydrogenation of methyl isobutyl ketone is further promoted;
in the catalyst composition, 1-10% of copper and 1-10% of chromium are contained, if the content of copper is more than 10% and the content of chromium is more than 10%, the loading capacity is too high, so that excessive cocatalyst enters the inside of catalyst pore channels to block the pore channels, the specific surface area of the catalyst is reduced, and the activity of the catalyst is reduced; if the content of copper is less than 1 percent and the content of chromium is less than 1 percent, the catalyst activity cannot be affected due to too small load, so that the copper accounts for 1 to 10 percent and the chromium accounts for 1 to 10 percent.
The hydrogenation reaction is carried out in a gas-solid phase fixed bed reactor, and the methyl isobutyl ketone needs to be preheated and gasified before entering the reactor, so that the raw material can be in full contact with active sites on the inner surface of the catalyst, and the reaction efficiency is improved.
Compared with the prior art, the invention has the following beneficial effects:
1) the catalyst of the invention has simpler preparation process and milder production process conditions;
2) the method has mild reaction conditions, and has the characteristics of keeping high MIBK conversion rate and high MIBC selectivity under the working condition of larger load;
3) the preparation method is simpler, has low energy consumption and cost, and can be applied to industrial production.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples 1 to 4 are methods for preparing the catalyst of the present invention
Example 1
This example provides a method for preparing a catalyst for use in the present invention, comprising the steps of:
(1) 200g of alumina, 39.89g of nickel oxide and 228g of deionized water were mixed in a ball mill and then ball-milled to form a ball.
(2) And roasting for 4 hours at the temperature of 600 ℃ after forming to obtain the carrier containing the nickel oxide.
(3) According to the water absorption of the nickel oxide carrier, 10.6g of copper nitrate and 32.86g of chromium nitrate were loaded on the surface of the catalyst by an equivalent impregnation method.
(4) Finally, the catalyst is reduced for 20 hours at the temperature of 450 ℃ under the condition of hydrogen to obtain a finished product of the catalyst.
(5) The prepared catalyst finished product comprises 16 mass percent of nickel, 2 mass percent of copper, 4 mass percent of chromium and 78 mass percent of alumina carrier, and is numbered JYA-1.
Example 2
This example provides a method for preparing a catalyst for use in the present invention, comprising the steps of:
(1) 200g of alumina, 51.85g of nickel oxide and 239g of deionized water were mixed in a ball mill and then ball-rolled to form a ball.
(2) And roasting for 6 hours at 550 ℃ after molding to obtain the carrier containing nickel oxide.
(3) According to the water absorption of the nickel oxide carrier, 16.53g of copper nitrate and 17.09g of chromium nitrate were loaded on the surface of the catalyst by an equivalent impregnation method.
(4) Finally, the catalyst is reduced for 20 hours at the temperature of 450 ℃ under the condition of hydrogen to obtain a finished product of the catalyst.
(5) The prepared catalyst finished product comprises, by mass, 20% of nickel, 3% of copper, 2% of chromium and 75% of alumina carrier, and is numbered JYA-2.
Example 3
This example provides a method for preparing a catalyst for use in the present invention, comprising the steps of:
(1) 200g of alumina, 59.41g of nickel oxide and 246g of deionized water were mixed in a ball mill and then ball-milled to form a ball.
(2) And roasting for 4 hours at 700 ℃ after molding to obtain the carrier containing nickel oxide.
(3) According to the water absorption of the nickel oxide carrier, 22.96g of copper nitrate and 17.80g of chromium nitrate are loaded on the surface of the catalyst by an equivalent impregnation method.
(4) Finally, the catalyst is reduced for 20 hours at the temperature of 450 ℃ under the condition of hydrogen to obtain a finished product of the catalyst.
(5) The prepared catalyst finished product comprises, by mass, 22% of nickel, 4% of copper, 2% of chromium and 72% of alumina carrier, and is numbered JYA-3.
Example 4
This example provides a method for preparing a catalyst for use in the present invention, comprising the steps of:
(1) 200g of alumina, 70.45g of nickel oxide and 257g of deionized water were mixed in a ball mill and then ball-rolled to form a ball.
(2) And roasting for 5 hours at 650 ℃ after molding to obtain the carrier containing nickel oxide.
(3) 29.94g of copper nitrate and 9.29g of chromium nitrate were loaded on the surface of the catalyst by an equivalent impregnation method according to the water absorption of the nickel oxide carrier.
(4) Finally, the catalyst is reduced for 20 hours at the temperature of 450 ℃ under the condition of hydrogen to obtain a finished product of the catalyst.
(5) The prepared catalyst finished product comprises 25% of nickel, 5% of copper, 1% of chromium and 69% of alumina carrier by mass percent, and is numbered JYA-4.
Examples 5 to 21 are applications of the preparation method of highly selective methyl isobutyl alcohol of the present invention
Example 5
100mL of catalyst with the number of JYA-1 is filled into a gas-solid phase fixed bed reactor, methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be sent into the reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 120 ℃, the reaction pressure is 0.6MPa, and the space velocity is 0.6h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:6, under which the conversion of methyl isobutyl ketone was 99.90% and the product selectivity of methyl isobutyl alcohol was 100%.
Example 6
100mL of catalyst with the number of JYA-2 is filled into a gas-solid phase fixed bed reactor, methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be sent into the reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 120 ℃, the reaction pressure is 0.6MPa, and the space velocity is 0.6h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:6, under which the conversion of methyl isobutyl ketone was 99.91% and the product selectivity of methyl isobutyl alcohol was 100%.
Example 7
100mL of catalyst with the number of JYA-3 is filled into a gas-solid phase fixed bed reactor, methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be sent into the reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 120 ℃, the reaction pressure is 0.6MPa, and the space velocity is 0.6h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:6, under which the conversion of methyl isobutyl ketone was 99.96% and the product selectivity of methyl isobutyl alcohol was 100%.
Example 8
100mL of catalyst with the number of JYA-4 is filled into a gas-solid phase fixed bed reactor, methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be sent into the reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 120 ℃, the reaction pressure is 0.6MPa, and the space velocity is 0.6h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:6, under which the conversion of methyl isobutyl ketone was 99.92% and the product selectivity of methyl isobutyl alcohol was 100%.
Example 9
100mL of catalyst with the number of JYA-1 is filled into a gas-solid phase fixed bed reactor, methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be fed into the reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 90 ℃, the reaction pressure is 0.6MPa, and the space velocity is 0.6h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:6, under which the conversion of methyl isobutyl ketone was 99.65% and the product selectivity of methyl isobutyl alcohol was 99.73%.
Example 10
100mL of catalyst with the number of JYA-1 is filled into a gas-solid phase fixed bed reactor, methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be fed into the reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 100 ℃, the reaction pressure is 0.6MPa, and the space velocity is 0.6h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:6, under which the conversion of methyl isobutyl ketone was 99.87% and the product selectivity of methyl isobutyl alcohol was 99.95%.
Example 11
Numbering 100mL asJYA-1 catalyst is filled in a gas-solid phase fixed bed reactor, methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be sent into the reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 110 ℃, the reaction pressure is 0.6MPa, and the space velocity is 0.6h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:6, under which the conversion of methyl isobutyl ketone was 99.91% and the product selectivity of methyl isobutyl alcohol was 100%.
Example 12
100mL of catalyst with the number of JYA-1 is filled into a gas-solid phase fixed bed reactor, methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be fed into the reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 120 ℃, the reaction pressure is 0.6MPa, and the space velocity is 0.6h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:6, under which the conversion of methyl isobutyl ketone was 99.96% and the product selectivity of methyl isobutyl alcohol was 100%.
Example 13
100mL of catalyst with the number of JYA-1 is filled into a gas-solid phase fixed bed reactor, methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be fed into the reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 130 ℃, the reaction pressure is 0.6MPa, and the space velocity is 0.6h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:6, under which the conversion of methyl isobutyl ketone was 99.93% and the product selectivity of methyl isobutyl alcohol was 100%.
Example 14
100mL of catalyst with the number of JYA-1 is filled into a gas-solid phase fixed bed reactor, methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be fed into the reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 140 ℃, the reaction pressure is 0.6MPa, and the space velocity is 0.6h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:6, under which the conversion of methyl isobutyl ketone was 99.94% and the product selectivity of methyl isobutyl alcohol was 99.92%.
Example 15
100mL of catalyst numbered JYA-1 was charged in a gas-solid fixed bed reactor, and methyl was addedThe isobutyl ketone is vaporized by a vaporizer, mixed with hydrogen and sent into a reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 120 ℃, the reaction pressure is 0.5MPa, and the space velocity is 0.6h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:6, under which the conversion of methyl isobutyl ketone was 99.86% and the product selectivity of methyl isobutyl alcohol was 100%.
Example 16
100mL of catalyst with the number of JYA-1 is filled into a gas-solid phase fixed bed reactor, methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be fed into the reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 120 ℃, the reaction pressure is 0.7MPa, and the space velocity is 0.6h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:6, under which the conversion of methyl isobutyl ketone was 99.90% and the product selectivity of methyl isobutyl alcohol was 99.97%.
Example 17
100mL of catalyst with the number of JYA-1 is filled into a gas-solid phase fixed bed reactor, methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be fed into the reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 120 ℃, the reaction pressure is 0.6MPa, and the space velocity is 0.5h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:6, under which the conversion of methyl isobutyl ketone was 99.96% and the product selectivity of methyl isobutyl alcohol was 100%.
Example 18
100mL of catalyst with the number of JYA-1 is filled into a gas-solid phase fixed bed reactor, methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be fed into the reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 120 ℃, the reaction pressure is 0.6MPa, and the space velocity is 0.7h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:6, under which the conversion of methyl isobutyl ketone was 99.81% and the product selectivity of methyl isobutyl alcohol was 100%.
Example 19
100mL of JYA-1 catalyst is filled in a gas-solid phase fixed bed reactor, and methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be fed into the reactorCarrying out hydrogenation reaction under the following reaction conditions: the reaction temperature is 120 ℃, the reaction pressure is 0.6MPa, and the space velocity is 0.6h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:5, under which the conversion of methyl isobutyl ketone was 99.89% and the product selectivity of methyl isobutyl alcohol was 99.94%.
Example 20
100mL of catalyst with the number of JYA-1 is filled into a gas-solid phase fixed bed reactor, methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be fed into the reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 120 ℃, the reaction pressure is 0.6MPa, and the space velocity is 0.6h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:7, under which the conversion of methyl isobutyl ketone was 99.93% and the product selectivity of methyl isobutyl alcohol was 100%.
Example 21
100mL of catalyst with the number of JYA-1 is filled into a gas-solid phase fixed bed reactor, methyl isobutyl ketone is vaporized by a vaporizer and then mixed with hydrogen to be fed into the reactor for hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 120 ℃, the reaction pressure is 0.6MPa, and the space velocity is 0.6h-1The ratio of the amounts of methyl isobutyl ketone and hydrogen was 1:8, under which the conversion of methyl isobutyl ketone was 99.95% and the product selectivity of methyl isobutyl alcohol was 100%.
The catalyst and the preparation method thereof improve the interaction between metal components and alumina, so that metal nickel, cocatalyst copper and chromium are more easily dispersed on a carrier and are more easily reduced, nickel crystal grains are not easy to aggregate and grow in the using process, the active site on the inner surface of the catalyst is better, and the catalyst has stronger hydrogenation function, thereby further promoting the hydrogenation of methyl isobutyl ketone; the hydrogenation reaction is carried out in a gas-solid phase fixed bed reactor, and the methyl isobutyl ketone needs to be preheated and gasified before entering the reactor, so that the raw material is in full contact with active sites on the inner surface of the catalyst, the reaction efficiency is improved, the conversion rate of the methyl isobutyl ketone is more than 99.50 percent, and the product selectivity of the methyl isobutyl alcohol is more than 99.7 percent.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of high-selectivity methyl isobutyl alcohol is characterized in that methyl isobutyl ketone is used as a raw material, and after gasification, the methyl isobutyl ketone and hydrogen are subjected to hydrogenation reaction under the action of a catalyst to prepare the methyl isobutyl alcohol; the catalyst is prepared by taking an aluminum oxide and a nickel oxide as carriers and loading cocatalyst copper and chromium, wherein in the catalyst composition, the nickel accounts for 10-30% of the final catalyst, the copper accounts for 1-10%, the chromium accounts for 1-10%, and the balance is the aluminum oxide.
2. The method for preparing methyl isobutyl alcohol with high selectivity according to claim 1, wherein the molar ratio of methyl isobutyl ketone to hydrogen is 1: 2-10.
3. The method for preparing methyl isobutyl alcohol with high selectivity according to claim 2, wherein the molar ratio of methyl isobutyl ketone to hydrogen is 1: 5-8.
4. The method for preparing methyl isobutyl alcohol with high selectivity according to claim 1, wherein the reaction conditions are as follows: the reaction temperature is 90-140 ℃, and the liquid space velocity is 0.1-1h-1The pressure is normal pressure-1.0 MPa.
5. The method for preparing methyl isobutyl alcohol with high selectivity according to claim 4, wherein the reaction conditions are as follows: the reaction temperature is 100 ℃ and 120 ℃, and the liquid space velocity is 0.5-0.7h-1The pressure is 0.5-0.7 MPa.
6. The method for preparing methyl isobutyl alcohol with high selectivity according to claim 1, wherein the catalyst composition comprises nickel 20-25 wt%, copper 2-5 wt%, chromium 1-3 wt% and the rest is aluminum oxide carrier.
7. The method for preparing methyl isobutyl alcohol with high selectivity according to any one of claims 1-6, wherein the method for preparing the catalyst comprises the following steps:
1) mixing one or more of aluminum oxide, nickel oxide or nickel protoxide with water, and rolling and molding;
2) roasting the raw materials in the step 1) to obtain a catalyst carrier;
3) loading copper and chromium serving as promoters on the surface of the catalyst carrier obtained in the step 2) by an impregnation method;
4) reducing the catalyst carrier loaded with the cocatalyst and obtained in the step 3) in a reducing gas atmosphere to obtain a catalyst finished product.
8. The method as claimed in claim 7, wherein the calcination temperature in step 2) is 400-700 ℃ and the calcination time is 4-6 h.
9. The method as claimed in claim 7, wherein in the step 4), the reducing gas is hydrogen, and the temperature for reduction is 400-500 ℃.
10. The method of claim 7, wherein in the step 3), the promoter selected from the group consisting of copper and chromium is one of nitrate, acetate and carbonate.
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