CN214060374U - Reaction system for preparing formic acid by carbon dioxide hydrogenation - Google Patents
Reaction system for preparing formic acid by carbon dioxide hydrogenation Download PDFInfo
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- CN214060374U CN214060374U CN202022713579.XU CN202022713579U CN214060374U CN 214060374 U CN214060374 U CN 214060374U CN 202022713579 U CN202022713579 U CN 202022713579U CN 214060374 U CN214060374 U CN 214060374U
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 170
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 115
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 84
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 58
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 58
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 6
- 238000000066 reactive distillation Methods 0.000 claims description 85
- 239000007788 liquid Substances 0.000 claims description 84
- 238000000926 separation method Methods 0.000 claims description 47
- 239000007789 gas Substances 0.000 claims description 31
- 238000000746 purification Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 description 25
- 239000012071 phase Substances 0.000 description 24
- 239000007791 liquid phase Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000007792 gaseous phase Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- -1 inorganic base potassium carbonate Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000012327 Ruthenium complex Substances 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- CJBFZKZYIPBBTO-UHFFFAOYSA-N isotetradecane Natural products CCCCCCCCCCCC(C)C CJBFZKZYIPBBTO-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 2
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- PQQAOTNUALRVTE-UHFFFAOYSA-L iron(2+);diformate Chemical compound [Fe+2].[O-]C=O.[O-]C=O PQQAOTNUALRVTE-UHFFFAOYSA-L 0.000 description 1
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 1
- BHVPEUGTPDJECS-UHFFFAOYSA-L manganese(2+);diformate Chemical compound [Mn+2].[O-]C=O.[O-]C=O BHVPEUGTPDJECS-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The utility model provides a reaction system of carbon dioxide hydrogenation system formic acid, reaction system of carbon dioxide hydrogenation system formic acid includes: a first reaction rectifying tower, a second reaction rectifying tower and a fine reactor; the side wall of the reaction rectifying tower is sequentially provided with a hydrogen inlet, a carbon dioxide inlet and a solvent and catalyst mixing inlet from top to bottom; the reaction rectifying tower is internally provided with a pneumatic micro-interface generator and a hydraulic micro-interface generator, the pneumatic micro-interface generator is arranged between tower plates in the reaction rectifying tower and is communicated with a hydrogen inlet for dispersing and crushing the entering hydrogen, and the hydraulic micro-interface generator is arranged at the bottom close to the reaction rectifying tower and is communicated with a carbon dioxide inlet for dispersing and crushing the entering carbon dioxide; the mixed inlet of the solvent and the catalyst is arranged at the bottom of the reaction rectifying tower. The reaction system of the utility model reduces the temperature and the pressure of the hydrogenation reaction.
Description
Technical Field
The utility model relates to a formic acid reaction preparation field particularly, relates to a reaction system of carbon dioxide hydrogenation system formic acid.
Background
Formic acid (CAS number: 64-18-6), also known as formic acid, is carboxylic acid with the least carbon number, has stronger acidity and is an important raw material for modern organic chemical industry. The formic acid synthesis method comprises (1) a methanol carbonylation synthesis method, wherein methanol and carbon monoxide are catalyzed by a catalyst to react to generate methyl formate, and then the methyl formate is hydrolyzed to obtain formic acid and methanol; (2) the formamide method is characterized in that carbon monoxide and amine are catalyzed by a catalyst to generate formamide in a methanol solution, and then the formamide is hydrolyzed under an acidic condition to obtain formic acid; (3) the carbon dioxide method directly prepares the formic acid by catalyzing the hydrogenation of carbon dioxide through a catalyst.
Among the above formic acid synthesis methods, the carbon dioxide hydrogenation for formic acid production which has been emerging for nearly 20 years has the highest theoretical atom economy, and is a very potential formic acid synthesis route. However, since the formation of formic acid by the reaction of carbon dioxide and hydrogen is thermodynamically limited, the existing processes all require the addition of an organic or inorganic base to react with formic acid to form formate in the reaction system to drive the reaction to move in the direction of forming formic acid. For example, Nature Catal (2018,1, 743-; angew. chem. int. Ed. (2019,58,722-726) reports a method for preparing formic acid by catalyzing the reaction of carbon dioxide and hydrogen with tris (pentafluorophenyl) boron as a catalyst, but excessive inorganic base potassium carbonate is added for the reaction with formic acid; in patent CN201810255395.8, a method for preparing formic acid by using ruthenium complex as a catalyst to catalyze carbon dioxide hydrogenation is reported, and excessive KHCO is required for the reaction3To react with formic acid to drive the process; in patent CN105367404B, a method for preparing formic acid by carbon dioxide hydrogenation with a nano-porous palladium catalyst is reported, in which an excessive amount of sodium hydroxide or sodium tert-butoxide is required to react with formic acid to drive the process; patent CN106622224A reports a method for preparing formic acid by hydrogenation of carbon dioxide with a nanogold-based catalyst, and the reaction needs an excessive amount of triethylamine or triethanolamine to react with formic acid to drive the process to proceed. In addition, because formic acid is strong in acidity and can react with a plurality of organic metal compounds, the catalyst reported by the existing method is unstable under the formic acid condition, so that the catalyst is quickly deactivated.
In view of this, the present invention is especially provided.
SUMMERY OF THE UTILITY MODEL
A first object of the utility model is to provide a reaction system, this reaction system promotes going on smoothly of reaction through setting up the reaction rectifying column on the one hand, thereby avoided adding organic or inorganic alkali to promote the process of reaction preparation formic acid, reaction efficiency has been improved and reaction operation has been simplified, on the other hand is through setting up the high-efficient micron order bubble that breaks into of gaseous phase that micro-interface generator will get into in the reaction rectifying column, and disperse to the solvent, form the micro-interface system in the catalyst, with the gas-liquid phase interfacial area in the tens of times ground improvement reaction gas-liquid, improve the mass transfer rate of gaseous phase to the liquid phase by a wide margin.
A second object of the present invention is to provide a reaction method for producing formic acid using the above reaction system, which is simple and convenient to operate, high in purity of the obtained formic acid, high in product quality, and worthy of wide popularization and application.
In order to realize the above purpose of the utility model, the following technical scheme is adopted:
the utility model provides a reaction system of carbon dioxide hydrogenation system formic acid, include: the device comprises a first reactive distillation tower, a second reactive distillation tower and a fine reactor, wherein the first reactive distillation tower and the second reactive distillation tower are connected in parallel; the side walls of the first reactive distillation tower and the second reactive distillation tower are sequentially provided with a hydrogen inlet, a carbon dioxide inlet and a mixed inlet of a solvent and a catalyst from top to bottom;
the first reactive distillation tower and the second reactive distillation tower are internally provided with a pneumatic micro-interface generator and a hydraulic micro-interface generator, the pneumatic micro-interface generator is arranged between tower plates in the reactive distillation towers and is communicated with a hydrogen inlet for dispersing and crushing the entering hydrogen, the hydraulic micro-interface generator is arranged at the bottom close to the first reactive distillation tower and the second reactive distillation tower and is communicated with a carbon dioxide inlet for dispersing and crushing the entering carbon dioxide, and the pneumatic micro-interface generator and the hydraulic micro-interface generator are arranged in liquid descending pipes in the first reactive distillation tower and the second reactive distillation tower;
the mixed inlet of the solvent and the catalyst is arranged at the bottoms of the first reactive distillation tower and the second reactive distillation tower so as to fill the whole first reactive distillation tower and the second reactive distillation tower with the entered solvent and the entered catalyst;
the top of the first reactive distillation tower and the second reactive distillation tower is provided with a formic acid outlet for discharging formic acid product, formic acid from the formic acid outlet subsequently enters the fine reactor for fine reaction, a shunting type micro-interface generator is arranged in the fine reactor, and the shunting type micro-interface generator is provided with a plurality of shunting channels on a micro-interface generator body.
In the formic acid synthesis method in the prior art, because the formation of formic acid by the reaction of carbon dioxide and hydrogen is thermodynamically limited, organic or inorganic base needs to be added into a reaction system in the prior art to react with formic acid to form formate, so as to push the reaction to move towards the formation of formic acid. For example, Nature Catal (2018,1, 743-; angew. chem. int. Ed. (2019,58,722-726) reports a method for preparing formic acid by catalyzing the reaction of carbon dioxide and hydrogen with tris (pentafluorophenyl) boron as a catalyst, but excessive inorganic base potassium carbonate is added for the reaction with formic acid; in patent CN201810255395.8, a method for preparing formic acid by using ruthenium complex as a catalyst to catalyze carbon dioxide hydrogenation is reported, and excessive KHCO is required for the reaction3To react with formic acid to drive the process; in patent CN105367404B, a method for preparing formic acid by carbon dioxide hydrogenation with a nano-porous palladium catalyst is reported, in which an excessive amount of sodium hydroxide or sodium tert-butoxide is required to react with formic acid to drive the process; report in patent CN106622224A with method of nanometer gold base catalyst catalysis carbon dioxide hydrogenation system formic acid, the reaction need come with excessive triethylamine or triethanolamine etc. and the formic acid reaction goes on in order to promote the process, it all needs to add going on that a certain amount of organic or inorganic alkali promoted the reaction among the prior art to see, the utility model discloses a solve above-mentioned technical problem and provide a neotype reaction system, replaced reaction mode in the past through having adopted reaction rectifying column equipment in this reaction system, directly reach the purpose of rectifying while reacting in the reaction rectifying column to through set up little interfacial generator in the reaction rectifying column and improved reaction efficiency, increase substantially mass transfer rate, reduced hydrogenation catalyst and made hydrogenReaction temperature and pressure.
The utility model discloses a reaction rectifying tower, no matter be first reaction rectifying tower or all be provided with a plurality of column plates in the second reaction rectifying tower, general catalyst and solvent get into from the tower cauldron, hydrogen and carbon dioxide get into from the middle section of first reaction rectifying tower and second reaction rectifying tower, in order to improve reaction effect, the micro interface generator in first reaction rectifying tower and the second reaction rectifying tower is two, and two kinds of type are inconsistent, the micro interface generator who is located upper portion is pneumatic micro interface generator, be located the lower part for hydraulic type micro interface generator, hydraulic type micro interface generator sets up the tower cauldron position of reaction rectifying tower is in order to be close to solvent, catalyst mix import to hydraulic type micro interface generator select with the carbon dioxide import communicates with each other. Since this allows better reaction of the carbon dioxide introduced first with the liquid phase.
The utility model discloses a so the reaction rectifying column sets up to two, and connects in parallel each other between two and operate simultaneously, is in order to improve the handling capacity, also corresponding improvement reaction efficiency.
During actual hydrogenation operation, firstly introducing carbon dioxide into a reaction rectifying tower for vacuum displacement for 2-3 times, then introducing the carbon dioxide to a certain pressure, introducing the carbon dioxide into a micro-interface generator for dispersion and crushing, subsequently introducing hydrogen to a certain pressure, introducing the hydrogen into the micro-interface generator for dispersion and crushing, performing dispersion and crushing on two gas phases after dispersion and crushing, remarkably improving the reaction effect of the subsequent hydrogenation reaction, heating to the reaction temperature, reacting for 8-10 hours generally, and collecting a formic acid solution product from the top of the tower.
It should be noted that, the utility model discloses a every micro-interface generator that sets up among the reaction system not only the type itself is different, the gaseous phase type that lets in is also different, pneumatic micro-interface generator and hydrogen import intercommunication, hydraulic micro-interface generator and carbon dioxide import intercommunication, carbon dioxide lets in earlier, hydrogen lets in afterwards, so the micro-interface generator that the bottom set up is hydraulic micro-interface generator, be close to the liquid phase that gets into from the bottom, use the liquid phase that gets into as the entrainment power, thereby improve gaseous entrainment crushing effect more, the carbon dioxide that gets into can disperse the breakage better under the condition of catalyst, solvent as the medium like this, improve the effect of mutual intimate contact, after carbon dioxide is dispersed the breakage fully, let in hydrogen again from the gaseous micro-interface generator that is located the top of the tower position this moment, can guarantee the hydrogen and the violent reaction of carbon dioxide that get into, the reaction effect is improved.
It can be seen that, the utility model discloses a reaction system is exactly because two kinds of gaseous phase raw materials that get into all need adopt little interface generator to disperse the breakage, so need adjust little interface generator's the position that sets up, concrete type and advance the kind mode according to the gaseous phase type that gets into to reach the optimal reaction effect.
In particular, the utility model is specially provided with a shunting type micro-interface generator in the fine reactor, and the specific structure of the shunting type micro-interface generator is that a plurality of shunting channels are arranged on the body of the micro-interface generator. The reposition of redundant personnel passageway is the best curved form, sets up in the exit of little interface generator body, especially to this smart reactor, and the product export just in time faces the broken export of the gaseous dispersion of little interface generator, sets up a plurality of reposition of redundant personnel passageways and can carry out the effect of cloth collection to the dispersion bubble that comes out like this at the broken export of gaseous dispersion to can make more microbubble gathering around the product export, improve reaction effect, so visible the utility model discloses what novelty combine micro-interface generator and reposition of redundant personnel passageway to use, improved the application effect of little interface generator of itself. The micro-interface generator body is of a pneumatic type.
In a word, the micro-interface generator in the first reaction rectifying tower, the second reaction rectifying tower and the rectifying reactor breaks the gas phase into micro-bubbles with micron scale, and releases the micro-bubbles to the reaction rectifying tower and the rectifying reactor so as to increase the mass transfer area of the phase boundary between the gas phase and the liquid phase in the hydrogenation reaction, thus leading the two phases to be fully contacted, improving the reaction efficiency, shortening the reaction time and fully reducing the reaction pressure and temperature.
It will be appreciated by those skilled in the art that the micro-interface generator of the present invention has been embodied in the prior patents of the present invention, such as the patents having application numbers CN201610641119.6, CN201610641251.7, 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, no matter be the hydraulic formula micro-interface generator, still gas-liquid linkage micro-interface generator all belongs to a specific form of micro-interface generator, however the utility model discloses the micro-interface generator who adopts is not limited to above-mentioned several kinds of forms, and the specific structure of the bubble breaker who records in the patent in advance is only one of them form that the micro-interface generator 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.
Because the initial stage of earlier patent application, little interfacial surface generator just has just developed, so the early name is micron bubble generator (CN201610641119.6), bubble breaker (201710766435.0) etc. along with continuous technological improvement, later stage renames as little interfacial surface generator, now the utility model provides a little interfacial surface generator is equivalent to micron bubble generator, bubble breaker etc. before, and only the name is different. To sum up, the utility model discloses a little interface generator belongs to prior art.
Preferably, liquid ejectors are arranged in the first reactive distillation tower and the second reactive distillation tower, and the liquid ejectors are communicated with the mixed inlets of the solvent and the catalyst.
Preferably, the liquid ejector is of a semicircular shape, the bottom surface of the liquid ejector is tightly attached to the side walls of the first reaction rectifying tower and the second reaction rectifying tower, a plurality of liquid ejecting pipes are arranged in the liquid ejector, the liquid ejecting pipes are connected with ejecting heads, and the ejecting heads are uniformly distributed on the semicircular surface.
Preferably, the bottom surface of the liquid injector is in communication with the solvent and catalyst mixing inlet.
The liquid phase that gets into is catalyst and solvent mainly, in order to improve the catalytic effect of catalyst, disperses the inside of reaction rectifying column with the mode of liquid ejector injection with the catalyst, more can improve its reaction effect, especially has laid many liquid injection pipes in liquid ejector inside, and every liquid injection pipe is equivalent to a microchannel, and through carrying out the multichannel with the liquid phase and laying and spraying away with the mode of spraying, strengthened the interact with the gaseous phase. Therefore, the injection pipe arranged in the liquid injector plays a good flow guide role, so that after the liquid phase is better distributed, the micro-interface generator is adopted to disperse and crush the gas phase, and meanwhile, the purpose of carrying out corresponding micro-operation on the liquid phase is also realized.
Preferably, the fine reactor is connected with a gas-liquid separation tank, and reactants after reaction in the fine reactor enter the gas-liquid separation tank for gas-liquid separation and purification.
Preferably, the top of the gas-liquid separation tank is connected with a gas phase return pipeline for separating the gas phase in the formic acid and returning the gas phase to the first reactive distillation tower and the second reactive distillation tower.
Preferably, the gas-liquid separation tank is connected with a separation tower for further purifying and separating the materials extracted from the gas-liquid separation tank.
Preferably, the top of the separation tower and the top of the fine reactor are both provided with pipelines communicated with the gas phase return pipeline, so that the gas phase is returned to the first reactive distillation tower and the second reactive distillation tower after being separated.
Preferably, the bottom of the gas-liquid separation tank is connected with a purification tower, and the purification tower is used for purifying the bottom material and then sending the bottom material into the separation tower.
The rectifying reactor is arranged for further reacting the material from the top of the tower to improve the yield, then the material enters the gas-liquid separation tank, the gas phase separated from the gas-liquid separation tank mainly contains carbon dioxide and hydrogen, and the gas phase returns to the reactive rectifying tower to be reacted and utilized again. Similarly, the gas phase separated from the top into the separation column is mainly carbon dioxide and hydrogen, and can be returned for reuse.
In addition, the material that comes out from the gas-liquid separation tank bottom also contains partial purpose product formic acid, separates the collection in order to separate the formic acid in this part of material, the utility model discloses still set up the purification tower, through the purification by distillation of purification tower, return the component that has wherein gathered formic acid to mix the purification separation with the material that the gas-liquid separation tank came in the last knockout tower, finally obtain the purpose product and store in the product jar.
In addition, the utility model also provides a reaction method of carbon dioxide hydrogenation system formic acid, including the following step:
dispersing and crushing a mixed micro interface of hydrogen, carbon dioxide, a solvent and a catalyst, then carrying out hydrogenation reaction, and purifying to obtain formic acid, wherein the temperature of the hydrogenation reaction is 120-160 ℃, and the pressure of the hydrogenation reaction is 0.05-2 MPa.
Preferably, the solvent is a linear or branched alkane containing 10 to 16 carbons;
the catalyst is formate, and comprises one or more of copper formate, iron formate, cobalt formate, manganese formate and nickel formate;
the mass ratio of the solvent to the catalyst is (10:1) - (1000: 1).
Compared with the method for preparing formic acid by hydrogenating carbon dioxide in the prior art, the method of the utility model uses the formate which is very stable in formic acid as the catalyst, thereby ensuring the stability of the catalyst in long-term use and further improving the stability of reaction.
Compared with the prior art, the beneficial effects of the utility model reside in that:
(1) the utility model has the advantages that the two reaction rectifying towers are arranged simultaneously to promote the smooth reaction, thereby avoiding the need of adding organic or inorganic alkali to promote the reaction, improving the reaction efficiency and simplifying the reaction operation through the process of preparing formic acid by formate acidification;
(2) the reaction system of the utility model efficiently crushes the entered gas phase into micron-sized bubbles through the micro-interface generators arranged in the two reaction rectifying towers, and disperses the micron-sized bubbles into the solvent and the catalyst to form a micro-interface system, so as to improve the gas-liquid interface area in the gas-liquid reaction by tens of times and greatly improve the mass transfer rate of the gas phase to the liquid phase;
(3) the method of the utility model uses the formate which is very stable in the formic acid as the catalyst, thereby ensuring the stability of the catalyst in long-term use and further improving the stability of the reaction.
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 preparing formic acid by hydrogenation of carbon dioxide provided in embodiment 1 of the present invention;
fig. 2 is a schematic structural diagram of a liquid ejector of a reaction system for preparing formic acid by hydrogenation of carbon dioxide according to embodiment 1 of the present invention.
Description of the drawings:
10-a first reactive distillation column; 101-a hydrogen inlet;
102-a carbon dioxide inlet; 103-solvent and catalyst mixing inlet;
104-a pneumatic micro-interface generator; a 105-formic acid outlet;
106-a liquid ejector; 1061-liquid jet tube;
1062-jet head; 107-a hydrodynamic micro-interface generator;
20-a gas-liquid separation tank; 30-a product tank;
40-a hydrogen storage tank; 50-a carbon dioxide storage tank;
60-solvent, catalyst storage tank; 70-fine reactor;
701-split flow type micro-interface generator; 7011-micro interface generator body;
7012-a shunt channel; 80-a separation column;
90-gas phase return line 100-purification column;
110-second reactive distillation column.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings and 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. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative work belong to 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", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific 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 is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; 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 meaning of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In order to clarify the technical solution of the present invention, the following description is made in the form of specific embodiments.
Example 1
Referring to fig. 1, a reaction system for preparing formic acid by hydrogenation of carbon dioxide according to an embodiment of the present invention mainly includes a first reactive distillation column 10, a second reactive distillation column 110, a fine reactor 70, a gas-liquid separation tank 20, a separation column 80, and a purification column 100; the side walls of the first reactive distillation tower 10 and the second reactive distillation tower 110 are sequentially provided with a hydrogen inlet 101, a carbon dioxide inlet 102 and a solvent and catalyst mixing inlet 103 from top to bottom, the solvent and catalyst mixing inlet 103 is arranged at the bottoms of the first reactive distillation tower 10 and the second reactive distillation tower 110 for filling the whole first reactive distillation tower 10 and the whole second reactive distillation tower 110 with the entering solvent and catalyst, the tops of the first reactive distillation tower 10 and the second reactive distillation tower 110 are provided with a formic acid outlet 105 for discharging a product formic acid, the formic acid discharged from the formic acid outlet 105 subsequently enters the gas-liquid separation tank 20 for further purification, the hydrogen gas entering from the hydrogen inlet 101 is stored in the hydrogen storage tank 40, the carbon dioxide entering from the carbon dioxide inlet 102 is stored in the carbon dioxide storage tank 50, and the solvent entering from the catalyst mixing inlet 103 are further purified, The catalyst is stored in a solvent, catalyst storage tank 60.
The first reactive distillation tower 10 and the second reactive distillation tower 110 are internally provided with a pneumatic micro-interface generator 104 and a hydraulic micro-interface generator 107, the pneumatic micro-interface generator 104 is respectively arranged between tower plates, the hydraulic micro-interface generator 105 is arranged at the bottom close to the first reactive distillation tower 10 and the second reactive distillation tower 110, the hydraulic micro-interface generator 104 is communicated with the carbon dioxide inlet 102, and the pneumatic micro-interface generator 104 is communicated with the hydrogen inlet 101 for dispersing and crushing the entering hydrogen.
In addition, the first reactive distillation column 10 and the second reactive distillation column 110 are internally provided with a liquid ejector 106, the liquid ejector 106 is communicated with the solvent and catalyst mixing inlet 103, the liquid ejector 106 is semicircular, the bottom surface of the liquid ejector 106 is tightly attached to the side walls of the first reactive distillation column 10 and the second reactive distillation column 110, a plurality of liquid ejecting pipes 1061 are distributed in the liquid ejector 106, the liquid ejecting pipes 1061 are connected with ejecting heads 1062, the ejecting heads 1062 are uniformly distributed on the semicircular surfaces, and the bottom surface of the liquid ejector 106 is communicated with the solvent and catalyst mixing inlet 103.
The formic acid product from the formic acid outlet 105 passes through the fine reactor 70 and the gas-liquid separation tank 20 in sequence, the reactant after the reaction in the fine reactor 70 enters the gas-liquid separation tank 20 for gas-liquid separation and purification, the top of the gas-liquid separation tank 20 is connected with a gas phase return pipeline 90, so as to separate the gas phase in the formic acid and return the gas phase to the first reactive distillation column 10 and the second reactive distillation column 110, the gas-liquid separation tank 20 is connected with a separation column 80 for further purifying and separating the material extracted from the gas-liquid separation tank 20, the tops of the separation column 80 and the fine reactor 70 are provided with pipelines communicated with the gas phase return pipeline 90, the gas phase is separated and then returned to the first reactive distillation column 10 and the second reactive distillation column 110, and the bottom of the gas-liquid separation tank 20 is connected with a purification column 100, so that the bottom material is purified in the purification column 100 and then sent to the separation column 80.
The flow-splitting type micro-interface generator 701 is arranged in the fine reactor 70, the flow-splitting type micro-interface generator 701 is provided with a plurality of flow-splitting channels 7012 on a micro-interface generator body 7011, and the flow-splitting type micro-interface generator 701 is preferably arranged at the bottom in the fine reactor 70 and below a catalyst bed layer, so that the flow-splitting type micro-interface generator is closer to a product outlet and is more favorable for improving the reaction efficiency of the product.
In the specific reaction process, 200ml of n-dodecane and 10g of copper formate are added into the tower kettles of the first reactive distillation tower 10 and the second reactive distillation tower 110, carbon dioxide and vacuum displacement is carried out for 3 times, then carbon dioxide is introduced to 2MPa, hydrogen is introduced to 2MPa, the tower kettles are heated to 120 ℃ for reaction for 8 hours, 3.7g of liquid is collected at the tower top, the formic acid content is calibrated to be 98.9% through nuclear magnetism, the liquid collected at the tower top is subjected to gas-liquid separation through a fine reactor and a gas-liquid separation tank 20 in sequence, and the product obtained through gas-liquid separation is stored in a product tank 30 after passing through a separation tower.
Examples 2 to 5
The other operating steps are identical to those of example 1, except that the reaction is carried out with different catalysts, the results being shown in table 1:
TABLE 1 results of reactions using different catalysts
| Examples | 2 | 3 | 4 | 5 |
| Catalyst and process for preparing same | Iron formate | Cobalt formate | Manganese formate | Nickel formate |
| Overhead liquid (g) | 2.8 | 4.4 | 1.6 | 2.0 |
| Formic acid content (%) | 98.5 | 98.3 | 98.8 | 98.9 |
Examples 6 to 10
The other operating steps are identical to those of example 1, except that the reaction is carried out using different solvents, the results being shown in table 2:
TABLE 2 reaction results using different solvents
| Examples | 6 | 7 | 8 | 9 | 10 |
| Solvent(s) | N-decane | Isododecane | N-tetradecane | Isotetradecane | N-hexadecane |
| Overhead liquid (g) | 3.4 | 3.8 | 3.7 | 3.7 | 3.9 |
| Formic acid content (%) | 96.6 | 98.7 | 98.6 | 98.6 | 98.9 |
Examples 11 to 13
The other operating steps are identical to those of example 1, except that the reaction is carried out at different temperatures, the results being shown in Table 3:
TABLE 3 results of reactions using different temperatures
| Examples | 11 | 12 | 13 |
| Temperature (. degree.C.) | 130 | 140 | 160 |
| Overhead liquid (g) | 2.3 | 2.9 | 3.3 |
| Formic acid content (%) | 99.2 | 98.9 | 98.7 |
Example 14
The other operation steps are the same as example 1, except that carbon dioxide is introduced to 0.05MPa, then hydrogen is introduced to 0.05MPa, 3.3g of liquid is collected at the top of the tower, and the content of formic acid is calibrated to 97.5% by nuclear magnetism.
In the above embodiment, the specific contents of formic acid in the substances respectively coming out from the tops of the first reactive distillation column 10 and the second reactive distillation column 110 are calibrated, and in actual operation, the contents of formic acid coming out from the tops of the two reactive distillation columns are substantially consistent, so that the values are directly recorded in a consistent manner, and the formic acid content in the product coming out after subsequently passing through the rectifying reactor 70 is inevitably higher than the formic acid contents in the substances coming out from the tops of the first reactive distillation column 10 and the second reactive distillation column 110. In addition, in order to increase the dispersion and mass transfer effects, additional micro-interface generators may be additionally provided, the installation position is not limited, the micro-interface generators may be external or internal, and the micro-interface generators may be installed on the side walls of the first reactive distillation column 10 and the second reactive distillation column 110 in a manner of being opposite to each other when the micro-interface generators are internally installed, so as to realize the opposite flushing of micro-bubbles discharged from the outlets of the micro-interface generators.
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.
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; although the present invention has been described in detail with reference to the foregoing embodiments, it should 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; such modifications and substitutions do not depart from the spirit and scope of the present invention.
Claims (8)
1. A reaction system for preparing formic acid by hydrogenation of carbon dioxide is characterized by comprising: the device comprises a first reactive distillation tower, a second reactive distillation tower and a fine reactor, wherein the first reactive distillation tower and the second reactive distillation tower are connected in parallel; the side walls of the first reactive distillation tower and the second reactive distillation tower are sequentially provided with a hydrogen inlet, a carbon dioxide inlet and a mixed inlet of a solvent and a catalyst from top to bottom;
the first reactive distillation tower and the second reactive distillation tower are internally provided with a pneumatic micro-interface generator and a hydraulic micro-interface generator, the pneumatic micro-interface generator is arranged between tower plates in the reactive distillation towers and is communicated with a hydrogen inlet for dispersing and crushing the entering hydrogen, the hydraulic micro-interface generator is arranged at the bottom close to the first reactive distillation tower and the second reactive distillation tower and is communicated with a carbon dioxide inlet for dispersing and crushing the entering carbon dioxide, and the pneumatic micro-interface generator and the hydraulic micro-interface generator are arranged in liquid descending pipes in the first reactive distillation tower and the second reactive distillation tower;
the mixed inlet of the solvent and the catalyst is arranged at the bottoms of the first reactive distillation tower and the second reactive distillation tower so as to fill the whole first reactive distillation tower and the second reactive distillation tower with the entered solvent and the entered catalyst;
the top of the first reactive distillation tower and the second reactive distillation tower is provided with a formic acid outlet for discharging formic acid product, formic acid from the formic acid outlet subsequently enters the fine reactor for fine reaction, a shunting type micro-interface generator is arranged in the fine reactor, and the shunting type micro-interface generator is provided with a plurality of shunting channels on a micro-interface generator body.
2. The reaction system of claim 1, wherein the fine reactor is connected with a gas-liquid separation tank, and reactants after reaction in the fine reactor enter the gas-liquid separation tank for gas-liquid separation and purification.
3. The reaction system of claim 2, wherein a gas phase return pipeline is connected to the top of the gas-liquid separation tank, and is used for returning the gas phase in the formic acid to the first reactive distillation tower and the second reactive distillation tower after separation.
4. The reaction system of claim 3, wherein a separation tower is connected to the gas-liquid separation tank for further purification and separation of the material withdrawn from the gas-liquid separation tank.
5. The reaction system of claim 4, wherein the top of the separation tower and the top of the fine reactor are provided with pipelines communicated with the gas phase return pipeline for returning the separated gas phase to the first reactive distillation tower and the second reactive distillation tower.
6. The reaction system as claimed in claim 4, wherein a purification column is connected to the bottom of the gas-liquid separation tank, for purifying the bottom material in the purification column and feeding the purified bottom material into the separation column.
7. The reaction system according to any one of claims 1 to 6, wherein liquid injectors are arranged in the first reactive distillation column and the second reactive distillation column, and the liquid injectors are communicated with the mixed inlet of the solvent and the catalyst.
8. The reaction system of claim 7, wherein the liquid ejector is semicircular, the bottom surface of the liquid ejector is tightly attached to the side walls of the first reactive distillation column and the second reactive distillation column, a plurality of liquid ejecting pipes are arranged in the liquid ejector, the liquid ejecting pipes are connected with ejecting heads, and the ejecting heads are uniformly distributed on the semicircular surface.
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