CN113045387A - Reaction system and method for preparing butanol and octanol through propylene carbonylation - Google Patents
Reaction system and method for preparing butanol and octanol through propylene carbonylation Download PDFInfo
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- CN113045387A CN113045387A CN202110308636.2A CN202110308636A CN113045387A CN 113045387 A CN113045387 A CN 113045387A CN 202110308636 A CN202110308636 A CN 202110308636A CN 113045387 A CN113045387 A CN 113045387A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 100
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 title claims abstract description 98
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 48
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 19
- 230000006315 carbonylation Effects 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 28
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 226
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 104
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 60
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 55
- 238000009833 condensation Methods 0.000 claims abstract description 48
- 230000005494 condensation Effects 0.000 claims abstract description 48
- 239000001257 hydrogen Substances 0.000 claims description 64
- 229910052739 hydrogen Inorganic materials 0.000 claims description 64
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 62
- 239000007789 gas Substances 0.000 claims description 49
- 239000003054 catalyst Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 29
- 239000012071 phase Substances 0.000 claims description 26
- 239000007791 liquid phase Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 11
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 238000009827 uniform distribution Methods 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 238000007037 hydroformylation reaction Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- PYLMCYQHBRSDND-SOFGYWHQSA-N (E)-2-ethyl-2-hexenal Chemical compound CCC\C=C(/CC)C=O PYLMCYQHBRSDND-SOFGYWHQSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000005501 phase interface Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 2
- -1 oxo butyraldehyde Chemical compound 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100001224 moderate toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
-
- 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
- C07C29/14—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 a —CHO group
- C07C29/141—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 a —CHO group with hydrogen or hydrogen-containing gases
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
Abstract
The invention provides a reaction system for preparing butanol and octanol through propylene carbonylation, which comprises: a synthesis reactor, an isomerate separator, a first hydrogenation reactor and a condensation reactor; the synthesis reactor is connected with the isomer separator; the isomerate separator is provided with a n-butyl aldehyde outlet and a mixed butyraldehyde outlet; the mixed butyraldehyde outlet is connected with the first hydrogenation reactor, and the n-butyraldehyde outlet is connected with the condensation reactor; an external micron bubble generator and a condenser are arranged between the isomer separator and the first hydrogenation reactor; mixed butyraldehyde is followed mixed butyraldehyde export is discharged, and partly direct entering in the external micron bubble generator, another part warp the condenser condensation back gets into in the external micron bubble generator. The reaction system has the advantages of low energy consumption, low cost, high safety, low required reaction temperature and pressure, less side reaction and high butyraldehyde conversion rate, and is worthy of wide popularization and application.
Description
Technical Field
The invention relates to the field of propylene hydroxylation reaction preparation, and particularly relates to a reaction system and method for preparing butanol and octanol through propylene carbonylation.
Background
The butanol and octanol are important raw materials for synthesizing fine chemical products, the yield of the butanol and octanol in China is huge at present and accounts for about 21% of the total amount of the world, the butanol and octanol take synthesis gas and propylene as raw materials, and the n-isobutyraldehyde is generated through formylation reaction to obtain n-isobutanol, and the octanol can also be obtained through the condensation and the addition of unsaturated bonds of two molecules of n-butanol, so the octanol is habitually called as the butanol and octanol. The butanol and octanol have the typical characteristics of alcohol organic matters, have special smell, are colorless transparent and flammable liquids, have moderate toxicity and can form an azeotrope with water. The method is mainly used for producing plasticizers, solvents, dehydrating agents, defoaming agents, dispersing agents, flotation agents, petroleum additives, synthetic spices and the like. Due to its wide use, the yield and the amount of butanol and octanol are also increased year by year.
The major production methods of butanol and octanol include fermentation, acetaldehyde condensation, and propylene oxo synthesis, which is a major method for producing butanol and octanol, and is rapidly developing with significant advantage worldwide.
The method for preparing butanol and octanol by the propylene oxo synthesis method comprises the following steps:
(1) butyraldehyde generation: taking synthesis gas and propylene as raw materials, taking rhodium carbonyl, triphenylphosphine complex or other similar substances used in industry as catalysts, reacting to produce mixed butyraldehyde, separating the catalysts, and then further rectifying and separating to obtain a butyraldehyde mixture;
(2) production of butanol: the butyraldehyde mixture enters a butyraldehyde hydrogenation system to generate butanol, and the butanol is rectified to remove light and heavy components and separate isomers to obtain n-butanol and isobutanol;
(3) and (3) generating octanol: n-butyl aldehyde enters a condensation system for carbonyl condensation to produce octenal, and then the light and heavy components are removed by hydrogenation and rectification to finally produce octanol.
The main equation for the preparation of butanol and octanol by the propylene oxo process is as follows:
(1) hydroformylation of propylene to form n-butyraldehyde (n-Bal):
CH3CH＝CH2+CO+H2→CH3CH2CH2CHO
(2) hydroformylation of propylene to isobutyraldehyde (i-Bal):
CH3CH＝CH2+CO+H2→CH3CH2(CHO)CH3
(3) mixed butyraldehyde is hydrogenated to generate isobutanol and n-butanol:
CH3CH2CH2CHO+H2→CH3CH2CH2CH2OH
CH3CH2(CHO)CH3+H2→CH3CH(CH3)CH2OH
(4) condensation of n-butyraldehyde to produce 2-ethyl-3-propylacrolein (EPA):
2CH3CH2CH3CHO→CH3CH2CH2CH＝C(C2H5)CHO+H2O
(5) hydrogenation of 2-ethyl-3-propylacrolein to octanol:
CH3CH2CH2CH＝C(C2H5)CHO+2H2→CH3CH2CH2CH(CH2CH3)CH2OH
chinese patent publication No.: CN103012089A discloses a method for synthesizing propylene by carbonyl, which comprises feeding propylene, stripping synthesis gas and hydroformylation catalyst solution into a first butyraldehyde condensation unit for contact reaction, feeding foam components containing hydroformylation catalyst in the butyraldehyde condensation unit into a first separator for separation, feeding a part of the obtained gas phase components back, feeding the other part of the obtained gas phase components, synthesis gas and hydroformylation catalyst solution into a second butyraldehyde condensation unit for contact reaction, and feeding foam components containing hydroformylation catalyst in the butyraldehyde condensation unit into a second separator for separation; feeding at least part of the liquid phase at the bottom of the first and second oxo butyraldehyde condensation unit and the synthesis gas into a stripping tower for stripping, obtaining liquid phase components at the bottom of the tower, and obtaining the stripped synthesis gas at the top of the tower; and (3) feeding the liquid-phase component at the bottom of the stripping tower into a separation tower for separation, collecting a butyraldehyde crude product at the tower top, and collecting a catalyst solution at the tower bottom. The method can effectively improve the utilization rate of the propylene and reduce the content of the propylene in the tail gas. It can be seen that the method has the following problems:
firstly, in the method, propylene and synthesis gas are contacted with a catalyst only through a first oxo butyraldehyde condensation unit, and a gas-phase component enters the first oxo to form large bubbles, but the gas-phase component cannot be fully contacted with a liquid-phase component catalyst due to overlarge bubble volume, so that the reaction efficiency of the system is reduced.
Secondly, the reaction rate of the synthesis gas and the propylene with the catalyst is reduced in the method, so that the utilization rate of the propylene and the synthesis gas is reduced, the waste of raw materials is caused to a great extent, the production cost of the butanol and the octanol is increased, and the requirement of the existing circular economy is not met.
Thirdly, the method does not consider the problems of small phase interface area, serious liquid drop coagulation phenomenon, low reaction efficiency and the like in the direct reaction of the alkali liquor and the n-butyl aldehyde solution.
Fourthly, in the method, a fixed bed reactor is used for hydrogenation reaction, and because the fixed bed reactor is a strong exothermic reaction, a large amount of heat needs to be removed in the process, and the reaction energy consumption is large and the efficiency is low.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a reaction system for preparing butanol and octanol through propylene carbonylation, which comprises the steps of crushing mixed butyraldehyde into micron-level microbubbles by using an external micron bubble generator, dispersing and crushing hydrogen into hydrogen microbubbles by using a first micron bubble generator, increasing the mass transfer area between the mixed butyraldehyde and the hydrogen, improving the mass transfer effect, greatly improving the mass transfer rate, and reducing the temperature and pressure required by the reaction; on the other hand, the first disperser is arranged to disperse the hydrogen into large bubbles in advance, and the first micro-bubble generator breaks the large bubbles into micro-bubbles, so that the micro-bubble generation efficiency is improved.
The second purpose of the invention is to provide a reaction method for preparing butanol and octanol by using the reaction system, the reaction method is simple and convenient to operate, the butyraldehyde conversion rate is high, the product quality is high, the energy consumption is reduced, and the reaction effect better than that of the existing process is achieved.
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 butanol and octanol through propylene carbonylation, which comprises: a synthesis reactor, an isomerate separator, a first hydrogenation reactor and a condensation reactor; the synthesis reactor is connected with the isomer separator; the isomerate separator is provided with a n-butyl aldehyde outlet and a mixed butyraldehyde outlet; the mixed butyraldehyde outlet is connected with the first hydrogenation reactor, and the n-butyraldehyde outlet is connected with the condensation reactor;
an external micron bubble generator and a condenser are arranged between the isomer separator and the first hydrogenation reactor; discharging the mixed butyraldehyde from the mixed butyraldehyde outlet, directly feeding one part of the mixed butyraldehyde into the external micron bubble generator, and condensing the other part of the mixed butyraldehyde by the condenser and then feeding the other part of the mixed butyraldehyde into the external micron bubble generator; after being dispersed and crushed into micro-bubbles at the micron level by the external micro-bubble generator, the mixed butyraldehyde flows into the first hydrogenation reactor;
the bottom of the first hydrogenation reactor is provided with a hydrogen inlet; the hydrogen inlet is connected with a hydrogen cylinder; a first disperser is arranged between the first hydrogenation reactor and the hydrogen cylinder; the first disperser is provided with a liquid phase inlet and a gas phase inlet; a liquid phase inlet of the first disperser is connected with an outlet of the condenser, a gas phase inlet of the first disperser is connected with the hydrogen cylinder, and hydrogen is dispersed and crushed into large bubbles by the first disperser and then enters the first hydrogenation reactor;
a first sprayer and a first micron bubble generator are arranged in the first hydrogenation reactor, and the first sprayer is positioned above the first micron bubble generator; the first sprayer is connected with the external micro-bubble generator; the first micron bubble generator is connected with the hydrogen inlet so as to disperse and break the hydrogen big bubbles into micron-level micro bubbles.
In the prior art, carbonylation of propylene to butanol and octanol is generally carried out by propylene and a synthesizer, n-butyl aldehyde and mixed butyraldehyde are further separated from a generated crude product, wherein the mixed butyraldehyde is directly subjected to hydrogenation reaction with hydrogen, but the reaction efficiency is seriously influenced due to small phase boundary mass transfer area of the mixed butyraldehyde and the hydrogen, the product yield is low, and the raw material waste is serious.
In order to solve the technical problems, the invention provides a reaction system for preparing butanol and octanol through propylene carbonylation, which is characterized in that an external micron bubble generator is used for crushing mixed butyraldehyde into micron-level microbubbles, the microbubbles and the liquid mixed butyraldehyde are mixed into a gas-liquid emulsion and then are introduced into a first hydrogenation reactor, and hydrogen is dispersed and crushed into hydrogen microbubbles through the first micron bubble generator, so that the mass transfer area between the mixed butyraldehyde and hydrogen is increased, the mass transfer effect is improved, the mass transfer rate is greatly improved, and the temperature and the pressure required by the reaction are reduced; the first disperser is arranged to disperse the hydrogen into large bubbles in advance, and the first micro-bubble generator is used for crushing the large bubbles into micro-bubbles, so that the micro-bubble generation efficiency is improved; through using first sprayer to spray down the gas-liquid emulsion that mixes butyraldehyde from the top, further increased the area of contact of mixing butyraldehyde and hydrogen bubble, improved reaction efficiency.
Preferably, a reboiler and a second disperser are arranged between the isomer separator and the condensation reactor; the reboiler divides the n-butyraldehyde into gas-liquid two-phase material flows which are all introduced into the second disperser, and the n-butyraldehyde enters the condensation reactor after being dispersed into large bubbles by the second disperser. The n-butyl aldehyde is separated into gas-liquid two-phase material flows by arranging a reboiler, and a liquid-phase medium and a gas-phase raw material are provided for crushing the n-butyl alcohol by a second disperser; the n-butyraldehyde is dispersed and crushed into large bubbles by arranging the second disperser, so that the phase boundary mass transfer area of the n-butyraldehyde is increased.
Preferably, a second micro bubble generator and a second sprayer are arranged in the condensation reactor, and the second micro bubble generator is connected with the second disperser so as to disperse and break the large bubbles dispersed by the second disperser into micro-sized micro bubbles; the second sprayer is positioned above the second micron bubble generator and is connected with an alkali liquor storage tank. Through setting up second micron bubble generator with the further dispersion of n-butanal large bubble become the microbubble of micron level, further improved the looks liquid mass transfer area between n-butanal and alkali lye, through setting up the second spray thrower, be convenient for in time supply alkali lye raw materials on the one hand, on the other hand is through the mode of spraying, also is convenient for improve the area of contact of alkali lye and n-butanal, and then improves reaction efficiency.
Preferably, a material outlet of the condensation reactor is connected with a second hydrogenation reactor; an evaporator is arranged between the condensation reactor and the second hydrogenation reactor, and the material flowing out of the condensation reactor is gasified by the evaporator and then flows into the second hydrogenation reactor. The evaporator gasifies the product, which is convenient for the subsequent reaction.
Preferably, the second hydrogenation reactor is connected with the hydrogen cylinder, a third disperser is arranged between the hydrogen cylinder and the second hydrogenation reactor, a gas-phase inlet of the third disperser is connected with the hydrogen cylinder, a liquid-phase inlet of the third disperser is connected with the second hydrogenation reactor, and hydrogen flows into the second hydrogenation reactor after being dispersed into large bubbles in the third disperser.
Preferably, the first hydrogenation reactor and the second hydrogenation reactor are both slurry bed reactors.
Preferably, the first disperser and the second disperser have the same structure as the third disperser, and include a disperser housing and a granular material layer disposed in the middle of the disperser housing, and the granular material layer is formed by piling a plurality of circular granular materials having different particle diameters. The material of the granular body can be selected to be made of acid-resistant and corrosion-resistant materials, the circular granular bodies between the bottom layer and the upper layer are matched with each other to form a plurality of gaps with the same size, and gas forms bubbles through the gaps, so that the mass transfer area of the surface of the gas is increased.
Preferably, two third micron bubble generators with opposite outlets are arranged in the second hydrogenation reactor, the third micron bubble generator positioned above is connected with the third distributor so as to break the hydrogen big bubbles into micron-level micro-bubbles, and the third micron bubble generator positioned below is connected with the evaporator. The two third micron bubble generators disperse hydrogen and octenal into micron-level microbubbles respectively, so that the phase interface area is increased, the liquid drop coagulation phenomenon is effectively avoided, and the reaction efficiency is improved.
Preferably, the micro-interface generator, the first micro-bubble generator, the second micro-bubble generator and the third micro-bubble generator are provided with distributors at outlets for uniformly distributing bubbles. The micro-bubble uniform distribution that produces when setting up the distributor can.
Preferably, the distributor is a conical disc; a plurality of distribution holes are uniformly distributed on the distributor. The bubbles are partially distributed along the conical surface of the distributor and partially uniformly diffused along the distribution holes.
Preferably, a catalyst inlet, a propylene inlet and a synthesis gas inlet are sequentially arranged on the side wall of the synthesis reactor from top to bottom; two micro-interface generators are arranged in the synthesis reactor from top to bottom and are respectively connected with the propylene inlet and the synthesis gas inlet; the outlets of the two micro-interface generators are opposite.
The synthesis reactor is internally provided with two micro-interface generators for respectively dispersing and crushing propylene and synthesis gas, and during reaction, the propylene and the synthesis gas are respectively dispersed and crushed into micro bubbles at the micron level by the micro-interface generators and then subjected to carbonylation reaction, so that the phase boundary mass transfer area of the propylene and the synthesis gas is increased; the outlets of the two micro-interface generators are opposite, so that the opposite impact effect can be achieved, and the uniform distribution of micro-bubbles can be realized.
It should be noted that, when the micro-interface generators are arranged, the micro-interface generator positioned at the upper part is connected with the propylene inlet, the micro-interface generator positioned at the lower part is connected with the synthesis gas inlet, the synthesis gas is synthesized in advance by a gas source relatively speaking, and the raw materials are all flammable and explosive gases, therefore, in order to improve the safety, the air inlet is arranged at a lower position, and in view of easier flowing towards the top of the reactor after entering the inside of the reactor, therefore, the micro-interface generator for crushing propylene is arranged at the upper part, the micro-interface generator for crushing synthesis gas is arranged at the lower part, the arrangement mode also fully considers factors in various aspects such as safety, reaction efficiency and the like, after the synthesis gas is fully crushed and dispersed by the micro-interface generator, there is also a greater probability of passing through the gas distributor located above the micro-interfacial generator to achieve a more uniform distribution.
In the mixed butyraldehyde hydrogenation reaction, the mixed butyraldehyde is crushed into micro bubbles at a micron level by using an external micron bubble generator, the micro bubbles and the liquid mixed butyraldehyde are mixed into a gas-liquid emulsion and then are introduced into a first hydrogenation reactor, and hydrogen is dispersed and crushed into hydrogen micro bubbles by the first micron bubble generator, so that the mass transfer area between the mixed butyraldehyde and the hydrogen is increased, the mass transfer effect is improved, the mass transfer rate is greatly improved, and the temperature and the pressure required by the reaction are reduced; the first disperser is arranged to disperse the hydrogen into large bubbles in advance, and the first micro-bubble generator is used for crushing the large bubbles into micro-bubbles, so that the micro-bubble generation efficiency is improved; through using first sprayer to spray down the gas-liquid emulsion that mixes butyraldehyde from the top, further increased the area of contact of mixing butyraldehyde and hydrogen bubble, improved reaction efficiency.
In the reaction of generating octanol from n-butyl aldehyde, firstly, pre-dispersing n-butyl aldehyde into large bubbles through a second disperser, and dispersing the large bubbles into micro-bubbles through a second micro-bubble generator arranged in a condensation reactor, so that the dispersion efficiency is high, and the mass transfer area of a phase boundary is large; the contact area of the alkali liquor and the n-butyraldehyde is further increased through the second sprayer; through be provided with the third micron bubble generator that two exports are relative in second hydrogenation ware, can break into the microbubble with the raw materials dispersion on the one hand, increase mass transfer area, on the other hand produces the hedging phenomenon through relative export, promotes the evenly distributed of microbubble.
In addition, the invention is provided with the distributors for uniformly distributing the bubbles at the outlets of the micro-interface generator, the first micron bubble generator, the second micron bubble generator and the third micron bubble generator, and the generated micro-bubbles are sprayed to different directions through the distribution holes on the distributors, so that the running direction of the micro-bubbles is changed, and the micro-bubbles are more uniformly distributed. Therefore, the invention improves the application effect of the micro-interface generator by combining and applying the distributor, the micro-interface generator, the micro-bubble generator and the disperser.
It will be appreciated by those skilled in the art that the micro-interface generator used in the present invention is described in the prior patents of the present inventor, such as the patents of 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, 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 was named as a micro-bubble generator (CN201610641119.6), a bubble breaker (201710766435.0) and the like in the early stage, and is named as a micro-interface generator in the later stage along with the continuous technical improvement, and the micro-interface generator in the present invention is equivalent to the micro-bubble generator, the bubble breaker and the like in the prior art, and has different names. In summary, the micro-interface generator of the present invention belongs to the prior art.
Preferably, the second hydrogenation reactor is connected with a second rectification tower, and octanol generated by the second hydrogenation reactor is discharged after being rectified by the second rectification tower.
Preferably, a catalyst circulation device for replenishing a catalyst is connected to each of the synthesis reactor, the condensation reactor, the first hydrogenation reactor and the second hydrogenation reactor. The catalyst circulating device can promote the recycling of the catalyst, and the cost is saved.
Preferably, the first hydrogenation reactor is sequentially connected with a first rectifying tower and a separating tower, and a product in the hydrogenation reactor flows into the separating tower after being rectified in the first rectifying tower.
Preferably, a demister is arranged between the synthesis reactor and the isomer separator, and the product of the synthesis reactor is defoamed by the demister and then flows into the isomer separator.
The invention also provides a reaction method adopting the reaction system, which comprises the following steps:
mixing propylene, synthesis gas and a catalyst, carrying out hydroxyl synthesis reaction, removing foams to obtain a crude product, and separating the crude product to obtain n-butyl aldehyde and mixed butyraldehyde;
carrying out micro-interface crushing on n-butyl aldehyde, carrying out condensation reaction on the n-butyl aldehyde and alkali liquor to generate octenal, carrying out micro-interface crushing on the octenal and hydrogen respectively, carrying out hydrogenation reaction to obtain an octanol crude product, and rectifying and purifying the octanol crude product to obtain a product octanol;
respectively carrying out micro-interface crushing on the mixed butyraldehyde and hydrogen, carrying out hydrogenation reaction in the presence of a catalyst to generate mixed butanol, and then rectifying, purifying and separating to obtain the n-butanol and the isobutanol.
Preferably, the hydroxyl synthesis reaction temperature is 80-95 ℃, and the pressure is 0.8-1.3 MPa; preferably, the catalyst is a rhodium catalyst.
Preferably, the reaction temperature in the condensation reactor is 65-75 ℃, and the reaction pressure is 0.23-0.28 MPa.
Further, the reaction temperature in the first hydrogenation reactor and the second hydrogenation reactor is 60-78 ℃, and the reaction pressure is 0.50-0.80 MPa.
Furthermore, the first hydrogenation reactor and the second hydrogenation reaction catalyst are metal such as nickel, chromium and the like, and oxide catalyst triphenylphosphine solution or other industry-approved additives of the same type participate in the reaction.
The butanol and octanol product obtained by the reaction method of the invention has good quality and high yield. And the preparation method has the advantages of low reaction temperature, greatly reduced pressure and remarkably reduced cost.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the reaction system, the mixed butyraldehyde is crushed into micro bubbles at the micron level by using the external micron bubble generator, the micro bubbles and the liquid mixed butyraldehyde are mixed into a gas-liquid emulsion and then are introduced into the first hydrogenation reactor, and hydrogen is dispersed and crushed into hydrogen micro bubbles by the first micron bubble generator, so that the mass transfer area between the mixed butyraldehyde and the hydrogen is increased, the mass transfer effect is improved, the mass transfer rate is greatly improved, and the temperature and pressure required by the reaction are reduced;
(2) the first disperser is arranged to disperse the hydrogen into large bubbles in advance, and the first micro-bubble generator is used for crushing the large bubbles into micro-bubbles, so that the micro-bubble generation efficiency is improved;
(3) through using first sprayer to spray down the gas-liquid emulsion that mixes butyraldehyde from the top, further increased the area of contact of mixing butyraldehyde and hydrogen bubble, improved reaction efficiency.
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 butanol and octanol through propylene carbonylation according to example 1 of the present invention;
fig. 2 is a schematic structural diagram of a first disperser provided in embodiment 1 of the present invention;
fig. 3 is a schematic structural diagram of a catalyst circulation device provided in example 1 of the present invention.
Description of the drawings:
10-a synthesis reactor; 101-catalyst inlet;
102-a propylene inlet; 103-a syngas inlet;
104-solvent inlet; 105-a micro-interface generator;
106-a distributor; 20-a demister;
30-an isomer separator; 301-mixed butyraldehyde outlet;
a 302-n-butyraldehyde outlet; 40-external micron bubble generator;
50-a condenser; 60-a first hydrogenation reactor;
601-a first sprayer; 602-a first micro bubble generator;
70-a first rectification column; 80-a separation column;
90-hydrogen gas cylinder; 100-a first disperser;
1001-disperser housing; 1002-granular bulk layer;
110-an alkali liquor storage tank; 120-a reboiler;
130-a second disperser; 140-a condensation reactor;
1401-a second micro bubble generator; 1402-a second sprayer;
150-a second hydrogenation reactor; 1501-third micron bubble generator;
160-a second rectification column; 170-catalyst circulation means;
180-a third disperser; 190-evaporator.
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.
Example 1
Referring to fig. 1-3, this example provides a reaction system for preparing butanol and octanol through propylene carbonylation, comprising: a synthesis reactor 10, an isomerate separator 30, a first hydrogenation reactor 60 and a condensation reactor 140; the synthesis reactor 10 is connected to an isomerate separator 30; a demister 20 is provided between the synthesis reactor 10 and the isomer separator 30, and the product of the synthesis reactor 10 is defoamed by the demister 20 and then flows into the isomer separator 30.
The side wall of the synthesis reactor 10 is provided with a catalyst inlet 101, a propylene inlet 102 and a synthesis gas inlet 103 from top to bottom in sequence; the bottom of the synthesis reactor 10 is provided with a solvent inlet 104; two micro-interface generators 105 are arranged in the synthesis reactor 10 from top to bottom, and the two micro-interface generators 105 are respectively connected with the propylene inlet 102 and the synthesis gas inlet 103; the outlets of the two micro-interface generators 105 are opposite.
The isomer separator 30 is provided with a n-butyl aldehyde outlet 302 and a mixed butyraldehyde outlet 301; a mixed butyraldehyde outlet 301 is connected with the first hydrogenation reactor 60, and a n-butyraldehyde outlet 302 is connected with the condensation reactor 140;
wherein, an external micron bubble generator 40 and a condenser 50 are arranged between the isomer separator 30 and the first hydrogenation reactor 60; the mixed butyraldehyde is discharged from a mixed butyraldehyde outlet 301, one part of the mixed butyraldehyde directly enters the external micron bubble generator 40, and the other part of the mixed butyraldehyde enters the external micron bubble generator 40 after being condensed by the condenser 50; the mixed butyraldehyde is dispersed and crushed into micro-bubbles at the micron level by an external micro-bubble generator 40, and then flows into a first hydrogenation reactor 60;
the bottom of the first hydrogenation reactor 60 is provided with a hydrogen inlet; the hydrogen inlet is connected with a hydrogen cylinder 90; a first disperser 100 is arranged between the first hydrogenation reactor 60 and the hydrogen cylinder 90; the first disperser 100 is provided with a liquid phase inlet and a gas phase inlet; the liquid phase inlet of the first disperser 100 is connected with the outlet of the condenser 50, the gas phase inlet of the first disperser 100 is connected with the hydrogen cylinder 90, and the hydrogen is dispersed and broken into large bubbles by the first disperser 100 and then enters the first hydrogenation reactor 60;
a first sprayer 601 and a first micron bubble generator 602 are arranged in the first hydrogenation reactor 60, and the first sprayer 601 is positioned above the first micron bubble generator 602; the first sprayer 601 is connected with the external micro bubble generator 40; the first micro-bubble generator 602 is connected to the hydrogen inlet to disperse the hydrogen macro-bubbles into micro-bubbles on a micro-scale.
The first hydrogenation reactor 60 is connected with a first rectifying tower 70 and a separating tower 80 in sequence, and the product in the hydrogenation reactor flows into the separating tower 80 after being rectified in the first rectifying tower 70.
A reboiler 120 and a second disperser 130 are disposed between the isomer separator 30 and the condensation reactor 140; the reboiler 120 divides the n-butyraldehyde into gas-liquid two-phase streams, and the streams are introduced into the second disperser 130, and the n-butyraldehyde is dispersed into large bubbles by the second disperser 130, and then enters the condensation reactor 140. By providing the reboiler 120, the n-butyraldehyde is separated into a gas-liquid two-phase stream, providing a liquid-phase medium and a gas-phase feedstock for the second disperser 130 to break up the n-butanol.
The condensation reactor 140 is provided with a second micro-bubble generator 1401 and a second sprayer 1402, and the second micro-bubble generator 1401 is connected with the second disperser 130 to disperse and break the large bubbles dispersed by the second disperser 130 into micro-scale micro-bubbles; the second sprayer 1402 is positioned above the second micron bubble generator 1401, and the second sprayer 1402 is connected with the lye storage tank 110.
The material outlet of the condensation reactor 140 is connected with a second hydrogenation reactor 150; an evaporator 190 is arranged between the condensation reactor 140 and the second hydrogenation reactor 150, and the material flowing out of the condensation reactor 140 flows into the second hydrogenation reactor 150 after being gasified by the evaporator 190.
The second hydrogenation reactor 150 is connected with the hydrogen cylinder 90, a third disperser 180 is arranged between the hydrogen cylinder 90 and the second hydrogenation reactor 150, the gas phase inlet of the third disperser 180 is connected with the hydrogen cylinder 90, the liquid phase inlet of the third disperser 180 is connected with the second hydrogenation reactor 150, and the hydrogen gas flows into the second hydrogenation reactor 150 after being dispersed into large bubbles in the third disperser 180.
In this embodiment, the first hydrogenation reactor 60 and the second hydrogenation reactor 150 are slurry bed reactors.
In this embodiment, the first disperser 100 and the second disperser 130 have the same structure as the third disperser 180, and include a disperser housing 1001 and a granular material layer 1002 disposed in the middle of the disperser housing 1001, and the granular material layer 1002 is formed by stacking a plurality of circular granular materials having different particle diameters. The material of the granular body can be selected to be made of acid-resistant and corrosion-resistant materials, the circular granular bodies between the bottom layer and the upper layer are matched with each other to form a plurality of gaps with the same size, and gas forms bubbles through the gaps, so that the mass transfer area of the surface of the gas is increased.
Two third micron bubble generators 1501 with opposite outlets are arranged in the second hydrogenation reactor 150, the third micron bubble generator 1501 at the upper part is connected with the third disperser 180 to break the hydrogen big bubbles into micron-level micro-bubbles, and the third micron bubble generator 1501 at the lower part is connected with the evaporator 190. The two third micron bubble generators 1501 respectively disperse hydrogen and octenal into micron-level microbubbles, increase the phase interface area, effectively avoid the phenomenon of droplet coalescence, and improve the reaction efficiency.
Wherein, the first hydrogenation reactor 60 and the second hydrogenation reactor 150 are both slurry bed reactors.
The second hydrogenation reactor 150 is connected to a second rectification tower 160, and octanol generated by the second hydrogenation reactor 150 is discharged after being rectified by the second rectification tower 160.
In the present embodiment, the outlets of the micro-interface generator 105, the first micro-bubble generator 602, the second micro-bubble generator 1401 and the third micro-bubble generator 1501 are all provided with a distributor 106 for uniformly distributing bubbles. The distributor 106 is arranged to evenly distribute the generated microbubbles.
Wherein the distributor 106 is a conical disk; a plurality of distribution holes are uniformly distributed on the distributor 106. The bubbles are distributed partly outward along the tapered surface of the distributor 106 and partly spread uniformly along the distribution holes.
In order to ensure sufficient catalyst during the reaction process, a catalyst circulation device 170 for replenishing the catalyst is connected to the synthesis reactor 10, the condensation reactor 140, the first hydrogenation reactor 60 and the second hydrogenation reactor 150. The catalyst circulation device 170 can also promote the recycling of the catalyst, saving the cost.
In this embodiment, the solvent in the synthesis reactor 10 is n-butyraldehyde, the solvent in the first hydrogenation reactor 60 is n-butanol, the solvent in the second hydrogenation reactor 150 is octanol, and the solvent in the condensation reactor 140 is octanol.
During the specific operation, propylene gas and synthesis gas are introduced into the synthesis reactor 10, the reaction temperature in the synthesis reactor 10 is set to 80 ℃, the reaction pressure is set to 0.8MPa, the micro-interface generator 105 breaks the propylene and the synthesis gas into micro-bubbles with micron scale, and the micro-bubbles are released into the synthesis reactor 10, so that the materials are fully contacted, and the oxo-synthesis reaction is carried out.
The product of the oxo reaction is delivered to the isomer separator 30, n-butyraldehyde enters the second micron bubble generator 1401 via the second disperser 130, and the second micron bubble generator 1401 breaks the n-butyraldehyde into micron-sized microbubbles and releases the microbubbles into the condensation reactor 140, so that the n-butyraldehyde is fully contacted with the alkali liquor for condensation reaction. The reaction temperature in the condensation reactor 140 was set to 60 ℃ and the reaction pressure was set to 0.18 MPa.
The condensation reaction product is gasified by the evaporator 190 and then enters the second hydrogenation reactor 150, the reaction temperature in the second hydrogenation reactor 150 is set to 60 ℃, and the reaction pressure is set to 0.50 MPa. The hydrogenation reaction product is rectified by a second rectifying tower 160 to obtain octanol.
The mixed butyraldehyde enters an external micron bubble generator 40, the external micron bubble generator 40 breaks the mixed butyraldehyde into micron-scale microbubbles, and the microbubbles are released into the first hydrogenation reactor 60, so that the mixed butyraldehyde is in full contact with hydrogen to carry out hydrogenation reaction. The reaction temperature in the first hydrogenation reactor 60 is set to 60 ℃ and the reaction pressure is set to 0.50 MPa.
The resulting hydrogenation product is purified by rectification and separated into n-butanol and isobutanol by a separation column 80. Through detection, after the system and the process are used, the conversion rate of propylene is 98.6%, the conversion rate of butyraldehyde is 98.0%, and the synthesis efficiency of the process is improved by 4.0%.
Example 2
The reaction system of this example was identical to that of example 1 except that the reaction temperature in the synthesis reactor 10 in this example was set to 88 ℃ and the reaction pressure was set to 1.1 MPa; the reaction temperature in the condensation reactor 140 was set to 65 ℃ and the reaction pressure was set to 0.21 MPa; the reaction temperature in the first hydrogenation reactor 60 is set to 70 ℃, and the reaction pressure is set to 0.70 MPa; the reaction temperature in the second hydrogenation reactor 150 is set to 70 ℃ and the reaction pressure is set to 0.70 MPa.
Through detection, after the system and the process are used, the conversion rate of propylene is 98.8%, the conversion rate of butyraldehyde is 98.2%, and the synthesis efficiency of the process is improved by 4.5%.
Example 3
The reaction system of this example was identical to that of example 1 except that the reaction temperature in the synthesis reactor 10 in this example was set to 95 ℃ and the reaction pressure was set to 1.3 MPa; the reaction temperature in the condensation reactor 140 was set to 70 ℃ and the reaction pressure was set to 0.25 MPa; the reaction temperature in the second hydrogenation reactor 150 is set to 78 ℃, and the reaction pressure is set to 0.80 MPa; the reaction temperature in the first hydrogenation reactor 60 was set at 78 deg.c and the reaction pressure was set at 0.80 MPa.
Through detection, after the system and the process are used, the conversion rate of propylene is 99.0%, the conversion rate of butyraldehyde is 98.4%, and the synthesis efficiency of the process is improved by 5.0%.
In a word, compared with the reaction system for preparing butanol and octanol through propylene carbonylation in the prior art, the reaction system disclosed by the invention is low in energy consumption, low in cost, high in safety, low in required reaction temperature and pressure, less in side reaction, high in butyraldehyde conversion rate, and 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 butanol and octanol through propylene carbonylation is characterized by comprising: a synthesis reactor, an isomerate separator, a first hydrogenation reactor and a condensation reactor; the synthesis reactor is connected with the isomer separator; the isomerate separator is provided with a n-butyl aldehyde outlet and a mixed butyraldehyde outlet; the mixed butyraldehyde outlet is connected with the first hydrogenation reactor, and the n-butyraldehyde outlet is connected with the condensation reactor;
an external micron bubble generator and a condenser are arranged between the isomer separator and the first hydrogenation reactor; discharging the mixed butyraldehyde from the mixed butyraldehyde outlet, directly feeding one part of the mixed butyraldehyde into the external micron bubble generator, and condensing the other part of the mixed butyraldehyde by the condenser and then feeding the other part of the mixed butyraldehyde into the external micron bubble generator; after being dispersed and crushed into micro-bubbles at the micron level by the external micro-bubble generator, the mixed butyraldehyde flows into the first hydrogenation reactor;
the bottom of the first hydrogenation reactor is provided with a hydrogen inlet; the hydrogen inlet is connected with a hydrogen cylinder; a first disperser is arranged between the first hydrogenation reactor and the hydrogen cylinder; the first disperser is provided with a liquid phase inlet and a gas phase inlet; a liquid phase inlet of the first disperser is connected with an outlet of the condenser, a gas phase inlet of the first disperser is connected with the hydrogen cylinder, and hydrogen is dispersed and crushed into large bubbles by the first disperser and then enters the first hydrogenation reactor;
a first sprayer and a first micron bubble generator are arranged in the first hydrogenation reactor, and the first sprayer is positioned above the first micron bubble generator; the first sprayer is connected with the external micro-bubble generator; the first micron bubble generator is connected with the hydrogen inlet so as to disperse and break the hydrogen big bubbles into micron-level micro bubbles.
2. The reaction system for preparing butanol and octanol through propylene carbonylation according to claim 1, wherein a reboiler and a second disperser are arranged between the isomer separator and the condensation reactor; the reboiler divides the n-butyraldehyde into gas-liquid two-phase material flows which are all introduced into the second disperser, and the n-butyraldehyde enters the condensation reactor after being dispersed into large bubbles by the second disperser.
3. The system as claimed in claim 2, wherein a second micron bubble generator and a second sprayer are disposed in the condensation reactor, and the second micron bubble generator is connected to the second disperser for dispersing and breaking the large bubbles dispersed by the second disperser into micron-sized micro-bubbles; the second sprayer is positioned above the second micron bubble generator and is connected with an alkali liquor storage tank.
4. The reaction system for preparing butanol and octanol through carbonylation of propylene according to claim 3, wherein the material outlet of the condensation reactor is connected with a second hydrogenation reactor; an evaporator is arranged between the condensation reactor and the second hydrogenation reactor, and the material flowing out of the condensation reactor is gasified by the evaporator and then flows into the second hydrogenation reactor.
5. The reaction system for preparing butanol and octanol according to claim 4, wherein the second hydrogenation reactor is connected to the hydrogen cylinder, a third disperser is arranged between the hydrogen cylinder and the second hydrogenation reactor, a gas-phase inlet of the third disperser is connected to the hydrogen cylinder, a liquid-phase inlet of the third disperser is connected to the second hydrogenation reactor, and hydrogen gas is dispersed into large bubbles in the third disperser and then flows into the second hydrogenation reactor.
6. The reaction system for preparing butanol and octanol through propylene carbonylation according to claim 5, wherein the first disperser, the second disperser and the third disperser have the same structure and comprise a disperser shell and a granular bulk layer arranged in the middle of the disperser shell, and the granular bulk layer is formed by piling a plurality of round granular bulk with different grain sizes.
7. The reaction system for preparing butanol and octanol through carbonylation of propylene according to claim 5, wherein two opposite outlet third micron bubble generators are arranged in the second hydrogenation reactor, the third micron bubble generator positioned at the upper part is connected with the third disperser to break up hydrogen gas big bubbles into micron-level micro-bubbles, and the third micron bubble generator positioned at the lower part is connected with the evaporator.
8. The reaction system for preparing butanol and octanol through carbonylation of propylene according to claim 7, wherein the outlets of the micro-interface generator, the first micro-bubble generator, the second micro-bubble generator and the third micro-bubble generator are all provided with a distributor for uniform distribution of bubbles.
9. The reaction method using the reaction system for producing butanol and octanol through carbonylation of propylene according to any one of claims 1 to 8, comprising the steps of:
mixing propylene, synthesis gas and a catalyst, carrying out hydroxyl synthesis reaction, removing foams to obtain a crude product, and separating the crude product to obtain n-butyl aldehyde and mixed butyraldehyde;
carrying out micro-interface crushing on n-butyl aldehyde, carrying out condensation reaction on the n-butyl aldehyde and alkali liquor to generate octenal, carrying out micro-interface crushing on the octenal and hydrogen respectively, carrying out hydrogenation reaction to obtain an octanol crude product, and rectifying and purifying the octanol crude product to obtain a product octanol;
respectively carrying out micro-interface crushing on the mixed butyraldehyde and hydrogen, carrying out hydrogenation reaction in the presence of a catalyst to generate mixed butanol, and then rectifying, purifying and separating to obtain the n-butanol and the isobutanol.
10. The reaction method according to claim 9, wherein the hydroxyl group synthesis reaction temperature is 80 to 95 ℃ and the pressure is 0.8 to 1.3 MPa; preferably, the catalyst is a rhodium catalyst; preferably, the reaction temperature in the first hydrogenation reactor and the second hydrogenation reactor is 60-78 ℃, and the reaction pressure is 0.50-0.80 MPa.
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| CN115650833A (en) * | 2022-11-01 | 2023-01-31 | 中国石油化工股份有限公司 | Process method for enhancing olefin hydroformylation by micro bubble flow |
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