CN105254473A - Method for preparing ethyl alcohol by adopting methyl alcohol homologization process - Google Patents
Method for preparing ethyl alcohol by adopting methyl alcohol homologization process Download PDFInfo
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- CN105254473A CN105254473A CN201510755844.1A CN201510755844A CN105254473A CN 105254473 A CN105254473 A CN 105254473A CN 201510755844 A CN201510755844 A CN 201510755844A CN 105254473 A CN105254473 A CN 105254473A
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- rhodium
- ruthenium
- 000ppm
- promotor
- halogenide
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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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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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
- C07C29/1512—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 reaction conditions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a method for preparing ethyl alcohol by adopting methyl alcohol homologization process. The method for preparing the ethyl alcohol by adopting the methyl alcohol homologization process is characterized in that right amount of acetic acid and halide or acetate of alkali metal is added in an existing reaction system (namely in the presence of a rhodium-based catalytic system and organic phosphino-substituted alkane (ligand)). Therefore, selectivity of ethyl alcohol can be improved to more than 90%.
Description
Technical field
The present invention relates to a kind of preparation method of ethanol, specifically, relate to a kind of method being prepared ethanol by methyl alcohol and synthesis gas reaction.
Background technology
Ethanol is industrial modal solvent, is also one of very important industrial chemicals, is widely used in the industries such as chemical industry, daily use chemicals, medicine.
Methyl alcohol and synthetic gas prepare the method (being again methyl alcohol homologization legal system for the method for ethanol) of ethanol through single stage method, are a kind of methods preparing ethanol that extremely this area scientist pays close attention to.
EP0283586B1 reports the method for a kind of homologization legal system for ethanol, and its key step is: based under the catalyst system of rhodium and organophosphorus based replacement alkane (part) existence condition, by methyl alcohol and synthetic gas (H
2+ CO) reaction, obtained ethanol.In this reaction system, the selectivity of ethanol is up to 80%, still has room for improvement.
Summary of the invention
The present inventor finds after deliberation: in existing reaction system, and add appropriate acetic acid and alkali-metal halogenide or acetate, the selectivity of ethanol can be increased to more than 90%.
Accordingly, the invention provides the method for a kind of methyl alcohol homologization legal system for ethanol.
The key step of method of the present invention is: exist at the catalyst system based on rhodium, temperature be 100 DEG C ~ 200 DEG C and pressure is under the condition of 2.0MPa ~ 6.0MPa, by methyl alcohol and synthetic gas (H
2be 1: 10 ~ 10: 1 with the mol ratio of CO) react, obtained ethanol;
Wherein, the described catalyst system based on rhodium forms primarily of Primary Catalysts, promotor, promotor, part, an alkali metal salt and acetic acid,
Described Primary Catalysts is: the oxygen-containing inorganic acid salt of the title complex of the halogenide of simple substance rhodium, rhodium, the oxide compound of rhodium, rhodium, the carbonyl compound of rhodium, rhodium or/and the organic acid salt of rhodium,
Described promotor is: the oxygen-containing inorganic acid salt of the title complex of the halogenide of simple substance ruthenium, ruthenium, the oxide compound of ruthenium, ruthenium, the carbonyl compound of ruthenium, ruthenium or/and the organic acid salt of ruthenium,
Described promotor is containing iodine organification compound,
Described part is that triphenylphosphine is or/and (Ph)
2pXP (Ph)
2, X is C
1~ C
3divalent alkyl, Ph is phenyl,
Described an alkali metal salt is alkali-metal halogenide or acetate.
Embodiment
In the present invention's preferred technical scheme, described an alkali metal salt is halogenide or the acetate of lithium (Li), sodium (Na) or potassium (K);
Preferred technical scheme is further: the iodide of Li, Na or K or acetate;
Further preferred technical scheme is: the iodide of Li, Na or K or the acetate mass concentration in reaction system is 100ppm ~ 1,000ppm.
In another preferred technical scheme of the present invention, temperature of reaction is 120 DEG C ~ 140 DEG C, and reaction pressure is 3MPa ~ 5MPa.
In a further preferred technical solution of the present invention, in reaction system, the mass concentration of rhodium (Rh) is 500ppm ~ 5,000ppm; The mass concentration of ruthenium (Ru) is 1,000ppm ~ 10,000ppm.
In a further preferred technical solution of the present invention, in reaction system, the mass concentration of part is 1,000ppm ~ 10,000ppm.
In a further preferred technical solution of the present invention, described promotor is methyl iodide, and its mass concentration in reaction system is 2,000ppm ~ 20,000ppm.
In a further preferred technical solution of the present invention, in reaction system, the mass concentration of methyl alcohol is more than or equal to 60%.
In a further preferred technical solution of the present invention, described Primary Catalysts is the carbonyl compound of rhodium-containing (as rhodium dicarbonyl acetylacetonate etc.);
Described promotor is: the halogenide (being more preferably ruthenium chloride) of ruthenium;
Described promotor is: iodo C
1~ C
3alkane (as methyl iodide, methylene iodide, triiodomethane or four methyl iodide etc.).
In sum, methyl alcohol homologization legal system provided by the invention is for the method for ethanol, its key step is: by methyl alcohol and based on rhodium catalyst system included by component be placed in reactor with whipping appts, seal described reactor, and the air of replacing with the synthetic gas that H:Cmoleratio (value) is 0.5 ~ 1 in this reactor, heating, reactor temperature controls at 120 DEG C ~ 140 DEG C, reaction internal pressure maintains 3MPa ~ 5MPa (absolute pressure), open and stir, stir after at least 1 hour, adopt again H:Cmoleratio (value) be 1.5 ~ 2 synthetic gas replacement(metathesis)reaction gas reactor, it is 120 DEG C ~ 140 DEG C at reactor temperature, reaction internal pressure is be retained to reacting kettle inner pressure under 3MPa ~ 5MPa (absolute pressure) and whipped state no longer to decline, stopped reaction, obtain target compound (ethanol).
Detect liquid phase and gas-phase product, detect and adopt gas-chromatography, adopt HP-5 capillary chromatographic column, fid detector marker method detects the organism in liquid phase and gas phase, and in liquid product, water-content adopts titration method.
The method of calculation of methyl alcohol and ethanol selectivity are as follows:
Methanol conversion (X
methyl alcohol):
Ethanol selectivity (S
ethanol):
Be further elaborated the present invention below by embodiment, its object is only better to understand content of the present invention.Therefore, the row lifted do not limit the scope of the invention.
Embodiment 1
Consisting of of the catalyst system added in the titanium material reactor of 500mL: rhodium dicarbonyl acetylacetonate (in rhodium) 0.3g, hydrate ruthenium trichloride 1.2g, ligand 1, 3-pairs of 2-phenyl-phosphine oxide 0.96g, methyl iodide 5.68g, methyl alcohol 40g, acetic acid 80g, lithium iodide 0.16g, temperature of reaction 130 DEG C, reaction pressure 5.0MPa, with H:Cmoleratio (value) be 0.5 synthetic gas replacement reaction kettle in air (namely to reacting kettle inner pressure no longer declines), after this state keeps 1 hour, H:Cmoleratio (value) is adopted to be gas in the synthetic gas replacement reaction kettle of 1.5 again, constant voltage keeps 2 hours again, stopped reaction, obtain target compound,
Through stratographic analysis and to can be calculated methanol conversion be 90.19%, ethanol selectivity is 90.33%.
Embodiment 2
Consisting of of the catalyst system added in the titanium material reactor of 500mL: rhodium dicarbonyl acetylacetonate (in rhodium) 0.3g, hydrate ruthenium trichloride 1.2g, ligand 1, 3-pairs of 2-phenyl-phosphine oxide 0.96g and triphenylphosphine 0.2g, methyl iodide 5.68g, methyl alcohol 40g, acetic acid 80g and Lithium Acetate 0.16g, temperature of reaction 130 DEG C, reaction pressure 5.0MPa, with H:Cmoleratio (value) be 0.5 synthetic gas replacement reaction kettle in air (namely to reacting kettle inner pressure no longer declines), after this state keeps 1 hour, H:Cmoleratio (value) is adopted to be gas in the synthetic gas replacement reaction kettle of 1.5 again, constant voltage keeps 2 hours again, stopped reaction, obtain target compound.
Through stratographic analysis and to can be calculated methanol conversion be 98.95%, ethanol selectivity is 92.63%.
Claims (9)
1. methyl alcohol homologization legal system is for a method for ethanol, and its key step is: exist at the catalyst system based on rhodium, temperature be 100 DEG C ~ 200 DEG C and pressure is under the condition of 2.0MPa ~ 6.0MPa, by methyl alcohol and synthesis gas reaction, and obtained ethanol;
Wherein, the described catalyst system based on rhodium forms primarily of Primary Catalysts, promotor, promotor, part, an alkali metal salt and acetic acid,
Described Primary Catalysts is: the oxygen-containing inorganic acid salt of the title complex of the halogenide of simple substance rhodium, rhodium, the oxide compound of rhodium, rhodium, the carbonyl compound of rhodium, rhodium or/and the organic acid salt of rhodium,
Described promotor is: the oxygen-containing inorganic acid salt of the title complex of the halogenide of simple substance ruthenium, ruthenium, the oxide compound of ruthenium, ruthenium, the carbonyl compound of ruthenium, ruthenium or/and the organic acid salt of ruthenium,
Described promotor is containing iodine organification compound,
Described part is that triphenylphosphine is or/and (Ph)
2pXP (Ph)
2, X is C
1~ C
3divalent alkyl, Ph is phenyl,
Described an alkali metal salt is alkali-metal halogenide or acetate.
2. the method for claim 1, is characterized in that, wherein said an alkali metal salt is: the halogenide of lithium, sodium or potassium or acetate.
3. method as claimed in claim 2, it is characterized in that, wherein said an alkali metal salt is: the iodide of lithium, sodium or potassium or acetate.
4. as the method in claims 1 to 3 as described in any one, it is characterized in that, Primary Catalysts wherein used is the carbonyl compound of rhodium-containing, and promotor used is: the halogenide of ruthenium, and promotor used is: iodo C
1~ C
3alkane.
5. method as claimed in claim 4, it is characterized in that, Primary Catalysts wherein used is rhodium dicarbonyl acetylacetonate, and promotor used is: ruthenium chloride, and promotor used is: methyl iodide.
6. as the method in Claims 1 to 5 as described in any one, it is characterized in that, in described reaction system, the mass concentration of rhodium is 500ppm ~ 5,000ppm; The mass concentration of ruthenium is 1,000ppm ~ 10,000ppm.
7. as the method in Claims 1 to 5 as described in any one, it is characterized in that, in described reaction system, the mass concentration of part is 1,000ppm ~ 10,000ppm.
8. as the method in Claims 1 to 5 as described in any one, it is characterized in that, in described reaction system, the mass concentration of promotor is 2,000ppm ~ 20,000ppm.
9. as the method in Claims 1 to 5 as described in any one, it is characterized in that, in described reaction system, the mass concentration of an alkali metal salt is 100ppm ~ 1,000ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510755844.1A CN105254473B (en) | 2015-11-09 | 2015-11-09 | The method that methanol homologization method prepares ethyl alcohol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510755844.1A CN105254473B (en) | 2015-11-09 | 2015-11-09 | The method that methanol homologization method prepares ethyl alcohol |
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| CN105254473A true CN105254473A (en) | 2016-01-20 |
| CN105254473B CN105254473B (en) | 2018-10-26 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4133966A (en) * | 1977-12-23 | 1979-01-09 | Gulf Research & Development Company | Selective formation of ethanol from methanol, hydrogen and carbon monoxide |
| US4233466A (en) * | 1979-11-15 | 1980-11-11 | Union Carbide Corporation | Homologation process for the production of ethanol from methanol |
| US4409404A (en) * | 1980-12-29 | 1983-10-11 | Gulf Research & Development Company | Process for producing ethanol using said novel catalyst system |
| US4954665A (en) * | 1985-11-07 | 1990-09-04 | Union Carbide Chemicals And Plastics Company Inc. | Methanol homologation |
-
2015
- 2015-11-09 CN CN201510755844.1A patent/CN105254473B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4133966A (en) * | 1977-12-23 | 1979-01-09 | Gulf Research & Development Company | Selective formation of ethanol from methanol, hydrogen and carbon monoxide |
| US4233466A (en) * | 1979-11-15 | 1980-11-11 | Union Carbide Corporation | Homologation process for the production of ethanol from methanol |
| US4409404A (en) * | 1980-12-29 | 1983-10-11 | Gulf Research & Development Company | Process for producing ethanol using said novel catalyst system |
| US4954665A (en) * | 1985-11-07 | 1990-09-04 | Union Carbide Chemicals And Plastics Company Inc. | Methanol homologation |
Non-Patent Citations (3)
| Title |
|---|
| G. DOYLE: "Homologation of Methanol with Cobalt-Ruthenium Catalysts", 《JOURNAL OF MOLECULAR CATALYSIS》 * |
| PATRICK B. FRANCOISSE ET AL.: "Methanol to ethanol by homologation: kinetic approach", 《INDUSTRIAL ENGINEERING CHEMISTRY PRODUCT RESEARCH AND DEVELOPMENT》 * |
| 陈英赞等: "合成气与甲醇制乙醇工艺的研究", 《石油化工》 * |
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| CN105254473B (en) | 2018-10-26 |
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