CN114524719A - Method for preparing acetaldehyde, ethanol and ethyl acetate by methanol reduction carbonylation - Google Patents
Method for preparing acetaldehyde, ethanol and ethyl acetate by methanol reduction carbonylation Download PDFInfo
- Publication number
- CN114524719A CN114524719A CN202011322345.0A CN202011322345A CN114524719A CN 114524719 A CN114524719 A CN 114524719A CN 202011322345 A CN202011322345 A CN 202011322345A CN 114524719 A CN114524719 A CN 114524719A
- Authority
- CN
- China
- Prior art keywords
- methanol
- catalyst
- carbonylation
- halogen
- reaction
- 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.)
- Pending
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 322
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 58
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 230000006315 carbonylation Effects 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000009467 reduction Effects 0.000 title claims abstract description 19
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 103
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 16
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 12
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 229910052737 gold Inorganic materials 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 26
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000002367 halogens Chemical class 0.000 claims description 24
- 230000002829 reductive effect Effects 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 4
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 229910000856 hastalloy Inorganic materials 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- -1 carbonyl halides Chemical class 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 39
- 239000006185 dispersion Substances 0.000 description 21
- 229910052739 hydrogen Inorganic materials 0.000 description 20
- 230000004075 alteration Effects 0.000 description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 description 19
- 239000011943 nanocatalyst Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 18
- 235000013162 Cocos nucifera Nutrition 0.000 description 18
- 244000060011 Cocos nucifera Species 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 238000000862 absorption spectrum Methods 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 239000003610 charcoal Substances 0.000 description 17
- 238000001035 drying Methods 0.000 description 17
- 238000001704 evaporation Methods 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 235000019439 ethyl acetate Nutrition 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- 229910019891 RuCl3 Inorganic materials 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 229910004042 HAuCl4 Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910003609 H2PtCl4 Inorganic materials 0.000 description 3
- 229910002666 PdCl2 Inorganic materials 0.000 description 3
- 229910019029 PtCl4 Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- QOTAEASRCGCJDN-UHFFFAOYSA-N [C].CO Chemical compound [C].CO QOTAEASRCGCJDN-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J37/082—Decomposition and pyrolysis
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a method for preparing acetaldehyde, ethanol and ethyl acetate by reducing and carbonylating methanol, which uses CO and CH3OH、CH3I、H2The method is characterized in that methanol reduction carbonylation reaction is carried out on the raw materials containing one or two of carbonylation active metal Rh or Ir and one or more of hydrogenation active metal Ru, Pd, Pt and Au under certain conditions, and acetaldehyde, ethanol and ethyl acetate can be directly prepared from methanol. Characterized in that the method requires the use of an atomically dispersed metal with carbonylation activity (Rh or Ir atom) and an atomically dispersed further monoatomic metal with hydrogenation activity (Ru, Pd, Pt, Au), and in that both metals are atomically monodispersed on the surface of the carbon support in the form of a mononuclear complex of carbonyl halides. Under the action of the double-active-site single-atom catalyst loaded by the carbon carrier and under certain reaction conditions, the application of methanol in one-step direct preparation of acetaldehyde, ethanol and ethyl acetate can be realized in methanol reduction carbonylation.
Description
Technical Field
The application belongs to the technical field of chemical industry, and particularly relates to a method for preparing acetaldehyde, ethanol and ethyl acetate by methanol reduction carbonylation.
Background
In 2017, 9 months, fifteen departments such as national development and improvement committee and the like jointly issue an implementation scheme about expanding the production of biofuel ethanol and popularizing and using vehicle ethanol. By 2025, the complete coverage of the ethanol gasoline for the vehicle can be basically realized nationwide. The fuel ethanol yield of China in 2016 is 260 ten thousand tons. If the fuel ethanol is calculated to be used according to the proportion of 10 percent added into the gasoline, 1190 ten thousand tons of fuel ethanol is used, and compared with the current fuel ethanol yield, the fuel ethanol production has an ethanol demand gap of nearly 930 ten thousand tons. Compared with bioethanol, coal-based ethanol has a great cost advantage, and under the background that the gap of fuel ethanol supply and demand is continuously enlarged, coal-based ethanol is expected to open up a new way for the development of fuel ethanol.
The coal-based ethanol mainly takes synthesis gas obtained by separating coal gasification or coke oven gas as a raw material. The direct route mainly comprises the direct preparation of ethanol from synthesis gas, and the indirect route mainly comprises the preparation of methanol from synthesis gas, the preparation of acetic acid and acetic ester from methanol by carbonylation, and the preparation of ethanol from hydrogenation. In addition, the method also comprises a route of preparing methanol from synthesis gas, preparing methyl nitrite from the methanol by nitration, preparing dimethyl oxalate by carbonylation, and preparing ethanol or ethylene glycol by hydrogenation.
In various routes, the ethanol is directly prepared from the synthesis gas, although the route is short, the yield is too low. Although the yield of ethanol is high through the acetic acid and acetic ester hydrogenation route, the reaction route is longer, the number of intermediate steps is more, and the investment and production cost are higher. Compared with the prior art, the route for preparing ethanol by methanol reduction carbonylation has the advantages of high ethanol selectivity and less intermediate steps, and is paid attention by a plurality of researchers. However, in most researches, the reaction pressure of the ethanol prepared by the reduction and carbonylation of the methanol is higher than 19MPa, the reaction temperature is higher than 190 ℃, the reaction system is corrosive, and the overhigh reaction pressure is a main factor for restricting the industrial application of the process.
In recent years, a supported single metal active site catalyst, also called a monatomic catalyst, has the characteristics of metal monatomic level dispersion and single catalytic active site. Since 2011, a monatomic catalyst attracts people's extensive attention by virtue of nearly 100% utilization efficiency of metal atoms, more unsaturated site coordination sites and an ideal homogeneous catalysis heterogenization research model, and has very high catalytic efficiency compared with other nano or sub-nano catalysts. In addition, the monatomic metal catalyst has the characteristics of uniform and single active center of a homogeneous catalyst and stable and easily separated structure of the heterogeneous catalyst, combines heterogeneous catalysis and homogeneous catalysis together, and has excellent catalytic performance in the aspects of oxidation, reduction, water gas conversion, electrocatalysis and the like.
However, compared to single-metal active-site catalysts, bimetallic active-site catalysts are more attractive, not only have the essential characteristics of single-site catalysis, but also have double catalytic active sites, which often show better catalytic activity, and can realize series catalysis of different reactions on adjacent sites. The process can be expressed as double-active-site cooperative catalysis or double-active-site relay catalysis.
Rh and Ir have proven to be good catalysts for the carbonylation of methanol to acetic acid and its acetate. The main catalyst of the industrialized Monsanto catalytic system is [ Rh (CO) ]2I2]-A catalyst. Cartiva of British BPTMThe process system uses Ir (CO)2I2]-A catalyst. In the above catalytic system, if a catalytic active site for preparing acetaldehyde and ethanol by hydrogenating and reducing acetic acid and acetic ester is continuously introduced, the continuous operation of methanol carbonylation reaction and catalytic hydrogenation reduction reaction can be realized, thereby realizing the preparation of acetaldehyde and ethanol by reducing and carbonylating methanol.
Rh and Ir have the highest catalytic activity in a methanol carbonylation system, while Ru, Pd, Pt and Au have good hydrogenation activity on aldehyde, ketone, carboxylic acid and ester. Therefore, the construction of double catalytic active centers mainly comprising Ir or Rh has strong practical significance for realizing one-step preparation of ethanol, acetaldehyde and ethyl acetate by reduction and carbonylation of methanol.
In the invention patent of the application, the carbon-supported double-active-site nano alloy particles containing the carbonylation active metal and the hydrogenation active metal can be prepared by adopting conventional impregnation, roasting and reduction means, and then CO and CH are utilized3I, etc. contains halogen to carry out heat treatment on the carbon-supported double-active-site nano particles, and the carbon-supported double-active-site nano particles are subjected to monatomic-level dispersion, so that the double-metal active-site catalyst with methanol carbonylation activity and hydrogenation activity is prepared efficiently, simply and universally.
Disclosure of Invention
A method for preparing acetaldehyde, ethanol and ethyl acetate by methanol reduction carbonylation is characterized in that CO and CH are used3OH、CH3I、H2The method is characterized in that a reductive carbonylation reaction is carried out on the raw materials containing one or two of carbonylation active metal Rh or Ir and one or more of hydrogenation active metal Ru, Pd, Pt and Au under certain reaction conditions, and methanol is directly used for preparing acetaldehyde, ethanol and ethyl acetate in one step.
The mass contents of the carbonylation active metal and the hydrogenation active metal in the catalyst are respectively 0.05-5%; preferably 0.1-3%; more preferably 0.1 to 1%.
The reaction temperature is 100-280 ℃, the pressure is 0.5-8.0 MPa, and CO and CH3The molar ratio of OH is (0.5-3.0): 1, CH3OH and CH3The mass ratio of I (5-20) to H (1)2The molar ratio of the CO to the methanol is (0.1-10): 1, and the liquid hourly space velocity of the methanol is 0.5-10 h-1。
The reductive carbonylation reaction can be carried out in a zirconium material kettle type reactor or a hastelloy fixed bed reactor.
In the catalyst, the carbonylation active metal and the hydrogenation active metal are dispersed on the surface of the carbon carrier in atomic level and are both mononuclear complexes containing carbonyl and halogen ligands. The carbon carrier is coconut shell carbon.
The preparation process of the catalyst comprises the following steps: preparing carbon-loaded double-active-site nano alloy particles, and performing heat treatment on the nano particles by using CO and halogen-containing substances to prepare the active carbon-loaded double-active-site single-atom catalyst. The halogen-containing substance is one or more than two of halogen, halogen acid or halogenated hydrocarbon.
Carbon-carried double-active-site nano alloy particles are prepared by soaking metal precursor liquid on a carbon carrier in equal volume, roasting with nitrogen at 300-500 deg.C, and calcining with H2Reduction (300 ℃ C. -.
The halogen, halogen acid or halogenated alkane used includes Cl2、Br2、I2Etc. halogen, or HCl, HBr, HI or CH3Cl、CH3Br、CH3CH2Br、CH3CH2CH2Br、CH3I、CH3CH2I、CH3CH2CH2I、C6H5One or more than two of I; preferably one or more of bromine, iodine, bromide or iodide, and more preferably one or two of iodine or iodide; the introduction mode of halogen, halogen acid or halogenated alkane can be introduced into a reaction system carried by CO through CO bubbling,or may be introduced into the reaction system by a pump.
Benefits of the present application include, but are not limited to:
(1) the application provides an innovative method for directly preparing acetaldehyde, ethanol and ethyl acetate in one step by methanol reduction carbonylation. The method uses a double-active-site single-atom catalyst which is formed by carbon-supported metal with methanol carbonylation activity and metal with hydrogenation activity. The metal atoms in the catalyst are dispersed on the surface of the carbon carrier in the form of a mononuclear complex of halide or carbonyl halide. The catalyst is used for one-step preparation of ethanol, acetaldehyde and ethyl acetate by reduction and carbonylation of methanol. The catalyst has the advantages of good reaction activity, strong catalyst stability, uniform dispersion, adjustable loading capacity in a wider range, no loss of noble metal, good stability and the like.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, all materials and reagents used in the present application were purchased commercially and were not used directly, and the equipment used was the manufacturer's recommended protocol and parameters.
In the embodiment, after all catalyst evaluation results are stable for 24 hours, a liquid sample in 24 hours is taken, and the liquid phase composition is analyzed by adopting an Agilent 7890B type liquid chromatograph, an FID detector and a capillary column by a normalization method; an Agilent 7890B liquid chromatograph, a TCD detector, a PQ packed column and an internal standard method are adopted to analyze the composition of tail gas, and isobutanol is used as an internal standard substance.
And calculating according to the composition of each product to obtain the product selectivity.
In the examples of the present application, the conversion of the raw material and the selectivity of the product are calculated based on the mole number of the converted methanol carbon.
Example 1
0.27gRhCl is measured3Dissolving in 15ml of deionized water to obtain RhCl3Then 10.0g of coconut charcoal was impregnated. Evaporating the solvent at 90 deg.C, oven drying at 120 deg.C for 8h, roasting at 300 deg.C under nitrogen protection for 4h, and reducing with hydrogen at 300 deg.CObtaining an activated carbon-loaded 1% Rh nano-catalyst which is recorded as sample Rh/AC; then, a mixed atmosphere of carbon monoxide and methyl iodide (pressure: 0.1 MPa; molar ratio CO: CH)3I ═ 2) at 240 ℃ for 2h to give an activated carbon-supported single-site monatomic catalyst, designated sample Rh1and/AC. The prepared catalyst is in an atomic monodisperse state as can be seen by a spherical aberration electron microscope HADDF-STEM, the prepared catalyst does not contain metal-metal bonds as can be seen by X-ray absorption spectrum, and the catalyst prepared on the surface is in atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was passed in at a reaction temperature of 140 ℃ C2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210/CO, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the methanol liquid hourly space velocity is 2h-1The methanol reductive carbonylation reaction was carried out in a fixed bed under the conditions of (1).
Example 2
0.27gRhCl is measured3And 0.27 gGluCl3Dissolving in 15ml of deionized water to obtain RhCl3-RuCl3Then 10.0g of coconut shell charcoal is impregnated. Evaporating the solvent at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing with hydrogen at 300 ℃ for 2h to obtain 1% of Rh-Ru (1:1) nano-catalysts loaded by active carbon; then, a mixed atmosphere of carbon monoxide and methyl iodide (pressure: 0.1 MPa; molar ratio CO: CH)3I ═ 2) at 240 ℃ for 2h, and the resulting activated carbon-supported double active site monatomic catalyst, designated as sample Rh1-Ru1and/AC. The prepared catalyst is in an atomic monodisperse state as can be seen by a spherical aberration electron microscope HADDF-STEM, the prepared catalyst does not contain metal-metal bonds as can be seen by X-ray absorption spectrum, and the catalyst prepared on the surface is in atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was passed in at a reaction temperature of 140 ℃ C2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210/CO, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1Under the conditions ofThe methanol reductive carbonylation reaction was carried out in a fixed bed. Adding CH into a 50ml zirconium high-pressure reaction kettle at 190 ℃ and 6MPa3OH/CH3I-10/1 (mass) mixed solution. Introduction of CO/H2Mixed gas (molar ratio H)2CO 10) to a pressure of 24h at the same time.
Example 3
0.27gRhCl is measured3And 0.53 gGluCl3Dissolving in 15ml of deionized water to obtain RhCl3-RuCl3Then 10.0g of coconut shell charcoal is impregnated. Evaporating the solvent at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing with hydrogen at 300 ℃ for 2h to obtain the active carbon-loaded Rh-Ru (1:2) nano-catalyst with 1% of Rh and 2% of Ru; then using a mixed atmosphere of carbon monoxide and methyl bromide (pressure: 0.1 MPa; molar ratio CO: CH)3Br ═ 2) at 240 ℃ for 2h to give an activated carbon-supported double active site monatomic catalyst, denoted sample Rh2-Ru2and/AC. The prepared catalyst is in an atomic monodisperse state as can be seen by a spherical aberration electron microscope HADDF-STEM, the prepared catalyst does not contain metal-metal bonds as can be seen by X-ray absorption spectrum, and the catalyst prepared on the surface is in atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was passed in at a reaction temperature of 140 ℃ C2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210 of/CO, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1The methanol reductive carbonylation reaction was carried out in a fixed bed under the conditions of (1).
Example 4
0.27gRhCl is measured3And 0.81 gGluCl3Dissolving in 15ml of deionized water to obtain RhCl3-RuCl3Then 10.0g of coconut shell charcoal is impregnated. Evaporating the solvent at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing with hydrogen at 300 ℃ for 2h to obtain the active carbon-loaded Rh-Ru (1:3) nano-catalyst with 1% of Rh and 3% of Ru; then, a mixed atmosphere of carbon monoxide and chloromethane (pressure: 0.1 MPa; molar ratio CO: CH) is used3Cl ═ 2) at 240 ℃ for 2h to give an activated carbon supported double active site single atom catalyst, designated sample Rh3-Ru3and/AC. The catalyst prepared by the HADDF-STEM can be seen to be in an atomic monodispersion state by a spherical aberration electron microscope, the catalyst prepared by the HADDF-STEM does not contain metal-metal bonds by X-ray absorption spectrum, and the catalyst prepared on the surface is in the atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was passed in at a reaction temperature of 140 ℃ C2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210 of/CO, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1The methanol reductive carbonylation reaction was carried out in a fixed bed under the conditions of (1). Adding CH into a 50ml zirconium material high-pressure reaction kettle at 190 ℃ and 6MPa3OH/CH3I-10/1 (mass) mixed solution. Introduction of CO/H2Mixed gas (molar ratio H)2CO 10) to a pressure of 24h at the same time.
Example 5
0.27gRhCl is measured3And 1.35 gGluCl3Dissolving in 15ml of deionized water to obtain RhCl3-RuCl3Then 10.0g of coconut shell charcoal is impregnated. Evaporating the solvent at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing with hydrogen at 300 ℃ for 2h to obtain the active carbon-loaded Rh-Ru (1:5) nano-catalyst with 1% of Rh and 5% of Ru; then treating the mixture for 2 hours at 240 ℃ in a mixed atmosphere of carbon monoxide and hydrogen iodide (pressure is 0.1 MPa; molar ratio CO: HI ═ 2) to obtain an activated carbon supported bimetallic single-atom catalyst, and recording the sample as Rh4-Ru4and/AC. The prepared catalyst is in an atomic monodisperse state as can be seen by a spherical aberration electron microscope HAADF-STEM, the prepared catalyst does not contain metal-metal bonds as can be seen by an X-ray absorption spectrum, and the catalyst prepared on the surface is in a mononuclear complex atomic-level dispersion of carbonyl halide. Subsequently, H was passed in at a reaction temperature of 140 ℃ C2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210 of/CO, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1The methanol reductive carbonylation reaction was carried out in a fixed bed under the conditions of (1). Adding CH into a 50ml zirconium high-pressure reaction kettle at 190 ℃ and 6MPa3OH/CH3I-10/1 (mass) mixed solution. Introduction of CO/H2Mixed gas (molar ratio H)2CO 10) to a pressure of
The reaction is carried out for 24 hours for methanol reduction carbonylation.
Example 6
0.36g of IrCl is measured out3Dissolving in 15ml of deionized water to obtain IrCl3Then 10.0g of coconut shell charcoal is impregnated. Evaporating the solvent at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing with hydrogen at 300 ℃ for 2h to obtain an active carbon-loaded 1% Ir nano catalyst; then treating the mixture for 2 hours at 240 ℃ in a mixed atmosphere of carbon monoxide and hydrogen bromide (pressure is 0.1 MPa; molar ratio CO: HBr ═ 2) to obtain an activated carbon supported single-active-site single-atom catalyst, and marking as a sample Ir1and/AC. The prepared catalyst is in an atomic monodisperse state as can be seen by a spherical aberration electron microscope HADDF-STEM, the prepared catalyst does not contain metal-metal bonds as can be seen by X-ray absorption spectrum, and the catalyst prepared on the surface is in atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was passed in at a reaction temperature of 140 ℃ C2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210 of/CO, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1The methanol reductive carbonylation reaction was carried out in a fixed bed under the conditions of (1).
Example 7
0.36g of IrCl is measured out3And 0.27 gGluCl3Dissolving in 15ml of deionized water to obtain IrCl3-RuCl3Then 10.0g of coconut shell charcoal is impregnated. Evaporating the solvent at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing with hydrogen at 300 ℃ for 2h to obtain an active carbon-loaded Ir-Ru (1:1) nano catalyst with the content of 1% Ir and 1% Ru; then using a mixed atmosphere of carbon monoxide and hydrogen chloride(pressure: 0.1 MPa; molar ratio CO: HCl ═ 2) at 240 ℃ for 2h to give an activated carbon-supported double-active-site monoatomic catalyst, denoted as sample Ir1-Ru1and/AC. The prepared catalyst is in an atomic monodisperse state as can be seen by a spherical aberration electron microscope HADDF-STEM, the prepared catalyst does not contain metal-metal bonds as can be seen by X-ray absorption spectrum, and the catalyst prepared on the surface is in atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was passed in at a reaction temperature of 140 ℃ C2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210 of/CO, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1The methanol reductive carbonylation reaction was carried out in a fixed bed under the conditions of (1).
Example 8
0.36g of IrCl is measured out3And 0.81 gGluCl3Dissolving in 15ml of deionized water to obtain IrCl3-RuCl3Then 10.0g of coconut shell charcoal is impregnated. Evaporating the solvent at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing with hydrogen at 300 ℃ for 2h to obtain an active carbon-loaded Ir-Ru (1:3) nano catalyst with the content of 1% Ir and 3% Ru; then, a mixed atmosphere of carbon monoxide and chlorine (pressure: 0.1 MPa; molar ratio CO: Cl) is used22) at 240 ℃ for 2h to obtain an activated carbon supported double-active-site single-atom catalyst, which is recorded as a sample Ir2-Ru2and/AC. The prepared catalyst is in an atomic monodisperse state as can be seen by a spherical aberration electron microscope HADDF-STEM, the prepared catalyst does not contain metal-metal bonds as can be seen by X-ray absorption spectrum, and the catalyst prepared on the surface is in atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was passed in at a reaction temperature of 140 ℃ C2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210 of/CO, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1The methanol reductive carbonylation reaction was carried out in a fixed bed under the conditions of (1). Adding CH into a 50ml zirconium high-pressure reaction kettle at 190 ℃ and 6MPa3OH/CH3I-10/1 (mass) mixed solution. Introduction of CO/H2Mixed gas (molar ratio H)210/CO) to 24h of pressure reaction.
Example 9
0.36g of IrCl is measured out3And 1.35 gGluCl3Dissolving in 15ml of deionized water to obtain RhCl3-RuCl3Then 10.0g of coconut shell charcoal is impregnated. Evaporating the solvent at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing with hydrogen at 300 ℃ for 2h to obtain an active carbon-loaded Ir-Ru (1:5) nano catalyst with the content of 1% Ir and 5% Ru; then, a mixed atmosphere of carbon monoxide and iodoethane (pressure: 0.1 MPa; molar ratio CO: CH) is used3CH2I-2) at 240 ℃ for 2h to obtain the active carbon supported double-active-site single-atom catalyst which is marked as a sample Ir3-Ru3and/AC. The prepared catalyst is in an atomic monodisperse state as can be seen by a spherical aberration electron microscope HADDF-STEM, the prepared catalyst does not contain metal-metal bonds as can be seen by X-ray absorption spectrum, and the catalyst prepared on the surface is in atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was passed in at a reaction temperature of 140 ℃ C2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210 of/CO, molar ratio CO/CH3OH 1, mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1The methanol reductive carbonylation reaction was carried out in a fixed bed under the conditions of (1).
Example 10
0.18g of PdCl is measured out2Dissolving in 15ml of deionized water to obtain PdCl2Then 10.0g of coconut shell charcoal (specific surface area 1000 m) is impregnated2(ii)/g; average pore diameter 1.6 nm). Evaporating the solvent at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing with hydrogen at 300 ℃ for 2h to obtain an activated carbon-supported 1% Pd nano-catalyst; then, a mixed atmosphere of carbon monoxide and iodobenzene (pressure: 0.1 MPa; molar ratio CO: C)6H5I ═ 2) at 240 ℃ for 2h, giving an activated carbon-supported single-site monatomic catalyst, noted as sample Pd1and/AC. The prepared catalyst is in an atomic monodisperse state as can be seen by a spherical aberration electron microscope HADDF-STEM, the prepared catalyst does not contain metal-metal bonds as can be seen by X-ray absorption spectrum, and the catalyst prepared on the surface is in atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was passed in at a reaction temperature of 140 ℃ C2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210 of/CO, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1The methanol reductive carbonylation reaction was carried out in a fixed bed under the conditions of (1).
Example 11
0.27gRhCl is measured3And 0.18gPdCl2Dissolving in 15ml of deionized water to obtain RhCl3-PdCl2Then 10.0g of coconut shell charcoal (specific surface area 1000 m) is impregnated2(iv) g; average pore diameter 1.6 nm). Evaporating the solvent at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing with hydrogen at 300 ℃ for 2h to obtain the Rh-Pd nano-catalyst with 1% Rh and 1% Pd respectively on the activated carbon; then, a mixed atmosphere of carbon monoxide and bromoethane (pressure: 0.1 MPa; molar ratio CO: CH) is used3CH2Br ═ 2) at 240 ℃ for 2h, and the resulting activated carbon-supported double active site monatomic catalyst, designated as sample Rh1-Pd1and/AC. The prepared catalyst is in an atomic monodisperse state as can be seen by a spherical aberration electron microscope HADDF-STEM, the prepared catalyst does not contain metal-metal bonds as can be seen by X-ray absorption spectrum, and the catalyst prepared on the surface is in atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was passed in at a reaction temperature of 140 ℃ C2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210/CO, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1The methanol reductive carbonylation reaction was carried out in a fixed bed under the conditions of (1). Adding CH into a 50ml zirconium high-pressure reaction kettle at 190 ℃ and 6MPa3OH/CH3I-10/1 (mass) mixed solution. Introduction of CO/H2Mixed gas (molar ratio H)210/CO) to pressure for 24h to carry out the methanol reductive carbonylation reaction.
Example 12
0.36g of IrCl is measured out3And 0.18gPdCl2Dissolved in 15ml of deionized water to obtain IrCl3-PdCl2Then 10.0g of coconut shell charcoal (specific surface area 1000 m) is impregnated2(ii)/g; average pore diameter 1.6 nm). Evaporating the solvent at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing with hydrogen at 300 ℃ for 2h to obtain an Ir-Pd nano catalyst with 1% of Ir and 1% of Pd loaded on active carbon; then, a mixed atmosphere of carbon monoxide and bromoethane (pressure: 0.1 MPa; molar ratio CO: CH) is used3CH2Br ═ 2) at 240 ℃ for 2h, and the resulting activated carbon-supported dual active site monatomic catalyst, designated as sample Ir1-Pd1and/AC. The catalyst prepared by the HADDF-STEM can be seen to be in an atomic monodispersion state by a spherical aberration electron microscope, the catalyst prepared by the HADDF-STEM does not contain metal-metal bonds by X-ray absorption spectrum, and the catalyst prepared on the surface is in the atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was fed in at a reaction temperature of 140 ℃2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210 of/CO, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the methanol liquid hourly space velocity is 2h-1The methanol reductive carbonylation reaction was carried out in a fixed bed under the conditions of (1). Adding CH into a 50ml zirconium high-pressure reaction kettle at 190 ℃ and 6MPa3OH/CH3I-10/1 (mass) mixed solution. Introduction of CO/H2Mixed gas (molar ratio H)210/CO) to 24h of pressure reaction.
Example 13
Measuring 0.44gH2PtCl4·6H2O was dissolved in 15ml of deionized water to give H2PtCl4Then 10.0g of coconut shell charcoal (specific surface area 1000 m) is impregnated2(ii)/g; average pore diameter 1.6 nm). Evaporating the solvent at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, then reducing by hydrogen at 300 ℃ for 2h,obtaining the Pt nano catalyst with 1 percent of activated carbon load; then, a mixed atmosphere of carbon monoxide and iodopropane (pressure: 0.1 MPa; molar ratio CO: CH) is used3CH2CH2I ═ 2) at 240 ℃ for 2h to give an activated carbon-supported monometallic monatomic catalyst, designated as sample Pt1and/AC. The prepared catalyst is in an atomic monodisperse state as can be seen by a spherical aberration electron microscope HADDF-STEM, the prepared catalyst does not contain metal-metal bonds as can be seen by X-ray absorption spectrum, and the catalyst prepared on the surface is in atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was passed in at a reaction temperature of 140 ℃ C2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210 of/CO, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1The methanol reductive carbonylation reaction was carried out in a fixed bed under the conditions of (1).
Example 14
0.27gRhCl is measured3And 1.32gH2PtCl4·6H2Dissolving O in 15ml of deionized water to obtain RhCl3-H2PtCl4Then 10.0g of coconut shell charcoal (specific surface area 1000 m) is impregnated2(ii)/g; average pore diameter 1.6 nm). Evaporating the solvent at 90 ℃, drying in a 120 ℃ oven for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing for 2h with hydrogen at 300 ℃ to obtain the Rh-Pt nano catalyst with 1% of Rh and 1% of Pt loaded on the activated carbon; then, a mixed atmosphere of carbon monoxide and bromopropane (pressure: 0.1 MPa; molar ratio CO: CH) is used3CH2CH2Br ═ 2) at 240 ℃ for 2h to give an activated carbon-supported double active site monatomic catalyst, denoted sample Rh1-Pt1and/AC. The prepared catalyst is in an atomic monodisperse state as can be seen by a spherical aberration electron microscope HADDF-STEM, the prepared catalyst does not contain metal-metal bonds as can be seen by X-ray absorption spectrum, and the catalyst prepared on the surface is in atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was passed in at a reaction temperature of 140 ℃ C2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210 of/CO, molar ratio CO/CH3OH 1, massBiCH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the methanol liquid hourly space velocity is 2h-1The methanol reductive carbonylation reaction was carried out in a fixed bed under the conditions of (1).
Example 15
0.36g of IrCl is measured out3And 1.32gH2PtCl4·6H2O is dissolved in 15ml of deionized water to obtain IrCl3-H2PtCl4Then 10.0g of coconut shell charcoal (specific surface area 1000 m) is impregnated2(ii)/g; average pore diameter 1.6 nm). Evaporating the solvent at 90 ℃, drying in a 120 ℃ oven for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing for 2h by using hydrogen at 300 ℃ to obtain an Ir-Pt nano catalyst with 1% of Ir and 1% of Pt loaded on the activated carbon; then, a mixed atmosphere of carbon monoxide and bromopropane (pressure: 0.1 MPa; molar ratio CO: CH) is used3CH2CH2Br ═ 2) at 240 ℃ for 2h to give an activated carbon-supported double-active-site monoatomic catalyst, which was designated as sample Ir1-Pt1and/AC. The prepared catalyst is in an atomic monodisperse state as can be seen by a spherical aberration electron microscope HADDF-STEM, the prepared catalyst does not contain metal-metal bonds as can be seen by X-ray absorption spectrum, and the catalyst prepared on the surface is in atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was passed in at a reaction temperature of 140 ℃ C2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210 of/CO, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1The methanol reductive carbonylation reaction was carried out in a fixed bed under the conditions of (1). Adding CH into a 50ml zirconium high-pressure reaction kettle at 190 ℃ and 6MPa3OH/CH3I-10/1 (mass) mixed solution. Introduction of CO/H2Mixed gas (molar ratio H)210/CO) to 24h under pressure.
Example 16
0.40g of HAuCl was measured out4·4H2O was dissolved in 15ml of deionized water to give HAuCl4Then 10.0g of coconut shell charcoal (specific surface area 1000 m) was impregnated2(ii)/g; average pore diameter 1.6 nm). 90Evaporating the solvent, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing with hydrogen at 300 ℃ for 2h to obtain an Au nano catalyst with 1% of activated carbon load, and recording as a sample Au/AC; then using a mixed atmosphere of carbon monoxide and methyl iodide (pressure: 0.1 MPa; molar ratio CO: CH)3I ═ 2) at 240 ℃ for 2h to give an activated carbon-supported single-site monatomic catalyst, denoted as sample Au1and/AC. The prepared catalyst is in an atomic monodisperse state as can be seen by a spherical aberration electron microscope HADDF-STEM, the prepared catalyst does not contain metal-metal bonds as can be seen by X-ray absorption spectrum, and the catalyst prepared on the surface is in atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was passed in at a reaction temperature of 140 ℃ C2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210 of/CO, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1Under the conditions of (1) carrying out a methanol reductive carbonylation reaction in a fixed bed.
Example 17
0.27gRhCl is measured3And 1.20g of HAuCl4·4H2Dissolving O in 15ml of deionized water to obtain RhCl3-HAuCl4Then 10.0g of coconut shell charcoal (specific surface area 1000 m) is impregnated2(ii)/g; average pore diameter 1.6 nm). Evaporating the solvent at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing with hydrogen at 300 ℃ for 2h to obtain the Rh-Au nano catalyst with activated carbon loaded with 1% of Rh and 1% of Au; then, a mixed atmosphere of carbon monoxide and methyl iodide (pressure: 0.1 MPa; molar ratio CO: CH)3I ═ 2) at 240 ℃ for 2h, giving an activated carbon-supported double active site monoatomic catalyst, denoted sample Rh1-Au1and/AC. The prepared catalyst is in an atomic monodisperse state as can be seen by a spherical aberration electron microscope HADDF-STEM, the prepared catalyst does not contain metal-metal bonds as can be seen by X-ray absorption spectrum, and the catalyst prepared on the surface is in atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was fed in at a reaction temperature of 140 ℃2Mixed gas of CO, methanol and methyl iodide (molar ratio H)2/CO＝10, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1Under the conditions of (1) carrying out a methanol reductive carbonylation reaction in a fixed bed. Adding CH into a 50ml zirconium high-pressure reaction kettle at 190 ℃ and 6MPa3OH/CH3I-10/1 (mass) mixed solution. Introduction of CO/H2Mixed gas (molar ratio H)210/CO) to 24h of pressure reaction.
Example 18
0.36g of IrCl is metered in3And 1.20g of HAuCl4·4H2O is dissolved in 15ml of deionized water to obtain IrCl3-HAuCl4Then 10.0g of coconut shell charcoal (specific surface area 1000 m) is impregnated2(ii)/g; average pore diameter 1.6 nm). Evaporating the solvent at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, and then reducing with hydrogen at 300 ℃ for 2h to obtain an Ir-Au nano catalyst with 1% of Ir and 1% of Au loaded on activated carbon; then, a mixed atmosphere of carbon monoxide and methyl iodide (pressure: 0.1 MPa; molar ratio CO: CH)3I ═ 2) at 240 ℃ for 2h, giving an activated carbon-supported double active site monoatomic catalyst, denoted as sample Ir1-Au1and/AC. The catalyst prepared by the HADDF-STEM can be seen to be in an atomic monodispersion state by a spherical aberration electron microscope, the catalyst prepared by the HADDF-STEM does not contain metal-metal bonds by X-ray absorption spectrum, and the catalyst prepared on the surface is in the atomic-level dispersion of a mononuclear complex of carbonyl halide. Subsequently, H was fed in at a reaction temperature of 140 ℃2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210/CO, molar ratio CO/CH3OH 1, mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1The methanol reductive carbonylation reaction was carried out in a fixed bed under the conditions of (1). Adding CH into a 50ml zirconium high-pressure reaction kettle at 190 ℃ and 6MPa3OH/CH3I-10/1 (mass) mixed solution. Introduction of CO/H2Mixed gas (molar ratio H)210/CO) to pressure for 24h to carry out the methanol reductive carbonylation reaction.
Application of catalyst in reduction carbonylation of methanol
The catalyst is applied to the application of heterogeneous reduction carbonylation of methanol.
Fixed bed reaction conditions: 0.5g of the catalyst in the example, having an average particle size of 500 μm, was placed in the middle of the reaction in a fixed bed quartz tube, and 20-40 mesh quartz sand was charged into both ends. Introducing CO and H into the reactor before the catalyst is used2Mixed gas (molar ratio CO/H)24), mixed gas GHSV of 7500h-1Carrying out in-situ reduction activation under the conditions of: the temperature was raised from room temperature to 240 ℃ at a rate of 5 ℃/min under normal pressure and held for 1 hour. At a reaction temperature of 140 ℃, H is introduced2Mixed gas of CO, methanol and methyl iodide (molar ratio H)210/CO, molar ratio CO/CH3OH 1 and mass ratio CH3OH/CH3I is 10/1), the reaction pressure is 6.0MPa, and the hourly space velocity of methanol liquid is 2h-1The reaction was stable for 24 h.
Reaction conditions of the kettle reactor: 0.5g of the catalyst in the example, having an average particle diameter of 500 μm, was placed in a zirconium autoclave (50ml) equipped with a magnetic stirring rod and an automatic temperature controller, and charged with magnetons. Measuring appropriate amount of methanol and iodomethane (mass ratio CH)3OH/CH3I-10/1) was charged into the kettle. Introduction of CO/H2Mixed gas (molar ratio H)2CO ═ 10) to a pressure of 6MPa, and reacted at 190 ℃ for 24 h.
The reaction results were as follows:
note: denotes the reaction results of the catalysts in the respective examples in the tank reactor. Reduction of the carbonylation product: comprises ethyl acetate, acetaldehyde, ethanol, methanol carbonylation reaction products acetic acid and methyl acetate.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (9)
1. A method for preparing acetaldehyde, ethanol and ethyl acetate by methanol reduction carbonylation is characterized in that CO and CH are used3OH、CH3I、H2The method comprises the steps of taking the raw materials as reaction raw materials, carrying out reductive carbonylation reaction in the presence of one or two of carbonylation active metal Rh or Ir and one or more of hydrogenation active metal Ru, Pd, Pt and Au under certain reaction conditions, and directly preparing acetaldehyde, ethanol and ethyl acetate from methanol in one step.
2. The method according to claim 1, wherein the mass contents of the carbonylation active metal and the hydrogenation active metal in the catalyst are respectively 0.05-5%; preferably 0.1-3%; more preferably 0.1 to 1%.
3. The method according to claim 1 or 2, wherein the reaction temperature is 100 to 280 ℃, the pressure is 0.5 to 8.0MPa, and the CO and CH are present3The molar ratio of OH is (0.5-3.0): 1, CH3OH and CH3The mass ratio of I (5-20) to H (1)2The molar ratio of the CO to the methanol is (0.1-10): 1, and the liquid hourly space velocity of the methanol is 0.5-10 h-1。
4. The process of claim 1, wherein the reductive carbonylation reaction is carried out in a zirconium tank reactor or a hastelloy fixed bed reactor.
5. The process of claim 2, wherein the carbonylation active metal and the hydrogenation active metal are atomically dispersed on the carbon support and are each a mononuclear complex containing a carbonyl and a halogen ligand.
6. The method of claim 2, wherein the catalyst is prepared by: preparing carbon-supported double-active-site (wherein one or two of carbonylation active metal Rh or Ir and one or more of hydrogenation active metal Ru, Pd, Pt and Au exist) nano alloy particles, and then carrying out heat treatment on the nano particles by utilizing CO and halogen-containing substances to prepare an active carbon-supported double-active-site single-atom catalyst; the halogen-containing substance is one or more than two of halogen, halogen acid or halogenated hydrocarbon.
7. The method of claim 6, wherein: carbon-carried double-active-site nano alloy particles are prepared by soaking metal precursor liquid on a carbon carrier in equal volume, roasting with nitrogen at 300-500 deg.C, and calcining with H2Reduction (300 ℃ C. -.
8. The method of claim 6, wherein: the halogen, halogen acid or halogenated alkane used includes Cl2、Br2、I2Etc. halogen, or HCl, HBr, HI or CH3Cl、CH3Br、CH3CH2Br、CH3CH2CH2Br、CH3I、CH3CH2I、CH3CH2CH2I、C6H5One or more than two of I; preferably one or more of bromine, iodine, bromide or iodide, and more preferably one or two of iodine or iodide; the halogen, the halogen acid or the halogenated alkane can be introduced into the reaction system by CO carried by bubbling or by a pump.
9. The method of claim 6, wherein: the heat treatment conditions are that the temperature is 100-350 ℃, the pressure is 0.1-3.0 MPa, the molar ratio of CO to halogen-containing substances (one or more than two of halogen, halogen acid or halogenated hydrocarbon) is 0.1-10, and the treatment time is 10 min-10 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011322345.0A CN114524719A (en) | 2020-11-23 | 2020-11-23 | Method for preparing acetaldehyde, ethanol and ethyl acetate by methanol reduction carbonylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011322345.0A CN114524719A (en) | 2020-11-23 | 2020-11-23 | Method for preparing acetaldehyde, ethanol and ethyl acetate by methanol reduction carbonylation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114524719A true CN114524719A (en) | 2022-05-24 |
Family
ID=81619332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011322345.0A Pending CN114524719A (en) | 2020-11-23 | 2020-11-23 | Method for preparing acetaldehyde, ethanol and ethyl acetate by methanol reduction carbonylation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114524719A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115709072A (en) * | 2022-11-17 | 2023-02-24 | 陕西延长石油（集团）有限责任公司 | Catalyst for catalyzing carbonylation of methanol to prepare acetic acid, preparation method and application thereof |
| CN116082120A (en) * | 2022-11-25 | 2023-05-09 | 中国科学院大连化学物理研究所 | Technological method and device for preparing ethanol by continuous reaction of methanol |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0131998A1 (en) * | 1983-07-06 | 1985-01-23 | Shell Internationale Researchmaatschappij B.V. | Process for the preparation of ethanol and/or ethyl acetate |
| US4727200A (en) * | 1987-03-27 | 1988-02-23 | Union Carbide Corporation | Alcohol homologation |
| EP0636599A1 (en) * | 1993-07-27 | 1995-02-01 | Korea Institute Of Science And Technology | Process for the carbonylation of methanol to form acetic acid, methyl acetate and acetic anhydride |
| US5414161A (en) * | 1992-06-30 | 1995-05-09 | Korea Institute Of Science And Technology | Process for the preparation of ethanol from methanol |
| US20130143972A1 (en) * | 2011-12-02 | 2013-06-06 | Celanese International Corporation | Biomass gasification and integrated processes for making industrial chemicals through an acetic acid intermediate |
| CN104892360A (en) * | 2014-03-04 | 2015-09-09 | 中国科学院大连化学物理研究所 | Method for preparing ethanol through catalytic conversion of methanol |
| CN111195532A (en) * | 2018-11-20 | 2020-05-26 | 中国科学院大连化学物理研究所 | Atomic-level monodisperse iridium-based catalyst, preparation method thereof and application of atomic-level monodisperse iridium-based catalyst in preparation of methyl acetate through methanol gas-phase carbonylation |
| CN111195516A (en) * | 2018-11-20 | 2020-05-26 | 中国科学院大连化学物理研究所 | Atomic-level monodisperse rhodium-based catalyst, preparation method thereof and application of atomic-level monodisperse rhodium-based catalyst in preparation of methyl acetate through methanol gas-phase carbonylation |
-
2020
- 2020-11-23 CN CN202011322345.0A patent/CN114524719A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0131998A1 (en) * | 1983-07-06 | 1985-01-23 | Shell Internationale Researchmaatschappij B.V. | Process for the preparation of ethanol and/or ethyl acetate |
| US4727200A (en) * | 1987-03-27 | 1988-02-23 | Union Carbide Corporation | Alcohol homologation |
| US5414161A (en) * | 1992-06-30 | 1995-05-09 | Korea Institute Of Science And Technology | Process for the preparation of ethanol from methanol |
| EP0636599A1 (en) * | 1993-07-27 | 1995-02-01 | Korea Institute Of Science And Technology | Process for the carbonylation of methanol to form acetic acid, methyl acetate and acetic anhydride |
| US20130143972A1 (en) * | 2011-12-02 | 2013-06-06 | Celanese International Corporation | Biomass gasification and integrated processes for making industrial chemicals through an acetic acid intermediate |
| CN104892360A (en) * | 2014-03-04 | 2015-09-09 | 中国科学院大连化学物理研究所 | Method for preparing ethanol through catalytic conversion of methanol |
| CN111195532A (en) * | 2018-11-20 | 2020-05-26 | 中国科学院大连化学物理研究所 | Atomic-level monodisperse iridium-based catalyst, preparation method thereof and application of atomic-level monodisperse iridium-based catalyst in preparation of methyl acetate through methanol gas-phase carbonylation |
| CN111195516A (en) * | 2018-11-20 | 2020-05-26 | 中国科学院大连化学物理研究所 | Atomic-level monodisperse rhodium-based catalyst, preparation method thereof and application of atomic-level monodisperse rhodium-based catalyst in preparation of methyl acetate through methanol gas-phase carbonylation |
Non-Patent Citations (1)
| Title |
|---|
| 陈英赞等: ""较温和条件下甲醇还原羰基化制乙醇研究"", 《天然气化工—C1化学与化工》, vol. 43, pages 43 - 49 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115709072A (en) * | 2022-11-17 | 2023-02-24 | 陕西延长石油（集团）有限责任公司 | Catalyst for catalyzing carbonylation of methanol to prepare acetic acid, preparation method and application thereof |
| CN115709072B (en) * | 2022-11-17 | 2023-08-18 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing acetic acid by catalyzing methanol carbonylation and preparation method and application thereof |
| CN116082120A (en) * | 2022-11-25 | 2023-05-09 | 中国科学院大连化学物理研究所 | Technological method and device for preparing ethanol by continuous reaction of methanol |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111195515B (en) | Monoatomic dispersion noble metal catalyst, preparation method and application thereof | |
| Ciriminna et al. | Industrial applications of gold catalysis | |
| CN103896768B (en) | A kind of method preparing methyl acetate | |
| Gholinejad et al. | Applications of bimetallic PdCu catalysts | |
| EP3092072B1 (en) | A process for vapor-phase methanol carbonylation to methyl formate | |
| Grass et al. | Dependence of gas-phase crotonaldehyde hydrogenation selectivity and activity on the size of Pt nanoparticles (1.7–7.1 nm) supported on SBA-15 | |
| CN103896769B (en) | A kind of method of preparing methyl acetate by carbonylating dimethyl ether | |
| EP1755780A1 (en) | A catalyst and process for the synthesis of c2-oxygenates by the hydrogenation of carbon monoxide | |
| CN114524719A (en) | Method for preparing acetaldehyde, ethanol and ethyl acetate by methanol reduction carbonylation | |
| Guo et al. | Ru nanoparticles stabilized by ionic liquids supported onto silica: highly active catalysts for low-temperature CO 2 methanation | |
| Kim et al. | Ordered mesoporous carbon supported uniform rhodium nanoparticles as catalysts for higher alcohol synthesis from syngas | |
| CN114950419B (en) | Metal catalyst for preparing methanol by carbon dioxide hydrogenation and application thereof | |
| Zhang et al. | In situ topologically induced PtZn alloy@ ZnTiOx and the synergistic effect on glycerol oxidation | |
| CN105457631A (en) | Catalyst for preparing ethyl alcohol acid ester through oxalic ester gas phase hydrogenation and preparation method | |
| CN114522682A (en) | Carbon-supported bimetallic monatomic catalyst and preparation method thereof | |
| CN110665546A (en) | Noble metal/amino MOFs selective hydrogenation catalyst, preparation method and application thereof | |
| Sohrabi et al. | In-situ one-step deposition of highly dispersed palladium nanoparticles into zirconium metal–organic framework for selective hydrogenation of furfural | |
| Kip et al. | Preparation and characterization of very highly dispersed iridium on Al2O3 and SiO2 | |
| Humayun et al. | Metal oxides confine single atoms toward efficient thermal catalysis | |
| Pan et al. | The cooperation effect of Ni and Pt in the hydrogenation of acetic acid | |
| Zhang et al. | Effects of metal size on supported catalysts for CO 2 hydrogenation | |
| CN114534724A (en) | Method for preparing acetic acid and acetic ester by halogen-free gas-phase carbonylation of methanol | |
| CN114539056B (en) | Method for preparing methyl acetate by methanol carbonylation | |
| CN114522683B (en) | Carbon-supported Pd-M bimetallic single-atom catalyst and application thereof in C2H2Application in double carbonylation reaction | |
| CN112898149B (en) | Method for preparing acetic acid by low-temperature catalytic oxidation of ethane with monatomic catalyst |
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 |