CN113209930A - Aldehyde condensation reaction equipment and reaction method - Google Patents
Aldehyde condensation reaction equipment and reaction method Download PDFInfo
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- CN113209930A CN113209930A CN202110577419.3A CN202110577419A CN113209930A CN 113209930 A CN113209930 A CN 113209930A CN 202110577419 A CN202110577419 A CN 202110577419A CN 113209930 A CN113209930 A CN 113209930A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
- B01J19/2465—Stationary reactors without moving elements inside provoking a loop type movement of the reactants externally, i.e. the mixture leaving the vessel and subsequently re-entering it
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
- B01F33/836—Mixing plants; Combinations of mixers combining mixing with other treatments
- B01F33/8362—Mixing plants; Combinations of mixers combining mixing with other treatments with chemical reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—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
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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
- C07C45/61—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 aldehyde condensation reaction equipment and a reaction method, wherein the aldehyde condensation reaction method comprises the following steps: dispersing the dispersed phase in the mobile phase through first dispersion to obtain a reaction material flow; the reactant flow is divided into a circulating flow and a reaction product flow after entering a reaction device for reaction; the circulating material flow returns to the reaction device after second dispersion; the apparent liquid velocity of the dispersed phase in the reactant stream through the cross section of the reaction device is less than 0.1 m/s. The reaction equipment does not need to be provided with a stirrer and a distributor, so that the structure of the reaction device is simplified, and the equipment and maintenance cost of the reactor are reduced; the reaction method can strengthen aldehyde condensation reaction and improve aldehyde conversion rate and olefine aldehyde product yield.
Description
Technical Field
The invention belongs to the field of organic synthesis, and relates to aldehyde condensation reaction equipment and a reaction method.
Background
Aldol condensation is a well-known reaction that can occur between the same class of aldehydes, different aldehydes or aldehydes ketones, the reaction product being aldol, some unstable aldol products will further dehydrate to produce enal. The aldol condensation reaction can be carried out by using an acid or a base as a catalyst, and an alkali metal hydroxide (e.g., NaOH) is generally used as a catalyst in industry, and the reaction is as follows:
two molecules of aldehyde are dimerized under the action of alkali catalyst to produce aldol, and the aldol may be further dehydrated to produce unsaturated olefine aldehyde. For aldehydes having more than four carbon atoms, the reaction is a two-phase reaction due to the relatively low solubility of the aldehyde and water in each other. A side Reaction occurring simultaneously with this Reaction is Cannizzaro Reaction (Cannizzaro Reaction):
2RCH2CHO+NaOH→RCH2COONa+RCH2CH2OH
in such reactions, 2-ethyl-hexenal (2-propylheptenal and its isomeric hexenal) obtained by condensation of n-butyraldehyde (valeraldehyde) and 2-ethyl-hexanol (2-propylheptanol and its isomeric decanol) obtained by hydrogenation are industrially mass-produced products. The diester of phthalic acid (DOP, DPHP) generated by the reaction of 2-ethyl-hexanol (2-propyl heptanol and isomeric decanol) and phthalic acid is used as a general plasticizer, is mainly used for processing polyvinyl chloride, and can also be used for processing high polymers such as chemical fiber resin, acetic acid resin, ABS resin and rubber, or used for making paint, dye, dispersant and the like. The other important product is hydroxypivalaldehyde generated by condensing isobutyraldehyde and formaldehyde, neopentyl glycol is obtained by further hydrogenation, and the product is also an important chemical raw material. Neopentyl glycol is mainly used for producing esters, polymer plasticizers, alkyd resins and the like used for saturated polyester resins, unsaturated polyester resins, polyester polyols and synthetic lubricants. Neopentyl glycol derivatives are widely used in the fields of automobiles, textiles, medicines, coatings, pesticides, plastics, petroleum and the like, and at present, countries in the united states, japan and the like are developing new application fields of neopentyl glycol.
Currently, most of the aldehyde condensation reactors in industry are stirred tank reactors which are distributors, and baffles are usually added in the reactors to enhance the mixing effect. The stirring kettle adopting the structure can generally obtain better mixing effect, but the reactor has complex structure and higher equipment investment. Also, due to the large number of internal components of the stirrer and the reaction process often involving dynamic sealing under pressure, the equipment is prone to failure. This problem can be partially solved if a plurality of smaller stirrers are used instead of a single large stirred tank, but this further increases the equipment investment. Another possible reactor form is a tubular reactor, which omits the stirrer, but only uses a tubular reactor, which does not have a high conversion per pass of the reaction.
CN1227207 discloses a tubular reactor with packing, which has a significantly increased pressure drop after packing, and in order to determine suitable operating conditions, the literature proposes the concept of a load factor B, and when the load factor B is greater than or equal to 0.8, the aldehyde condensation reaction can obtain a better reaction result. In order to achieve a high degree of dispersion of the organic phase of the starting aldehyde in the continuous phase (catalyst solution), the mass ratio of the continuous phase to the organic phase entering the reactor is >10:1, even up to 100: 1.
CN101838186 discloses a condensation reaction method of valeraldehyde, which is characterized in that a static mixer with the volume ratio of more than 50% is placed in a tubular reactor, so that the average droplet size of an organic phase in a continuous phase is 0.2-2 mm, and the ideal valeraldehyde conversion rate is obtained under the condition that the mass ratio of the continuous phase to the organic phase is 10-20: 1. This method avoids the use of a stirrer relative to a stirred tank, but placing a static mixer inside the reactor is a negative factor for the maintenance of the reactor.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides aldehyde condensation reaction equipment and a reaction method, wherein the reaction equipment does not need to be provided with a stirrer and a distributor, so that the structure of a reaction device is simplified, and the equipment and maintenance cost of the reactor are reduced; the reaction method can strengthen aldehyde condensation reaction and improve aldehyde conversion rate and olefine aldehyde product yield.
In order to achieve the technical effects, the invention adopts the following technical scheme;
one of the purposes of the invention is to provide aldehyde condensation reaction equipment which comprises a dispersed phase pipeline, a continuous phase pipeline, a circulating pipeline, a reaction device and a dispersing device;
the dispersing device, the reaction device, the circulating pipeline and the continuous phase pipeline are sequentially and circularly connected;
the dispersed phase pipeline is connected with the liquid inlet of the dispersing device.
As the preferable technical scheme of the invention, the liquid outlet of the dispersing device is connected with the sample inlet of the reaction device;
preferably, the sample outlet of the reaction device is connected with the inlet of the circulating pipeline;
preferably, the circulation line outlet is connected to the continuous phase line;
preferably, the continuous phase pipeline is connected with the liquid inlet of the dispersing device;
preferably, a reaction product outlet is arranged on the circulating pipeline.
The second purpose of the invention is to provide another aldehyde condensation reaction device, wherein the acetal reaction device comprises a dispersed phase pipeline, a continuous phase pipeline, a circulating pipeline, a reaction device, a first dispersing device and a second dispersing device;
the reaction device, the circulating pipeline and the second dispersing device are sequentially and circularly connected;
the dispersed phase pipeline and the continuous phase pipeline are respectively and independently connected with the liquid inlet of the first dispersing device;
the liquid outlet of the first dispersion device is connected with the sample inlet of the reaction device.
As the preferable technical scheme of the invention, the sample outlet of the reaction device is connected with the inlet of the circulating pipeline;
preferably, the outlet of the circulating pipeline is connected with the liquid inlet of the second dispersing device;
preferably, the liquid outlet of the second dispersing device is connected with the sample inlet of the reaction device;
preferably, a reaction product outlet is arranged on the circulating pipeline.
In the invention, an external circulation material flow is formed by arranging the circulation pipeline, the two-phase mixture in the reactor is pumped out of the reactor and returns to the reactor after passing through the dispersing device, and the high dispersion of the reaction dispersion phase in the reactor is enhanced.
In the present invention, although two different aldehyde condensation reaction apparatuses are included, the dispersion of the dispersed phase in the mobile phase and the dispersion of the dispersed phase in the circulating feed are carried out by the same dispersing device in the first reaction apparatus. And the second reaction device realizes the dispersion of the dispersed phase in the mobile phase through the first reaction device and realizes the dispersion of the dispersed phase in the ring material through the second dispersion device.
In the invention, the reaction device can adopt a single reactor or a form of connecting a plurality of reactors in series, and the reactor can be a tubular reactor or a kettle type reactor.
The invention also aims to provide an aldehyde condensation reaction method, which comprises the following steps:
dispersing the dispersed phase in the mobile phase through first dispersion to obtain a reaction material flow;
the reactant flow is divided into a circulating flow and a reaction product flow after entering a reaction device for reaction;
the circulating material flow returns to the reaction device after second dispersion;
the apparent liquid velocity of the dispersed phase in the reactant stream through the cross section of the reaction device is less than 0.1 m/s.
Wherein the apparent liquid velocity of the dispersed phase in the reactant stream across the cross-section of the reaction apparatus may be 0.09m/s, 0.08m/s, 0.07m/s, 0.06m/s, 0.05m/s, 0.04m/s, 0.03m/s, 0.02m/s, or 0.01m/s, but is not limited to the recited values, and other values not recited within this range are equally applicable.
In the present invention, the dispersion phase is dispersed before the reaction to disperse the dispersion phase sufficiently in the mobile phase, and although high dispersion of the liquid-liquid two-phase at the inlet of the reaction apparatus can be achieved, coalescence of droplets of the dispersion phase (organic phase) is difficult to avoid in a reaction apparatus having a large volume. In order to avoid the use of structurally complex internals inside the reactor, it is necessary to control some process conditions during the reaction, and the flow rate of the dispersed phase into the reactor and the dimensions of the reactor are factors which influence the dispersion of the dispersed phase in the liquid phase. The gas flow rate exceeding the atmospheric bubble causes coalescence in the reactor rapidly, thereby losing the dispersing effect. The invention therefore further defines that the apparent liquid velocity of the dispersed phase in the reactant stream through the cross-section of the reaction apparatus is less than 0.1 m/s.
As a preferred technical scheme of the invention, the apparent liquid velocity of the dispersed phase in the reactant flow passing through the cross section of the reaction device is less than 0.05 m/s.
In a preferred embodiment of the present invention, the volume ratio of the dispersed phase to the mobile phase is 10 to 1:1, such as 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, or 2:1, but not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable, preferably 3 to 1: 1.
Preferably, the dispersed phase is dispersed in the continuous phase after the first and second dispersions, respectively, independently, with a droplet diameter of less than 100 μm, such as 10nm, 20nm, 50nm, 100nm, 200nm, 500nm, 1 μm, 2 μm, 5 μm, 10 μm, 20 μm, 50 μm or 80 μm, but not limited to the values listed, and other values not listed in this range are equally applicable, preferably 100nm to 10 μm.
In a preferred embodiment of the present invention, the mass flow ratio of the recycle stream to the reaction product stream is greater than 8:1, such as 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 60:1, 70:1, 80:1, or 100:1, but is not limited to the recited values, and other values not recited in this range are equally applicable, preferably 10 to 40: 1.
As a preferred embodiment of the present invention, the dispersed phase is an organic phase.
Preferably, the organic phase comprises any one of or a combination of at least two of C1-C20 aldehyde or C3-C20 ketone.
The aldehyde of C1 to C20 may be formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, n-valeraldehyde, isovaleraldehyde, benzaldehyde, phenylacetaldehyde, or the like, and the ketone of C3 to C20 may be acetone, butanone, cyclobutanone, 3-pentanone, cyclopentanone, cyclohexanone, or the like, and these compounds are merely examples and are not limited to the above compounds.
Preferably, the continuous phase is a catalyst solution.
Preferably, the catalyst comprises any one of alkali metal hydroxide or amine organic base or a combination of at least two thereof.
The alkali metal hydroxide may be sodium hydroxide or potassium hydroxide, the amine organic base may be ethylamine, dimethyl triamine, trimethylamine or triethylamine, and the above compounds are merely examples and are not limited thereto.
Preferably, the solvent of the catalyst solution comprises any one of water, alcohol or phenol or a combination of at least two thereof.
The alcohol may be methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, cyclopentanol, cyclohexanol, etc., and the phenol may be substituted or unsubstituted phenol, naphthol, etc., which are merely exemplary and not limited thereto.
As a preferred technical scheme of the invention, the aldehyde condensation reaction method comprises the following steps:
dispersing a dispersed phase in a mobile phase through first dispersion, wherein the diameter of a droplet of the dispersed phase dispersed in the continuous phase is less than 100 mu m, and obtaining a reactant flow;
the dispersed phase is an organic phase which comprises any one or the combination of at least two of C1-C20 aldehyde or C3-C20 ketone; the continuous phase is a catalyst solution, the catalyst comprises any one or the combination of at least two of alkali metal hydroxide or amine organic base, and the solvent of the catalyst solution comprises any one or the combination of at least two of water, alcohol or phenol;
after entering a reaction device for reaction, the reactant flow is divided into a circulating flow and a reaction product flow, wherein the mass flow ratio of the circulating flow to the reaction product flow is more than 8: 1;
the circulating material flow returns to the reaction device after second dispersion;
the apparent liquid velocity of the dispersed phase in the reactant stream through the cross section of the reaction device is less than 0.1 m/s.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention provides aldehyde condensation reaction equipment and a reaction method, wherein the reaction equipment is not required to be provided with a stirrer and a distributor, so that the structure of a reaction device is simplified, and the equipment and maintenance cost of the reactor are reduced; the reaction method can strengthen aldehyde condensation reaction and improve aldehyde conversion rate and olefine aldehyde product yield.
Drawings
FIG. 1 is a schematic view of an aldehyde condensation reaction apparatus according to the present invention;
FIG. 2 is a schematic view showing the structure of another aldehyde condensation reaction apparatus according to the present invention;
FIG. 3 is a schematic view of the structure of an aldehyde condensation reaction apparatus according to example 1 of the present invention;
FIG. 4 is a schematic view of the structure of an aldehyde condensation reaction apparatus according to example 2 of the present invention;
in the figure: a dispersing device: f-1, F-2 and F-3, reaction device: r-1 and R-2, circulating pump: p-1, P-2, P-3, P-4, P-5, P-6, P-7 and P-8, heat exchanger: hx-1, Hx-2, Hx-3 and Hx-4, chromatography: d-1 and D-2, pipeline: 101. 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, and 213.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
the invention provides aldehyde condensation reaction equipment, the structure of which is shown in figure 1, wherein the aldehyde condensation reaction equipment comprises a dispersed phase pipeline, a continuous phase pipeline, a circulating pipeline, a reaction device R-1 and a dispersing device F-1; the dispersing device F-1, the reaction device R-1, the circulating pipeline and the continuous phase pipeline are sequentially and circularly connected; the dispersed phase pipeline is connected with the liquid inlet of the dispersing device F-1. The liquid outlet of the dispersing device F-1 is connected with the sample inlet of the reaction device R-1, the sample outlet of the reaction device R-1 is connected with the inlet of the circulating pipeline, the outlet of the circulating pipeline is connected with the continuous phase pipeline, the continuous phase pipeline is connected with the liquid inlet of the dispersing device F-1, the circulating pipeline is sequentially provided with a circulating pump P-1 and a heat exchanger Hx-1 along the circulating logistics direction, and the circulating pipeline is provided with a reaction product outlet.
Another aldehyde condensation reaction apparatus according to an embodiment of the present invention is partly provided, and has a structure as shown in FIG. 2, and the aldehyde condensation reaction apparatus comprises a dispersed phase line, a continuous phase line, a circulation line, a reaction device R-2, a first dispersing device F-2, and a second dispersing device F-3; the reaction device R-2, the circulating pipeline and the second dispersing device F-3 are sequentially connected in a circulating manner; the dispersed phase pipeline and the continuous phase pipeline are respectively and independently connected with a liquid inlet of the first dispersing device F-2; and the liquid outlet of the first dispersing device F-2 is connected with the sample inlet of the reaction device R-2. The reaction device R-2 sample outlet is connected with the inlet of the circulation pipeline, the outlet of the circulation pipeline is connected with the liquid inlet of the second dispersing device F-3, the liquid outlet of the second dispersing device F-3 is connected with the sample inlet of the reaction device R-2, the circulation pipeline is sequentially provided with a circulation pump P-5 and a heat exchanger Hx-4 in front of the second dispersing device F-3 along the circulation material flow direction, and the circulation pipeline is provided with a reaction product outlet.
In the invention, after the product is separated by a chromatographic device, a water phase and a circulating material flow are combined and then are dispersed and returned to a reactor, and an organic phase is taken as a product to be extracted and subjected to subsequent purification treatment.
In the invention, the reaction pipeline is provided with a circulating pump, a heat exchanger and other devices, the positions of the circulating pump and the heat exchanger can be adjusted according to the specific production requirements, the arrangement mode is known in the field, and details are not repeated herein.
Example 1
This example provides an aldehyde condensation reaction apparatus, the structure of which is shown in FIG. 3, wherein the aldehyde condensation reaction apparatus comprises a dispersed phase pipeline, a continuous phase pipeline, a circulation pipeline, a reaction device R-1 and a dispersion device F-1; the dispersing device F-1, the reaction device R-1, the circulating pipeline and the continuous phase pipeline are sequentially and circularly connected;
the dispersed phase pipeline 101 and the catalyst supplementing pipeline 102 are respectively and independently connected with a liquid inlet of the dispersing device F-1, a liquid outlet of the dispersing device F-1 is connected with a sample inlet of the reaction device R-1 through a pipeline 103, a sample outlet of the reaction device R-1 is connected with a liquid inlet of a circulating pump P-1 on the circulating pipeline through a pipeline 104, a liquid outlet of the circulating pump P-1 is connected with a liquid inlet of a heat exchanger Hx-1 through pipelines 105 and 106, a liquid outlet of the heat exchanger Hx-1 is connected with the continuous phase pipeline through a pipeline 107, and the continuous phase pipeline is connected with a liquid inlet of the dispersing device F-1 through a pipeline 112;
the circulating pipeline is provided with a product outlet, the product outlet is positioned at the joint of pipelines 105 and 106, the product outlet is connected with a liquid inlet of a circulating pump P-3, a liquid outlet of the circulating pump P-3 is connected with a liquid inlet of a heat exchanger Hx-2 through a pipeline 108, a liquid outlet of the heat exchanger Hx-2 is connected with a chromatography D-1 through a pipeline 109, a water phase outlet of the chromatography D-1 is connected with a liquid inlet of the circulating pump P-2 through a pipeline 111, a liquid outlet of the circulating pump P-2 is connected with a pipeline 112, and an organic phase outlet of the chromatography D-1 is connected with a circulating pump P-4 through a pipeline 110.
Example 2
The invention provides aldehyde condensation reaction equipment, the structure of which is shown in figure 4, wherein the aldehyde condensation reaction equipment comprises a dispersed phase pipeline, a continuous phase pipeline, a circulating pipeline, a reaction device R-2, a first dispersion device F-2 and a second dispersion device F-3; the reaction device R-2, the circulating pipeline and the second dispersing device F-3 are sequentially connected in a circulating manner;
the dispersed phase pipeline 201 and the catalyst supplementing pipeline 202 are respectively and independently connected with a liquid inlet of the first dispersing device F-2, and a liquid outlet of the first dispersing device F-2 is connected with a sample inlet of the reaction device R-2 through a pipeline 203. A sample outlet of the reaction device R-2 is connected with a liquid inlet of a circulating pump P-5 on the circulating pipeline through a pipeline 204, a liquid outlet of the circulating pump P-5 is connected with a liquid inlet of a heat exchanger Hx-4 through pipelines 205 and 206, a liquid outlet of the heat exchanger Hx-4 is connected with a liquid inlet of a second dispersing device F-3 through a pipeline 208, and a liquid outlet of the second dispersing device F-3 is connected with a sample inlet of the reaction device R-2 through a pipeline 209;
the circulating pipeline is provided with a product outlet, the product outlet is positioned at the joint of the pipelines 205 and 206 and is connected with a liquid inlet of a circulating pump P-6, a liquid outlet of the circulating pump P-6 is connected with a liquid inlet of a heat exchanger Hx-5 through a pipeline 207, a liquid outlet of the heat exchanger Hx-5 is connected with a chromatography D-2 through a pipeline 210, a water phase outlet of the chromatography D-2 is connected with a circulating pump P-7 through a pipeline 212, a liquid outlet of the circulating pump P-7 is connected with a liquid inlet of the second dispersing device F-3 through a pipeline 213, and an organic phase outlet of the chromatography D-2 is connected with a circulating pump P-8 through a pipeline 211.
Example 3
This example provides an aldehyde condensation reaction process using the apparatus provided in example 1, comprising the steps of:
mixed valeraldehyde (92% n-valeraldehyde, 4.8% isovaleraldehyde, 2.1% butene and butane, 1.0% water, 77kg/hr) from line 101 was passed through a static mixer of the SK type F-1 with make-up aqueous NaOH solution (30% NaOH, maintaining NaOH concentration in the reaction solution at 2%) from line 102, reactor recycle stream from hx-1 and recycled aqueous NaOH solution from line 112 (the volume ratio of recycled aqueous phase to valeraldehyde feed was about 2:1), dispersed in the aqueous phase as droplets of 1-5 μm size after passing through the static mixer F-1 and passed through line 103 from the bottom of reactor R-1 into R-1. The reactor R-1 was a 100L tank reactor (level 80%) having an inner diameter of 0.35 m. The reactor was maintained at a pressure of 0.4-0.6MPa by nitrogen. The reaction temperature was 120 ℃.
The liquid phase at the upper part of the reactor is extracted from the reactor by a circulating pump P-1 and then divided into two parts, most of the circulating liquid phase is cooled by a heat exchanger HX-1 to remove reaction heat, then mixed with the circulating catalyst aqueous solution from the chromatographic apparatus D-1 through a pipeline 107, mixed with the reaction raw material through a pipeline 112, and then fed into the reactor through a mixer F-1. One stream is withdrawn from the recycle stream as the reaction product stream (mass ratio of recycle stream to product stream 15: 1). The apparent liquid velocity of the organic phase through the reactor cross-section under these conditions was 0.005 m/s. The catalyst solution is fed into a heat exchanger HX-2 through a pipeline 110 by a pump P-3 and cooled by cooling water, then the two-phase flow is separated by a layer analyzer D-1, and the water phase is the catalyst solution and returns to the reactor through the pump P-2. The organic phase is a product decenal and a small amount of unreacted valeraldehyde, and can be sent into a storage tank or a hydrogenation reactor for hydrogenation reaction to obtain decanol. The flow of inlet and outlet streams of the device is measured within a certain time, and the conversion rate of valeraldehyde and the yield of decenal (PBA) products after reaction by using the device can be obtained by combining the chromatographic analysis result of each stream, and the specific results can be shown in Table 1.
Example 4
This example provides an aldehyde condensation reaction process using the apparatus provided in example 2, comprising the steps of:
n-butyraldehyde (99.8%, 120kg/hr) from a line 201 was mixed with a supplemental aqueous NaOH solution (30 wt% NaOH, maintaining the NaOH concentration in the reaction solution at 2%) from a line 202, and then passed through a gas-liquid disperser F-2. The gas-liquid disperser F-2 is composed of an inner sleeve and an outer sleeve, the inner pipe is a ceramic material with micropores distributed on the surface, the outer pipe is stainless steel, and n-butyl aldehyde enters the water phase of the outer pipe in the form of micro-droplets through the wall of the inner pipe. After passing through the disperser F-2, n-butyraldehyde was dispersed in the aqueous phase in droplets of 100nm to 1 μm in size, and entered from the bottom of the reactor R-2 after being joined via the line 203 with the mixture stream of the reactor recycle stream from the line 209 and the recycle aqueous NaOH solution from the decanter D-2. The reactor R-2 was a 100L tubular reactor having an inner diameter of 0.2 m. The reactor pressure was self-increasing and the temperature was 120 ℃.
The two-phase mixture of the reactor was withdrawn by means of a circulation pump P-5 and divided into two streams (mass ratio of circulation stream to product stream 20: 1), under which conditions the superficial liquid velocity of the organic phase across the cross-section of the reactor was 0.032 m/s. Most of the circulating liquid phase is cooled by cooling water of a heat exchanger HX-4 to remove reaction heat, then mixed with a catalyst solution from the bottom of a layer analyzer D-2 through a pipeline 208, and then dispersed into tiny droplets with the size of 100nm-1 mu m again through a gas-liquid disperser F-3 (the same type as F-2), and then mixed with a reaction raw material from a reactor 203 through a pipeline 209 and then enters a reactor R-2 from the bottom. One material flow is extracted from the circulating stream to be used as a reaction product flow, the reaction product flow is sent to a heat exchanger HX-5 by a pump P-6 through a pipeline 207 to be cooled, then the two-phase flow is chromatographically separated by a chromatographic analyzer D-2, and the water phase is mixed with the circulating material flow after passing through a pump P-7 and then returns to the reactor. The organic phase is a product of octenal and a small amount of unreacted butyraldehyde, and is sent to a storage tank or a hydrogenation reactor by a pump P-8 for hydrogenation reaction. The flow of the inlet and outlet streams of the device is measured within a certain period of time, and the conversion rate of butyraldehyde and the yield of the octenal product after the reaction by using the device can be obtained by combining the chromatographic analysis result of the composition of each stream, and the specific results can be shown in table 1.
Example 5
The process flow and the apparatus used in this example were the same as in example 3. Except that the reactor used was increased in volume to 15M3(80% of liquid level), and the inner diameter of the reactor was 2.0 m. The mass ratio of the reactor recycle stream (line 109 stream) to the product stream (line 110 stream) was 40: 1. The superficial liquid velocity of the organic phase through the cross-section of the reactor under these conditions was 0.047 m/s. The flow rate of the reaction feed mixed valeraldehyde was adjusted to 12000 kg/hr. The flow of inlet and outlet streams of the device is measured within a certain period of time, and the conversion rate of valeraldehyde and the yield of decenal products after reaction by using the device can be obtained by combining the chromatographic analysis result of each stream composition, and the specific results can be shown in table 1.
Comparative example 1
The comparative example used the same experimental conditions as in example 1, except that the liquid-liquid dispersion apparatus was omitted from the flow, and the reactor was replaced with a stirred tank equipped with a gas distributor.
Comparative example 2
The comparative example employed the same experimental conditions as in example 2, except that the reactor was changed to a straight tube in series of multiple stages, the diameter was reduced to 0.08m, and the apparent liquid velocity of the organic phase across the cross-section of the reactor under these conditions was 0.2 m/s.
Comparative example 3
This comparative example used the same experimental conditions as example 3, except that the mass ratio of the reactor recycle stream (line 206 stream) to the product stream (line 207 stream) was 5: 1.
Comparative examples 1-3 the results of the reactions are shown in Table 1.
TABLE 1
| Starting olefin | Aldehyde conversion% | The yield of the olefine aldehyde product is% | |
| Example 3 | Mixed pentanal | 78.9％ | 77.6％ |
| Example 4 | N-butyraldehyde | 84.7％ | 84.1％ |
| Example 5 | MixingPentanal | 76.5％ | 75.6％ |
| Comparative example 1 | Mixed pentanal | 75.2％ | 74.4％ |
| Comparative example 2 | N-butyraldehyde | 80.2％ | 78.8％ |
| Comparative example 3 | Mixed pentanal | 72.2％ | 71.3％ |
It can be known from the comparison of the experimental results of the examples and the comparative examples that the high dispersion of the organic phase in the catalyst solution is realized by adopting a liquid-liquid two-phase dispersing device and a forced large-flow external circulation mode, and the aldehyde conversion rate and the product selectivity are slightly higher than those of the traditional stirred tank (comparative example 1) and the tubular reactor (comparative example 2). When the superficial gas velocity of the organic phase across the cross section of the reactor exceeds 0.1m/s (comparative example 2), the effect of dispersing the synthesis gas in the liquid phase of the reaction is affected, resulting in a decrease in the aldehyde conversion and the product yield. At lower reactor recycle flow rates (comparative example 3), the dispersion of the synthesis gas in the liquid reaction phase is also affected, resulting in a decrease in aldehyde conversion and product selectivity. This illustrates the necessity of the present invention to define the apparent liquid velocity of the organic phase across the reactor cross-section and the ratio of the reactor recycle stream to the product stream. The invention simplifies the structure of the reactor, reduces the manufacturing and maintenance cost of equipment, and has important breakthrough on the aldehyde condensation reaction.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. An aldehyde condensation reaction device is characterized by comprising a dispersed phase pipeline, a continuous phase pipeline, a circulating pipeline, a reaction device and a dispersing device;
the dispersing device, the reaction device, the circulating pipeline and the continuous phase pipeline are sequentially and circularly connected;
the dispersed phase pipeline is connected with the liquid inlet of the dispersing device.
2. The aldehyde condensation reaction apparatus as recited in claim 1 wherein said dispersion apparatus liquid outlet is connected to said reaction apparatus sample inlet;
preferably, the sample outlet of the reaction device is connected with the inlet of the circulating pipeline;
preferably, the circulation line outlet is connected to the continuous phase line;
preferably, the continuous phase pipeline is connected with the liquid inlet of the dispersing device;
preferably, a reaction product outlet is arranged on the circulating pipeline.
3. An aldehyde condensation reaction device is characterized by comprising a dispersed phase pipeline, a continuous phase pipeline, a circulating pipeline, a reaction device, a first dispersing device and a second dispersing device;
the reaction device, the circulating pipeline and the second dispersing device are sequentially and circularly connected;
the dispersed phase pipeline and the continuous phase pipeline are respectively and independently connected with the liquid inlet of the first dispersing device;
the liquid outlet of the first dispersion device is connected with the sample inlet of the reaction device.
4. The acetal reaction apparatus according to claim 3, wherein the sample outlet of the reaction device is connected to the inlet of the circulation line;
preferably, the outlet of the circulating pipeline is connected with the liquid inlet of the second dispersing device;
preferably, the liquid outlet of the second dispersing device is connected with the sample inlet of the reaction device;
preferably, a reaction product outlet is arranged on the circulating pipeline.
5. An aldehyde condensation reaction process, comprising:
dispersing the dispersed phase in the mobile phase through first dispersion to obtain a reaction material flow;
the reactant flow is divided into a circulating flow and a reaction product flow after entering a reaction device for reaction;
the circulating material flow returns to the reaction device after second dispersion;
the apparent liquid velocity of the dispersed phase in the reactant stream through the cross section of the reaction device is less than 0.1 m/s.
6. The aldehyde condensation reaction process according to claim 5, wherein the apparent liquid velocity of the dispersed phase in the reactant stream through the cross-section of the reaction apparatus is less than 0.05 m/s.
7. The aldehyde condensation reaction process according to claim 5 or 6, wherein the volume ratio of the dispersed phase to the mobile phase is 10 to 1:1, preferably 3 to 1: 1;
preferably, the diameter of the droplets dispersed in the continuous phase after the dispersed phase is subjected to the first dispersion and the second dispersion independently is less than 100 μm, preferably 100nm to 10 μm.
8. The aldehyde condensation reaction process according to any one of claims 5-7, characterised in that the mass flow ratio of the recycle stream and the reaction product stream is greater than 8:1, preferably from 10 to 40: 1.
9. The aldehyde condensation reaction process according to any one of claims 5-8, characterised in that the dispersed phase is an organic phase;
preferably, the organic phase comprises any one of or a combination of at least two of C1-C20 aldehyde or C3-C20 ketone;
preferably, the continuous phase is a catalyst solution;
preferably, the catalyst comprises any one of alkali metal hydroxide or amine organic base or a combination of at least two of the above;
preferably, the solvent of the catalyst solution comprises any one of water, alcohol or phenol or a combination of at least two thereof.
10. The aldehyde condensation reaction process according to any one of claims 5-9, comprising:
dispersing a dispersed phase in a mobile phase through first dispersion, wherein the diameter of a droplet of the dispersed phase dispersed in the continuous phase is less than 100 mu m, and obtaining a reactant flow;
the dispersed phase is an organic phase which comprises any one or the combination of at least two of C1-C20 aldehyde or C3-C20 ketone; the continuous phase is a catalyst solution, the catalyst comprises any one or the combination of at least two of alkali metal hydroxide or amine organic base, and the solvent of the catalyst solution comprises any one or the combination of at least two of water, alcohol or phenol;
after entering a reaction device for reaction, the reactant flow is divided into a circulating flow and a reaction product flow, wherein the mass flow ratio of the circulating flow to the reaction product flow is more than 8: 1;
the circulating material flow returns to the reaction device after second dispersion;
the apparent liquid velocity of the dispersed phase in the reactant stream through the cross section of the reaction device is less than 0.1 m/s.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114768637A (en) * | 2022-04-28 | 2022-07-22 | 清华大学 | Continuous countercurrent device based on micro-dispersion technology |
| CN116063167A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Method and device for preparing 2-propyl-2-heptenal and obtained 2-propyl-2-heptenal |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297877A (en) * | 1999-11-30 | 2001-06-06 | 奥克森诺奥勒芬化学股份有限公司 | Catalytic hydroxyal condensation process with polyphase reaction |
| CN1328485A (en) * | 1998-11-26 | 2001-12-26 | Basf公司 | Reactor for carrying out gas-liquid, liquid-liquid or gas-liquid-solid chemical reactions |
| CN101838186A (en) * | 2009-03-17 | 2010-09-22 | 赢创奥克森诺有限责任公司 | Process for preparing α, β-unsaturated C10-aldehydes |
| CN102093180A (en) * | 2009-12-15 | 2011-06-15 | 上海焦化有限公司 | Method for continuously producing unsaturated aldehyde compound |
| CN102442893A (en) * | 2010-10-08 | 2012-05-09 | 中国石油化工股份有限公司 | Separation method of aldehyde condensation products |
| CN103492352A (en) * | 2011-03-03 | 2014-01-01 | Oxea有限责任公司 | Method for carrying out multiphase aldol condensation reactions to obtain mixed alpha,beta-unsaturated aldehydes |
| US20140155656A1 (en) * | 2012-11-30 | 2014-06-05 | Basf Se | Process for the Catalytic Aldol Condensation of Aldehydes |
-
2021
- 2021-05-26 CN CN202110577419.3A patent/CN113209930A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328485A (en) * | 1998-11-26 | 2001-12-26 | Basf公司 | Reactor for carrying out gas-liquid, liquid-liquid or gas-liquid-solid chemical reactions |
| CN1297877A (en) * | 1999-11-30 | 2001-06-06 | 奥克森诺奥勒芬化学股份有限公司 | Catalytic hydroxyal condensation process with polyphase reaction |
| CN101838186A (en) * | 2009-03-17 | 2010-09-22 | 赢创奥克森诺有限责任公司 | Process for preparing α, β-unsaturated C10-aldehydes |
| CN102093180A (en) * | 2009-12-15 | 2011-06-15 | 上海焦化有限公司 | Method for continuously producing unsaturated aldehyde compound |
| CN102442893A (en) * | 2010-10-08 | 2012-05-09 | 中国石油化工股份有限公司 | Separation method of aldehyde condensation products |
| CN103492352A (en) * | 2011-03-03 | 2014-01-01 | Oxea有限责任公司 | Method for carrying out multiphase aldol condensation reactions to obtain mixed alpha,beta-unsaturated aldehydes |
| US20140155656A1 (en) * | 2012-11-30 | 2014-06-05 | Basf Se | Process for the Catalytic Aldol Condensation of Aldehydes |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116063167A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Method and device for preparing 2-propyl-2-heptenal and obtained 2-propyl-2-heptenal |
| CN114768637A (en) * | 2022-04-28 | 2022-07-22 | 清华大学 | Continuous countercurrent device based on micro-dispersion technology |
| CN114768637B (en) * | 2022-04-28 | 2024-02-23 | 清华大学 | Continuous countercurrent device based on micro-dispersion technology |
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