CN113072421A - Preparation method of deuterated ethanol - Google Patents
Preparation method of deuterated ethanol Download PDFInfo
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- CN113072421A CN113072421A CN202110204015.XA CN202110204015A CN113072421A CN 113072421 A CN113072421 A CN 113072421A CN 202110204015 A CN202110204015 A CN 202110204015A CN 113072421 A CN113072421 A CN 113072421A
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- deuterated ethanol
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- LFQSCWFLJHTTHZ-LIDOUZCJSA-N ethanol-d6 Chemical compound [2H]OC([2H])([2H])C([2H])([2H])[2H] LFQSCWFLJHTTHZ-LIDOUZCJSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 239000007789 gas Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 15
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052703 rhodium Inorganic materials 0.000 claims description 11
- 239000010948 rhodium Substances 0.000 claims description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 239000010431 corundum Substances 0.000 claims description 8
- 229910052573 porcelain Inorganic materials 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000009833 condensation Methods 0.000 abstract description 5
- 230000005494 condensation Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000011112 process operation Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000009509 drug development Methods 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002558 medical inspection Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- 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
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
- C07B59/001—Acyclic or carbocyclic compounds
-
- 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
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
- C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
- C07C29/158—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof containing rhodium or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/05—Isotopically modified compounds, e.g. labelled
Abstract
The invention relates to a preparation method of deuterated ethanol, belonging to the technical field of preparation of deuterated chemicals. Under the action of a catalyst, the mixed gas of deuterium gas, carbon monoxide and nitrogen reacts at the pressure of 4 MPa-8 MPa and the temperature of 230-300 ℃, and the reaction product is subjected to condensation gas-liquid separation and rectification treatment to obtain the deuterated ethanol with the chemical purity and the deuterated rate both greater than 99.8%. The method has the advantages of easily obtained raw materials, simple process operation, low equipment investment, high conversion rate, less side reaction and high purity, is suitable for fine industrial production of the deuterated ethanol, and has good application prospect.
Description
Technical Field
The invention relates to a preparation method of deuterated ethanol, belonging to the technical field of preparation of deuterated chemicals.
Background
Deuterated ethanol, molecular formula CD3CD2OD is ethanol (CH)3 CH2OH) is replaced by deuterium (D), which is one of the deuterated chemicals, and is a chemical with special physicochemical properties. The deuterated chemicals are mainly applied to the fields of nuclear magnetic resonance spectrometers (NMR), tracers, medical inspection, optical fibers, deuterated drugs, semiconductors, OLEDs, nuclear energy, high polymer material modification, agricultural breeding, neutron logging and the like. In particular, in recent years, nuclear magnetic resonance has been increasingly important in the fields of chemistry and chemistry, biochemistry, and medicine, and is most widely used in the fields of proteomics/chromonomy and pharmaceutical research. Because the deuterated reagent is an indispensable solvent for nuclear magnetic resonance testing work. The magnetic field strength inside the nuclear magnetism requires very accurate locking, while the deuterated reagent is mainly used for locking the field in the nuclear magnetism. Because the deuterated drugs can improve the safety of the drugs and have the pharmacokinetic advantage, the deuterated drugs are a new direction for drug development, and accordingly, the demand of deuterated ethanol is increasing day by day.
At present, the preparation method of the deuterated ethanol in China is very limited, and the deuterated ethanol product basically depends on import. Chinese patent CN110545911A discloses a method for preparing a catalyst from acetic acid, acetate or amide by reacting with D in the presence of a transition metal catalyst2A method for preparing deuterated ethanol by reaction. Chinese patent CN110545912A discloses a composite material of ethanol and D2O, ruthenium catalyst and cosolvent. The catalyst raw material cost related to the preparation of the deuterated ethanol by the method is high, the conditions are strict, and the method is only suitable for a small amount of raw materials in a laboratoryAnd (4) producing.
Disclosure of Invention
Aiming at the problems existing in the conventional preparation of the deuterated ethanol, the invention provides the preparation method of the deuterated ethanol, which has the advantages of easily obtained raw materials, low cost, simple process operation, high conversion rate, less side reaction and high purity, and meets the requirement of industrial production of the deuterated ethanol.
The purpose of the invention is realized by the following technical scheme.
A preparation method of deuterated ethanol comprises the following steps:
introducing mixed gas of deuterium gas, carbon monoxide and nitrogen into a fixed bed reactor filled with a catalyst, reacting at the pressure of 4 MPa-8 MPa and the temperature of 230-300 ℃, condensing, carrying out gas-liquid separation on reaction products, collecting liquid, and rectifying the collected liquid to obtain the deuterated ethanol with the chemical purity and the deuterated rate both higher than 99.8%.
The catalyst consists of active components and a carrier, wherein the active components are two or more of rhodium, copper, cobalt, platinum and iron, and the carrier is silicon oxide, aluminum oxide, titanium dioxide or graphitized carbon.
Further, the active components of the catalyst are rhodium, copper, cobalt, platinum and iron; wherein, the total mass of the catalyst is 100%, the mass percentages of the components in the catalyst are as follows: 0.5 to 5 percent of rhodium, 2 to 10 percent of copper, 1 to 5 percent of cobalt, 3 to 8 percent of platinum, 2 to 6 percent of iron and the balance of carrier.
Furthermore, the fixed bed reactor is also filled with filler, and the filler is inert corundum porcelain balls or copper particles.
Further, in the fixed bed reactor, the mass loading ratio of the catalyst to the filler is (1-2): (2-3).
Further, the mol ratio of deuterium gas, carbon monoxide and nitrogen gas is (2-8): 1: (1-4), the unreacted gas can be recycled.
Further, a mixed gas of deuterium, carbon monoxide and nitrogen passes through the catalyst layer in the fixed bed reactor at a rate of 10L/s to 15L/s.
Further, the condensation temperature for condensing gas-liquid separation is 0-10 ℃.
Further, in the rectification process, the temperature of the tower kettle is 95-115 ℃, and the temperature of the tower top is 76-79 ℃.
Has the advantages that:
the method has the advantages of easily obtained raw materials, simple process operation, low equipment investment, high conversion rate, less side reaction and high purity, and can obtain the deuterated ethanol with the chemical purity and the deuterated rate both greater than 99.8 percent through simple condensation and rectification treatment, wherein the conversion rate reaches more than 60 percent.
Detailed Description
The present invention is further illustrated by the following detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public source without further specification.
Example 1
Filling a catalyst and inert corundum porcelain balls into a fixed bed reactor according to the mass ratio of 1:1 to form a catalyst layer, preparing mixed gas from deuterium gas, carbon monoxide and nitrogen according to the molar ratio of 2:1:1, enabling the mixed gas to pass through the catalyst layer at the speed of 10L/s, reacting at the pressure of 5MPa and the temperature of (250 +/-5) DEG C, cooling reaction products by using condensed circulating water at the temperature of 10 ℃ to realize gas-liquid separation, collecting liquid, transferring the collected liquid into a rectifying tower for rectification, wherein the temperature of a tower bottom of the rectifying tower is 100-110 ℃ and the temperature of a tower top is 76-79 ℃, and after rectification, collecting deuterated ethanol with the chemical purity of 99.83 wt%, the deuterated rate is 99.84%, and the total conversion rate is 62% measured by using a carbon monoxide meter.
Wherein, the total mass of the catalyst is 100%, the components and the mass percentages of the components are as follows: 0.5% of rhodium, 2% of copper, 1% of cobalt, 3% of platinum, 2% of iron and the balance of an alumina carrier.
Example 2
Filling a catalyst and inert corundum porcelain balls into a fixed bed reactor according to the mass ratio of 1:1 to form a catalyst layer, preparing mixed gas from deuterium gas, carbon monoxide and nitrogen according to the molar ratio of 4:1:1, enabling the mixed gas to pass through the catalyst layer at the speed of 12L/s, reacting at the pressure of 6MPa and the temperature of (260 +/-5) DEG C, cooling reaction products by using condensed circulating water at the temperature of 10 ℃ to realize gas-liquid separation, collecting liquid, transferring the collected liquid into a rectifying tower for rectification, wherein the temperature of the bottom of the rectifying tower is 100-110 ℃ and the temperature of the top of the rectifying tower is 76-79 ℃, and after rectification, collecting deuterated ethanol with the chemical purity of 99.85 wt%, the deuterated ethanol has the deuterated rate of 99.86%, and the total conversion rate of 63 measured by using a carbon monoxide.
Wherein, the total mass of the catalyst is 100%, the components and the mass percentages of the components are as follows: 2% of rhodium, 5% of copper, 2% of cobalt, 3% of platinum, 4% of iron and the balance of an alumina carrier.
Example 3
Filling a catalyst and inert corundum porcelain balls into a fixed bed reactor according to the mass ratio of 2:3 to form a catalyst layer, preparing mixed gas from deuterium gas, carbon monoxide and nitrogen according to the molar ratio of 4:1:1, enabling the mixed gas to pass through the catalyst layer at the speed of 15L/s, reacting at the pressure of 7MPa and the temperature of (280 +/-5) DEG C, cooling reaction products by condensation circulating water at the temperature of 10 ℃ to realize gas-liquid separation, collecting liquid, transferring the collected liquid into a rectifying tower for rectification, wherein the temperature of a tower bottom of the rectifying tower is 100-110 ℃ and the temperature of a tower top is 76-79 ℃, and after rectification, collecting deuterated ethanol with the chemical purity of 99.84 wt%, the deuterated ethanol has the deuterated rate of 99.85%, and the total conversion rate is 62% measured by carbon monoxide.
Wherein, the total mass of the catalyst is 100%, the components and the mass percentages of the components are as follows: 3% of rhodium, 4% of platinum, 2% of iron and the balance of titanium dioxide carrier.
Example 4
Filling a catalyst and inert corundum porcelain balls into a fixed bed reactor according to the mass ratio of 2:3 to form a catalyst layer, preparing mixed gas from deuterium gas, carbon monoxide and nitrogen according to the molar ratio of 5:1:1, enabling the mixed gas to pass through the catalyst layer at the speed of 12L/s, reacting at the pressure of 6MPa and the temperature of (270 +/-5) DEG C, cooling reaction products by using condensed circulating water at the temperature of 10 ℃ to realize gas-liquid separation, collecting liquid, transferring the collected liquid into a rectifying tower for rectification, wherein the temperature of a tower bottom of the rectifying tower is 100-110 ℃ and the temperature of a tower top is 76-79 ℃, and after rectification, collecting deuterated ethanol with the chemical purity of 99.85 wt%, the deuterated ethanol has the deuterated rate of 99.85%, and the total conversion rate of 62% is measured by using a carbon monoxide meter.
Wherein, the total mass of the catalyst is 100%, the components and the mass percentages of the components are as follows: 3% of rhodium, 2% of cobalt and 2% of iron, and the balance being a graphitized carbon carrier.
Example 5
Filling a catalyst and inert corundum porcelain balls into a fixed bed reactor according to the mass ratio of 2:3 to form a catalyst layer, preparing mixed gas from deuterium gas, carbon monoxide and nitrogen according to the molar ratio of 6:1:1, enabling the mixed gas to pass through the catalyst layer at the speed of 11L/s, reacting at the pressure of 6.5MPa and the temperature of (280 +/-5) DEG C, cooling reaction products by condensation circulating water at the temperature of 10 ℃ to realize gas-liquid separation, collecting liquid, transferring the collected liquid into a rectifying tower for rectification, wherein the temperature of a tower bottom of the rectifying tower is 100-110 ℃ and the temperature of a tower top is 76-79 ℃, and collecting deuterated ethanol with the chemical purity of 99.84 wt% after rectification, the deuterated ethanol has the deuterium substitution rate of 99.85%, and the total conversion rate of 61% is measured by using a carbon monoxide meter.
Wherein, the total mass of the catalyst is 100%, the components and the mass percentages of the components are as follows: 5% of copper, 5% of platinum, 4% of iron and the balance of silicon oxide carrier.
Example 6
Filling a catalyst and inert corundum porcelain balls into a fixed bed reactor according to the mass ratio of 1:3 to form a catalyst layer, preparing mixed gas from deuterium gas, carbon monoxide and nitrogen according to the molar ratio of 5:1:1, enabling the mixed gas to pass through the catalyst layer at the speed of 14L/s, reacting at the pressure of 7MPa and the temperature of (280 +/-5) DEG C, cooling reaction products by using condensed circulating water at the temperature of 10 ℃ to realize gas-liquid separation, collecting liquid, transferring the collected liquid into a rectifying tower for rectification, wherein the temperature of the bottom of the rectifying tower is 100-110 ℃ and the temperature of the top of the rectifying tower is 76-79 ℃, and after rectification, collecting deuterated ethanol with the chemical purity of 99.85 wt%, the deuterated ethanol has the deuterated rate of 99.86%, and the total conversion rate of 63 measured by using a carbon monoxide.
Wherein, the total mass of the catalyst is 100%, the components and the mass percentages of the components are as follows: 1% of rhodium, 5% of copper, 2% of cobalt, 4% of iron and the balance of alumina carrier.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of deuterated ethanol is characterized by comprising the following steps: the steps of the method are as follows,
introducing mixed gas of deuterium gas, carbon monoxide and nitrogen into a fixed bed reactor filled with a catalyst, reacting at the pressure of 4 MPa-8 MPa and the temperature of 230-300 ℃, condensing, carrying out gas-liquid separation on reaction products, collecting liquid, and rectifying the collected liquid to obtain deuterated ethanol with the chemical purity and the deuteration rate of more than 99.8%;
the catalyst consists of active components and a carrier, wherein the active components are two or more of rhodium, copper, cobalt, platinum and iron, and the carrier is silicon oxide, aluminum oxide, titanium dioxide or graphitized carbon.
2. The method of claim 1, wherein the deuterated ethanol is prepared by: the active components of the catalyst are rhodium, copper, cobalt, platinum and iron;
wherein, the total mass of the catalyst is 100%, the mass percentages of the components in the catalyst are as follows: 0.5 to 5 percent of rhodium, 2 to 10 percent of copper, 1 to 5 percent of cobalt, 3 to 8 percent of platinum, 2 to 6 percent of iron and the balance of carrier.
3. The method of claim 1, wherein the deuterated ethanol is prepared by: the fixed bed reactor is also filled with filler, and the filler is inert corundum porcelain balls or copper particles.
4. The method of claim 3, wherein the deuterated ethanol is prepared by: in a fixed bed reactor, the mass filling ratio of a catalyst to a filler is (1-2): (2-3).
5. The method of claim 1, wherein the deuterated ethanol is prepared by: the mol ratio of deuterium gas, carbon monoxide and nitrogen gas is (2-8): 1: (1-4).
6. The method of claim 1, wherein the deuterated ethanol is prepared by: the mixed gas of deuterium gas, carbon monoxide and nitrogen gas passes through the catalyst layer in the fixed bed reactor at the speed of 10L/s-15L/s.
7. The method of claim 1, wherein the deuterated ethanol is prepared by: the condensing temperature for condensing gas-liquid separation is 0-10 ℃.
8. The method of claim 1, wherein the deuterated ethanol is prepared by: in the rectification process, the temperature of the tower kettle is 95-115 ℃, and the temperature of the tower top is 76-79 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114904518A (en) * | 2022-05-07 | 2022-08-16 | 南京凝氘生物科技有限公司 | Catalyst for synthesizing deuterated ethanol-d 6 from deuterium gas, preparation method and application thereof |
| CN115572211A (en) * | 2022-09-22 | 2023-01-06 | 华南理工大学 | Preparation method of deuterated ethanol |
| WO2024007464A1 (en) * | 2022-07-05 | 2024-01-11 | 宁波萃英化学技术有限公司 | Method for producing deuterated compound with tower device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1288191A (en) * | 1970-04-22 | 1972-09-06 | ||
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| CN114904518A (en) * | 2022-05-07 | 2022-08-16 | 南京凝氘生物科技有限公司 | Catalyst for synthesizing deuterated ethanol-d 6 from deuterium gas, preparation method and application thereof |
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| WO2024007464A1 (en) * | 2022-07-05 | 2024-01-11 | 宁波萃英化学技术有限公司 | Method for producing deuterated compound with tower device |
| CN115572211A (en) * | 2022-09-22 | 2023-01-06 | 华南理工大学 | Preparation method of deuterated ethanol |
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