CN116082120A - Technological method and device for preparing ethanol by continuous reaction of methanol - Google Patents
Technological method and device for preparing ethanol by continuous reaction of methanol Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 438
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 19
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 88
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 45
- 239000002994 raw material Substances 0.000 claims abstract description 36
- 230000006315 carbonylation Effects 0.000 claims abstract description 34
- 239000010949 copper Substances 0.000 claims abstract description 28
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 16
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 90
- 238000000926 separation method Methods 0.000 claims description 71
- 238000005984 hydrogenation reaction Methods 0.000 claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 238000005886 esterification reaction Methods 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 150000002148 esters Chemical class 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 23
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 22
- 230000032050 esterification Effects 0.000 claims description 21
- 238000011084 recovery Methods 0.000 claims description 20
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 18
- 238000005831 deiodination reaction Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 9
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- 235000009827 Prunus armeniaca Nutrition 0.000 claims description 3
- 244000018633 Prunus armeniaca Species 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000010924 continuous production Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 description 27
- 239000000047 product Substances 0.000 description 23
- 239000011701 zinc Substances 0.000 description 16
- 239000010948 rhodium Substances 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
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- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/06—Flash distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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- 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
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Abstract
The application discloses a process method and a device for preparing ethanol by continuous reaction of methanol. According to the process method, methanol and carbon monoxide react under the action of a single-atom catalyst to be converted into methyl acetate, the methyl acetate is hydrogenated under the action of a copper-based catalyst to be converted into ethanol and methanol, and the methanol is returned to be used as a raw material. The invention is characterized in that two reaction technologies of integrated carbonylation and catalytic hydrogenation are a system, and continuous production of methanol to ethanol is realized under the continuous action of supported single-atom Rh or Ir catalytic carbonylation and supported copper-based catalyst.
Description
Technical Field
The application relates to a process method and a device for preparing ethanol by continuous reaction of methanol, belonging to the field of chemical catalytic conversion.
Background
The method is a large country of coal, and the development of non-petrochemical technologies such as ethanol production from coal, olefin production from coal and the like has important strategic significance for guaranteeing the energy safety of China. Ethanol, which is a bulk chemical, can be used not only as a raw material or a solvent for preparing various fine chemicals, but also as a fuel aid, such as ethanol gasoline, etc., has a positive effect on improving the combustion value of fuel and environmental protection.
At present, most of ethanol comes from fermentation technology, has high cost and threatens the grain safety of China. In addition, the synthetic route of the non-grain ethanol mainly comprises (1) a cellulose straw fermentation method and (2) a direct ethanol preparation method by using the synthetic gas. The former technology is immature, low in energy density, high in cost and difficult to scale up and apply. The latter is costly, the catalyst efficiency is not high enough and the selectivity is poor.
Therefore, the development of indirect ethanol production from synthesis gas is a good break. Firstly, preparing primary products such as methanol from synthesis gas, then converting the methanol into products such as acetic acid, methyl acetate and the like, and then hydrogenating the acetic acid and the methyl acetate to prepare the ethanol with high selectivity.
The process for preparing the methanol by the synthesis gas is mature, the cost of raw materials of the methanol is low, and a trigger is provided for developing a methanol route to prepare the ethanol. Methanol carbonylation to produce acetic acid is a well established technology that has been industrialized for decades. The main processes for the production of acetic acid currently include the acetaldehyde oxidation process, the direct oxidation of olefins, and the methanol carbonylation process. Among them, the methanol carbonylation method has the highest conversion rate and less byproducts, and becomes one of the most main methods for producing acetic acid. However, the conventional methanol carbonylation process is carried out in a kettle reactor using homogeneous [ Rh (CO) 2 I 2 ]-and [ Ir (CO) 2 I 2 ]-a catalyst. The method comprisesThe method has the advantages of high water content, serious corrosion of reaction medium and easy conversion of the catalyst into insoluble RhI 3 And IrI 3 Precipitation causes catalyst loss, and the homogeneous catalysis system has the defects of difficult separation of reactant products and the catalyst, and the like, thereby increasing the production cost of the process.
Therefore, the heterogeneous methanol carbonylation catalytic system is developed, and the heterogeneous methanol carbonylation catalytic system becomes a very valuable and meaningful way for developing a new way in the heterogeneous catalysis field. In heterogeneous catalytic systems, single-atom catalysts act as bridges connecting homogeneous catalysis and heterogeneous catalysts with nearly 100% utilization of metal atoms, as well as with quasi-homogeneous molecular structure active sites. By regulating the chemical environment of the single metal atom, the catalytic activity of the single-atom catalyst is expected to be comparable with or even exceed that of a corresponding homogeneous catalytic system.
On the other hand, acetic acid hydrogenation generally requires a noble metal catalyst such as Pd-based catalyst, and the catalyst cost is high, so that the raw material is corrosive.
Disclosure of Invention
The technological process for preparing ethanol by methanol carbonylation and continuous catalytic hydrogenation of products comprises the steps of reacting methanol and carbon monoxide under the action of a single-atom catalyst to convert the methanol and the carbon monoxide into methyl acetate, then carrying out hydrogenation under the action of a copper-based catalyst to convert the methyl acetate and the methanol into ethanol and methanol, and returning the methanol to serve as raw materials. The invention is characterized in that two reaction technologies of integrated carbonylation and catalytic hydrogenation are a system, and continuous production of methanol to ethanol is realized under the continuous action of supported single-atom Rh or Ir catalytic carbonylation and supported copper-based catalyst.
According to one aspect of the present application, there is provided a process for preparing ethanol by continuous reaction of methanol, comprising the steps of:
a) Introducing a reaction raw material containing methanol, methyl iodide, carbon monoxide and hydrogen into a fixed bed tubular reactor to contact with a single-atom catalyst for carbonylation reaction to obtain a product a;
b) Separating the product a to obtain a product containing methyl acetate;
c) And (3) introducing the product containing methyl acetate and hydrogen into an ester hydrogenation reactor to contact with a copper-based catalyst for hydrogenation reaction, so as to obtain ethanol.
In the above process, methanol and carbon monoxide are first carbonylated in a fixed bed tubular reactor and a single atom Rh or Ir catalyst to convert into methyl acetate, which is then hydrogenated in the presence of a copper-based catalyst to produce ethanol, thereby realizing the continuous production of methanol from methyl acetate to ethanol.
Optionally, in step b), the separation comprises gas-liquid separation I, flash separation and azeotropic separation;
the product a is subjected to gas-liquid separation I to obtain a gas phase raw material b containing carbon monoxide and hydrogen and a liquid phase raw material c containing methanol, methyl iodide, methyl acetate and acetic acid;
flash-evaporating and separating the liquid-phase raw material c to obtain a light component d containing methanol and methyl iodide and a heavy component e containing methyl acetate and acetic acid;
the gas phase raw material b and the light component d are circularly sent to the fixed bed tubular reactor to participate in carbonylation reaction;
the heavy component e is subjected to azeotropic separation to obtain a mixture I containing methyl acetate and methanol and a mixture II containing acetic acid.
Because the product after the carbonylation reaction contains a small amount of acetic acid, the acetic acid needs to be converted into methyl acetate through a catalytic rectification esterification unit, and then the methyl acetate is introduced into a catalytic hydrogenation reaction for hydrogenation to prepare ethanol, so that the selectivity of the ethanol product is improved.
Optionally, the mixture I containing methyl acetate and methanol is respectively fed into an esterification rectifying tower and a deiodination tower;
introducing the mixture II containing acetic acid into an esterification rectifying tower to perform esterification reaction with methanol in the mixture I to obtain a mixture III containing methyl acetate;
and the mixture I and the mixture III enter the ester hydrogenation reactor after being deiodinated and purified by the deiodination tower.
Optionally, the product after hydrogenation reaction is respectively subjected to gas-liquid separation II, methanol recovery and ethanol separation to obtain ethanol;
the hydrogen after gas-liquid separation II is circularly sent to the ester hydrogenation reactor to participate in hydrogenation reaction;
and circularly delivering the methanol recovered by the methanol to the fixed bed tubular reactor to participate in the carbonylation reaction.
Alternatively, the carbonylation reaction conditions are: the temperature is 120-260 ℃, the pressure is 1.0-4.0 Mpa, and the liquid hourly space velocity is 2-12 h -1 。
Optionally, the hydrogenation reaction conditions are: the temperature is 180-260 ℃, the pressure is 4.0-10.0 Mpa, and the liquid hourly space velocity is 0.2-2.0 h -1 。
Optionally, the molar ratio of hydrogen to methyl acetate in the hydrogenation reaction is 20-100:1.
Optionally, the single-atom catalyst is a supported Rh or Ir-based catalyst, the carrier of the single-atom catalyst is a carbon-based carrier, and the loading of Rh or Ir atoms accounts for 0.1-2.0% of the mass of the single-atom catalyst.
Optionally, the carbon-based carrier is selected from one of coconut shell activated carbon carrier, apricot shell activated carbon carrier or carbon-based carrier containing nitrogen, phosphine, sulfur and functional groups.
Optionally, the copper-based catalyst comprises copper oxide, zinc oxide, aluminum oxide, and a precipitant.
Optionally, the precipitant is selected from at least one of graphene, carbon nanotubes, activated carbon, molecular sieves, silica, nitrogen or phosphine containing organics, nitrogen or phosphine containing inorganics.
According to the process provided herein, the high pressure knockout drum after the carbonylation reactor is primarily used for gas-liquid separation. And the liquid phase component in the tower bottom of the high-pressure separation tank enters a low-pressure flash tank to continuously separate methanol and methyl iodide. And the heavy components (methyl acetate, acetic acid and water) at the bottom of the low-pressure flash tank tower enter an azeotropic tower to separate the methyl acetate. Methyl acetate flows out from the top of the azeotropic tower and enters the deiodination tower. A small amount of acetic acid in the tower bottom of the azeotropic tower is converted into methyl acetate after being esterified with methanol in the esterification rectifying tower, and then the methyl acetate is introduced into the deiodination tower. Introducing the deiodinated components into a catalytic hydrogenation reactor for hydrogenation. The hydrogenated components are introduced into a high-pressure separation tower to separate gas-phase components, and the tower bottom is a mixed liquid-phase component such as ethanol, methanol, water and the like. The mixed liquid phase component is introduced into a methanol recovery tower to separate methanol, and the tower bottom component is introduced into an ethanol separation tower to separate water, so that the product ethanol is obtained.
According to still another aspect of the present application, there is provided an apparatus for continuously reacting methanol to ethanol, comprising a fixed bed tubular reactor, a separation unit, and an ester hydrogenation reactor;
the fixed bed tubular reactor, the separation unit and the ester hydrogenation reactor are connected in sequence.
The fixed bed tubular reactor is a corrosion-resistant tubular reactor, and is made of C276 or Zr 704.
Optionally, the separation unit comprises a first high-pressure separation tank, a low-pressure flash tank and an azeotropic column;
a condenser is arranged between the fixed bed tubular reactor and the first high-pressure separation tank, so that the gas-liquid separation effect of the reacted product in the first high-pressure separation tank is better;
the first high-pressure separation tank, the low-pressure flash tank and the azeotropic tower are sequentially connected, and the methyl iodide and methanol discharge port of the low-pressure flash tank is communicated with the methyl iodide and methanol feed port of the fixed bed tubular reactor;
the gas discharge port of the first high-pressure separation tank is connected with a high-pressure washing tower, and the hydrogen and carbon monoxide discharge port and the methanol and methyl iodide discharge port of the high-pressure washing tower are respectively connected with the hydrogen and carbon monoxide feed port and the methanol and methyl iodide feed port of the fixed bed tubular reactor.
Optionally, the separation unit further comprises an esterification rectifying tower and a deiodination tower;
the methanol and methyl acetate discharge ports of the azeotropic tower are respectively communicated with the methanol and methyl acetate feed ports of the esterification rectifying tower and the deiodination tower;
the acetic acid discharge port of the azeotropic tower is communicated with the acetic acid feed port of the esterification rectifying tower;
and a methyl acetate discharge port of the esterification rectifying tower is communicated with a methyl acetate feed port of the deiodination tower.
Optionally, the device further comprises a second high-pressure separation tank, a methanol recovery tower and an ethanol separation tower;
the feed inlet of the second high-pressure separation tower is connected with the discharge outlet of the ester hydrogenation reactor, the gas discharge outlet of the second high-pressure separation tower is connected with the hydrogen feed inlet of the ester hydrogenation reaction tower, the liquid discharge outlet of the second high-pressure separation tower is connected with the feed inlet of the methanol recovery tower, and the methanol discharge outlet of the methanol recovery tower;
the methanol discharge port of the methanol recovery tower is connected with the feed port of the high-pressure washing tower;
and an ethanol discharge port of the methanol recovery tower is connected with a feed port of the ethanol separation tower.
The beneficial effects that this application can produce include:
1) The process method provided by the application has the advantages of methyl acetate hydrogenation, mild conditions and high catalytic activity and selectivity;
2) According to the process method, the process technology of single-atom catalytic methanol carbonylation and catalytic esterification rectification and catalytic hydrogenation of the fixed bed tubular reactor is integrated, and the process production path of methanol from methyl acetate to ethanol is innovatively realized.
Drawings
FIG. 1 is a flow chart of a process for preparing ethanol by catalytic hydrogenation of methanol carbonylation in an embodiment of the present application;
FIG. 2 is a schematic diagram of a catalytic rectification column in an embodiment of the present application;
FIG. 3 is a single-atom catalyst electron microscope image of an embodiment of the present application;
wherein, 1, fixed bed tubular reactor, 2, ester hydrogenation reactor, 3, first high pressure knockout drum, 4, low pressure flash tank, 5, azeotropic column, 6, esterifying rectifying column, 7, deiodination tower, 8, second high pressure knockout drum, 9, methanol recovery tower, 10, ethanol knockout tower, 11, high pressure scrubber, 2-1, tower top condenser, 2-2, reflux column, 2-3, reflux pump, 2-4, tower kettle reboiler.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The copper-based catalyst is prepared by adopting a coprecipitation method, and is prepared from copper oxide, zinc oxide and aluminum oxide by washing, filtering, drying, calcining and tabletting. Graphene, carbon nano tubes, activated carbon, molecular sieves, silicon dioxide, nitrogen-containing organic or inorganic matters and the like can be added into the precipitant.
In the embodiment of the application, the conversion rate and the selectivity calculation formula are as follows:
the formula of the conversion of methanol is:
conversion of methanol= (moles of methanol in product)/(moles of methanol in feed) 100%
The formula of ethanol selectivity is:
ethanol selectivity = moles of ethanol/(moles of ethanol + moles of methyl acetate + moles of ethyl acetate)
Wherein TOF calculation refers to the molar ratio of the product ethanol, methyl acetate and ethyl acetate per unit time to the catalyst in the shell-and-tube reactor.
According to one embodiment of the present application, the process for preparing ethanol by continuous reaction of methanol is as follows:
a) Introducing a reaction raw material containing methanol, methyl iodide, carbon monoxide and hydrogen into a fixed bed tubular reactor to contact with a single-atom catalyst for carbonylation reaction to obtain a product a;
b) Separating the product a to obtain a product containing methyl acetate;
c) Introducing the product containing methyl acetate and hydrogen into an ester hydrogenation reactor to contact a copper-based catalyst for hydrogenation reaction, so as to obtain ethanol;
in step b), the separation includes gas-liquid separation, flash separation and azeotropic separation;
the product a is subjected to gas-liquid separation to obtain a gas phase raw material b containing carbon monoxide and hydrogen and a liquid phase raw material c containing methanol, methyl iodide, methyl acetate and acetic acid;
flash-evaporating and separating the liquid-phase raw material c to obtain a light component d containing methanol and methyl iodide and a heavy component e containing methyl acetate and acetic acid;
the gas phase raw material b and the light component d are circularly sent to the fixed bed tubular reactor to participate in carbonylation reaction;
the heavy component e is subjected to azeotropic separation to obtain a mixture I containing methyl acetate and methanol and a mixture II containing acetic acid;
the mixture I containing methyl acetate and methanol is respectively introduced into an esterification rectifying tower and a deiodination tower;
introducing the mixture II containing acetic acid into an esterification rectifying tower to perform esterification reaction with methanol in the mixture I to obtain a mixture III containing methyl acetate;
the mixture I and the mixture III enter the ester hydrogenation reactor after being deiodinated and purified by a deiodination tower;
the product after hydrogenation reaction is subjected to gas-liquid separation, methanol recovery and ethanol separation to obtain ethanol;
the hydrogen after gas-liquid separation is circularly sent to the ester hydrogenation reactor to participate in hydrogenation reaction;
the methanol after methanol recovery is circularly sent to the fixed bed tubular reactor to participate in carbonylation reaction;
the carbonylation conditions are as follows: the temperature is 120-260 ℃, the pressure is 1.0-4.0 Mpa, and the liquid hourly space velocity is 2-12 h -1 ；
The hydrogenation reaction conditions are as follows: the temperature is 180-260 ℃, the pressure is 4.0-10.0 Mpa, and the liquid hourly space velocity is 0.2-2.0 h -1 ；
The molar ratio of the hydrogen to the methyl acetate in the hydrogenation reaction is 20-100:1;
the single-atom catalyst is a supported Rh or Ir-based catalyst, the carrier is a carbon-based carrier, and the loading amount of Rh or Ir atoms accounts for 0.1-2.0% of the mass of the single-atom catalyst;
the carbon-based carrier is selected from one of coconut shell activated carbon carrier, apricot shell activated carbon carrier or carbon-based carrier containing nitrogen, phosphine, sulfur and functional groups;
fig. 3 is an electron microscope image of the single-atom Ir catalyst in the present embodiment, and it is known from fig. 3 that the metal Ir is single-atom-level dispersed on the surface of the carrier AC.
The copper-based catalyst comprises copper oxide, zinc oxide, aluminum oxide and a precipitant;
the precipitant is at least one of graphene, carbon nano tube, active carbon, molecular sieve, silicon dioxide, nitrogen-containing and phosphine-containing organic matters and nitrogen-containing and phosphine-containing inorganic matters;
the process method is characterized in that the device shown in fig. 1 is used for continuously reacting methanol to prepare ethanol, and the device specifically comprises the following steps:
comprises a fixed bed tubular reactor 1, a separation unit and an ester hydrogenation reactor 2;
the fixed bed tubular reactor 1, the separation unit and the ester hydrogenation reactor 2 are connected in sequence;
the separation unit comprises a first high-pressure separation tank 3, a low-pressure flash tank 4 and an azeotropic tower 5;
the first high-pressure separation tank 3, the low-pressure flash tank 4 and the azeotropic tower 5 are sequentially connected, and the discharge port of the methyl iodide and the methanol of the low-pressure flash tank 4 is communicated with the feed port of the methyl iodide and the methanol of the fixed bed tubular reactor 1;
the gas discharge port of the first high-pressure separation tank 3 is connected with a high-pressure washing tower 11, and the hydrogen and carbon monoxide discharge port and the methanol and methyl iodide discharge port of the high-pressure washing tower 11 are respectively connected with the hydrogen and carbon monoxide feed port and the methanol and methyl iodide feed port of the fixed bed tubular reactor 1;
the separation unit also comprises an esterification rectifying tower 6 and a deiodination tower 7;
the methanol and methyl acetate discharge ports of the azeotropic tower 5 are respectively communicated with the methanol and methyl acetate feed ports of the esterification rectifying tower 6 and the deiodination tower 7;
the acetic acid discharge port of the azeotropic tower 5 is communicated with the acetic acid feed port of the esterification rectifying tower 6;
the methyl acetate discharge port of the esterification rectifying tower 6 is communicated with the methyl acetate feed port of the deiodination tower 7;
the device also comprises a second high-pressure separation tank 8, a methanol recovery tower 9 and an ethanol separation tower 10;
the feed inlet of the second high-pressure separation tower 8 is connected with the discharge outlet of the ester hydrogenation reactor 2, the gas discharge outlet of the second high-pressure separation tower 8 is connected with the hydrogen feed inlet of the ester hydrogenation reactor 2, the liquid discharge outlet of the second high-pressure separation tower 8 is connected with the feed inlet of the methanol recovery tower 9, and the methanol discharge outlet of the methanol recovery tower 9;
the methanol discharge port of the methanol recovery tower 9 is connected with the feed port of the high-pressure washing tower 11;
the ethanol discharge port of the methanol recovery tower 9 is connected with the feed port of the ethanol separation tower 10.
As shown in FIG. 2, the ester hydrogenation reactor 2 comprises an overhead condenser 2-1, a reflux drum 2-2, a reflux pump 2-3 and a tower kettle reboiler 2-4.
Example 1
Catalyst: ir (Ir) 1 /AC+Cu/Zn/Al
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 5 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 1.0 h) -1 Pressure of 8.0MPa, H 2 Methyl acetate=50 (molar ratio)
Example 2
Catalyst: ir (Ir) 1 /AC+Cu/Zn/Al
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 1 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 1.0 h) -1 Pressure of 8.0MPa, H 2 Methyl acetate=50 (molar ratio)
Example 3
Catalyst: ir (Ir) 1 /AC+Cu/Zn/Al
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 3 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 1.0 h) -1 Pressure of 8.0MPa, H 2 Methyl acetate=50 (molar ratio)
Example 4
Catalyst: ir (Ir) 1 /AC+Cu/Zn/Al
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 8 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 1.0 h) -1 Pressure of 8.0MPa, H 2 Methyl acetate=50 (molar ratio)
Example 5
Catalyst: ir (Ir) 1 /AC+Cu/Zn/Al
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 12 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 1.0 h) -1 Pressure of 8.0MPa, H 2 Methyl acetate=50 (molar ratio)
Example 6
Catalyst: ir (Ir) 1 /AC+Cu/Zn/Al
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 5 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 0.5 h) -1 Pressure of 8.0MPa, H 2 Methyl acetate=50 (molar ratio)
Example 7
Catalyst: ir (Ir) 1 /AC+Cu/Zn/Al
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 5 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 2.0 h) -1 Pressure of 8.0MPa, H 2 Methyl acetate=50 (molar ratio)
Example 8
Catalyst: rh (rhodium) 1 /AC+Cu/Zn/Al
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 5 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 1.0 h) -1 Pressure of 8.0MPa, H 2 Methyl acetate=50 (molar ratio)
Example 9
Catalyst: rh (rhodium) 1 /AC+Cu/Zn/Al
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 5 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 0.5 h) -1 Pressure of 8.0MPa, H 2 Methyl acetate=50 (molar ratio)
Example 10
Catalyst: rh (rhodium) 1 /AC+Cu/Zn/Al
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 5 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 2.0 h) -1 Pressure of 8.0MPa, H 2 Methyl acetate=50 (molar ratio)
Example 11
Catalyst: rh (rhodium) 1 /AC+Cu/Zn/Al
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 5 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 1.0 h) -1 Pressure of 8.0MPa, H 2 Methyl acetate=20 (molar ratio)
Example 12
Catalyst: ir (Ir) 1 /AC+Cu/Zn/Al/CNTs
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 5 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 1.0 h) -1 Pressure of 6.0MPa, H 2 Methyl acetate=20 (molar ratio)
Example 13
Catalyst: ir (Ir) 1 /AC+Cu/Zn/Al/Graphene
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 5 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 1.0 h) -1 Pressure of 6.0MPa, H 2 Methyl acetate=20 (molar ratio)
Example 14
Catalyst: ir (Ir) 1 /AC+Cu/Zn/Al/C
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 5 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 1.0 h) -1 Pressure of 6.0MPa, H 2 Methyl acetate=20 (molar ratio)
Example 15
Catalyst: ir (Ir) 1 /AC+Cu/Zn/Al/P
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 5 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 1.0 h) -1 Pressure of 8.0Mpa, H 2 Methyl acetate=50 (molar ratio)
Example 16
Catalyst: ir (Ir) 1 /AC+Cu/Zn/Al/N
Raw materials: methanol+CO+H 2
Production conditions: methanol carbonylation unit (235 ℃,1.7MPa, space velocity 5 h) -1 ，CO/H 2 =10 (volume ratio), CO/CH 3 Oh=1 (molar ratio), CH 3 OH/CH 3 I=6 (mass ratio)); methyl acetate catalytic hydrogenation (240 ℃ C., space velocity 1.0 h) -1 Pressure of 8.0Mpa, H 2 Methyl acetate=50 (molar ratio)).
Acetic acid was prepared using examples 1-16, and its carbonylation activity and product acetic acid selectivity are shown in Table 1.
TABLE 1
From the results of examples 1-16, it is known that after the integrated carbonylation and catalytic hydrogenation process, the process route of preparing ethanol from methanol through methyl acetate can be realized under the action of single-atom Rh, ir and solid acid-base catalyst.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (10)
1. The technological method for preparing ethanol by continuous reaction of methanol is characterized by comprising the following steps:
a) Introducing a reaction raw material containing methanol, methyl iodide, carbon monoxide and hydrogen into a fixed bed tubular reactor to contact with a single-atom catalyst for carbonylation reaction to obtain a product a;
b) Separating the product a to obtain a product containing methyl acetate;
c) And (3) introducing the product containing methyl acetate and hydrogen into an ester hydrogenation reactor to contact with a copper-based catalyst for hydrogenation reaction, so as to obtain ethanol.
2. The process according to claim 1, wherein the single-atom catalyst is a supported Rh or Ir-based catalyst, the carrier of the single-atom catalyst is a carbon-based carrier, and the loading amount of Rh or Ir atoms accounts for 0.1-2.0% of the mass of the single-atom catalyst;
preferably, the carbon-based carrier is selected from one of coconut shell activated carbon carrier, apricot shell activated carbon carrier or carbon-based carrier containing nitrogen, phosphine, sulfur and functional groups;
preferably, the copper-based catalyst comprises copper oxide, zinc oxide, aluminum oxide, and a precipitant;
preferably, the precipitant is selected from at least one of graphene, carbon nanotubes, activated carbon, molecular sieves, silica, nitrogen or phosphine containing organics, nitrogen or phosphine containing inorganics.
3. The process according to claim 1, wherein in step b) the separation comprises gas-liquid separation I, flash separation and azeotropic separation;
the product a is subjected to gas-liquid separation I to obtain a gas phase raw material b containing carbon monoxide and hydrogen and a liquid phase raw material c containing methanol, methyl iodide, methyl acetate and acetic acid;
flash-evaporating and separating the liquid-phase raw material c to obtain a light component d containing methanol and methyl iodide and a heavy component e containing methyl acetate and acetic acid;
the gas phase raw material b and the light component d are circularly sent to the fixed bed tubular reactor to participate in carbonylation reaction;
the heavy component e is subjected to azeotropic separation to obtain a mixture I containing methyl acetate and methanol and a mixture II containing acetic acid.
4. A process according to claim 3, wherein the mixture I comprising methyl acetate and methanol is fed to an esterification rectifying column and a deiodination column, respectively;
introducing the mixture II containing acetic acid into an esterification rectifying tower to perform esterification reaction with methanol in the mixture I to obtain a mixture III containing methyl acetate;
and the mixture I and the mixture III enter the ester hydrogenation reactor after being deiodinated and purified by the deiodination tower.
5. The process according to claim 4, wherein the product after hydrogenation is separated from gas and liquid to obtain ethanol after recovering methanol and separating ethanol;
the hydrogen after gas-liquid separation II is circularly sent to the ester hydrogenation reactor to participate in hydrogenation reaction;
and circularly delivering the methanol recovered by the methanol to the fixed bed tubular reactor to participate in the carbonylation reaction.
6. The process according to claim 1, characterized in that the carbonylation conditions are: the temperature is 120-260 ℃, the pressure is 1.0-4.0 Mpa, and the liquid hourly space velocity is 2-12 h -1 ；
Preferably, the hydrogenation reaction conditions are: the temperature is 180-260 ℃, the pressure is 4.0-10.0 Mpa, and the liquid hourly space velocity is 0.2-2.0 h -1 ；
Preferably, the molar ratio of hydrogen to methyl acetate in the hydrogenation reaction is 20-100:1.
7. The device for preparing the ethanol by the continuous reaction of the methanol is characterized by comprising a fixed bed tubular reactor, a separation unit and an ester hydrogenation reactor;
the fixed bed tubular reactor, the separation unit and the ester hydrogenation reactor are connected in sequence.
8. The apparatus of claim 7, wherein the separation unit comprises a first high pressure separation tank, a low pressure flash tank, an azeotropic column;
the first high-pressure separation tank, the low-pressure flash tank and the azeotropic tower are sequentially connected, and the methyl iodide and methanol discharge port of the low-pressure flash tank is communicated with the methyl iodide and methanol feed port of the fixed bed tubular reactor;
the gas discharge port of the first high-pressure separation tank is connected with a high-pressure washing tower, and the hydrogen and carbon monoxide discharge port and the methanol and methyl iodide discharge port of the high-pressure washing tower are respectively connected with the hydrogen and carbon monoxide feed port and the methanol and methyl iodide feed port of the fixed bed tubular reactor.
9. The apparatus of claim 8, wherein the separation unit further comprises an esterification rectification column and a deiodination column;
the methanol and methyl acetate discharge ports of the azeotropic tower are respectively communicated with the methanol and methyl acetate feed ports of the esterification rectifying tower and the deiodination tower;
the acetic acid discharge port of the azeotropic tower is communicated with the acetic acid feed port of the esterification rectifying tower;
and a methyl acetate discharge port of the esterification rectifying tower is communicated with a methyl acetate feed port of the deiodination tower.
10. The apparatus of claim 9, further comprising a second high pressure separator tank, a methanol recovery column, an ethanol separation column;
the feed inlet of the second high-pressure separation tower is connected with the discharge outlet of the ester hydrogenation reactor, the gas discharge outlet of the second high-pressure separation tower is connected with the hydrogen feed inlet of the ester hydrogenation reaction tower, the liquid discharge outlet of the second high-pressure separation tower is connected with the feed inlet of the methanol recovery tower, and the methanol discharge outlet of the methanol recovery tower;
the methanol discharge port of the methanol recovery tower is connected with the feed port of the high-pressure washing tower;
and an ethanol discharge port of the methanol recovery tower is connected with a feed port of the ethanol separation tower.
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