CN111848344A - Reaction system and method for preparing ethanol by adopting synthesis gas - Google Patents
Reaction system and method for preparing ethanol by adopting synthesis gas Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 134
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 58
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 371
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 184
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000005810 carbonylation reaction Methods 0.000 claims description 64
- 239000007789 gas Substances 0.000 claims description 60
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- 238000000926 separation method Methods 0.000 claims description 40
- 239000000047 product Substances 0.000 claims description 35
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- 239000000463 material Substances 0.000 claims description 27
- 238000000605 extraction Methods 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 18
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 16
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 16
- 239000007791 liquid phase Substances 0.000 claims description 16
- 238000002309 gasification Methods 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000003860 storage Methods 0.000 claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- QPXZALHPZYRQIT-UHFFFAOYSA-N ethanol;methoxymethane Chemical compound CCO.COC QPXZALHPZYRQIT-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000002994 raw material Substances 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000005265 energy consumption Methods 0.000 description 9
- 230000007246 mechanism Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
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- 239000005977 Ethylene Substances 0.000 description 3
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- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
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- 229910003158 γ-Al2O3 Inorganic materials 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
- C07C29/15—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
- C07C29/152—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 reactor used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
- B01F23/2366—Parts; Accessories
- B01F23/2368—Mixing receptacles, e.g. tanks, vessels or reactors, being completely closed, e.g. hermetically closed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
- B01F23/237—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media
- B01F23/2373—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media for obtaining fine bubbles, i.e. bubbles with a size below 100 µm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/29—Mixing systems, i.e. flow charts or diagrams
- B01F23/291—Mixing systems, i.e. flow charts or diagrams for obtaining foams or aerosols
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
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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
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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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
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
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Abstract
The invention provides a reaction system and a method for preparing ethanol by using synthesis gas. The reaction system comprises: the methanol preparation unit, the reaction unit for preparing dimethyl ether from methanol and the reaction unit for preparing ethanol from dimethyl ether which are connected in sequence, wherein the methanol preparation unit comprises: the system comprises a micro-bubble generator and a synthesis tower, wherein inert oil and synthesis gas are simultaneously introduced into the micro-bubble generator, mixed, dispersed and crushed, and then enter the synthesis tower to react and synthesize crude methanol, and the crude methanol is rectified by a primary rectifying tower and a secondary rectifying tower in sequence to obtain refined methanol which is sent to a reaction unit for preparing dimethyl ether from methanol.
Description
Technical Field
The invention relates to the field of ethanol preparation, and particularly relates to a reaction system and a method for preparing ethanol by using synthesis gas.
Background
The production routes of ethanol worldwide include grain fermentation routes, petrochemical routes, and carbon-chemical routes such as coal and natural gas. The grain fermentation route is widely applied internationally, and large-scale ethanol production enterprises mostly adopt grain fermentation processes. Influenced by the 'grain crisis', the new corn fuel ethanol project is stopped to be approved in China at present. The cellulose fuel ethanol project fermented by cassava and corn straws has poor economic benefit due to high production cost, excessive dependence on national subsidies, imperfect production technology and other factors. The petrochemical route uses ethylene as raw material to prepare fuel ethanol by ethylene hydration method. China depends on import of a large amount of petroleum, and the price of ethylene is often higher than that of ethanol, so that the application and popularization of the method in China are restricted.
The carbon chemical industrial route of coal, natural gas and the like is a method for preparing synthetic gas and methanol by using coal or natural gas as raw materials and then preparing ethanol by a dimethyl ether method or an acetic acid method. However, the method has a series of problems of high reaction pressure, high temperature, high energy consumption, low raw material utilization rate, low productivity and the like.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the present invention is to provide a reaction system for producing ethanol by using syngas, which combines the reaction system with a micro interface generator and a micro bubble generator, thereby reducing energy consumption, reducing reaction temperature, increasing reaction yield, especially increasing the utilization rate of reaction gas phase, and effectively increasing productivity, thereby increasing product quality and yield, and further saving equipment cost and equipment floor space.
The second objective of the present invention is to provide a reaction method for preparing ethanol from syngas by using the above reaction system, wherein the reaction method sufficiently disperses and crushes the reaction raw materials, improves the mass transfer efficiency of the reaction, improves the conversion rate of the reaction raw materials, and correspondingly improves the yield of the product.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a reaction system for preparing ethanol by adopting synthesis gas, which comprises: the device comprises a methanol preparation unit, a methanol-to-dimethyl ether reaction unit and a dimethyl ether-to-ethanol reaction unit which are connected in sequence;
the methanol preparation unit includes: the system comprises a micro-bubble generator and a synthesis tower, wherein inert oil and synthesis gas are simultaneously introduced into the micro-bubble generator, mixed, dispersed and crushed, and then enter the synthesis tower to react and synthesize crude methanol, and the crude methanol is rectified by a primary rectifying tower and a secondary rectifying tower in sequence to obtain rectified methanol which is sent to a reaction unit for preparing dimethyl ether from methanol;
the reaction unit for preparing dimethyl ether from methanol comprises: a dimethyl ether reactor; introducing the rectified methanol into the dimethyl ether reactor to carry out gas phase catalytic dehydration reaction, introducing a product after reaction into a first rectifying tower to carry out dimethyl ether purification and rectification, condensing a rectified gas phase, then partially returning to the first rectifying tower, partially returning to the dimethyl ether reactor to carry out re-reaction, and collecting a rectified dimethyl ether side line to a dimethyl ether ethanol preparation reaction unit;
the dimethyl ether-to-ethanol reaction unit comprises: the device comprises a carbonylation reactor, wherein a first micro-interface generator is arranged on the outer side of the carbonylation reactor, the first micro-interface generator is filled with dimethyl ether separated by rectification of a first rectifying tower and carbon monoxide, the dimethyl ether and the carbon monoxide are dispersed and crushed by the first micro-interface generator and then enter the carbonylation reactor for reaction, the carbonylation reactor is connected with a second micro-interface generator so as to be filled with a carbonylation product, the second micro-interface generator is filled with hydrogen at the same time, the hydrogen is dispersed and crushed by the second micro-interface generator and then enters a hydrogenation reactor for methyl acetate hydrogenation, and a reaction product after the hydrogenation reaction is subjected to methanol and ethanol separation by a second rectifying tower to obtain ethanol.
The reaction system is provided with the micro-bubble generator in front of the synthesis tower, and the micro-interface generators are correspondingly arranged in front of the carbonylation reactor and the hydrogenation reactor to disperse and crush the entering gas phase into micro-bubbles, so that the mass transfer effect is improved.
In addition, in the reaction system of the invention, a micro-bubble generator is required to be arranged in front of the synthesis tower, and micro-interface generators are required to be arranged in front of the carbonylation reactor and the hydrogenation reactor, because the reactions in the synthesis tower and the two reactors are both gas-liquid two-phase reactions, the arranged micro-interface generators and micro-bubble generators can just play a role in dispersing and crushing gas phase, and the micro-interface generators are arranged in the subsequent process, dimethyl ether does not need to be gasified in advance, and can be directly introduced into the micro-interface generators to be mixed with carbon monoxide for dispersing and crushing, so that the operation steps are simplified.
Preferably, the number of the micro-bubble generators, the first micro-interface generators and the second micro-interface generators is not unique, and in order to increase the mass transfer effect, the number of the micro-bubble generators and the first micro-interface generators and the second micro-interface generators can be correspondingly increased, the micro-bubble generators and the second micro-interface generators are preferably arranged in sequence from top to bottom, and the micro-interface generators are preferably connected in parallel.
The micro-bubble generator, the first micro-interface generator and the second micro-interface generator are all in a pneumatic type, and the gas phase is introduced into the micro-interface generator and then is directly broken with the liquid phase to form micro-bubbles, so that the mass transfer effect is improved.
Certainly, except for the mode that the micro-interface generator and the micro-bubble generator are arranged outside the reactor, the micro-interface generator and the micro-bubble generator can also be correspondingly arranged inside the reactor, but the optimal mode is that the micro-interface generator is arranged in front of the reactor, and the micro-interface generator is required to be arranged in front of the carbonylation reactor and the hydrogenation reactor, so that the pressure in the reaction process is not required to be too high, the raw materials are not required to be gasified, the centralized control is facilitated, the safety of equipment operation is improved, if one micro-interface generator is arranged less, the controllability of the material pressure in the whole process flow is reduced, the pressure is different, and the effect of reducing the energy consumption cannot be fully achieved.
It will be understood by those skilled in the art that the micro-interface generator and micro-bubble generator used in the present invention are embodied in the prior patents of the present inventor, such as the patents with application numbers CN201610641119.6, 201610641251.7, CN201710766435.0, CN106187660, CN105903425A, CN109437390A, CN205833127U and CN 207581700U. The detailed structure and operation principle of the micro bubble generator (i.e. micro interface generator) is described in detail in the prior patent CN201610641119.6, which describes that "the micro bubble generator comprises a body and a secondary crushing member, wherein the body is provided with a cavity, the body is provided with an inlet communicated with the cavity, the opposite first end and second end of the cavity are both open, and the cross-sectional area of the cavity decreases from the middle of the cavity to the first end and second end of the cavity; the secondary crushing member is disposed at least one of the first end and the second end of the cavity, a portion of the secondary crushing member is disposed within the cavity, and an annular passage is formed between the secondary crushing member and the through holes open at both ends of the cavity. The micron bubble generator also comprises an air inlet pipe and a liquid inlet pipe. "the specific working principle of the structure disclosed in the application document is as follows: liquid enters the micro-bubble generator tangentially through the liquid inlet pipe, and gas is rotated at a super high speed and cut to break gas bubbles into micro-bubbles at a micron level, so that the mass transfer area between a liquid phase and a gas phase is increased, and the micro-bubble generator in the patent belongs to a pneumatic micro-interface generator.
In addition, the first patent 201610641251.7 describes that the primary bubble breaker has a circulation liquid inlet, a circulation gas inlet and a gas-liquid mixture outlet, and the secondary bubble breaker communicates the feed inlet with the gas-liquid mixture outlet, which indicates that the bubble breakers all need to be mixed with gas and liquid, and in addition, as can be seen from the following drawings, the primary bubble breaker mainly uses the circulation liquid as power, so that the primary bubble breaker belongs to a hydraulic micro-interface generator, and the secondary bubble breaker simultaneously introduces the gas-liquid mixture into an elliptical rotating ball for rotation, thereby realizing bubble breaking in the rotating process, so that the secondary bubble breaker actually belongs to a gas-liquid linkage micro-interface generator. In fact, the micro-interface generator is a specific form of the micro-interface generator, whether it is a hydraulic micro-interface generator or a gas-liquid linkage micro-interface generator, however, the micro-interface generator adopted in the present invention is not limited to the above forms, and the specific structure of the bubble breaker described in the prior patent is only one of the forms that the micro-interface generator of the present invention can adopt.
Furthermore, the prior patent 201710766435.0 states that the principle of the bubble breaker is that high-speed jet flows are used to achieve mutual collision of gases, and also states that the bubble breaker can be used in a micro-interface strengthening reactor to verify the correlation between the bubble breaker and the micro-interface generator; moreover, in the prior patent CN106187660, there is a related description on the specific structure of the bubble breaker, see paragraphs [0031] to [0041] in the specification, and the accompanying drawings, which illustrate the specific working principle of the bubble breaker S-2 in detail, the top of the bubble breaker is a liquid phase inlet, and the side of the bubble breaker is a gas phase inlet, and the liquid phase coming from the top provides the entrainment power, so as to achieve the effect of breaking into ultra-fine bubbles, and in the accompanying drawings, the bubble breaker is also seen to be of a tapered structure, and the diameter of the upper part is larger than that of the lower part, and also for better providing the entrainment power for the liquid phase. Since the micro-interface generator was just developed in the early stage of the prior patent application, the micro-interface generator (CN201610641119.6), bubble breaker (201710766435.0) and the like were named in the early stage, and the micro-interface generator and the micro-bubble generator are named as the micro-interface generator in the later stage with the continuous technical improvement, and the micro-interface generator and the micro-bubble generator in the present invention are equivalent to the micro-bubble generator, the bubble breaker and the like in the prior art, but the names are different.
In summary, the micro-interface generator of the present invention belongs to the prior art, although some bubble breakers belong to the type of pneumatic bubble breakers, some bubble breakers belong to the type of hydraulic bubble breakers, and some bubble breakers belong to the type of gas-liquid linkage bubble breakers, the difference between the types is mainly selected according to the different specific working conditions, and in addition, the connection between the micro-interface generator and the reactor and other equipment, including the connection structure and the connection position, is determined according to the structure of the micro-interface generator, which is not limited.
The reaction system comprises a methanol preparation unit, a reaction unit for preparing dimethyl ether from methanol and a reaction unit for preparing ethanol from dimethyl ether.
Wherein, the methanol preparation unit mainly comprises the following equipment: a microbubble generator, a synthesis tower, a gasification tower, a primary rectifying tower and a secondary rectifying tower.
And introducing inert oil and synthetic gas into the microbubble generator at the same time, mixing, dispersing and crushing the inert oil and the synthetic gas, then introducing the mixture into a synthesis tower to perform synthesis reaction to synthesize crude methanol, and sequentially rectifying the crude methanol in a primary rectifying tower and a secondary rectifying tower to obtain refined methanol which goes to the methanol-to-dimethyl ether reaction unit to perform subsequent reaction.
The synthesis gas is mainly converted from natural gas, petroleum, coal and other raw materials to form CO and CO2、H2The synthesis raw material gas is purified to adjust the hydrogen-carbon ratio, and finally the pressure required by the synthesis of the methanol is achieved through the subsequent compression process to form the synthesis gas.
The synthesis gas usually needs high temperature and high pressure conditions when the methanol synthesis is carried out, but the synthesis of the methanol is a stronger exothermic reaction, from the analysis of thermodynamics, the temperature reduction is favorable for the reaction to move towards the direction of generating the methanol, so the operation temperature and the pressure can be obviously reduced by adopting a liquid phase synthesis mode, the synthesis gas passes through a micro-bubble generator in advance, is dissolved in an inert oil medium and is micro-converted into small bubbles by the large bubbles, and then is subsequently conveyed into a synthesis tower, the synthesis gas taking inert oil as a medium can more easily reach the surface of a catalyst, because the inert oil adopted as the medium, the specific surface area of the catalyst dispersed in the medium is larger, the reaction process is accelerated, the reaction temperature and the reaction pressure can be greatly reduced, and because the micro-bubble generator is arranged in front of the synthesis tower, the reaction temperature and the reaction pressure are more obviously reduced, the reaction energy consumption is fully reduced.
The synthesis gas is compressed by a compressor, exchanges heat with the product from the synthesis tower in a heat exchanger and then is conveyed to a micro-bubble generator.
The synthesis tower is a fixed bed reactor, a solid catalyst is placed on a fixed bed layer, and the type of the solid catalyst can be a copper-based catalyst or a zinc-chromium catalyst.
Preferably, a gasification tower is arranged between the synthesis tower and the primary rectifying tower and used for removing dimethyl ether, methyl formate and other low-boiling-point substances in the crude methanol, and the side wall of the primary rectifying tower is connected with the bottom of the gasification tower through a pipeline and used for rectifying the crude methanol after impurities are removed in the primary rectifying tower.
The gasification tower is arranged to remove dimethyl ether, methyl formate and other low boiling point substances in the crude methanol, the dimethyl ether, the methyl formate and other low boiling point substances return to the top of the gasification tower for re-reaction, and the crude methanol goes to the primary rectifying tower from the bottom of the gasification tower for rectification, generally enters between two tower sections of the primary rectifying tower.
Preferably, the side of rectifying column is provided with be used for with return again after the gaseous phase condensation that the rectifying column top came out on the first material circulation line of rectifying column, follow the material outflow on the first material circulation line the top of the tower direction of rectifying column has set gradually first condenser, first condensing tank and first circulating pump, the lateral wall of first condensing tank pass through the pipeline with the top of the tower of secondary rectifying column is connected.
Preferably, the side of the secondary rectifying tower is provided with a second material circulation line for condensing the refined methanol part extracted from the side line of the secondary rectifying tower and returning to the secondary rectifying tower, and a second condenser, a second condensing tank and a second circulating pump are sequentially arranged in the tower top direction of the secondary rectifying tower along the material return on the second material circulation line.
The substance from the top of the primary rectifying tower contains 50% of methanol, and the substance from the top of the primary rectifying tower is circulated to one part of the primary rectifying tower through the first material circulating line, and the other part of the substance is condensed by the first condenser and then sent to the top of the secondary rectifying tower for re-rectification.
Preferably, a side line extraction line is arranged at the upper position of the side wall of the secondary rectifying tower, the end part of the side line extraction line is connected with a refined methanol storage tank, a third condenser is arranged on the side line extraction line, and a side branch of the side line extraction line between the secondary rectifying tower and the third condenser is connected with the second material circulating line.
And rectifying the methanol containing heavy components from the bottom of the primary rectifying tower in a secondary rectifying tower through a methanol channel, condensing the methanol from the secondary rectifying tower through a third condenser to obtain refined methanol, storing the refined methanol in a refined methanol storage tank, and preparing for a subsequent reaction unit for preparing dimethyl ether from methanol. Of course, a part of the methanol from the secondary rectification tower returns to the secondary rectification tower for rectification again through a second material circulating line.
The reaction unit for preparing dimethyl ether from methanol mainly comprises the following equipment: a dimethyl ether reactor and a first rectifying tower.
The methanol is firstly subjected to gas phase catalytic dehydration reaction in a dimethyl ether reactor to generate dimethyl ether, the reaction temperature is 250-270 ℃, the pressure is 1.2MPa, and the catalyst is generally a molecular sieve, such as a ZSM molecular sieve, aluminum phosphate or gamma-Al2O3. The dimethyl ether generated by methanol dehydration is an exothermic reaction, and the temperature of the product gas at the outlet of the reactor is 320-330 ℃. The main reaction products are dimethyl ether and water, and the side reaction products are carbon oxide, methane, hydrocarbon and the like.
Preferably, the reaction unit for preparing dimethyl ether from methanol comprises a heat exchanger, and the heat exchanger is used for carrying out heat exchange on raw material methanol and a gas-phase catalytic dehydration reaction product.
Preferably, the heat exchanger is arranged between the dimethyl ether reactor and the first rectifying tower, and a preheater is further arranged between the heat exchanger and the dimethyl ether reactor. Just because the dimethyl ether prepared by dehydrating methanol belongs to exothermic reaction, a preheater and a heat exchanger are correspondingly arranged, and the heat exchanger can exchange heat between a reaction product and a raw material, thereby achieving the purpose of effectively utilizing heat.
The reaction product enters a first rectifying tower after heat exchange for purification and rectification, and then a pure dimethyl ether product can be formed for subsequent ethanol synthesis.
The first rectifying tower is mainly used for purifying dimethyl ether products, after the gas-phase methanol recovered from the top of the first rectifying tower is liquefied by the tower top condenser, one part of the gas-phase methanol flows back to the first rectifying tower, and the other part of the gas-phase methanol returns to the dimethyl ether reactor to be reused as reaction raw materials. Most of the materials coming out of the bottom of the first rectifying tower are dimethyl ether and a small amount of methanol, and the separated methanol can be directly used as a reaction raw material of the dimethyl ether reactor after being directly extracted and simply separated.
Preferably, the first rectifying tower is provided with a recovery mechanism for laterally recovering dimethyl ether, and the recovery mechanism is connected with the first micro-interface generator. The main product of the first rectifying tower is extracted through a side extraction mechanism, and the dimethyl ether product is conveyed to a first micro-interface generator after side extraction for a subsequent ethanol synthesis process.
The reaction unit for preparing ethanol from dimethyl ether mainly comprises the following equipment: the device comprises a carbonylation reactor, a separation tower, a hydrogenation reactor and a second rectifying tower.
The carbonylation reactor for carrying out the carbonylation reaction is preferably a fixed bed reactor, three layers of fixed tower plates are arranged in the carbonylation reactor, carbonylation reaction catalysts are distributed on the fixed tower plates on each layer, a plurality of reaction mixture inlets are arranged on the carbonylation reactor, and the reaction mixture inlets are respectively arranged at the top of the carbonylation reactor and between the adjacent fixed tower plates.
Dimethyl ether products from the reaction unit for preparing dimethyl ether from methanol are not required to be gasified and are directly introduced into the first micro-interface generator, carbon monoxide is also introduced into the first micro-interface generator, the carbon monoxide is crushed into micro-bubbles under the action of liquid-phase dimethyl ether and then enters the carbonylation reactor to carry out carbonylation reaction, and in order to improve the reaction effect, mixture inlets on the carbonylation reactor are respectively arranged between adjacent fixed bed layers on the side wall and at the top.
Preferably, a separation column is provided between the carbonylation reactor and the second micro-interface generator for removing gas phase impurities from the carbonylation product.
Preferably, a separation tank is arranged at the top of the separation tower, the gas phase separated by the separation tank is sent to the first micro-interface generator, and the liquid phase is returned to the separation tower for re-stripping separation.
The method comprises the steps that carbon monoxide and dimethyl ether are subjected to carbonylation reaction under the action of a catalyst to obtain a carbonylation product, the main component of the carbonylation product is methyl acetate, and then some unreacted dimethyl ether exists, after the carbonylation product is subjected to steam stripping through a separation tower, the top of the separation tower is mainly unreacted dimethyl ether, the unreacted dimethyl ether can be directly returned to a first micro-interface generator through a separation tank arranged at the top of the separation tower to serve as reaction feeding of carbonylation, and a liquid phase discharged from the bottom of the separation tank is directly returned to the separation tower to be subjected to steam stripping separation and purification again.
Preferably, the bottom of the separation tower is provided with a methyl acetate outlet, and the methyl acetate outlet is connected with the second micro-interface generator through a pipeline.
And the substances discharged from the bottom of the separation tower are mainly methyl acetate and are conveyed into the second micro-interface generator through a pump, and in order to improve the action effect of the second micro-interface generator, the methyl acetate is preheated by a preheater and then is introduced into the second micro-interface generator. And simultaneously introducing hydrogen into the second micro-interface generator, and after the hydrogen is crushed into micro bubbles under the action of the liquid-phase methyl acetate, feeding the micro bubbles into the hydrogenation reactor for hydrogenation reaction.
Preferably, the hydrogenation reactor for hydrogenation reaction is a fixed bed reactor, the catalyst in the fixed bed reactor is fixed on the bed layer, the catalyst for hydrogenation reaction is generally nickel-based catalyst, preferably the catalyst can be supported nickel-based catalyst, or nickel-based catalyst modified by alkaline earth metal oxide or rare earth metal oxide is more preferable.
Methyl acetate generates methanol and ethanol after hydrogenation reaction, and then enters a second rectifying tower for ethanol refining, the operating pressure of the top of the second rectifying tower is about 0.03MPa, steam at the top of the second rectifying tower is condensed to 61.7 ℃, and part of a condensed liquid phase (a large amount of methanol) returns to the second rectifying tower and part of the condensed liquid phase goes to a reaction unit for preparing dimethyl ether from methanol, and is used as a reaction raw material for preparing dimethyl ether.
Preferably, a methanol outlet is formed in the top of the second rectifying tower, the methanol outlet returns to the dimethyl ether reactor through a pipeline to be used as a methanol raw material, and a product extraction outlet is formed in the bottom of the second rectifying tower and used for extracting ethanol product.
And after the substances discharged from the methanol outlet are condensed by the overhead condenser, one part of the substances returns to the second rectifying tower again, and the other part of the substances is communicated with the dimethyl ether reactor through a pipeline so as to reuse the methanol as the raw material.
And a product extraction port arranged at the bottom of the second rectifying tower is used for extracting refined ethanol, the temperature is about 101 ℃, the refined ethanol extracted from the extraction port is cooled to 40 ℃ in an ethanol cooler, then the cooled refined ethanol passes through an ethanol buffer tank and is conveyed to an ethanol product tank area by a pump, and an ethanol unqualified product tank is arranged in an intermediate tank area and is used when the automobile is started or the production is abnormal. And a small amount of rectification waste liquid, mainly comprising acetic acid, is generated at the bottom of the second rectifying tower in the process of refining the ethanol, and is cooled to normal temperature and then sent to a heavy component tank for storage.
The invention also provides a micro-interface reaction method for preparing ethanol by adopting the synthesis gas, which comprises the following steps:
mixing, dispersing and crushing fresh synthesis gas and inert oil, catalytically synthesizing crude methanol, and rectifying the crude methanol to obtain refined methanol;
carrying out gas-phase catalytic dehydration and rectification on the refined methanol to obtain dimethyl ether;
after dimethyl ether and carbon monoxide are mixed, dispersed and crushed, carbonylation reaction is carried out to obtain a carbonylation reaction product;
and mixing, dispersing and crushing the carbonylation reaction product and hydrogen, carrying out hydrogenation reaction, and rectifying to obtain the ethanol.
Preferably, the pressure of the reaction for synthesizing the crude methanol by catalyzing the synthesis gas is 2.5-4.0MPa, and the temperature is 180-200 ℃.
Preferably, the pressure of the carbonylation reaction is 2.5-3.0MPa and the temperature is 200-230 ℃.
Preferably, the pressure of the hydrogenation reaction is 2.5-3.0MPa, and the temperature is 200-210 ℃.
In the prior art, the temperature of the dimethyl ether carbonylation reaction is selected to be 240-260 ℃, the pressure is selected to be 5.0MPa, the temperature of the hydrogenation reaction is selected to be 230-260 ℃, and the pressure is 5.0MPa, although the reaction activity of the catalyst and the selectivity of the product can be obviously improved by increasing the temperature, the catalyst deactivation can be accelerated by increasing the reaction temperature too high; the higher reaction pressure is beneficial to the carbonylation reaction and promotes the dimethyl ether conversion, but the liquefaction of raw materials or products and the inactivation of the catalyst are accelerated due to the overhigh reaction pressure, so that the reaction method not only properly reduces the reaction temperature and the reaction pressure and ensures the activity of the catalyst, but also reduces the energy consumption and ensures the reaction effect, and the yield and the conversion rate of the raw materials are still kept at a higher level.
The ethanol obtained by the reaction method for preparing the ethanol by using the synthesis gas has high yield and high purity, and the purity can reach 99.9%.
The reaction method has the advantages of low reaction temperature, greatly reduced pressure and high liquid hourly space velocity, which is equivalent to improving the productivity and the product yield.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the reaction system, the carbonylation reactor, the hydrogenation reactor and the micro-interface generator are combined, so that the energy consumption is reduced, the reaction temperature is reduced, the reaction yield is improved, and the utilization rate of raw materials is improved;
(2) the reaction system of the invention is most beneficial to simplifying operation steps and reducing energy consumption of the whole process by arranging the micro-interface generator and the micro-bubble generator at specific positions;
(3) the reaction method has the advantages of low reaction temperature, greatly reduced pressure, high liquid hourly space velocity, high productivity, high yield of ethanol obtained by reaction, high purity and high product purity up to 99.9 percent.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
Fig. 1 is a schematic structural diagram of a reaction system for producing ethanol from syngas according to an embodiment of the present invention.
Description of the drawings:
a 10-dimethyl ether reactor; 20-a preheater;
30-a heat exchanger; 40-a first rectification column;
401-overhead condenser; 402-column bottoms reboiler;
50-a first micro-interface generator; 60-CO storage tank;
a 70-carbonylation reactor; 80-a separation column;
90-a second micro-interface generator; 100-a hydrogen storage tank;
110-a hydrogenation reactor; 120-a second rectification column;
1201-methanol outlet; 1202-product extraction and export;
701-fixed column plate; 702-a mixture inlet;
801-a separation tank; an 802-methyl acetate outlet;
130-a microbubble generator; 140-a synthesis column;
150-a gasification tower; 160-primary rectification column;
170-a first material circulation line; 1701-first condenser;
1702-a first condensate tank; 1703-a first circulation pump;
180-secondary rectification column; 190-second material circulation line;
1901-second condenser; 1902-a second condensate tank;
1903-second circulation pump; 200-side line extraction line;
210-a refined methanol storage tank; 220-third condenser.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In order to more clearly illustrate the technical solution of the present invention, the following description is made in the form of specific embodiments.
Examples
Referring to fig. 1, a schematic diagram of a specific structure of a reaction system for preparing ethanol from syngas according to an embodiment of the present invention is shown, where the reaction system includes three units, namely a methanol preparation unit, a methanol-to-dimethyl ether reaction unit, and a dimethyl ether-to-ethanol reaction unit.
The methanol preparation unit includes: the device comprises a micro-bubble generator 130, a synthesis tower 140, a gasification tower 150, a primary rectifying tower 160 and a secondary rectifying tower 180, wherein inert oil and synthesis gas are introduced into the micro-bubble generator 130 to be mixed, dispersed and crushed, and then enter the synthesis tower 140 to perform a reaction for synthesizing methanol, so as to synthesize crude methanol, and then the crude methanol sequentially passes through the subsequent gasification tower 150, the primary rectifying tower 160 and the secondary rectifying tower 180 to be purified and rectified to obtain refined methanol, and then the refined methanol goes to a reaction unit for preparing dimethyl ether from methanol to perform subsequent reaction. The synthesis gas is compressed in advance by a compressor, exchanges heat with the product from the synthesis tower in a heat exchanger and then is conveyed to the micro-bubble generator.
The crude methanol from the bottom of the synthesis tower is cooled by heat exchange through a heat exchanger and then sent to the gasification tower 150 to remove dimethyl ether, methyl formate and other low boiling point substances in the crude methanol, and the methanol after the low boiling point substances are removed by gasification is sent to the primary rectifying tower 160 from the bottom of the gasification tower 150 through a pipeline for rectification.
The side of the primary rectifying tower 160 is provided with a first material circulation line 170 for re-returning the gas phase coming out from the top of the primary rectifying tower 160 to the primary rectifying tower after condensation, a first condenser 1701, a first condensation tank 1702 and a first circulation pump 1703 are sequentially arranged on the first material circulation line along the direction of the top of the primary rectifying tower from which the material flows out, and the side wall of the first condensation tank 1702 is connected with the top of the secondary rectifying tower 180 through a pipeline. A second material circulating line 190 for partially condensing the refined methanol extracted from the side line of the secondary rectifying tower 180 and returning the condensed refined methanol to the secondary rectifying tower 180 is arranged beside the secondary rectifying tower 180, and a second condenser 1901, a second condensing tank 1902 and a second circulating pump 1903 are sequentially arranged on the second material circulating line 190 along the direction of the material returning to the top of the secondary rectifying tower 180.
A side line extraction line 200 is arranged at the upper position of the side wall of the secondary rectifying tower 180, the end part of the side line extraction line 200 is connected with a refined methanol storage tank 210, a third condenser 220 is arranged on the side line extraction line, a second material circulation line 190 is connected to a side branch of the side line extraction line between the secondary rectifying tower 180 and the third condenser 220, methanol containing heavy components from the bottom of the primary rectifying tower 160 is rectified in the secondary rectifying tower 180, and the methanol from the secondary rectifying tower 180 is condensed by the third condenser 220 to obtain refined methanol which is stored in the refined methanol storage tank 210 for use in a subsequent reaction unit for preparing dimethyl ether from methanol. Of course, a part of the methanol from the secondary rectification column 180 is returned to the secondary rectification column 180 through the second feed circulation line 190 to be rectified again.
The dimethyl ether reaction unit comprises: the dimethyl ether reactor 10 and the first rectifying tower 40 are used for enabling the refined methanol stored in the refined methanol storage tank to go to the dimethyl ether reactor 10, after gas-phase catalytic dehydration reaction, reaction products enter the first rectifying tower 40 to purify dimethyl ether, after the top gas phase (mainly a small amount of gas-phase dimethyl ether, methanol and the like) after rectification is condensed, part of the top gas phase returns to the first rectifying tower, part of the top gas phase returns to the dimethyl ether reactor 10 to react again, and the rectified dimethyl ether goes to the dimethyl ether ethanol preparation reaction unit after being directly extracted from the lateral line.
The top of the first rectifying tower 40 is provided with an overhead condenser 401, and after the overhead gas phase passes through the overhead condenser 401, a part of the overhead gas phase returns to the first rectifying tower 40 again, and the other part of the overhead gas phase goes out of the overhead condenser 401 to the washing tower 140. The bottom of the first rectifying tower 40 is provided with a tower kettle reboiler 402, and under the action of the tower kettle reboiler 402, the product (mainly liquid phase dimethyl ether) flowing out of the tower kettle can be returned to the dimethyl ether reactor 10 as a reaction raw material for simple subsequent purification operation.
The first rectifying tower 40 is provided with a side line extraction mechanism for extracting the product dimethyl ether, and the extraction mechanism is connected with the first micro-interface generator for the subsequent reaction and synthesis of ethanol.
A heat exchanger 30 for exchanging heat between the raw material methanol and the gas phase catalytic dehydration reaction product is arranged between the dimethyl ether reactor 10 and the first rectifying tower 40, and a preheater 20 for preheating the raw material entering the dimethyl ether reactor 10 is also arranged between the heat exchanger 30 and the dimethyl ether reactor 10, so as to improve the reaction efficiency of the dimethyl ether reactor 10.
The reaction unit for preparing ethanol from dimethyl ether comprises: carbonylation reactor 70, first micro-interface generator 50, separation column 80, second micro-interface generator 90, hydrogenation reactor 110, and second rectification column 120.
The side line extraction mechanism for extracting the dimethyl ether product, which is arranged on the first rectifying tower 40, is communicated to the first micro-interface generator 50, CO is also introduced into the first micro-interface generator 50, carbon monoxide is conveyed from the CO storage tank 60, the carbon monoxide is dispersed and crushed after being mixed with the dimethyl ether in the first micro-interface generator 50, and then enters the carbonylation reactor 70 for carbonylation, the main components of the carbonylation reaction product are methyl acetate and some unreacted dimethyl ether, the unreacted dimethyl ether goes to the separation tower 80 from the bottom of the carbonylation reactor 70, the carbonylation reactor 70 is a fixed bed reactor, three layers of fixed tower plates 701 are arranged inside the fixed bed reactor, a carbonylation reaction catalyst is distributed on each layer of fixed tower plates 701, a plurality of mixture inlets 702 are also arranged on the carbonylation reactor 70, and the mixture inlets 702 are respectively arranged at the top of the carbonylation reactor 70 and between the adjacent fixed tower plates 701.
After the separation tower 80 is used for stripping, the top of the separation tower 80 is mainly unreacted dimethyl ether, the separation tank 801 arranged at the top of the separation tower 80 can directly return to the first micro-interface generator 50 to be used as a reaction feed for carbonylation, and the liquid phase from the bottom of the separation tank 801 directly returns to the separation tower 80 for stripping separation and purification.
The bottom of the separation tower is provided with a methyl acetate outlet 802, the substance discharged from the methyl acetate outlet 802 at the bottom of the separation tower 80 is mainly methyl acetate, and is conveyed into the second micro-interface generator 90 through a pump, in order to improve the effect of the second micro-interface generator 90, the methyl acetate is preheated by the preheater 20 and then is conveyed into the second micro-interface generator 90, meanwhile, hydrogen is simultaneously introduced into the second micro-interface generator 90, the hydrogen is conveyed through the hydrogen storage tank 100, and the hydrogen is fully mixed with the liquid-phase methyl acetate in the second micro-interface generator 90 and is crushed into micro-bubbles, and then enters the hydrogenation reactor 110 for hydrogenation reaction.
Methyl acetate generates methanol and ethanol after hydrogenation reaction, the methanol and the ethanol are conveyed to the second rectifying tower 120 for ethanol refining, a methanol outlet 1201 is formed in the top of the second rectifying tower 120, the methanol outlet 1201 returns to the dimethyl ether reactor 10 through a pipeline to be used as a methanol raw material, and a product extraction outlet 1202 is formed in the bottom of the second rectifying tower 120 and used for extracting product ethanol. The top of the second rectifying tower 120 is provided with a tower top condenser, the tower bottom is provided with a tower bottom reboiler, a part of substances discharged from the methanol outlet 1201 is condensed by the tower top condenser and then returns to the second rectifying tower 120, and a part of the substances is discharged, and the discharged part can be directly returned to the dimethyl ether reactor 10 to be used as reaction raw materials.
The micro-interface reaction system of the embodiment is provided with the micro-interface generator at a specific position, so that the mass transfer effect of the whole reaction is improved, the energy consumption is reduced, and the utilization rate of raw materials is improved.
In the above embodiment, it is not limited to setting a single micro-interface generator, and in order to increase the dispersion and mass transfer effects, additional micro-interface generators may be additionally provided, the installation position is not limited in practice, and the micro-interface generators may be external or internal, and when the micro-interface generators are internally installed, the micro-interface generators may be installed on the side wall in the kettle and arranged oppositely, so as to realize the opposite flushing of the micro-bubbles coming out from the outlet of the micro-interface generator, which is of course the best for the solution of the present invention, is to use the external micro-interface generator.
In the above embodiment, the number of the pump bodies is not specifically required, and the pump bodies may be arranged at corresponding positions as required.
The working process and principle of the coal-to-ethanol micro-interface reaction system of the invention are briefly explained as follows:
nitrogen purges each device in the micro-interface reaction system, then operation is carried out by starting, synthetic gas and inert oil are introduced into the micro-bubble generator 130 to disperse and break the synthetic gas into small bubbles, then the synthetic gas enters the synthetic tower 140 to carry out methanol synthetic reaction, the obtained crude methanol is rectified and purified by the gasification tower 150, the primary rectifying tower 160 and the secondary rectifying tower 180 in sequence and then is stored in the refined methanol storage tank 210, the refined methanol coming out of the refined methanol storage tank 210 is firstly carried out gas phase catalytic dehydration reaction in the dimethyl ether reactor 10, then the refined methanol goes to the first rectifying tower 40 to be rectified, the dimethyl ether taken out from the side line taking mechanism of the first rectifying tower 40 goes to the first micro-interface generator 50 to be mixed with CO for dispersion and breaking, the dispersed and broken mixture enters the carbonylation reactor 70 to carry out carbonylation reaction, the carbonylation reaction product goes to the separation tower 80 to carry out steam stripping separation, then the mixture is sent to a second micro-interface generator 90 after coming out from the bottom of the separation tower 80 and is mixed, dispersed and crushed with hydrogen, and then the mixture is sent to a hydrogenation reactor 110 for hydrogenation reaction, and finally the hydrogenation reaction product is sent to a second rectifying tower 120 for rectification to obtain the final product, namely the refined ethanol.
Wherein the pressure of the reaction for catalytically synthesizing the crude methanol by the synthesis gas is 2.5-4.0MPa, and the temperature is 180-200 ℃.
The pressure of the carbonylation reaction is 2.5-3.0MPa, and the temperature of the carbonylation reaction is 200-230 ℃.
The pressure of the hydrogenation reaction is 2.5-3.0MPa, and the temperature of the hydrogenation reaction is 200-210 ℃.
The above steps are repeated circularly to make the whole synthesis system run smoothly.
In a word, compared with the reaction system in the prior art, the reaction system disclosed by the invention has the advantages of fewer equipment components, small occupied area, low energy consumption, low cost, high safety, controllable reaction and high raw material conversion rate, is equivalent to providing a reaction system with stronger operability for the field of preparing ethanol from synthesis gas, and is worthy of wide popularization and application.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A reaction system for preparing ethanol by using synthesis gas is characterized by comprising: the device comprises a methanol preparation unit, a methanol-to-dimethyl ether reaction unit and a dimethyl ether-to-ethanol reaction unit which are connected in sequence;
the methanol preparation unit includes: the system comprises a micro-bubble generator and a synthesis tower, wherein inert oil and synthesis gas are simultaneously introduced into the micro-bubble generator, mixed, dispersed and crushed, and then enter the synthesis tower to react and synthesize crude methanol, and the crude methanol is rectified by a primary rectifying tower and a secondary rectifying tower in sequence to obtain rectified methanol which is sent to a reaction unit for preparing dimethyl ether from methanol;
the reaction unit for preparing dimethyl ether from methanol comprises: a dimethyl ether reactor; introducing the rectified methanol into the dimethyl ether reactor to carry out gas phase catalytic dehydration reaction, introducing a product after reaction into a first rectifying tower to carry out dimethyl ether purification and rectification, condensing a rectified gas phase, then partially returning to the first rectifying tower, partially returning to the dimethyl ether reactor to carry out re-reaction, and collecting a rectified dimethyl ether side line to a dimethyl ether ethanol preparation reaction unit;
the dimethyl ether-to-ethanol reaction unit comprises: the device comprises a carbonylation reactor, wherein a first micro-interface generator is arranged on the outer side of the carbonylation reactor, the first micro-interface generator is filled with dimethyl ether separated by rectification of a first rectifying tower and carbon monoxide, the dimethyl ether and the carbon monoxide are dispersed and crushed by the first micro-interface generator and then enter the carbonylation reactor for reaction, the carbonylation reactor is connected with a second micro-interface generator so as to be filled with a carbonylation product, the second micro-interface generator is filled with hydrogen at the same time, the hydrogen is dispersed and crushed by the second micro-interface generator and then enters a hydrogenation reactor for methyl acetate hydrogenation, and a reaction product after the hydrogenation reaction is subjected to methanol and ethanol separation by a second rectifying tower to obtain ethanol.
2. The reaction system of claim 1, wherein a gasification tower is arranged between the synthesis tower and the primary rectification tower for removing dimethyl ether, methyl formate and other low boiling point substances in the crude methanol, and the side wall of the primary rectification tower is connected with the bottom of the gasification tower through a pipeline for rectifying the crude methanol after impurities are removed in the primary rectification tower.
3. The reaction system of claim 2, wherein a first material circulation line for condensing the gas phase coming out from the top of the primary rectification tower and then returning to the primary rectification tower is arranged beside the primary rectification tower, a first condenser, a first condensing tank and a first circulation pump are sequentially arranged on the first material circulation line along the direction of the top of the primary rectification tower along the material outflow direction, and the side wall of the first condensing tank is connected with the top of the secondary rectification tower through a pipeline.
4. The reaction system of claim 3, wherein a second material circulation line for partially condensing the refined methanol extracted from the side line of the secondary rectification tower and returning the condensed refined methanol to the secondary rectification tower is arranged beside the secondary rectification tower, and a second condenser, a second condensation tank and a second circulation pump are sequentially arranged on the second material circulation line along the direction of the materials returning to the top of the secondary rectification tower.
5. The reaction system of claim 4, wherein a side line extraction line is arranged at the upper position of the side wall of the secondary rectifying tower, the end part of the side line extraction line is connected with a refined methanol storage tank, a third condenser is arranged on the side line extraction line, and a side branch of the side line extraction line between the secondary rectifying tower and the third condenser is connected with the second material circulating line.
6. The reaction system of claim 1, wherein the carbonylation reactor is a fixed bed reactor, three layers of fixed tower plates are arranged in the carbonylation reactor, each layer of fixed tower plate is provided with a carbonylation reaction catalyst, the carbonylation reactor is provided with a plurality of reaction mixture inlets, and the reaction mixture inlets are respectively arranged at the top of the carbonylation reactor and between the adjacent fixed tower plates.
7. A reaction system according to claim 1 wherein a separation column is provided between the carbonylation reactor and the second micro-interface generator for removing gas phase impurities from the carbonylation product.
8. The reaction system of claim 7, wherein a separation tank is arranged at the top of the separation tower, the gas phase separated by the separation tank is sent to the first micro-interface generator, and the liquid phase is returned to the separation tower for re-stripping separation.
9. The reaction method of the reaction system for producing ethanol by using synthesis gas according to any one of claims 1 to 8, comprising:
mixing, dispersing and crushing fresh synthesis gas and inert oil, catalytically synthesizing crude methanol, and rectifying the crude methanol to obtain refined methanol;
carrying out gas-phase catalytic dehydration and rectification on the refined methanol to obtain dimethyl ether;
after dimethyl ether and carbon monoxide are mixed, dispersed and crushed, carbonylation reaction is carried out to obtain a carbonylation reaction product;
and mixing, dispersing and crushing the carbonylation reaction product and hydrogen, carrying out hydrogenation reaction, and rectifying to obtain the ethanol.
10. The reaction method as claimed in claim 9, wherein the pressure of the reaction for catalytically synthesizing the crude methanol from the synthesis gas is 2.5-4.0MPa, and the temperature is 180-200 ℃;
preferably, the pressure of the carbonylation reaction is 2.5-3.0MPa, and the temperature is 200-230 ℃;
preferably, the pressure of the hydrogenation reaction is 2.5-3.0MPa, and the temperature is 200-210 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010683561.1A CN111848344A (en) | 2020-07-16 | 2020-07-16 | Reaction system and method for preparing ethanol by adopting synthesis gas |
| PCT/CN2020/122720 WO2022011865A1 (en) | 2020-07-16 | 2020-10-22 | Reaction system and method for preparing ethanol using syngas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113816829A (en) * | 2021-09-15 | 2021-12-21 | 东华工程科技股份有限公司 | System for directly producing ethanol by synthesis gas |
| CN114854536A (en) * | 2022-06-14 | 2022-08-05 | 南京工业大学 | Micro-interface reinforced efficient bioreactor for synthesis gas conversion and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115197047B (en) * | 2022-08-22 | 2023-08-22 | 西南化工研究设计院有限公司 | Coupling reaction method for preparing ethanol from dimethyl ether |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012062A (en) * | 2012-12-20 | 2013-04-03 | 上海戊正工程技术有限公司 | Process for indirectly producing alcohol with synthetic gas and application of process |
| CN110591763A (en) * | 2019-09-10 | 2019-12-20 | 南京延长反应技术研究院有限公司 | Intelligent enhanced control system and process for coal indirect liquefaction |
| CN210045215U (en) * | 2019-01-29 | 2020-02-11 | 南京延长反应技术研究院有限公司 | Low-pressure gas-liquid reinforced emulsion bed reaction device |
| CN111359547A (en) * | 2019-03-15 | 2020-07-03 | 南京延长反应技术研究院有限公司 | Oil-coal co-hydrogenation micro-interface reinforced emulsion bed reaction system |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389446A (en) * | 2002-05-20 | 2003-01-08 | 清华大学 | Methane synthesizing method and equipment with slurry bed member |
| CN203033918U (en) * | 2012-12-20 | 2013-07-03 | 上海戊正工程技术有限公司 | Process system for indirectly producing ethanol by using synthesis gases |
| CN109503326B (en) * | 2018-11-30 | 2020-10-09 | 西南化工研究设计院有限公司 | Process for indirectly producing ethanol by dimethyl ether |
| CN210229906U (en) * | 2019-01-29 | 2020-04-03 | 南京延长反应技术研究院有限公司 | Underneath type gas-liquid reinforced emulsification fixed bed reaction device |
| DE212019000177U1 (en) * | 2019-03-15 | 2020-09-03 | Nanjing Yanchang Reaction Technology Research Institute Co. Ltd | Microinterfacial enhanced hydrogenation reaction system |
| CN210079476U (en) * | 2019-03-15 | 2020-02-18 | 南京延长反应技术研究院有限公司 | Hydrogenation reaction system of micro-interface enhanced fluidized bed |
-
2020
- 2020-07-16 CN CN202010683561.1A patent/CN111848344A/en active Pending
- 2020-10-22 WO PCT/CN2020/122720 patent/WO2022011865A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012062A (en) * | 2012-12-20 | 2013-04-03 | 上海戊正工程技术有限公司 | Process for indirectly producing alcohol with synthetic gas and application of process |
| CN210045215U (en) * | 2019-01-29 | 2020-02-11 | 南京延长反应技术研究院有限公司 | Low-pressure gas-liquid reinforced emulsion bed reaction device |
| CN111359547A (en) * | 2019-03-15 | 2020-07-03 | 南京延长反应技术研究院有限公司 | Oil-coal co-hydrogenation micro-interface reinforced emulsion bed reaction system |
| CN110591763A (en) * | 2019-09-10 | 2019-12-20 | 南京延长反应技术研究院有限公司 | Intelligent enhanced control system and process for coal indirect liquefaction |
Non-Patent Citations (1)
| Title |
|---|
| 张志炳等: "多相反应体系的微界面强化简述", 《化工学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113816829A (en) * | 2021-09-15 | 2021-12-21 | 东华工程科技股份有限公司 | System for directly producing ethanol by synthesis gas |
| CN114854536A (en) * | 2022-06-14 | 2022-08-05 | 南京工业大学 | Micro-interface reinforced efficient bioreactor for synthesis gas conversion and application thereof |
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| WO2022011865A1 (en) | 2022-01-20 |
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