CN112206820B - Composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde one-step method and preparation method thereof - Google Patents
Composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde one-step method and preparation method thereof Download PDFInfo
- Publication number
- CN112206820B CN112206820B CN202011059503.8A CN202011059503A CN112206820B CN 112206820 B CN112206820 B CN 112206820B CN 202011059503 A CN202011059503 A CN 202011059503A CN 112206820 B CN112206820 B CN 112206820B
- Authority
- CN
- China
- Prior art keywords
- isobutyraldehyde
- catalyst
- metal oxide
- isobutyl isobutyrate
- oxide catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 title claims abstract description 80
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 49
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 31
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000006229 carbon black Substances 0.000 claims abstract description 22
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- 239000012530 fluid Substances 0.000 claims abstract description 6
- 238000005470 impregnation Methods 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 238000006482 condensation reaction Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- -1 isobutanol aluminum Chemical compound 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- PBZJABRHZRYANY-UHFFFAOYSA-K aluminum;2-methylpropanoate Chemical compound [Al+3].CC(C)C([O-])=O.CC(C)C([O-])=O.CC(C)C([O-])=O PBZJABRHZRYANY-UHFFFAOYSA-K 0.000 claims 2
- 229920000428 triblock copolymer Polymers 0.000 claims 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- JSJSIMXBGUAKDX-UHFFFAOYSA-N 2-methylpropoxyalumane Chemical compound C(C(C)C)O[AlH2] JSJSIMXBGUAKDX-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 244000099147 Ananas comosus Species 0.000 description 2
- 235000007119 Ananas comosus Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- DAOVYDBYKGXFOB-UHFFFAOYSA-N tris(2-methylpropoxy)alumane Chemical compound [Al+3].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] DAOVYDBYKGXFOB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
-
- 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
- B01J23/72—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
- 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
- B01J23/83—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 rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a composite metal oxide catalyst for preparing isobutyl isobutyrate by using a one-step method of isobutyraldehyde and a preparation method thereof. Carbon black is used as an inert substrate, and a space synthesis method is combined with a hydrothermal microwave method to synthesize the nano CuO-M with a mesoporous structure x O y (M = Ce, cr, ti) carrier, and then the catalyst is prepared by loading the aluminum iso-butoxide on the surface of the carrier by a supercritical fluid impregnation method. The preparation method is simple, the catalyst has a good structure and a good surface distribution state, the mesoporous structure remarkably improves the stability of the catalyst, prolongs the service life of the catalyst, and enables the catalyst to have a higher specific surface area.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a composite metal oxide catalyst for preparing isobutyl isobutyrate by using a one-step method of isobutyraldehyde and a preparation method thereof.
Background
Isobutyl isobutyrate (IBIBIBE) is a colorless or light yellow liquid, has pineapple, grape skin or ether fragrance, is a good green product because the isobutyl isobutyrate is basically harmless to human and livestock and does not cause environmental pollution, is widely used as pineapple essence in food, beverage and perfume industries, and is also an excellent organic solvent, a dry paint remover and an extractive distillation additive. With the improvement of environmental protection requirements, the application of isobutyl isobutyrate is more and more extensive. Isobutyl isobutyrate is generally synthesized by fischer-tropsch esterification of isobutyric acid (IBAC) and Isobutanol (IBOH), which is a traditional process using sulfuric acid as an acid catalyst, and has problems such as low reaction conversion, many byproducts, severe corrosion of equipment, and acidic waste discharge.
Isobutyl isobutyrate is prepared by one step from isobutyraldehyde through Tishchenko condensation reaction, the raw material is single, and the method is a molecular economic reaction. The petrochemical research institute of Heilongjiang province used isobutoxy aluminum as a catalyst, and isobutyl isobutyrate was prepared by one-step reaction of isobutyraldehyde, but the isobutoxy aluminum catalyst is not stable, and is inactivated after reaction due to the fact that a ligand of the catalyst is easily replaced by hydroxyl in the reaction process, and cannot be recycled. These problems have prompted the search for alternative catalysts that combine aluminum isobutoxide with improved long-term stability.
Disclosure of Invention
The invention provides a composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde through a one-step method, a preparation method and application thereof. Aiming at the problems that the isobutoxy aluminum catalyst is unstable, and the ligand of the catalyst is easy to be substituted by hydroxyl to inactivate in the reaction process, and the like, the invention synthesizes the nano CuO-M with the mesoporous structure by combining a space synthesis method with a hydrothermal microwave method x O y And (M = Ce, cr and Ti) carriers, and isobutylaluminum alcoholate is loaded on the surfaces of the carriers by using a supercritical fluid impregnation method, so that the catalyst has more active centers and stronger adsorption and mass transfer capabilities, the stability and the service life of the catalyst are obviously improved, and the catalyst can be recycled for multiple times. The method is used for the reaction of preparing isobutyl isobutyrate from isobutyraldehyde in one step, and can obviously improve the reactivity of the catalyst and the selectivity of methacrylic acid.
The specific preparation method of the composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde through one-step method is as follows:
(1) Dissolving copper nitrate and nitrate of M in water to prepare a metal salt mixed solution; then dispersing the pretreated carbon black in an alkali solution of TPAOH, dropwise adding the prepared metal salt mixed solution into the alkali solution, and stirring the mixture for 5 to 6 hours at room temperature; then add IIIA block copolymer F127 to which an ammonium hydroxide solution is added dropwise with stirring until the pH is about 10 (about 9 to 12); then placing the mixture into a high-pressure kettle, and crystallizing the mixture for 5 to 6 hours in a microwave system at the temperature of between 160 and 180 ℃; then filtering the product, fully washing the product with distilled deionized water, drying the product, and finally calcining the product in a muffle furnace to obtain CuO-M x O y The carrier, wherein the element M is one of Ce, cr and Ti;
(2) Loading aluminum isobutyl alkoxide on CuO-M prepared in step (1) based on a supercritical fluid impregnation method x O y And (3) washing and drying the surface of the carrier to obtain the composite metal oxide catalyst for preparing isobutyl isobutyrate by using the isobutyraldehyde one-step method.
Further, in the step (1), the mass ratio of the copper nitrate to the nitrate of M is 1; the adding mass of the F127 is 10-20% of the total mass of the copper nitrate and the nitrate of the M. The purpose of the optimization is to prepare the carrier which has more stable structural morphology and is easier to load aluminum iso-butoxide.
Furthermore, in the step (1), the calcining temperature is 500-600 ℃, and the calcining time is 3-4 hours.
Further, the pretreatment method of the carbon black in the step (1) comprises the following steps: the carbon black after drying treatment is dipped by ethanol, and then the ethanol is removed by evaporation.
Further, the aluminum iso-butoxide in the step (2) is prepared by the following method: adding isobutanol and metal aluminum into a reaction container with a reflux condensing device, wherein a drying device of anhydrous calcium chloride is arranged at the top of the reflux condensing device, stirring and refluxing at constant temperature until no gas is discharged, and stopping reaction to obtain the isobutanol aluminum; wherein the mass ratio of the metallic aluminum to the isobutanol is 1-1, and the reaction temperature is 120 +/-5 ℃.
Further, the mass of the added aluminum iso-butoxide in the step (2) is CuO-M x O y 10-50% of the mass of the carrier.
Further, the specific operation method in the step (2) comprises the following steps: adding aluminum isobutyl alkoxide to the CuO-M prepared in the step (1) x O y Putting the open container into an autoclave filled with ethanol in the open container of the carrier, heating to 270 +/-10 ℃, keeping the temperature for 3 +/-4 hours under the pressure of 8.27 +/-1 MPa, washing the solid with ethanol, and drying in vacuum to obtain the composite metal oxide catalyst for preparing isobutyl isobutyrate by the one-step method of isobutyraldehyde.
The composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde through one-step method is prepared by the preparation method of the composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde through one-step method.
The application of the composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde through one-step method is used for catalyzing Tishchenko condensation reaction of isobutyraldehyde to prepare isobutyl isobutyrate.
Further, the method comprises the following steps: filling the composite metal oxide catalyst for preparing isobutyl isobutyrate by using a one-step method of isobutyraldehyde in a fixed bed microreactor, introducing nitrogen under normal pressure, raising the temperature to Tishchenko condensation reaction temperature, adding reactant isobutyraldehyde into the reactor to start reaction, and collecting reaction products after the reaction is stable.
Further, the dosage of the composite metal oxide catalyst for preparing isobutyl isobutyrate by using the isobutyraldehyde through the one-step method is 0.4-0.8 ml; the Tishchenko condensation reaction temperature is 250-270 ℃, and the contact time of reactants and the catalyst is 2-4 seconds.
Has the beneficial effects that: the invention takes carbon black as an inert substrate, and synthesizes nano CuO-M with a mesoporous structure by combining a space synthesis method with a hydrothermal microwave method x O y And (M = Ce, cr and Ti) carriers, so that the catalyst has more active centers, stronger adsorption and mass transfer capacities and better surface distribution state. The copper-based catalyst has the advantages of high activity, few byproducts, mild use conditions and the like, and the reaction activity is further improved by compounding Cu with metal oxides such as Ce, cr, ti and the like. And then the supercritical fluid impregnation method is utilized to load the aluminum iso-butoxide on the surface of the carrier, the loading amount of the active component is high, the distribution of the active component on the carrier is very uniform, the bonding force between the carrier and the active component is stronger, and the improvement of the bonding force between the carrier and the active component is remarkableThe stability and the service life of the catalyst are prolonged, so that the catalyst can be recycled for multiple times. The method is used for the reaction of preparing isobutyl isobutyrate from isobutyraldehyde in one step, and higher yield and conversion rate are obtained through experiments.
Detailed Description
The present invention is further described below with reference to examples, but is not limited thereto.
Example 1
(1) Preparation of the support
9.0g of copper nitrate and 3.0g of cerium nitrate were weighed, and dissolved in 120 ml of water after being uniformly mixed to prepare a metal salt mixed solution. Drying 3.6g of carbon black at 150 ℃ for 24h, then fully soaking the carbon black with ethanol, using the ethanol after the ethanol is evaporated, and carrying out surface active treatment on the carbon black to enhance the adsorption capacity of the carbon black. Then, the pretreated carbon black was dispersed in an alkali solution having a concentration of 0.1mol/L TPAOH, and the prepared metal salt mixed solution was added dropwise thereto and stirred at room temperature for 5 hours. Then, 1.2g of F127 was added thereto, and a 2mol/L ammonium hydroxide solution was added dropwise thereto with stirring until the pH was 10. Then, the mixture was placed in an autoclave and crystallized at 180 ℃ for 6 hours in a microwave system. The product was then filtered, washed several times with distilled deionized water and dried in an oven at 80 ℃ for 24h. Finally calcining the mixture for 4 hours at the high temperature of 600 ℃ in a muffle furnace to obtain CuO-CeO 2 And (3) a carrier.
(2) Preparation of aluminium iso-butoxide
Adding 10.0g of metal aluminum and 60g of isobutanol into a three-neck flask, connecting a drying device filled with anhydrous calcium chloride at the top end of a reflux condensation tube, stirring, heating and refluxing at 120 ℃ until no gas is discharged, and stopping reaction to obtain the aluminum iso-butoxide.
(3) Preparation of composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde one-step method
3.0g of CuO-CeO was weighed 2 Adding carrier and 0.3g of aluminum iso-butoxide into a flask, placing the flask into an autoclave filled with ethanol, heating to 270 deg.C, introducing ethanol into the flask in vapor state, maintaining at 8.27MPa for 3 hr, washing the solid with ethanol, and drying in a vacuum drying oven for 12 hr to obtain isobutyraldehyde by one-step methodA composite metal oxide catalyst for preparing isobutyl isobutyrate.
(4) Reaction for preparing isobutyl isobutyrate from isobutyraldehyde in one step
And (3) weighing 0.6ml of the composite metal oxide catalyst prepared in the step (3) and used for preparing isobutyl isobutyrate by the one-step method of isobutyraldehyde, filling the composite metal oxide catalyst into a fixed bed microreactor, filling the place where the catalyst is not filled with quartz sand, and plugging two ends of a reaction tube by using a small amount of quartz wool. Under normal pressure, nitrogen is introduced, the reaction temperature is increased to 270 ℃, then reactant isobutyraldehyde is added into the reactor to start reaction, and the contact time of the reactant and the catalyst is 2 seconds. After the reaction was stabilized, the reaction product was collected and analyzed by gas chromatography equipped with FID and TCD detectors.
Example 2
The operation in step (3) was carried out in the same manner as in example 1 except that 0.3g of aluminum isobutylalkoxide was changed to 0.6g of aluminum isobutylalkoxide.
Example 3
The procedure of example 1 was otherwise the same as that of example 1 except that 0.3g of aluminum isobutylalkoxide in step (3) was changed to 0.9g of aluminum isobutylalkoxide.
Example 4
In the step (3), 0.3g of aluminum isobutylalkoxide was changed to 1.2g of aluminum isobutylalkoxide, and the other operations were performed in the same manner as in example 1.
Example 5
In the step (3), 0.3g of aluminum isobutylalkoxide was changed to 1.5g of aluminum isobutylalkoxide, and the other operations were performed in the same manner as in example 1.
Example 6
The reaction temperature in the step (4) was changed to 260 ℃ and the other operations were the same as in example 1.
Example 7
The reaction temperature in the step (4) was changed to 250 ℃ and the other operations were the same as in example 1.
Example 8
The contact time in the step (4) was changed to 4 seconds, and the other operations were the same as in example 1.
Example 9
A metal salt mixed solution was prepared by weighing 9.0g of copper nitrate and 3.0g of chromium nitrate and dissolving them in 120 ml of water after mixing them uniformly, and the other operations were the same as in example 1.
Example 10
9.0g of copper nitrate and 3.0g of titanium nitrate were weighed, and dissolved in 120 ml of water after being uniformly mixed to prepare a metal salt mixed solution. The other operations were the same as in example 1.
Example 11
9.0g of copper nitrate and 6.0g of cerium nitrate were weighed and mixed uniformly, and a metal salt mixed solution was prepared in the same manner as in example 1 except that the operation was changed.
Example 12
9.0g of copper nitrate and 9.0g of cerium nitrate were weighed and mixed uniformly, and a metal salt mixed solution was prepared in the same manner as in example 1.
Example 13
The calcination temperature in step (1) was changed to 550 ℃ and the operation was otherwise the same as in example 1.
Example 14
The calcination temperature in step (1) was changed to 500 ℃ and the other operations were the same as in example 1.
Example 15
The calcination time in step (1) was changed to 3 hours, and the other operations were the same as in example 1.
Example 16
The same procedure as in example 1 was repeated except that 3.6g of carbon black in step (1) was changed to 4.8g of carbon black.
Example 17
The same procedure as in example 1 was repeated except that 3.6g of carbon black in step (1) was changed to 6.0g of carbon black.
Comparative example 1
9.0g of copper nitrate was dissolved in 120 ml of water to prepare a metal salt solution. 3.6g of carbon black is dried at 150 ℃ for 24 hours, and then the carbon black is fully impregnated with ethanol, and the ethanol is used after being evaporated. Then, the pretreated carbon black was dispersed in an alkali solution having a concentration of 0.1mol/L TPAOH, and the prepared metal salt solution was added dropwise thereto and stirred at room temperature for 5 hours. 1.2g of F127 was further added thereto, and 2mol/L ammonium hydroxide solution was added dropwise thereto with stirring until the pH was 10. Then, the mixture was placed in an autoclave and crystallized at 180 ℃ for 6 hours in a microwave system. The product was then filtered, washed several times with distilled deionized water and dried in an oven at 80 ℃ for 24h. And finally calcining the mixture for 4 hours at the high temperature of 600 ℃ in a muffle furnace to obtain the carrier. The other operations were the same as in example 1.
Comparative example 2
No carbon black was added.
9.0g of copper nitrate and 3.0g of cerium nitrate were weighed and dissolved in 120 ml of water after being mixed well. The prepared metal salt mixed solution was added dropwise to a 0.1mol/L alkali solution of TPAOH, and stirred at room temperature for 5 hours. Then, 1.2g of F127 was added thereto, and a 2mol/L ammonium hydroxide solution was added dropwise thereto with stirring until the pH was 10. Then, the mixture was placed in an autoclave and crystallized at 180 ℃ for 6 hours in a microwave system. The product was then filtered, washed several times with distilled deionized water and dried in an oven at 80 ℃ for 24h. And finally calcining the mixture for 4 hours at the high temperature of 600 ℃ in a muffle furnace to obtain the carrier. The other operations were the same as in example 1.
Comparative example 3
The reaction was carried out in the same manner as in example 1 except that aluminum isopropoxide was used as a catalyst.
0.6ml of aluminum iso-butoxide was weighed and charged in a fixed bed microreactor. The place where the catalyst is not filled is filled with quartz sand, and a small amount of quartz wool is used for plugging the two ends of the reaction tube. Under normal pressure, nitrogen is introduced, the reaction temperature is increased to 270 ℃, then reactant isobutyraldehyde is added into the reactor to start reaction, and the contact time of the reactant and the catalyst is 2 seconds. After the reaction was stabilized, the reaction product was collected and analyzed by gas chromatography equipped with FID and TCD detectors.
Comparative example 4
Without the use of a microwave system. The other operations were the same as in example 1.
9.0g of copper nitrate and 3.0g of cerium nitrate were weighed and dissolved in 120 ml of water after being mixed well. The prepared metal salt mixed solution was added dropwise to a 0.1mol/L alkali solution of TPAOH, and stirred at room temperature for 5 hours. Then, 1.2g of F127 was added thereto, and a 2mol/L ammonium hydroxide solution was added dropwise thereto with stirring until the pH was 10. Then the mixture is placed in an autoclave and crystallized for 6 hours in an oven at 180 ℃. The product was then filtered, washed several times with distilled deionized water and dried in an oven at 80 ℃ for 24h. And finally calcining the mixture for 4 hours at the high temperature of 600 ℃ in a muffle furnace to obtain the carrier.
Comparative example 5
The supercritical load is changed to be loaded by a conventional method.
3.0g of the carrier was weighed into 25ml of distilled deionized water and stirred for 10 minutes. 0.3g of aluminum iso-butoxide was then weighed out and dissolved in 25ml of distilled deionized water, and the solution was gradually added dropwise to the suspension of the support and stirred for 6 hours. Then dried in a vacuum drying oven for 12 hours to obtain the catalyst.
The performance of the catalysts obtained in the respective examples and comparative examples is shown in Table 1.
TABLE 1
The catalyst performance data for the catalysts obtained in example 1 and comparative example were repeated 5 times and are shown in table 2.
TABLE 2
The catalyst prepared by the invention is prepared by combining a space synthesis method with a hydrothermal microwave method to synthesize nano CuO-M with a mesoporous structure x O y And (M = Ce, cr and Ti) carriers, so that the catalyst has more active centers, stronger adsorption and mass transfer capacity and better surface distribution state. The copper-based catalyst has the advantages of high activity, few byproducts, mild use conditions and the like, and the reaction activity of the copper-based catalyst is further improved by compounding Cu with metal oxides of Ce, cr, ti and the like. And then the supercritical fluid impregnation method is utilized to load the aluminum iso-butoxide on the surface of the carrier, the loading amount of the active component is high, the distribution of the active component on the carrier is uniform, the binding force between the carrier and the active component is stronger, the stability of the catalyst is further improved, the catalyst can be recycled for multiple times, and the isobutoxy aluminum catalytic activity is greatly compensatedThe reagent is not stable, and the ligand is easy to be substituted by hydroxyl in the reaction process, so that the catalyst is inactivated after reaction and cannot be recycled for many times, and the conversion rate of isobutyraldehyde and the selectivity of methacrylic acid are obviously improved. In addition, the catalyst prepared by the invention is an environment-friendly catalyst and has good industrial application prospect.
Claims (10)
1. The preparation method of the composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde through one-step method is characterized by comprising the following steps:
(1) Dissolving copper nitrate and nitrate of M in water to prepare a metal salt mixed solution; then dispersing the pretreated carbon black in an alkaline solution of TPAOH, dropwise adding the prepared metal salt mixed solution into the solution, and stirring the solution at room temperature for 5 to 6 hours; then adding the triblock copolymer F127, and dropwise adding an ammonium hydroxide solution into the triblock copolymer F127 under the stirring condition until the pH value is 9-12; then placing the mixture into a high-pressure kettle, and crystallizing the mixture for 5 to 6 hours in a microwave system at the temperature of between 160 and 180 ℃; then filtering the product, fully washing the product by using distilled deionized water, drying the product, and finally calcining the product in a muffle furnace to obtain CuO-M x O y The carrier, wherein the element M is one of Ce, cr and Ti;
(2) Based on a supercritical fluid impregnation method, loading aluminum iso-butoxide on the CuO-M prepared in the step (1) x O y And (3) washing and drying the surface of the carrier to obtain the composite metal oxide catalyst for preparing isobutyl isobutyrate by using the isobutyraldehyde one-step method.
2. The method for preparing a composite metal oxide catalyst for one-step preparation of isobutyl isobutyrate from isobutyraldehyde according to claim 1, wherein the mass ratio of the copper nitrate to the nitrate of M in step (1) is 1 to 1, and the amount of carbon black added is 30 to 50% of the total mass of the copper nitrate and the nitrate of M; the adding mass of the F127 is 10-20% of the total mass of the copper nitrate and the nitrate of the M.
3. The method for preparing a composite metal oxide catalyst for the one-step preparation of isobutyl isobutyrate from isobutyraldehyde according to claim 1, wherein the calcination temperature in step (1) is 500 to 600 ℃ and the calcination time is 3 to 4 hours;
and/or the pretreatment method of the carbon black in the step (1) comprises the following steps: the carbon black after drying treatment is dipped by ethanol, and then the ethanol is removed by evaporation.
4. The method of preparing a composite metal oxide catalyst for the one-step preparation of isobutyl isobutyrate from isobutyraldehyde according to claim 1, wherein the aluminum isobutyrate in the step (2) is prepared by: adding isobutanol and metal aluminum into a reaction container with a reflux condensing device, wherein a drying device of anhydrous calcium chloride is arranged at the top of the reflux condensing device, stirring and refluxing at constant temperature until no gas is discharged, and stopping reaction to obtain the isobutanol aluminum; wherein the mass ratio of the metallic aluminum to the isobutanol is 1-1, and the reaction temperature is 120 +/-5 ℃.
5. The method of preparing a complex metal oxide catalyst for the one-step preparation of isobutyl isobutyrate from isobutyraldehyde according to claim 1, wherein the mass of aluminum isobutyrate added in the step (2) is CuO-M x O y 10-50% of the mass of the carrier.
6. The method for preparing a composite metal oxide catalyst for the one-step preparation of isobutyl isobutyrate from isobutyraldehyde according to claim 1, wherein the specific operation method in the step (2) comprises the steps of: adding aluminum iso-butoxide to the CuO-M prepared in step (1) x O y Putting the open container into an autoclave filled with ethanol in an open container of a carrier, heating to 270 +/-10 ℃, keeping for 3 +/-4 hours under the pressure of 8.27 +/-1 MPa, washing the solid with ethanol, and drying in vacuum to obtain the composite metal oxide catalyst for preparing isobutyl isobutyrate by the one-step method of isobutyraldehyde.
7. A composite metal oxide catalyst for the one-step method of producing isobutyl isobutyrate from isobutyraldehyde, which is obtained by the method of any one of claims 1 to 6.
8. The use of the composite metal oxide catalyst for preparing isobutyl isobutyrate by the one-step method of isobutyraldehyde according to claim 7, wherein the composite metal oxide catalyst is used for catalyzing Tishchenko condensation reaction of isobutyraldehyde to prepare isobutyl isobutyrate.
9. The use of the catalyst of claim 8 for the one-step preparation of isobutyl isobutyrate from isobutyraldehyde, wherein the catalyst comprises: the method comprises the following steps: filling the composite metal oxide catalyst for preparing isobutyl isobutyrate by using a isobutyraldehyde one-step method into a fixed bed microreactor, introducing nitrogen at normal pressure, raising the temperature to Tishchenko condensation reaction temperature, adding a reactant isobutyraldehyde into the reactor to start reaction, and collecting a reaction product after the reaction is stable.
10. The use of the catalyst of claim 9, wherein the amount of said catalyst is 0.4-0.8 ml; the Tishchenko condensation reaction temperature is 250-270 ℃, and the contact time of reactants and the catalyst is 2-4 seconds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011059503.8A CN112206820B (en) | 2020-09-30 | 2020-09-30 | Composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde one-step method and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011059503.8A CN112206820B (en) | 2020-09-30 | 2020-09-30 | Composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde one-step method and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112206820A CN112206820A (en) | 2021-01-12 |
| CN112206820B true CN112206820B (en) | 2022-11-22 |
Family
ID=74051722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011059503.8A Active CN112206820B (en) | 2020-09-30 | 2020-09-30 | Composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde one-step method and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112206820B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185395B (en) * | 2021-04-09 | 2022-12-23 | 润泰新材料股份有限公司 | Process for the production of isobutyric acid |
| CN114870872A (en) * | 2022-05-25 | 2022-08-09 | 润泰化学（泰兴）有限公司 | Preparation method and application of solid superacid catalyst for synthesizing methyl isopropyl ketone by isobutyraldehyde catalysis |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1439627A (en) * | 2003-03-21 | 2003-09-03 | 黑龙江省石油化学研究院 | Production of isobutyl isobutyrate from isobutyraldehyde by condensation |
| WO2004047990A1 (en) * | 2002-11-27 | 2004-06-10 | Showa Denko K. K. | Catalyst for the preparation of carboxylic esters and process for the preparation of carboxylic esters with the same |
| CN101559370A (en) * | 2009-05-27 | 2009-10-21 | 天津大学 | Cu-Cr series ethyl acetate catalyst added with modified additive and manufacturing method thereof |
| CN101711983A (en) * | 2009-11-14 | 2010-05-26 | 宜兴市恒兴精细化工有限公司 | Catalyst for one-step synthesis of isobutyl isobutyrate from isobutanol and preparation method thereof |
-
2020
- 2020-09-30 CN CN202011059503.8A patent/CN112206820B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004047990A1 (en) * | 2002-11-27 | 2004-06-10 | Showa Denko K. K. | Catalyst for the preparation of carboxylic esters and process for the preparation of carboxylic esters with the same |
| CN1439627A (en) * | 2003-03-21 | 2003-09-03 | 黑龙江省石油化学研究院 | Production of isobutyl isobutyrate from isobutyraldehyde by condensation |
| CN101559370A (en) * | 2009-05-27 | 2009-10-21 | 天津大学 | Cu-Cr series ethyl acetate catalyst added with modified additive and manufacturing method thereof |
| CN101711983A (en) * | 2009-11-14 | 2010-05-26 | 宜兴市恒兴精细化工有限公司 | Catalyst for one-step synthesis of isobutyl isobutyrate from isobutanol and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 异丁醛缩合法制异丁酸异丁酯;王晶等;《化工进展》;20041130;第23卷(第11期);1240-1242 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112206820A (en) | 2021-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108236955B (en) | Preparation method of catalyst for synthesizing ethanol by dimethyl oxalate hydrogenation, catalyst obtained by preparation method and application of catalyst | |
| CN112206820B (en) | Composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde one-step method and preparation method thereof | |
| US20220062872A1 (en) | Catalyst and Method for Preparation of 2-Ethoxyphenol by Catalytic Depolymerization of Lignin | |
| CN101786943A (en) | Catalytic synthesis method for preparing cresol by toluene one-step hydroxylation reaction | |
| CN112206808B (en) | Catalyst for synthesizing isobutyl isobutyrate and preparation method and application thereof | |
| CN113908840A (en) | Fe-based multifunctional catalyst and preparation method and application thereof | |
| CN111389445A (en) | Composite solid acid catalyst for preparing 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate and preparation method thereof | |
| CN101439294A (en) | Molecular sieve catalyst for producing ethylene from ethanol dehydration as well as preparation and use | |
| US20110263726A1 (en) | Process for selective oxidative dehydrogenation of a hydrogen-containing co mixed gas | |
| CN105727979B (en) | A kind of method for preparing catalyst for preparing propene by oxidative dehydrogenation of propane | |
| CN112979414B (en) | Method for preparing aromatic compound from lignin | |
| CN101176850B (en) | Catalyzer for preparing ethylene by ethanol dehydration as well as preparation method and usage | |
| CN109174159A (en) | A kind of novel fixed point adds deuterium photochemical catalyst | |
| CN111203267B (en) | Solid acid catalyst for catalyzing decarboxylation of gamma-valerolactone to prepare butene, and preparation method and application thereof | |
| CN107876040B (en) | Catalyst for one-step synthesis of isobutyraldehyde from methanol and ethanol and preparation method thereof | |
| CN113351232A (en) | Spherical nano catalyst for synthesizing isobutyraldehyde by methanol and ethanol one-step method and preparation method thereof | |
| CN112062673A (en) | Method for directionally synthesizing methyl lactate by catalytically converting fructose by one-pot method | |
| CN101463016A (en) | Method for synthesizing 2,6-dimethyl piperazine | |
| CN1095396C (en) | Catalyst carrying inorganic potassium compound | |
| CN114950535B (en) | Preparation method of solid acid catalyst and application of solid acid catalyst in unsaturated ketone synthesis | |
| CN106861726B (en) | A kind of preparation method and application of the solid base catalyst of synthesizing propylene glycol monomethyl ether | |
| CN1033742C (en) | Solid strengthened catalyst for preparation of glycol ether | |
| CN114515600B (en) | Metal hetero element modified titanium nitride-polyaniline catalyst, preparation method and application thereof in synthesizing para-hydroxyanisole | |
| CN116354807B (en) | Solvent-free synthesis method of nonmetal catalyst and application thereof | |
| CN115477568B (en) | Method for synthesizing 2, 5-dimethyl-2, 4-hexadiene based on Prins condensation reaction catalyzed by heteropolyacid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |